JPH0243552A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To make it possible to improve the sticking property of the title composition to a metal surface without generating a red stain and the peeling of a plating surface by incorporating a specified heterocyclic compd. in the composition. CONSTITUTION:A nongaseous ethylenic unsatd. compd. which has at least two numbers of terminal-unsatd. groups and is capable of forming a polymer, a binding agent of a thermoplastic org. polymer, a photopolymerization initiator capable of being activated by active rays and the heterocyclic ring compd. shown by formulas I and II are incorporated in the composition. In formulas I and II, R1 is hydrogen atom or alkyl group, etc., R2 and R3 are each hydrogen atom or aryl group, etc., R4 and R5 are each hydrogen atom or aralkyl group, etc., R7-R11 are each hydrogen atom or alkyl or aryl group, X is oxygen or sulfur atom, etc., Y is oxygen or sulfur atom. Thus, the photosensitive composition which has the improved sticking property to the metal surface and a less tendency for generating the red stain and the peeling of the plating surface, is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photopolymerizable composition that can be polymerized and cured by irradiation with actinic rays. Specifically, the present invention relates to a photopolymerizable composition that has good adhesion to metal surfaces, especially copper, and does not cause red discoloration or peeling of plating. More particularly, the present invention relates to photopolymerizable compositions useful for forming photoresists that are readily curable and resistant to plating fluids and etchants.

[Conventional technology]

Tokuko Shogu used in the manufacture of printed wiring boards! −
Dry film photoresist as seen in Publication No. 2jλ37 is laminated on a copper-clad laminate (substrate)! @, and irradiated with actinic rays through the original with wiring and e-turns,
The unexposed areas are then dissolved using a suitable developer to obtain a hardened image on the substrate.

Using the resulting cured image as a resist, the exposed copper is
It is modified by various methods, such as etching, plating or anodizing, to produce printed circuit boards. However, dry film resists have weaker adhesion to metal surfaces than liquid photoresists, and undesirable smearing phenomena occur during etching or plating. For example, when spraying with etching solution or dipping into plating solution, the solution enters between the resist and the copper substrate, causing the resist to separate and lift off from the copper substrate, resulting in underetching and underblating. Phenomena such as this occur. As a result, the edges of the image become unclear, the resist image is damaged, and a desired n-degree pattern cannot be obtained, resulting in a large number of substrates being wasted.

In the manufacture of printed wiring boards using dry film resist, when creating a resist pattern on a board, there are cases in which the resist nog turn portion is brought into close contact with the entire surface of the board. A metal layer such as copper is placed on the front and back screens of the board and the inner surface of the through holes.Finally, printed wiring is created on both the front and back sides of the board, and When creating printed wiring in which the wiring on both the front and back sides is electrically connected through the inside of the through-hole, a resist film is placed over or below the through-hole without making the entire surface of the resist film adhere to the metal surface. (This is called the tenting method). This is to prevent the metal layer inside the through hole from being etched when printed wiring is created by etching. In the case of such a tenting method, the formed resist (Ill) is in close contact with the substrate only in a small area around the exit of the through hole, and the other parts of the film are in close contact with the substrate due to its own cohesive force. The through-hole requires an adhesive that does not peel off even when sprayed with the spray-type etching method that is normally used, but it is not always large enough, so the etching solution sometimes seeps into the tent belly. .

In order to improve these problems, a method of pre-treating the metal surface has been proposed (Tokuko Sho J'Hiro-j
2 Octopus, JP-A-31-A Hiro/ri, JP-A-J7-Otohiro 720).

On the other hand, methods have been proposed to improve adhesion by adding various compounds to the photosensitive resin layer (Tokuko Shota O-Tough No. 77, Tokko Shoyo≠-yo, Tokko Shoyo 2 Octopus No. Kimiaki!!-22.≠r1, JP-A-5)-6 Hiro, Ri/ri,
Tokukai Showayu l-6≠.

No. 720, JP-A No. 30-63,017, JP-A No. 2-
No. 2.72μ, JP-A-63-702, JP-A-J-J-
/2≠,! Hiroshi 7, Tokukai Sho! 3-/2 Hiromu, 39≠ issue, Tokukai Sho! Hiro-/33. ! ;r! No., JP-A-Shoj≠-/33.
! rIts, Tokukai Sho 5-6, Rihiro 7, Tokuko Shoj
7-≠A, No. 04r3, Tokuko Shoyo 7-Hiroshi 6. O! ≠No.,
JP-A-Shoj-A-//.

Ri0hiro No., Tokuko Sho J-7-, 2/, Otsu No. 27, Tokukai Shoyo&-7j, j≠2 No., Tokukai Shoyo Otsu-&7. ♂≠Hiro issue, special public Sho J7-Hiro o, zoo issue, JP 56-49, 202
No., JP-A-5T-IOO, GO-3, JP-A-37-1.
No. 0,327, Japanese Patent Publication No. 7-62, Q≠7, DAS Ko Hirohiro♂♂jO, US Hirohiro No. 622679, Special Publication Shoj7-
Hiroshi? 77 Hiro, JP-A 37-/Ko♂13 Octopus, JP-A Show Tough-/9.2.94tt, Toku'HHHHt-io
o, txttwt issue, JP-A-Shoj Ku //3,413
No. 2, Tokukai Akira! Tar 12, 72! No., Tokukai Akira! Tar/
2! , No. 726, Tokukai Sho! Tar/2j, No. 727, JP-A Shoyo Tar/uj, No. 721, JP-A 52-/Yuλ,
≠No. 37, Tokukai Show Tatar/! ≠, Hiro≠θ, Tokukai Sho! Tar/Tahiro, ≠≠ No. 1, Tokukai Shoj Tar/Otsuyo, No. 051,
JP-A No. 60-/2,5413, JP-A No. 1pO-/2゜j Hiroshi≠, JP-A No. 60-/3! , F3/issue, Tokukai Sho AO
-/31. ! 'AO issue, JP-A-60-/! A.

