JP3156559B2 - Method for producing photosensitive resin and liquid photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solder resist for producing a printed wiring board, an electroless plating resist, an insulating layer of a build-up method printed wiring board, or a black matrix or a color filter for producing a liquid crystal display panel. More specifically, the present invention relates to a photosensitive resin material, and more specifically, has high sensitivity to ultraviolet light exposure, has good developability with an alkaline aqueous solution, and has little change with time in developability, and further has electrical properties, mechanical properties, heat resistance, and heat resistance. The present invention relates to a method for producing a photosensitive resin capable of forming a cured coating film having excellent chemical properties and the like, and a liquid photosensitive resin composition using the resin obtained by the method.

[0002]

2. Description of the Related Art In recent years, with the increase in the density of ICs and VLSIs,
Printed wiring boards are also becoming more and more dense and fine-patterned, and it has become necessary to reduce circuit width and circuit spacing. Therefore, solder resists, electroless plating resists, and the like that have higher dimensional accuracy and resolution than before have been strongly demanded.

In order to form a solder resist or the like on a printed wiring board, a method of forming a pattern of a heat-curable or photo-curable resist ink by a screen printing method and thermally or photo-curing a transfer portion is generally used. Met. However, there is a limit to the formation of fine patterns in the screen printing method, and accordingly, as the density of printed circuit boards has been increased and miniaturized, the use of photolithographic principles has been shifted to developing resists. At first, dry film was used as a development type resist formation method, but there is a problem that air bubbles easily enter at the time of press bonding to the substrate, and liquid development type resist which is not limited to the coating method is now in the spotlight. I have. Among them, from the viewpoint of environmental measures, an alkali developing type, which can be developed with a dilute weak alkaline aqueous solution, has become mainstream, and an epoxy (meth) acrylate obtained by reacting an epoxy resin with (meth) acrylic acid has an acid anhydride. A carboxyl group-containing epoxy (meth) acrylate obtained by reacting a product to introduce a carboxyl group has been used as a photosensitive resin for an alkali development type resist (for example, JP-A-61-243869 and JP-A-63-63869).
-258975).

A liquid made of a photosensitive resin composition suitable for a solder resist for producing a printed wiring board, an electroless plating resist, an insulating layer of a build-up method printed wiring board, or a black matrix or a color filter for producing a liquid crystal display panel. A pattern forming method using a developing type resist is such that a resist is first coated on a printed wiring board, heated and dried to form a coating film, and a film for pattern formation is pressed on the coating film, exposed, and developed. Is adopted. In the above process, if the adhesiveness remains in the coating film after heating and drying, some resist adheres to the pattern film after peeling, and the pattern cannot be accurately reproduced. There was a problem that peeling was not possible. For this reason, the tack-free property after the formation of the coating film is an important required characteristic of the liquid development type resist.

Another important characteristic is alkali developability after exposure. That is, in order to form a fine pattern with high reliability and good reproducibility, the unexposed portion of the coating film must be promptly removed at the time of development. But,
Alkali developability and the above-mentioned tack-free property are properties that contradict each other, and there is a tendency for tack-free property to deteriorate when trying to improve developability. The appearance of a conductive resin has been desired.

On the other hand, black matrices and color filters used in liquid crystal display panels have conventionally been black, red, green,
After applying a blue colored acrylic-based photosensitive resin composition solution to the substrate by spin coating or the like and bonding a glass plate for pattern formation, the necessary parts are cured by irradiation with active energy rays, and the uncured parts are cured. Although it has been formed by dissolving and removing with a solvent, the manufacturing process of the liquid crystal display panel includes a heating process at a high temperature of 200 ° C. or more, and a black matrix made of an acrylic photosensitive resin and The color filter had a problem in heat resistance.
Also, in order to improve the image quality of liquid crystal display panels, fine patterns are being developed for black matrices and color filters as well, and high reliability is required. As with the solder resist field, photosensitive resins with excellent dimensional accuracy and resolution are also required. Is required. Further, since acrylic-based photosensitive resins are mainly of the solvent development type, the transition to alkali development-type photosensitive resins for black matrices and color filters is also required from the viewpoint of environmental measures.

[0007]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a high photosensitivity, excellent tack-free property of a coating film, can be accurately developed with a weak alkaline aqueous solution quickly, and has good adhesion to a substrate, chemical resistance, and the like. An object of the present invention is to find a method for producing a photosensitive resin capable of forming a cured coating film having excellent heat resistance. Further, by providing a liquid photosensitive resin composition containing the photosensitive resin, a solder resist for manufacturing a printed wiring board, an electroless plating resist, an insulating layer of a build-up method printed wiring board, or a liquid crystal display board. It is an object of the present invention to solve the above-mentioned various problems of a conventional liquid development type resist used for a black matrix or a color filter.

