text:
|Publication number||US4304838 A|
|Application number||US 05/834,020|
|Publication date||Dec 8, 1981|
|Filing date||Sep 16, 1977|
|Priority date||Mar 27, 1973|
|Also published as||DE2414240A1|
|Publication number||05834020, 834020, US 4304838 A, US 4304838A, US-A-4304838, US4304838 A, US4304838A|
|Inventors||Eiichi Hasegawa, Hisatake Ono, Shigeo Tanaka|
|Original Assignee||Fuji Photo Film Co., Ltd.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (2), Referenced by (19), Classifications (27), Legal Events (1)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This is a continuation of co-pending application Ser. No. 634,707, filed Nov. 24, 1975, now abandoned, which is in turn a continuation-in-part application of co-pending application Ser. No. 455,087, filed Mar. 27, 1974, now abandoned.
1. Field of the Invention
This invention relates to a photopolymerizable composition comprising a chlorinated polyolefin as polymeric binder, a monomer having one unsaturated olefinic bond capable of addition polymerization and an initiator promoting the photopolymerization of the monomer. This invention also relates to recording materials prepared by coating on a plastic film support a layer of the photopolymerizable composition and further, if desired, providing a protective plastic film over this layer.
2. Description of the Prior Art
Photopolymerizable compositions, utilized in photo resists, offset plate masters, relief printing plates, transfer type photopolymerizable materials and, moreover, recording materials such as "Crolux", trade name, produced by E. I. DuPont de Nemours, which is based on a photoadhesion phenomenon, usually comprise (a) a polymeric material as a binder, (b) a monomer having an ethylenically unsaturated linkage, (c) an initiator for photopolymerization, and other ingredients. Some specific compositions are disclosed, for example, in the following patent specifications; Japanese Patent Publication No. 16614/1960, Japanese Patent Publication No. 15810/1963, and Japanese Patent Publication No. 9663/1963 and U.S. Pat. No. 3,353,955. Here, the monomer having an unsaturated double bond functions, prior to exposure to radiation, as a plasticizer or a tackifier for the polymeric binder used, and upon exposure to actinic radiation forms three-dimensional cross-linkages, thus losing its previous plasticizing or tackifying characteristics. Therefore, how well the monomer can exhibit its intrinsic properties depends to a great extent on the kind, the properties or the mixing ratio of the polymer binder.
Especially, where a photopolymerizable composition is used for the preparation of a printing plate, the composition must exhibit, first of all, a sufficiently high photosensitivity for practical applications. However, from the practical point of view, other characteristics are also quite important including the oleophilic nature of the image area (in other words, the degree of hydrophilicity in the background area), the ease with which the developing operation can be carried out, and a high resolving power. If the resolving power is rather poor, the middle portion of the English letter "o" or "e" will be filled in, which cannot be permitted in the printing master. Considering these aspects, the interaction between the polymer binder and the monomer is very significant.
Further, in the case of a transfer type photopolymerizable recording material, in addition to an acceptable level of polymerization speed, a distinct difference must be developed in the exposed and non-exposed areas in some physical property, for example, such as softening point, adhesive property or hue (color formation or color fading). Such a difference in a physical property results at the subsequent transfer procedure in an imagewise transfer either of the exposed or non-exposed area onto a receiving material. In the transfer procedure, the system may be heated, if necessary.
Recently, a recording process has been developed in which the difference in the surface tackiness of a photopolymer layer at the exposed and non-exposed areas is detected by dusting a finely-divided coloring powder (for example, a toner powder) to provide proofs for multi-color printing. In these applications as in the preparation of the printing plate, the selection and combination of a polymer material as the binder and of the monomer used is quite important in order to increase the difference in properties between the exposed and non-exposed areas.
On the other hand, image forming processes are known as described in detail in some patent specifications including Japanese Patent Publication Nos. 9663/1963 and 7728/1972 and U.S. Pat. No. 3,353,955 wherein an image is obtained by the use of a difference in adhesive properties at the exposed and non-exposed areas. This method, using a recording material prepared by providing a photosensitive layer mainly comprising as components a polymeric binder, an ethylenically unsaturated monomer and a photopolymerization initiator as described above on a support such as a plastic film, a metal plate or a paper, and then placing a thin transparent film over this layer, comprises: an image exposure through an original from above the film, and a peeling-off of the film whereby either the exposed or non-exposed area of the photosensitive layer stays unchanged on the support and the complementary, remaining area is transferred or held on the cover film, thus giving a negative and positive image on each of the support and the cover. In this process, a separation of the photosensitive layer essentially takes place at the boundaries between the exposed and non-exposed areas. The mechanical properties related with such a phenomenon primarily depend on those of the polymer binder and of the monomer used in the layer. The most important factors are the molecular weight, the softening point, the degree of crystallinity, the compatibilities with other materials, and the adhesion strength to the support of the polymer binder used. The resulting image, which will subsequently be utilized for various applications, further should meet certain requirements depending on the end use application, such as resistance to abrasion, chemicals and to weathering, etc.
The importance of the properties of the ingredients used in the recording materials comprising a polymer binder, an ethylenically unsaturated monomer and a polymerization initiator has been explained. However, most materials already known in the art do not at present completely satisfy all the requirements described above, and exhibit a rather poor image forming capability. In Japanese Patent Publication 9663/1963, polymer materials are disclosed as binder which can also impart tackiness to the recording layer. The materials disclosed include polyvinylbutyral, polyvinyl acetate, polyvinylpyrolidone, gelatin, coumarone-indene resins, silicone resins, rubbers, etc. Also, Japanese Patent Publication 7728/1972 discloses that polymers such as vinylidene chloride copolymers, cellulose esters, synthetic rubbers, polyvinyl acetate, polyalkyl acrylates, polyvinylchloride, etc. can be used as a binder. However, according to our experimental evaluations, combinations of these polymers with a variety of monomers and of polymerization initiators failed to give satisfactory results. Especially, with respect to polyvinyl chloride, U.S. Pat. Nos. 3,867,153 (MacLachlan) and 3,261,686 (Celeste et al) disclose that polyvinyl chloride are used in combination with monomer for light sensitive materials. However, from the results of our detailed experiment, as polyvinyl chloride has defects that polyvinyl chloride has poor compatibility with monomer, furthermore, there is a few organic solvents capable of dissolving polyvinyl chloride so that kind of the organic solvent is limited, it is clear that polyvinyl chloride is very unsuitable for the effective use as the binder of photopolymerization composition.
The inventors, as a result of extensive research to improve the disadvantages in conventional technology, have found that chlorinated polyolefins have an excellent property as a binder polymer. Thus, a principal object of the present invention is to provide a photopolymerizable composition comprising (a) a chlorinated polyolefin, (b) a monomer having an ethylenically unsaturated bond capable of addition polymerization and (c) a photopolymerization initiator.
The chlorinated polyolefins which can be used in the present invention are high molecular weight compounds obtained by chlorination of polyolefins and are described in Japanese Patent Publication 11190/1971, etc. Of the many chlorinated polyolefins which can be used in the present invention, chlorinated polyethylene, chlorinated polypropylene and chlorinated copolymer of poly(ethylene/propylene) are most preferred. Chlorinated polyethylene is commercially available as Superchlon-CPE (trade name, produced by Sanyo Kokusaku Pulp Co.) or Erathrene (trade name, produced by Showa Denko Co.), and can be regarded as a new plastic material, since it has unique features as to weather-resistance, thermal resistance, flame resistance, chemical resistance, ozone resistance, etc., as well as other features which conventional polymer materials possess. A commercially available example of chlorinated polypropylene is Superchlon-CPP (trade name, produced by Sanyo Kokusaku Pulp Co.). The properties of this product are quite similar to those of chlorinated polyethylene. Both compounds have a white powdery appearance. The chlorinated polyolefins used in the present invention should have a degree of polymerization ranging from about 300 to 20,000, and more preferably from about 1,000 to 8,000. The chlorine content can be from about 20 to 80% by weight, more preferably being from 50 to 75% by weight. As the chlorine content of a chlorinated polyolefin increases, its density increases and the solubility in various solvents improves. In addition, the chlorine content affects the softening point, the tensile elongation, the tensile strength, the degree of crystallinity, etc. It should be noted that chlorinated polyolefins are superior in compatibility with many other resins, plasticizers, monomers, polymerization initiators, etc.
As for component (b) of the present invention, any monomer can be used, provided that it has at least one unsaturated bond which is capable of addition polymerization. Such unsaturated compounds capable of addition polymerization include, for example, acrylic acid esters, acrylamide compounds, methacrylic acid esters, vinyl ethers, allylic compounds, vinyl esters, N-vinyl compounds, styrene compounds, crotonic acid esters, etc.
Compounds having one unsaturated bond capable of addition polymerization include acrylic acid compounds such as, for example, acrylic acid, alkyl acrylates (e.g., propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, diethylene glycol monoacrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), or aryl acrylates (e.g., phenyl acrylate, chloro phenyl acrylates, etc.); methmethacrylic acid compounds such as methacrylic acid, alkyl methacrylates (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, ethyleneglycol monomethacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, diethyleneglycol monomethacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.), or aryl methacrylates (e.g., phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.); acrylamide compounds such as, for example, acrylamide, N-alkylacrylamides containing methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, benzyl, hydroxymethyl, hydroxyethyl, etc. groups as alkyl group, N,N-dialkylacrylamides containing methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl, etc. groups as alkyl groups, N,N-diarylacrylamides containing as the aryl group, for example, phenyl groups, N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, or N-2-acetamidoethyl-N-acetylacrylamide; methacrylamide compounds such as methacrylamide, N-alkylmethacrylamides having methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl, etc. groups as alkyl group, N-arylmethacrylamides having a phenyl group as the aryl group, N,N-dialkylmethacrylates having ethyl, propyl, butyl, etc. as the alkyl groups, N,N-diarylmethacrylamides having phenyl groups as the aryl group, for example, N-hydroxyethyl-N-methyl methacrylamide, N-methyl-N-phenyl methacrylamide, N-ethyl-N-phenyl methacrylamide, etc.; allyl compounds such as, for example, allyl esters (e.g., allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, or allyl lactate) or 2-allyloxyethanol; vinyl ethers such as alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl ether, hydroxyethyl vinyl ether, diethyleneglycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.); vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethylacetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthenate; N-vinyl compounds such as, for example, N-vinyloxazolidone, N-vinylimidazole, N-vinylpyrolidone, N-vinylcarbazole, or N-vinylethylacetamide; styrene compounds such as styrene, alkylstyrenes (e.g., methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene,, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrenes (e.g., methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogenated styrenes (e.g., chlorostyrene, dichlorostyrene, trichlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), or carboxystyrenes (e.g., vinylbenzoic acid, methyl vinylbenzoate, etc.); or crotonic acid esters such as alkyl crotonates (e.g., butyl crotonate, hexyl crotonate, glycerol monocrotonate, etc.).