No. 233, JP-A Show Otsu/-≠, 03g issue, JP-A Show tl-Otsu, Otsu≠μ issue, JP-A Show 7/-! ,,&≠No. 6, JP-A-Sho A/
-/6t,! ≠/issue, JP-A-1986/-/7λ, /3ri issue,
Tokukai Akiotsu/-/? Otsu,! Pyo No. 2, Tokukai Sho Otsu/-/ri0
, No. 330, JP-A No. 6/-/Rir, /4L-Otsu, JP-A No. 4/-223, 136, JP-A No. 1, No. 1. /-212,I
r36, JP-A No. 6/-3 Otsu 01237, JP-A No. 6
2-ta/, ri-3j, JP-A-Sho-Otsu-ko 76. ri3ri issue, JP-A-1.2-/10.3j', JP-A-1999-1s2-/l
rO, 33! No., JP-A No. 62-/ZA0.334, JP-A No. 62-/lrO, 337, JP-A No. 1.2-/I/
, No. 303, JP-A No. 62-201, 0IIt2, JP-A t2-2≠o, ri No. 50, JP-A No. 62-277, ≠0
! No., JP-A-62-211. ．． No. 03jt, JP-A No. 6 Kokota No. 0.702, JP-A No. 6 Kokota, No. 03J-/3. ! No. 24, JP-A-43-. 2 Hiroshi, 2 Hiroshi No. 3, Tokukai Sho-Otsu J-67゜62
No. 2, JP-A-1.3-1. /, 2≠/issue).

``Problem to be solved by the invention'' It is clear that the former method requires an additional process, and the latter is superior, but the problem is that the exposed copper surface of the substrate after development is The phenomenon of red discoloration has been observed, which may have a negative effect on post-processing such as etching, plating, and soldering, or may decolorize the dye9, inhibit photopolymerization reactions, or dissolve into photopolymerizable resin compositions. It has various problems such as poor performance and many manufacturing inconveniences. In particular, as an effective additive for improving adhesion, JP-A-1
, 0-/2j≠≠ (the compound of the present application (1)) is known, but it was not sufficient because it caused red discoloration and peeling of the plating.

[Purpose of the invention]

The object of the present invention is to avoid the above-mentioned problems, and to
It is an object of the present invention to provide a photopolymerizable composition that has good adhesion to metal surfaces and does not cause reddishing or peeling of plating.

More particularly, it is an object to provide photopolymerizable compositions useful in forming dry film resists utilized in the manufacture of printed circuit boards.

[Means for Solving the Problems] The present inventors have discovered that a photopolymerizable composition containing the heterocyclic compounds of general formulas (I) and (It) shown below can be used to reduce redness and mattness. It has been found that adhesion to metal surfaces is improved without peeling.

That is, the object of the present invention has been achieved by a photopolymerizable composition characterized by containing at least (1) to (4).

(1) a non-gaseous ethylenically unsaturated compound having at least two terminal unsaturated groups and capable of forming a polymer; (2) a thermoplastic organic polymer binder; and (3) capable of being activated by actinic radiation. Photopolymerization initiator system (4) Heterocyclic compound represented by general formulas (I) and (II) General formula (I) R1 is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group , represents an amino group, or a substituted amino group, R2 and R3 represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or an aralkyl group, 几4 and R5 represent a hydrogen atom, an alkyl group, a substituted alkyl group , aryl group, or aralkyl group, together with N atom, pyrrolidine, piperidine, morpholine or N-
Substituted piperazine nuclei may also be formed. X represents an oxygen atom, a sulfur atom, an alkyl group or an aryl group. ], and Y[represents an oxygen atom or a sulfur atom.

General formula (II) In addition, in R1 to R, 11, the alkyl group has a carbon number/
~20 is preferred.

The preferable addition amount of these heterocyclic compounds is as follows: compound of formula (I): 0,00/~o,i wt %, based on the solid content of the photopolymerizable composition.
) compound: o, oi ~ o, z %, more preferably 1
Compound of Shikke formula (I): o, oi -o, o≠wt% formula (
Compound II): o, o4! ~0.2% by weight.

If the amount of the compound of formula (I) added is less than 0.00%, the adhesion of the resist will be insufficient, causing plating and lifting of the resist during etching, and thin lines will peel off during development. Tashi.

If the amount of the compound added is 0.1% by weight or more, the copper plate tends to turn red or the plating peels off.

If the amount of the compound of formula (H) added is less than 0.0% by weight, the effect of preventing red discoloration will be lost.

If the amount of the compound added is 0.5% by weight or more, the leuco dye develops color during storage or the plating peels off.

Suitable ethylenically unsaturated compounds for use in the present invention are:
It is a compound that has at least two terminal unsaturated groups and can be photopolymerized by irradiation with actinic light. Hereinafter, it will be abbreviated as polyfunctional monomer.

Specifically, Tokuko Sho Jj-4,0ri No. 3 Publication, Tokuko Sho 3
Turf≠, 7/ri issue, special public show≠≠-21r, 727
The following compounds are described in the following publications.

