JPH09160237A - Photo soldering resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist compsn. attaining high-speed curing, excellent in surface curability, less liable to reduction in volume in photosetting and excellent in adhesion to a substrate by incorporating a specified compd. and a photopolymn. initiator. SOLUTION: This resist compsn. consists of a compd. having at least two propenyl ether terminal groups and a photopolymn. initiator. The compd. is, e.g. a (poly)ether oligomer represented by the formula, wherein (n) is an integer of 2-200, each of 2-200 (m)'s is an integer of 0-200, at least one of (m)'s is >=1, at least two of 2-200R<1> 's are alkylene, arylene, aralkylene or cycloalkylene, in the case of m>=2, A's may be different from each other, (AO)m portion may bond by any of random addition and block addition and X<1> is a residue of polyhydric alcohol or a residue of polyhydric phenolic hydroxyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosolder resist composition containing a photocurable propenyl ether end group compound used in manufacturing a printed wiring board.

[0002]

2. Description of the Related Art Solder resists are indispensable materials in printed wiring board manufacturing, as a protector for preventing unnecessary adhesion of solder in a soldering process and as a permanent mask. Conventionally, a thermosetting type resist is often used as a solder resist, and a method of printing this with a screen printing method has been generally used. However, with the recent increase in density of printed wiring boards, the resolution of the screen printing method has been increased. There is a limit to this, and a photo solder resist that forms a pattern by a photographic method has been widely used. However, the photosensitive resin used in the conventional photo solder resist is an acrylic photo-radical UV curable resin,
In the case of the resin, there is a problem that the surface curability is lowered due to oxygen inhibition, the volume shrinkage during photocuring is large, and the adhesiveness to the substrate is lowered, so that the developability and the sensitivity are lowered. An epoxy photocationic UV curable resin is a composition that overcomes these problems, but it requires a large amount of UV energy during curing due to its low photoreactivity. Therefore, there are drawbacks that a high UV energy irradiation device is required and that irradiation time is long. As a method for improving such low reactivity of the cationic UV curable resin, a method using an alicyclic epoxy compound as a base resin or a diluent is known (JP-A-1-209442). Gazette). However, this is slower than the reaction rate of the radical UV curable resin, the types of alicyclic epoxies that are industrially available are limited, and it was difficult to obtain a product that satisfies practical performance. .

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and cures at a high speed by irradiating active energy rays such as UV and has excellent surface curability, and photocuring. It is an object of the present invention to provide a photo solder resist composition having high developability and high sensitivity due to its small volume shrinkage and excellent adhesion to a substrate.

[0004]

The present inventor has arrived at the present invention as a result of extensive studies in order to solve the above problems. That is, the present invention relates to a compound (A) having at least two propenyl ether end groups, and a photopolymerization initiator (B).
Is a photo solder resist composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION (A) of the present invention includes the following. That is, at least one selected from the group consisting of a (poly) ether oligomer having a propenyl ether end group, a polyester oligomer having a propenyl ether end group, a urethane oligomer having a propenyl ether end group, and a monomer having a propenyl ether end group. And is preferably a urethane oligomer having a propenyl ether end group.

The (poly) ether oligomer having a propenyl ether terminal group in (A) of the present invention is a compound represented by the following general formula (1). ^{X 1 [-O- (AO) m} -R 1] n (1) { wherein, n is an integer of 2 to 200, the n-number of m 0 to
It is an integer of 200 and at least one of m is 1 or more. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. A is an alkylene, arylene, aralkylene or cycloalkylene group having 2 to 12 carbon atoms, and when m is 2 or more, A may be the same or different, and the (AO) m portion may be random addition or block addition. good. X ¹ is a polyhydric alcohol residue or a polyhydric phenolic hydroxyl group residue. ｝

In the general formula (1), A is alkylene,
It is a divalent group selected from the group consisting of arylene, aralkylene and cycloalkylene groups, and examples of alkylene groups that can be used include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene,
Examples include octylene, nonylene, decylene, undecylene and dodecylene. Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Examples of alkylene are benzylene, 1
-Phenylene, 2-phenylene, 3-phenylpropylene, 2-phenylpropylene, 1-phenylpropylene and the like. Examples of cycloalkylene groups include:
Examples include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, ethylene group and propylene group are preferable. When the alkylene group becomes long, the solubility of the initiator deteriorates.

