JP4326862B2 - Active energy ray resin composition - Google Patents

Description

  The present invention relates to an active energy ray resin composition, an active energy ray photoresist, an active energy ray resin film, and a method for forming a resin pattern.

  Resin or resin composition that is sensitive to active energy rays is an image-forming substrate that utilizes the chemical structural change caused by the action of active rays such as light, infrared rays, far-infrared rays, electron rays, or X-rays. It is used for surface coating. Of the actinic rays, the widely used one is light. Hereinafter, the actinic energy rays may be specifically described as light, but the activity on the composition of the present invention or a photoresist or film obtained from the composition may be described. Energy rays are not limited to light.

  A resin or composition having a photosensitive function is practically used in a large amount and in many fields as a pattern forming material exhibiting high resolution as in the photolithography technology (edited by Atsuo Yamaoka, Mototaro Matsunaga, “ Photopolymer Technology ", Nikkan Kogyo Shimbun (1988)). The polymer photosensitive material not only has excellent resolution, but can be used in accordance with the application because, for example, a wide photosensitive region can be set by selecting the wavelength of light. Furthermore, the resin layer patterned by light irradiation plays an important role of functioning as a resist material when the substrate is chemically, physically or mechanically etched. Alternatively, it is practically used as a relief printing plate, intaglio printing plate, lithographic printing plate, or stencil printing plate material for transferring an optical pattern with ink. Utilizing such characteristics, it is used as a wide range of photolithography materials from submicron to centimeter.

  In the high molecular weight photosensitive resin, a pattern is formed by performing development processing based on a change in physical properties such as solubility based on a chemical structure change between an exposed portion and an unexposed portion. Alternatively, when used as a surface coating material, the protective action of the base material is manifested by changes in physical properties that are markedly altered in chemical structure by exposure. Such a chemical structural change in the resin is based not only on the photochemical reaction but also on the sum of various secondary chemical reactions induced by the photochemical reaction. As a result, for example, the solubility of the resin layer in the solvent before and after exposure can be arbitrarily selected. That is, when the solubility of the exposed area is reduced, it becomes a negative photosensitive resin by the solvent development process, and when the solubility of the exposed area is improved, it becomes a positive photosensitive resin.

  When a relief pattern is formed from a photosensitive resin by solvent development, it is essential to use water that is the cheapest and safest solvent as it is directly related to environmental issues such as work environment and waste countermeasures. Furthermore, in order for such a water-developable photosensitive resin to be used as, for example, a screen printing plate-making material, it is necessary that the pattern obtained exhibits solvent resistance and water resistance due to the ink. In particular, since a pattern formed by water development is often hydrophilic, a photosensitive resin exhibiting remarkable water resistance is required.

  As a method for improving water resistance, a photosensitive resin composition comprising a photoradically polymerizable aqueous emulsion and a photocrosslinking agent has been widely adopted. For example, a composition in which a photo radical polymerizable compound is dispersed in polyvinyl alcohol together with an aqueous resin emulsion (JP-A-6-230568), an ethylenically unsaturated compound and a photo radical polymerizable initiator are emulsified in polyvinyl alcohol, Proposed are water-developable compositions (JP 49-121852, JP 50-108003, JP 59-107343, JP 5-127377, etc.) containing a photocrosslinking agent. Has been. In this case, a photocrosslinking agent such as dichromate or diazo resin is added because a crosslinked structure is not formed in the polyvinyl alcohol itself even if the photo radical polymerization reaction proceeds. However, the dichromate-based photosensitive resin contains environment-contaminating heavy metal ions and is inferior in storage stability, so it is a two-component type, and its use has been limited or excluded. In addition, when water-soluble diazo resin is used as a photocrosslinking agent, the photosensitivity is low, and the light transmission is limited as the exposed portion is colored, so that it is not suitable for a thick photosensitive layer. In addition to the above point, the storage stability over a long period of time is poor, and it is unavoidable to be a two-component type in which a photosensitive composition is prepared immediately before use. That is, the inconvenience of the two-component type has not been solved.

  As a one-component water-developable photosensitive resin, a photosensitive resin composed of polyvinyl alcohol substituted with a photocrosslinkable residue typified by styrylpyridinium and a photo-radical polymerizable composition has been proposed (Japanese Patent Laid-Open No. Sho). 55-62446, JP-A-60-10245, JP-A-61-17141, JP-A-56-122784, JP-A-60-10245). However, since the photocrosslinkable residue is hydrophilic, the water resistance of the resulting relief pattern is not sufficient. JP-A-9-31980 proposes a water-developable photosensitive composition obtained by adding a water-soluble photoacid generator to polyvinyl alcohol and an acid-reactive crosslinking agent. However, the acid generated by light irradiation is a carboxylic acid, and since the acid strength is low, a sufficient mechanical strength cannot be obtained, and the crosslinked polyvinyl alcohol has poor water resistance in order to maintain hydrophilicity. .

