TWI400567B - A photosensitive resin composition, and a photosensitive film and a screen printing plate using the same - Google Patents

Description

Photosensitive resin composition and photosensitive film and screen printing template using the same

The present invention relates to a photosensitive resin composition and a photosensitive film and a template for screen printing using the same. More specifically, the present invention relates to a photosensitive resin composition and a photosensitive film and a template for screen printing using the same, wherein the photosensitive resin composition can be developed in water, and has sufficient water resistance and long-term storage. Excellent stability.

The photosensitive resin composition is used as a pattern forming material in a large number of and various applications in photo-engraving technology (refer to Yamaoka Yasuo, Matsunaga Yoshitaro, "photopolymer technology", Nikkan Kogyo Shimbun (1988) ). The polymer-based photosensitive material is excellent in resolution, and can be used depending on the application, for example, by selecting a light-receiving region in a wide range by selecting a light wavelength. Further, the resin layer which is patterned by light irradiation plays an important role as a photoresist material when the substrate is chemically, physically or mechanically etched. Further, the photosensitive resin composition can also be used as a printing plate for a relief printing plate, a gravure plate, a lithographic plate, and a stencil for transferring a light pattern by ink.

By utilizing these features, the photosensitive resin composition can be used for photolithographic materials ranging from submicron to centimeters.

In general, when a polymer-based photosensitive material is used, physical properties such as solubility are changed depending on the chemical structure change of the exposed portion and the unexposed portion, and a pattern is formed by performing development processing in accordance with changes in physical properties such as solubility. Alternatively, in the case of using a surface-coated material, the physical property change due to the change in the chemical structure caused by the exposure exhibits a protective effect on the substrate. The chemical structural changes in such resins are not solely caused by photochemical reactions, which are based on the sum of various secondary chemical reactions induced by photochemical reactions. As a result, for example, the solubility of the resin layer before and after exposure with respect to a solvent can be arbitrarily selected.

When a concave-convex pattern is formed from a photosensitive resin by solvent development, it is directly related to environmental problems such as a work environment and waste countermeasures, and as a solvent, it is indispensable to use the cheapest and safe water. Further, for example, such a water-developable photosensitive resin can be used as a screen printing plate material, and the obtained pattern must exhibit solvent resistance and water resistance required for use of the ink. In particular, since the pattern formed by water development is mostly hydrophilic, a photosensitive resin which exhibits exceptionally excellent water resistance is required.

As a method of improving water resistance, a photosensitive resin composition containing a photoradical polymerizable aqueous emulsifier and a photocrosslinking agent is widely used. For example, a composition is disclosed (Patent Document 1: Japanese Patent Laid-Open No. Hei 6-230568), wherein a photoradical polymerizable compound is dispersed in a polyvinyl alcohol together with an aqueous resin emulsifier; or a water-developing composition (Patent Document 2: Japanese Patent Laid-Open No. SHO-49-121852, Patent Document 3: Japanese Patent Laid-Open Publication No. SHO-50-108003, No. JP-A No. 59-107343, and Patent Document 5: Japanese Laid-Open Patent Publication No. Hei 5-127377, etc., which emulsifies an ethylenically unsaturated compound and a photoradical polymerizable initiator in polyvinyl alcohol, and a photocrosslinking agent is added thereto. In this case, even if a photoradical polymerization reaction occurs, the polyvinyl alcohol itself does not form a crosslinked structure, and thus a photocrosslinking agent such as a dichromate or a diazo resin can be added. However, the dichromate-based photosensitive resin contains not only heavy metal ions which may pollute the environment, but also poor storage stability, so that a two-liquid type photosensitive resin can be used to limit or eliminate its use. Further, when a water-soluble diazo resin is used as the photocrosslinking agent, the photospeed is low, and the light transmission is limited by the coloring of the exposed portion, so that there is a problem that it cannot be applied to the thick film photosensitive layer. The lack of long-term storage stability can only be used as a two-liquid type for preparing a photosensitive resin composition immediately before use. That is, the problem of the two-liquid type cannot be solved anyway.

A polyvinyl alcohol substituted with a photocrosslinkable residue represented by styrylpyridinium is proposed as a one-liquid type water-developing photosensitive resin (Patent Document 6: Japanese Patent Laid-Open No. 55-23941) Japanese Patent Laid-Open Publication No. SHO 55-62905. As a screen printing plate, there is proposed a composition (Patent Document 8: JP-A-55-62446, JP-A-59-102232), which contains the photocrosslinkability. Polyvinyl alcohol and an aqueous emulsifier. However, since the photocrosslinkable residue has hydrophilicity, the water resistance of the obtained concavo-convex pattern is not sufficient. Therefore, the following suggestions are made. A composition in which a photo-radical polymerizable emulsifier is added (Patent Document 10: JP-A-60-10243, JP-A No. 60-10244, and JP-A-60-10244 Japanese Patent Laid-Open No. Hei 60-247637. Further, there is also proposed a method (Japanese Patent Laid-Open Publication No. SHO 60-10245) in which a dichromic acid or a diazo resin as a water-soluble photocrosslinking agent is added to the composition. Alternatively, a method has been proposed (Patent Document 13: JP-A-1-229005), which improves water resistance by adding a phosphoric acid or a phosphorous acid compound. Further, a photosensitive resin composition which is formed by adding a water-soluble photoacid generator to a polyvinyl alcohol and an acid-reactive crosslinking agent and which is water-developable is also proposed (Patent Document 14: Japanese Patent Laid-Open No. Hei 9-319080) ).

