JP3523857B2 - Photosensitive resin and photosensitive resist ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin and a photosensitive resist ink composition which have excellent developing properties in an aqueous dilute alkaline solution, a little burr in the cured coating, excellent flexing resistance, and besides, are excellent in flexibility, heat resistance, solder heat resistance, adhesion, water resistance, chemical resistance, or the like. <P>SOLUTION: The photosensitive resin comprises reacting (a) a compound having at least one carboxyl group and two hydroxyl groups in a molecule, (b) a diol compound, and (c) a polyisocyanate to obtain (X) an end isocyanate compound, and reacting the end isocyanate compound with (d) a compound having a polymerizable unsaturated group, a carboxyl group and at least one hydroxyl group in a molecule to obtain (Y) the object resin, or further reacting (Y) the object resin with (e) a polyactic anhydride to obtain (Z) still the object resin. The photosensitive resist ink composition comprises compounding (Y) the resin or (Z) the resin, (B) an epoxy resin, (C) a photopolymerization initiator, (D) a polymerizable unsaturated compound and/or a solvent. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin and a photosensitive resist ink composition. For more details,
In the field of electronic materials such as printed wiring board solder resist, semiconductor package solder resist, flexible printed wiring board resist ink, and high-density multilayer board interlayer insulating film, it has excellent developability in dilute alkaline aqueous solution and a coating film after curing. Especially when applied on a film, there is little warpage when cured, excellent bending resistance, and further flexibility,
The present invention relates to a photosensitive resin and a photosensitive resist ink composition which are excellent in heat resistance, solder heat resistance, adhesion, water resistance, chemical resistance and the like.

[0002]

2. Description of the Related Art Conventionally, a permanent mask resist in the production of printed wiring boards has been manufactured by a method of screen-printing a heat- or ultraviolet-curable resist ink, but from the viewpoint of productivity, it is currently an alkali-developing liquid solder photo resist. It is shifting to resist. For example, Japanese Patent Publication 1-54
No. 390, a liquid resist ink composition which is excellent in photocurability, thermosetting property, heat resistance, solvent resistance, and acid resistance and which can be developed with an alkaline aqueous solution, contains a novolac epoxy compound and an unsaturated monocarboxylic acid. A photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride with the reaction product of
A liquid resist ink composition containing a photopolymerization initiator, a diluent, and an epoxy compound having at least two epoxy groups has been proposed, and is currently in the mainstream in rigid substrate applications such as a glass epoxy substrate.

In such a trend, in recent years, along with the miniaturization, weight reduction and high performance of electronic equipment, the miniaturization of semiconductor packages and the increase in the number of pins have been put into practical use, and BGAs are being mass-produced.
In the case of semiconductor packages such as (ball grid array) and CSP (chip size package), PCT resistance (pressure cooker resistance) is particularly high in terms of high reliability.
is necessary. However, under such a severe condition, the conventional liquid resist ink composition is present for only several hours to several tens of hours at present. Further, in the method of mounting a semiconductor package, since the whole is heated by infrared rays and the solder is reflowed to be fixed, a conventional liquid resist ink composition such as Japanese Patent Publication No. 1-54390 is applied by thermal shock. There is a decrease in so-called reflow resistance, such as cracks in the film and separation from the substrate, and improvements are required.

