WO1991009880A1

WO1991009880A1 - Photopolymerizable composition

Info

Publication number: WO1991009880A1
Application number: PCT/JP1990/001683
Authority: WO
Inventors: Fumio Takenaka; Kouji Toya
Original assignee: Daicel Chemical Industries, Ltd.
Priority date: 1989-12-28
Filing date: 1990-12-25
Publication date: 1991-07-11
Also published as: KR920701262A; KR0169085B1

Abstract

A photopolymerizable composition comprising at least a photopolymerization initiator and an addition-polymerizable compound, wherein the photopolymerization initiator is composed of at least a sulfide compound, a benzophenone compound, an alkylaminobenzophenone compound, a 2,4,5-triarylimidazolyl dimer, and a triarylmethane leuco dye, and further preferably an alkyl p-(dialkylamino)-benzoate. This composition is used for coating and as a photoresist. In the latter use, the composition contains a thermoplastic polymer, preferably an alkali-soluble polymer including non-styrenic and styrenic polymers.

Description

Specification

Photopolymerizable composition Technical field

The present invention relates to a photopolymerizable composition useful as a coating material, a photo resist, and the like. Background art

Conventionally, organic solvent-containing coating compositions and aqueous coating compositions have been known as coating compositions applied to paper, plastic films, sheets, metals, and the like. . Coatings made of these coating compositions are usually formed by heat curing. However, since the energy efficiency is not sufficient and the curing speed is slow, a large amount of heat energy is required for heat curing. To increase productivity, it is necessary to lengthen the heat-cured line.

On the other hand, as a coating composition having high energy efficiency and productivity and having excellent properties of a cured film, a photopolymerizable composition which is polymerized and cured by irradiation with light such as ultraviolet rays is known. Such a photopolymerizable composition usually contains an addition polymerizable compound having at least one ethylenic unsaturated bond and a photopolymerization initiator.

In addition, the photopolymerizable composition is widely used as a printed wiring board, a printing plate, or a photoresist for forming a metal relief image. This type of photopolymerizable composition usually contains an addition polymerizable compound having a non-ethylenically unsaturated bond, a photopolymerization initiator, and a thermoplastic polymer. This photopolymerizable composition can be used in a liquid form. However, from the viewpoints of workability and environmental pollution, the photosensitive layer made of the photopolymerizable composition is coated with a light-transmitting substrate film and a protective film. It is widely used in the form of a photosensitive film interposed between it and the film. When producing a printed wiring board, the photosensitive film is peeled off from the protective film, and usually, a copper clad laminate is used. A substrate film such as a layer plate is exposed through a photosensitive layer to a base film, and the exposed portion is cured by exposing the substrate to actinic light through a predetermined pattern mask or the like. '

Such a photopolymerizable composition is required to be excellent in photopolymerizability. The light platform speed of the photopolymerizable composition largely depends on the type of the photopolymerization initiator. Conventionally, benzoin, benzoin methyl ether, benzoin ethyl ether, benzyl and the like have been known as photopolymerization initiators. In addition, as photopolymerization initiators having more excellent photomultiplier than the above various photopolymerization initiators, photopolymerization initiators obtained by combining benzophenone with N ,, ′-bis (diethylamino) benzophenone, A photopolymerization initiator comprising a dimer or mouth fin dimer and a leukotriphenyl methane dye (Japanese Patent Publication No. 45-377377) has been proposed. However, the photopolymerizable composition containing these photopolymerization initiators does not yet have a sufficient photopolymerization rate.

In addition, when the thermoplastic polymer in the photopolymerizable composition for photo resist is a solvent-soluble polymer or an alkali-soluble polymer, after the exposed portion is cured, the exposed portion and the exposed portion are hardened. Utilizing the difference in solubility, unexposed areas are dissolved and removed with a developing solution composed of an organic solvent or an aqueous solution of alkali and developed to form a resist image. When the thermoplastic polymer is chlorinated polyethylene or the like, the base film is peeled off using the difference in the adhesiveness between the exposed and unexposed areas of the photosensitive film on the substrate, and the image is formed. A resist image is formed by peeling and developing. Therefore, the photopolymerizable composition is required to have excellent developability and resolution. When developing with a developing solution, it is also required to have excellent resistance to the developing solution. As the above-mentioned developer, an organic solvent-type developer such as 1,1,1,1-trichloroethane is known. However, this developer is not suitable for the work environment, the surrounding environment, and increases in production cost. In recent years, a developer comprising an aqueous alkaline solution containing a basic compound such as sodium carbonate has been widely used. After forming a resist image by the above-described development, when a print substrate is manufactured, an etching process and a masking process are performed using the resist image as a mask to form a pattern corresponding to the resist image. The resist image is peeled off with a peeling liquid. Therefore, the resist image is required not only to have excellent adhesion to the substrate, exhibit excellent resistance to an etching solution and a plating solution, but also to be quickly peeled off by a stripping solution. These properties greatly depend on the composition of the photopolymerizable composition, and a resist image exhibiting excellent resistance to an etching solution and a plating solution generally has high resistance to a stripping solution and poor stripping properties. In particular, the photopolymerizable composition capable of alkali image formation contains a thermoplastic polymer having an active carboxyl group. Therefore, the resist image can be formed from sodium hydroxide or calcium hydroxide. When peeling with a strong aqueous solution such as rubber, it takes a long time to peel. Therefore, not only does the productivity of printed wiring boards and the like decrease, but also the so-called “alkaline burning” occurs in which the metal foil, particularly the copper foil of the laminated laminate, is darkened by the aqueous alkali solution. Adversely affect the process.

Furthermore, the photosensitive film must have cold flow resistance, that is, the photopolymerizable composition does not leak from the end of the photosensitive film stored in a wound state. Is done.

U.S. Pat. No. 3,933,865 discloses a polymerizable monomer having a carboxyl group, a methacrylate having an alkyl group having 4 or more carbon atoms, and 1 to 35% by weight. A photopolymerizable composition containing a thermoplastic polymer composed of a styrene-based monomer and a styrene-based monomer is disclosed. Japanese Patent Application Laid-Open No. 58-127777 discloses that a polymerizable monomer having a carboxyl group is 10 to 40% by weight and a metal having a C6 to C12 alkyl group. A photopolymerizable composition containing a thermoplastic polymer composed of 35 to 83% by weight of a lylic acid ester and 3 to 25% by weight of a styrene monomer is disclosed. These photopolymerizable compositions contain a styrene monomer as a component of the thermoplastic polymer and a methacrylic acid. Perhaps because it is combined with an ester, it has excellent anti-alkaline solution properties and excellent anti-etching properties, and exhibits some degree of cold flow resistance, but the resolution is still insufficient. '

Further, Japanese Patent Publication No. 54-25957 discloses that a polymerizable monomer having a carboxyl group has a content of 15 to 40% by weight, a methacrylate having an alkyl group having 1 to 6 carbon atoms, A photopolymerizable composition containing a polymer composed of 15 to 45% by weight of an acrylic acid ester and 40 to 60% by weight of a styrene monomer is disclosed. Although the photopolymerizable composition is more excellent in cold flow resistance than the thermoplastic polymer, the resolution is still insufficient as described above.

As described above, the components constituting the photopolymerizable composition greatly affect the photopolymerizability, imageability, resolution, resistance of the resist film, and peelability, but the conventional photopolymerizable composition Objects still do not have these properties.

Therefore, an object of the present invention is to provide a photopolymerizable composition having excellent photopolymerizability.

Another object of the present invention is to provide a photopolymerizable composition capable of peeling a resist film in a short time.

Still another object of the present invention is to provide a photopolymerizable composition which can be alkali-developed and is excellent in alkali developing solution resistance, etching solution resistance and plating solution resistance.

Another object of the present invention is to provide a photopolymerizable composition having excellent resolution and cold flow resistance. Disclosure of the invention

The present invention relates to a photopolymerizable composition containing at least a photopolymerization initiator and a liquid or solid addition polymerizable compound at normal temperature and normal pressure, wherein the photopolymerization initiator comprises at least the following (A) )-Provide an optically active composition comprising the component (E). Sulfide represented by the formula [I]

(Wherein, R ¹ , R 2 and R ³ are the same or different and are each a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, A group selected from the group consisting of an alkoxy group and an aralkyl group, and n is an integer of 1 to 5, and m is an integer of:! To 4),

(B) a benzophenone-based compound optionally having a substituent selected from the group consisting of a halogen atom, an alkyl group, an optionally substituted aryl group, an alkoxycarbonyl group, and an alkoxy group ,

(C) a halogen atom, an alkyl group, an optionally substituted aryl group, an alkoxycarbonyl group, or an optionally substituted alkylaminobenzophenone selected from the group consisting of an alkoxy group; System compound,

(D) 2,4,5-triallylimidazolyl dimer which may have a substituent, and

(B) Triarylmethan leuco dye

Preferred initiators include p- (dialkylamino) alkyl benzoates.

The present invention also provides a photopolymerizable composition containing the photopolymerization initiator, an addition-polymerizable compound that is liquid at room temperature and normal pressure, and a thermoplastic polymer. This photomultiplier composition is Arikawa as a photoresist. Preferred addition-polymerizable compounds include, for example, phthalic acid derivatives having a (meth) acryloyl group. The preferred addition ffi i ^ r-modified A product is the above-mentioned phthalic acid derivative, a (meth) acrylate having a (meth) acrylyl group having a molecular width of 3 倘, and Polyoxyalkylene (meta) acrylate and di (meta) having a bisphenol A skeleton And the rate.

Preferred thermoplastic polymers are alkaline soluble polymers, especially those having an acid value.