First, acrylic esters and methacrylic esters include polyacrylates and polymethacrylates (herein, "poly" refers to diacrylate or higher) of polyhydric alcohols.

Examples of the polyhydric alcohols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polycyclohexene oxide, polystyrene oxide, polyoxetane, polytetrahydrofuran, cyclohexanediol, xylylene diol, di(β
-Hydroxyethoxy)benzene, glycerin, diglycerin, neopentyl glycol, trimethylolethane, trimethylolethane, hantaerythritol, dipentaerythritol, nrubitan, sorbitol, butanediol, butanetriol, copten-1
, Hiro-diol, co-n-butyl-2-ethylpro/
Carbon Diol 1,2-Futhine-l.

Hiro-diol, 3-chloro-72-propanedio-k,
/, ≠-cyclohexane dimetatool, 3-cyclohexene-/, /-dimethator, tecarindiol,
3-dibromocoptene-/, ≠-diol, 2.2
-diethyl-/,3-furopanediol,l,! -dihydroxy-7゜23 ≠-tetrahydronaphthalene, 2
．． Terdimethyl-2,! -hexanediol, 2,2-
Dimethyl-/, 3--10-diol, 2,2-diphenyl-/, 3-propanediol, dodecanediol, mesoerythritol, coethyl/3-hexanediol, coethyl-co(hydroxymethyl)-
/,! --f'lonoξandiol, 2-ethyl-λ-
Methyl/, 3-furo/dionediol, heptanediol, hexanediol, 3-hexene-2,terdiol, hydroxybenzyl alcohol, hydroxyethylresorcinol, λ-methyl/, ≠-butanediol, -monomethyl-x, 4L- -: ntanediol, nonanediol, octanediol, bentanediol, /-
Phenyl-/, +2-ethanediol, furonoξanediol, 212. ≠, l/--tetramethyl-/.

3-Cyclobutanediol, λ, J, j, 6-titramethel-p-xylene-α, α′-diol, /, /l≠
, ≠-tetraphenyl/, ≠-butanediol, /,
/,≠,4I--tetraphenyl-λ-butyne-/l≠
l ziel, /ll trihydroxyhexane, i
, i'-binonaphthol, dihydroxynaphthalene, /, /'-methylene diconaphthol, /,
2. ≠-benzenetriol, biphenol 1. l, 2
'-bis(≠-hydroxyphenyl)butane, /, /-
Bis(Hiro-hydroxyphenyl)cyclohexane, bis(hydroxyphenyl)methane, catechol, ≠-chlorresol 7nol, 3. Hiro-dihydroxyhydrocinnamic acid, hydroquinone, hydroxybenzyl alcohol, methylhydroquinone, methyl, Z,
Hiroshi, A-) Rehydroxybenzoate, phloroglucinol, pyrogallol, resol 7nol, glucose, α
-(/-Aminoethyl)-p-hydroxybenzyl alcohol, -monoamino-coethyl/, 3-propanediol, λ-amino-comethyl/, 3-propanediol, 3-amino-1,2- Propanediol, N-
(J-aminopropyl)-jetanolamine, N,N
' -bis-(λ-hydroxyethyl)piperidino,
2,2-bis(hydroxymethyl)-2,2',2
”-Nitrilotriethanol, Co, Corbis(hydroxymethyl)propionic acid, /, 3-Bis(hydroxymethyl)urea, /, 2-bis(≠-pyridyl)-/, Coethanediol, N-n-butyl Jetanolamine, jetanolamine, N-ethylenediethanolamine, 3-merkart/.

2-propanediol, 3-piperidino-/, 2-propanediol, 2-(2-pyridyl)-/.

3-pronone diol, triethanolamine, α-
Examples include (/-aminoethyl)-p-hydroxybenzyl alcohol and 3-amino-≠-hydroxyphenyl sulfone. Among these acrylic esters and methacrylic esters, the most preferred are ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and ethylene glycol because of their ease of availability. Dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetrapropylene glycol diacrylate, dodecapropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate , pentaerythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, dipentaerythritol pentaacrylate, glycerin triacrylate, diglycerin dimethacrylate), /, J--! Ronoden diol diacrylate, /, 2. μm butanetriol trimethacrylate), /, Hiro-cyclohexanediol diacrylate, /, j-bentanediol diacrylate, neopentyl glycol diacrylate, triacrylic acid ester of trimef D-propane added with ethylene oxide, etc. .

On the other hand, examples of acrylamides and methacrylamides include methylenebisacrylamide, methylenebismethallylamide, ethylenediamine, diaminopropane, diaminobutane, pentamethylenediamine, hexamethylene, bis(2-aminopropyl)amine, and diethylenetriaminediamine. , heptamethylene diamine, octamethylene diamine as well as nine-polyamines interrupted by heteroatoms, polyamines containing rings (e.g. phenylene diamine, xylylene diamine, β-(≠-aminophenyl) ethylamine, diaminobenzoic acid,
There are polyacrylamides and polymethacrylamides (diaminotoluene, diaminoanthraquinone, diaminofluorene, etc.).

Examples of allyl compounds include phthalic acid, terephthalic acid, sepacic acid, adipic acid, geltaric acid, malonic acid,
Diallyl esters of dicarboxylic acids such as oxalic acid, such as anthraquinone disulfonic acid, benzene disulfonic acid, 2
．． Examples include diallyl esters and diallylamides of disulfonic acids such as terdihydroxy-p-benzenedisulfonic acid, dihydroxynaphthalenedisulfonic acid, and naphthalenedisulfonic acid.