However, according to the inventors of the present invention, the crosslinked polyvinyl alcohol remains hydrophilic, and thus the water resistance is not sufficient anyway. When the screen printing is carried out using aqueous ink, the template obtained by using the composition is used. In addition, it is still impossible to achieve sufficient solvent resistance and water resistance at the same time, and there is still a problem to be solved for a single-liquid photosensitive resin composition that satisfies various physical properties including mechanical strength.

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. SHO-59-102232 [Patent Document No. 5] Japanese Patent Laid-Open Publication No. SHO 59-102232 Japanese Patent Laid-Open Publication No. SHO-60-247637 [Patent Document No. 1] Japanese Patent Laid-Open No. Hei. No. Hei. Kaiping 9-319080

An object of the present invention is to provide a photosensitive resin composition, a photosensitive film using the composition, and a template for screen printing, wherein the photosensitive resin composition has long-term storage properties due to one liquid property, and can improve a concave-convex pattern. Solvent resistance and water resistance.

The present inventors have finally completed the present invention after repeated efforts to solve the above problems. That is, according to the present invention, it is possible to provide a photosensitive resin composition, a photosensitive film, and a template for screen printing which are single-liquid type which exhibits excellent long-term storage stability and which can be developed in neutral water.

Therefore, the photosensitive resin composition of the present invention contains the following components (A), (B) and (C).

Component (A): a polyvinyl alcohol polymer represented by the following general formula (1) or (2) (wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aralkyl group, and these may also be substituted by a hydroxyl group or an amine carbenyl group, and the carbon-carbon bond may also block an oxygen atom or Unsaturated bond, R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 1 to 6, n is 0 or 1, and X ^- represents a halogen ion, a phosphate ion, a methyl sulfate ion, a sulfonic acid a ionic or a mixture of such anions.) Component B: a radical polymerizable monomer component C having at least one ethylenically unsaturated bond and having an anionic dissociation ability: a radical polymerization initiator

As a preferred aspect of the photosensitive resin composition of the present invention, the component (A) includes a cationic group other than the quaternary heteroaryl ring cationic group.

The preferred embodiment of the photosensitive resin composition of the present invention further comprises a water-based resin emulsifier (component (D)).

The preferred embodiment of the photosensitive resin composition of the present invention further comprises a diazo resin (component (E)).

The preferred embodiment of the photosensitive resin composition of the present invention further comprises an inorganic or organic powder (component (F)).

The photosensitive film of the present invention is characterized by comprising the above-mentioned photosensitive resin composition.

Moreover, the template for screen printing of the present invention is characterized by comprising the above-mentioned photosensitive resin composition.

Further, the template for screen printing of the present invention comprises the photosensitive film.

The photosensitive resin composition of the present invention, the photosensitive film obtained from the composition, and the template for screen printing using the same, and the solvent-based water used as described above have the advantage of not causing environmental pollution. And has the following effects.

(1) When the active energy ray resin composition and the development treatment are prepared, only water is used as the solvent, which is advantageous for the safety of the working environment, fire prevention, pollution prevention, and the like.

(2) Since it is a single liquid type, it is excellent in workability.

(3) A plurality of photosensitive sensitizers can be used in combination, so that a composition can be provided which is sensitizable in a wide wavelength region from a far ultraviolet ray to a near infrared ray region.

(4) The composition can be applied to a film or a screen substrate as an active energy ray resin film to form a photosensitive film which can be stored for a long period of time.

(5) The composition can be applied to a film to form a dry film.

<ingredient (A)>

The component (A) in the present invention is a polyvinyl alcohol-based polymer represented by the following formula (1) or (2).

(wherein R ¹ represents a hydrogen atom, an alkyl group or an aralkyl group, and these may be substituted by a hydroxyl group or an amine carbenyl group, and the carbon-carbon bond may also intervene an oxygen atom or an unsaturated bond, and R ² represents A hydrogen atom or an alkyl group having a carbon number of 1 to 3, m is an integer of 1 to 6, n is 0 or 1, and X ^- represents a halogen ion, a phosphate ion, a methyl sulfate ion, a sulfonate ion or a mixture of such anions. .)