X ¹ is a polyhydric alcohol residue or a polyhydric phenolic hydroxyl group residue, and examples of the polyhydric alcohol include the following. For example, ethylene glycol, triethylene glycol, glycerin, polyglycerin (glycerin 2-18, for example, diglycerin, triglycerin, tetraglycerin, etc.), ring-opening polymer of glycidol (compound having a degree of polymerization of 2-5000) ), Trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their dimers and trimers, monopentaerythritol, dipentaerythritol, 1,3,5-pentaerythritol, sorbitol, sorbitan sorbitan. Examples of the polyhydric phenolic hydroxyl group-containing compound include glycerin condensates, and phenol novolac resins, cresol novolac resins, and carboxylic acid-containing phenols obtained by partially reacting these resins with maleic anhydride. Novolak resin or carboxylic acid-containing cresol novolac resins, and the like. Of these, carboxylic acid-containing phenol novolac resins and carboxylic acid-containing cresol novolac resins are preferable.

N is usually an integer from 0 to 200 and m
At least one is 1 or more, preferably 1 to 8
0, particularly preferably an integer of 1 to 5. When m exceeds 200, the viscosity is usually high and it becomes difficult to dissolve the initiator.

N is 2 to 200, preferably 3 to 100,
Particularly preferably, it is an integer of 3 to 5. When n exceeds 200, the viscosity is usually high and it becomes difficult to dissolve the initiator. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups.

The polyester oligomer having a propenyl ether terminal group in the present invention is represented by the following general formula (2):
Examples thereof include compounds represented by (3) or (4).

[0012] {In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are HOX ² OH and HOX ³ OH, respectively.
Represented by alkylene diol, arylene diol,
It is a residue of any one of polyether diol, polyurethane diol or polycarbonate diol, Y ¹ is a polyvalent carboxylic acid residue, and Y ² is a divalent carboxylic acid residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

X ² in the general formula (2) is HOX ² OH.
Represented by alkylene diol, arylene diol,
It is the residue of a diol, either a polyether diol, a polyurethane diol or a polycarbonate diol.

Examples of the alkylene diol represented by HOX ² OH include ethylene glycol, propylene glycol, 1,3-butane diol, 1,4-butane diol, 1,6-hexane diol and 1,9-nonane diol. , Neopentyl glycol, 1.4-cyclohexanediol and the like. Of these, preferably,
They are ethylene glycol and propylene glycol.

Examples of the arylene diol represented by HOX ² OH include catechol, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane and bisphenol A. Of these, bisphenol A is preferred.

Examples of the polyether diol represented by HOX ² OH include poly (oxyethylene) diol,
Examples thereof include poly (oxypropylene) diol, poly (oxytetramethylene) diol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A. Of these, poly (oxyethylene) diol and poly (oxypropylene) diol are preferable.

The degree of polymerization of the above polyether diol is usually 1 to 200, preferably 2 to 100, particularly preferably 3
-20.

Examples of polyurethane diol represented by HOX ² OH include reaction products of the following (i) and (ii). (I) Compound represented by H (OX ⁵ ) m-OH (m is an integer of 0 to 200, X ⁵ is selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups having 2 to 12 carbon atoms. (Ii) OCN-Z ³ -NCO (in the formula, Z ³ is 2 selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene).
Is the basis of valence)

In the above polyether diol (i), m is usually 0 to 200, preferably 3 to 20.

In the polyether diol (i), X ⁵ is a divalent group selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups having 2 to 12 carbon atoms, and usable alkylene groups. Examples of methylene, ethylene, propylene, butylene,
Pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene and the like can be mentioned. Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like.
Examples of alkylene are benzylene, 1-phenylene, 2-phenylene, 3-phenylpropylene, 2-
Examples thereof include phenyl propylene and 1-phenyl propylene. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, ethylene and propylene groups are preferable. When the alkylene group becomes long, the solubility of the initiator deteriorates.