Next, specific compounds having two or more unsaturated bonds capable of addition polymerization are illustrated. These compounds are preferred for use in the present invention over those with one unsaturated bond. Such compounds include, first of all, esters of acrylic and methacrylic acid comprising the polyacrylates or polymethacrylates of polyhydric alcohols (here, the term "poly" implies esters containing two or more acrylic or methacrylic residues). Suitable polyhydric alcohols include polyethylene glycol, polypropylene oxide, polybutylene oxide, polycyclohexene oxide, polyethylene oxide-propylene oxide, polystyrene oxide, polyoxetane, polytetrahydrofuran, cyclohexanediol, xylylene-diol, di-(β-hydroxyethoxy)benzene, glycerol, diglycerol, neopentyl glycol, trimethylolpropane, triethylolpropane, pentaerythritol, dipentaerythritol, sorbitan, sorbitol, butanediol, 2-butene-1,4-diol, 2-n-butyl-2-ethylpropanediol, 2-butyne-1,4-diol, 3-chloro-1,2-propanediol, 1,4-cyclohexanedimethanol, 3-cyclohexene-1,1-dimethanol, decalindiol, 2,3-dibromo-2-butene-1,4-diol, 2,2-diethyl-1,3-propanediol, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2,5-diphenyl-1,3-propanediol, dodecanediol, mesoerythritol, 2-ethyl-1,3-hexanediol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, heptanediol, hexanediol, 3-hexene-2,5-diol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 2-methyl-1,4-butanediol, 2-methyl-2,4-pentanediol, nonanediol, octanediol, pentanediol, 1-phenyl-1,2-ethanediol, propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,3,5,6-tetramethyl-p-xylene-α,α-diol, 1,1.4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,2,6-trihydroxyhexane, 1,1'-methylenedi-2-naphthol, 1,2,4-benzenetriol, biphenol, 2,2'-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(hydroxyphenyl)methane, catechol, 4-chlororesorcinol, 3,4-dihydroxyhydrocinnamic acid, hydroquinone, hydroxybenzyl alcohol, methylhydroquinone, methyl-2,4,6-trihydroxybenzoate, phloroglucinol, pyrogallol, resorcinol, glucose, α-(1-aminoethyl)-p-hydroxybenzyl alcohol, 2-amino-2-ethyl-1-,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, N-(3-aminopropyl)-diethanolamine, N,N'-bis-(2-hydroxyethyl)piperazine, 2,2-bis(hydroxymethyl)-2,2',2"-nitrilotriethanol, 2,2-bis(hydroxymethyl)propionic acid, 1,3-bis(hydroxymethyl)urea, 1,2-bis(4-pyridyl)-1,2-ethanediol, N-n-butyldiethanolamine, diethanolamine, N-ethyldiethanolamine, 3-mercapto-1,2-propanediol, 3-piperidino-1,2-propanediol, 2-(2-pyridyl)-1,3-propanediol, triethanolamine, α-(1-aminoethyl)-p-hydroxybenzyl alcohol, 3-amino-4-hydroxyphenylsulfone, etc. Of these acrylic and methacrylic esters, the following ones are most preferred because of their commercial availability: ethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol dimethacrylate, dipentaerythritol pentaacrylate, glycerol triacrylate, diglycerol dimethylacrylate, 1,3-propanediol diacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, the triacrylate ester of the trimethylolpropane reaction product with ethylene oxide, etc.
On the other hand, acrylamide and methacrylamide compounds having two or more unsaturated bonds include: methylene-bis-acrylamide, methylene-bis-methacrylamide, and the polyacrylamides and polymethacrylamides of ethylenediamine, diaminopropane, diaminobutane, pentamethylenediamine, hexamethylene-bis(2-aminopropyl)amine, diethylenetriamine-diamine, heptamethylenediamine, octamethylenediamine, polyamines having a chain containing a hetero atom, and polyamines having a ring structure such as, for example, phenylenediamine, xylylenediamine, β-(4-aminophenyl)ethylamine, diaminobenzoic acid, diaminotoluene, diaminoanthraquinone, or diaminofluorene.
Allyl compounds include, for example, the diallyl esters of phthalic acid, terephthalic acid, sebacic acid, adipic acid, glutaric acid, malonic acid, or oxalic acid, and the diallyl esters or the diallylamides of disulfonic acids such as anthraquinonedisulfonic acid, benzenedisulfonic acid, 2,5-dihydroxy-p-benzenedisulfonic acid, dihydroxynaphthalenedisulfonic acid, naphthalenedisulfonic acid, etc.
Vinyl ether compounds are exemplified by the polyvinyl ethers of the above-described polyhydric alcohols, including ethylene glycol divinyl ether, 1,3,5-tri-β-vinyloxyethoxybenzene, glycerol trivinyl ether, etc.
Vinyl ester compounds include divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate, divinylbutane-1,4-disulfonate, etc.
Styrene compounds include divinylbenzene, p-allylstyrene, p-isopropenestyrene, etc.
Those compounds which possess two or more unsaturated functional groups different from each other, including N-β-hydroxyethyl-β-(methacrylamide)ethyl acrylate, N,N-bis(β-methacryloxyethyl)acrylamide, or allyl methacrylate, can also advantageously used in the present invention.
Two or more of these monomers having unsaturated groups capable of addition polymerization can be used in combination. Such a monomer(s) can be incorporated in the recording layer in the range of from about 10 to 500, more preferably from 30 to 200, parts by weight per 100 parts by weight of the chlorinated polyolefin polymer binder.
Polymerization initiators which are already known in the art can be used in the present invention, including those described in J. Kosar, Light Sensitive Systems, chapter 5, such as carbonyl compounds, organic sulfur compounds, peroxides, redox initiators, azo and diazo compounds, halogen compounds, and photo-reducible dyestuffs. Typical examples are benzoin, benzoin methyl ether, benzophenone, 9,10-anthraquinone, 2-methyl-anthraquinone, 2-tert-butylanthraquinone, 9,10-phenanthrenequinone, diacetyl, benzil, and the compounds represented by the following general formula: ##STR1## where, R1 represents an alkyl group conventionally present in cyanine dyes, including an unsubstituted lower alkyl group such as, for example, methyl, ethyl, or propyl, a hyroxyalkyl group such as 2-hydroxyethyl, an alkoxyalkyl group such as 2-methoxyethyl, a carboxyalkyl group such as carboxymethyl, or 2-carboxyethyl, a sulfoalkyl group such as 2-sulfoethyl, or 3-sulfopropyl, an aralkyl group such as benzyl, phenethyl, p-sulfophenethyl or p-carboxyphenethyl, or a vinylmethyl group; R2 represents, preferably, an alkyl group such as methyl, ethyl, propyl or other lower alkyl groups, an aryl group such as phenyl, p-hydroxyphenyl, p-methoxyphenyl, p-chlorophenyl, or naphthyl groups, or thienyl group; Z represents the non-metallic atom group necessary to complete a nitrogen-containing heterocyclic ring which is usually contained in cyanine dyes, including, for example, a benzothiazole nucleus such as benzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 4-methylbenzothiazole, 6-methylbenzothiazole, 5-phenylbenzothiazole, 6-methoxybenzothiazole, 4-ethoxybenzothiazole, 5-methoxybenzothiazole, 5-hydroxybenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, etc., a naphthothiazole nucleus such as α-naphthothiazole, or β-naphthothiazole, a benzoselenazole nucleus such as benzoselenazole, 5-chlorobenzoselenazole, 6-methylbenzoselenazole, 6-methoxybenzoselanazole, etc., a naphthoselenazole nucleus such as α-naphthoselenazole, β-naphthoselenazole, etc., a benzoxazole nucleus such as benzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methoxybenzoxazole, etc., or a naphthoxazole nucleus such as α-naphthoxazole, β-naphthoxazole, etc.
Specific examples of the compounds described above are, for example, 2-benzoylmethylene-3-methyl-β-naphthothiazoline, 2-benzoylmethylene-3-ethyl-β-naphthothiazoline, 3-ethyl-2-(2-thenoyl)methylene-β-naphthothiazoline, 3-ethyl-2-propionylmethylene-β-naphthotiazoline, 5-chloro-3-ethyl-2-p-methoxybenzoylmethylenebenzothiazoline, etc. Suitable organic sulfur compounds include di-n-butyl disulfide, di-n-octyl disulfide, dibenzyl disulfide, diphenyl disulfide, dibenzoyl disulfide, diacetyl disulfide, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, thiophenol, thiocresol, p-methoxybenzenethiol, carboxymethyl-N,N-dimethyldithiocarbamate, ethyl trichloromethanesulfenate, etc.
Examples of peroxides are hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, etc.
Redox initiator systems are provided by the combinations of a peroxide with a reducing agent and include Fe++ ion/hydrogen peroxide, Fe++ ion/persulfate ion, Fe+++ ion/peroxide, etc.
Azo and diazo compounds include α,α'-azobisisobutyronitrile, 2-azobis-2-methylbutyronitrile, 1-azo-bis-cyclohexanecarbonitrile, the diazonium salt of p-aminodiphenylamine, etc.
Examples of halogen compounds include chloromethylnaphthyl chloride, phenacyl chloride, chloroacetone, β-naphthalene sulfonyl chloride, xylene sulfonyl chloride, etc.
Suitable photo-reducible dyestuffs include rose bengal, erythrosine, eosine, acryflavine, riboflavine, thionine, etc.
The polymerization initiator suitably can be used in an amount of about 0.1 to 20 parts, more preferably, 1 to 10 parts per 100 parts by weight of the unsaturated monomer used.
Although the photo-polymerizable compositions in accordance with the present invention comprise mainly the ingredients described above, the compositions can also preferably contain a thermal polymerization inhibitor, which includes, for example, p-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinones, t-butylcatechol, pyrogallol, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, methylene blue, the copper salt of an organic acid such as copper acetate, etc. Such as inhibitor can be used in the range of from about 0.001 to 5 parts by weight per 100 parts by weight of the unsaturated monomer used.
The photopolymerizable compositions of the present invention can further contain a coloring agent, plasticizer, resinous materials and other additives. Suitable coloring agents include, for example, pigments such as titanium dioxide, carbon black, ferric oxide, phthalocyanine pigments, azo pigments, and dyes such as methylene blue, crystal violet, rhodamine B, fuchsine, auramine, azo dyes and anthraquinone dyes. Of these, those are preferred which do not absorb light in the spectral region where light absorption by the polymerization initiator takes place. Such a coloring agent can be preferably used in an amount of about 0.1 to 30 parts by weight for the pigment and in an amount of about 0.01 to 10 parts by weight for the dyestuff per 100 total parts by weight of the polymer binder and the unsaturated monomer.
Suitable plasticizers include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diaryl phthalate, etc., glycol esters such as dimethylglycol phthalate, ethylphthalylethyl glycolate, methylphthalylmethyl glycolate, butylphthalylbutyl glycolate, triethylene glycol dicaprylate, etc., phosphoric acid esters such as tricresyl phosphate, triphenyl phosphate, etc., aliphatic dicarboxylic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl azelate, dibutyl maleate, etc., and other esters such as triethyl citrate, the triacetyl ester of glycerol, and butyl laurate. A suitable amount of plasticizer ranges from about 0.1% to 20%, preferably 1 to 10% by weight.
Suitable resinous materials which can be present are rosin, xylene resins and polybutadiene in an amount ranging from about 1% to 30%, preferably 5 to 20% by weight to the total composition.
An epoxy resin as a stabilizer for the chlorinated polyolefin also can be suitably present in an amount of about 0.01% to 10%, preferably 0.1 to 5% by weight.
The photopolymerizable compositions used in the present invention are dissolved in suitable solvent systems to form a coating solution, which are coated on suitable supports and then dried.