Further, in recent years, with the miniaturization, weight reduction and high performance of electronic equipment, thin and flexible flexible circuit boards have begun to be used. Flexible circuit boards include single-sided boards, double-sided boards, and multi-layer boards, for motherboards,
Alkali development type resists and dry films for chip-on-film (COF) have been studied. As the required performance, since a polyimide film called a coverlay film is used, the adhesion with the polyimide film is good, the bending resistance is excellent, and it is necessary that the warpage when cured is small, and High resolution, good electrical reliability, electrolytic / electroless gold, tin plating resistance, etc. are added. In order to meet these requirements, it is necessary to increase the elongation of the coating film without significantly lowering Tg. Therefore, it is necessary to study the skeleton of the epoxy acrylate and a part of the unsaturated monobasic acid introduced during the epoxy acrylate synthesis. A method of substituting saturated monobasic acid or the like for adjusting the crosslinking density has been studied, but it is not sufficient, and recently, a proposal of introducing a rubber component has been made. For example, JP-A-8-13
4331 discloses an alkali-developable liquid solder resist using a reaction product obtained by adding an acid anhydride to a rubber-modified epoxy acrylate as a base polymer.
However, although the solder resist film obtained by the above composition shows an improvement in flexibility, it contains a polybutadiene skeleton in the main chain and is susceptible to air oxidation derived from an internal olefin bond, and thus has physical properties (flexibility and resistance). It has a drawback that it lacks in long-term reliability (such as PCT property) and lacks in adhesion to a base material because the diameter of dispersed polybutadiene particles is on the order of microns. In addition, JP-A-9-4075
Japanese Unexamined Patent Application Publication No. 1-58242 discloses an alkali-developable liquid solder resist containing an acrylic rubber dispersion / epoxy resin and a polybasic acid anhydride-modified epoxy acrylate as a base polymer. This technique is disclosed in the above-mentioned Japanese Patent Laid-Open No. 8-134.
Compared with the technique described in Japanese Patent No. 331 publication, the dispersed acrylic rubber particle diameter is submicron, and the adhesion and flexibility to the substrate are improved. However, when synthesizing acrylic rubber dispersion / epoxy resin, an emulsifier enters in the emulsification process, and when used as a resist ink, foaming is remarkable in the compounding and kneading process of the epoxy resin, photopolymerization initiator, diluent, filler and the like. It had drawbacks. Further, a proposal has been made to use urethane acrylate having a carboxyl group. For example, JP-A-2000-131836 discloses a composition in which a urethane acrylate having a carboxyl group, a photopolymerization initiator and a diluent are combined.
28957 discloses a composition in which a urethane acrylate having a carboxyl group, a polybasic acid anhydride-modified epoxy acrylate, a photopolymerization initiator, and a diluent are combined. By using these resin compositions,
Although it is possible to impart flexibility, there are other problems such as surface tackiness during heat drying and pressure cooker resistance. Further, proposals using urethane-modified vinyl ester resins have also been made. For example, JP-A-9
No. 52925 discloses a composition in which a urethane modified vinyl ester resin obtained by reacting a vinyl ester resin or a mixture of the vinyl ester resin and a diol compound having a carboxyl group with polyisocyanate, a photopolymerization initiator, and a diluent is combined. It is disclosed. Since these resins are reacted with polyisocyanate to a vinyl ester resin or a mixture of the vinyl ester resin and a diol compound having at least one carboxyl group in one molecule, the unsaturated group of the vinyl ester resin has a urethane-modified vinyl ester resin. The skeleton was randomly dispersed in the skeleton, and although it had dryness to the touch and heat resistance to solder, it had the drawback that it could not have sufficient flexibility. Further, as means for imparting alkali developability, a method of adding an acid anhydride to the terminal of the resin or introducing a carboxyl group into the resin skeleton is taken, but by adding an acid anhydride only to the terminal, alkali In order to provide sufficient alkali developability without developing property, if many compounds having at least one carboxyl group and at least two hydroxyl groups such as dimethylolbutanoic acid in the urethane skeleton are introduced, the urethane bond is However, there are problems such as increase in flexibility and loss of flexibility.

[0005]

Therefore, an object of the present invention is to provide a solder resist for a printed wiring board, particularly a solder resist for a semiconductor package, a resist ink for a flexible printed wiring board, which has excellent developability in a dilute alkaline aqueous solution. Moreover, the coating film after curing, particularly when applied on a film, has little warpage when cured and has excellent flex resistance, and further has flexibility, heat resistance, solder heat resistance, adhesion, water resistance, and resistance to heat. It is intended to provide a photosensitive resin and a photosensitive resist ink composition having excellent chemical properties and the like.

[0006]

In order to solve the above problems, a compound (a) having at least one carboxyl group and two hydroxyl groups in one molecule, a diol compound (b) and a polyisocyanate compound. A terminal isocyanate compound (X) having a carboxyl group is once synthesized by reacting with (c), and a compound having a polymerizable unsaturated group, a carboxyl group and at least one hydroxyl group in one molecule (d) ) Are successively reacted to form a photosensitive resin (Y)
Got Further, the polybasic acid anhydride (e) is added to the hydroxyl groups remaining in the photosensitive resin (Y) to form the photosensitive resin (Z).
Got Further, the photosensitive resin (Y) or (Z)
Then, (B) epoxy resin, (C) photopolymerization initiator, and (D) polymerizable unsaturated compound and / or solvent were added to obtain a photosensitive resist ink composition.

The present inventors have found that the above-mentioned photosensitive resin has excellent dilute alkali developability, and its cured film has excellent flexibility, adhesion, solder heat resistance, PCT resistance, and electroless gold plating resistance. And so on. Further, they have found that a resin composition using the photosensitive resin is suitable as a solder resist ink, especially as a resist ink for a flexible printed wiring board, and based on this finding, the present invention has been completed.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be further described below.
The compound (a) having at least one carboxyl group and two hydroxyl groups in one molecule used in the present invention is not particularly limited, and examples thereof include 1,6-hydroxyhexadecanoic acid, dimethylolacetic acid, and dimethylolpropion. Examples thereof include acids, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid, and reaction products of trifunctional or higher functional polyol compounds with polybasic acid anhydrides. Among these, dimethylolpropionic acid and dimethylolbutanoic acid are particularly preferable. The compound (a) may be used alone or in combination of two or more.

The diol compound (b) used in the present invention is not particularly limited, but general diols, preferably oligomer diols can be used. Examples of oligomer diols include polyether polyols such as polyethylene glycol, polypropylene glycol and polytetraethylene glycol, lactone polyester polyols such as polycaprolactone and polybutyrolactone, and polycarbonate polyols. Among them, a polyol having a molecular weight of 500 to 3000 can be advantageously used.