Examples of the diisocyanate of (ii) above include toluene diisocyanate (TDI), p- and m-phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4. -Trimethylhexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (Desmodur W), 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'- Diphenylmethane diisocyanate,
1,5-tetrahydronaphthalene diisocyanate, naphthalene-1,5′-diisocyanate, bis (2-methyl-3-isocyanatephenyl) methane, 4,4 ′
-Diphenylpropane diisocyanate, tetramethyl xylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI) and the like. Of these, toluene diisocyanate (TD) is preferred.
I), 4,4′-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPD
I), tetramethyl xylene diisocyanate (TMX
DI), 4,4'-dicyclohexylmethane diisocyanate (Desmodur W), 1,6-hexamethylene diisocyanate.

Examples of the polycarbonate diol represented by HOX ² OH include compounds represented by the following general formula. (M is an integer of 1 to 200, X ⁶ has 2 to 12 carbon atoms
Is a divalent group selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups).

In the above general formula, m is usually an integer of 1 to 200, preferably 3 to 20.

In the above polycarbonate diol, X ⁶ is a divalent group selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups having 2 to 12 carbon atoms. Examples of alkylene groups that can be used include , Methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene and the like. Examples of arylene groups are phenylene, naphthylene,
Examples include anthrylene and phenanthrylene. Examples of alkylene are benzylene, 1-phenylene,
2-Phenylene, 3-phenylpropylene, 2-phenylpropylene, 1-phenylpropylene and the like can be mentioned. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, ethylene and propylene groups are preferable. When the alkylene group becomes long, the solubility of the initiator deteriorates.

[0025] X in the general formula (2) ^3, the same as those shown in the above X ² may be mentioned, X ² and X ³ may be the same or different.

In the general formula (2), Y ¹ is a polyvalent carboxylic acid residue and Y ² is a divalent carboxylic acid residue. Examples of the divalent carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid. Examples thereof include meritic acid and other polycarboxylic acids. Of these, Y ¹ and Y ² are preferably isophthalic acid, terephthalic acid, and adipic acid.

In the general formula (2), m is usually 1 to 20.
It is an integer of 0, preferably 1-80, particularly preferably 1-20. When m exceeds 200, the viscosity becomes high and it becomes difficult to dissolve the initiator.

In the general formula (2), n is usually 2 to 20.
It is an integer of 0, preferably 3 to 100, particularly preferably 3 to 20. When n is larger than 200, the viscosity becomes high and it becomes difficult to dissolve the initiator. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups.

The general formula (3) is {In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, X ² is an alkylene or arylene group,
X ¹ is a polyhydric alcohol residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. It is represented by｝.

X ¹ in the general formula (3) is represented by the general formula (1)
And the same as those represented by the general formula (2) for X ² , m and n.

The general formula (4) is {In the formula, m is 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are alkylene diols, arylene diols, polyether diols, and polyurethanes represented by HOX ² OH and HOX ³ OH, respectively. X ¹ is a polyhydric alcohol residue, which is the residue of either a diol or a polycarbonate diol. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. It is represented by｝.

X ¹ in the general formula (4) is represented by the general formula (1)
The same ones as those shown in X. ² , X ³ , M
Examples of n and n are the same as those shown in the general formula (2), and X ² and X ³ may be the same or different.

The urethane oligomer having a propenyl ether terminal group in (A) of the present invention is represented by the following general formula (5). {In the formula, m is 0 to 200, n is an integer of 2 to 200, and Q ¹ is -OX ² O- or -N (R ² ) -X ⁴ -N (R
² )-, and Q ² is a group represented by -OX ² O-. X ² is an alkyl diol represented by HOX ² OH, an aryl diol, a polyether diol,
It is the residue of a diol, either a polyester diol or a polycarbonate diol. -N (R ²⁾ -X ⁴
—N (R ² ) — is a diamine residue represented by HN (R ² ) —X ⁴ —N (R ² ) H, and X ⁴ is alkylene, arylene, aralkylene or cycloalkylene having 2 to 12 carbon atoms. And R ² is an alkyl, aryl, aralkyl or cycloalkyl group having 2 to 12 carbon atoms. Z ¹
Is a polyvalent isocyanate residue, and Z ² is a divalent isocyanate residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

In the general formula (5), as the divalent isocyanate for Z ² , the same ones as mentioned in the above formula (ii) can be mentioned. The polyvalent isocyanate in Z ¹ is lysine ester triisocyanate,
Examples include hexamethylene triisocyanate and polyphenyl polyisocyanate.