The alkyl group or the aralkyl group of R ¹ preferably has a carbon number of from 1 to 10. Especially good is the number of carbon is 1~7. Specific examples of the residue include methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methoxyethyl, 3-methoxy Alkyl group, allyl group, crotyl group, benzyl group and the like. When m exceeds the range of 1 to 6, the film after insolubilization becomes easy to expand, and m is more preferably 1 to 4. n can be any one of 0 or 1. As X ^- , a phosphate ion or a methyl sulfate ion is preferred; as a halogen ion, Cl ^- or Br ^{- is} preferred; and as a sulfonate ion, a CH ₃ SO ₃ ^- , CH ₃ CH ₂ SO is preferred. ₃ ^- , C ₆ H ₅ SO ₃ - and p-CH ₃ C ₆ H ₄ SO ₃ -.

Further, the compound represented by the formula (1) can be expressed as a polyvinyl alcohol-based polymer having a pyridinyl group substituted with a styryl group; the compound represented by the formula (2) can be expressed It is a polyvinyl alcohol-based polymer having a styryl group substituted with a styryl group.

The polyvinyl alcohol-based polymer represented by the above formula (1) or (2) is preferably obtained in the following manner: for example, in an aqueous solution, under acidic conditions, the following formula (3) Or the aldehyde represented by the formula (4) is reacted with polyvinyl alcohol.

(R ¹ , R ² , m, n and X ^- in the formulas (3) and (4) have the same meanings as in the formulas (1) and (2).)

As the polyvinyl alcohol used at this time, the degree of saponification is 60 to 100 mol%, and the degree of saponification is more preferably 70 to 100 mol% of a vinyl acetate polymer, as long as it is not water-soluble, Other copolymers with vinyl monomers. When the degree of saponification is at most this value, the water solubility becomes insufficient. Preferably, the average degree of polymerization is from 200 to 5,000, more preferably from 300 to 4,000. When the degree of polymerization is below this range, the light insolubilization rate is remarkably slow, and the sensitivity is insufficient. If it is in the range or more, the viscosity of the composition is too high and it is not resistant to use. The addition amount of the styrenepyridinium group or the styrenequinolyl group to the vinyl alcohol unit of polyvinyl alcohol is usually 0.2 to 7.0 mol%, preferably 0.5 to 5.0 mol%. If the above range is not satisfied, an image may not be sufficiently formed; if it exceeds the above range, water solubility may be deteriorated.

The method of obtaining the polyvinyl alcohol-based polymer of the present invention represented by the above formula (1) or (2) may be any method, and in the present invention, for example, according to Japanese Patent Laid-Open No. 55-136265 It is obtained by the method disclosed in Japanese Laid-Open Patent Publication No. SHO 56-8365.

In the photosensitive resin composition of the present invention, the ethylenic monomer having dissociable ability to an anion is characterized in that it is ionic bonded to the styrylpyridinium salt represented by the general formula (1) or The cation moiety of the quinoline salt represented by the formula (2) has a crosslinked structure due to radical polymerization in addition to cross-linking due to photodimerization reaction. Therefore, it is preferred to introduce a cation moiety into the polyvinyl alcohol which reacts with the photosensitive aldehyde derivative represented by the formula (3) or (4). As a polyvinyl alcohol suitable for the purpose, for example, according to Japanese Patent Laid-Open No. Hei 60-129742, it is also possible to use 3-methylpyridinium sulfonium salt, 4-methylpyridinium sulfonium salt, 4 a method in which a quaternary ammonium group is introduced into a polyvinyl alcohol by a acetal bond, a decyl phenyl trimethyl ammonium salt, a decyl methyl trimethyl ammonium salt, or the like. It is preferred that the cationic group introduced in this manner is 0.5 to 10 mol% relative to the vinyl alcohol unit. Alternatively, as the cationically modified polyvinyl alcohol, C-506, CM-318 manufactured by Kuraray Co., Ltd., and K-210 manufactured by Nippon Synthetic Chemical Co., Ltd. may be used.

<ingredient (B)>

The component (B) in the present invention has at least one ethylenically unsaturated bond and is a radical polymerizable monomer having an anion dissociation ability.