As the polyisocyanate compound (c) having at least two isocyanate groups in one molecule used in the present invention, known isocyanate compounds can be used. For example, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, propane-1,3-diisocyanate, butane-1,2-diisocyanate, 2-methylbutane-1,4-diisocyanate, pentane-1,5-
Diisocyanate, ω, ω'-1,3-dimethylbenzene diisocyanate, ω, ω'-1,4-dimethylnaphthalene diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3- Phenylene diisocyanate, 1-methylbenzene-2,4-diisocyanate, diphenyl ether-4,4'-diisocyanate, naphthalene-1,4-diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4, 4'-diisocyanate, diphenylmethane-4,4'-diisocyanate,
3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, polymeric diphenylmethane diisocyanate, naphthalene diisocyanate, tetramethyl xylylene diisocyanate, norbornene Diisocyanate, methylene bis (4
-Cyclohexyl isocyanate), diisocyanates such as 1,6-hexamethylene diisocyanate, trimer of hexamethylene diisocyanate, and isocyanurate compounds such as trimer of isophorone diisocyanate. When an isocyanurate compound having three isocyanate groups is used, it may thicken and gel during the synthesis of the photosensitive resin, and among the polyisocyanate compounds, a diisocyanate having two isocyanate groups is preferable. More preferably, from the viewpoints of developability, tack-free property and solder heat resistance of the cured coating film, isophorone diisocyanate, 1,6-
Examples include hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and tetramethyl xylylene diisocyanate.

The compound (d) having a polymerizable unsaturated group, a carboxyl group and at least one hydroxyl group in one molecule used in the present invention includes (1) at least 1.2 epoxy groups in one molecule. Unsaturated polybasic group, a carboxyl group obtained by adding an unsaturated monobasic acid to an epoxy compound having ## STR3 ## and further reacting this with a polybasic acid anhydride so that at least one hydroxyl group remains in the molecule. And a resin having at least one hydroxyl group, (2) an epoxy compound having at least 1.2 epoxy groups in one molecule, at least one alcoholic hydroxyl group and one carboxyl group in one molecule A polymerizable unsaturated polymer obtained by adding a compound having a group to an unsaturated monobasic acid and further reacting it with a polybasic acid anhydride so that at least one hydroxyl group remains in the molecule. Group, or the like resin so as to have a carboxyl group and at least one hydroxyl group.

The epoxy compound used for preparing the compound (d) is at least 1.2 per molecule.
The number of epoxy groups is preferably 1.8, and preferably 1.8.
It is possible to advantageously use those containing ˜4.0, more preferably 1.9 to 2.2. Examples of the compound (d) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene-phenol novolac type epoxy resin. , Phenol-cresol novolac co-condensation type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin or halogenated epoxy compounds thereof, triphenylol methane type epoxy resin, alkyl-substituted triphenylol methane type epoxy resin, Epoxy resins obtained by reacting polyphenylphenol such as tetraphenylolethane type epoxy resin with epichlorohydrin, and polyfunctional hydroxynaphthalenes Epoxy resins obtained by reacting chlorohydrin,
Examples thereof include silicone-modified epoxy resin, ε-caprolactone-modified epoxy resin, glycidylamine type epoxy resin obtained by reaction of epichlorohydrin with primary or secondary amine, and heterocyclic epoxy resin such as triglycidyl isocyanate. One of these epoxy resins
You may use together 1 type (s) or 2 or more types. Among these, a bisphenol type epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, and an alicyclic epoxy resin having a core pair number of 1 having a small hydroxyl group content in the resin are preferable. Further, it is also effective to use an isocyanate-modified epoxy resin for the purpose of improving Toughness while securing Tg, or to use a phosphorus-containing epoxy resin from the viewpoint of imparting flame retardancy. Specific examples of the isocyanate-modified epoxy resin are synthetic ones using the above epoxy resin and an isocyanate compound in the presence of an oxazolidone-forming catalyst. Details are disclosed in JP-B-53-45757 and JP-A-5-43657. There is a description. Commercially available isocyanate-modified epoxy resins having an oxazolidone ring include trade names XAC4151 and XAC4152 (manufactured by Asahi Kasei Epoxy Co., Ltd.).

As the unsaturated monobasic acid used for preparing the compound (d), known ones can be used. A specific example thereof is a monobasic acid having one carboxyl group and at least one polymerizable unsaturated group, and acrylic acid or methacrylic acid can be preferably used. Acrylic acid is preferable in order to obtain a particularly high actinic energy photocurability. In addition, crotonic acid, cinnamic acid, sorbitan acid, acrylic acid dimer, monomethylmalate, monopropylmalate, monobutylmalate, a polyfunctional acrylate or methacrylate having one hydroxyl group and at least one acryloyl group, and later described Among these polybasic acid anhydrides, a carboxyl group-containing polyfunctional acrylate or methacrylate, which is a reaction product with a dibasic acid, can be mentioned. Two or more kinds of these unsaturated monobasic acids may be used in combination.

The compound having at least one alcoholic hydroxyl group and one carboxyl group in one molecule used for preparing the compound (d) is not particularly limited, and examples thereof include glycolic acid and 2-hydroxy. -2-Methylbutyric acid, 2-ethyl-2-hydroxybutyric acid, 1,6-
Examples thereof include hydroxyhexadecanoic acid, dimethylolpropionic acid, and dimethylolbutanoic acid, and reaction products of trifunctional or higher functional polyol compounds and polybasic acid anhydrides. Of these, glycolic acid, dimethylolpropionic acid, and dimethylolbutanoic acid are particularly preferable. You may use the said compound individually by 1 type,
You may use it in combination of 2 or more type.

The polybasic acid anhydride used for preparing the compound (d) is preferably the same as the polybasic acid anhydride (e) described below.