1 0 C! ~ 350 thermoplastic polymers. Thermoplastic polymers are broadly classified into non-styrene polymers and styrene polymers. Preferred non-styrene polymers include (a) 15 to 40% by weight of an acid addition polymerizable monomer having a carboxyl group, and (b) (meta) acrylate having a phenoxy group. And (c) a copolymer with a non-acidic addition polymerizable monomer.

Preferred styrene polymers are acidic addition polymerizable monomers having a carboxyl group, 15 to 40% by weight, and styrene monomers:! To 35% by weight, acrylic acid ester and methacrylic acid ester 84 to 25% by weight. Detailed description of the invention

The photopolymerization initiator includes a sulfide compound represented by the general formula [I] as the component (A). In the sulfide compound represented by the general formula [I], the alkyl group for the substituents R ¹ , R 2 and R 3 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl. Tert-butyl, pentyl, hexyl, octyl and the like.

Examples of the aryl group include phenyl, naphthyl, and anthryl groups.

Examples of the substituent of the alkyl group include a halogen atom such as fluorine, chlorine, and bromine, an alkoxy group such as a hydroxy group, a methoxy, ethoxy, and a propoxy group, a carboxyl group, a methoxycarbonyl, ethoxycarbonyl, and a propoxy group. Examples thereof include an alkoxycarbonyl group such as a carbonyl group, an amino group, an alkylamino group such as a dimethylamino group and a getylamino group, a nitrogen atom, a cyano group, and the like. Examples of the substituent of the aryl group include the alkyl group and the substituent of the alkyl group. Examples of the alkoxy group include a methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy group and the like.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a 3-phenylpropyl group and a benzhydryl group.

The substituents R ¹ , R 2 and R 3 may be substituted at an appropriate position on the benzene ring, or the same benzene ring may be substituted by the same or different substituents.

Preferred groups for R and R 2 are each a hydrogen atom. R 3 is a lower alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 4 to 4 carbon atoms.

Among the sulfide compounds represented by the general formula [I], particularly preferred compounds include, for example, 4-benzoyl-4'-methyldiphenyl-2-norethsulfide, 4-benzoinole-4'-ethyldiphenylsnosulfide, 4-Benzoinole 4'-Propyridinyl phenol, 4-Benzoinolene 4 '-Iso propyl diphenylenolenolide, 4-Benzoyl 4'-Butyl diphenyl sulfide . One or more of these sulfide compounds can be used.

Further, the photopolymerization initiator contains at least one benzofuyunone-based compound which may have a substituent as the component (B). Examples of the substituent include a halogen atom, an alkyl group, an aryl group which may have a substituent, an alkoxy group, and an alkoxycarbonyl group described above. A preferred benzophenone-based compound is benzophenone. At least one of these benzophenone compounds is used.

The benzofuunone-based compound is usually used in an amount of 50 to 500 parts by weight, preferably 100 to 400 parts by weight, based on 100 parts by weight of the compound represented by the general formula [I]. It is more preferable to use a base of 200 to 350 parts by weight. used. When the amount of the benzofunonone compound is out of the upper ti range, the photosensitivity decreases.

The substituent of the alkylaminobenzophenone-based compound contained as the component (C) in the photopolymerization initiator may have a halogen atom, an alkyl group or a substituent exemplified above. Examples include an aryl group, an alkoxy group, and an alkoxycarbonyl group. Alkylaminobenzophenone-based compounds include, for example, 4-methyl-4'-Jetylaminobenzophenone and 4-methoxy-4'-Jetylaminobenzophenone, 4,4'-bis (methylamine D) Benzophenone, 4-methylamino 4'-ethylaminobenzophenone, 4-ethylaminobenzophenone, etc. A preferred alkylaminobenzophenone compound is 4,4'-bis (alkylamino) benzophenone. 4,4'-bis (alkylamino) benzophenone is, for example, 4,4'-bis (dimethylamino) benzophenone, 4-dimethylamino-1 4'-jetylaminobenzophenone , 4, 4 ^r one-bis (Jechirua Mi Roh) Benzofueno down, 4, 4 '- bis (dipropionate Pirua Mi Roh) Benzofuyuno down, 4, 4' - bis (diisopropyl Sopu opening Pirua Mi Roh) Benzofueno down, 4, 4 '-Bis (dibutylamino) benzophenone, 4,4'-bis (diisobutylamino) benzophenone, 4,4 'monobis (ditert-butylamino) benzophenone. Of these compounds, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (getylamino) benzophenone are particularly preferred.

At least one alkylaminobenzofuyunone compound is used.

—The proportion of the alkylaminobenzophenone-based compound to 100 parts by weight of the compound represented by the general formula [I] is usually 5 to 250 parts by weight, preferably 10 to 20 parts by weight. More preferably, it is 20 to 175 parts by weight. When the amount of the alkylaminobenzophenone compound is In this case, the photosensitivity decreases.

Further, the photopolymerization initiator contains, as component (D), a 2,4,5-triarylimidazolyl dimer which may have a substituent. This 2,4,5-triary-imidazolidyl divalent break is represented by the following general formula [Π].

(Wherein, Ar ^1. , A “2 and Ar 3 each represent an aryl group which may have a substituent.)

Examples of the substituent include the above-described halogen atoms and alkoxy groups, and alkylthio groups such as methylthio and ethylthio groups. —2,4,5— Triarylimidazolyl dimer represented by the general formula [Π] is, for example, 2,2 ′, 4,4 ′, 5,5 ′ Phenylbisimidazole, 2,2'-di (ο—cro-phenyl) —4,4 ', 5,5'—tetraphenylbisimidazole, 2,2'—di (ρ—chloro Mouth phenyl) 1,4 ', 5,5'-Tetraphenylbisimidazole, 2,2'-Di (ο-Cro-mouth phenyl) 1-4,4', 5,5 ' Tora (m—methoxyfenyl) bisimidazole, 2, 2 '— di (p-cloth phenyl) 1-4, 4', 5, 5 '— tetra (m— (Methoxyphenyl) bisimidazole, 2,2 '-(o-fluorophenyl)-1,4', 5,5'-tetraphenylbisimidazole, 2,2'-di (p — Fluorophenyl One, 4, 4 ', 5, 5'-Tetrafurenylbisimidazole, 2, 2 '(o-Methoxifenyl) One, 4, 4', 5, 5 '-Tetraf Enylbisimidazole, 2, 2'-di (ρ-methoxyphenyl) 1-4,4 ', 5,5'-Tetraphenylbisimidazole, 2, 2'-age (2,4—dimethyoxyphenyl) 1-4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'4,4'-tetra (p— Methoxyphenyl) 1,5,5'-diphenylbisimidazole, 2,2'-di (p-methylthiophenyl) 1,4,4 ', 5,5'-tetraphenylbisimidazole Is done. The above general formula

The 2,4,5—triarylimidazolyl dimer represented by [Π] is used in at least one kind.

2,4,5-Triallylimidazolyl dimer is generally used in an amount of 50 to 400 parts by weight, preferably 1 to 100 parts by weight of the compound represented by the general formula [I]. It is used as a base for 00 to 300 parts by weight. If the amount of 2,4,5—triarylimidazolyl dimer is out of the above range, the photosensitization is not sufficient.

Furthermore, the photopolymerization initiator contains a trimethylmethan dye as component (E). The triarylmethan leuco dye preferably has a substituted amino group, particularly at least one dialkylamino group, and functions as a free radical generator. Examples of triarylmethan leuco dyes include, for example, tris (4-N, N-getylamino-o-tolyl) methanthane hydrochloride and bis (4—N, N —Jetylamino o —trinole) Chenylmethan, bis (4-N, N—Jetilamino o —tolyl) benzylthiophenenylmethan, Leucomalakai trigreen (C.I.Basic) green 4), leuco crisp violet (C.I.Basic violet 3), brilliant green (C.I.Basic green 1), victoria green 3B (C Basic green 4), acid green GG (C.1. Acid green 3), methyl violet (CI basic violet 1), roseaniline (CI basic violet) 14) and the like. These triarylmethan leuco dyes can be used as mineral salts such as hydrochloride and sulfate, and as organic salts such as p-toluenesulfonate. At least one triarylmethan leuco dye can be used. Triarylmethan leuco dye is a compound represented by the general formula [I]: usually 10 to 70 parts by weight, preferably 25 to 55 parts by weight, based on 100 parts by weight of I. Used in parts by weight. When the amount of the triarylmethan leuco dye is out of the above range, the photosensitivity decreases by ίδ.

5 In order to further enhance the photopolymerizability of the photopolymerizable composition containing the photopolymerization initiator comprising the combination of the above (A), (B), (C), (D) and (Ε), Preferably, the initiator contains (F) p- (dialkylamino) benzoic acid alkyl ester.

p — (Dialkylamino) benzoic acid alkyl ester is

It is represented by the general formula [m].

(Wherein, R 4, R 5 and R 6 are the same or different and represent a lower alkyl carpet 15)

Examples of the lower alkyl group include linear or branched Ιβ alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl and octyl groups. Of these alkyl groups, alkyl groups having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, are preferred.

Preferred Ρ — (dialkylamino) benzoic acid alkyl esters include, for example, ρ — (dimethylamino) methyl benzoate, ρ — (dimethylamino) ethyl benzoate, Ρ — (dimethylamino) Mino) Propyl benzoate, ρ — (Dimethylamino) Isopropyl benzoate, ρ 5 — (Ν-methyl-Ν-ethyl-amino) Metyl benzoate, ρ— (Ν-methyl) Ν —ethylamino) ethyl benzoate, ρ — (getylamino) methyl benzoate, Ρ — (ethylethylamino) ethyl benzoate, ρ-I (ethylethylamino) propyl benzoate, ρ — (ethylethylamino) G) Isopropyl benzoate, Ρ — (Jib mouth pilamino) Methinole benzoate p- (dipropylamino) ethyl benzoate, P— (dipropylamino) propyl benzoate, P— (dipropylamino) benzoic acid pill. One or more of p- (dialkylamino) benzoic acid alkyl esters represented by the general formula [ΠΙ] can be used.

p— (Dialkylamino) benzoic acid alkyl ester is usually 25 to 200 parts by weight, preferably 50 to 1 part by weight, per 100 parts by weight of the sulfide compound represented by the above general formula [I]. Used at a rate of 00 parts by weight. When the amount of P— (dialkylamino) alkyl benzoate is out of the above range, the polymerization rate of the photopolymerizable composition tends to decrease.