Examples of vinyl ether compounds include polyvinyl ethers of the aforementioned polyhydric alcohols, such as ethylene glycol divinyl ether, 3. Examples include j-tri-β-vinyloxyethoxybenzene, 3-di-β-vinyloxyethoxybenzene, and glycerol trivinyl ether.

Examples of vinyl esters include divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, and divinylbenzene.

Examples include 3-disulfonate, divinylbutane-/, and ≠-disulfonate.

Examples of styrene compounds include divinylbenzene, p-allylstyrene, and p-inpropene styrene.

N-β-hydroxyethyl-β-(methacrylamide)
Compounds having λ or more of different addition-polymerizable unsaturated bonds, such as ethyl acrylate, N,N-bis(β-methacryloxyethyl)acrylamide, allyl methacrylate, etc., are also suitably used in the present invention.

Furthermore, the reaction product obtained by reacting a polyol compound having at least two hydroxyl groups with a slightly excess polyisocyanate compound having at least two incyanate groups has at least one hydroxyl group and at least one ethylenically unsaturated group. A polyfunctional urethane compound having at least two ethylenically unsaturated groups obtained by reacting the compounds is also suitably used in the present invention.

These polyfunctional monomers can be used alone or in combination of two or more, and can be used depending on the solid content of the photopolymerizable composition.
It is used in a range of 0% by weight, preferably 60% by weight.

As the binder used in the photopolymerizable composition of the present invention, one that satisfies the following conditions is used from among a wide variety of synthetic, semi-synthetic, and natural polymeric substances. That is, the compatibility with the polyfunctional monomer, the photopolymerization initiator, and the heterocyclic compound of the present invention is such that demixing does not occur during the manufacturing process from preparation of the coating solution to coating and drying. Properties depending on the usage of the invention, for example, when used in a photoresist for tenting, the strength, stretchability, abrasion resistance, chemical resistance, etc. of the polymer are appropriate, and the molecular weight and intermolecular Appropriate strength, hardness, softening temperature, crystallinity, fracture elongation, etc.

Specific examples of binders include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, and poly(meth)acrylic acid alkyl esters such as polymethyl methacrylate (alkyl groups include methyl, ethyl, butyl, etc.) ), copolymer of (meth)acrylic acid and (meth)acrylic acid alkyl ester (alkyl group is same as above), poly(meth)acrylic acid, (meth)acrylic acid alkyl ester (alkyl group is same as above) and acrylonitrile, Copolymers with at least one monomer such as vinyl chloride, vinylidene chloride, styrene, butadiene, polyvinyl chloride, copolymers of vinyl chloride and acrylonitrile, polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile, Copolymers of vinyl acetate and vinyl chloride, polyacrylonitrile, copolymers of acrylonitrile and styrene, copolymers of acrylonitrile with butadiene and styrene, styrene with unsaturated dibasic rIl anhydrides such as maleic anhydride Examples include copolymers, homopolymers and copolymers of polyvinyl butyral, styrene butadiene rubber, chlorinated rubber, cyclized rubber, and acetyl cellulose.

In the case of a copolymer, the content ratio of the monomer can take a wide range of values, but it is generally preferable that the copolymer contains other copolymer monomers in a molar ratio of j% or more. Further, polymers other than these can also be used as the binder of the present invention as long as they satisfy the above conditions.

Among the above polymers, those particularly preferably used as the binder of the present invention are chlorinated polyethylene, chlorinated polypropylene, polymethyl methacrylate, methyl methacrylate-acrylonitrile copolymer (mole content of methyl methacrylate 20 to 0.0 %), vinyl chloride-acrylonitrile copolymer (mole content of vinyl chloride 2 o-ro
z), vinylidene chloride-acrylonitrile copolymer (mole content of vinylidene chloride 1120-tO%), styrene-
Maleic anhydride copolymer, special request! Tarl/≠736 (the binder is methyl methacrylate/methacrylic acid/2-
Ethylhexyl methacrylate/benzyl methacrylate quaternary copolymer), Tokko Shoyo≠-3≠327 (
The binder is, for example, a terpolymer of methyl methacrylate/coethylhexyl methacrylate/methacrylic acid). No. -317A/ (the binder is, for example, styrene/maleic acid mono-butyl ester copolymer), Tokko Sho! Hiroshi-2393-7 (the binder is, for example, a quaternary copolymer of styrene/methyl methacrylate/ethyl acrylate/methacrylic acid), JP-A Sho-Taco-2? ?
Fu No. 0 (the binder is, for example, methacrylic acid (synthetic acid/methacrylic acid copolymer), Japanese Patent Publication Showjar-12377
(the binder is, for example, a terpolymer of acrylonitrile/coethylhexyl methacrylate/methacrylic acid) and Tokkosho! J--4210 (the binders are, for example, a terpolymer of methyl methacrylate/ethyl acrylate/acrylic acid and a partially esterified sitastyrene/maleic anhydride copolymer with isopro, e-ol)
and the binders described in each specification.

These polymers may be used alone as a binder, but it is necessary to use polymers that are compatible with each other to the extent that no demixing occurs during the manufacturing process, from the preparation of two or more coating solutions to coating and drying. They can be mixed in a suitable ratio and used as a binder.

The molecular weight of the polymeric substance used as a binder can vary widely depending on the type of polymer, but -
, 000 to 2,000,000, more preferably θ, 000 to i, ooo, o.