As the residue having anion dissociation ability in the component (B), a sulfonic acid, a carboxylic acid, and a phosphoric acid can be mentioned. By using these basic salts or ammonium salts of aliphatic amines, it can be used as a radical monomer having an anionic group. Examples of the radical polymerizable unsaturated group in the monomer used for this purpose include an acrylonitrile group, a methacryl fluorenyl group, a maleic acid monoester group, a styryl group, and an allyl group. Examples of the acid-type monomer which does not dissociate include acrylate, methacrylate, monomethyl maleate, monoethyl maleate, and 2-(methyl) propylene oxyl phthalate. Ethyl ester, 3-(methyl)propenyloxy-2-propyl phthalate, 3-(methyl)propenyloxy-2-propyl phthalate, cyclohexane-3-ene-1 2-(methyl)propenyloxyethyl 2-carboxylate, 2-(methyl)propenyloxyethyl succinate, 2-(methyl)cyclohexane-1,2-carboxylic acid Propylene methoxyethyl ester, 2-(methyl) propylene methoxyethyl maleate, ω-carboxy-polycaprolactone monoacrylate, acrylic acid dimer, 2-(meth) propylene decyloxy Ethyl phosphate, 3-(meth) propylene methoxy propyl phosphate, 2-(methyl) propylene methoxy-3-propyl phosphate, ω-(methyl) propylene fluorenyl polyethylene Ethylene phosphate, ω-(meth)acrylonitrile-based polypropylene oxyethylene phosphate, styrene sulfonate, N-(2-sulfoethyl) acrylamide, and N-(2-sulfonate B Base) methacrylamide, etc., but is not limited thereto. Among these, particularly preferred is 2-(methyl)propenyloxyethyl phthalate, 3-(methyl)propenyloxy-2-propyl phthalate, and phthalic acid 3- (Meth) propylene decyloxy-2-propyl ester, 2-(methyl) propylene methoxyethyl succinate, cyclohexane-1,2-carboxylic acid 2-(methyl) propylene methoxy ethoxylate Ester, 2-(methyl) propylene methoxyethyl maleate, ω-carboxy-polycaprolactone monoacrylate, 2-(meth) propylene methoxyethyl phosphate, 3-(methyl ) acryloxypropyl phosphate, 2-(methyl) propylene methoxy-3-propyl phosphate, ω-(meth) propylene thiopolyethylene oxyethylene phosphate, and ω-(methyl) Propylene decyl propylene oxyethylene phosphate. In the present specification, "(meth)acryloyl group" means both "acryloyl group" and "methacryl fluorenyl group".

The component (B) may be used in an amount of a cationic moiety which is represented by the formula (1) or (2) and which contains a pyridinium group or a quinolyl group substituted with a styryl group and is introduced into the polyvinyl alcohol. 50~200% by mole, and more preferably 80~150% by mole. When it is less than this range, sufficient water resistance and solvent resistance cannot be imparted to the light-insoluble coating film, and even if it is added to the above range, water resistance and solvent resistance cannot be improved.

<ingredient (C)>

The component (C) in the present invention is a radical polymerization initiator. In the present invention, preferred examples of the component (C) include a sultone derivative having a water-soluble ammonium group or a benzophenone derivative. Further, as for the oil-soluble photoradical polymerization initiator, there are: benzoin and benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, acetophenone, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1 -ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane- Acetones such as 1-ketone, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- Amines such as [4-(methylthio)phenyl]-2-morpholinylpropane-1,2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 Acetophenones, anthraquinones such as 2-methylindole, 2-ethylindole, 2-tert-butylindole, 1-chloroindole, etc., 2,4-dimethyl ketoxime, 2,4-diethyl sultone, 2-chlorosultone, 2,4-diisopropyl ketoxime, etc., acetophenone dimethyl ketal, benzyl dimethyl condensate ketone a benzophenone or a benzophenone such as a benzophenone or a benzophenone; these may be used singly or in combination of two or more kinds, and a third-grade amine may be used alone or in combination of two or more. Such as the well-known photosensitive sensitizer. These may be used after being dissolved or dispersed.

The oil-soluble radically polymerizable monomer or oligomer may be dispersed as an aqueous emulsifier in a composition comprising a styrene-substituted pyridine represented by the formula (1) or (2) A photocrosslinkable polyvinyl alcohol having an anthracene or a quinolyl group, an anionic radical polymerizable monomer, and a photoradical polymerization initiator. In particular, it is preferred that the oil-soluble photopolymerization initiator is dispersed in water after being dissolved in a monomer or an oligomer. Further, the photocrosslinkable polyvinyl alcohol having a photosensitive group represented by the formula (1) or (2) itself can function as a monomer dispersion stabilizer. As the monofunctional monomer used for this purpose, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) ) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2-ethoxyethoxy) ethyl (meth) acrylate , n-butoxyethyl (meth)acrylate, morpholinyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, methoxydiethylene glycol (methyl) Acrylate, methoxytriethyl (propylene) glycol (meth) acrylate, methoxytetraethyl (propylene) diol (meth) acrylate, methoxy polyethylene glycol (methyl) acrylate (A) Acrylate, ethoxydiethyl (meth) acrylate, ethoxytriethyl (propylene) diol (meth) acrylate, cyclohexyl (meth) acrylate, (a) Tetrahydrofurfuryl acrylate, isobornyl (meth)acrylate, dicyclopentanal (meth)acrylate, N,N-dimethylamine ethyl (meth)acrylate, and (methyl) N,N-diethylamine ethyl acrylate or the like. In this specification, the term "(meth) acrylate" means both "acrylic" and "methacrylic"; the so-called "B (C)", which means both "B" and "C" .

As the polyfunctional monomer, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,3-trimethylglycol di(meth)acrylate, 1, 4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, bis(acryloxy neopentyl glycol) Adipate, bis(methacryloxy neopentyl glycol) adipate, epichlorohydrin modified 1,6-hexanediol di(meth)acrylate hydroxypivalate Diol di(meth)acrylate, caprolactone modified hydroxypivalic acid neopentyl glycol di(meth)acrylate polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate , dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tris(methyl) Acrylate, ditrimethylolpropane tri(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, ethylene oxide modified trimethylolpropane tri Methyl) acrylate, epoxy Alkane-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, two Pentaerythritol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol poly(meth)acrylate, caprolactone-modified dipentaerythritol poly(meth)acrylate, glycerol di(meth)acrylate , epichlorohydrin modified glycerol tri (meth) acrylate, tris(propylene oxyethyl) isocyanurate, tris(methacryloyloxyethyl) isocyanurate, Ester-modified tris(propylene oxyethyl) isocyanurate and caprolactone-modified tris(methacryloyloxyethyl)isocyanurate.