Japanese Patent Application No. 9-319080

  An object of the present invention is to provide an active energy ray resin composition that is one-component, has long-term storage stability, and improves the water resistance of a relief pattern, and a pattern forming method using the resist and film. .

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, according to the present invention, the active energy ray resin composition that can be developed with neutral water, the active energy ray resin film that can be developed with water, and the resin are shown below. A method of forming a pattern is provided.

(1) In a water-soluble resin aqueous solution, (i) a photopolymerization initiator that generates Bronsted acid or Lewis acid and radical species by the action of active energy rays, (ii) a radically polymerizable monomer having an ethylenically unsaturated group And (iii) an active energy ray resin composition obtained by dissolving or dispersing a cationically polymerizable monomer as an essential component.
(2) A photoresist obtained by coating the active energy ray resin composition according to (1) on a substrate.
(3) An active energy ray resin film obtained by forming the active energy ray resin composition according to (1) into a film.
(4) An active energy ray resin film for screen printing plate making, wherein the active energy ray resin composition according to (1) is formed into a film.
(5) The active energy ray resin film according to (2) or the active energy ray resin film according to any one of (3) to (4) is irradiated with active energy, and heat treatment is performed as necessary. A method for forming a resin pattern, which is later developed with water.

The active energy ray resin composition according to the present invention, the active energy ray resin film obtained from the composition, and the pattern forming method using the same are composed as described above, and the solvent used is mainly water. It has environmentally friendly characteristics and has the following effects.
(1) Since only water is used as a solvent for the preparation and development processing of the active energy ray resin composition, it is suitable for safety of work environment, fire prevention, pollution prevention and the like.
(2) Since it is a one-pack type, it is excellent in workability.
(3) Since the photocationic polymerization initiator generates acid not only by light but also by the action of active energy rays such as electron beams and X-rays, the composition is sensitive not only to photosensitivity but also to electron beams and X-rays. Can be manufactured.
(4) Since various sensitizers can be used in combination, a composition sensitive to a wide wavelength range from far ultraviolet to near infrared is provided.
(5) The composition can be applied to a film or screen substrate to form an active energy ray resin film, which can be a photosensitive film that can be stored for a long period of time.
(6) The composition can be applied to a film to form an active energy resin film, which can be a dry film that is not subject to oxygen inhibition.
(7) A surface-curing coating agent is provided by light irradiation or electron beam irradiation.
(8) The active energy ray resin composition and the film therefrom of the present invention can be advantageously used as a coating composition, an adhesive composition, etc., in addition to being advantageously used in the printing field such as screen printing plate making. .

  As the water-soluble resin used in the present invention, any of natural polymers, semi-synthetic polymers, and synthetic polymers can be used (see “Technology for developing water-soluble polymers”, CMC (1999)). Examples of natural polymers include chitin, chitosan, casein, collagen, egg white, starch, carrageenan, xanthan gum, dextran, pullulan and the like. Examples of the semi-synthetic polymer include dialdehyde starch, starch partial hydrolyzate, hydroxyethyl starch, cyclodextrin, dextrin, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and the like. Synthetic polymers include polyvinyl alcohol, partially saponified polyvinyl alcohol, polyvinyl alcohol acetalized to such an extent that water solubility is not impaired, polyvinylpyrrolidone and copolymers, polyacrylamide and copolymers, N-isopropylacrylamide and copolymers , Acrylamide and copolymer, N, N-dimethylacrylamide and copolymer, poly (N-acetylvinylamine), polyethylene glycol, and the like.

  The photoacid generator that generates Bronsted acid or Lewis acid and radical species by the action of active energy rays in the present invention is a conventionally known compound having a cationic polymerization initiating ability, and is a chemically amplified photoresist or photocationic polymerization. The photoinitiator used for the system is used (see Organic Electronics Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), pages 187 to 192). As the photopolymerization initiator suitably used in the present invention, an onium salt-type photocationic polymerization initiator that generates radical species together with a strong acid having cationic polymerization initiating ability is particularly preferable. Examples of suitable compounds are as follows.

Examples of the onium salt-type photocationic polymerization initiator include various salts of onium cations such as diazonium, ammonium, iodonium, sulfonium, phosphonium, and ferrocenium. Examples of the salt-forming anion in this case include ZnCl ₃ ⁻ , HSO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , Fluorobutane sulfonate, perfluorooctane sulfonate, camphor sulfonate, benzene sulfonate, p-toluene sulfonate, 9,10-dimethoxyanthracene-2-sulfonate, (C ₆ F ₅ ) ₄ B ⁻ , (C ₄ H ₉ ) ₄ B ⁻ And so on.

