JPH0643638A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To provide an alkali developable photopolymerizable composition suitable for a dry film photoresist or photomask for forming a printed board, a planographic printing plate, a resin letter press or the like and excellent in preservable stability in the state laminated on a metallic plate and to provide the alkali developable photopolymerizable composition suppressed in reddening, development residue and sensitivity degradation generated at the time of preserving in the state laminated on the metallic plate and high in sensitivity and excellent in adhesive strength, plating property and etching property. CONSTITUTION:The alkali developable photopolymerizable composition contains (1) a carboxyl group-containing high polymer binder, (2) a compound having in average at least one ethylenic unsaturated double bond and in average at least one triazol ring, (3) a photopolymerizable monomer except (2) and (4) a photopolynaerization initiator base.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition containing a compound having at least one ethylenically unsaturated double bond and at least one triazole ring in a molecule. More specifically, a dry film photoresist or photomask for making a printed circuit board, a lithographic printing plate,
The present invention relates to an alkali-developable photopolymerizable composition suitable for applications such as a resin relief plate and having excellent storage stability when laminated on a metal plate.

[0002]

2. Description of the Related Art In recent years, dry film resists have been widely used in fields such as printed circuit board production. It has been widely known that a polymer binder having a carboxyl group is conventionally used as a composition of a dry film resist so that the dry film resist can be treated with an alkaline aqueous solution.

However, when a polymer binder having a carboxyl group is used, after the resist is laminated on the copper clad laminate, the surface of the unexposed portion of the copper plate which appears after development is reddish brown (so-called reddish) after development. Or residual development (or scum) is likely to occur. This tendency tends to increase with time. In actual use, a resist is laminated on a copper clad laminate and then left for several days. The occurrence of red discoloration and development residue often causes etching residue and peeling of the plated film, which is a serious problem.

Conventionally, additives and the like to the photopolymerization system have been proposed in order to prevent the occurrence of red discoloration or residual development. For example, JP-B-58-22486 and JP-A-61-
In each specification of 194438, low molecular weight carboxylic acids such as citric acid and malonic acid are proposed. Certainly, by adding these carboxylic acids, it is possible to reduce red discoloration and development residue. However, when the addition amount is small, a sufficient effect cannot be obtained, and when added in a large amount in order to obtain a sufficient effect, the sensitivity is lowered and the alkali resistance of the resist is lowered (as a result, for example, the penetration of plating occurs). It was not yet sufficient as an anti-reddensing agent.

The present inventors previously filed Japanese Patent Application No. 2-242977.
As shown in the specification, it has been found that the addition of the triazole compound is effective. However, although these compounds certainly have a sufficient effect of preventing red discoloration and an etching property, there is a case in which the plating may go under the resist during the subsequent plating treatment.

Means for improving such plating properties include, for example, imidazole derivatives described in JP-A-55-65203 and tetrazole derivatives described in JP-A-59-125726. Kosho 5
No. 0-9177, benzimidazole, benzthiazole, benztriazole, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole described in JP-A-53-702, and JP-A-59-113432, JP-A-59-
16501, JP-A-60-12543, JP-A-60
There is known a method of increasing adhesion to a metal substrate by adding compounds described in JP-A-12544, JP-A-61-272139 and JP-A-3-240063. However, when these compounds are used, the plating property is certainly improved, but the metal surface after development is liable to cause red coloration or residual development. Thus, sufficient compounds have not been found to improve redness without compromising the performance required for dry film resists.

[0007]

DISCLOSURE OF THE INVENTION The present invention suppresses red discoloration, residual development and sensitivity decrease which occur when a photopolymerizable composition developable with an alkaline aqueous solution is stored in a state of being laminated on a metal plate, It is an object of the present invention to provide a photopolymerizable composition having high sensitivity, good adhesion to a metal plate, and excellent etching property and plating property.

[0008]

Means for Solving the Problems As a result of various studies, the present inventors have found a photopolymerizable composition that can achieve the above object. That is, the object of the present invention is to provide a compound having (1) a carboxyl group-containing polymer binder, (2) an average of at least one ethylenically unsaturated double bond and an average of at least one triazole ring in the molecule. ,
(3) A photopolymerizable composition developable with an alkaline aqueous solution, which comprises a photopolymerizable monomer other than (2) above and (4) a photopolymerization initiator system.