Those within the range of O are preferably used in the present invention. The amount of binder is the solid content of the photomixable composition! ~yr71% by weight, preferably 4Ao-to% by weight.

On the other hand, as the photopolymerization initiator used in the present invention, conventionally known ones can be suitably used, such as J,
Carbonyl compounds, organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds, norogen compounds, photoreducible dyes, etc., as described in Chapter 5 of "Light Sensitive Systems" by Kosar. be.

To give typical specific examples, examples of carbonyl compounds include benzophenone, ≠, Hiro'-bis(dimethylamino)benzophenone, 44.44'-bis(diethylamine)benzophenone, and ≠-methoxy Hiro'-dimetelaminobenzophenone. Non, ≠, Hiro'-dimethoxybenzophenone, Hiro-dimethylaminobenzophenone, Hiro-dimethylaminoacetophenone, anthraquinone, λ
-tert-butylanthraquinone, λ-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, λ-chlorothioxanthone, co,≠-dimethylthioxanthone, co,hiro-diethylthioxanthone, fluorenone, acridone and benzoin, benzoin ethers, e.g. Examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, and benzyl dimethyl ketal.

Examples of organic sulfur compounds include di-n-butyl disulfide, dibenzyl diulfide, 2-mercaptobenzthiazole, λ-mercaptobenzoxazole, thiophenol, and ethyltrichloromethanesulfenate.

λ, Hiro! -Triarylimidazole dimers include, for example, λ-(0-chlorophenyl)-4, j-diphenylimidazole dimer, λ-(0-chlorophenyl)-≠, j-di(m-methoxyphenyl)imidazole dimer, λ-(O-fluorophenyl)-a, t-diphenylimidazole dimer, 2-(o-methoxypher)-Hiroshi,! -diphenylimidazole dimer, 2-(
Examples include p-methoxyphenyl)-μ, j-diphenylimidazole dimer.

Examples of polyhalogen compounds include carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, and JP-A No. 33-334T.
Special public Akira! No. 7-/I/RI, Special Publication Shoyo No. 7-&OPJ and US Patent No. 3t/j Hiro! ! Mention may be made of the compounds disclosed in No.

These compounds may be used alone or in combination of two or more. Preferred combinations include, for example, the combination of λ,≠,j-IJ arylimidazole dimer and 2-mercaptobenzoxazole or leuco crystal violet, and the combination of λ, ′-bis(dimethylamino)benzophenone and benzophenone or benzoin methyl ether in combination, and the U.S. patent cylinder≠23′? Benzoyl-N- as described in No. 160
Methylnaphthothiazoline and 1. The combination of Hiro-bis(trichloromethyl)-Koichi Otsu methoxyphenyltriazole, the combination of dimethyl oxanthone and Hiro-dialkylamine benzoate described in JP-A-7-23602, and JP-A-7-23602; As stated in the issue,
Examples include a mixture of 4',4''-bis(dialkylamino)benzophenone, benzophenone, and a polyhalogen compound.

Examples of peroxides include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.

Redox compounds consist of a combination of a peroxide and a reducing agent69, and include ferrous ions and persulfate ions, ferric ions and peroxides, and the like.

Examples of azo and diazo compounds include α,α'-azobisisobutyronitrile, co-azobis-comethylbutyronitrile, and diazonium salts of p-aminodiphenylamine.

Examples of the halogen compound include chloromethylnaphthyl chloride, phenacyl chloride, chloroacetone, naphthalenesulfonyl chloride, phenyltribromomethylsulfone, and tris(trichloromethyl)-S-triazine.

Photoreducible pigments include rose bengal, erythrosin, eosin, acriflavin, riboflavin, and thionin.

The content of these photopolymerization initiators and their combination system is 0.1 to 20 parts by weight per 100 parts by weight of the polyfunctional monomer.
It is used in a range of parts by weight, preferably in a range of o, r to 10 parts by weight.

It is preferable to further add a thermal polymerization inhibitor to the photopolymerizable composition used in the present invention. Specific examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t
-Butylcatechol, pyrogallol, cuprous chloride, floranil, naphthylamine, β-naphthol, 2. A-
Examples include monobutyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, methylene blue, organic steel, and methyl salicylate. These thermal polymerization inhibitors are 0.00/
~! The content is preferably in the range of % by weight.

In the present invention, a plasticizer may be added to control the physical properties of the film, and typical examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octylcabryl phthalate, and dicyclohexyl phthalate. , ditridecyl phthalate, butyl benzyl phthalate, diindecyl phthalate, diaryl phthalate and other phthalic acid esters, dimethyl glycose phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol Glycol esters such as licorcicarylic acid ester, phosphoric acid esters such as tricresyl phosphate and triphenyl phosphate, diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, dibutyl maleate, etc. Examples include aliphatic dibasic acid esters, amides such as benzenesulfonamide, p-)luenesulfonamide, and N-n-7' tylacetamide, triethyl citrate, glycerin triacetyl ester, and butyl laurate.

A combination system of an organic halogen compound and a leuco dye can be mixed into the photopolymerizable composition of the present invention.

Examples of organic halogen compounds having such functions include halogenated hydrocarbons, halogenated alcohol compounds, halogenated carbonyl compounds, halogenated ether compounds, halogenated ester compounds, halogenated amide compounds, and halogenated sulfone compounds. can be mentioned.

Examples of halogenated hydrocarbons include carbon tetrabromide, iodoform, /2,2-dibromoethane, /,l.