The method for producing a photosensitive resin according to the present invention is characterized in that the resin (A) having two or more (meth) acryloyl groups and one or more carboxyl groups in one molecule has two
The point is that the bifunctional epoxy resin (B) having two epoxy groups is reacted. Photocurable resin (A)
Can produce a photosensitive resin whose molecular weight is increased by the bifunctional epoxy resin (B). Further, a resin (A) having two or more (meth) acryloyl groups and one or more carboxyl groups in one molecule is referred to as a bifunctional epoxy resin (B) having two epoxy groups in one molecule. The present invention also includes a production method of reacting and further reacting polybasic acid anhydride (II). According to this method, a photosensitive resin having more excellent alkali developability can be produced.

The bifunctional epoxy resin (B) is obtained by reacting a bisphenol-type epoxy resin or a polyalkylene glycol or a dihydric alcohol which is an adduct of an alkylene oxide and a bisphenol compound with epichlorohydrin. Diglycidyl ether type epoxy resin is a preferred embodiment of the present invention.

The resin (A) has an epoxy resin (C) having two or more epoxy groups in one molecule, is reacted with (meth) acrylic acid (I), and then a polybasic acid anhydride (II) is added. (Meth) acrylic acid (I) and an alkylphenol (III) represented by the following general formula are added to an epoxy resin (C) obtained by reacting or having three or more epoxy groups in one molecule. It is also preferably obtained by reacting and then reacting with polybasic acid anhydride (II).

[0011]

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(However, R ¹ and R ² are the same or different and each represent a saturated or unsaturated alkyl group having 5 to 35 carbon atoms.) The epoxy resin (C) has three or more epoxy groups in one molecule. Novolak type epoxy resin or 1
It is preferable to use a bisphenol-type epoxy resin having two epoxy groups in the molecule.

In the present invention, the epoxy group in the bifunctional epoxy resin (B) is 0.1 to 0.8 chemical equivalent to 1.0 chemical equivalent of the carboxyl group in the resin (A). It is recommended to react. In the present invention,
The present invention also includes all photosensitive resins included in the present invention, and a liquid photosensitive resin composition containing a photopolymerization initiator and a diluent together with the photosensitive resin.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, the resin (A) having two or more (meth) acryloyl groups and one or more carboxyl groups in one molecule. ) Is reacted with a bifunctional epoxy resin (B) to give the resin (A)
It has been found that a photosensitive resin having a high molecular weight can simultaneously exhibit good tack-free properties and alkali developability. That is, the photosensitive resin obtained in the present invention exhibited good alkali developability, despite having excellent tack-free properties because the resin itself has a high molecular weight. Hereinafter, the present invention will be described in detail.

The method of the present invention comprises a resin (A) having two or more photopolymerizable (meth) acryloyl groups and one or more carboxyl groups necessary for developing alkali developability, and a bifunctional epoxy resin. (B) is reacted. As the resin (A) used in the present invention, an epoxy resin (C) having two or more epoxy groups in one molecule is used as a starting material, and this is mixed with (meth) acrylic acid (I) and polybasic acid anhydride. (II) and, if necessary, a photosensitive resin obtained by reacting an alkylphenol (III) can be preferably used.

The epoxy resin (C) as a starting material of the resin (A) is not particularly limited, and any known epoxy resin having two or more epoxy groups in one molecule can be used. Among them, bisphenol-type epoxy resins and novolak-type epoxy resins are preferred because of their excellent electrical properties, heat resistance, chemical resistance and the like. Specific examples of the bisphenol type epoxy resin include a bisphenol A type epoxy resin, a tetrabromobisphenol A type epoxy resin, a bisphenol S type epoxy resin, a bisphenol F type epoxy resin, and the like.

As a specific example of a novolak type epoxy resin known as an epoxy resin having three or more epoxy groups in one molecule, a phenol compound such as phenol or cresol is reacted with an aldehyde in the presence of an acid catalyst. Polyphenolic compounds obtained by reacting not only a novolak-type epoxy resin derived from a resin having a novolak skeleton obtained as described above, but also a phenol compound and a diolefin compound such as divinylbenzene or dicyclopentadiene in the presence of an acid catalyst. And epoxy resins derived therefrom. Among them, phenol novolak type epoxy resin, brominated phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin and the like can be preferably used.

The resin (A) is obtained by reacting (meth) acrylic acid (I) with an epoxy group in the epoxy resin (C) as a starting material to introduce two or more (meth) acryloyl groups. Then, a polybasic acid anhydride (II) is ester-bonded to a hydroxyl group formed by ring-opening of an epoxy group to introduce at least one carboxyl group.