Solvents which can be used to prepare coating solutions include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl formate, ethyl propionate, dimethyl phthalate, ethyl benzoate, etc.; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene, etc.; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, monochlorobenzene, chloronaphthalene, etc.; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, etc.; and nitrogen-containing and sulfur-containing solvents such as dimethylformamide and dimethylsulfoxide. On the surface of the support another coating can be provided in order to improve the adhesion of the photosensitive coating to the support, if desired, or an anti-halation coating. A suitable coating solution concentration can range from about 1 to 60%, preferably 10 to 40%, by weight on a solids basis.
The suppport which is used in the present invention must have a good light transmittancy as well as a sufficiently uniform surface structure. Suitavle supports include a variety of plastic films such as polyethylene terephthalate, polypropylen, polyethylene, cellulose triacetate, cellulose diacetate, poly(vinyl chloride), poly(vinyl alcohol), polycarbonate, polystyrene, cellophane, vinylidene chloride copolymers, polyamide, polyimide, vinyl chloride-vinyl acetate copolymers, poly(tetrafluoroethylene), poly(trifluoroethylene), etc. In addition, composite materials comprising two or more of these plastic materials can also be used.
The support usually has a thickness of from about 10 to 150 microns, preferably 10-100 microns, and more preferably from 20 to 50 microns. However, those with a thickness greater or smaller than the above limits can also be used.
The thickness of the photopolymerizable layer provided on the support is determined so that the image ultimately obtained satisfies the desired function, and generally a suitable of thickness is between about 5 and 100 microns and, more preferably between 10 and 60 microns.
The recording material prepared according to the present invention comprises a support and a photopolymerizable layer provided on the support, however, a protective overlying film can be provided on the photopolymerizable layer, if desired. Suitable materials for such a protective film include those illustrated as being suitable for the support as well as paper and paper laminated with polyethylene or polypropylene. The covering film can be in general about 8 to 80 microns thick, and, more preferably, 10 to 50 microns thick. In the selection of the support and the cover film, the adhesive strength A between the photopolymerizable layer and the support needs to be made greater than the adhesive strength B between the photopolymerizable layer and the cover film. This condition can be satisfied, for example, by using the following combinations of support and cover (protective) film as shown in Table 1.
TABLE 1______________________________________Combination Support Protective Film______________________________________1 Polyethylene Terephthalate Polypropylene2 Polyethylene Terephthalate Polyethylene3 Polyamide (6-Nylon) Polyethylene4 Polyvinyl Chloride Cellophane5 Polyimide Polypropylene______________________________________
Instead of using different materials as a support and a protective film, the adhesion requirement can also be satisfied by surface treatment of either the support or the protective film. Such surface treatment made on the support, which is generally carried out to improve the adhesion of the photopolymerizable composition layer to the support, includes the coating of a subbing layer, a corona discharge treatment, a flame treatment, an irradiation with ultraviolet light, an irradiation with high frequency waves, a glow discharge treatment, an active plasma treatment or an irradiation with the radiation of a laser.
On the protective film, on the contrary, the surface treatment is effected in order to reduce the adhesion between the photopolymerizable composition layer and the protective film and such treatments include subbing with a polyorganosiloxane, a fluorinated polyolefin, or a polyfluoroethylene.
The image forming processes utilizing the recording materials of the present invention will be explained in greater detail in the following.
Where the recording material in accordance with the present invention possesses a protective film, the photopolymerizable layer is, after the protective film has been peeled off, brought into intimate contact under pressure with a substrate. Then, image exposure is carried out through the transparent support. A light source emitting a sufficient amount of light in a wavelength ranging from about 350 to 450 mμ is advantageously used, such as, for example, a mercury lamp, a xenon lamp, a carbon arc lamp or a fluorescent lamp for duplication use. In addition, laser beams, electron beams or X-rays can be used. The exposure time will, of course, vary depending on the light source, but generally a suitable exposure time to a 1 kw light source at a distance of 30 cm can range from about 30 seconds to 5 minutes. After the image exposure, the support is peeled off whereby the exposed area of the photopolymerizable layer remains on the substrate and the non-exposed area is removed together with the support, thus leaving an image on the substrate.
The photopolymerizable composition of the present invention can be advantageously used in the fields of photography, photo copying, producing of relief patterns, offset printing, and gravure printing, but it is most advantageously used in the formation of resist images.
The recording material in accordance with the present invention can be used to form an image with a higher resolution compared with those obtained using conventional materials. Thus, reproduction of minute patterns can be very accurately carried out. Moreover, images obtained using the recording material of the present invention are superior in the resistance to abrasion as well as to chemicals, thus showing excellent suitability for the formation of resist images. In the following the present invention will be explained in further detail illustrating specific examples, which are given for the purpose of illustration and not for the purpose of limiting the scope of the present invention. In the examples, all percents, ratios and the like are by weight if not otherwise designated.
A photosensitive composition liquid was prepared with the following ingredients;
______________________________________Chlorinated Polyethylene (CPE-907LTA, trade name, 50 gproduced by Sanyo Kokusaku Pulp Co., [η] = 0.105 inbenzene at 30° C.; degree of chlorination = 70% byweight)Trimethylolpropane Triacrylate 40 g2-Methylanthraquinone 4 gPigment (Microlith Red RT, trade name, produced 0.1 gby Ciba Ltd.)p-Methoxyphenol 0.2 g______________________________________
These solid ingredients were added to 300 ml of methyl ethyl ketone to provide a coating solution which was coated uniformly on the anodized surface of an aluminum plate using a whirler uniformly. The coating was dried at 80° C. for 15 minutes. The thickness of the coating was 2 microns. Then, an image exposure was carried out in a vacuum printing frame using a 2 kw mercury lamp as a light source and a negative original containing alphabetic images therein as an original. The distance from the light source to the photosensitive material was 30 cm and the exposure time was 30 seconds. Then the material was subjected to spray development using a developer liquid comprising a 2:1 by volume mixture of methanol and methyl ethyl ketone whereby the non-photopolymerized portion of the photosensitive coating was selectively removed. A clear and distinct positive image corresponding to the original image resulted. The image exhibited a sufficient degree of oleophilic property, showing good receptivity to printing inks when used for printing.
The photosensitive coating mixture described in Example 1 was spray coated on a zinc plate for a letterpress printing master, and dried. The thickness of the coating was 20 microns and the coating had a clear appearance with no phase separation. After a polyethylene terephthalate film 25 microns thick was lightly laminated on the photosensitive coating, an image exposure was carried out through a silver halide photographic film original carrying therein a half-toned image, with a distance of 70 cm to a 1000 watt carbon arc lamp for 60 seconds. Development was carried out with the same developing liquid as described in Example 1 to give a sharp image on the zinc plate. Then etching was carried out using a 10% aqueous nitric acid solution, during which time the photopolymerized resist image remained firmly bonded onto the zinc plate surface without any tendency to peel away. A printing master for letterpress use was obtained by removing the resist image with methylene chloride.
A coating comprising the following ingredients was prepared in the manner described below.
______________________________________Chlorinated Polypropylene (CPP-406, trade name, 20 gproduct of Sanyo Kokusaku Pulp Co., [η] = 0.100in benzene at 30° C.; degree of chlorination = 68%by weight)Pentaerythritol Triacrylate 30 g2-t-Butylanthraquinone 0.3 gMethylene Blue 0.1 gHydroquinone 0.1 g______________________________________
Of these ingredients, methylene blue was dissolved in 1 ml of ethanol, while the remaining ingredients were dissolved in 50 ml of trichloroethylene, and the two solutions were mixed to give a viscous, colored photosensitive coating mixture. A support was prepared by placing a nylon screen mesh on a 25 micron thick polyethylene terephthalate film. On this support the coating mixture was coated on the mesh placed side, and then dried at 70° C. for 10 minutes. By overlaying on the photosensitive coating another film of polyethylene terephthalate, an assembly of multi-layer structure in which the nylon screen mesh and the photosensitive composition were sandwiched resulted. The thickness of the photosensitive coating was about 100 microns including the nylon screen mesh. After an image exposure was carried out through a positive original in a printer installed with fluorescent lamps (Plano PS-Printer-A3, trade name, a product of Fuji Photo Film Co., Ltd.) for 1 minute, the two polyethylene terephthalate films were separated whereby the unexposed portion of the photosensitive composition was removed and only the exposed portion which had been cured by light remained on the nylon screen mesh. The screen thus obtained could be used as is as a master for mimeograph printing.
A photosensitive coating mixture comprising the following ingredients was coated using whirler coating on a cleaned copper substrate for printed circuit use so as to give a dried thickness of about 20 microns.
______________________________________Chlorinated Polyethylene (Elaslen-401A, 20 ga trade name, a product of Showa DenkoLtd.)*Glycelol Triacrylate 20 g1-Methyl-2-benzoylmethylene-β-naphtho- 0.4 gthiazolinep-Methoxyphenol 0.2 gPigment (Microlith Blue 4GA, a product 0.1 gof CIBA Co.)Methyl Ethyl Ketone 100 ml______________________________________ *Elaslen-401A has a chlorine content of 40% by weight, a density of 1.20 g/cm3 and a Mooney viscosity of 80 (MS4' 100° C.).
On this coating was provided an oxygen impervious layer by overcoating a 2% aqueous solution of polyvinylpyrrolidon (molecular weight about 40,000) to give a dried thickness of about 1 micron. After an image exposure was carried out in the same manner as described in Example 1 using a negative circuit pattern original, development was conducted by spraying a developer comprising a 2:1 by volume mixture of ethyl alcohol and methyl ethyl ketone onto the surface, which gave a photo resist pattern. Etching was then carried out with a ferric chloride solution (40° Be') at 40° C. for 5 minutes to etch the copper. A printed circuit pattern resulted with an improved degree of side etching.
The following ingredients;
______________________________________Chlorinated Polyethylene (CPE-907MAI, trade name, 10 ga product of Sanyo Kokusaku Pulp Co., [η] = 0.174in benzene at 30° C.; degree of chlorination = 72%by weight)Pentaerythritol Dimethacrylate 16 g2-t-Butylanthraquinone 0.3 gHydroquinone 0.1 gPigment (Microlith Blue-4GK, trade name, 0.3 ga product of Ciba Ltd.)______________________________________
were dissolved in a mixture of 100 ml methyl ethyl ketone and 20 ml dimethylformamide to provide a photosensitive coating solution. A part of this solution was coated on a 25 micron thick polyethylene terephthalate film using a coating rod to a dried thickness of 15 microns and dried at 80° C. for 20 minutes. Then the coating was laminated under pressure onto a cleaned copper substrate for printed circuit use. The resulting assembly was exposed to a negative printed circuit pattern using a 2 kw mercury lamp for 1 minute. Immediately after the exposure, the polyethylene terephthalate cover film was peeled off whereby a photopolymerized positive image was formed on the copper substrate and the complementary portion which was not photopolymerized was removed together with the cover film. The image bearing copper substrate was subjected to an etching operation using a 40° Be' ferric chloride aqueous solution at 40° C. as described in Example 4. During the etching operation, the photosensitive coating remained firmly adhered onto the copper surface, thus showing no tendency at all toward peeling off or formation of pinholes. The removal of the polymerized image was readily accomplished using methylene chloride. It proved that the composition of the present example is superior in the ease of the removal of the resist to many conventional photo resist films such as Riston, trade name, a product of DuPont Co., which has the disadvantage of difficulty in the removal of the resist image.