  Specific examples of the onium cation include phenyldiazonium, p-methoxydiazonium, α-naphthyldiazonium, biphenyldiazonium, diphenylamine-4-diazonium, 3-methoxydiphenylamine-4-diazonium, 2,5-diethoxy-4-methoxy. Benzoylamidophenyldiazonium, 2,5-dipropoxy-4- (4-tolyl) thiophenyldiazonium, 4-methoxydiphenylamine-4-diazonium, condensates of 4-diazodiphenylamine and formaldehyde, 1-methoxyquinolinium, 1 -Ethoxyisoquinolinium, 1-phenacylpyridinium, 1-benzyl-4-benzoylpyridinium, 1-benzylquinolinium, N-substituted benzothiazolium (JP-A-5-140143) Broadcast reference), and the like.

  Further, benzyltriphenylsulfonium, p-methoxyphenyldiphenylsulfonium, bis (p-methoxyphenyl) phenylsulfonium, tris (p-methoxyphenyl) sulfonium, p-phenylthiophenyldiphenylsulfonium, benzyltetramethylenesulfonium, phenacyltetramethylene Sulfonium, phenacyldimethylsulfonium, p-methoxyphenyldiethylsulfonium, naphthyldialkylsulfonium (see JP-A-9-118663, JP-A-5-140209), (2-naphthylcarbonylmethyl) tetramethylenesulfonium, (p-hydroxyphenyl) ) Dithymersulfonium, (4-hydroxynaphthyl) -dimethylsulfonium, (4,7-dihydroxynaphthyl) -1-dimethyl Rusulfonium, (4,8-dihydroxynaphthyl) -1-dimethylsulfonium, diphenyliodonium, phenyl (4-methoxyphenyl) iodonium, phenyl {4- (tert-butyl) phenyl} iodonium, bis {4- (tert-butyl) ) Phenyl} iodonium, bis (4-dodecylphenyl) iodonium, (4-methoxyphenyl) (4-octyloxyphenyl) iodonium, phenacyltriphenylphosphonium, cyanomethyltriphenylphosphonium, and the like.

  The photocationic polymerization initiators exemplified above alone generate corresponding Bronsted acids or Lewis acids and radicals by the action of active energy rays, but in the present invention, sensitizers can coexist. Since the photocationic polymerization initiators exemplified above function as an electron acceptor, the sensitizers used in the present invention are disclosed in JP-A-54-151024, JP-A-58-40302, JP-A-60. -76740, JP-A-60-78443, JP-A-60-88005, JP-A-60-112802, JP-A-61-97650, JP-A-61-180359, JP-A-62-161820 As described in Japanese Patent Application Laid-Open No. 63-243102, an electron donating compound is desirable. Sensitizers suitable for the present invention having such characteristics include aromatic polycyclic compounds, porphyrin compounds, phthalocyanine compounds, polymethine dye compounds, merocyanine compounds, coumarin compounds, thiopyrylium compounds, pyrylium compounds, p-dialkylaminostyryl. Examples thereof include, but are not limited to, compounds and thioxanthene compounds. Many of these are edited by Taiga, Hirashima, Matsuoka, Kitao, “Dye Handbook” (Kodansha), Color Materials Association, “Color Material Engineering Handbook”, Asakura Shoten (published in 1989), Hayashibara Biochemical Research Institute It is published in “Dye Catalogue” etc.

  Examples of the aromatic polycyclic compound include those having a basic skeleton composed of hydrocarbons such as naphthalene, phenanthrene, pyrene, anthracene, tetracene, chrysene, pentacene, picene, coronene, hexacene, and ovarene. In addition, aromatic heterocyclic 5-membered polycyclic compounds such as benzofuran, dibenzofuran, indole, carbazole, benzothiophene, dibenzothiophene, and the like having oxygen atom, nitrogen atom, and sulfur atom as constituent atoms can also be mentioned. Examples of the basic skeleton of the aromatic hetero 6-membered polycyclic compound include α-benzopyrone, β-benzopyrone, α-thiabenzopyrone, β-thiabenzopyrone, flavone, xanthone, thioxanthone, phenoxazine, and phenothiazine. Further, these basic skeletons may be substituted with at least one electron donating group such as an alkyl group, a hydroxy group, an alkoxy group, and an alkylthio group. Examples of sensitizers composed of substituted aromatic polycyclic compounds include 1-methoxynaphthalene, 1,4-dimethylnaphthalene, 1,8-dimethylnaphthalene, 9,10-dimethylphenanthrene, 9-methylanthracene, 9 , 10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,8-dimethyl-9,10-bis (phenylethynyl) anthracene, 9,10-dimethoxyanthracene, 9, Examples include 10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 1-methylpyrene. Examples of the substituted product of the polycyclic heterocyclic compound include N-methylcarbazole, N-ethylcarbazole, thioxanthone, isopropylthioxanthone, and the like.