The reaction of the (meth) acrylic acid (I) and the polybasic anhydride (II) with the epoxy resin (C) as a starting material is carried out by reacting the epoxy resin (C) with the (meth) acrylic acid (I) and the polybasic acid. The acid anhydride (II) may be reacted at the same time. However, considering the hydroxyl group formation reaction (epoxy group ring opening reaction), first, the epoxy resin (C) and (meth) acrylic acid
The method of reacting (I) and then reacting with polybasic acid anhydride (II) is preferred.

Epoxy resin (C) and (meth) acrylic acid
The reaction of (I) is based on one of the epoxy groups in the epoxy resin (C).
It is preferable that the carboxyl groups of the (meth) acrylic acid (I) are reacted with 0.8 to 1.1 chemical equivalents so that the carboxyl groups become substantially equivalent to the chemical equivalents. This reaction, in the presence or absence of a diluent described below, hydroquinone, monomethyl ether hydroquinone, polymerization inhibitors such as oxygen,
And in the presence of a reaction catalyst such as a tertiary amine, tertiary phosphine, lithium chloride, quaternary ammonium salt, or quaternary phosphonium salt at 80 to 130 ° C.

When the epoxy resin (C) is a trifunctional or higher epoxy resin, an alkylphenol (III) represented by the following general formula may be reacted with the (meth) acrylic acid (I) to the epoxy group.

[0022]

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(However, R ¹ and R ² are the same or different and each represent a saturated or unsaturated alkyl group having 5 to 35 carbon atoms.)

In the resin (A), the above alkylphenol (I
This is because the introduction of (II) improves the flexibility and chemical resistance of the coating film after curing of the obtained photosensitive resin, which is an effect of introducing a long-chain alkyl group portion in alkylphenol. it is conceivable that.

When the alkylphenol (III) is allowed to react with the epoxy resin (C) as a starting material together with the (meth) acrylic acid (I), the reaction is carried out with respect to one chemical equivalent of the epoxy group in the epoxy resin (C). The sum of (I) and (III) is set to 0.8 to 1.1 chemical equivalent so that the sum of the carboxyl group of (meth) acrylic acid (I) and the hydroxyl group of alkylphenol (III) is almost equivalent. Is good. The equivalent ratio of the two is such that (I) :( III) is (1: 1) to (99: 1). If the equivalent ratio of the two is out of this range, the amount of alkylphenol (III) becomes larger than that of (meth) acrylic acid (I), and the amount of photopolymerizable (meth) acryloyl groups in the resin (A) decreases, That is, the amount of the photopolymerizable double bond in the finally obtained photosensitive resin decreases, which is not preferable.

Epoxy resin (C) and (meth) acrylic acid
When (I) reacts, the epoxy group is opened to introduce a (meth) acryloyl group into the epoxy resin (C) and generate a hydroxyl group. Polybasic anhydride (II) was added in 0.1 equivalent to 1.0 chemical equivalent of hydroxyl group generated.
If a carboxyl group for imparting alkali developability is introduced by a monoesterification reaction after reacting with a chemical equivalent of 1.0 to 1.0, the resin (A) having a (meth) acryloyl group and a carboxyl group can be obtained. Polybasic acid anhydride (I
If I) is less than 0.1 chemical equivalent, the resulting resin (A)
The amount of the carboxyl group introduced therein is small, and alkali developability is not exhibited.

The polybasic anhydrides (II) include phthalic anhydride, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydroanhydride Dibasic acid anhydrides such as phthalic acid, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic acid, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride , Butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, aliphatic or aromatic tetrabasic dianhydrides such as benzophenonetetracarboxylic dianhydride, and the like. One or more of them can be used.

The monoesterification reaction of the polybasic acid anhydride (II) with respect to the hydroxyl group is carried out in the presence of a polymerization inhibitor such as hydroquinone, monomethyl ether hydroquinone, oxygen, etc., without a catalyst, or with a tertiary amine or tertiary phosphine. The reaction may be performed at 50 to 130 ° C. in the presence of a reaction catalyst such as lithium chloride, quaternary ammonium salt, quaternary phosphonium salt and the like.

By the above reaction, a resin (A) having a (meth) acryloyl group and a carboxyl group is obtained.
Although the resin (A) itself can be used as a photosensitive resin, in order to solve both the tack-free property and the alkali developability, which is the object of the present invention, the resin (A) has the following properties.
Further, it is necessary to react the bifunctional epoxy resin (B). By reacting the bifunctional epoxy resin (B), a photosensitive resin in which the resins (A) and (B) have a high molecular weight can be obtained. However, this structure has good tack-free properties and alkali developability simultaneously. It is important to be able to demonstrate.