As the oligomer, a polyester (meth) acrylate oligomer, a bisphenol A type epoxy (meth) acrylate, a caprolactone addition (meth) acrylate, a phenol novolac type epoxy resin can be used. Epoxy (meth) acrylate such as (meth) acrylate or cresol novolak type epoxy (meth) acrylate, (meth) acrylate urethane or the like. A preferred embodiment of such an oligomer is disclosed, for example, in "Light Hardening Technical Information Booklet" (2000), 84-119, issued by Technonet.

Further, a polyester dendrimer containing an ethylenically unsaturated group or the like can be used. Specific examples of such a polyester dendrimer containing an ethylenically unsaturated group are disclosed, for example, in Japanese Patent Laid-Open Publication No. 2005-76005, Japanese Patent Publication No. 2005-47979, Japanese Patent Publication No. 2005-76005, and the like. in.

In the photosensitive resin composition of the present invention, the solvent resistance can be improved as compared with the case of containing only the photocrosslinkable polyvinyl alcohol having a photosensitive group represented by the general formula (1) or (2). It can also improve water resistance. The reason for this is presumed to be as follows: by the photodimerization reaction of the photosensitive group, not only the crosslinked structure of the polyvinyl alcohol chain is formed, but also the monomer having an anion dissociation ability is polymerized by photoradical polymerization. Further, by the ionic interaction, a crosslinked structure is further formed on the cation portion of the polyvinyl alcohol chain.

The amount of the component (C) to be added is preferably from 0.01 to 0.5, particularly preferably from 0.02 to 0.1, based on 1 part by weight of the component (B). In the case where an oil-soluble radical polymerizable monomer or oligomer is further added, the amount of addition is set to 1 part by weight based on the total amount of the radical polymerizable monomers or oligomers.

<ingredient (D)>

In the photosensitive resin composition of the present invention, a water-based resin emulsifier may be further added as needed. As the preferred aqueous resin emulsifier in the present invention, for example, polyvinyl acetate, vinyl acetate/ethylene copolymer, vinyl acetate/acrylate copolymer (here, as an acrylate, for example, acrylic acid is present) Ester, 2-ethylhexyl acrylate, etc.), (meth)acrylic acid polymer, styrene/butadiene copolymer, methyl methacrylate/butadiene copolymer, acrylonitrile/butadiene copolymer, A chloroprene polymer, an isoprene polymer, a polyvinyl chloride, a polyvinylidene chloride, a polystyrene, an anthrone resin, a polyethylene, a polyurethane, a fluororesin, or the like. The hydrophobic polymer particles may, for example, be a polyvinyl acetate emulsifier, an ethylene/vinyl acetate copolymer emulsifier, a vinyl acetate/acrylic acid copolymer emulsifier, an ethylene/vinyl acetate/acrylic acid obtained in a polymerization step. Ternary copolymer emulsifier, vinyl chloride/vinyl acetate copolymer emulsifier, acrylic emulsifier, styrene/butadiene latex emulsifier, MBR latex emulsifier, acrylonitrile/butadiene rubber emulsifier, chloroprene Rubber emulsifier and vinylidene chloride emulsifier. As the synthetic polymer dispersion, a polyethylene dispersion, a polyolefin ionic polymer dispersion, a urethane ion polymer dispersion, or the like can be used. Further, those in which a synthetic polymer fine powder or refined starch is dispersed may also be used.

The amount of the component (D) to be added is preferably from 0.05 to 10 parts by weight, particularly preferably from 0.2 to 5 parts by weight, per part by weight of the aqueous solution containing the component (A).

<ingredient (E)>

In the photosensitive resin composition of the present invention, a diazo resin may be added as needed. As such a diazonium resin, for example, 4-amino-4'-methyldiphenylamine other than an aminodiphenylamine can be used by using an aldehyde such as paraformaldehyde, acetaldehyde, propionaldehyde or n-butyraldehyde. 4-amino-4'-ethyldiphenylamine, 4-amino-4'-methoxydiphenylamine, 4-amino-4'-chlorodiphenylamine, 4-amino-4'-nitro A water-soluble diazo resin in which a diazoline such as diphenylamine is condensed.

The amount of the component (E) to be added is preferably 0.001 to 0.10 parts by weight, particularly preferably 0.002 to 0.05 parts by weight, per part by weight of the aqueous solution containing the component (A).