______________________________________Chlorinated Polyethylene (Superchlone CPE-907LTA, 10 gtrade name, a product of Sanyo Kokusaku Pulp Co.)*Pentaerythritol Dimethacrylate 10 g2-Methylanthraquinone 0.2 gHydroquinone 0.1 gCopper Phthalocyanine Pigment 0.2 g______________________________________ *A 40 weight % toluene solution of Superchlone CPE907LTA has a viscosity of about 90 cps at 25° C. and Superchlone has a chlorine content o more than 66 weight %.
The above ingredients were dissolved in a mixture of 100 ml of methyl ethyl ketone and 20 ml of dimethylformamide to provide a photosensitive coating solution. Part of this solution was coated using a coating rod onto a 25 micron thick polyethylene terephthalate film, which was dried at 80° C. for 20 minutes. The thickness of the coating was 15 microns after drying. The coating was then laminated under pressure onto a cleaned copper substrate for printed circuit use. The laminated assembly was exposed to light from a 2 kw mercury lamp through a negative original for 1 minute. Immediately after the exposure, the polyethylene terephthalate film was peeled off from the assembly whereby the unhardened area of the photosensitive coating was removed together with the polyethylene terephthalate film, thus leaving a photopolymerized positive image on the copper substrate. The copper substrate was subjected to etching with a 40° Be' ferric chloride aqueous solution at 40° C. During this operation, no tendency toward peeling or pinhole generation of the image was observed, since the photosensitive cured coating firmly adhered onto the copper surface. The image could easily be removed with methylene chloride after etching. A conventional photoresist film such as Riston gave an image which was difficult to remove at the final procedure after etching. This means that the composition of the present invention is superior to such a conventional composition in respect to the ease of image removal.
The photosensitive coating mixture described in Example 1 was coated on a 30 micron thick polypropylene film in a similar manner to that of Example 1 to provide a dried thickness of 20 microns. This material was laminated onto a cleaned flexible copper plate under pressure. Using a negative original containing circuit pattern information, exposure was made through the polypropylene film with a carbon arc separated by a distance of 50 cm for 40 seconds. Without delay, the polypropylene film was removed off from the photosensitive coating, which operation provided a clear and distinct photoresist pattern comprising the photopolymerized coating on the flexible copper substrate. On the other hand, the non-irradiated, non-polymerized area was removed adhering to the polypropylene film. The resist pattern thus obtained could resolve fine lines with a 100 micron width and could withstand a subsequent etching operation using a 40° Be' ferric chloride aqueous solution.
The following ingredients,
______________________________________Chlorinated Polypropylene (Superchlone CPP-306, 20 gtrade name, a product of Sanyo Kokusaku Pulp Co.)*Trimethylolpropane Triacrylate 30 g2-t-Butylanthraquinone 0.3 gMethylene Blue 0.1 gHydroquinone 0.1 g______________________________________ *Superchlone CPP306 has a chlorine content not less than 66% by weight an a viscosity of about 95 cps at 25° C. when dissolved in toluene to make a 40% by weight solution.
were dissolved in 50 ml of ethylene chloride except the methylene blue which was dissolved in 1 ml of ethanol. The two solutions were mixed together to provide a colored viscous solution. This solution was uniformly coated on a 25 micron thick polyethylene terephthalate film and the coating was then dried. The thickness of the coating was 10 microns. A 20 micron thick polyethylene film was superimposed on the surface of this coating. The assembly was stored under ordinary conditions. Observation after one month proved that no degradation had occurred. After removal of the polyethylene film, the coating was laminated at room temperature onto a copper plate for printed circuit use. An image exposure was made through a negative original using a 2 kw mercury lamp for 40 seconds, and after the exposure the polyethylene terephthalate film was peeled off, giving a high quality resist pattern. This resist pattern was exactly equivalent to that obtained by processing the same material immediately after the manufacture as to image quality, and uniformity. Also no reduction in photographic speed was observed at all. The image bearing copper plate was etched with an etching solution mainly comprising ammonium persulfate. To this etching operation, the resist pattern could perfectly withstand, showing good etch resistance as well as an improved side-etching performance.
The photosensitive coating coated on a 25 micron thick polyethylene terephthalate film prepared in a similar manner to that described in Example 1 was laminated on a copper substrate for printed circuit use. (The coating thickness on dry basis was 30 microns.) In contrast to Example 1, a positive original was used in the image exposure, which was carried out using a 2 kw mercury lamp at a distance of 40 cm and an exposure time of 40 seconds, immediately followed by peeling off of the polyethylene terephthalate film. A negative resist pattern comprising the photopolymerized coating appeared on the copper plate. The exposed copper surface was then subjected to solder plating in the following way.
The plating bath.
______________________________________Sn(BF4)2 (45% aqueous solution) 300 gPb(BF4)2 (45% aqueous solution) 100 gHBF4 (42% aqueous solution) 220 gH3 BO3 28 gWater to make 100______________________________________
A solder rod comprising a 6:4 by weight mixture of tin and lead was used as the positive pole, and the plating conditions were; the temperature of the bath=30° C., the current density at the negative pole=3.0 amperes/dm2, and the plating period=30 minutes. A good solder layer was plated, and the resist was not removed nor were any pinholes generated. By immersing the copper substrate in methyl ethyl ketone, the resist image could be easily removed. Then etching was carried out with a 20% ammonium persulfate aqueous solution, which ultimately provided a circuit pattern plated with solder.
The following solution was prepared.
______________________________________Chlorinated Polyethylene (Erathrene-401A, 15 gtrade name, a product of Showa Denko Ltd.)*Diglycerol Trimethacrylate 25 g1-Methyl-2-benzoylmethylene-β-naphthothiazoline 0.5 gp-Methoxyphenol 0.2 gCarbon Black (mean particle diameter 20 milli- 0.2 gmicrons)Methyl Ethyl Ketone 100 ml______________________________________ *Erathrene-401A has a chlorine content of 40%, a density of 1.20 g/cm3 and a Mooney viscosity of 80 (MS4' 100° C.).
The solution of the above composition was coated on a polyethylene terephthalate film and then dried at 80° C. for 10 minutes. The dried coating was pressed onto a copper substrate for printed circuit use at room temperature. Subsequent procedures were carried out in the similar manner as described in Example 4 to form a resist pattern for plating. Tin plating was performed on the copper not covered by the resist whereby the resist image was firmly bonded to the copper surface even in the plating bath and no peeling was observed.
A resist pattern was formed on a copper plate in a similar manner to that described in Example 1, except that in the photopolymerizable composition the amount of chlorinated polyethylene was varied using 15, 20 and 30 g, respectively. In all cases, a good quality image was obtained as in Example 1.
In each of Examples 1 and 6-8, the chlorinated polyethylene was replaced by polymethyl methacrylate (Torex-G, trade name, a product of Toray Co., [η]=0.310 at 30° C. in methyl ethyl ketone).
In each case, it was impossible to form a clear and sharp image, and the quality of the image obtained was far inferior to the images obtained using recording materials prepared according to the present invention.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
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|US3867153 *||Sep 11, 1972||Feb 18, 1975||Du Pont||Photohardenable element|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4402887 *||Jul 30, 1979||Sep 6, 1983||Dainippon Ink And Chemicals Inc.||Sheet-like articles of polyvinyl chloride|
|US4590146 *||Jul 6, 1984||May 20, 1986||Basf Aktiengesellschaft||Stabilization of photopolymerizable mixtures|
|US4634562 *||Sep 8, 1981||Jan 6, 1987||The Goodyear Tire & Rubber Company||Photocurable polyvinyl chloride composition|
|US4761360 *||Feb 24, 1987||Aug 2, 1988||Fuji Photo Film Co., Ltd.||Light-sensitive material containing silver halide, reducing agent, polymerizable compound and a silver diazotate|
|US4767883 *||Jul 24, 1987||Aug 30, 1988||Eastman Kodak Company||Polymerizable cyclohexyleneoxyalkyl acrylates|
|US4895787 *||Jul 18, 1988||Jan 23, 1990||Hoechst Celanese Corporation||Photopolymerizable positive working, peel developable, single sheet color proofing system|
|US4902605 *||Jul 24, 1987||Feb 20, 1990||Eastman Kodak Company||Photoresist composition comprising cyclohexyleneoxyalkyl acrylates|
|US5236806 *||Jun 13, 1991||Aug 17, 1993||Hoechst Celanese Corporation||Photopolymerizable, positive working, peel developable, single sheet color proofing system|
|US5294515 *||May 17, 1991||Mar 15, 1994||Hoechst Celanese Corporation||Photopolymerizable, negative working, peel developable, single sheet color proofing system|
|US5519136 *||May 22, 1992||May 21, 1996||Wade; John R.||Radiation sensitive compounds|
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|US7597195 *||Dec 27, 2001||Oct 6, 2009||Hitachi Chemical Company, Ltd.||Method for packaging a photosensitive film roll, resin case therefor, method for recovering and reusing the case, and photosensitive film roll package and method for conveying the same|
|US7677014||Mar 16, 2010||Hitachi Chemical Company, Ltd.||Method for packaging a photosensitive film roll, resin case therefor, method for recovering and reusing the case, and photosensitive film roll package and method for conveying the same|
|US7879525 *||Dec 3, 2004||Feb 1, 2011||Tokyo Ohka Kogyo Co., Ltd.||Chemically amplified photoresist composition, laminated product, and connection element|
|US20050256272 *||Feb 17, 2004||Nov 17, 2005||Mitsuo Najima||Acrylic modified chlorinated polyolefin resin, process for producing the same, and coating composition containing the same for polyolefin material|
|US20070275320 *||Dec 3, 2004||Nov 29, 2007||Yasushi Washio||Chemically Amplified Photorestist Composition, Laminated Product, and Connection Element|
|US20080149514 *||Feb 21, 2008||Jun 26, 2008||Hitachi Chemical Company, Ltd.||Method for packaging a photosensitive film roll, resin case therefor, method for recovering and reusing the case, and photosensitive film roll package and method for conveying the same|
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|U.S. Classification||430/253, 522/121, 522/123, 430/271.1, 522/34, 522/46, 522/39, 430/273.1, 430/907, 430/281.1, 522/40, 522/37, 522/48, 430/288.1|
|International Classification||C08F2/50, G03F7/004, G03F7/038, C08F2/00, H01L21/027, C08F2/48, G03F7/033, C08F255/02|
|Cooperative Classification||C08F255/023, G03F7/033, Y10S430/108|
|European Classification||G03F7/033, C08F255/02B|
|Jul 29, 1981||AS||Assignment|
Owner name: FUJI PHOTO FILM CO., LTD., NO. 210, NAKANUMA, MINA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:ONO, HISATAKE;TANAKA, SHIGEO;HASEGAWA, EIICHI;REEL/FRAME:003885/0257
Effective date: 19751110
Owner name: FUJI PHOTO FILM CO., LTD., JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ONO, HISATAKE;TANAKA, SHIGEO;HASEGAWA, EIICHI;REEL/FRAME:003885/0257
Effective date: 19751110