  Porphyrin compounds include tetraphenylporphine, octaethylporphine, mesoporphyrin, protoporphyrin, hematoporphyrin, chlorin, tetrabenzoporphine, and other basic skeletons and their magnesium complexes, zinc complexes, May include chlorophyll.

  The phthalocyanine compound includes a naphthocyanine compound, and at least one substituent such as an alkyl group, an alkoxy group, an alkylthio group, an aryl group, or a halogen group may be introduced into their basic skeleton. Further, magnesium, zinc, cadmium, and aluminum are particularly preferable as the central metal.

  As the polymethine dye compound, a cyanine type or merocyanine type having a structure in which a heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or the like is connected by polymethine can be used. Examples include the dye compounds described in Shin Okawara, Shinjiro Kitao, Kosuke Hiraoka, Ken Matsuoka, “Dye Handbook”, Kodansha Scientific (1986), pages 382 to 417. Specifically, in addition to a cyanine group consisting of a quinoline ring, an indocyanine group consisting of an indole ring, a thiocyanine group consisting of a benzothiazole ring, a polymethine group consisting of an iminocyclohexadiene ring, a benzoxazole system, a pyrylium system, a thiapyrylium system, Examples include squarylium-based and croconium-based.

  As coumarin compounds, there are monocoumarin compounds described in Nobu Okawara, Shinjiro Kitao, Tsuneaki Hiraoka, Ken Matsuoka, “Dye Handbook”, Kodansha Scientific (1986), pages 432 to 438, and 3- (2- Benzothiazolyl) -7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (dibutylamino) coumarin, 3- (2-benzothiazolyl) -7- (dioctylamino) coumarin, 3- (2-benzimidazolyl)- 7- (diethylamino) coumarin, 10- (2-benzothiazolyl) -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7 , 8-ij] quinolizin-11-one, 3,3-carbonylbis (7-diethylaminocoumarin), 3,3 And the like carbonyl bis (7-dibutyl-amino coumarin).

  Examples of the p-dialkylaminostyryl compound include 4-diethylaminobenzylideneacetophenone, 4-diethylaminobenzylidene (p-methoxy) acetophenone, 4-diethylaminobenzylidenemalondinitrile, 4-dimethylaminobenzylideneacetoacetic acid ethyl ester, 4-dimethylaminobenzylidenemalon Acid diethyl ester, 4-dimethylaminobenzylidene-α-cyanoacetophenone, 2,6-bis (4-dimethylaminobenzylidene) cyclohexanone, 4-dimethylaminocinnamylideneacetophenone, 4-dimethylaminocinnamylidenemalondinitrile, 4- Dimethylaminocinnamylidene cyanoacetic acid ethyl ester, 4-dimethylaminocinnamylidenemalonic acid diethyl ester, 4-dimethylamino N'namiriden -α- cyanoacetophenone, 4-dimethylamino cinnamylidene - bis (4-dimethylamino benzylidene) cyclohexanone, and the like.

  The absorption wavelength of these spectral sensitizers covers a wide range from ultraviolet to infrared, and not only these alone but also two or more sensitizers can be mixed to efficiently emit light in a wide wavelength range. It can absorb and generate acids and radicals.

  In addition to these photocationic polymerization initiators, radical photopolymerization initiators can be added (see JP Fouassier, Photopolymerization and Photocuring, Hans Publishers (1995)). As such a photo radical polymerization initiator, a substance that easily generates a radical under light irradiation, such as a thioxanthone derivative such as benzoin alkyl ether, Michler's ketone, ditertiary butyl peroxide, chlorothioxanthone, or the like is used.

  The radical polymerizable monomer in the present invention has at least one radical polymerizable unsaturated bond such as acryloyl group, methacryloyl group, allyl group, and maleimide group, and has a number average molecular weight of 10,000 or less. Oligomers are also included. These photoactive unsaturated compounds can be used alone or in combination of two or more.