The photopolymerizable composition containing the photopolymerization initiator composed of the components (A) to (E) or the components (A) to (F) exhibits a high photopolymerization rate because the photopolymerization initiator is excited by light irradiation. It is presumed that the energy transition proceeds smoothly and that the addition polymerizable compound is efficiently subjected to radical polymerization.

The photopolymerization initiator may be substituted or unsubstituted polynuclear quinones, benzoins, benzoin ethers, substituted or unsubstituted thioxanthones, or other photopolymerization initiators, if necessary. Examples of _t- substituted or unsubstituted polynuclear quinones that may contain an agent include 2-methylanthraquinone, 2-ethylanthraquinone, 2-propylanthraquinone, and 2-tert-butylanone. Traquinonone, octylmethylanthraquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, benz [a] anthraquinone, benz [b] anthraquinone, 2-phene 2,3-Diphenylanthraquinone, 1,3-Curoanthraquinone, 2-Curoanthraquinone, 3-Cro-1,2-Methylanthraquinone, 1,4,1 Butaquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthaquinone, 2,3-dichloronaphthaquinone, 7,8,9,10-tetrahydronaphthacenequinone Is exemplified. Benzoins and benzo Examples of the ethers include benzoin, methyl benzoin, ethyl benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether. Examples of the substituted or unsubstituted thioxanthonones include thioxanthonone, 2-cyclothioxanthone, 2-methylthioxanthone, 2-ethylenoxanthone, and 2-isopropylthioxanthone. And 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dibutylthioxanthone. Examples of other light-loading initiators include benzyl, α, α-diethoxyacetophenone, and oxime esters such as benzophenone ogsimime acetate.

Further, it is useful to use the above-mentioned optical platform initiator in combination with an appropriate amount of an aliphatic or aromatic amine. Examples of the aliphatic or aromatic amines include, for example, 2-mercaptobenzoxazole, ethanol enoreamin, diethanolamine, triethanolamine, getyl aminoenoamine, Ν— Metilgeynoolamine, Ν-ethyldiethanolanolamine, Ν-π —butinoresietanoleamine, arynorethiourea, Ν, Ν — getylglycine, aniline, Ν—methylylaniline, Ν , Ν—Jetilaniline, Ν—Ethylmorpholine, and the like.

The photopolymerizable composition of the present invention is roughly classified into a coating composition and a photo resist composition.

Hereinafter, the photopolymerizable composition for coating will be described.

The photopolymerizable composition for coating contains at least the photopolymerization initiator and an addition polymerizable compound. The addition polymerizable compound is liquid or solid at normal temperature and normal pressure, and is not particularly limited as long as it has at least one —ethylenically unsaturated group in the molecule. From the viewpoint of photopolymerizability, a compound having two or more acryloyl groups and two or more methacryloyl groups in the molecule is preferable. Two acrilo in the molecule Examples of the acrylate having a hydroxyl group include, for example, ether glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, and tetraethylene glycol diacrylate. , Polyethylene glycol dichloride, propylene glycol dichloride, dipropylene glycol dichlorate, tripropylene glycol dichlorate, tetrapropylene glycol dichloride, polypropylene glycol dichloride 1,4-butanediol diacrylate neopentyl glycol diacrylate, 1,6—hexanediol diacrylate, 2,2-bis (4-acrylonitrile ethoxyphenyl) propane, 2, 2 — Screw (4 Diacrylic acid pen ethoxyphenyl) Diethylene chloride adduct of bisphenol A, such as propane, with ethylene oxide adduct, 2, 2-bis (4-acrylyl dipropoxyphenyl) resin, 2 , 2 — Bis (4-acryloyl penoxypropoxyphenyl) Diacrylate of propylene oxide adduct of bisphenol A such as propane, diacrylate of hydrogenated bisphenol A with ethylene oxide. And N, N'-methylenebisacrylamide, N, N'-benzylidenebisacrylamide, etc. are exemplified by diacrylate of propylene oxide adduct of hydrogenated bisphenol A.

Examples of the acrylyl having three or more acryloyl groups in the molecule include glyceryl acrylate, methyl propylene acrylate, trimethylol acrylate, and trimethylol acrylate. Rate, pentaerythritol retort rerate, pentaerythritol retort rerate, and zipperite erythritol hexarelate are exemplified.

Examples of the methacrylate having two or more methacryloyl groups in the molecule include methacrylates corresponding to the above acrylates. In addition, two or more acryloyl groups and / or The addition-polymerizable compound having an aryl group may be an oligomer such as epoxy acrylate, epoxy acrylate, oligo acrylate, urethan acrylate, or the like. The metarelation rates corresponding to these are exemplified.

One or more of these addition-polymerizable compounds can be used. The photopolymerization initiator is used in an amount of usually 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, per 100 parts by weight of the addition-polymerizable compound. If the amount of the photopolymerization initiator is less than 0.1 part by weight, the photopolymerizability decreases, and if it exceeds 30 parts by weight, the stability of the photopolymerizable composition decreases.

Further, the photopolymerizable composition for coating may be an organic polymer, for example, an acrylic polymer, a styrene polymer, a polyvinyl polyacrylate, an ethylene monovinyl acetate, or a polyvinyl chloride. , Vinyl chloride-vinyl acetate copolymer, chlorinated polyethylene, chlorinated polypropylene, vinylidene chloride-based polymer, polyester, polyamide, polyurethane, polyvinylacetal, alkyd resin, fuynol resin, epoxy Resin, cellulose-based cellulose, cellulose polymers such as nitrated cotton, styrene-polypropylene copolymer, styrene-acrylonitrile copolymer, synthetic rubber such as chlorinated rubber, cyclized rubber, natural rubber, etc. It may be contained. The organic polymer may be an alkali-soluble polymer having a carboxylic acid group. The photopolymerizable composition may contain fats and oils, wax and the like.

The photopolymerizable composition for coating may contain an organic solvent, if necessary. Examples of the organic solvent include alcohols such as methanol, ethanol and propanol, alicyclic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and acetic acid. Esters such as ethyl, ketones such as acetate and methyl ketone, ethers such as getyl ether and tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, and the like. A mixed solvent is exemplified. The photopolymerizable composition for coating can also be used as an adhesive.

The photo resist ffl photopolymerizable compound is described below.

The photopolymerizable composition for photoresist contains the photopolymerization initiator, an addition polymerizable compound, and a thermoplastic polymer.

The amount of the photopolymerization initiator to be used is generally 0.1 to 30 parts by weight, preferably 1 to 15 parts by weight, per 100 parts by weight of the thermoplastic polymer. When the amount of the photopolymerization initiator is less than 0.1 part by weight, the photopolymerizability decreases, and when the amount exceeds 30 parts by weight, the stability of the photopolymerizable composition decreases.

The addition polymerizable compound is a liquid or a solid at normal temperature and normal pressure, and includes a compound having at least two α, ethylenic unsaturated groups in a molecule. As the addition-polymerizable compound, a compound having two or more acryloyl groups and no or methacryloyl groups per minute is preferable. Such an addition-polymerizable compound provides the photopolymerizable composition with excellent photopolymerizability, developing solution resistance, etching solution resistance and plating solution resistance.

In order to remove the resist film in a short time, it is preferable that the addition-polymerizable compound contains at least a component (a compound represented by the following general formula [IV] as 0).

(In the formula, R 7 and R′O are the same or different, a hydrogen atom or a methyl group R 8 or R 3 is the same or different and represents a linear or branched alkylene group, and R ″ is Hydrogen atom, halogen atom or carbon number: represents an alkyl group having an integer of 1 to 10. P and q each represent an integer of 1 to 10, and r represents an integer of 1 to 20.) —In the general formula [IV], the alkylene group of R 8 and RS includes methylene, ethylene, propylene, trimethylene, tetramethylenehexamethylene And heptamethylene and octamethylene groups. Examples of the halogen atom and alkyl group for R "include the same halogen atom and alkyl group as described above.

—The compound represented by the general formula [W] is a terminal hydroxy group of a compound obtained by reacting an aromatic dicarboxylic acid which may have a substituent with an alkylene oxide dihydric alcohol. Is esterified with a (meth) acrylate having a carboxyl group. In the compound represented by the above general formula [IV], the carbonyl group substituted on the benzene ring is such that the other carbonyl group is located at the o-position, m-position, and p-position with respect to one carbonyl group. . That is, a phthalic acid derivative, an isophthalic acid derivative, and a terephthalic acid derivative. General formula

Examples of the preferable compound represented by [IV] include phthalic acid derivatives shown in the following table.

Two

Table 4

Table 5

Table 6

The compound represented by the general formula [IV] as the component (1) can be used as one kind or as a mixture of two or more kinds.

The compound represented by the general formula [IV] is contained in the addition-polymerizable compound at least 5% by weight or more, preferably 1 ° to 75% by weight, and more preferably 15 to 50% by weight. % By weight. If the amount of the compound represented by the general formula [W] is less than 5% by weight, it takes a long time for the resist film to be stripped by the stripper depending on the type of the thermoplastic polymer.