Although the reasons for these effects are not clear, they are considered as follows. That is, a compound having an average of at least one ethylenically unsaturated double bond and an average of at least one triazole ring in the molecule is reddish due to the action of the triazole ring, and suppresses the development residue.
On the other hand, it is considered that the exposed area has alkali resistance and sufficient resistance to the plating solution due to polymerization of ethylenically unsaturated double bond.

The constituent components of the photopolymerizable composition of the present invention will be described in order. As the carboxyl group-containing polymer binder used in the photopolymerizable composition of the present invention, those satisfying the following conditions are used from a wide variety of synthetic, semi-synthetic and natural polymer substances. That is, a photopolymerizable monomer,
It has good compatibility with the photopolymerization initiator system, does not cause demixing during the manufacturing process from preparation of the coating solution to coating, drying, and storage of the resulting mixture, according to the usage of the present invention. Properties, for example, soluble in an alkaline aqueous solution, or at least swellable, when used for a photoresist for tenting, the strength, stretchability, abrasion resistance, chemical resistance, etc. of the binder are appropriate, The molecular weight, intermolecular force, hardness, softening temperature, crystallinity and fracture elongation of the binder are appropriate.

Specific examples of the binder include (meth) acrylic acid and (meth) acrylic acid ester (as the ester, methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, benzyl ester,
2-hydroxyethyl ester, etc.), poly (meth) acrylic acid, a copolymer of styrene and an unsaturated dibasic acid anhydride such as maleic anhydride, and a reaction product of the polymer with alcohols. , A reaction product of polybasic acid anhydride of cellulose, and the like. Among the above polymers, those which are particularly preferably used as the binder of the present invention are styrene / maleic anhydride copolymers, JP-A-60-2585.
39, methyl methacrylate / methacrylic acid / 2-ethylhexyl methacrylate / benzyl methacrylate quaternary copolymer, styrene / maleic acid mono-n-butyl ester copolymerization described in JP-B-55-38961. Combined, styrene / methyl methacrylate / ethyl acrylate / methacrylic acid quaternary copolymers described in JP-B-54-25957, benzyl methacrylate / methacrylic acid copolymers described in JP-A-52-99810. Coalescing,
Acrylonitrile / 2-ethylhexyl methacrylate / methacrylic acid terpolymer described in JP-B-58-12577 and methyl methacrylate / ethyl acrylate / acrylic acid described in JP-B-55-6210. Two kinds of styrene / maleic anhydride copolymer partially esterified with the original copolymer and isopropanol.

These binders may be used alone as binders, but they have good compatibility and are demixed during the manufacturing process from preparation of the coating solution to coating, drying and storage of the resulting mixture. Two or more polymers that do not cause the above may be mixed at an appropriate ratio and used as a binder. The molecular weight of the polymer substance used as the binder can take a wide range of values depending on the type of polymer, but generally, it is 5,000 to
2,000,000, preferably 10,000-20
50,000, more preferably 40,000 to 85.0
Those in the range of 00 are preferably used in the present invention. If the molecular weight is less than 5,000, the mechanical strength of the resist obtained by photopolymerization becomes insufficient, and if it exceeds 2,000,000, the developability is deteriorated, which is not suitable for the purpose of the present invention. The amount of the binder is preferably 40 to 90 wt%, more preferably 50 to 70, based on the solid content of the photopolymerizable composition.
wt%. If it is less than 40 wt%, the fluidity of the photopolymerizable composition is too high, and the creep phenomenon is likely to occur. If it exceeds 90 wt%, the difference in solubility between the exposed portion and the unexposed portion becomes too small, resulting in good image quality. I can't get it,
Neither is suitable for the purpose of the invention.

Examples of compounds having an average of at least one ethylenically unsaturated double bond and an average of at least one triazole ring in the molecule which are preferably used in the present invention include the following compounds.