  Such unsaturated compounds include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, triallyl isocyanurate, lauryl (meth) acrylate, methoxyethylene glycol (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, trifluoroethyl (meth) acrylate, terafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, benzyl (meth) acrylate, Hexyl diglycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylene ester Lenglycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, pentamethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, ethylene glycol diglycidyl ether (meth) acrylate, phenylglycidyl ether (meta ) Ethylene such as acrylate, trimethylolpropane polyglycidyl ether (meth) acrylate, terephthalic acid diglycidyl ether (meth) acrylate, reaction product of tolylene diisocyanate and 2-hydroxypropyl (meth) acrylate, maleic glycol ester And unsaturated polyester having an unsaturated bond and a molecular weight of 10,000 or less.

  The cationic polymerizable monomer in the present invention is cured by causing a polymerization reaction by the action of Bronsted acid or Lewis acid generated by the action of active energy rays, and also causing a crosslinking reaction and a modification reaction of the water-soluble resin. It means a compound that insolubilizes the resin. As a suitable cationic polymerizable monomer in the present invention, a compound having an epoxy group, an oxetane group, a vinyl ether group, a propenyl ether group, and a cyclic orthoester group can be used, and a mixture of two or more of these can also be used. it can. In order to effectively cause insolubilization, compounds having two or more of these cationic polymerizable groups are particularly preferred.

  Examples of monofunctional epoxy monomers include EX-111, EX-121, EX-141, EX-145, EX-146, EX-171, EX-192, EX, which are Denacol series described in the Nagase ChemteX Corporation catalog. -111, EX-147, M-1230, EHDG-L, and 100MF, which are Epolite series described in Kyoeisha Chemical Co., Ltd. catalog. If these are used as reactive diluents, high viscosity or solid epoxy resins can be used. For example, the BPF type epoxy resin, BPA type epoxy resin, BPF type epoxy resin, novolak type epoxy resin, brominated epoxy resin, flexible epoxy resin, and Yuka Shell Epoxy Co., Ltd. catalog listed in the catalog of Toto Kasei Co., Ltd. Epicoat basic solid type, Epicoat bis F solid type, EHPE alicyclic solid epoxy resin described in the catalog of Daicel Chemical Industries, Ltd., and the like can be used.

  Examples of the monomer having two or more glycidyl type epoxy groups include EX-611, EX-612, EX-614, EX-614B, EX-614, and EX, which are Denacol series described in the catalog of Nagase ChemteX Corporation. -622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-201, EX-211, EX-212, EX-252, EX-810 , EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-861, EX-911, EX-941, EX-920, EX-721, EX -221, EM-150, EM-101, EM-103, YD-115, YD-115 described in the catalog of Toto Kasei Co., Ltd. YE-115CA, YD-118T, YD-127, 40E, 100E, 200E, 400E, 70P, 200P, 400P, 1500NP, 1600, 80MF, 100MF, 4000, 3002 which are Epolite series described in Kyoeisha Chemical Co., Ltd. catalog 1500, etc. Furthermore, examples of the alicyclic epoxy monomer include Celoxide 2021, Celoxide 2080, Celoxide 3000, Epolide GT300, Epolide GT400, Epolide D-100ET, Epolide D-100OT, Epolide D-100DT, Epolide described in the catalog of Daicel Chemical Industries, Ltd. And D-100ST, Epolide D-200HD, Epolide D-200E, Epolide D-204P, Epolide D-210P, Epolide D-210P, Epolide PB3600, Epolide PB4700, and the like.

  Examples of oxetane monomers include J.M. V. Crivello and H.C. Sasaki, J .; M.M. S. Pure Appl. Chem. A30 (2 & 3), 189 (1993) or J.A. H. Sasaki and V.M. Crivello, J.M. M.M. S. Pure Appl. Chem. , A30 (2 & 3), 915 (1993). For example, OT-101, OXT-121, OXT-221, OXT-221, OXT-212, OXT-611, Ube Industries, Ltd. ETRNALCOL-OXA, OXBP, OXTP, oxetane methacrylate, etc. it can. These oxetane monomers can be used by mixing with the above epoxy monomers.

  Examples of the vinyl ether include butanediol divinyl ether, hexanediol divinyl ether, cyclohexanediol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, octadecyl vinyl ether, and butanediol monovinyl ether.

  Examples of propenyl ether monomers include glycerin tripropenyl ether and pentaerythritol tripropenyl ether.

  Furthermore, a cation polymerizable monomer having an unsaturated group having radical polymerization ability in the same molecule is preferably used. Examples thereof include glycidyl (meth) acrylate, oxetanyl (meth) acrylate, a compound obtained from a compound having two or more epoxy groups and meth (acrylic) acid (see JP-A-8-277321), and the like. Can be mentioned.

  In the polymerizable monomer used in the present invention, the ratio of the radical polymerizable monomer is 10 to 80%, preferably 20 to 50%, based on the total monomer amount, that is, the total weight of the radical polymerizable monomer and the cationic polymerizable monomer. %. When the ratio of the radical polymerizable monomer is larger than the above range, problems such as a significant decrease in water resistance of the photocured film occur. On the other hand, when the amount is less than the above range, problems such as a decrease in development speed occur.