In the general formula (5), Q ¹ is -OX ² O-.
Or ^{-N (R 2) -X 4 -N} (R 2) - in a group represented, Q ² is a group represented by -OX ² O-. X ² is H
OX ² OH is a diol residue represented by alkylene diol, arylene diol, polyether diol, polyester diol or polycarbonate diol, and X ² is the same as X ² in general (2). can give.

When the HOX ² OH is a polyester diol, the reaction products of the following (iii) and (iv) can be mentioned. (Iii) H (OX ⁷ ) m-OH (m is an integer of 0 to 200, X ⁷ is a divalent group selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups having 2 to 12 carbon atoms. in a) (iv) in HOOC-Y ³ -COOH (wherein, Y ³ is 2 selected alkylene, arylene, from the group consisting of groups aralkylene and cycloalkylene
Is the basis of valence)

In the above-mentioned (iii) polyether diol, m is usually 0 to 200, preferably 3 to 20.

In the polyether diol of (iii) above, X ⁷ is a divalent group selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene groups having 2 to 12 carbon atoms. Examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene and the like. Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Examples of alkylene are benzylene, 1-phenylene, 2-phenylene, 3-phenylpropylene,
2-phenyl propylene, 1-phenyl propylene, etc. are mentioned. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, ethylene group and propylene group are preferable. When the alkylene group becomes long, the solubility of the initiator deteriorates.

Examples of the dicarboxylic acid (iv) include phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and polycarboxylic acid. Of these, preferred are isophthalic acid, terephthalic acid, and adipic acid. X ⁴ is the same as X ² in the general formula (2), R ² is the same as that represented by A in the general formula (1), and m and n are the general formulas. The same thing as shown in (2) can be mentioned.

The monomer having a propenyl ether terminal group in (A) of the present invention is represented by the following general formula (6) or general formula (7). ^{X 1 [-O-R 1]} n (6) ( wherein, n is an integer of 2 to 200, X ¹ is a polyhydric alcohol residue .n number of at least two is propenyl group for R ¹ And the rest may be hydrogen atoms, alkyl, acyl or aryl groups.)

In the general formula (6), n is usually 2 to 20.
It is an integer of 0, preferably 2 to 6. When n exceeds 200, the viscosity is high and the handling becomes poor. Examples of X ¹ are the same as those shown in the general formula (1).

[0042] {In the formula, n is 2-200, X ² is a diol residue represented by HOX ² OH, which is any one of alkylene diol, arylene diol, polyether diol, polyurethane diol or polycarbonate diol, and Y
¹ is a polyvalent carboxylic acid residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. } In general formula (7), n is an integer of usually 2 to 200, preferably 2 to 6. When n exceeds 200, the viscosity is high and the handling becomes poor. Examples of Y ¹ and X ² are the same as those given in the general formula (2).

As the photopolymerization initiator (B) used in the present invention, known photocationic polymerization initiators can be used. For example, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, P- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, P- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4-diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4
-Diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe-hexafluorophosphate, and the like. These are readily available from the market. For example, Asahi Denka Co., Ltd., SP-150, SP-
170, manufactured by Ciba Geigy, Irgacure 261,
Union Carbide, UVR-6974, UVR-
6990 etc. can be mentioned.

In the present invention, a reactive diluent (C) can be optionally used for the purpose of adjusting the viscosity of the composition.

Examples of the compound (C) include compounds represented by the following general formula (8). CH ₃ —CH═CH—O—X ² —O—R ³ (8) (In the formula, X ² represents an alkylene diol, arylene diol, polyether diol, polyurethane diol, or polycarbonate diol represented by HOX ² OH. It is a residue of any diol, and R ³ has 2 to 2 carbon atoms.
12 alkyl, aryl, aralkyl, cycloalkyl group or hydrogen atom. ｝

In the above general formula, X ² is the same as that shown in the general formula (2), and R ³ is an alkyl, aryl, aralkyl, cycloalkyl group or hydrogen atom having 2 to 12 carbon atoms. Is.

In the present invention, the use ratio of (A) and (B) is usually such that the weight ratio of (A) :( B) is (95 to 99.
9): (0.01 to 5), preferably (97 to 9)
9): (1 to 3).

In the present invention, (C) is usually contained in an amount of 5 to 40% by weight, preferably 10 based on the total weight of (A) and (B).
-30% by weight, and when (C) exceeds 40% by weight,
The curing speed is significantly reduced.