[0014]

[Chemical 1]

[0015]

[Chemical 2]

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[In the formula, R ₁ and R ₂ : H, carbon number 1 to 10
Alkyl group, C6-10 aryl group, C7
~ 20 aralkyl groups, OR ', SR', or N
_{R '2 R 3, R 4} : H or methyl _{R 5, R 6, R 7} : H, alkyl group having 1 to 10 carbon atoms,
Aryl group having 6 to 10 carbon atoms or 7 to 20 carbon atoms
Aralkyl group R _8: or a alkylene (branched having 2 to 20 carbon atoms,
A ring may be formed), arylene (which may have a substituent), or aralkylene (which may have a substituent) R ′: H, an alkyl group having 1 to 10 carbon atoms, and 6 carbon atoms ~ 1
0 aryl group or aralkyl group having 7 to 20 carbon atoms 1: 1 to 3, m: 1 to 2, n: 1 to 20, i: 0 to 3,
j: 0 to 3 and i + j: 1 to 5 are shown]

Examples of the method for synthesizing such a compound include a reaction of a triazole derivative having an OH group or an amino group with (meth) acrylic acid or (meth) acrylic acid chloride. In addition, a triazole derivative containing an alcohol is synthesized by a reaction of the triazole derivative with an aldehyde or a precursor thereof, a reaction with a halogen-containing alcohol, and the like, and further, the (meth) acrylic acid or (meth) acrylic acid chloride It is also synthesized by reaction. It can also be obtained by methylating a triazole derivative with a triazole derivative and an aldehyde or a precursor thereof, and then reacting it with a primary amine or secondary amine having at least one ethylenically unsaturated double bond. Such compounds and synthetic methods are described in JP-A-59-93058. However, there is no description about the effect on a specific compound as in the present invention, and there is no description about applications such as dry film photoresists or photomasks for producing printed boards, lithographic printing plates and resin relief printing plates.

Further, a Michael addition reaction product of a triazole derivative and (meth) acrylic acid was synthesized, and further, a compound containing at least one epoxy group and at least one ethylenically unsaturated double bond or at least one OH group was synthesized. And a method of reacting with a compound containing at least one ethylenically unsaturated double bond, a triazole derivative and a (meth) acrylic acid ester containing at least one OH group, or a (meth) acrylamide containing at least one OH group A Michael addition reaction product with is synthesized, and this is further mixed with (meth) acrylic acid or (meth)
It is also synthesized by a method of reacting with acrylic acid chloride or the like. Also, m (meth) acryloyl groups, and /
Alternatively, a product obtained by reacting 1 mol of the compound containing a (meth) acrylamide group with the triazole derivative represented by the general formula (I) or the general formula (II) in an amount of n mol can also be used. (M is 2 or more, n is 1 or more.
≧ 1)

[0022]

[Chemical 6]

This reaction is carried out with NH in the case of the general formula (I),
The case of the general formula (II) is a Michael addition reaction of SH with a (meth) acryloyl group and / or a (meth) acrylamide group. When such a reaction is used, it is very easy to average n to (n) (meth) acryloyl groups and / or (meth) acrylamide groups in the molecule.
A compound having individual triazole rings is obtained. On this occasion,
It is possible to easily change the number of (meth) acryloyl groups and / or (meth) acrylamide groups and the number of triazole rings in the molecule simply by changing the combination of m and n. Among these, particularly preferable specific examples include, for example, the following compounds, but the present invention is not limited thereto.

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

The amount of the compound having an average of at least one ethylenically unsaturated double bond and an average of at least one triazole ring in the molecule is 0.001 to 10 wt% of the solid content of the photopolymerizable composition. , Preferably 0.00
It is in the range of 2 to 5 wt%. If it is less than 0.001 wt%, the effect of preventing red discoloration is weakened, and if it exceeds 10 wt%, the resist property deteriorates and it cannot withstand etching or plating, so it is not suitable for the purpose of the present invention. These compounds may be used alone or in combination of two or more kinds.