  Next, a method for obtaining the composition of the present invention comprising the above components will be described. The preparation method can be appropriately selected depending on the solubility of the cationic photopolymerization initiator used in the present invention, the sensitizer used by mixing as necessary, the cationic polymerizable monomer and the radical polymerizable monomer in water. When the cationic photopolymerization initiator and sensitizer, and also the cationic polymerizable monomer and radical polymerizable monomer are soluble in water, the composition is prepared by dissolving them in the aqueous solution of the water-soluble resin used in the present invention. To do. When the cationic photopolymerization initiator and the sensitizer are hardly soluble or insoluble in water, they are dissolved or dispersed in a cationically polymerizable monomer and a radically polymerizable monomer that are insoluble or hardly soluble in water. What is necessary is just to emulsify in the aqueous solution of water-soluble resin. An organic solvent such as ethanol, isopropyl alcohol, ethylene carbonate, propylene carbonate, toluene, or xylene can be used to promote dissolution of the photo cationic polymerization initiator and sensitizer in the cationic polymerizable monomer.

  The photosensitive composition of the present invention is prepared from the water-soluble resin when the amount of the photocationic polymerization initiator that generates acid and radicals by the action of active energy rays is small. Irradiation of active energy rays to the coating does not cause insolubilization of the water-soluble resin in water. Alternatively, even if insolubilized, the coating film is mechanically fragile and cannot be used for screen plate making.

  The above-described sensitizer can be added to the cationic photopolymerization initiator, and the amount of the sensitizer is 5 to 300 parts, preferably 10 to 200 parts with respect to 100 parts by weight of the cationic photopolymerization initiator. If it is less than this range, a sufficient sensitization effect cannot be obtained, and if it exceeds this range, the sensitization effect will not be improved, but the light transmittance will be reduced, so that it will be uniform in the thickness direction of the coating film. Insolubilization does not occur. The total amount of the cationic polymerizable monomer and the radical polymerizable monomer is 10 to 2000 parts by weight, preferably 50 to 1000 parts by weight, and more preferably 100 to 800 parts by weight with respect to 100 parts by weight of the water-soluble resin. The addition amount of the cationic polymerizable monomer is 10 parts by weight or more, preferably 50 parts by weight or more per 100 parts by weight of the water-soluble resin.

  The reason why the composition of the present invention exhibits high-efficiency photoinsolubility is considered to be as follows. The radical species generated from the photocationic polymerization initiator initiates polymerization of the radically polymerizable monomer and causes polymerization, while the strong acid simultaneously occurring initiates polymerization of the cationically polymerizable monomer. Furthermore, for example, an epoxy compound or an oxetane compound easily causes a graft reaction by an acid catalyst at the active hydrogen site of the water-soluble resin. As a result, the water-soluble resin loses water solubility and also proceeds with a crosslinking reaction. Insoluble. As described above, the radical polymerization reaction hardly causes a graft reaction to the water-soluble resin, but improves the photocuring rate by the radical polymerization monomer and gives water resistance to the film properties, while the cationic polymerization reaction is a cationic polymerization monomer. Since the polymerization reaction and graft polymerization to a water-soluble resin occur efficiently, water insolubilization occurs. Due to these synergistic effects, high-performance photosensitive characteristics with respect to active energy rays are exhibited without adding a photocrosslinking agent as another component. It is widely known that a cationic photopolymerization resin composed of an epoxy compound is susceptible to curing inhibition by moisture or an alkali component (supervised by Ichimura and Kakuoka, “Practical Guide for Photocuring Technology”, Technonet (2002). In the photosensitive composition of the present invention, it was surprising that a good photocrosslinking effect was obtained even though water was used as a solvent.

  The composition in the present invention can contain an acid-reactive cross-linking agent that causes a dehydration condensation reaction with a water-soluble resin in order to utilize the acid-catalyzed reactivity of the photocationic polymerization initiator. Examples of acid-reactive crosslinking agents include N-hydroxymethyl acrylamide, N-hydroxymethylated urea, N-hydroxymethylated malonamide, N-hydroxymethylated phthalimide, hexahydroxymethylated melamine, p-hydroxymethylphenol, o-hydroxy A compound having at least one, more preferably two or more methylphenol, 2,6-bis (hydroxymethyl) -p-cresol, resol resin, formyl group or acetal group can be used. Further, diazo resin or dichromate may be used in combination as a photocrosslinking agent. The usage ratio of the acid-reactive crosslinking agent is 1 to 100 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the water-soluble resin. Furthermore, extender pigments such as aluminum oxide, silicon oxide, titanium oxide, zinc white and talc, quinacridone pigments, azo pigments, diketopyrrolopyrrole pigments, perylene pigments, phthalocyanine pigments, isoindoline pigments and other organic pigments Can be dispersed and added.