The photosensitive resin obtained in the present invention is a resin in which the resin (A) is connected to both sides of the bifunctional epoxy resin (B), and has a high molecular weight and thus has excellent tack-free properties. Nevertheless, it is considered that the presence of the hydroxyl group contained in the bifunctional epoxy moiety (B) does not cause a decrease in developability even in alkaline development. In this case, as the epoxy resin, a trifunctional or higher epoxy resin having three or more epoxy groups in one molecule cannot be used. A trifunctional or higher epoxy resin is unsuitable for the present invention because it causes gelation as the molecular weight increases and the above effects cannot be obtained.

What can be used as the bifunctional epoxy resin (B) is a known epoxy resin having two epoxy groups in one molecule, and includes bisphenol A type, tetrabromobisphenol A type, bisphenol S type, bisphenol Bisphenol type epoxy resin such as F type or alicyclic epoxy resin; diglycidyl ester type epoxy resin; diglycidyl ether type epoxy resin of polyhydric alcohol, especially polyglycol such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol Diglycidyl ether obtained by reacting alkylene glycols or a dihydric alcohol obtained by adding an alkylene oxide to a bisphenol compound which is a precursor of the bisphenol-type epoxy resin, with epichlorohydrin Bifunctional epoxy resins such as diglycidylamine type epoxy resins, among which bisphenol type epoxy resins and polyhydric alcohols which are polyalkylene glycols or adducts of alkylene oxides and bisphenol compounds can be used. A diglycidyl ether type epoxy resin obtained by reacting epichlorohydrin can be preferably used because both the alkali developing property and the tack-free property are particularly improved.

The reaction between the resin (A) and the bifunctional epoxy resin (B) is such that the carboxyl group in the resin (A) has a chemical equivalent of 1.0 and the epoxy group in the resin (B) has a chemical equivalent of 0.1 to 0.1. It is preferable to make the reaction to be 8 chemical equivalents. If the epoxy group is less than 0.1 equivalent, the reaction between (A) and (B) is insufficient, so that the high molecular weight of the photosensitive resin is not achieved, and no tack-free property is exhibited. Further, when the epoxy group is reacted in excess of 0.8 chemical equivalent, the absolute amount of the carboxyl group remaining in the photosensitive resin decreases, and alkali development cannot be performed.

The reaction between the two is carried out in the presence or absence of a diluent, which will be described later, in the presence of a polymerization inhibitor such as hydroquinone, monomethyl ether hydroquinone, or oxygen, with a tertiary amine, tertiary phosphine, lithium chloride, 8 in the presence of a reaction catalyst such as a quaternary ammonium salt or a quaternary phosphonium salt.
It can be performed at 0 to 130 ° C.

In the present invention, in the photosensitive resin obtained after the reaction of the resin (A) and the bifunctional epoxy resin (B), the hydroxyl group formed by ring opening of the epoxy group of the bifunctional epoxy resin, With respect to the hydroxyl group contained in the functional epoxy resin (B), a polybasic acid anhydride (I
I) may be reacted. Since the carboxyl group is further introduced into the photosensitive resin by the monoesterification reaction of the polybasic acid anhydride (II), the amount of the carboxyl group increases,
This has the effect of further improving alkali developability. The polybasic acid anhydride (II) and the reaction conditions that can be used are the same as those described in the description of the method for producing the resin (A).

The liquid photosensitive resin composition of the present invention can be obtained by adding a photopolymerization initiator and a diluent to the photosensitive resin obtained by the method of the present invention.

Known photopolymerization initiators can be used, and specific examples thereof include benzoin such as benzoin, benzoin methyl ether and benzoin ethyl ether and their alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone. Acetophenones such as 1,1,1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; 2
-Methylanthraquinone, 2-amylanthraquinone,
Anthraquinones such as 2-t-butylanthraquinone and 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone,
Thioxanthones such as chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,
Benzophenones such as 3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides, xanthones, and the like.

These photopolymerization initiators are used as one kind or as a mixture of two or more kinds, and preferably 0.5 to 30 parts by weight based on 100 parts by weight of the photosensitive resin.
When the amount of the photopolymerization initiator is less than 0.5 parts by weight,
Light irradiation time must be increased, or polymerization is difficult to occur even if light irradiation is performed, so that an appropriate surface hardness cannot be obtained. When the amount of the photopolymerization initiator is 30
Even if it exceeds parts by weight, there is no merit of using a large amount.

As the diluent, a solvent or a diluent monomer capable of participating in the photopolymerization reaction may be used alone or in a mixture of two or more, and is used in an amount of 5 to 500 parts by weight based on 100 parts by weight of the photosensitive resin. Is preferably blended in accordance with the optimum viscosity of each coating method. In particular, when a diluting monomer is used alone or as a mixture as a diluent, it is preferable in terms of physical properties that the diluting monomer is blended in an amount of 5 to 100 parts by weight based on 100 parts by weight of the photosensitive resin.