The photopolymerizable monomer other than the compound having an average of at least one ethylenically unsaturated double bond and an average of at least one triazole ring in the molecule which can be used in the present invention is, for example, Kaisho 6
Known (meth) acrylic acid esters such as those described in the specifications of 0-258539 and Japanese Patent Application No. 1-91247 can be mentioned. Specifically, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, nona Propylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri (meth) acrylate of ethylene oxide adduct of trimethylolpropane, pentaerythritol di (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin Di (meth) acrylate, (meth) acrylic acid esters of 1,3-propanediol di (meth) polyols such acrylate.

Examples of the (meth) acrylamides include methylenebis (meth) acrylamide, ethylenediamine, diaminopropane, diaminobutane, pentamethylenediamine, bis (2-aminopropyl) amine, diethylenetriaminediamine, phenylenediamine and diaminobenzoic acid. There are poly (meth) acrylamides derived from Examples of the allyl compound include diallyl esters such as phthalic acid and malonic acid, diallyl esters such as benzenedisulfonic acid and 2,5-dihydroxydisulfonic acid. Examples of vinyl ether compounds include ethylene glycol divinyl ether,
1,3,5-tri-β-vinyloxyethoxybenzene and the like. Examples of vinyl esters include divinyl succinate and divinyl adipate. Examples of the styrene compound include divinylbenzene, p-allylstyrene and vinylbenzoic acid. Further, a reaction product of a polyisocyanate compound having at least two isocyanate groups and at least one hydroxyl group and a compound having at least one ethylenically unsaturated group, or a polyol compound having at least two hydroxyl groups, and a slight excess of at least The reaction product obtained by reacting with a polyisocyanate compound having two isocyanate groups,
Obtained by further reacting at least one hydroxyl group and a compound having at least one ethylenically unsaturated group,
A polyfunctional urethane compound having at least two ethylenically unsaturated groups can also be suitably used in the present invention.

The amount of the photopolymerizable monomer other than the compound having an average of at least one ethylenically unsaturated double bond and an average of at least one triazole ring in the molecule is 10% of the solid content of the photopolymerizable composition. It is used in the range of -60 wt%, preferably 25-50 wt%. 10 wt
If it is less than 60%, the difference in solubility between the exposed area and the unexposed area is too small, so that good image quality cannot be obtained, and if it exceeds 60% by weight, the fluidity of the photopolymerizable composition is too high and a creep phenomenon occurs. It is not suitable for the purpose of the present invention because it is easy.

Suitable photoinitiators that can be used in the present invention are about 300 to 800 nm, more preferably 330.
It is preferable to contain at least one component having a molecular extinction coefficient of at least about 50 in the range of ˜500 nm. For example, aromatic ketones, lophine dimers, benzoin and benzoin ethers, polyhalogens, and combinations of two or more thereof. Specific examples of these include the following compounds.

Examples of aromatic ketones include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone and 4-dimethylaminobenzophenone. , 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert
-Butyl anthraquinone, 2-methyl anthraquinone,
Xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone,
There is Akridon.

Suitable examples of the lophine dimer include those described in JP-B-45-37377, JP-B-48-38403, JP-A-56-35134, and JP-A-63-200605. And the like are listed. For example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-
(O-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2-
(O-Methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5
-Diphenylimidazole dimer and the like.

Examples of benzoin and benzoin ethers include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin phenyl ether. Examples of the polyhalogen compound include carbon tetrabromide, phenyltribromomethylphenyl sulfone, phenyltrichloromethyl ketone, and JP-A-53-133428 and JP-B-57.
-1819, Japanese Patent Publication No. 57-6096, and U.S. Pat. No. 3
There are compounds described in each specification. Particularly preferred examples are 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 2,4-diethylthioxanthone, 4,4′-bis (diethylamino) benzophenone and benzophenone. And a combination of 4,4′-bis (diethylamino) benzophenone and phenyltribromomethylphenyl sulfone.

The content of the photopolymerization initiator system is preferably 0.1 to 20 wt% with respect to the solid content of the photopolymerizable composition,
More preferably, it is 0.2 to 10 wt%. 0.1 wt
If it is less than%, the sensitivity is insufficient, and if it exceeds 20% by weight, the physical properties of the film of the photopolymerizable composition are adversely affected, so that it is not suitable for the purpose of the present invention.