The addition-polymerizable compound includes, in addition to the component (1), that is, the compound represented by the general formula [IV], at least one of the following components (2) to ((preferably, a plurality of components, In particular, it is preferable to use all components of components (2) to (4) In the case of an optically-positive composition containing an addition-polymerizable compound composed of such a combination, the resist film is shortened. It can be peeled off in a short time and satisfies various requirements such as photopolymerization, developability, developer resistance, etchant resistance and plating liquid resistance in a well-balanced manner. (Meta) acrylate having three (meta) acryloyl groups

Examples of the (meth) acrylate having three (meth) acryloyl groups in the molecule as the component (2) include, for example, glycerol triacrylate. Rate, trimethylolpropane triacrylate, trimethylol pentaureate rerate, pen erythritol thorelaterate, and corresponding metabolites. A rate is exemplified. Trimethylolpropane tris of these (methyl) acrylates

(Meta) A rate is preferred. Component (2) can be used as one kind or as a mixture of two or more kinds.

Component (3): a compound represented by the following general formula [V]

R ¹³ R ¹² R ^½

I I I [V]

CH ₂ = C-CC OCH ₂ CH¾0〇C-C = CH ₂

(Wherein, R, RB and are the same or different and are each a hydrogen atom or Represents a methyl group, and s represents an integer of 7 to 11)

Examples of the compound represented by the general formula [V] as the component (3) include, for example, heptane ethylene glycol diacrylate, octaethylene glycol diacrylate, and nonaethylene glycol diacrylate. , Decaethylene glycol diacrylate, propylene glycol diacrylate, heptane propylene glycol dilate, okpe propylene glycol diacrylate, nonapropylene glycol diacrylate, decapropylene glycol dilate Relays, propylene glycol glycolates, and the corresponding dimethacrylates. Among these compounds, R ¹³ is a hydrogen atom, R ¹² and R ^w are Ri hydrogen atom or a methyl group der each of the repeating units s ==. 8 to] 0 Jiaku Re, single preparative or dimethyl data click Relay Ten is preferred. Component (3) can be used as one kind or as a mixture of two or more kinds.

Component (4): a compound represented by the following general formula [VI]

(Wherein, R 15, R 16, R 17 and R 18 are the same or different and each represent a hydrogen atom or a methyl group, and t and u each represent an integer of 1 to 15)

Examples of the compound represented by the above general formula [VI] as the component (4) include, for example, 2,2-bis (4-acrylyloytoxifenyl) propane, 2,2- Bis (4-acrylonitrile toxifunil) propane, 2,2—bis (4-acrylonitrile toxifenyl) propane, 2,2-bis (4-acrylyl lutetraethoxyphenyl) pulp, 22_bis (4-acrylylpentapentaethoxyphenyl) pu bread, 2,2-bis (4 Acryloylhexaetoxyfenyl) propane, 2,2-bis (4-acryloyloxy ethoxylate) propylene, 2,2—bis (4-acryloyl rudecaethoxyf) Enyl) propane, 22-bis (4-acrylonitrile dodecaethoxyphenyl) prohane, 2,2-bis (4-acrylylylpentadecaethoxyphenyl) propane, 2,2-bis (4 —Acryloyl-lep mouth-poxyfenyl) propane, 2,2-bis (4-acryloyl-norezorepropoxyfenyl) propane, 2,2-bis (4-acryloyltripropoxyfenyl) propa 2-, 2-bis (4-acryloyltetrapropoxyphenyl)

(Cryroyl pentapropoxyphenyl) propane, 2, 2-bis

(4-Acryloylhexapropoxyfenyl) propane, 2,2—Bis (4-Acryloyloctapropoxyl unil) Propane, 2,2-bis (4-Acryloylhexapropoxyfoxy) Enyl) pun, 2,2-bis (4-acryloyl-norde dodecapropoxyphenyl) propane, 2,2-bis (4-acryloylpentadecapropoxyphenyl) propane, etc. It includes the meta-rate to be performed.

Among the components (4) represented by the general formula [VI], preferred compounds are those in which Ris R16 and RI8 are all hydrogen atoms, the repeating unit t−15, and the repeating unit = 1 5, especially = 24 u = 24 compounds. Component (4) can be used as one kind or as a mixture of two or more kinds.

The ratio of each of the above components (1) to (4) with respect to the thermoplastic polymer can be determined within a range that does not impair photopolymerizability, developability, developer resistance, and the like. The proportions of the components (1) to) are as follows: 100 parts by weight of the thermoplastic polymer, 500 parts by weight of the component (1), 100 parts by weight of the component (2), and 400 parts by weight of the component (3) 2 -1 5 parts by weight, Component (4): 5 to 20 parts by weight. Preferred proportions of each component (1) to (4) are 100 parts by weight of thermoplastic polymer, 5 to 15 parts by weight of component (1), and 1 ° to 30 parts by weight of component (2). Component (3) is 2 to 10 parts by weight, and component (4) is 5 to 15 parts by weight.

The addition-polymerizable compound is liquid or solid at normal temperature and normal pressure within a quantitative range that does not impair properties such as photopolymerizability, and has at least one β-ethylenic unsaturated group in the molecule. May contain other compounds. Among such compounds, compounds having one α, β-ethylenically unsaturated group in the molecule include, for example, acrylic acid, mer acrylate, ethyl acrylate, acrylyl Acrylic acid such as butyl acrylate, hexyl acrylate, octyl acrylate, dimethylaminoethyl acrylate, getylaminoethyl acrylate, acrylyl amide, and methylol acrylyl amide Derivatives thereof; methacrylic acid and derivatives thereof corresponding thereto; styrene, pinyl ester and the like. Examples of the compound having two α, ^ monoethylenically unsaturated groups in the molecule include, for example, an addition polymerizable compound represented by the general formula [V], wherein s = 1 to 6, and s = 12 or more; In the general formula [VI], t and u are 16 or more additional overlapping compounds; In the general formula [VI], t and u are 1 or more, and the benzene ring is substituted with a cyclohexyl ring. 1,4—butanediol diacrylate, neopentylglycol diacrylate, 1,6—hexanediol diacrylate, and the corresponding dimethacrylates N, N'-methylenebisacrylamide, N, N'-methylenebismethacryloleamide, N, N'-benzylidenebisacrylamide, N, Ν'-benzylidenebismethacrylamide, etc. Is exemplified. Examples of the compound having four or more non-; 3-ethylenically unsaturated groups in the molecule include pentyl erythritol toltrachlorate, dipentyl erythritol hexyl acrylate, and the like. , And metarelation rates corresponding to these are exemplified. In addition, two or more α, β-ethylene The compound having an unsaturated group may be the above-mentioned oligomer such as epoxyacrylate or oligoesteracrylate.

The ratio of the addition-polymerizable compound to 100 parts by weight of the thermoplastic polymer is 25 to 80 parts by weight, preferably 30 to 60 parts by weight. When the amount of the addition-polymerizable compound is less than 25 parts by weight, the resolution decreases, and when it exceeds 80 parts by weight, the cold flow resistance decreases.

The photopolymerizable composition for photo resist of the present invention contains various thermoplastic polymers suitable for a developing system. For example, when the development method is peeling development, the thermoplastic polymer includes chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene; methyl acrylate, ethyl acrylate, and polyacrylate. Acrylic polymers such as methyl methacrylate and ethyl methacrylate; vinyl chloride polymers such as polyvinyl chloride and vinyl chloride vinyl acetate copolymer; polyvinylidene chloride, vinylidene chloride Vinylidene chloride-based polymers such as rilonitrile copolymer, vinylidene chloride-acrylate copolymer, vinylidene chloride-vinyl acetate copolymer; polyvinyl acetate; saturated polyester; polyvinyl butyral , Polyvinyl acetal such as polyvinyl formal, etc .; polyisoprene; Chlorosulfonated polyolefins such as sulfonated polyethylene and chlorosulfonated polypropylene; and chlorinated rubber. Preferred release development thermoplastic polymers are chlorinated polyethylene, chlorinated polypropylene, polymethyl methacrylate, and saturated polyester. One or more of these thermoplastic polymers can be used.

As the solvent-developing type thermoplastic polymer, a conventionally used polymer, for example, in addition to the above-mentioned polymer, a cyclized rubber, a styrene-butadiene copolymer, and a styrene-acrylonitrile copolymer may be used. Synthetic rubbers such as polymers, styrene-butadiene acrylonitrile copolymer, and copolymers of styrene, acrylonitrile copolymer, polyurethane, styrene-based polymers, cellulose acetate, nitro Cellulose-based polymers such as cellulose are exemplified. You. One or more of these thermoplastic polymers can be used for convenience.

The thermoplastic polymer in the photopolymerizable composition of the present invention is preferably an aqueous polymer. These alkali-soluble polymers are broadly classified into non-styrene polymers containing no styrene monomer as a constituent unit and styrene polymers containing a styrene monomer as a constituent unit. proper composition of the molecule, that differs depending on the presence or absence of styrene monomer _c

The alkali-soluble polymer does not impair the developability, the resolution, the adhesion to the substrate, and the peelability of the resist film. What is necessary is just to have an acid value. The acid value of a thermoplastic polymer depends on the type of polymer. The preferred acid value of the thermoplastic polymer containing no styrene unit is 100 to 35 °, particularly 125 to 250 °, and the acid value of the thermoplastic polymer containing a styrene unit is 100 to 350, preferably 125-300. When the acid value of the thermoplastic polymer is less than 100, it changes depending on the composition of the thermoplastic polymer, but generally, the developability and the resolution are lowered, and when it exceeds 350, the resolution is generally lowered. descend.