Examples of the solvent include hydrocarbons such as toluene and xylene; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; esters such as cellosolve acetate and carbitol acetate; methyl isobutyl ketone; Ketones such as methyl ethyl ketone; ethers such as diethylene glycol dimethyl ether; Diluent monomers include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate,
β-hydroxyethyl (meth) acrylate, (2-oxo-1,3-dioxolan-4-yl) -methyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth)
Examples include acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tris (hydroxyethyl) isocyanurate tri (meth) acrylate.

In the photosensitive resin composition of the present invention, if necessary, fillers such as talc, clay and barium sulfate, coloring pigments, defoaming agents, coupling agents, leveling agents, etc., and novolak Epoxy resin, bisphenol A
An epoxy resin such as a type epoxy resin, a bisphenol F type epoxy resin, an alicyclic epoxy resin, and triglycidyl isocyanurate, and an epoxy curing agent such as dicyandiamide and imidazole compounds can also be added.

The photosensitive resin composition of the present invention can be alkali-developed because the portion not irradiated with light is dissolved in an aqueous alkali solution. Examples of the alkali that can be used for development include alkali metal compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide; ammonia; monomethylamine, dimethylamine, trimethylamine, and monomethylamine. Water-soluble organic amines such as ethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, and polyethyleneimine; Alternatively, two or more kinds can be used.

[0042]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention.
Modifications and alterations that do not depart from the spirit described below are all included in the technical scope of the present invention. The parts and percentages in the examples are on a weight basis.

Synthesis Example 1 Cresol novolak type epoxy resin ESCN-195
XL (manufactured by Sumitomo Chemical Co., epoxy equivalent 195) 1000
337 parts of ethyl carbitol acetate and 337 parts of toluene were added to the mixture and dissolved by heating.
, 4.1 parts of triphenylphosphine and 1.1 parts of methylhydroquinone were added and reacted at 110 ° C for 12 hours. The reaction product was cooled to 100 ° C., 467 parts of tetrahydrophthalic anhydride, 115 parts of ethyl carbitol acetate and 115 parts of toluene were added, and the mixture was reacted for 5 hours. Ethyl carbitol acetate containing 67% of a resin having an acid value of 97 and toluene were added. To obtain a resin mixture (R-1).

Synthesis Example 2 Cresol novolak type epoxy resin YDCN-703
S (manufactured by Toto Kasei, epoxy equivalent: 200), 1000 parts of ethyl carbitol acetate, 349 parts of toluene
Then, 333 parts of acrylic acid, 83 parts of paranonylphenol as an alkylphenol, 4.2 parts of triethylammonium bromide and 1.2 parts of methylhydroquinone were added, and the mixture was reacted at 110 ° C. for 14 hours. The reaction product was cooled to 100 ° C., 456 parts of tetrahydrophthalic anhydride, 112 parts of ethyl carbitol acetate and 112 parts of toluene were added, and the mixture was reacted for 4 hours. Ethyl carbitol acetate containing 67% of a resin having an acid value of 93 and toluene were added. To obtain a resin mixture (R-2).

Synthesis Example 3 100 parts of the resin mixture (R-1) obtained in Synthesis Example 1 was added to
Bisphenol A type epoxy resin Araldite GY-2
Addition of 2.1 parts of 50 (Ciba Geigy, epoxy equivalent: 185), reaction at 110 ° C. for 4 hours, a resin mixture of ethyl carbitol acetate containing 64.5% of a resin having an acid value of 84 and toluene (R-3) I got

Synthesis Example 4 100 parts of the resin mixture (R-1) obtained in Synthesis Example 1 was added to
Add 5.4 parts of bisphenol A type epoxy resin YD-014 (manufactured by Toto Kasei, epoxy equivalent 954), and add 110 ° C.
For 5 hours to obtain a resin mixture (R-4) of ethyl carbitol acetate and toluene containing 68.5% of a resin having an acid value of 85.

Synthesis Example 5 100 parts of the resin mixture (R-1) obtained in Synthesis Example 1 was added to
10.2 parts of bisphenol A type epoxy resin YD-017 (manufactured by Toto Kasei, epoxy equivalent 1820) was added, and 11
The mixture was reacted at 0 ° C. for 5 hours to obtain a resin mixture (R-5) of ethyl carbitol acetate and toluene containing 70.0% of a resin having an acid value of 79.

Synthesis Example 6 100 parts of the resin mixture (R-2) obtained in Synthesis Example 2 was added to
Add 1.7 parts of bisphenol F type epoxy resin YDF-8170 (manufactured by Toto Kasei, epoxy equivalent: 162), and add 11 parts.
The mixture was reacted at 0 ° C. for 4.5 hours, and the resin having an acid value of 82 was converted to 67.4.
% Of ethyl carbitol acetate and toluene to obtain a resin mixture (R-6).