As described above, the photopolymerizable composition of the present invention comprises (1) a carboxyl group-containing polymer binder, (2) at least one ethylenically unsaturated double bond and at least one triazole ring in the molecule. A compound having
(3) Photopolymerizable monomer other than the above (2), and (4)
The main component is a photopolymerization initiator (system), but if necessary, a thermal polymerization inhibitor, a plasticizer, a dye, a discoloring agent, an adhesion promoter, etc. may be used in combination. A wide range of resists, resin letterpress plates, planographic printing plates, photomasks, etc. can be prepared.

The thermal polymerization inhibitor is added to prevent thermal polymerization or temporal polymerization of the photopolymerizable composition.
This makes it possible to enhance chemical stability during preparation of the photopolymerizable composition and storage before use by laminating it on a metal plate. Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, benzoquinone, o-toluquinone, p-toluquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2.
-Hydroxybenzophenone, cuprous chloride, phenothiazine, floranyl, chloranil, naphthylamine, pyridine, p-toluidine, β-naphthol, 2,6-di-
Examples thereof include t-butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, an aluminum salt or ammonium salt of N-nitrosophenylhydroxylamione, methylene blue organic copper, methyl salicylate, and aryl phosphite. The preferred addition amount of the thermal polymerization inhibitor is 0. 0 with respect to the solid content of the photopolymerizable composition.
001 to 10 wt%, more preferably 0.01 to 3 w
t%. If it is less than 0.001 wt%, the thermal stability is poor, and if it exceeds 10 wt%, the sensitivity is lowered.

The plasticizer is added to adjust the film quality before and after photocuring of the photopolymerizable composition, other physical properties, photosensitivity and the like. Examples of the plasticizer include phthalates such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate, glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate, p-toluene sulfone. Amides, benzenesulfonamide, Nn-butylbenzenesulfonamide and other acid amides, diisobutyl adipate, dioctyl azelate, dibutyl maleate and other aliphatic dibasic acid esters, tributyl citrate, glycerin triacetate, lauric acid Butyl 4,5-diepoxycyclohexane-1,2-dicarboxylic acid dioctyl and the like can be mentioned. The preferable addition amount of the plasticizer is 0.001 to 50 wt% of the solid content of the photopolymerizable composition, and more preferably 0.01 to 20 wt%. If it exceeds 50 wt%, the developability and the image quality are adversely affected.

The pigment is added for coloring the photopolymerizable composition. Examples of dyes include malachite green, methyl green, brilliate green, methyl violet, crystal violet, ethyl violet, Victoria pure blue BOH, oil blue # 603.
(Manufactured by Orient Chemical Industry Co., Ltd.), eosin, erythrosin B, rose bengal, rhodamine B, rhodamine 6G, 2,7-dichlorofluorescein, phenolphthalein, alizarin red S, thymolphthalein,
Quinaldine red, methanyl yellow, thymol sulfophthalein, diphenyltriazene, xylenol blue, methylcongo red, diphenylthiocarbazone,
Paramethyl red, Congo red, benzobulbulin 4B, α-naphthyl red, Nile blue A, phenacetaline, parafuchsin, basic fuchsin and the like can be mentioned. The preferable addition amount of the dye is 0.001 to 10 wt% of the solid content of the photopolymerizable composition, and more preferably 0.1 to 5 wt%. If it exceeds 10 wt%, the sensitivity is adversely affected.

The color-changing agent is added so that a visible image can be obtained when the photopolymerizable composition is irradiated with light through a photomask. Examples of the color-changing agent include diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4,4′-biphenyldiamine, o-chloroaniline, in addition to the above dyes. p, p ', p "-hexamethyltriaminotriphenylmethane, p, p'-tetramethyldiaminotriphenylmethane, p, p', p" -triaminotriphenylcarbinol and the like can be mentioned. The preferred amount of the color changing agent is 0.001 to 10 wt% of the solid content of the photopolymerizable composition, and more preferably 0.01 to 5%.
wt%. If it exceeds 10 wt%, the sensitivity is likely to decrease and fog is likely to occur.