The total amount of the soluble thermoplastic polymer contained in the photopolymerizable composition is 15 to 40% by weight, preferably 20 to 35% by weight, of the acidic addition-polymerizable monomer (a) having a carboxyl group. %, And 85 to 60% by weight, preferably 80 to 65% by weight, of the non-acidic addition-polymerizable monomer (b). Such a photopolymerizable composition containing a soluble thermoplastic polymer is useful for forming a fine pattern because the development time is short and the resistance of the resist film to the developer is large. .

Examples of the acidic addition-polymerizable monomer (a) having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, diconic acid, fumaric acid, bromionic acid, sorbin II, and gay cinnamate. And at least one kind is used. Among the acidic addition-polymerizable monomers (A) having a carboxyl group, methacrylic acid and acrylic acid, particularly a mixture of both, are preferred. What A dicarboxylic acid such as maleic acid can also be used as a half ester or an anhydride.

Thermoplastic polymers containing units of the acidic addition-polymerizable monomer (a) have the property of swelling or dissolving in an alkaline liquid. Therefore, in order to impart resistance to an alkaline developer, styrene and its derivative, a non-acidic addition-polymerizable monomer (b) such as acrylate or methacrylate are copolymerized. Use as an ingredient.

As the styrene monomer, styrene; α-substituted styrene in which the α-position is substituted with an alkyl group or a halogen atom, for example, methyl styrene, α-chlorostyrene Substituted styrene in which a hydrogen atom of the benzene ring is substituted, for example, ρ-methylstyrene, ρ-ethylstyrene, ρ-propylstyrene, ρ-isopropylstyrene, ρ- (tert-butyl) styrene; At least one is used. Of the styrene monomers, styrene, monomethylstyrene and the like are preferred.

Examples of the acrylate include acrylates having an alkyl group having 1 to 20 carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, and the like. Isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, acrylic acid Octyl, mono-2-acrylyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, stearyl acrylate, phenyl acrylate, acryl Examples thereof include cyclohexyl acrylate, 2-phenylenoxyl acrylate and the like. Examples of the methacrylate include methacrylate corresponding to the above acrylate. One or more of these acrylates and methacrylates are used, respectively.

In particular, as a non-styrene polymer, copolymerization of the following components (a) to (c) A photopolymerizable composition containing a soluble thermoplastic polymer composed of a body is hard to swell with an alkaline etchant, and is useful for imparting etching resistance. -

(a) an acid addition substrate having a carboxyl group and a single unit of 15 to 4 ° weight%,

(b) The following general formula [W]

[VE]

(Wherein, R represents a hydrogen atom or a methyl group, R ²⁰ is Killen group of 1 to 6 carbon atoms, R ² i is a hydrogen atom, a carbon number of 1 to] 0 alkyl group or a C androgenic atoms, V is 1 - At least 5% by weight of the non-acidic weighted monomer represented by the formula:

(c) Relational expression [VI]

0.25 <(QA / Qc) E p [-e A (e A-e C)] <

4.00 [Vffi]

(Where Q and e are the stability and polarity of the monomer as defined by the Alfrey-Price equation, and the symbol A is the addition polymerizable amount , The symbol C represents a non-acidic addition polymer (c).) The balance of the non-acidic addition-polymerizable polymer having a Q value and e 暄

In the compound represented by the general formula [VII], the alkylene group for R∞ may be a methylene, ethylene, propylene, trimethylene, tetramethylene, or hexamethylene group. Etc. are exemplified. Examples of the alkyl group and halogen atom for R ² i include the same alkyl group and halogen atom as described above.

Preferred non-acid addition polymerizable compounds (b) of the compound represented by the general formula [VE] include 2-acryloxy acrylate, 2-acryloxy acrylate, and acryl acrylate. Lylic acid 3-phenolic mouth pill, phenoxyethyl ethoxylate acrylate, phenoxylate acrylate Shexyl, phenoxytrioxytoxyl acrylate, phenoxypropoxypropyl acrylate, phenoxydipropoxypropyl acrylate, phenoxytripropoxypropyl acrylate, acryloxylate, acrylic acid ( p— (chlorophenoxy) ethyl, acrylic acid (p—methylphenoxy) ethyl, methacrylic acid 2-phenoxhetyl, methyl acrylate 3—phenoxypropyl, methacrylic acid phenyloxetyl, methacrylyl Phenoxydiethoxy propyl methacrylate, Phenoxytriethoxy methacrylate, Phenoxypropoxy propyl methacrylate, Phenoxy dipropoxy propyl methacrylate, Phenoxy propyl methoxy methacrylate , Methacrylic acid (p-chlorophenol Ci) ethyl, methacrylic acid (p-methylphenoxy) ethyl and the like.

The unit of these non-acidic addition-polymerizable monomers (b) is contained in the copolymer at least 5% by weight, preferably 10 to 70% by weight.

The acidic addition polymerizable monomer (a) having a carboxyl group and the non-acid addition polymerizable monomer (b) are copolymerized with the non-acid addition polymerizable monomer (c) satisfying the above relational formula []. Is done. The non-acidic addition polymerizable monomer (c) is composed of at least one of a styrene monomer, an acrylate and a methacrylate.

When copolymerized with the non-acidic addition polymerizable monomer (C) satisfying the above relational formula [], a copolymer in which the units of the acid addition polymerizable monomer (a) are uniformly distributed is obtained. Excellent. That is, as the acid addition-polymerizable monomer (a) and the non-acid addition-polymerizable monomer (c), the copolymerization property of Alfrey-Price is represented by the formula of Alfrey-Price. The use of monomers having similar Q values as indicators and opposite signs of e and having a large difference in absolute values can significantly improve the copolymerizability. Therefore, if a monomer that does not satisfy the above-mentioned relational expression [All is used, a copolymer or a free polymer in which units of the acidic addition-polymerizable monomer (a) are unevenly distributed is obtained. Poor development or, if significant, precipitation of the copolymer during loading May occur.

The non-acidic addition-polymerizable monomer (C) is suitably selected according to the properties of the acidic addition-polymerizable monomer (a), as previously proposed by the present applicant. 2-1 533 0 08 publication).

When a plurality of acidic addition-polymerizable monomers (a) are used, the non-acidic addition-polymerizable monomer (c) is combined with at least one of the acidic addition-polymerizable monomers (a). It suffices to satisfy the relational expression [Cor] in between.

The non-acidic addition-polymerizable monomer (c) constitutes the remainder of the thermoplastic polymer other than the acidic addition-polymerizable monomer (a) and the non-acidic addition-polymerizable monomer (b). It is determined to be 100% by weight.

Styrene-based polymers have excellent resistance to etching solutions and the like, and have excellent resolution and cold flow resistance. In particular, as the styrene-based polymer, 15 to 40% by weight, preferably 20 to 35% by weight of the acidic addition-polymerizable monomer (a) having a carboxyl group, and the styrene-based monomer 1 ~ 35% by weight, preferably 10-35% by weight, acrylates and methacrylates 84-25% by weight, preferably 7C! Up to 30% by weight of the copolymer exhibits excellent resistance to alkaline developers, etching solutions and Messenger solutions, and has remarkably excellent resolution and cold flow resistance.

The styrene-based monomer and acrylic acid are more soluble than the thermoplastic polymer obtained by combining the styrene-based monomer with one of the acrylate and the methacrylate. A photopolymerizable composition containing an alcohol-soluble thermoplastic polymer polymerized by using an ester and a methacrylate in combination has excellent resolution.

In order to further improve the resolution, a styrene monomer, an acrylic acid ester having an alkyl group having 7 or more carbon atoms, and a component other than the acid addition polymerizable monomer, i.e., having 1 to 2 carbon atoms A combination of a methacrylate having an alkyl group of 0; a styrene monomer, an acrylate having an alkyl group of 1 to 20 carbon atoms, and an acrylate of 1 to 3 carbon atoms; A combination with a methacrylate having an alkyl group is preferable. In particular, it is preferable to use a combination of an acrylate having an alkyl group having 7 or more carbon atoms and a methacryl ^ ester having an alkyl group having 1 to 3 carbon atoms.

The ratio of the acrylate and the methacrylate used together with the styrene monomer can be appropriately set within a range that does not reduce the resolution, and the acrylate and the methacrylate are used. ester

= 20-65 80-35% by weight, preferably 30-50 / 70-50% by weight.

The thermoplastic polymer is usually contained in the photopolymerizable composition in an amount of 30 to 80% by weight, preferably 40 to 70% by weight. Further, the thermoplastic polymer can be obtained by a conventional polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. The weight average molecular weight of the thermoplastic polymer is usually about 1 × 10 ⁴ to 1 × 10 6.

The photopolymerizable composition for coating and resist of the present invention may contain a stabilizer, a coloring agent, a plasticizer, a filler, etc., which suppresses a thermal polymerization reaction and increases storage stability. . Examples of the stabilizer include p-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol and the like, and are used in an appropriate amount as long as the photopolymerizability is not inhibited. Examples of the coloring agent include dyes and pigments such as crystal violet, malachite green, Victoria blue, and methylene blue. Examples of the plasticizer include phthalic acid esters such as getyl phosphate, dibutyl phosphate, diheptyl phthalate, and dioctyl phthalate; and fatty acid esters such as octyl adipate and dibutyl didialic alcohol adduct; Examples include phosphoric acid esters such as dimethyl phosphine; sulfonic acid amides such as toluene sulfonic acid amide. Examples of the filler include talc, kaolin, carbonated calcium carbonate, and barium sulfate ^). A photosensitizer composed of a photopolymerizable composition for coating is usually formed by printing or coating a liquid photopolymerizable composition on a material to be coated, for example, paper, plastic, or metal. it can. Conventional means such as spray coating, dip coating, mouth-coating, and doctor-blade coating can be used as the above-mentioned application means.