Synthesis Example 7 100 parts of the resin mixture (R-2) obtained in Synthesis Example 2 was added to
9.8 parts of bisphenol A type epoxy resin YD-017 (manufactured by Toto Kasei, epoxy equivalent 1820) was added, and 110
The mixture was reacted at 6 ° C. for 6 hours to obtain a resin mixture (R-7) of ethyl carbitol acetate and toluene containing 69.8% of a resin having an acid value of 78.

Synthesis Example 8 100 parts of the resin mixture (R-2) obtained in Synthesis Example 2 was added to
Polypropylene glycol diglycidyl ether type epoxy resin PG-207 (manufactured by Toto Kasei, epoxy equivalent 31
0) 3.3 parts were added and reacted at 110 ° C. for 5 hours to obtain a resin mixture (R-8) of ethyl carbitol acetate containing 68.1% of a resin having an acid value of 81 and toluene.

Synthesis Example 9 100 parts of the resin mixture (R-2) obtained in Synthesis Example 2 was added to
3.5 parts of Adeka Resin EP-4000 (produced by Asahi Denka, epoxy equivalent: 325) was added and reacted at 110 ° C. for 4.5 hours. Resin with ethyl carbitol acetate containing 68.1% of a resin having an acid value of 79 and toluene was used. Mixture (R-9)
I got

Examples 1 to 7 and Comparative Examples 1 to 3 Resin mixtures (R-1) to (R-
9) was kneaded with the components shown in Table 1 to give a photosensitive resin composition. Table 2 shows the results evaluated by the following methods.

[Evaluation of Developability] Degreasing and cleaning thickness 1.6
The photosensitive resin composition was applied to a thickness of 20 to 30 μm on a copper-clad laminate having a thickness of 20 mm and dried in a hot-air circulation drying oven.
C. for a predetermined time (30, 40, 50, 60 minutes) to obtain a coating film. Then, ₃ % using 1% Na ₂ CO ₃ aqueous solution.
Development was performed at 0 ° C. under a pressure of 2.1 kg / cm ² for 80 seconds, and the remaining resin was visually evaluated. ：: good developability… no resist remains on copper surface △: slightly poor developability… slightly resist left on copper surface ×: poor developability… considerable resist left on copper surface

[Evaluation of tack-free property] A photosensitive resin composition was applied to a thickness of 20 to 30 µm on a degreased and washed 1.6 mm thick copper-clad laminate, and dried in a hot-air circulation drying oven. The coating was obtained by drying at 30 ° C. for 30 minutes. Then
A polyester film was overlaid on the coated surface, sandwiched between silicon sheets, and pressed at 50 ° C. for 30 minutes. After the temperature of this sample was adjusted to 25 ° C., the polyester film was peeled off, and the peeling state was judged according to the following criteria. ：: no tack was observed at all Δ: slight tack was observed ×: marked tack was observed

[Evaluation of Adhesion] A coating film was formed in the same manner as in the evaluation of tack-free property and irradiated with a light amount of 500 mJ / cm ² using a 1 Kw ultra-high pressure mercury lamp.
After heating at 50 ° C. for 30 minutes, 100 squares of 1 mm × 1 mm were cut in accordance with the test method of JIS D-0202, and the peeling state after the peeling test with an adhesive tape was visually determined. ：: no change at 100/100 △: 80/100 to 99/100 ×: 0/100 to 79/100

[Solder heat resistance] The coating film after exposure was subjected to JIS
According to the test method of D-0202, it was immersed in a solder bath at 260 ° C. for 20 seconds, and the state of the coating film after immersion was evaluated. ：: No abnormality in appearance of coating film ×: Swelling, melting and peeling of appearance of coating film

[0057] [Electroless gold plating resistance] "autologous neck CI" (U.S. cell Rex Corp. gold plating liquid) the coating film after exposure at a current density of 1A / dm ² using 15
After gold plating for 2 minutes and attaching 2 μm thick gold,
A peeling test of the coating film with an adhesive tape was performed. It was visually evaluated according to the following criteria. ：: No abnormality in coating film △: Slight peeling ×: 20% or more of the whole peeled

[0058]

[Table 1]

[0059]

[Table 2]

In the comparative examples using the resins (R-1) and (R-2) which were not made high molecular weight by a bifunctional epoxy resin, the developability after heating for a long time of 60 minutes deteriorated. Moreover, the tack-free property is also inferior. However, Comparative Example 2 using an alkylphenol has better performance such as gold plating resistance and adhesion than Comparative Example 1. In Comparative Example 3, the bifunctional epoxy resin (GY-250) used to react with the resin in Example 1 was merely kneaded, so that the developability and tack-free property were poor, and the adhesion was poor. And poor gold plating resistance. Example 1
No. 7 to No. 7 show good developing property and tack-free property, and it is clear that both properties are compatible.