domain: chemistry


text:
Handling the fallout of a car accident in Escondido can be overwhelming. From dealing with insurance claims to recovering from injuries, the process is fraught with complexities and legal nuances. In such situations, having the right guidance is not just helpful; it’s crucial. This is where the role of adept legal counsel becomes apparent, providing clarity and direction in a time of chaos.
Particularly, the expertise of experienced car accident lawyers in Escondido is invaluable. They not only offer legal advice but also become the linchpin in securing the success of their client’s cases. These lawyers bring a wealth of experience and knowledge specific to Escondido’s legal landscape, ensuring that their clients are not just heard, but also compensated fairly.
Understanding the Role of Car Accident Lawyers in Escondido
Car accident lawyers in Escondido are adept at navigating the intricacies of local laws and regulations relevant to road accidents. Their area of expertise extends beyond mere legal representation; they are proficient in interpreting state and local traffic laws, adeptly handling negotiations with insurance companies, and, when necessary, fiercely advocating for their clients in court. The primary focus of these lawyers is to safeguard the rights of accident victims, ensuring they are not only heard but also receive just compensation for their losses and sufferings.
These legal professionals play a pivotal role in guiding their clients through the often complex and daunting legal landscape that follows a road accident. Their comprehensive understanding of legal procedures and commitment to their clients’ welfare is indispensable in securing favorable outcomes. Whether it’s battling bureaucratic hurdles or providing compassionate legal counsel, their contribution is crucial in turning the tide for those affected by car accidents in Escondido.
The Comprehensive Impact of Car Accidents
The effects of car accidents extend far beyond the immediate moment of impact, influencing various aspects of victims’ lives. Here are the key areas affected:
- Physical Health: Injuries can vary from minor to severe, potentially leading to long-term disability or chronic pain.
- Mental and Emotional Well-being: Trauma and stress disorders, including PTSD, anxiety, and depression, are common among accident victims.
- Financial Strain: Medical bills, repair costs, and potential loss of income can create significant financial challenges.
- Quality of Life: Daily life and routines can be disrupted, affecting personal relationships, work, and leisure activities.
- Legal and Administrative Burdens: Navigating insurance claims, legal processes, and potential litigation adds complexity and stress.
- Community Impact: Accidents contribute to broader societal costs, including emergency response resources and public health implications.
Negotiation and Advocacy: A Dual Approach
Another crucial aspect of what these lawyers offer is their proficiency in negotiation. Many car accident cases involve dealing with insurance companies, which can be daunting for individuals unfamiliar with the process. These lawyers excel in negotiating with insurance adjusters, ensuring that their clients receive the maximum compensation they are entitled to.
In cases where negotiation does not yield the desired results, these attorneys are prepared to advocate zealously for their clients in court. Their litigation skills are honed through years of experience, and they understand the importance of a meticulously prepared case.
Client-Centric Services: Beyond Legal Representation
What truly sets these Escondido lawyers apart is their commitment to a client-centric approach. Understanding that each case is unique, they offer personalized services tailored to meet the specific needs of each client. This involves not only providing legal representation but also offering emotional support and guidance throughout the process.
Their services extend to helping clients understand their rights, and the likely outcomes of their cases, and guiding them through the decision-making process. This holistic approach ensures that clients are not only represented legally but are also supported in every step of their journey towards justice.
Key Advantages of Choosing Skilled Legal Representation in Escondido
Choosing the right legal counsel after a car accident in Escondido is a decision that can significantly influence the outcome of your case. Experienced car accident lawyers bring a host of benefits to the table, each contributing to a more favorable and just resolution for their clients. Here are some key advantages:
- In-Depth Knowledge of Local Laws: Understanding the nuances of local traffic laws and regulations is crucial, and experienced lawyers have this knowledge at their fingertips.
- Effective Negotiation Skills: Skilled in negotiating with insurance companies, these lawyers ensure that their clients are not short-changed in settlement offers.
- Comprehensive Evidence Gathering: They possess the expertise to gather and present evidence effectively, strengthening the client’s case.
- Expertise in Litigation: If a settlement cannot be reached, these lawyers are well-equipped to represent their clients in court.
- Understanding of Medical Implications: Their familiarity with medical terminology and injury implications aids in arguing for fair compensation for medical expenses and ongoing care.
- Emotional Support and Guidance: Beyond legal assistance, they provide emotional support and clear guidance through difficult times.
Managing Towards Recovery: The Power of Expert Legal Support in Escondido
The path to recovery following a car accident is often fraught with challenges and uncertainties. In Escondido, however, victims of such accidents are not alone in this journey. With the backing of experienced car accident lawyers, they find an ally who offers more than just legal representation. These advocates shoulder the complexities of the legal process, enabling their clients to concentrate on what truly matters—their recovery and overall well-being. Their support transforms a daunting journey into one navigated with confidence and a sense of security, ensuring that every step taken is in the right direction towards healing and justice.
The importance of skilled legal counsel in these circumstances cannot be overstated. If you or a loved one ever find yourselves in the aftermath of a car accident, remember the profound impact that experienced legal professionals can make. It’s not merely a matter of winning a legal battle; it’s about having a compassionate and knowledgeable advocate by your side. Someone who is dedicated to safeguarding your rights and ensuring that your journey to recovery is supported at every turn. This level of advocacy is invaluable, and in Escondido, it’s within reach for those who need it most.