In the preparation of the compound (d), a reaction catalyst is used during the reaction of the epoxy compound, the unsaturated monobasic acid and the compound having at least one alcoholic hydroxyl group and one carboxyl group in one molecule. Is effective,
For example, a tertiary amine, quaternary ammonium salt, phosphine, antimony, organic metal salt or the like can be used. Examples of tertiary amines include triethylamine, pyridine, dimethylbenzylamine and the like. Examples of the quaternary ammonium salt include triethylbenzylammonium chloride, triethylbenzylammonium bromide, tetramethylammonium iodide and the like. Examples of phosphines include tributylphosphine and triphenylphosphine. Examples of antimonies include
Examples thereof include triphenyl antimony. Examples of organic metal salts include lithium naphthenate, chromium acetate, chromium octylate, chromium naphthenate, and iron naphthenate. The catalyst may be added in an amount of 0.001 to 5 parts by weight with respect to 100 parts by weight of the reaction product resin. To react the polybasic acid anhydride with the hydroxyl groups present in the resin thus obtained,
It is effective to use a reaction catalyst, and similarly to the above, for example, a tertiary amine, a quaternary ammonium salt, a phosphine, an antimony, an organic metal salt or the like can be used. The catalyst is 0.0 based on 100 parts by weight of the reaction product resin.
It can be added in a proportion of 01 to 2 parts by weight. In addition, it is preferable to blow air or use a polymerization inhibitor for the purpose of preventing gelation during the reaction. Examples of the polymerization inhibitor include hydroquinone, phenothiazine, p-toluquinone, p-methoxyphenol, triphenylantimony, copper chloride and the like. It is advantageous to add 0.001 to 2 parts by weight of the polymerization inhibitor to 100 parts by weight of the resin as the reaction product. Furthermore, in order to enhance the stirring efficiency during the reaction, it is effective to add a diluent in advance during the reaction. The reaction temperature can be synthesized at 50 to 160 ° C, preferably 80 to 130 ° C. In addition, the preparation of the compound (d) in the aspect of the above (2),
The equivalent ratio of the compound having at least one alcoholic hydroxyl group and one carboxyl group in one molecule to the epoxy group of the epoxy compound and the unsaturated monobasic acid is 0.
The reaction is preferably carried out so as to be 8 to 1.2, particularly preferably about 0.9 to 1.1. Further, the ratio of unsaturated monobasic acid to the compound having at least one alcoholic hydroxyl group and one carboxyl group in one molecule is preferably 0.25 or more, particularly preferably 1.0 or more in terms of molar ratio. When the ratio is less than 0.25, the double bond equivalent is large, the crosslink density is small, and the solder heat resistance of the cured coating film, the resistance to electroless gold plating, etc. may deteriorate.

The acid value of the compound (d) thus obtained is, for example, 20 to 350 KOHmg / g, preferably 30 to 150 KOHmg / g, more preferably 4
It is preferably 0 to 120 KOHmg / g.

The polybasic acid anhydride (e) used in the present invention may be a known saturated and / or unsaturated polybasic acid anhydride, such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, Dibasic acid anhydrides such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic acid; trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride, and the like, and preferably Mention may be made of tetrahydrophthalic anhydride, hexahydrophthalic anhydride or succinic anhydride.

Compound (a) and diol compound (b)
To obtain the terminal isocyanate compound (X) of the reaction product of the polyisocyanate compound (c) with the polyisocyanate compound (c) is equivalent to the total hydroxyl groups of the compound (a) and the diol compound (b) of the isocyanate group of the polyisocyanate compound (c). The reaction is preferably carried out so that the ratio becomes 1.0 or more, more preferably 1.1 to 3.0. When the charge equivalent ratio is less than 1.1, the isocyanate group equivalent is small, and the cured coating film has poor solder heat resistance and electroless gold plating resistance. When it is greater than 3.0, the isocyanate group equivalent is large and the developability is high. However, the flexibility of the cured coating film may decrease. The reaction may be carried out by charging (a), (b) and (c) at the same time, or by reacting (a) and (c) in advance and then reacting with (b), (b) You may make (a) react after reacting with (c).

In order to react the compound (d) with the terminal isocyanate compound (X), the reaction is carried out such that the equivalent ratio of the hydroxyl group of (d) to the isocyanate group of the terminal isocyanate compound (X) is 1.0 or more. Is good,
It is more preferably 1.1 to 2.0. Equivalent ratio is 1.1
When it is smaller, the developability may be lowered, and when the equivalent ratio is larger than 2.0, the tack-free property and the flexibility of the cured film may not necessarily be good because the molecular weight does not increase.

Known diluents (solvents) can be used in the reaction, such as ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, dipropylene glycol dimethyl ether and dipropylene. Glycol ethers such as glycol diethyl ether, esters such as ethyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic hydrocarbons such as octane and decane,
Organic solvents such as petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha can be mentioned. In addition, carbitol (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (hydroxyethyl) isocinurate tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate pentaerythritol diacrylate monostearate, polyester acrylate, etc. It is also possible to use the reactive monomers of.