Synthesis Example 10 1000 parts of bisphenol A type epoxy resin GY-250 (Ciba Geigy, epoxy equivalent: 185) was heated to 110 ° C.
Then, 389 parts of acrylic acid, 7.0 parts of triethylammonium bromide and 1.4 parts of methylhydroquinone were added, and the mixture was reacted for 10 hours. This reactant is
After cooling to 00 ° C, tetrahydrophthalic anhydride 822
, 544 parts of ethyl carbitol acetate and 544 parts of toluene were added and reacted for 6 hours to obtain a resin mixture (A). To 100 parts of this resin mixture (A), 15.1 parts of bisphenol A epoxy resin GY-250, 3.7 parts of ethyl carbitol acetate and 3.7 parts of toluene were added, and the mixture was reacted at 110 ° C. for 14 hours to obtain an acid. A resin mixture (R-10) containing ethyl carbitol acetate and toluene containing 67% of a resin having a valence of 61 was obtained.

Synthesis Example 11 Bisphenol A type epoxy resin GY-250 was added to 100 parts of the resin mixture (A) obtained in Synthesis Example 10 for 17.2.
And 6.2 parts of ethyl carbitol acetate and 6.2 parts of toluene, and reacted at 110 ° C. for 15 hours. The reaction product was cooled to 100 ° C., and 7.4 parts of tetrahydrophthalic anhydride, 2.0 parts of ethyl carbitol acetate and 2.0 parts of toluene were added and reacted for 4 hours. A resin mixture (R-11) with ethyl carbitol acetate and toluene containing 65% of a resin having an acid value of 83 was obtained.

Synthesis Example 12 61 parts of butyl cellosolve acetate was added to 100 parts of bisphenol S type epoxy resin EX-251 (manufactured by Nagase Kasei Kogyo Co., Ltd., epoxy equivalent: 198), and the mixture was dissolved by heating, and then 36 parts of acrylic acid and 0.41 of triphenylphosphine were added. Parts and 0.11 part of methylhydroquinone,
For 14 hours. The reaction product was cooled to 100 ° C., and 51 parts of succinic anhydride and 23 parts of butyl cellosolve acetate were added and reacted for 8 hours. To this resin mixture, 40 parts of bisphenol S type epoxy resin EX-251 and butyl cellosolve acetate 18 were added, and 110 ° C.
For 14 hours, and a resin mixture (R-12) with butyl cellosolve acetate containing 69% of a resin having an acid value of 78
I got

Synthesis Example 13 After heating 100 parts of bisphenol A type epoxy resin GY-250 (Ciba Geigy, epoxy equivalent: 185) to 110 ° C., 39 parts of acrylic acid, 0.67 part of triethylammonium bromide and 0.1 part of methylhydroquinone were added.
14 parts were added and reacted for 10 hours. Add 10
After cooling to 0 ° C., 33 parts of tetrahydrophthalic anhydride, 29 parts of ethyl carbitol acetate and 29 parts of toluene
The mixture was added and reacted for 5 hours to obtain a resin mixture (R-13) of ethyl carbitol acetate and toluene containing 75% of a resin having an acid value of 72.

Synthesis Example 14 To 100 parts of bisphenol S type epoxy resin EX-251 (Epoxy equivalent: 198, manufactured by Nagase Kasei Kogyo Co., Ltd.) was added 59 parts of butyl cellosolve acetate, and the mixture was dissolved by heating, and then 36 parts of acrylic acid and 0.41 of triphenylphosphine were added. Parts and 0.14 parts of methylhydroquinone.
For 14 hours. The reaction product was cooled to 100 ° C., and 28 parts of succinic anhydride and 12 parts of butyl cellosolve acetate were added and reacted for 6 hours. To this resin mixture, 40 parts of bisphenol S type epoxy resin EX-251 and butyl cellosolve acetate 18 were added, and 110 ° C.
And a reaction mixture with butyl cellosolve acetate containing 70% of a resin having an acid value of 97 (R-14).
I got

Examples 8 to 11 and Comparative Examples 4 to 6 Resin mixtures (R-10) obtained in Synthesis Examples 10 to 14
(R-14) was kneaded with the components shown in Table 3 to obtain a photosensitive colored resin composition for a color filter. After spin-coating this colored resin composition on a glass plate,
For 30 minutes to form a coating film of about 1 μm. Table 3 shows the results evaluated by the following methods. [Dryability of coating film] A negative film was pressed on the coating film, and the state of peeling was evaluated according to the following criteria. ：: No sound is produced at the time of peeling, and clean peeling is possible. ：: A peeling sound is produced at the time of peeling. X: The coating film adheres to the negative film.