The photopolymerizable composition for a photo resist is generally used in the form of a liquid, insoluble or dispersed in an organic solvent, preferably a photosensitive film. Examples of the organic solvent include alcohols such as methanol, ethanol, and propanol; alicyclic hydrocarbons such as hexane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene. , Esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as getyl ether and tetrahydrofuran, and halogenated hydrocarbons such as methylene chloride. And mixed solvents thereof. The photosensitive film is usually coated with a liquid photopolymerizable composition on a base film such as a polyethylene terephthalate film and dried, and a protective film such as a polyethylene film is pressed with a pressure roll or the like. It is made by laminating. Protective film is not always necessary. In the photosensitive film, the thickness of the photosensitive layer composed of the photopolymerizable composition is not particularly limited as long as the resolution and the workability are not reduced, but is usually from 5 to: L00 m, preferably _c photosensitive Fi Lum is 2 0 to 7 0 m is normally or wound into a roll and stored in a state stacked.

The photopolymerizable composition for a photo resist is prepared by applying a liquid photopolymerizable composition containing an organic solvent to a substrate, removing the organic solvent, and peeling off the protective film of the photosensitive film. The substrate film is laminated on the above-mentioned substrate by a rubber roll or the like via a photosensitive layer while heating as necessary.

The photosensitive layer, whether for coating or photo resist, Exposure is performed with a light source that generates chemically active light, such as a low-pressure mercury lamp, ultra-high-pressure mercury lamp, or xenon lamp. The actinic ray is a ray having a wavelength suitable for the absorption wavelength of the photopolymerization initiator, preferably an actinic ray having a wavelength in the ultraviolet to visible light range of 25 ° to 500 nm. Is mainly used. Note that electron beams, X-rays, etc. can also be used.

In the case of a photosensitive film, exposure is usually performed by a contact exposure method in which a negative or positive pattern mask film is brought into close contact with a substrate film, and a projection method.

After exposure, development is performed to form a resist image. As described above, the development can be performed by an appropriate development method depending on the type of the thermoplastic resin. The peeling development is carried out by peeling the base film together with the unexposed photosensitive layer. In the solvent development, a common organic solvent such as trichloroethylene and methylene chloride can be used. In alkaline development, an alkaline developer containing a basic compound is used. Examples of the basic compound include potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate. Alkali metal salts of potassium pyrophosphate such as sodium, sodium gayate, sodium phosphate, sodium pyrophosphate and potassium pyrophosphate; butylamine, dimethylamine Organic bases such as tilamine, trimethylamine, triethylamine, ethanolamine, jetanolamine, triethanolamine, morpholine and pyridine are exemplified. The pH of these alkaline developers is usually about 9 to 11, and an aqueous sodium carbonate solution is preferably used. The developer may contain an organic solvent such as ethylene glycol monobutyl ether, a surfactant, and an antifoaming agent.

In the manufacture of a printed wiring board, a resist image is used as a mask, and the resist image is treated with a plating solution or an etching solution. Remove with sodium hydroxide aqueous solution. Industrial applicability

The photopolymerizable composition of the present invention can be used as a coating material; an adhesive; a photo resist for producing a printed wiring board, a circuit board, a metal relief image, a printing plate, and the like.

Hereinafter, Examples and Comparative Examples of the present invention will be described, but the present invention is not limited to these Examples. Examples Examples 1 to 4 and Comparative Examples 1 to 8

A photopolymerization initiator was mixed in a solution shown in Table 8 with a solution of an addition polymerizable compound comprising the following components to obtain a photopolymerizable composition.

Trimethylolpropane triacrylate 15 g Tetraethylene glycol diacrylate 10 g Methylethyl ketone 30 g Apply each photopolymerizable composition to a copper plate and dry. Thus, a photosensitive layer was formed. The photosensitive layer was then irradiated with a 2 Kw ultra-high pressure mercury lamp from air at a distance of 50 cm until the photosensitive layer was no longer sticky, and this irradiation time was defined as the curing time. Table 8 shows the results.

成成成成成：

Funo / / No / Nufuno Ichino

Table 8

, Denotes the following T,

Ingredients () 4-benzoyl-4'methyldiphenyl sulfide

Benzophenone

4, 4'—Bis (getylamino) benzophenone

2, 2'-di (2-chlorophenyl) 1,4,5,4 ', 5'tetraphenylbisimidazole leuco crystal violet

Ρ-(dimethylamino) ethyl benzoate

As is clear from Table 8, the optically-positive composition of the valley example cures in a shorter time than the comparative examples.

Example 5

The curing time was examined in the same manner as in Example 1 except that 4-benzoyl-4′-ethyldiphenyl sulfide was used instead of the component (A). The curing time was 8 seconds.

Example 6

The curing time was examined in the same manner as in Example 1 except that 4,4′-bis (dimethylamino) benzophenone was used instead of the component (C). The curing time was 8 seconds.

Example 7

In the same manner as in Example 1 except that the component (D) was replaced with 2, 2'-di (p-methoxyphenyl) _4,4 ', 5,5'-tetraphenylbisimidazole When the curing time was examined, it was cured in 8 seconds.

Example 8

The curing time was examined in the same manner as in Example 1 except that leucomalachite green was used instead of component (E), and the curing time was 8 seconds.

Example 9

The curing time was examined in the same manner as in Example 1 except that ρ- (jetylamino) benzoyl was used instead of the component (F). The curing time was 8 seconds.

Examples 10 to 13 and Comparative Examples 9 to 12

The following components were mixed to obtain a solution A.

Copolymer of 20% by weight of methacrylic acid, 60% by weight of methyl methacrylate, and 20% by weight of butyl acrylate (acid value: 130) 50 g Trimethylolpropane Triacrylate 15 g 2,2'-bis (4-acryloyl ethoxylate) propane 10 g Diamond Dog Green GH 0.0 3 g Methylethyl ketone 70 g Tetrahydrofuran 20 g To this solution A, a photopolymerization initiator was mixed at a ratio shown in Table 9 to obtain a photopolymerizable composition. The photopolymerizable composition was applied to a base film composed of a polyethylene terephthalate film having a thickness of 25 m, and dried at a temperature of 75 ° C to prepare a photosensitive film. The thickness of the photosensitive layer was 50 m. The photosensitive film was polished to a stretched laminated board, and 1 0. C was laminated using a heated rubber roller. Stapler 2 A 1-step step tablet was placed on the substrate film, irradiated with a 2 Kw ultra-high pressure mercury lamp from a distance of 50 cm for 10 seconds, cured, and then the substrate film was peeled off. It was spray-developed with a 1% aqueous solution of sodium carbonate at a temperature of 30 ° C for 70 seconds to form a resist image. This resist image is formed corresponding to a step tablet in which the amount of transmitted light changes stepwise. Therefore, the photopolymerizability was determined based on the number of steps in the step shutter corresponding to the minimum exposure required to form a resist image. The larger the number indicating the number of steps in the step tablet, the higher the sensitivity of the photopolymerizable composition.

Next, the copper-clad laminate 1 on which the resist image was formed was etched with a second chloride etching solution and treated with a plating solution.

Table 9 shows the results together with the composition of the photopolymerization initiator.

Formation

Nono, Buzhusuno Table 9 d b 6 B c f

In the table, each component shows the following compounds.

4-benzoyl-4'-methyldiphenyl sulfide benzophenone

4, 4'—Bis (getylamino) benzophenone

2,2'-di (2-phenyl phenyl) 1,4,5,4 ', 5'-tetraphen leuco crystal violet

P-(Dimethylamino) ethyl benzoate

As is clear from Table 9, when the photopolymerization initiator of each Example is used, the composition is cured in a shorter time than in Comparative Examples 9 to 12. In addition, the resist images obtained from the photopolymerizable compositions of Examples 10 to 13 all showed sufficient resistance to the etching liquid and the stick liquid.

Examples 14 to 20 and Comparative Examples 13 to 15

Solution B was prepared by mixing the following components.

Copolymer of 20% by weight of methyl methacrylate, 60% by weight of methyl methacrylate, and 20% by weight of isobutyl acrylate (acid value: 130)

5 0 g 4 1 Benzoyl 4 '—methyldiphenylsnorefide

0.8 g p — (dimethylamino) ethyl benzoate 0.6 g benzophenone 2.0 g

4,4'-bis (getylamino) benzophenone 0.2 g 2,2'-di (2-chlorophenyl) -1,4 ', 5,5'-tetraphenylbisimidazole 1,5 g Leucocrystanolenolate 0.3 g Methylethylketone 70 g Tetrahydrofuran 20 g Addition-polymerizable compound was added to this solution B at the ratio shown in Table 10 to prepare the photopolymerizable composition. Obtained. In Table 10, “Compound No.” indicates the number of the phthalic acid derivative shown in Tables 1 to 7 above.

Then, a photosensitive film was prepared in the same manner as in Example 10, and the curing time of the photopolymerizable composition was measured. Further, the minimum time required for development was measured by spray development in the same manner as in Example 10. Further, the laminated laminate on which the resist image is formed is etched with a second chloride etching solution, and treated with a Mech solution, followed by 2% by weight sodium hydroxide at a temperature of 50 ° C. It was immersed in a real aqueous solution and the time until the resist image was peeled was measured. The results are shown in Table 10. 0

In the table, abbreviations indicate the following compounds.

T MPTA: Trimethylolpropane triacrylate

N E G D M A: Nonaethylene glycol dimethacrylate

A-BPE-4: 2,2-bis (4-acryloyljetoxyphenyl) propane

As is clear from Table 10, the photopolymerizable compositions of Comparative Examples 13 to 1 are not sufficient in any of the properties of light overlaying property, developability, and releasability of a resist image. On the other hand, it was found that the photomultiplier compositions of Examples 14 to 20 can be photopolymerized in a short time and developed in a short time, and the resist image can be peeled off in a short time. The resist images of Examples 14 to 20 all showed sufficient resistance to the etching liquid and the plating liquid.