domain: law


Author: The Mount Royal Montreal Group 夏星湖
On April 19, the official U.S. Strategic Command website issued a war warning tweet.
Overview of U.S. Strategic Command’s State of Military Affairs statement: The scale of today’s conflicts is neither linear nor predictable. We must recognize that situations that could lead to the outbreak of conflict would quickly prompt adversaries to use nuclear weapons as the least pessimistic option.
On April 13, Admiral Richard of U.S. Strategic Command presented a report at a hearing before the U.S. Senate Armed Services Committee (SASC). The report listed CCP China, Russia, North Korea and Iran as countries that pose a threat to the global security environment. Among them, CCP China and Russia have moved from “competitors” to “versatile challengers with advanced capabilities.” CCP China was at the top of the list.
Admiral Richard also noted, “For the first time in history, our nation faces two strategic adversaries with nuclear weapons, and we must both stop them in different ways.”
And according to the PACIFIC AIR FORCE website, four B-52 strategic bombers were deployed to Andrews Air Force Base, Guam, on April 16. Col. Dmytryszym, 2nd BW commander: “Weaponized and capable of intercontinental delivery, the B52 remains a universally recognized symbol of America’s assurance to our allies and the world!”
Today, the CCP virus is still rampant in the world, while the CCP threatens all kinds of forces in the Taiwan Strait and plays games in the South China Sea, and the ambition of the wolf is obvious. The CCP has enslaved 1.4 billion people on the mainland, brutally suppressed the democracy movement in Hong Kong and committed genocide in Xinjiang.
The U.S. Strategic Command’s statement is worth alerting the world to. The report on the threat of nuclear weapons must also be supported by intelligence. As a “doctor” out of the Liangjiahe ravine, will he have the courage and determination to take the risk? Now that people’s livelihoods are in decline, the Party is fighting to the death, the truth about the virus is about to be revealed, and global responsibility is imminent. How will the CCP respond? Judging from the way “Pandora’s Box” was opened to release the CCP virus, we cannot rule out the possibility that the CCP will undergo extreme reactions when there is nowhere to go.
How far away is the war?


text:
The unrest in Syria has changed everything, including the way people eat.
This summer’s wheat harvest is set to be the worst in recent memory, reaching just 50% of last year’s dismal crop. According to the United Nation’s Food and Agriculture Organization (FAO), “Syria’s food chain is disintegrating ”“ from production to markets ”“ and entire livelihood systems are collapsing.”
But for Syrians, life has continued. People must eat, and individuals and farmers have adopted special means of keeping food on the table.
Since revolt took hold of the country in 2011, Nuha (last name withheld by request), who lived in Columbus, Ohio, for 14 years before returning home to Syria in 2004, has been forced to store pickled vegetables, jams and pounds of frozen, cooked bread for the uncertain times ahead. Jars of Makdous ”“ eggplants filled with crushed walnuts and spicy pepper flakes ”“ line Nuha’s pantry.
“I have at least 30 jars of preserved food: jams, olives, pickles and artichokes,” says Nuha. “I work as a teacher, so I do everything I can to cut down on food preparation time.”
Her multi-compartment freezer was once the key food instrument in her house, she says, “but now in 24 hours we have only eight hours of electricity, so we’re trying to cook and use more dried food ”“ okra, Jute leaves and zucchini.”
‘I have at least 30 jars of preserved food: jams, olives, pickles and artichokes. I work as a teacher, so I do everything I can to cut down on food preparation time.’
Over the past few years, the security situation has deteriorated, making travel to social gatherings outside Nuha’s immediate neighborhood rare. As a result, gatherings with neighbors, ostensibly to make food, have become important social outlets.
Nuha and others regularly make dozens of balls of kebbeh ”“ a half ounce or so of minced beef set inside a thick bulgur shell shaped like a football, then deep-fried and eaten with yogurt. Nuha and her neighbors contribute ingredients, dividing up the kebbeh to be frozen for eating later.
Gone are the days when meat-heavy barbecues would go on until late in the night in her neighborhood. “Meat is too expensive now. You don’t see people doing barbecues anymore,” she says.
Across the country, people are being forced to adapt to a world where traditional paths to food are blocked. Families in the southern city of Deraa, where the revolt began in March 2011, plant vegetables in their gardens, as it’s often too dangerous to leave home to go to the local market.
Syria’s farmers are also adjusting to their new reality. Along Syria’s coast, the country’s fruit and vegetable breadbasket, one farmer last year began collecting methane gas from an enclosed tank used to dump animal and food waste. There is a shortage of cooking gas now, and highways used to transport what gas is available are often impassible due to clashes. Using an irrigation pipe, he collects methane to fuel his stove and the stoves in his neighbors’ homes. “In addition to the advantage of manufacturing gas, I use the waste as an organic fertilizer for crops,” farmer Mohsen Josef told Syrian business magazine, al-Iqtisadi.
But even as farmers come up with novel solutions to get by, the impact on Syrian farming has been crippling.
“I was there in June and met farmers in Homs,” says Abeer Etefa of the World Food Program (WFP). “They can’t access their lands, they’ve left their property,” she says. “Their machinery is gone and they’ve no access to seeds.” The organization is planning to assist 4.25 million people this year.
Shepherds once grazed sheep flocks along roadsides, but locals now fear being shot at by the soldiers and militias manning the hundreds of checkpoints scatter across Syria’s road network. Farmers delivering food in trucks to the capital, Damascus, and other urban areas, are regularly stopped from entering cities when a security threat is expected. The result? The food is lost and farmers don’t get paid.
Rising food prices, up to 300% in the case of tomatoes and bananas, have affected farmers and consumers alike. Livestock production has been decimated. Poultry production has halved while beef and sheep production levels have fallen by a quarter and a third respectively. Olive oil produced in Syria’s northwest is being sold across the border in Turkey, forcing Syrians to pay inflated prices for whatever remains.
In the besieged Palestinian camp of Yarmouk, five miles south of Damascus, an initiative called 15th Garden has seen local residents turn garbage lots and open ground into vegetable lots.
“We got the idea to grow food in spaces between the buildings last September but we didn’t have the materials until April this year,” said Osama (last name withheld by request), a supervisor at a cell phone company who left Yarmouk last November.
15th Garden has about three-quarters of an acre of vegetables growing in several plots around the camp. Eggplant, zucchini, cucumbers and radishes the most popular vegetables. “There are three people planting and working the ground daily … the biggest problem we face is the security issue ”“ rockets fall all the time; water is also difficult to find sometimes,” says Osama.
The FAO plans to spend $15 million on reconstructing small scale irrigation networks damaged by the fighting over the next five years.
‘We got the idea to grow food in spaces between the buildings last September but we didn’t have the materials until April this year.’
“[F]amilies face severely reduced purchasing power and rising food prices, including a twofold increase in the real price of wheat flour between 2011 and mid-2013,” reported an FAO study released earlier this year. Radical jihadists now control much of northeast Syria, where the vast majority of the country’s cereals are produced.
Jihad Yazigi, editor of the economic affairs newsletter, The Syria Report, says this summer’s wheat crop is forecast at well below two million tons, “probably even below 1.5 million tons, while average demand is estimated at around 4 million tons per year.”
Etefa of the WFP says that before the war, Syria was practically self-sufficient. “But many of the wheat mills in the northeast of Syria have been destroyed or damaged” she says.
Away from the war’s frontlines, it’s the rising cost of food that’s most difficult to deal with, says Nuha.
“Parsley for tabbouleh salad used to cost five lira (10 cents) a bunch and now is 25 lira. Minced beef was 250 ($5) a kilo and is 1,200 lira today,” she says. “It was the prime time here when we moved back from Ohio in 2004; everything was cheap. When the war started everything declined.”

domain: food


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Parental supervision is recommended
Create a cute Christmas craft with stick Santas. You can get kids involved right away by taking them out to hunt for small fallen branches and sticks to paint their masterpieces on.
What you'll need:
- Stick (see below)
- Tempera paint in white, flesh, and red
How to make it:
- Find a stick (1/2 - 1" diameter) that looks like a Y with an additional portion extending between the forks. The forks are Santa's arms, the center portion is Santa's head, and the base
of the Y is Santa's legs.
- Paint it appropriately, using tempera paint. (Paint the light colors first - white fur, then flesh, and then red suit.)