  The photosensitive composition of the present invention can be used for all substrates, for example, wood, fabric, paper, ceramics, glass, polyester, polyolefin, cellulose acetate, polyimide, synthetic resin such as epoxy resin, glass fiber reinforced resin, aluminum, Suitable for forming coating films (resin films) on semiconductor materials such as copper, nickel, iron, zinc, magnedium, cobalt, semiconductor materials such as silicon and gallium arsenide germanium, and insulating materials such as silicon nitride and silicon oxide ing. In order to improve the film-forming ability, it is desirable to perform a hydrophilic treatment in advance particularly in the case of a synthetic resin. A pattern or a protective layer is formed by irradiating the coating film made of the photosensitive composition of the present invention formed on these substrates with light.

  Application to the substrate surface is performed by a known method in which a uniform coating film is formed. That is, methods such as spin coating, brushing, spraying, reverse roll coating, dip coating, doctor knife coating, and curtain coating. The film thickness depends on the purpose and the type of the substrate, but is from 0.1 μm to 1000 μm.

  The photosensitive composition coated on the substrate is exposed after evaporating water. The photosensitive wavelength region is determined by the type of sensitizer together with the cationic photopolymerization initiator. In particular, since a wide range of sensitizers can be used, the wavelength range of light ranges from far ultraviolet to near infrared. Suitable light sources include low-pressure water source lamps, high-pressure mercury lamps, ultra-high mercury pressure lamps, xenon lamps, mercury-xenon lamps, halogen lamps, and fluorescent lamps, as well as various laser light sources that emit ultraviolet, visible, and near infrared rays. Used for. The exposure may be performed through a photomask or may be performed by writing directly on the photosensitive film with a laser beam. Furthermore, it goes without saying that exposure with active energy of high energy rays such as electron beams and X-rays is also possible.

  The exposed photosensitive film becomes insoluble in water, but may be subjected to heat treatment after the exposure in order to promote insolubilization. Although heating temperature is dependent on the kind of base material, it is room temperature to 250 degreeC, Preferably it is the range of room temperature-150 degreeC. The heating time depends on the type of the photosensitive composition and the heating temperature, but is about 30 seconds to 60 minutes. The film subjected to the exposure and, if necessary, the heat treatment is developed with neutral water. Development is achieved by immersing the photosensitive film in water to dissolve and remove the unexposed portions, or removing the unexposed portions by a water flow from a spray gun.

  A screen printing plate can be produced by applying the photosensitive composition of the present invention to a screen according to a conventional method, drying it, and then subjecting it to exposure, heat treatment as necessary, and development. Alternatively, according to a known method, a photosensitive resin composition is applied on a plastic film and dried to obtain a photosensitive film for screen plate making, and the film is attached to the screen plate surface with water or the like and dried. It is also possible to produce a screen printing plate by removing the film, exposing it to light, and subjecting it to heat treatment if necessary, followed by development. The heating temperature after exposure is room temperature to 80 ° C., more preferably room temperature to 60 ° C., and the overheating time is about 30 seconds to 60 minutes.

  The self-supporting film obtained by coating the photosensitive composition of the present invention on a plastic film can be used as a dry film based on the principle of laminating the film on a substrate. Since the photocationic polymerization reaction is not affected by the oxygen in the air, a dry film without a barrier film can be obtained. The film provided on the substrate can be exposed, subjected to heat treatment as necessary, developed, and subjected to chemical etching or sandblast treatment.

  Furthermore, surface hardening can also be performed by apply | coating the active energy ray composition of this invention to the base-material surface as an aqueous coating material, and irradiating an ultraviolet-ray, visible light, near-infrared rays, and an electron beam to this.

  The invention is explained in more detail below by means of examples.