[Exposure sensitivity] A 21-step Stofa step tablet was stuck to the coating film, and irradiated with a light amount of 500 mJ / cm ² using a 1 kW ultra-high pressure mercury lamp. Then 1
% Na ₂ CO ₃ aqueous solution, 2.1 kg / cm ²
The development was performed for 30 seconds under the above pressure, and the number of steps of the step tablet remaining on the glass plate was examined.

[Resolution] A 1 kW ultra-high pressure mercury lamp was used to irradiate 500 mJ / cm ² of light through a 10 μm line-and-space mask and developed in the same manner as in the measurement of exposure sensitivity. Evaluation was made according to the following criteria. ：: There is no abnormality in the pattern △: The pattern is partially lost ×: The pattern hardly remains

[Heat resistance] The coating film was exposed in the same manner as in the measurement of exposure sensitivity. Thereafter, heating was performed at 150 ° C. for 30 minutes, and after pattern fixing, heating was further performed at 250 ° C. for 1 hour. Discoloration and fading were evaluated. ：: No discoloration or fading ×: Discoloration or fading

[0070]

[Table 3]

[0071]

According to the method for producing a photosensitive resin of the present invention, a photosensitive resin having a high molecular weight and an appropriate amount of a carboxyl group can be obtained, which is impossible with a conventional photosensitive resin. It has become possible to achieve both tack-free property and alkali developability of the coating film before light curing. Further, the cured coating film was excellent in chemical resistance, adhesion, heat resistance, and chemical resistance. Therefore, a liquid photosensitive resin composition useful as a solder resist or an electroless plating resist used in manufacturing a printed wiring board, or as a black matrix or a color filter for manufacturing a liquid crystal display panel can be provided.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-61-243869 (JP, A) JP-A-5-339356 (JP, A) JP-A-7-36183 (JP, A) JP-A 8- 3273 (JP, A) JP-A-8-3274 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/14-59/17 G03F 7/027 515 C08F 299/02

Claims (11)

(57) [Claims] 1. A resin (A) having two or more (meth) acryloyl groups and one or more carboxyl groups in one molecule.
A method for producing a photosensitive resin, comprising reacting a bifunctional epoxy resin (B) having two epoxy groups in one molecule. 2. A resin (A) having two or more (meth) acryloyl groups and one or more carboxyl groups in one molecule.
Was reacted with a bifunctional epoxy resin (B) having two epoxy groups in one molecule, and further reacted with a polybasic acid anhydride (I
A method for producing a photosensitive resin, which comprises reacting (I). 3. The method for producing a photosensitive resin according to claim 1, wherein the bifunctional epoxy resin (B) is a bisphenol type epoxy resin. 4. The difunctional epoxy resin (B) is a diglycidyl ether type epoxy resin obtained by reacting a polyalkylene glycol or a dihydric alcohol which is an adduct of an alkylene oxide and a bisphenol compound with epichlorohydrin. A method for producing the photosensitive resin according to claim 1. 5. A resin (A) having an epoxy resin (C) having two or more epoxy groups in one molecule, reacting (meth) acrylic acid (I) with a polybasic acid anhydride (II) The method for producing a photosensitive resin according to any one of claims 1 to 4, which is obtained by reacting 6. An epoxy resin (C) in which the resin (A) has three or more epoxy groups in one molecule is added to (meth) acrylic acid (I) and an alkylphenol (III) represented by the following general formula: The method for producing a photosensitive resin according to any one of claims 1 to 4, which is obtained by reacting a polybasic acid anhydride (II). Embedded image (However, R ¹ and R ² are the same or different and each have 5 to 3 carbon atoms.
5 represents a saturated or unsaturated alkyl group) 7. The method for producing a photosensitive resin according to claim 5, wherein the epoxy resin (C) is a novolak type epoxy resin having three or more epoxy groups in one molecule. 8. The method for producing a photosensitive resin according to claim 6, wherein the epoxy resin (C) is a bisphenol type epoxy resin having two epoxy groups in one molecule. 9. A reaction in which the epoxy group in the bifunctional epoxy resin (B) is 0.1 to 0.8 chemical equivalent with respect to 1.0 chemical equivalent of the carboxyl group in the resin (A). The method for producing a photosensitive resin according to any one of claims 1 to 8, wherein 10. The method according to claim 1.
A photosensitive resin obtained by the following. 11. A liquid photosensitive resin composition comprising the photosensitive resin according to claim 10, a photopolymerization initiator and a diluent.