In order to accelerate the reaction between the isocyanate group and the hydroxyl group, for example, a tertiary amine or an organometallic compound can be used. Examples of tertiary amines include triethylamine, N, N-dimethylcyclohexylamine, triethylenediamine and the like. Examples of organometallic compounds include stannas octoate, dibutyltin diacetate, dibutyltin dilaurylate, and the like. The amount of the catalyst used is the reaction raw material mixture 1
It can be added preferably in a proportion of 0.01 to 5 parts by weight with respect to 00 parts by weight. The reaction temperature is 30 to 130.
It can be synthesized at 0 ° C, preferably 60 to 100 ° C. The reaction time is preferably 5 to 20 hours.

The reaction between the photosensitive resin (Y) obtained by sequentially reacting the terminal isocyanate compound (X) with the compound (d) and the polybasic acid anhydride (e) is carried out by the reaction of the hydroxyl group in the photosensitive resin (Y). The reaction can be carried out such that the equivalent ratio of the polybasic acid anhydride (e) to the group is 1.0 or less.
It is effective to use a reaction catalyst during the reaction. For example, when a tertiary amine, a quaternary ammonium salt or the like is used, the reaction time can be significantly shortened. Reaction temperature is 50
Can be synthesized at ~ 160 ° C, preferably 80-130
℃. The reaction time is preferably 1 to 5 hours.

Compound (a) and diol compound (b)
And the terminal isocyanate compound (X) of the reaction product of the polyisocyanate compound (c) and the photosensitive resin (Y) obtained by sequentially reacting the compound (d) with the polybasic acid anhydride (e). The acid value of the resulting photosensitive resin (Z) is, for example, 10 to 300 KOHmg / g, preferably 30 to 240 KOHmg / g.

Next, the photosensitive resist ink composition of the present invention will be described. The epoxy resin (B) used in the composition is, for example, one having at least one epoxy group in one molecule, and is bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin. , Phenol novolac type epoxy resin, cresol novolac type epoxy resin,
Dicyclopentadiene-phenol novolac type epoxy resin, phenol-cresol novolac co-condensation type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin or halogenated epoxy compounds thereof, triphenylolmethane type epoxy resin, alkyl Epoxy resin obtained by reacting polychlorophenol such as substituted triphenylol methane type epoxy resin and tetraphenylolethane type epoxy resin with epichlorohydrin, epoxy resin obtained by reacting polyfunctional hydroxynaphthalene with epichlorohydrin, silicone modification Epoxy resin, ε-
Examples thereof include caprolactone-modified epoxy resin, glycidylamine type epoxy resin obtained by reaction of epichlorohydrin with primary or secondary amine, and heterocyclic epoxy resin such as triglycidyl isocyanurate. You may use together 1 type (s) or 2 or more types of these epoxy resins. Further, it is also effective to use an isocyanate-modified epoxy resin for the purpose of improving Toughness while securing Tg, or to use a phosphorus-containing epoxy resin from the viewpoint of imparting flame retardancy. A specific example of the isocyanate-modified epoxy resin is a synthetic one using the above epoxy resin and an isocyanate compound in the presence of an oxazolidone-forming catalyst. For details, see JP-B-53-45757.
It is described in Japanese Patent No. 43657. Commercially available isocyanate-modified epoxy resins having an oxazolidone ring include trade names XAC4151 and XAC4152 (manufactured by Asahi Kasei Epoxy Co., Ltd.).

The purpose of using the epoxy resin (B) as the thermosetting component is to improve various properties as a solder resist such as adhesion, heat resistance and plating resistance.

The epoxy resin (B) is used alone or as a mixture of two or more kinds, and the amount of the epoxy resin contained in the composition of the present invention is 1 to 80% by weight, preferably 20 to 60% by weight in the composition. % By weight.

When the epoxy resin (B) as the thermosetting component is used, it is desirable to use an epoxy curing agent together in order to further improve properties such as adhesion, chemical resistance and heat resistance. Examples of such epoxy resin curing agents include imidazole derivatives, phenol derivatives, dicyandiamide, dicyandiamide derivatives, hydrazide derivatives, amines, acid anhydrides and the like. The above curing agents may be used alone or in combination of two or more. The amount of the above curing agent used is such that the amount of active hydrogen in the epoxy curing agent is 0.5 to 1. with respect to the epoxy groups of the epoxy resin (B).
A ratio of 2 equivalents is preferable.

Specific examples of the photopolymerization initiator (C) include benzoins, acetophenones, anthraquinones, thioxanthones, benzophenones, phosphorus compounds, and the like. For benzoins, for example, benzoin, benzoin methyl ether, Derivatives such as benzoin isopropyl ether, acetophenones include acetophenone,
Derivatives such as 2,2-dimethoxy-2-phenylacetophenone, anthraquinones, 2-methylanthraquinone, 2-chloroanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, derivatives, thioxanthones, thioxanthone, 2 Derivatives such as 4,4-dimethylthioxanthone and benzophenones include benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-dichlorobenzophenone and N, N-.
Derivatives such as dimethylaminobenzophenone, 2,4,6
Examples of trimethylbenzoyldiphenylphosphine oxide and phosphorus include acylphosphine oxide, which can be used alone or in combination of two or more kinds. The amount of the photopolymerization initiator (C) contained in the composition of the present invention is 0.5 to 25% by weight in the composition,
It is preferably 1.0 to 20% by weight. Further, the photopolymerization initiator (C) may be used in combination with a known photosensitizer. Specific examples thereof include triethanolamine, tripropanolamine, triethylamine, N, N-dimethylamino acid benzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, and pentyl-4-dimethylaminobenzoate. The above photosensitizers can be used alone or in combination of two or more.