Examples 1-11
(Preparation of photosensitive composition)
While stirring a 15% by weight aqueous solution of polyvinyl alcohol, a cationic photopolymerization initiator and, if necessary, a cationic polymerizable monomer and a radical polymerizable monomer to which a sensitizer and a photo radical polymerization initiator are added are added, and a dispersion liquid is added. A mold photosensitive composition was obtained. The photosensitive compositions thus prepared are summarized in Table 1. The compounds used here are as follows.
Examples of polyvinyl alcohol as a water-soluble resin include Kuraray K-217 (polymerization degree = 1700, saponification degree = 88%), Nippon Gosei Co., Ltd. GH-17 (polymerization degree = 1700, saponification degree = 88%), photocation. As polymerization initiators, Dow Chemical's sulfonium salt photocationic polymerization initiator UVI-6690, Nippon Soda's iodonium salt photocationic polymerization initiator (CI-5102), as photoradical polymerization initiators, Ciba-kaigi specialty Chemicals (IRA500), Nippon Kayaku isopropylthioxanthone (ITX), as sensitizers, Nippon Kayaku isopropylthioxanthone (ITX), Kawasaki Kasei 9,10-dibutoxyanthracene (DBA), as an epoxy compound Are manufactured by Tohto Kasei ST-3000, YD-128, Nagase ChemteX X-622, EX-411, manufactured by Daicel UCB CELLOXIDE 2021, The oxetane compound, manufactured by Toagosei Co. OXT-121, which is manufactured by Ube Industries, Ltd. oxetane methacrylate. Examples of the acrylic compound are Nippon Kayaku PET-30 and Shin-Nakamura Chemical Co., Ltd. A-BPE-4.
In addition, 25 parts by weight of FL-GB Blue manufactured by Dainichi Seika Kogyo Co., Ltd. was added as a (coloring) agent to these photosensitive compositions.

Reference Examples 1-4
(Preparation of photosensitive composition)
Except for the cationic polymerizable monomer, in the same manner as in Examples 1 to 11, while stirring a 15% by weight aqueous solution of polyvinyl alcohol, a photo cationic polymerization initiator and, if necessary, a sensitizer and a radical polymerizable monomer were added. The photosensitive composition was added as a dispersion. The photosensitive compositions thus prepared are summarized in Table 2.

Examples 12-23
(Preparation of photosensitive film and photosensitive properties)
The photosensitive composition prepared in Examples 1-11 was apply | coated on the polyester film, and it dried for 15 minutes at 40 degreeC, and obtained the photosensitive film whose film thickness is 25-30 micrometers. The film was irradiated from a distance of 1 meter with a 4 KW ultra-high pressure mercury lamp or a 3 KW halogen lamp through a photomask adhered to the film. Then, after standing at 40 ° C. for 30 minutes, the film was developed by spraying water with a spray gun. Photosensitivity characteristics were evaluated with ◯ when a 50 μm pattern was faithfully resolved, Δ when a partial defect was required in the pattern, and x when no pattern was formed. These results are summarized in Table 3.

Reference Examples 5-8
(Preparation of photosensitive film and photosensitive properties)
In the same manner as in Examples 12 to 23, the prepared photosensitive film was exposed and developed with water, and the photosensitive characteristics were evaluated. These results are also shown in Table 3, but no image formation was observed in the absence of the cationic polymerizable monomer.

Examples 24-34
(Preparation and photosensitivity of film for screen making)
The photosensitive composition prepared in Examples 1 to 14 was applied to a 250 mesh polyester screen and dried repeatedly to obtain a uniform film having a total thickness of 72 μm. After heat treatment at a predetermined temperature and time as necessary, the film was irradiated from a distance of 1 meter with a 3 KW metal halide lamp through a photomask pattern adhered to the film. After irradiation, the mixture was allowed to stand at 40 ° C. for 30 minutes, and then developed by spraying water with a spray gun. The evaluation of the resolution was performed with ◯ when the pattern of 50 μm was faithfully resolved, Δ when the pattern was partially broken, and x when the pattern was not obtained at all. Further, while pouring a solvent such as water, acetone, ethyl acetate, butyl cellosolve, etc. on the obtained coating film for plate making, the metal rod whose tip was covered with a cotton cloth was rubbed 100 times with a load of 1 kg. The water resistance and the solvent resistance were evaluated by ◯ marks when no pattern collapse was observed, Δ marks when a defect occurred in a part of the pattern, and x marks when the pattern collapse was significant. The above results are summarized in Table 4.

Claims (5)

(I) a photopolymerization initiator that generates a Bronsted acid or Lewis acid and radical species by the action of active energy rays, which is insoluble or hardly soluble in water, and (ii) has an ethylenically unsaturated group. radically polymerizable monomer and (iii) the actinic energy ray resin composition characterized by comprising a cationically polymerizable monomer is distributed as an essential component.   A photoresist comprising the active energy ray resin composition according to claim 1 coated on a substrate.   An active energy ray resin film comprising the active energy ray resin composition according to claim 1 formed into a film.   An active energy ray resin film for screen printing plate making, wherein the active energy ray resin composition according to claim 1 is formed into a film. A method for forming a resin pattern, wherein the photoresist according to claim 2 or the active energy ray resin film according to any one of claims 3 to 4 is irradiated with active energy and developed with water .