λ, 2-tetrabromoethane, /l/-bis(p-chlorophenyl)-1,2,2-toIJ chloroethane, /,
2-dibromo-/, I, 2-) dichloroethane, /, 2
．． 3-) ribromopropane, /-bromo-hiro-chlorobutane, /, 2,3. Examples include ≠-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentanediene, dibromocyclohexane, and the like.

Examples of halogenated alcohol compounds include.

2.2-t+) Chloroethanol, tribromoethanol 1 Tribromoethanol, l,3-dichloro-2-
Propertool, / , / , /-trichloro-j-propertool, di(iodohexamethylene)aminoisopropertool, tribromo-tert-butyl alcohol,
λ, 2,3-trichlorobutane-7, Hiro-diol and the like.

Examples of halogenated carbonyl compounds include /ll-dichloroacetone, /, 3-dichloroacetone, hexachloroacetone, hexabromoacetone, /, /, J, J-
Tetrachloroacetone, /.

/, /-t+) chloroacetone, 3. IA-dibromo-
Examples include 2-butanone, /,≠-dichloro-2-butanone, and dibromocyclohexanone.

Examples of halogenated ether compounds include 2-prosoethyl methyl ether, λ-bromoethyl ethyl ether, cy(2-7'' lomoethyl) ether, and 2-dichloroethyl ethyl ether.

The halogenated ester compound can be an ester of a halogenated carboxylic acid, a halogenated ester of a carboxylic acid, or a halogenated ester of a halogenated carboxylic acid. Examples of such esters include bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of λ,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, ethyl α,β-dichloroacrylate, etc. can be mentioned.

Examples of halogenated amide compounds include chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, -promoisoprobionamide, 2.2.1-)lichloroprobionamide, Examples include N-chlorosuccinimide and N-bromosuccinimide.

Examples of halogenated sulfone compounds include U.S. Pat.
0μ2j/! Examples include compounds described in the specifications of No. 3 and No. 3JO Kohiro 76, and the most representative example is phenyltribromomethylsulfone.

Among the halogen compounds, halides having one or more halogen atoms bonded to the same carbon atom are preferred, and halides having three halogen atoms to one carbon atom are particularly preferred. The organic halogen compounds may be used alone or in combination of two or more.

The amount of the organic compound used in the present invention ranges from 0 to 5% by weight of the solid content of the photopolymerizable composition.

More preferably, it is from o, ooz wt% to /wt%.

Typical leuco dyes that can be used in the present invention include the following. Bis(p-dibutylaminophenyl)-(p-(-2-cyanoethyl)methylaminophenylcomethane, bis(p-dimethylaminophenyl)
-2-quinolylmethane, aminotriarylmethanes such as tris(p-dipropylaminophenyl)methane, 3
T6-bis(diethylamino)-terphenylxanthine, 3-amino-6-dimethylamino-comethyl-7
Aminoxanthines such as -(0-chlorophenyl)xanthine, 3,6-bis(diethylamino)-ter(0-
ethoxycarbonylphenyl)thioxanthine, 3. t
-aminothioxanthines such as -bis(dimethylamino)thioxanthin, 3゜bis(diethylamino)-ta, 10-dihydroterphenylacridine, 3. z-
Aminophenoxazines such as bis(benzylamino)-ta, 10-dihydrotermethylacridine, J, 7-bis(diethylamino)phenoxazine, 3゜7-bis(ethylamine) ) Aminophenothiazines such as phenothiazine, 3,7-bis(diethylamino)-j-hexyl-! , aminodihydrophenazines such as 10-dihydrophenazine, aminophenylmethanes such as bis(p-dimethylaminophenyl)anilinomethane, ≠-amino≠'-dimethylaminodiphenylamine, ≠-amino α, β-dicyanohydrocinnamic acid Aminohydrocilinic acids such as methyl ester, hydrazines such as /-(2-naphthyl)-cophenylhydrazine, amino-2,3- such as /, Hirobis(ethylamino)-2,3-dihydroanthraquinone, etc. Dihydroanthraquinones, N, N
phenethylanilines such as -diethyl-p-phenethylaniline, acyl derivatives of leuco dyes containing basic Nl (groups such as 10-acetyl-3,7-bis(dimethylamine)phenothiazine, tris(≠-diethylamino-0- Leuco-like compounds that do not have oxidizing hydrogen such as tolyl) ethoxycarbonylmethane but can be oxidized to color-forming compounds, leuco indigoid dyes, U.S. Patent No. 3.0
≠2. Organic amines that can be oxidized to color-forming forms, such as those described in Sir No. 3°0≠2,577. Typical compounds of this type include the following: ≠, Hiro' -ethylenediamine, diphenylamine, N,N-dimethylaniline 4L, ≠'
Methylenediaminetriphenylamine, N-vinylcarbazole.

The leuco dye used in the present invention is in the range of 0.01 to 10 parts by weight per 100 parts by weight of the solid content of the photopolymerizable composition,
More preferably, it is in the range of 0.03 to 5 parts by weight.

Dyes used in the present invention include Victoria Pure Blue, aracite green oxalate, diamond green sulfate, auramine base, crystal violet,
These include Tsukushin, Oleozole Fast Blue, Methyl Orange, and Acid Violet.

The photopolymerizable resin composition of the present invention is dissolved or dispersed in a solvent to form a coating solution, coated on a support by an appropriate method, dried, and if necessary, a protective film is placed thereon to form an image. It is generally used as a material.