The adhesion promoter is added to enhance the adhesion of the photopolymerizable composition to the surface of a metal plate such as copper, stainless steel, anodized aluminum or silicon. Examples of the adhesion promoter include benzimidazole, benzthiazole, which are described in Japanese Patent Publication No. 50-9177.
Benztriazole, 2-mercaptobenzthiazole and 2-mercaptobenzimidazole described in JP-A-53-702, and JP-A-59-11.
3432, JP-A-59-16501, JP-A-60-
12543, JP-A-60-12544, JP-A-61
The compound described in each specification can be mentioned. However, when these compounds are added, it is important to use them so as not to cause undeveloped residue or red discoloration as described above. The preferred amount of the adhesion promoter added is
The solid content of the photopolymerizable composition is 0.001 to 10 wt%, more preferably 0.01 to 5 wt%. If it exceeds 10% by weight, it may be a cause of residual development.

The photopolymerizable composition of the present invention can form a resist image by laminating on a substrate and exposing it to an image, and then dissolving and removing (developing) the unexposed portion. The photopolymerizable composition of the present invention can be developed with an aqueous alkaline solution. As the developing solution, for example, a 0.1-10 wt% aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, ammonia or the like can be used.
In some cases, amines such as butylamine, hexylamine, benzylamine, allylamine and other primary amines, diethylamine, benzylethylamine and other secondary amines, triethylamine and other tertiary amines, ethanolamine, diethanolamine, triethanolamine,
Hydroxylamines such as 2-amino-1,3-propanediol, cyclic amines such as morpholine, pyridine, piperazine and piperidine, sulfates, carbonates, bicarbonates, alkali metal phosphates and pyrophosphates of the above amines. It is also possible to use a basic salt of, a hydroxy salt of tetramethylammonium hydroxide, choline or the like. less than,
The present invention will be described in more detail based on examples, but the present invention is not limited thereto. In addition, "part"
Means "parts by weight" unless otherwise specified.

[0043]

【Example】

Synthesis Example 1 6.9 parts of 1,2,4-triazole, 11.6 parts of 2-hydroxyethyl acrylate, 0.018 part of 2,5-di-t-hexyl hydroquinone and 2 parts of methyl ethyl ketone 2
It is dissolved in 0 part and heated and stirred at 75 ° C. for 40 hours. The reaction solution was concentrated and further vacuum dried at 120 ° C. for 1.5 hours to obtain a Michael adduct of triazole / 2-hydroxyethyl acrylate. 9.26 parts of this adduct and 5.57 parts of triethylamine are dissolved in 20 parts of THF, and a solution of 4.71 parts of acrylic acid chloride / 10 parts of THF is added dropwise under ice cooling. After standing overnight at room temperature, the insoluble material is filtered off and the solution is concentrated. The resulting oil was purified by silica gel column chromatography to obtain 5.5 parts of the compound of formula (26) (R ₃ is H) (yellow oil).

Synthetic Example 2 3.45 parts of 1,2,4-triazole, 17.6 parts of pentaerythritol tetraacrylate and 0.025 part of hydroquinone monomethyl ether were dissolved in 20 parts of methyl ethyl ketone and heated and stirred at 80 ° C. for 60 hours. . The reaction solution was concentrated to obtain 20.9 parts of the compound of formula (30) (pale orange oily substance).

Synthesis Example 3 Compound 14 of formula (33) was prepared in the same manner as in Synthesis Example 4 except that pentaerythritol tetraacrylate of Synthesis Example 2 was changed to 22.3 parts of an adduct of pentaerythritol triacrylate / phthalic anhydride. 0 part (orange to brown oil) was obtained.

Synthesis Example 4 Compound 1 of formula (35) was prepared in the same manner as in Synthesis Example 4 except that pentaerythritol tetraacrylate of Synthesis Example 2 was changed to 15.1 parts of tetraethylene glycol diacrylate.
5.3 parts (pale yellow oily substance) were obtained.