Example 2 1

The following components were mixed to obtain an optically-positive composition.

Co-base of 10% by weight of methacrylic acid, 15% by weight of methacrylic acid, 52% by weight of methyl methacrylate, and 23% by weight of 2-ethylhexyl acrylate Compound (acid value 182) 50 g Compound No. 6 30 g

4—Benzoinole 4'—methyldiphenyl sulfide

0.8 g

P — (dimethylamino) ethyl benzoate ◦. 6 g benzophenone 2.0 g 4,4'-bis (getylamino) benzophenone

0 2 g

2,2'-di (2-cyclophenyl) 1-4,4 ', 55'-tetraphenylbisimidazole 15 g Leuco stannoole violet 0 3 g Victory Ablue GH 0.1 methylethyl ketone 70 g tetrahydrofuran] 0 g Example 22

Example 21 Instead of the copolymer of 1, a copolymer of 20% by weight of methacrylic acid, 45% by weight of methyl methacrylate, and 35% by weight of 2-phenoxyshethyl acrylate (acid Example 2 1 In the same manner as in the above, a photopolymerizable composition was prepared.

Example 23

Example 21 Instead of the copolymer of 1, methacrylic acid] 4% by weight, acrylic acid 14% by weight, methyl methacrylate 40% by weight, 3-acryloxypropyl acrylate 32% by weight A photopolymerizable composition was prepared in the same manner as in Example 21 except that 50 g of the copolymer (acid value 200) was used. Example 24

Example 21 In place of the copolymer of 1, 14% by weight of methacrylic acid, 14% by weight of acrylic acid, 30% by weight of styrene, 2-ethylhexyl acrylate 17.5 A photopolymerizable composition was prepared in the same manner as in Example 2 except that 50 g of a copolymer (acid value: 200) containing 24.5% by weight of methyl methacrylate was used.

Example 25

Example 21 In place of the copolymer of 1, 14% by weight of methacrylic acid, 14% by weight of acrylic acid, 10% by weight of styrene, 22% by weight of 2-ethylhexyl acrylate, 40% by weight methyl methacrylate copolymer

A photopolymerizable composition was prepared in the same manner as in Example 21 except that (acid value: 200) was used. .

Example 26

Example 21 Instead of the copolymer of 1, 14% by weight of methacrylic acid, 14% by weight of acrylic acid, 25% by weight of styrene, 2-ethylhexyl acrylate 17 % By weight, 30% by weight of methyl methacrylate copolymer

A photopolymerizable composition was prepared in the same manner as in Example 21 except that (acid value: 200) was used.

Example 27

Example 21 Instead of the copolymer of 1, 20% by weight of methacrylic acid, 30% by weight of styrene, 24% by weight of 2-ethylhexyl acrylate, 26% by weight of methyl methacrylate An optically active composition was prepared in the same manner as in Example 21 except that the copolymer (acid value 130) was used. Example 28

Example 21 Instead of 30 g of the addition-polymerizable compound (compound No. 6) of the optically-positive composition of Example 1, 4 g of compound No. 22 was used, and trimethicone monopropane triac was used. Except using 11 g of relay, 4 g of 2,2'-bis (4-acrylonitrile resin ethoxyphenyl) prohane, and 3 g of nonaethylene glycol dimethacrylate A photopolymerizable composition was prepared in the same manner as in Example 21.

Comparative Example 16

Example 21 The copolymer of Example 1 was replaced with 6% by weight of methacrylic acid, 6% by weight of acrylic acid, 30% by weight of styrene, and 1-ethylhexyl acrylate 1 7. An optically overlaying composition was prepared in the same manner as in Example 2 except that a copolymer (acid value: 8.5.5) of 5% by weight and methyl methacrylate 40.5% by weight was used. did.

Then, a photosensitive film was prepared in the same manner as in Example 10 to evaluate the sensitivity of the optically-positive composition and the stripping time of the resist image. The cold flow property was evaluated as follows.

(1) Resolution evaluation method

As a pattern mask, a set of five silver halide pattern masks in which a line width and a space of 10 m to 150 m are formed in an area ratio of 1: 1 each in 1 Orri increments. The product was spray-developed, washed with water and dried in the same manner as in Example 10. Then, the resist image is observed with an optical microscope with a magnification of 200 times. .

(2) Evaluation method for resistance to alkaline liquid

In addition, without using the above mask, exposure was performed under the same conditions as in Example 0 to form a resist film. The resist film was immersed in a 1% by weight aqueous solution of sodium carbonate adjusted to pH 8.5 for 1 hour, and the resistance to the alkaline solution was visually determined. Al force Sex was evaluated according to the following criteria.

Excellent: No change in resist film

Good: Slight swelling of resist film ''

(3) Evaluation method for cold flow resistance

A 20 m-thick polyethylene film is laminated on the photosensitive layer of the photosensitive film, and is wound while applying tension to produce a wound-shaped dry film. did. The rolled-up dry film was stored upright at room temperature, and the time required for the photopolymerizable composition to leak from the edge of the dry film was examined according to the following criteria, and was used as an indicator of cold flow resistance. .

Excellent: 6 months or more

Good: 1 to 4 months

Table 11 shows the obtained results.

As shown in Table 11, as compared with the photopolymerizable composition of Comparative Example 16, the photopolymerizable compositions of Examples 21 to 28 showed higher photopolymerizability, releasability of the resist image, and resolution. Also, the resistance to alkali liquid was excellent, and the cold flow resistance was also good. 'Note that the resist images of Examples 21 to 28 all exhibited sufficient resistance to the etching liquid and the medicinal liquid.

Table 11

Remarks: With the optically overlaying composition of Comparative Example 16, after development, the residual film of the resist image adhered, and it was not possible to evaluate the accurate optical weight, resolution, and resistance to alkaline solution. C

Claims

The scope of the claims

A photopolymerizable composition comprising at least a photopolymerization initiator and an addition-polymerizable compound which is liquid or solid at ordinary temperature and pressure, wherein the photopolymerization initiation 剂 is at least the following ( A) A photopolymerizable composition containing the components.

(In the formula, R ¹ , R 2 and R 3 are the same or different and are each a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, An alkoxy group or an aralkyl group, and n represents an integer of 1 to 5, m represents an integer of 1 to 4),

(B) a benzophenone compound optionally having a substituent selected from the group consisting of a halogen atom, an alkyl group, an aryl group which may have a substituent, an alkoxycarbonyl group, and an alkoxy group ,

(C) an alkylaminobenzophene optionally having a substituent selected from the group consisting of a halogen atom, an alkyl group, an optionally substituted aryl group, an alkoxycarbonyl group, and an alkoxy group; Non-based compounds,

(D) 2, 4, 5 — triarylimidazolidini which may have a substituent, and

(E) Triarylmethan leuco dye

— The photopolymerizable composition according to claim 1, wherein in the sulfide compound represented by the general formula [I], R i and R ² are hydrogen atoms, and R 3 is an alkyl group having 1 to 6 carbon atoms. .

When the sulfide compound represented by the general formula [I] is 4-benzobenzoyl 4'-methinoresifenylsnolide, 4-benzoylone 4'-ethinoresif-enylsulfide, 4-benzoylol 4 '— Propi 2. The photopolymerizable composition according to claim 1, wherein the photopolymerizable composition is ludiphenylsulfonide, 4-benzoyl 4'-isopropyl dihydroeninolesulfide, or 4'-benzodiphenyl 1'-butyldifluorounylsulfide.

4. The photopolymerizable composition according to claim 1, wherein the benzophenone-based compound is benzophenone.

5. The optically-positive composition according to claim 1, wherein the alkylaminobenzophenone compound is 4,4′-bis (dialkylamino) benzophenone.

6. Alkylaminobenzophenone-based compound is 4,4'-bis (dimethylamino) benzofuenonone, 4-dimethylaminoamine 4 '

— Jestilamine benzophenone, 4,4 '— Bis (getylamine) benzophenone, 4,4'-bis (dipropylamino) benzofuenonone, 4,4'-bis ( Diisopropylamino benzophenone, 4,4'-bis (dibutylamino) benzophenone, 4,4'-bis (diisobutylamino) benzophenone, or 4,4'-bis (dibutylamino) benzophenone The photopolymerizable composition according to claim 1, which is 4'-bis (ditert-butylamino) benzophenone.

7. The photopolymerizable compound according to claim 1, wherein the 2,4,5—triarylimidazolyl dimer which may have a substituent is a compound represented by the following general formula [Π]. Composition.

(Wherein, A, Ar 2 and Ar 3 represent an aryl group which may have a substituent)

8. 2,4,5—triarylimidazolylny2,2,2 ′, 4,4 ′, 5,5′—hexaphenyl which may have a substituent Bisimidazols, 2, 2 '— di (o—black mouth phenyl) 1-4,

4 ', 5,5'-Tetraphenylbisimidazole, 2,2'-di (p-cro-phenyl) 1-4,4', 5,5'-Tetrafenylbis Midazole, 2,2'-di (o-cyclophenyl) 1-4,4 ', 5,5'-tetra (m-methoxyphenyl) bisimidazole, 2, 2 '— di (p — black mouth phenyl) 1 4, 4', 5,

5'-Tetra (m-methoxyphenyl) bisimidazole, 2,2'-Di (o-fluorophenyl)-4,4 ', 5,5'-Tetraphenylbisimidazole, 2 , 2 '-(p-fluorophenyl)-4,4', 5,5'-tetraphenylbisimidazole, 2,2'-di (o-methoxyphenyl) 1-4,4 ', 5,5'-Tetraphenylbisimidazole, 2,2'-(p-methoxyphenyl) 1-4,4 ', 5,5'-Tetraphenylbisimidazole, 2,2'-di (2,4-dimethyoxyphenyl) 1-4,4 ', 5,5'-tetrafenylbisimidazole, 2,2'4,4'tetra (p-methoxyphenyl) ) One 5, 5 '-diphenylphenylbisimidazole, 2, 2'-di (p-methylthiophenyl) _ 4, 4 ', 5, 5'-tetra Enirubisui Mi indazole in a claim 1 photopolymerizable composition.