The polymerizable unsaturated compound and / or the solvent (D) are curable and / or curable with respect to active energy rays.
Alternatively, it is used for the purpose of improving coatability when used as a resist ink. As the polymerizable unsaturated compound, active energy ray curable monomers are preferable, and 2-hydroxyethyl acrylate, 2-
Hydroxypropyl acrylate, N-pyrrolidone, N-
Acryloylmorpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, methoxy polyethylene glycol acrylate, ethoxy polyethylene glycol acrylate, melamine acrylate, phenoxy Ethyl acrylate, phenoxypropyl acrylate, ethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polydipropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexa Acrylate, glycerindia Relate, isobornyl acrylate, dicyclopentenyl oxyethyl acrylate and the corresponding various methacrylates thereof. These polymerizable unsaturated compounds (D) are one kind or two kinds.
You may use together 1 or more types.

On the other hand, as the solvent, methyl ethyl ketone,
Methyl isobutyl ketone, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene and xylene, ethyl cellosolve, butyl cellosolve, carbitol, carbitol such as butyl carbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, ethyl Examples thereof include carbitol acetate. The solvent used in the reaction may be used as it is. These solvents may be used alone or in combination of two or more.

The polymerizable unsaturated compound and / or the solvent (D) are used alone or as a mixture of two or more kinds. The amount of the polymerizable unsaturated compound and / or the solvent (D) used is 10 to 200 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). Is. If the amount used is less than 10 parts by weight, the photosensitivity is too low, while if it exceeds 200 parts by weight, the viscosity becomes too low when used as a resist ink, and a coating film of the required thickness is formed by one application. May become difficult, and the resistance as a cured coating film becomes insufficient.

In addition to the above, the composition of the present invention may optionally contain silica, calcium carbonate, barium sulfate, clay,
Inorganic fillers such as talc, phthalocyanine green, phthalocyanine blue, leuco dyes, coloring pigments such as titanium oxide and carbon black, defoaming agents such as silicone oil,
In addition to various additives such as a leveling agent, a polymerization inhibitor such as hydroquinone, resorcinol, catechol, pyroganol, hydroquinone monomethyl ether, t-butyl catechol and phenothiazine may be used. These additives are used in an amount of 0.001 to 150% by weight based on the composition.

The composition of the present invention is obtained by blending various components preferably in the above proportions and uniformly stirring and kneading with a resolver, roll mill or the like. When the composition of the present invention is used as a resist ink, it can be cured by the following method to obtain a cured product. That is, 1 is applied to a printed wiring board by a method such as a screen printing method, a spray method, a curtain coating method, a roll coating method, a dip coating method, a doctor knife method or an electrostatic coating method.
The composition of the present invention is applied in a film thickness of 0 to 200 μm, and the coating film is dried at 60 to 110 ° C. to remove the organic solvent. After drying, the negative film is placed in direct contact with the coating film or indirectly (non-contact) and irradiated with ultraviolet rays (exposure) using a high pressure mercury lamp, a metal halide lamp, etc.
After washing with a dilute alkaline solution of about 2%, to further improve various physical properties, irradiation with ultraviolet rays and / or heating (for example, 30 to 60 minutes at 100 to 200 ° C.) is performed to sufficiently cure and cure. Obtain a coating.

[0035]

EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples. In addition, "part" in each example shows a weight standard.
The present invention is not limited to these examples.

Synthesis Example 1 Bisphenol A type epoxy resin [YD-128, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 186] 186 parts (0.
5 mol), acrylic acid 72 parts (1.0 mol), methylhydroquinone 0.16 parts, carbitol acetate 13
0 part was charged, heated to 100 ° C., and after confirming that the above mixture was uniformly dissolved, dimethylbenzylamine 1.5 was added.
A part was charged, heated to 115 ° C., and reacted for about 8 hours.
The reaction product was once cooled to room temperature, charged with 45.6 parts (0.3 mol) of tetrahydrophthalic anhydride, heated to 100 ° C. and reacted for about 4 hours to obtain an acid anhydride-modified epoxy acrylate (d1). Next, in a nitrogen stream atmosphere,
749 parts (3.375 mol) of isophorone diisocyanate, polyether polyol [ACTCOL 22-1
10, manufactured by Mitsui Takeda Chemical Co., Ltd.] 382.5 parts (0.375 mol), dimethylolbutanoic acid 222 parts (1.5 mol), carbitol acetate 1315 parts,
Charge 6.0 parts of dibutyltin dilaurylate, 70 ℃
The mixture was heated to room temperature and reacted for about 6 hours. After stopping the nitrogen stream, the reaction mixture was cooled to room temperature, and the acid anhydride-modified epoxy acrylate (d
1) 2479 parts (2.875 mol) were charged, heated to 80 ° C. and reacted for about 5 hours. Solid content acid value 58.4KO
A photosensitive resin (1) having Hmg / g and a solid content concentration of 60% was obtained.