Synthesis Example 5 1.45 parts of 1,2,4-triazole, 8.81 parts of pentaerythritol tetraacrylate and 0.015 parts of hydroquinone monomethyl ether were dissolved in 15 parts of methyl ethyl ketone, and heated and stirred at 80 ° C. for 60 hours. . The reaction solution was concentrated to obtain 12.4 parts of the compound of the formula (32) (pale orange oily substance).

Synthesis Example 6 3-mercapto-1,2,4-triazole 1.01
Part, pentaerythritol tetraacrylate 3.52
And 0.005 parts of hydroquinone monomethyl ether are dissolved in 10 parts of methyl ethyl ketone, and the mixture is heated and stirred at 80 ° C. for 18 hours. By concentrating the reaction solution, the formula (40) is obtained.
4.5 parts of compound (pale yellow oily substance) was obtained.

Synthesis Example 7 Compound 5.2 of formula (38) was prepared in the same manner as in Synthesis Example 6 except that 1.01 part of 3-mercapto-1,2,4-triazole in Synthesis Example 6 was changed to 2.02 part. Part (pale yellow viscous solid) was obtained.

Synthesis Example 8 10.6 parts of ethylene glycol bis (3-aminopropyl) ether and 7.29 parts of triethylamine are dissolved in 20 parts of acetonitrile. A solution of 11.9 parts of acrylic acid chloride / 10 parts of acetonitrile is added dropwise to this solution over 1 hour under ice cooling. After further stirring at room temperature for 3 hours, the reaction solution is poured into 100 parts of ice water and extracted with chloroform, and the organic layer is dried and concentrated. The resulting oily substance is purified by silica gel column chromatography to obtain 1.8 parts of ethylene glycol bis (3-acrylamidopropyl) ether. 1.42 parts of this compound 1,2,4
0.35 parts of triazole and 0.004 parts of hydroquinone monomethyl ether are dissolved in 5 parts of ethanol, and 0.09 solution of 28% methanol of sodium methoxide is added.
Add 6 parts. This solution is heated and stirred at 75 ° C. for 18 hours. The reaction solution was concentrated to remove the hexane-soluble portion and the chloroform-insoluble portion, and further dried to obtain 1.4 parts of the compound of the formula (41) (pale yellow to orange oily substance).

Examples 1 to 8 and Comparative Examples 1 to 9 The following materials were mixed to prepare a uniform solution. -Methyl methacrylate / methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate copolymer (molar ratio = 55/28/12/5, 35 wt% solution of weight average molecular weight = 79,000, solvent is methyl ethyl ketone / 1 -Methoxy-2-propanol = 2/1) 45 parts-dodecapropylene glycol diacrylate 6.5 parts-tetraethylene glycol dimethacrylate 1.5 parts-p-toluene sulfonamide 0.5 parts-4,4'- Bis (diethylamino) benzophenone 0.05 part-Benzophenone 1.0 part 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer (25 wt% dichloromethane solution) 2.0 parts-Tribromomethylphenyl Sulfone 0.1 part ・ Leuco Crystal Violet 0.1 part ・Malachite Green 0.01 parts

In the solution thus obtained, a compound having an average of at least one ethylenically unsaturated double bond and an average of at least one triazole ring in the molecule of the present invention, and other compounds as comparative examples Was added in an amount shown in Table-1.

[0053]

[Table 1]

After further stirring and dissolving, each solution was applied onto a polyethylene terephthalate temporary support having a thickness of 20 μm, dried at 100 ° C. for 2 minutes, and a photosensitive material having a photosensitive resin coating film having a thickness of about 40 μm. Got This sensitive material was placed on a cleaned copper clad laminate (copper thickness: 35μ) at 105 ° C for 2
They were stacked one by one. One sheet was shielded from light and allowed to stand for 4 days at a temperature and humidity of 23 ° C. and 65% RH. The remaining one sheet, after 15 minutes, was passed through two types of negative originals having the characteristics described below,
kW Super high pressure mercury lamp (HMW-532 manufactured by Oak Co., Ltd.)
D) was used for exposure at various exposure doses.