domain: artistic


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A man stranded on an island builds a raft to try to escape to another island where people may be living hopeing to get help back to the America. The man was terribly afraid of sharks so upon approaching another island, he spots a man and calls out to him, "are there any sharks in the water?" the second man calls back "no".
The first man then proceeds to leap into the water so as to swim ashore, halfway there he yells out to the man on the island..."why arn't there any sharks in the water?"
The man replys, "Because the alligators ate them."

domain: literature


text: Emma and Andrew are two sad little ghosts. They love Christmas, but Santa totally missed their house last year. Andrew assures his little sis that Santa will not miss their house again. Meanwhile, Santa has his own issues to deal with. Back at the Ghostly house, Andrew has a great idea. It’s time for the little Ghostlys to get to work! Oh no! It’s really starting to snow! Will Santa break their little ghostly hearts again? Look for a surprise guest to come to the rescue. Brilliantly illustrated by Ed Luterio this Christmas book is sure to delight your little ones with a spooky side. With colorful holiday images and rhyming prose that sings off the page, your children will want you to read this delightfully different Christmas story over and over again! Extras Inside: Make Emma's hot cocoa and learn how to make sparkly spiders for your tree. Don't forget to make your Christmas list for Santa!

domain: library


text:
Table of contents
Masturbation or onanism is a very common sexual practice in our population (both in men and women), which begins before or during adolescence and offers many benefits: immunological, stress reduction, self-knowledge...
However, its excessive practice can be harmful, since it can sometimes become obsessive behavior and trigger an addiction to masturbation or compulsive masturbation.
Today, despite having undergone a great social evolution, masturbation is still a taboo subject, and therefore young people hardly have access to good sex education to know their bodies, know what masturbation is and how to perform it responsibly.
This, added to the only example they have of sex: porn creates a situation of ignorance about sexuality and, therefore, about masturbation.
Paradoxically, one of the most important and useful ways to learn about one's own sexuality is through masturbation, since it helps to get to know one's own body and identify the tastes, limitations, and preferences of each person, in order to be able to more responsible and satisfactory sexual practices for all parties.
When is masturbation considered an addiction?
The excessive practice of onanism is found in 30-75% of patients with hypersexuality, so it is seen as a symptom of this disorder.
Hypersexuality is characterized by a prolonged, frequent and intense dedication to sexual fantasies and behaviors that, in addition to causing suffering to the person, affects many areas of life: social events, work, family, self-esteem, etc.
It is important to know that compulsive masturbation cannot be measured according to the number of times the practice is performed since it depends on numerous factors (sex, age, culture, sexual appetite, sentimental situation, mood, etc.).
Being a behavioral addiction, it shares characteristics with other similar addictions:
- The compulsive need to masturbate: the individual constantly feels a great need to masturbate, even without having received an exciting stimulus.
- If the individual does not satisfy his desire, the withdrawal syndrome appears as malaise, nervousness, anxiety, anger, etc.
- Gradually, the need to masturbate increases, taking up a large part of your day.
- Other life activities are displaced: work, studies, family, friends, hobbies, leisure activities, etc.
- The person is unable to control it, despite knowing the danger and having suffered the consequences of addiction. Masturbation becomes uncontrollable, coming to perform this practice in unusual or correct situations.
In addition, addiction can be detected by the consequences of their compulsive behavior:
- By not being able to control compulsive behavior, the person has low self-esteem that affects other areas of his life.
- Alterations in sexual practices: as masturbation is the main sexual behavior, the rest of sexual practices are left aside, including those with other people.
- Erection problems or inability to reach orgasm.
- Problematic sexual practices: People addicted to masturbation frequently turn to pornography to obtain increasingly 'gratifying' or 'intense' stimuli, since it is increasingly difficult to achieve an erection or orgasm. This can influence sexual practices with other people, since pornography is taken as the only example of sexual relations.
How to overcome masturbation addiction
Compulsive masturbation is a behavioral addiction, so the treatment is similar to other behavioral addictions: individual therapy is combined with group therapy. First, the history of the person is assessed, and then the personalized work plan is established.
In addition, it is important to offer good sexual education during treatment, since in this way the person will acquire the necessary knowledge to carry out safe and satisfactory sexual practices.
❤ Enjoy this Newsletter?
If you enjoyed this edition, please share the love with your friends and family members. And let them know where they can subscribe [here]
Follow Me on Twitter [@f_djiometio]
Until next edition, take care.

domain: sociology


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Lasagna Alfredo Roll Ups--made salt and used lowfat cottage cheese instead of ricotta. They tasted even better the next day with tomato spaghetti sauce on top--just what it needed for some added flavor
Easy, light spinach lasagna roll ups VERDICT: Very good. I used 3 cloves of garlic but would use just 2 next time. Easy to make, no fancy ingredients, could easily add meat or mushrooms, etc. One child loved it, the other did not like the spinach.


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You Are Reading
Grey in 365Manga Grey Death on his quest to learn the mysteries of the infamous City. This deluxe collection of Tagami's tale of the future gone mad is presented in the same stunning format as the Mai Graphic Novel, with soft covers and full-color dust jackets. Grey loses the love of his life, Lips, when she dies in the line of duty as a "Trooper," a mercenary pawn of the government. Troopers fight in hopes of earning the rank of "Citizen" and escaping their dismal status as "People." After Lips' death, Grey becomes an exemplary "Trooper" himself, often the only one to return alive from the most hazardous missions. Together, he and sexy Trooper Nova set out on a personal mission to rescue Red, Grey's former squadron commander, risking demotion back to the lowly status of "People." Does Grey dare to love again?
Betrayed by the ones he cherished most, and after graduating from high school with a series of heart-breaks; Black left his home and lived away with a friend of his dad’s. In the greyscale life he lived, he longed for nothing but the end of his life, until a a person from the past crashes out of nowhere to re-add the contrast Black needs.
A Dark Grey Youth summary: A Dark Grey Youth summary is updating. Come visit Mangakakalot.com sometime to read the latest chapter of A Dark Grey Youth. If you have any question about this manga, Please don't hesitate to contact us or translate team. Hope you enjoy it.
365Manga is a place created
by the fans, Created for the fans. It’s a place where you can read high quality manga online absolutely free. Here you can Read manga online like no other. This website has been made specifically for manga lovers who want to read all kinds of manga
online, manhwa and even manhua.


The number of El Paso homes with some form of foreclosure filing quadrupled in January compared to a year ago, RealtyTrac reported Thursday.
El Paso had 183 homes with foreclosure filings in January, an increase of 149 homes from January 2012 when only 34 homes had foreclosure filings.
El Paso had one home foreclosure filing for every 1,481 homes in January.
That's well below the national rate of one in every 1,058 homes, but above the Texas rate of one in every 2,047 homes.
Texas had 4,835 homes with foreclosure filings in January, a decline of 13.4 percent from a year ago. The United States had 124,419 homes with foreclosure filings in January, a decline of 17.5 percent.
Foreclosure filings include default notices, scheduled auctions and bank repossessions.


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System C to work in partnership with University Hospitals Bristol on fast-tracking digital innovation
9th September 2016
University Hospitals Bristol NHS Foundation Trust (UH Bristol) has been selected as one of 12 acute trusts to become a global 'digital exemplar' for the NHS. Working in partnership with its EPR supplier, System C Healthcare, UH Bristol will be introducing a wide range of functionality including paperlite working, widespread mobile access, support for new models of care and a patient portal.
NHS England’s Centres of Global Digital Excellence initiative is designed as a springboard to accelerate clinical systems development in the NHS’ most digitally advanced trusts and put them on the world stage. Each Trust will receive up to £10m to advance its systems and share knowledge with other NHS providers.
Robert Woolley, chief executive at UH Bristol, said the Trust was delighted to have been selected as a digital exemplar. “We have a clear strategy of introducing digital systems to support the delivery of safe, high quality and efficient care to patients and all of the systems we deliver contribute towards this.
“With this additional support we will also focus on systems that cross organisational boundaries and work with our NHS partners to deliver innovative digital solutions that will improve care for patients in our area."
Dr Ian Denley, joint CEO at System C, congratulated UH Bristol following this week's announcement. “We are delighted to be working in partnership with the Trust on fast-tracking digital innovation,” he said. “This programme will translate to major advances which will benefit UH Bristol, our wider base of 22 hospital Trusts and our future customers.”
Steve Gray, director of UH Bristol’s Clinical Systems Information Programme, said the funded digital exemplar programme would enable the Trust to “accelerate and extend our existing digital programme to give our clinical and administrative teams the tools they need to help deliver safer, better care within UH Bristol and across the city of Bristol.
“Working with System C, we will act as a 'digital mentor' within our local community and across the country with Trusts using similar approaches and systems."