<ingredient (F)>

Further, in the photosensitive resin composition of the present invention, an inorganic or organic powder may be added as needed. For example, metals such as aluminum, zinc, copper, bronze, and lead, and alumina; and preferred examples of the component (F) include, for example, alumina, cerium oxide, iron oxide, zinc oxide, zinc white, and magnesium oxide. Metal oxides such as zirconia, yttria and titanium oxide, silicates such as kaolin clay and pyrophyllite clay, cerium oxide such as glass, diatomaceous earth, quartz powder, quartz sand, carbon black, nepheline, cryolite (artificial cryolite), graphite (graphite), ash stone, aluminum hydroxide, slate powder, zeolite, calcium carbonate, magnesium carbonate, talc, potassium titanate, boron nitride, feldspar powder, molybdenum dioxide, barium sulfate , mica, gypsum (anhydrous), etc. Among the inorganic solid materials, clay, talc, mica and the like are preferred for the present invention.

The amount of the component (F) to be added is preferably 0.01 to 2 parts by weight, particularly preferably 0.05 to 1 part by weight, based on 1 part by weight of the aqueous solution containing the component (A).

<Other ingredients (arbitrary components)>

The quinacridone pigment, the azo pigment, the diketopyrrolopyrrole pigment, the perylene pigment, the phthalocyanine pigment, and the isoporphyrin system may be dispersedly added to the photosensitive resin composition of the present invention. Organic pigments such as pigments.

Further, if necessary, a surfactant, an antifoaming agent, a thermal polymerization inhibitor, an antioxidant, an adhesion agent, a plasticizer, a solvent, a surface tension adjuster, a stabilizer, a chain transfer preventive agent, and a hindrance may be added. Fuel, antibacterial and preservatives.

<Photosensitive Resin Composition and Photosensitive Film>

The photosensitive film of the present invention includes the above-mentioned photosensitive resin composition. The photosensitive film of the present invention includes both of the above-mentioned photosensitive resin composition, and a resin material or a material other than the photosensitive resin composition and the photosensitive resin composition.

The above photosensitive resin composition of the present invention can be suitably used for forming a coating film (resin film) on all substrates, and the substrate can be exemplified by, for example, wood, woven fabric, paper, ceramic, glass, polyester, polyolefin. , synthetic resin such as cellulose acetate, polyimine, epoxy resin, glass fiber reinforced resin, metal such as aluminum, copper, nickel, iron, zinc, magnesium, cobalt, etc., semiconductor materials such as barium, gallium arsenide, and nitrogen. Insulating materials such as antimony oxide and antimony oxide. In order to improve the coating film forming ability, it is particularly preferable to carry out a hydrophilic treatment in advance in the case of a synthetic resin. A pattern or a protective layer can be formed by performing light irradiation on the coating film formed on the base material and including the photosensitive resin composition of the present invention.

The coating is applied to the surface of the substrate in accordance with a well-known method of forming a uniform coating film. That is, a method of applying by bucket coating, spin coating, brushing, spraying, reverse roller coating, dip coating, doctor blade coating, curtain coating, or the like. The film thickness is from 0.1 μm to 1000 μm depending on the purpose of use and the type of substrate.

The photosensitive resin composition applied to the substrate is exposed to light after evaporation. The photosensitive wavelength region is determined depending on the type of photocationic polymerization initiator and photosensitive sensitizer. In particular, since a wide range of photosensitive sensitizers can be used, the range of light wavelengths ranges from far ultraviolet to near infrared. As for the light source, in addition to the low-pressure mercury lamp, the high-pressure mercury lamp, the ultra-high pressure mercury lamp, the xenon lamp, the mercury-xenon lamp, the halogen lamp, the fluorescent lamp, etc., various kinds of thunder for oscillating ultraviolet rays, visible light, and near infrared rays can also be preferably used. Shoot the light source. Exposure can also be carried out via a photomask or by direct writing of a laser beam onto a photosensitive film. The exposed film can be developed in neutral water. The photosensitive film is immersed in water, the unexposed portion is dissolved and removed, and the unexposed portion is removed by a water flow from the spray gun to effect development.

<Template for Screen Printing>

The template for screen printing of the present invention includes the above-mentioned photosensitive resin composition. Such a template for screen printing can be produced by applying the above-mentioned photosensitive resin composition to a screen according to a usual method, drying it, exposing it, and then immersing it in water to dissolve and remove the unexposed part, or The unexposed portion is removed by water flow from the spray gun and developed. Alternatively, the photosensitive resin composition is applied onto a plastic film and dried according to a well-known method to obtain a photosensitive film for screen printing, and the film is adhered to a screen surface by using water or the like to be dried, and then the plastic is removed. The film is post-exposure, and if necessary, heat treatment is performed and developed, thereby producing a screen printing plate.

A self-sustaining film obtained by applying the photosensitive resin composition of the present invention to a plastic film can be used as a dry film based on the principle of laminating a self-supporting film on a substrate. The film provided on the substrate is exposed, and if necessary, subjected to heat treatment and developed, and chemical etching or sand blasting may be performed.