In the composition of the present invention, if necessary, a known radical photopolymerizable composition (D) can be used in combination with (A). The content of (D) is usually (A)
0 to 100 parts by weight is used per 100 parts by weight of the component, preferably 10 to 40%.

The composition of the present invention further comprises, if necessary,
An adhesion improver, a thermal polymerization inhibitor, a paint, a pigment, a plasticizer, a flame retardant, a fine particulate filler, a coatability improver, and various other additives can be contained.

[0051]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Examples 1 to 5 and Comparative Examples 1 to 3 Using the formulations prepared according to the formulations shown in Table 1, the photo-curability, developability and copper adhesion were evaluated according to the following evaluation methods and evaluation criteria. It was evaluated. Table 2 shows the obtained results.
Shown in Photocurability evaluation method: A test piece was prepared by applying each formulation to a copper clad laminate at a film thickness of 40 μm and then drying in a hot air circulation drying oven at 70 ° C. for 30 minutes. 1 for each test piece
The irradiation intensity is 1 using the negative of the linear line of 00μm.
A predetermined amount of ultraviolet rays was irradiated with a parallel exposure device of 0 mW / cm ² , and then the state of the coating film was visually evaluated after developing with "Etaner IR" (manufactured by Asahi Kasei Kogyo Co., Ltd.) as a developing solution for 1 minute. Evaluation criteria for photocurability: ◎ No change ○ Surface slightly changed △ Surface remarkably changed × Coating film dropped Developability evaluation method: Each test piece was "Etner IR" (Asahi Kasei Kogyo) Was used as a developing solution to perform development by spraying, and the developability at each time was visually evaluated with a microscope. Criteria for evaluation of developability: ◎ It was possible to develop to a fine area. ○ A part of the substrate surface that remained thin and could not be developed remained. △ Some that could not be developed remained. × Little developed. Copper adhesion evaluation method: JIS D-0202 According to the above-mentioned test method, each test piece was cross-cut in a grid pattern, and the state of peeling after the bee ring test with cellophane tape was visually determined. Evaluation criteria for copper adhesion: ◎ 100/100 with no change observed ○ 100/100 with slight peeling at the line edge △ 50/100 to 90/100 × 0/100 to 50/100

[0053]

[Table 1]

The compounds shown in Table 1 are as follows.
The CH ₃ —CH═CH— group (propenyl group) is Pr.
Abbreviated. Propenyl ether end groups Compound (1): Pr-O- ( CH 2 CH 2 O) 12 -Pr propenyl ether end groups of compound (2): Propenyl ether end groups Compound (3): Pr-O- ( CH 2 CH 2 O) 6 -XO- (CH 2 CH
₂ O) _6- Pr X: bisphenol A residue propenyl ether end group compound (4): Propenyl ether end group compound (5): X: triethylene glycol residue Z: 4,4'-diphenylmethane diisocyanate residue, propenyl ether terminal group compound (6): R [O-Pr] ₃ R: trimethylolpropane residue acrylate terminal group compound (7): Acrylate end group compound (8): R: trimethylolpropane residue Epoxy end group compound (9): EP-828 (bisphenol type epoxy resin manufactured by Yuka Shell Co., alicyclic epoxy end group compound (10): ERL-422
1 (UCC alicyclic epoxy resin) Photopolymerization catalyst (11): UVR-6974 (P- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoro 50% diluted antimonate mixture) Photopolymerization catalyst (12): Irgacure 184 (manufactured by Ciba Geigy) Binder poimer (13): Methacrylic acid / methyl methacrylate / n-butyl acrylate = 23/57 /
20 weight ratio of copolymer (weight average molecular weight of about 80,000
0) 40% methyl cellosolve solution

[0055]

[Table 2]

[0056]

As described above, a photo solder resist composition containing a compound having a propenyl ether terminal group cures faster than a radical polymerization type acrylate resin and has excellent surface curability, and It has the features of small volume shrinkage during curing and excellent adhesion to the substrate. Further, it is faster curable than an epoxy-based ultraviolet curable resin. For these reasons, the use of the photosolder resist composition of the present invention makes it possible to form a resist pattern having high resolution and high sensitivity, which is extremely useful for the production of printed wiring boards.