Examples of bath agents for the coating solution include alcohols such as methanol, ethanol, n-propatool, impropatool, n-butanol, 5ec-butanol, and n-hexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diimbutyl. Ketones such as ketones, ethyl acetate, butyl acetate, n-amyl acetate, Nisdels such as methyl acetate, ethyl propionate, dimethyl phthalate, and ethyl benzoate, aromatic carbonization of toluene, xylene, benzene, ethylbenzene, etc. Hydrogens, carbon tetrachloride, trichloroethylene, chloroform, /, /, /-) dichloroethane, methylene chloride, monochlorobenzene, nitrogenated hydrocarbons, tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol mono Examples include ethers such as ethyl ether and /-methoxy-2-propatol, dimethylformamide, and dimethylsulfoxide.

The support used as described above needs to have good light transmittance and a uniform surface.

Specifically, polyethylene terephthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly(meth)acrylic acid alkyl ester, poly(meth)acrylic ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene. Various plastic films can be used, such as cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene. Furthermore, a composite material consisting of two or more of these types can also be used.

The support generally has a diameter of 10 to 40 .mu.m, preferably 10 to 40 .mu.m, but may also be used in a range other than the above.

The thickness of the layer of the photopolymerizable composition provided on the support is determined so as to achieve the desired function of the finally formed image, but is generally within the range of j-700 μm. range, preferably 10-10 μm.

The photopolymerizable composition of the present invention is used by being coated on a support, and if necessary, a protective film can be provided on the photopolymerizable composition layer. Such a protective film can be appropriately selected from those commonly used for the support and paper such as paper laminated with polyethylene, polypropylene, etc. Thickness ili,
The thickness is generally 1 to 100 μm, and more preferably 70 to 50 μm.

At that time, it is necessary to make the relationship A)H between the adhesive force A between the photopolymerizable composition layer and the support and the adhesive force B between the photopolymerizable composition layer and the protective film. Specific examples of support/protective film combinations include polyethylene terephthalate/polypropylene, polyethylene terephthalate/polyethylene, polyamide (nylon 6)/polyethylene, polyvinyl chloride/cellophane, polyimide/polypropylene, and the like.

In addition to the method of selecting the support and the protective film from mutually different types as described above, it is also possible to satisfy the above-mentioned adhesive force relationship by surface-treating at least one of the support and the protective film. be able to. The surface treatment of the support is generally carried out to increase the adhesion with the photopolymerizable composition layer, such as applying an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, etc. Examples include high frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

Contrary to the above-mentioned surface treatment of the support, the surface treatment of the protective film is generally carried out to reduce the adhesive force with the photopolymerizable composition layer, such as polyorganosiloxane. There is a method of providing an undercoat layer of fluorinated polyolefin, polyfluoroethylene, etc.

Drying after blood cloth is generally done at 30°C to 1ro0c.

It is particularly preferable to carry out the heating at 0°C to 20°C for 7 to 30 minutes.

If the image-forming material has a protective film, it is removed to expose the surface of the photopolymerizable composition layer, which is then laminated under pressure onto the surface of a desired cleaned substrate.

Various substrates can be used depending on the purpose of use of the present invention, such as plastic films, paper, wood, and metal plates that have adhesive strength with a photopolymerizable layer different from that used for the support. , a glass plate, etc. are used. Particularly when the present invention is used as a resist for producing printed circuits, a thin layer of metal, such as copper, aluminum, silver, etc., is applied to the top or bottom of a plastic plate, or to the inner wall of a hole drilled through a plastic plate, i.e., a through-hole. On the surface is a printed wiring board with 9 mated or plated,
Alternatively, a substrate may be used in which a thin metal film is provided on a thin plastic film by vapor deposition or plating, and if the present invention is used in a printing plate, an aluminum plate or a plastic film provided with an aluminum layer may be used. It will be done. In this case, the surface of the metal such as aluminum is preferably subjected to treatments such as silicate treatment and anodic oxidation.

The photopolymerizable composition layer is laminated onto these substrates at room temperature (/j
~300C) or under heating (30~/r00C), and is particularly preferably carried out at ♂O~/≠o'(♂O~/≠o').

The photosensitive layer and support thus laminated onto the substrate are then imagewise exposed through the transparent support, typically through an original document. The light source is an electromagnetic wave that transmits through the transparent support and is active for the photopolymerization initiator used, with a wavelength of 31.
A light source is used that emits ultraviolet-visible light in the range of 0 to 700 nm, preferably 3!0 to 00 nm. For example, high pressure mercury lamps, xenon lamps, carbon arc lamps,
A halogen lamp, a fluorescent tube for copying, etc. are used. In addition, exposure may be performed using a laser beam, an electron beam, an X-ray, or the like.

After imagewise exposure, the transparent support is removed and the unexposed areas are bathed in a suitable developer, such as an organic solvent, an alkaline water bath solution containing an organic solvent, or an alkaline water bath solution, to form a photocured image on the substrate. get.

After image formation, desired processing can be performed if necessary. For example, when creating a printed wiring board, the exposed metal may be etched using a known etching solution such as a chloride bath solution or a ferric chloride bath solution, or a known etching solution such as birophosphate steel or copper sulfate may be used. Plating solution can be used to plate exposed metal.

Alternatively, a solution obtained by dissolving the photopolymerizable composition of the present invention in the above-mentioned solvent may be applied directly onto the substrate using a spinner, wheeler, etc.
A photoresist can also be created by drying.

The photopolymerizable resin composition of the present invention is particularly suitable for making printed wiring boards, but can also be used for a wide range of purposes such as making planographic or letterpress printing plates, making relief molds, optical reproduction, and photography. It can be used.