domain: news


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The administration of cannabidiol (CBD), a nonpsychotropic cannabinoid, is associated with improved quality of life in patients with Parkinson’s disease, according clinical trial data published online ahead of print in the Journal of Psychopharmacology. Authors reported that the administration of 300 mg doses of CBD per day was associated with “significantly different mean total scores” in subjects’ well-being and quality of life compared to placebo.
I’m playing the piano this week for a production of Noël Coward’s high-farce-comedy-of-manners Hay Fever at Illinois State University, and having a delightful time. Pre-show, intermission, and a few things directly involved in the show, playing music from the 1910′s and 1920′s. Kept me a bit busy.
I did get a chance to see […]

domain: medical


text:
Document Type: Original Article(s)
Specialist of Oral Medicine, Kerman Oral and Dental Diseases Research Center, Kerman University of Medical Sciences, Kerman, Iran
Associate Professor, Department of Medical Mycology and Parasitology, School of Medicine, Kerman University of Medical Sciences, Kerman, Iran
Assistant Professor, Kerman Oral and Dental Diseases Research Center, Department of Oral Medicine, School of Dentistry, Kerman University of Medical Sciences, Kerman, Iran
Radiotherapy, Oncology Unit, Shafa Hospital, Kerman, Iran
Dentist, Kerman Oral and Dental Diseases Research Center, Kerman University of Medical Sciences, Kerman, Iran
BACKGROUND: Oropharyngeal candidiasis is a common infection in patient receiving radiotherapy for head and neck cancer. Accurate and rapid identification of candida species is very important in clinical laboratory, because the incidence of candidiasis continues to rise after radiotherapy. The genus Candida has about 154 species that show different level of resistance to antifungal drugs and have high degree of phenotypic similarity. The aim of this study was to investigate oral yeast colonization and infection and resistance to antifungal drugs in these patients.METHODS: Thirty patients receiving a 6-week course of radiation therapy for treatment of head and neck cancer at the Oncology Unit in Shafa Hospital, in 2008, were enrolled in the study. Specimens from patients were cultured weekly for Candida. All isolates were plated on CHROM agar and RPMI-based medium. They were subcultured and submitted for antifungal susceptibility testing (nystatin, fluconazole, clotrimazole and ketoconazole) and molecular typing.RESULTS: Infection (clinical and microbiological evidence) occurred in 50% of the patients and Candida colonization (only microbiological evidence) occurred in 70% of subjects in the first week. Candida albicans alone was isolated in 94.9% of patient visits with positive cultures. Candida tropicalis was isolated from 5.1% of patient visits with positive cultures. All isolates were susceptible to nystatin, but did not respond to the other antifungal drugsCONCLUSIONS: The irradiation-induced changes of the intraoral environment such as xerostomia lead to increased intraoral colonization by Candida species. All yeast isolates were susceptible to nystatin. Thus prophylactic therapy with nystatin should be considered for these patients.


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Easy to make vegan salad bowl, with homemade spinach falafels and hummus served with pitta and salad. It’s packed with nutrients for a healthy lunch or supper
Spinach falafel & hummus bowl
DescriptionEasy to make vegan salad bowl, with homemade spinach falafels and hummus served with pitta and salad. It's packed with nutrients for a healthy lunch or supper
Heat the oven to 190C/170C fan/gas 5. Line a baking sheet with non-stick parchment. Put all the falafel ingredients, except for the oil, in a food processor and season lightly. Pulse until you have a rough mix.
Lightly oil your hands, then take tablespoons of the falafel mix, roll into around 16 balls and put on the baking sheet. Press each one down slightly with the palm of your hand. Brush using the 1 tbsp oil and bake for 20-25 mins until firm and golden, turning halfway through.
While the falafel is cooking, make the hummus. Put all of the hummus ingredients into a food processor with 50ml of water and blitz until smooth and silky.
Put the spinach, cucumber, red onion and falafel in different sections of each bowl, alongside some hummus, then drizzle with the extra olive oil. Grind over some black pepper. Serve with the pittas on the side and more lemon for squeezing
- Amount Per Serving
- Calories 379kcal
Nutritional Values per Serving
kcal 379 | fat 22g | saturates 3g |carbs 27g | sugars 4g |fibre 10g |protein 14g |salt 0.1g


text:
3DOcean color pen 8230301
Color \ Pens \ Pink \ Painting \ Paint \ Orange \ Purple \ White \ Yellow \ Spectrum
3D Model - color pen 8230301 by ArtsBlueBall @ 3DOcean
3D File Formats Included: .3ds (multi format), .fbx (multi format), .max (3ds Max), .mb (maya), .obj (multi format); Animated: No; Created In: maya 2014; Geometry: Polygons; Low-poly: Yes; Materials: Yes; Poly Count: 3920; Rigged: No; Textured: No; UV Layout: No.
Detailed 3D Model of color pen. Model is based on edge loop topology.
All Materials are Included.
Model is render ready and ready for use.
bus; truck; racing car; tharma coll cutter; racing car; sport car; car.
Keywords: art, artistic, blue, brown, color, color charts, color pen, color pencils, colored pencil, colorful, crayons, draw, drawing, green, isolated, orange, paint, painting, pen, pens, pink, purple, red, spectrum, white background, yellow.

domain: hobby


After the Black Stars of Ghana lost their final group stage match to Comoros, Partey didn’t return to Ghana with the team but flew straight to London to join the ‘gunners’ as they prepared for a clash with Liverpool on Thursday night in the second semi-final leg of the EFL Cup.
A couple of hours after the game, several football lovers criticized him for running to London right after Ghana exited the AFCON 2022 and also putting up an abysmal performance including getting a red card in the Arsenal game.
Partey mentioned in his post that he wasn’t very happy with how things turned out in the AFCON for Ghana; and continued by saying he could have been more careful in the Arsenal game considering being booked already.
Well, let’s just make all these slide and give Partey another chance to prove himself for country and club and we know he’ll deliver, especially now that we’re preparing for the FIFA World Cup.
Take a look at his post below and share your comments with us:


Cranfield Aerospace Ltd are proud to be exhibiting at the Farnborough International Airshow 2010, from 19th to 23rd July.
There will be a range of exhibits on show, including the Valkyrie Unmanned Air System, which successfully completed its first phase of flight testing in June, and the advanced air counter measures data logger, desgined to assist in the assessing and optimising munition life with the minimum of disruption to test and operational programmes.
A team of expert staff will be on hand throughout the week to discuss your requirements and how Cranfield Aerospace's wide range of services can bring innovative value to your business and support achievement of your programme goals.
Come and meet the team at Stand B18, Hall 1.
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Belle Vue Brass Band was formed in 2005. The band is continuing to grow and the band has performed a number of prestigious engagements since then. Now, in 2017, we’re still going strong and looking forward concerting and marching engagements around the North West.
We are also proud members of the North West Area Brass Band Association.
The band is primarily run by a management team consisting of the following people:
- President: Afzal khan MP
- Musical Director: Peter Brannigan
- Musical Director: Martin Moyse
- Band Manager: Matthew Brannigan
- Executive Officer: Philip Bate
- Instrument Officer: Alan Ryan
- Librarian: Sarah Ling
- Team Member: Iain Bailey
- Website: David Cox
- Band Ambassador: Eddie Fallowes (Previously of Reddish Prize Band)
- Senior Musicians: Mike Greaves & Alan Ryan

domain: entertainment


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Happy Monday, friends!
Today I’m sharing my thoughts on Denise Hunter’s newest release, A Novel Proposal, which comes out tomorrow. Grab a cup of tea (or coffee) and read on!
About the Book
When novelist Sadie Goodwin is forced to stop writing westerns and charged with penning a contemporary romance novel to rescue her lackluster sales, there’s only one tiny problem: She’s never been in love.
Desperate to salvage her career, Sadie begins devouring romance novels. Knowing she must devote herself to this confounding genre, she accepts an invitation to hole up at her friend’s beach duplex for the summer. Where better to witness love in bloom than on the beautiful North Carolina shore?
However, once ensconced in the charming ocean-front home with her sweet maltipoo Rio, she finds many ways to procrastinate. First there’s the beach, right outside her backdoor, with all its interesting visitors (research). Then there’s the free library she decides to build and set up by the back deck (She has to do something with all those romance novels). To say nothing of Sam Ford, the grumpy neighbor on the other side of the duplex . . . who she can’t seem to stop annoying.
A social butterfly by nature, Sadie soon gets to know all the beach regulars—sunbathers, walkers, and surfers alike. The free books draw a crowd right up to the house for nice little book chats, which further irritates her reclusive neighbor, to break up her “writing.” But things take an unexpected turn when Sadie opens a recently-placed novel to find a secret compartment—and tucked inside is a beautiful engagement ring. To whom does the ring belong? Sadie is convinced she needs to find the owner and save the man’s proposal from certain doom.
She draws a reluctant Sam into the project, and slowly their connection begins to develop. Are these weird fluttery feelings the first stirrings of love? Has Sadie managed to stumble upon the very subject about which she must write—and wouldn’t Sam make the perfect alpha hero?
Will Sadie find the ring’s rightful owner? And will she manage to pen a career-saving romance novel by summer’s end?
Amazon | B&N | CBD | Goodreads
A Novel Proposal is such a sweet, heart-warming book. Sadie quickly hooked me in the beginning, after all, she’s a fellow author. Her interactions with Sam kept me reading and the twist of finding a ring in a Little Free Library was fun to follow.
All in all, fans of Denise Hunter will enjoy her latest novel. She’ll transport the reader to the beach, to a little duplex where two people meet an have a chance to overcome their struggles in a relationship with one another.
*I received a complimentary copy from the publisher via NetGalley. My review was not required nor influenced.
About the Author
Denise Hunter is the internationally published bestselling author of more than 40 novels, three of which have been made into Hallmark movies. She has appeared on the The 700 club and won awards such as The Holt Medallion Award, The Carol Award, The Reader’s Choice Award, The Foreword Book of the Year Award, and is a RITA finalist.
Denise writes heartwarming, small-town love stories, peopled with layered characters who struggle with real-life issues. Her readers enjoy the experience of falling in love vicariously through her characters and can expect a happily-ever-after sigh as they close the pages of her books.
In 1996, inspired by the death of her grandfather, Denise began her first book, writing while her children napped. Two years later it was published, and she’s been writing ever since. Her husband says he inspires all her romantic stories, but Denise insists a good imagination helps too!
When Denise isn’t orchestrating love lives on the written page, she enjoys traveling with her family, drinking good coffee, and playing drums. Denise makes her home in Indiana where she and her husband have raised three boys and are currently enjoying an empty nest.