[Examples] <Preparation of photosensitive resin composition>

Example 1 40 g of polyvinyl alcohol having an average degree of polymerization of 1800 and a degree of saponification of 88% was dissolved in 500 mL of water, and 1-methyl-4-(methylphenylphenyl)methylsulfonium pyridinium salt 3.65 g was added thereto. 55% phosphoric acid 5 g, stirred for 12 hours. After the reaction liquid was made neutral by an ion exchange resin, 5 g of methacryloxyethylphosphoric acid monoethanolamine salt was mixed, and the solution was stirred while dissolving 2 as a photoradical polymerization initiator. -methyl-1[4-(methylthio)phenyl]-2-morpholinpropan-1-one 2.5 g of pentaerythritol triacrylate (80 g) to prepare a photosensitive resin composition.

Example 2 10 g of 3-pyridine aldehyde was dissolved in 50 mL of ethyl acetate, and 11.8 g of dimethyl sulfate was added thereto, and then left at room temperature overnight, whereby a composition of 1-methyl group was obtained. 19 g of brown oil of 3-methylpyridylmethylsulfate pyridine salt. 40 g of polyvinyl alcohol having an average degree of polymerization of 1800 and a degree of saponification of 88% was dissolved in 500 mL of water, and 10.6 g of 1-methyl-3-methylmethylsulfonium pyridinium salt and 5 g of 85% phosphoric acid were added thereto. Stir at 80 ° C for 24 hours. After dropping to room temperature, 3.65 g of 1-methyl-4-(methylphenylphenyl)methylsulfonium pyridinium salt was added to the reaction mixture, and the mixture was stirred for 12 hours. The reaction solution was made neutral by an ion exchange resin. 5 g of methyl propylene methoxyethyl phosphate monoethanolamine salt was mixed in the aqueous solution, and the solution was stirred while adding 2-methyl-1 [4-(methyl sulphide) as a photo-radical polymerization initiator. 80 g of pentaerythritol triacrylate of 2.5 g of phenyl]-2-morpholinan-1-one was prepared to prepare a photosensitive resin composition.

Example 3 40 g of cationically modified polyvinyl alcohol CM318 (degree of polymerization: 1800, degree of saponification: 88%, manufactured by Kuraray Co., Ltd.) was dissolved in 500 g of water, and phosphoric acid was added to adjust the pH to 1.5 to 2.0. After dissolving 3.65 g of 1-methyl-4-(methylphenylphenyl)methylsulfonium pyridinium salt therein, the mixture was stirred to obtain a photocrosslinkable polyvinyl alcohol aqueous solution having an introduction rate of 1.5 mol%. 5 g of methyl propylene methoxyethyl phosphate monoethanolamine salt was mixed in 300 g of this aqueous solution, and the solution was stirred while adding 2-methyl-1 [4-) as a photoradical polymerization initiator. 80 g of pentaerythritol triacrylate of (methylthio)phenyl]-2-morpholinan-1-one 2.5 g was prepared to prepare a photosensitive resin composition.

Example 4 In the composition obtained in Example 3, 100 g of GH-150 (nonvolatile matter 48%) manufactured by Saiden Chemical Co., Ltd. was added as the component (D), and 20 g of L-made by Talc Corporation of Japan was added. 1 is added as a component (F), and the photosensitive resin composition is prepared.

Example 5

In the composition obtained in Example 4, 1 g of a diazo resin manufactured by Respe Chemical Co., Ltd. was added as a component (E), followed by mixing to prepare a photosensitive resin composition.

Example 6

In addition to adding 5 g of light ester HO-MS (2-methylpropenyloxyethyl monoethanolamine succinate) manufactured by Kyrgyzstan Chemical Co., Ltd., instead of methacryloxyethyl phosphate monoethanolamine salt as a component (B) A photosensitive resin composition was obtained in the same manner as in Example 3 except for the above.

Example 7

In addition to the methacryloxyethyl phosphate monoethanolamine salt 2.5 g and the light ester HO-MS (succinic acid 2-methylpropenyloxyethyl monoethanolamine) manufactured by Kyoeisha Chemical Co., Ltd. as the component (B) A photosensitive resin composition was obtained in the same manner as in Example 3 except for 2.5 g of the salt.

Comparative example 1

40 g of polyvinyl alcohol having an average degree of polymerization of 1800 and a degree of saponification of 88% was dissolved in 500 mL of water, and 1.65 g of 1-methyl-4-(methylphenylphenyl)methylsulfate sulfonium salt was added thereto, and phosphoric acid was added thereto. The pH was 1.5 to 2.0 and stirred for 12 hours. After the reaction solution was made neutral by an ion exchange resin, the solution was stirred while adding 2-methyl-1[4-(methylthio)phenyl group as a photoradical polymerization initiator. ]-2-morpholinol-1-one 2.5 g of pentaerythritol triacrylate (80 g) to prepare a photosensitive resin composition.

Comparative Example 2 In the composition obtained in Comparative Example 1, 5 g of ethyl phosphate was added and mixed to prepare a photosensitive resin composition.