Synthesis Example 2 Bisphenol A type epoxy resin [YD-128, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 186] 186 parts (0.
5 mol), acrylic acid 72 parts (1.0 mol), methylhydroquinone 0.16 parts, carbitol acetate 13
0 part was charged, heated to 100 ° C., and after confirming that the above mixture was uniformly dissolved, dimethylbenzylamine 1.5 was added.
A part was charged, heated to 115 ° C., and reacted for about 8 hours.
The reaction product was once cooled to room temperature, charged with 30.4 parts (0.2 mol) of tetrahydrophthalic anhydride, heated to 100 ° C. and reacted for about 4 hours to obtain an acid anhydride-modified epoxy acrylate (d2). Next, in a nitrogen stream atmosphere,
Dicyclohexylmethane diisocyanate 655 parts (2.5 mol), polyether polyol [ACTCOL 22-110, manufactured by Mitsui Takeda Chemical Co., Ltd.] 510
Parts (0.5 mol), dimethylolbutanoic acid 148 parts (1.0 mol), carbitol acetate 1214 parts,
Charge 5.0 parts of dibutyltin dilaurate, 70 ℃
The mixture was heated to room temperature and reacted for about 6 hours. After stopping the nitrogen stream, the reaction mixture was cooled to room temperature, and the acid anhydride-modified epoxy acrylate (d
2) 1543 parts (1.875 mol) were charged, heated to 80 ° C., and reacted for about 5 hours. The reaction product was once cooled to room temperature, charged with 121.6 parts (0.8 mol) of tetrahydrophthalic anhydride, heated to 110 ° C. and reacted for about 4 hours. A photosensitive resin (2) having a solid content acid value of 57.0 KOH mg / g and a solid content concentration of 60% was obtained.

Synthesis Example 3 Bisphenol F type epoxy resin [R-110, manufactured by Mitsui Chemicals, Inc., epoxy equivalent 169] 169 parts (0.5
Mol), acrylic acid 50.4 parts (0.7 mol), dimethylolbutanoic acid 44.4 parts (0.3 mol), methylhydroquinone 0.10 part, carbitol acetate 152.
Then, after confirming that the above mixture was uniformly dissolved, 2.5 parts of triethylamine was charged, heated to 110 ° C., and reacted for about 20 hours. The reaction product was once cooled to room temperature, charged with 91.2 parts (0.6 mol) of tetrahydrophthalic anhydride, heated to 100 ° C. and reacted for about 4 hours to obtain an acid anhydride-modified epoxy acrylate (d3). Next, under a nitrogen stream atmosphere, isophorone diisocyanate 833 parts (3.75 mol), polyester polyol [P-1020, manufactured by Kuraray Co., Ltd.] 628 parts (0.625 mol), dimethylol butanoic acid 278 parts. (1.875 mol), carbitol acetate 1454 parts, and dibutyltin dilaurylate 6.0 parts were charged, heated to 70 ° C., and reacted for about 8 hours. After stopping the nitrogen stream, the reaction mixture was cooled to room temperature, and 1770 parts (1.75 mol) of the acid anhydride-modified epoxy acrylate (d3) was charged under a dry air stream atmosphere.
The mixture was heated to 80 ° C. and reacted for about 6 hours. Solid content acid value 7
A photosensitive resin (3) having 4.9 KOHmg / g and a solid content concentration of 60% was obtained.

Synthesis Example 4 Bisphenol A type epoxy resin [YD-128, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 186] 186 parts (0.
5 mol), 36 parts (0.5 mol) of acrylic acid, 74 parts (0.5 mol) of dimethylolbutanoic acid, 0.10 part of methylhydroquinone, 192 parts of carbitol acetate, and heated to 100 ° C. After confirming that the mixture was uniformly dissolved, charged with 3.0 parts of triethylamine, 1
It was heated to 10 ° C. and reacted for about 25 hours. Once the reaction is cooled to room temperature, tetrahydrophthalic anhydride 152
(1.0 mol), charged at 100 ° C. and reacted for about 5 hours to obtain an acid anhydride-modified epoxy acrylate (d4)
Got Next, in a nitrogen stream atmosphere, 1061 parts (4.05 mol) of dicyclohexylmethane diisocyanate and polyether polyol [ACTCOL 22-1
10, manufactured by Mitsui Takeda Chemical Co., Ltd.] 1071 parts (1.
(05 mol), dimethylolbutanoic acid 222 parts (1.5 mol), carbitol acetate 1996 parts, and dibutyltin dilaurate 5.0 parts were charged and heated to 70 ° C.
The reaction was carried out for about 8 hours. After stopping the nitrogen flow, the reaction mixture was cooled to room temperature, and under an atmosphere of dry air, 2560 parts (2.0 mol) of the acid anhydride-modified epoxy acrylate (d4) was charged and heated to 80 ° C. And reacted for about 6 hours. A photosensitive resin (4) having a solid content acid value of 74.4 KOH mg / g and a solid content concentration of 60% was obtained.