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited by these Examples. "Parts" means "parts by weight" unless otherwise specified.

Example/~Hiro A uniform bath liquid was prepared by mixing the materials shown below (
(Hereinafter, this will be referred to as the mother liquor).

Methyl methacrylate/Methacrylate ≠2.7 parts Rudic acid/2
- Etherhexyl methacrylate/benzyl methacrylate copolymer (mole ratio = yoj/21, I///, 7/hiro, !=weight average molecular weight rioooo) in a 3-part hex% bath solution (the solvent is methyl ethyl ketone) //=methoxy 2-propertool=λ//(weight ratio)) Polypropylene glycol di z, 5 parts acrylate (+average molecular weight ?22) Tetraethylene glycol di/, 5 parts methacrylate p-toluenesulfonamide)" 0. j part λ−
(0-chlorophenyl) 2.0 parts-Hiroshi! - 2 parts by weight % bath solution of diphenylimidazole dimer (B-C IM manufactured by Odougaya Kagaku ■, solvent is toluene/methanol = 2/l (weight ratio) solvent) Hiroshi, Pibis (diethylamino) 0.0 Hirobe Benzophenone Benzophenone i, o parts Tribromomethylphenylsul o, osm Hong leuco crystal violet 0.02 parts malachite green oxalate /, tij part (7% methanol solution) The compound of the present invention is added to the above mother liquor Heterocyclic compounds (Table/of/~6) corresponding to (I) or (I[) are shown in Table 2, respectively.
The amounts shown in Examples/~≠ were added.

After further stirring and dissolving, 2 parts of each coating solution was applied to a μm polyethylene terephthalate plate support.
The material was dried for 2 minutes at 0°C to obtain a photosensitive material having a coating film about 1.10 μm thick. This sensitive material was laminated on a cleaned copper-clad Ml board (substrate) at 200C, line width/space width=/3, line width=30. The jKw ultra-high pressure mercury lamp (
The entire surface was exposed for IO seconds using HMW (N) manufactured by Oak ■.

After 75 minutes of exposure, add 7% carbonic acid) IJum water bath solution (300
C) Spray development for ≠θ seconds (spray pressure 2Y/cIr
L2) Shita.

The resulting resist pattern was observed with an optical microscope, and the width of the thinnest line in close contact with the substrate was recorded.

Evaluation of red discoloration was performed as follows. After laminating the coating film on the smoothed substrate using the method described above, 300CZO
The film was placed in a constant temperature and humidity chamber at % R, H, and developed under the above conditions after 5 days. The redness of the exposed steel surface was visually compared. Note that redness tends to increase over time.

For plating, a chisel turn was used which was printed and developed on an original with a line width of 100 μm. Degrease this (PC-≠ Yoj Melch 22S Co., Ltd.; 2
After treatment with ammonium persulfate water bath solution (72%, 306C14L 0 seconds), io%
All parts were washed with sulfuric acid and plated with copper sulfate. After stripping the resist using a 5% caustic soda water bath solution (SO°C), a Mylar tape was applied to the resulting copper plating pattern and rapidly peeled off to perform a peel test.

Table 2 shows the evaluation results for the structures of the heterocyclic compounds used in Table 2.

Comparative Examples 1 to 2 Comparative Examples 1 to 2 were carried out in the same manner as in Examples, except that the type and/or amount of the heterocyclic compound added to the mother liquor shown in Examples was changed as shown in Comparative Examples 1 to 1 in Table 2. A photosensitive material was prepared and evaluated in the same way. The results are shown in Table 2.

As shown in Table 1, the use of the compound of the present invention (I) alone is highly effective in improving adhesion, but is insufficient in preventing reddening. (Comparative Examples λ~) The compound of the present invention (I[) and its analogs M7 and R have the effect of suppressing redness when used alone, but the adhesion and peeling of the plating are poor. (Comparative Examples 6 to 10).

The combination of present inventions (I) and (II) allows for close contact,
Prevention of red discoloration and peeling of plating could all be satisfied (Example 1-≠), which could not be achieved with other combinations (Comparative Examples //, /2).

(Effects of the Invention) By using a photopolymerizable composition containing the combination of compounds (I) and (II) of the present invention, a photoresist with excellent adhesion and no red discoloration or peeling of plating can be obtained. Ta.

Claims (1)

Claims: A photopolymerizable composition containing at least (1) to (4). (1) A non-gaseous ethylenically unsaturated compound having at least two ethylenically unsaturated groups and capable of forming a polymer. (2) A thermoplastic organic polymer binder. (3) A non-gaseous ethylenically unsaturated compound that can be activated by actinic light. Photopolymerization initiator system (4) Heterocyclic compounds represented by general formulas (I) and (II) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ R_1 is a hydrogen atom, an alkyl group, a substituted alkyl group group, aryl group, substituted aryl group, aralkyl group, amino group, or substituted amino group, R_2 and R_3 represent a hydrogen atom, alkyl group, substituted alkyl group, aryl group, or aralkyl group, R_4 and R_5 represent , represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or an aralkyl group, and together with the N atom, may form a pyrrolidine, piperidine, morpholine, or N-substituted piperazine nucleus. X is an oxygen atom, a sulfur atom ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [R_6 represents a hydrogen atom, an alkyl group, or an aryl group. ], and Y represents an oxygen atom or a sulfur atom. General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ R_7 to R_1_1: Hydrogen atom, alkyl group, aryl group