Chart A: line width / space width (L
/ S) = 1/3, line width = 30 μm to 100 μm (1
0 μ step, 5 lines of each width) ・ Chart B: Fuji Step Guide P (0.15 steps in density)

(1) Performance Evaluation Immediately After Exposure After 15 minutes of exposure, spray development was carried out for 40 seconds with a 1% sodium carbonate aqueous solution (30 ° C.), followed by washing with water at 20 ° C. for 40 seconds. The resist patterns of the A and B originals thus obtained were observed visually and with an optical microscope. The evaluation was performed as follows.

<Sensitivity> The number of clear steps in the pattern of chart B obtained when exposure was performed at 100 mj / cm ² was taken as the sensitivity. In this method, it can be seen that the larger the number of stages, the higher the sensitivity.

<Adhesiveness> The pattern of chart A obtained by exposing with an exposure amount of 8 steps clear exposure amount was observed, and all 5 lines remained the most thin line without being twisted or peeled off. The line width of the line was recorded as the adhesion. In this method, it can be seen that the smaller the line width, the higher the adhesion.

<Etching property> After observing red discoloration and solid particles, the sample was subjected to etching treatment under the following conditions. It is preferable that no copper remains in the non-image area of the obtained sample.・ Liquid composition: Copper chloride dihydrate 400 g / l, 35% hydrochloric acid 1
00g / l ・ Liquid temperature 45 ° C, Spray pressure 2.0kg / cm ²・ Etching time 2.0 minutes ・ Washing time 2.0 minutes

<Plating property> Line width / Space width (L /
S) = 1/1 and line width = 100 μm were used to perform exposure and development in the same manner as described above to obtain a corresponding pattern. This is degreased (PC-455 Meltex; 25;
%, 40 ° C., 3 minutes), followed by washing with water (1 minute), treatment with an ammonium persulfate aqueous solution (12%, 30 ° C., 40 seconds), washing with water (1 minute), 10% sulfuric acid, and copper sulfate plating. .
After removing the resist with a 2% aqueous solution of caustic soda (50 ° C.), the shape of the obtained copper plating pattern is observed with a microscope to determine whether or not the copper plating has penetrated into the lower part of the resist (the area where the resist was Is it not attached?)
Was evaluated comprehensively. It is better that there is no entanglement.
Further, a Mylar tape was attached to the obtained copper plating pattern, which was rapidly peeled off and a peeling test was conducted.

(2) Evaluation of performance after lamination After lamination, light is shielded and the temperature is 4 ° C. at 23 ° C. and 65% RH.
The sample that had been allowed to stand for a day was treated as described above. The following evaluation was performed on this sample. <Sensitivity> Same as above. <Red Discoloration> Using Chart A, the color of the non-image area of the pattern obtained by exposure and development was visually observed. The better that the reddish brown color has not progressed, the better. The above evaluation results are shown in Table-2.

[0062]

[Table 2]

[0063]

As shown in Table 2, the photopolymerizable composition to which the compound of the present invention is added does not show (1) red discoloration even when it is aged after being laminated on a copper clad laminate, (2) It can be seen that there is no decrease in sensitivity. Furthermore, in the evaluation immediately after being laminated on the copper clad laminate, (3) good etching property,
It is clear that the composition is superior to the conventionally known compositions in that (4) the plating property is good, (5) the sensitivity is high, and (6) the adhesion of the resist pattern is good.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H05K 3/00 F 6921-4E

Claims (4)

[Claims] 1. (1) A carboxyl group-containing polymer binder, (2) a compound having on average at least one ethylenically unsaturated double bond and on average at least one triazole ring, (3) ) A photopolymerizable composition developable with an alkaline aqueous solution, which comprises a photopolymerizable monomer other than the above (2) and (4) a photopolymerization initiator system. 2. The photopolymerizable composition according to claim 1, wherein the carboxyl group-containing polymer binder has a weight average molecular weight of 40 to 85,000. 3. The polymer binder according to claim 2, wherein the carboxyl group-containing polymer binder is methacrylic acid, methyl methacrylate,
A photopolymerizable composition, which is a copolymer of benzyl methacrylate and 2-ethylhexyl acrylate. 4. The photopolymerizable composition according to claim 1, 2, or 3, wherein the photopolymerization initiator system contains a lophine dimer.