9. Triarylmethan leuco dye is used for tris (4-N, N-Jethylamino o-tolyl) methane and bis (4N, N-Jethylamino). -O _ tolyl) chenylmethane, bis (4-N, N- getylamino o-tolyl) benzylthiophenylmethane, leucomalachite green (C. Basic green 4) Basic Lewis Violet (C.I. Basic violet 3), Brilliant Green (C ... Basic green 1), Victory Green 3B (C.I. I. Basic green 4), ash dog green. GG (C. I. Acid green 3), methyl violet (I. Basic violet 1), Kuchiichi zanirin (C. I. Basic vi) olet 14) or a light-positive composition according to claim 1 which is a salt thereof ₍

10 100 parts by weight of the compound represented by the general formula [I], 50 to 500 parts by weight of the benzophenone-based compound, 5 to 25 parts by weight of the perchloraminobenzophenone-based compound, 2, 4 2. The photopolymerizable composition according to claim 1, comprising 50 to 400 parts by weight of a triarylimidazolyl dimer, and 10 to 70 parts by weight of a triarylmethanine dye. .

1 1. The photopolymerizable composition according to claim 1, wherein the photopolymerization initiator contains P- (dialkylamino) benzoic acid alkyl ester.

12. The photopolymerizable composition according to claim 11, wherein the alkyl p- (dialkylamino) benzoate is a compound represented by the following general formula [一般].

(Wherein, R4, R5 and R6 are the same or different and represent a lower alkyl group)

1 3. p- (Dialkylamino) benzoic acid alkyl ester is p- (dimethylamino) methyl benzoate, p — (dimethylamino) ethyl benzoate, P — (dimethylamino) benzoic acid Propyl, p — (Dimethylamino) isopropyl benzoate, p — (N-methyl-1-N-ethylamino) Methyl benzoate, p — (N-methyl—N-ethylamino) Benzo Ethyl acid, p — (Getylamino) Methyl benzoate, p — (Getylamino) Ethyl benzoate, p — (Getylamino) Propyl benzoate, P — (Getylamino) Isopropyl benzoate Pill, p — (diproviramino) methyl benzoate, p-(pipylamino dibu) ethyl benzoate, p — (pirua mino dip) Propyl benzoate, P — (dipropylamino) Benzoic Sani Seo propyl and is claim 1 1 photopolymerizable composition.

14. — 100 parts by weight of a sulfide compound represented by the general formula [I] On the other hand, P — (dialkylamino) benzoic acid alkyl ester 2

The photopolymerizable composition according to claim 11, comprising 5 to 200 parts by weight.

5. The photopolymerizable composition according to claim 1, wherein the addition polymerizable compound has two or more acryloyl groups or methyl acryloyl groups in the molecule.

6. The photopolymerizable composition according to claim 1, comprising 0.1 to 30 parts by weight of a photopolymerization initiator based on 100 parts by weight of the addition polymerizable compound.

7. The photopolymerizable composition according to claim 1, comprising a photopolymerization initiator, a liquid or solid addition polymerizable compound at normal temperature and normal pressure, and a thermoplastic polymer.

8. The photopolymerizable composition according to claim 17, wherein the addition polymerizable compound includes at least a compound represented by the following general formula [IV].

(Wherein, R7 and RW are the same or different, a hydrogen atom or a methyl group, R8, R9 are the same or different straight-chain or branched-chain alkylene down group, R ¹¹ is a hydrogen atom, a halogen atom or a carbon Represents an alkyl group of the numbers 1 to 10. p and q are each an integer of 1 to 10, and r is an integer of 1 to 20.

1. The photopolymerizable composition according to claim 18, wherein the compound represented by the general formula [IV] is a phthalic acid derivative.

20. The photopolymerizable composition according to claim 17, wherein the addition polymerizable compound contains at least 5% by weight of a compound represented by the general formula [IV].

2 1. The addition-polymerizable compound is composed of a compound represented by the general formula [IV] and a (meth) acrylate having three (meth) acryloyl groups in a molecule. 18. The photopolymerizable composition according to claim 17, comprising:

2. A (meth) acrylate having three (meta) acryloyl groups in the molecule, which is a trimethylolpropane tri (meta) acrylate. 21. The photopolymerizable composition of 1.

3. The photopolymerizable composition according to claim 1, wherein the addition polymerizable compound includes a compound represented by the general formula [IV] and a compound represented by the following general formula [V].

(Wherein, R13 and RW are the same or different and each represent a hydrogen atom or a methyl group, and s represents an integer of 7 to 11)

4. —In the compound represented by the general formula [V], RB is a hydrogen atom,

23. The photopolymerizable composition according to claim 23, wherein R 12 and are a hydrogen atom or a methyl group, and s = 8 to 10.

5. The photopolymerizable composition according to claim 17, wherein the addition polymerizable compound includes a compound represented by the general formula [IV] and a compound represented by the following general formula [VI].

(Wherein, R] ⁵ , Ri 6, R ″ and R are the same or different and each represent a hydrogen atom or a methyl group, and t and u each represent an integer from〗 to! 5.) 6. General formula [VI R 15, R 16, R 17 and R are each a hydrogen atom, and t = l to 5, u = l to 5 26. The optically overlaying composition according to claim 25.

2 7. The addition-polymerizable compound is a compound represented by the general formula [IV], a (meth) acrylite having three (meth) acryloyl groups in a molecule, The photopolymerizable composition according to claim 17, comprising a compound represented by the general formula [V] and a compound represented by the general formula [VI].

28. 10 to 100 parts by weight of a thermoplastic polymer, 5 to 2 parts by weight of a compound represented by the general formula [IV], and three (meth) acryloyl groups in the molecule (Meta) 10 to 40 parts by weight, general formula

28. The photopolymerizable composition according to claim 27, comprising 2 to 15 parts by weight of the compound represented by [V] and 5 to 20 parts by weight of the compound represented by the general formula [VI].

29. The photopolymerizable composition according to claim 17, wherein the thermoplastic polymer is a soluble polymer.

30. The photopolymerizable composition according to claim 17, wherein the thermoplastic polymer has an acid value of 100 to 350.

3 1. The thermoplastic polymer is a copolymer of 15 to 40% by weight of acidic addition-polymerizable monomer having a carboxyl group and 85 to 60% by weight of non-acidic addition-polymerizable monomer. A photopolymerizable composition according to claim 17.

32. The photopolymerizable composition according to claim 31, wherein the acidic addition-polymerizable monomer having a carboxyl group is methacrylic acid, acrylic acid, or a mixture thereof.

3. The non-acidic addition-polymerizable monomer is at least one of styrene, α-methylstyrene, and a (meth) acrylic acid ester having 1 to 20 carbon atoms. A photopolymerizable composition.

34. The photopolymerizable composition according to claim 17, wherein the thermoplastic polymer is a copolymer of the following components (a) to (c).

(a) 15 to 40% by weight of an acidic addition-polymerizable monomer having a carboxyl group,

(b) at least 5% by weight of the non-acidic addition-polymerizable monomer represented by the following general formula [VE],

(Wherein, R represents a hydrogen atom or methylation group, R ²⁰ is § Ruki les down group of carbon number ~ 6, R ² i is a hydrogen atom, carbon number ~ 1 ◦ alkyl group or a halogen atom, V represents a positive integer from 1 to 20) and

(c) The balance of non-acidic addition-polymerizable monomers having Q and e values satisfying the relational formula [VI]

0.25 <(QA / Qc) E xp [-e A (e A-e C)] <4.00 [VBl]

(Where Q and e are the stability and polarity of the monomer as defined by the Alfrey-Price equation, and the symbol A is the additive monomer. (A), the symbol C represents a non-acidic addition-polymerizable monomer (c).) 3 5. The thermoplastic polymer is an acid-addition-polymerizable monomer having a carboxyl group, 15 to 40% by weight. The photopolymerization according to claim 17, wherein the photopolymerization is a copolymer of a styrene-based monomer having an amount of 1 to 35% by weight, acrylate and methacrylate 84 to 25% by weight. Composition.

3 6. Acrylates have an alkyl group of 7 or more carbon atoms, and acrylic acid esters have a carbon number of! 36. The photopolymerizable composition according to claim 35, which is a methacrylate having an alkyl group of from 20 to 20.

3 7. The acrylate ester has an alkyl group having 1 to 20 carbon atoms, and the acrylate ester and the methyl acrylate ester have the carbon number:! 36. The photopolymerizable composition according to claim 35, which is a methacrylate having an alkyl group of 1 to 3.

38. The acrylate ester has an alkyl group having 7 or more carbon atoms, and the acrylate ester and the methacrylate ester has the alkyl group having 3 to 3 carbon atoms. The photopolymerizable composition according to claim 35, which is an ester.

39. The light according to claim 35, wherein the ratio between the acrylic acid ester and the methacrylic acid ester is acrylic acid ester Z methacrylic acid ester = 20 to 65 to 8% to 35% by weight. Polymerizable composition.

40. The photopolymerizable composition according to claim 17, comprising 100 to 100 parts by weight of the thermoplastic polymer, 25 to 80 parts by weight of the addition polymerizable compound, and 0.1 to 30 parts by weight of the photopolymerization initiator. Composition.