Comparative Example 3 was produced by a cationically modified polyvinyl alcohol (manufactured by Kuraray, CM318 (polymerization degree: in the same manner as in Example 3) except that the methacryloxyethylethyl phosphate monoethanolamine salt was not added. 1800, degree of saponification: 88%)) A photosensitive resin composition was obtained.

<Implementation of printing plate making>

In Examples 8 to 14, the photosensitive resin compositions obtained in Examples 1 to 7 were used, and a template for screen printing was produced in the following manner. The photosensitive resin composition was filtered through a polyester mesh 250 mesh, and applied to a polyester mesh 250 fixed on an aluminum frame, and coated and dried using a stainless steel bucket coater. This operation was repeated to form a photosensitive film having a thickness of 15 μm. Then, a positive film was adhered to the photosensitive film, and exposed to a distance of 1 m for one minute using a 3 kW metal halide lamp. After immersing in water for two minutes, it was spray-developed using water, whereby a screen was obtained. With respect to the obtained template, the resolution of the template and the degree of weight expansion (% by weight) with respect to water were obtained. After the template weight was increased by 1 kg, the film thickness was measured 100 times after the water-repellent cotton yarn was used for back and forth, and the water resistance at this time was measured, and the water resistance was evaluated by using the film thickness reduction value expressed in μm. In addition, using a water-based ink (manufactured by Murakami Co., Ltd., printing color orange 21), the screen printing plate was subjected to a brush-resistant test, and when 2000 sheets or more were printable, it was set to ○, and 1000 sheets or more but less than 2000 sheets were printed. In the case of Δ, the case where 500 sheets or more could not be printed was set to ×, and the brush resistance was evaluated in the above manner. The above results are summarized in Table 1.

In Comparative Examples 4 to 6, the photosensitive resin compositions of Comparative Examples 1 to 3 were used in the same manner as in Examples 8 to 14 to prepare a template, and the resolution, the degree of swelling of water, and the film thickness reduction were The durability of the brush is evaluated. These results are summarized in Table 1.

<Photosensitive film>

In Examples 15 to 20, the photosensitive resin compositions prepared in Examples 2 to 7 were applied onto a polyester film, and dried at 40 ° C for 15 minutes to obtain a photosensitive film having a film thickness of 25 to 30 μm. The film was irradiated with a 4 kW ultra-high pressure mercury lamp or a 3 kW metal halide lamp, separated by a positive film attached to the film, at a distance of 1 m. Then, using a spray gun to blow off the water and develop it, it was confirmed that the 70 μm pattern could be faithfully solved.

In Example 21, the photosensitive resin composition obtained in Example 15 was adhered to the polyester resin 250 mesh fixed on an aluminum frame, and the photosensitive film obtained in Example 15 was adhered. After drying at 40 ° C for 30 minutes, the positive film was adhered thereto, and exposure was performed for one minute at a distance of 1 m using a 3 kW metal halide lamp. After immersing in water for two minutes, it was spray-developed using water, whereby a screen was obtained. The template has a resolution of 70 μm and a weight expansion of 20% for water. After performing the brush test using aqueous ink, it was found that even after printing 3000 sheets, the photosensitive film was not damaged, and it had excellent water resistance and brush resistance.

Examples 22 to 26 The same tests as in Example 21 were carried out on the films obtained in Examples 16 to 20, and the same results as in Example 21 were obtained.

Claims (9)

A photosensitive resin composition comprising the following component (A), component (B), and component (C): component A: polyethylene represented by the following formula (1) or formula (2) Alcohol polymer (wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aralkyl group, and these may also be substituted by a hydroxyl group or an amine carbenyl group, and the carbon-carbon bond may also block an oxygen atom or Unsaturated bond, R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 1 to 6, n is 0 or 1, and X ^- represents a halogen ion, a phosphate ion, a methyl sulfate ion, a sulfonic acid a mixture of ions or such anions; Component B: a radical polymerizable monomer having at least one ethylenically unsaturated bond and having a sulfonic acid, a carboxylic acid, and a phosphoric acid, the residue of which forms a basic or ammonium salt; C: a radical polymerization initiator. The photosensitive resin composition of claim 1, wherein the component (A) has a 3-methylpyridinium salt, a 4-methylpyridinium salt, a 4-methylphenylphenyltrimethylammonium salt, and At least one of the quaternary ammonium groups, or the acetal compound of the salts, is substituted with a quaternary ammonium group of an acetal bond, of the group consisting of the methylidenemethyltrimethylammonium salt. The photosensitive resin composition of claim 1, further comprising the component (D): an aqueous resin emulsifier. The photosensitive resin composition of claim 2, further comprising a component (D): an aqueous resin emulsifier. The photosensitive resin composition according to any one of claims 1 to 4, further comprising the component (E): a diazo resin. The photosensitive resin composition according to any one of claims 1 to 4, further comprising the component (F): an inorganic or organic powder. A photosensitive film comprising the photosensitive resin composition according to any one of claims 1 to 6. A template for screen printing, comprising the photosensitive resin composition according to any one of claims 1 to 6. A template for screen printing comprising the photosensitive film of claim 7.