Claims (10)

[Claims] 1. A compound (A) having at least two propenyl ether terminal groups, and a photopolymerization initiator (B).
A photo solder resist composition comprising: 2. A (poly) ether oligomer (A) having a propenyl ether terminal group, a polyester oligomer having a propenyl ether terminal group, a urethane oligomer having a propenyl ether terminal group, a novolak type epoxy resin having a propenyl ether terminal group, and The composition according to claim 1, which is one or more compounds selected from the group of monomers having a propenyl ether end group. 3. The composition according to claim 2, wherein the (poly) ether oligomer having a propenyl ether terminal group is an oligomer represented by the following general formula (1). ^{X 1 [-O- (AO) m} -R 1] n (1) { wherein, n is an integer of 2 to 200, the n-number of m 0 to
It is an integer of 200 and at least one of m is 1 or more. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. A is an alkylene, arylene, aralkylene or cycloalkylene group having 2 to 12 carbon atoms, and when m is 2 or more, A may be the same or different, and the (AO) m portion may be random addition or block addition. good. X ¹ is a polyhydric alcohol residue or a polyhydric phenolic hydroxyl group residue. ｝ 4. The composition according to claim 2, wherein the polyester oligomer having a propenyl ether terminal group is an oligomer represented by the following general formula (2), general formula (3), or general formula (4). {In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are HOX ² OH and HOX ³ OH, respectively.
Represented by alkylene diol, arylene diol,
It is a residue of any one of polyether diol, polyurethane diol or polycarbonate diol, Y ¹ is a polyvalent carboxylic acid residue, and Y ² is a divalent carboxylic acid residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ {In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, X ² is an alkylene or arylene group,
X ¹ is a polyhydric alcohol residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ {In the formula, m is 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are alkylene diols, arylene diols, polyether diols, and polyurethanes represented by HOX ² OH and HOX ³ OH, respectively. X ¹ is a polyhydric alcohol residue, which is the residue of either a diol or a polycarbonate diol. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 5. The composition according to claim 2, wherein the urethane oligomer having a propenyl ether terminal group is an oligomer represented by the following general formula (5). {In the formula, m is 0 to 200, n is an integer of 2 to 200, and Q ¹ is -OX ² O- or -N (R ² ) -X ⁴ -N (R
² )-, and Q ² is a group represented by -OX ² O-. X ² is a residue of any one of alkyl diol, aryl diol, polyether diol, polyester diol or polycarbonate diol represented by HOX ² OH. -N (R ²⁾ -X ⁴ -
N (R ²⁾ - is ^{HN (R 2) -X 4 -N} (R 2) a diamine residue represented by H, X ⁴ is alkylene having 2 to 12 carbon atoms, arylene, aralkylene or cycloalkylene group And R ² is an alkyl, aryl, aralkyl or cycloalkyl group having 2 to 12 carbon atoms. Z ¹ is a polyvalent isocyanate residue and Z ² is a divalent isocyanate residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 6. The composition according to claim 2, wherein the monomer having a propenyl ether terminal group is represented by the following general formula (6) or general formula (7). ^{X 1 [-O-R 1]} n (6) ( wherein, n is an integer of 2 to 200, X ¹ is a polyhydric alcohol residue .n number of at least two is propenyl group for R ¹ And the rest may be hydrogen atoms, alkyl, acyl or aryl groups.) {In the formula, n is 2-200, X ² is a diol residue represented by HOX ² OH, which is any one of alkylene diol, arylene diol, polyether diol, polyurethane diol or polycarbonate diol, and Y
¹ is a polyvalent carboxylic acid residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 7. A weight ratio of (A) :( B) is (95-9).
9.9): (0.01-5), The composition in any one of Claims 1-6. 8. A reactive diluent (C) is further compounded, and the content of (C) is 5 to 40% of the total weight of (A) and (B). 7. The composition according to any one of 7. 9. The composition according to claim 8, wherein (C) is a reactive diluent represented by the following general formula (8). CH ₃ —CH═CH—O—X ² —O—R ³ (8) (In the formula, X ² represents an alkylene diol, arylene diol, polyether diol, polyurethane diol, or polycarbonate diol represented by HOX ² OH. It is a residue of any diol, and R ³ has 2 to 2 carbon atoms.
12 alkyl, aryl, aralkyl, cycloalkyl group or hydrogen atom. ｝ 10. A cured product of the solder resist composition according to claim 1.