Synthesis Example 5 Bisphenol A type epoxy resin [YD-128, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 186] 186 parts (0.
5 mol), acrylic acid 43.2 parts (0.6 mol), dimethylolbutanoic acid 59.2 parts (0.4 mol), methylhydroquinone 0.10 part, carbitol acetate 17
6 parts were charged and heated to 100 ° C., and after confirming that the above mixture was uniformly dissolved, 3.0 parts triethylamine was charged, heated to 110 ° C., and reacted for about 20 hours. The reaction product was once cooled to room temperature, charged with 121.6 parts (0.8 mol) of tetrahydrophthalic anhydride, heated to 100 ° C. and reacted for about 5 hours to obtain an acid anhydride-modified epoxy acrylate (d5). Next, 655 parts of dicyclohexylmethane diisocyanate (2.
5 mol), polyester polyol [P-1020,
Kuraray Co., Ltd.] 1005 parts (1.0 mol), dimethylolbutanoic acid 74 parts (0.5 mol), carbitol acetate 1500 parts, dibutyltin dilaurylate 6.
0 part was charged, heated to 70 ° C., and reacted for about 8 hours.
After stopping the nitrogen flow, cool the reaction mixture to room temperature,
In an atmosphere of dry air, 1759 parts (1.5 mol) of the acid anhydride-modified epoxy acrylate (d5) was charged, heated to 80 ° C., and reacted for about 6 hours. Once the reaction has cooled to room temperature, tetrahydrophthalic anhydride 76
A part (0.5 mol) was charged, heated to 110 ° C. and reacted for about 5 hours. A photosensitive resin (5) having a solid content acid value of 62.7 KOH mg / g and a solid content concentration of 60% was obtained.

Synthesis Example 6 Bisphenol F type epoxy resin [R110, manufactured by Mitsui Chemicals, Inc., epoxy equivalent 169] 169 parts (0.5 mol), acrylic acid 36 parts (0.5 mol), dimethylolbutanoic acid 74 parts (0.5 mol), methylhydroquinone 0.10 part, and carbitol acetate 185 parts were charged, heated to 100 ° C., and after confirming that the above mixture was uniformly dissolved, charged with triethylamine 3.0 parts, 11
The mixture was heated to 0 ° C. and reacted for about 25 hours. The reaction product was once cooled to room temperature, charged with 152 parts (1.0 mol) of tetrahydrophthalic anhydride, heated to 100 ° C. and reacted for about 5 hours to obtain an acid anhydride-modified epoxy acrylate (d6). Next, under a nitrogen stream atmosphere, isophorone diisocyanate 832.5 parts (3.75 mol), polycarbonate polyol [PMHC-1050, manufactured by Kuraray Co., Ltd.] 747 parts (0.75 mol), dimethylolbutanoic acid. 222 parts (1.5 mol), carbitol acetate 1
662 parts and 6.5 parts of dibutyltin dilaurylate were charged, heated to 70 ° C. and reacted for about 8 hours. After stopping the nitrogen stream, the reaction mixture was cooled to room temperature, and under an atmosphere of a dry air stream, 2463 parts (2.0 mol) of the acid anhydride-modified epoxy acrylate (d6) was charged, and the temperature was adjusted to 80 ° C.
The mixture was heated to room temperature and reacted for about 6 hours. Once the reaction was cooled to room temperature, 76 parts of tetrahydrophthalic anhydride (0.5
Mol) was charged, and the mixture was heated to 110 ° C. and reacted for about 4 hours. Solid content acid value 93.5 KOHmg / g, solid content concentration 6
0% of photosensitive resin (6) was obtained.

Synthesis Example 7 Bisphenol A type epoxy resin [YD-128, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 186] 186 parts (0.
5 mol), 54 parts (0.75 mol) of acrylic acid, 37 parts (0.25 mol) of dimethylolbutanoic acid, 0.15 parts of methylhydroquinone and 151 parts of carbitol acetate were charged and heated to 100 ° C. After confirming that the mixture was uniformly dissolved, 2.5 parts of dimethylbenzylamine was charged, heated to 110 ° C., and reacted for about 15 hours. The reaction product was once cooled to room temperature, charged with 76 parts (0.5 mol) of tetrahydrophthalic anhydride, heated to 100 ° C. and reacted for about 4 hours to obtain an acid anhydride-modified epoxy acrylate (d7). Next, under a nitrogen stream atmosphere, 555 parts (2.5 mol) of isophorone diisocyanate, 1020 parts (1.0 mol) of polyether polyol [ACTCOL 22-110, manufactured by Mitsui Takeda Chemical Co., Ltd.], diester 74 parts (0.5 mol) of methylolbutanoic acid, 1402 parts of carbitol acetate and 5.0 parts of dibutyltin dilaurate were charged, heated to 70 ° C. and reacted for about 6 hours. After stopping the nitrogen stream, the reaction mixture was cooled to room temperature, and 1513 parts (1.5 mol) of the acid anhydride-modified epoxy acrylate (d7) was charged under a dry air stream atmosphere and heated to 80 ° C. For about 5 hours. The reaction product was once cooled to room temperature, charged with 76 parts (0.5 mol) of tetrahydrophthalic anhydride, and heated to 110 ° C. for about 4 minutes.
Reacted for hours. Solid content acid value 50.4 KOHmg / g,
A photosensitive resin (7) having a solid content concentration of 60% was obtained.

Comparative Synthesis Example 1 Bisphenol A type epoxy resin [YD-128, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 186] 781 parts (2.
1 mol), 302 parts of acrylic acid (4.2 mol), 0.60 parts of methylhydroquinone, 1 carbitol acetate
After charging 083 parts and heating to 100 ° C. and confirming that the above mixture was uniformly dissolved, 5.0 parts of triphenylphosphine was charged and heated to 110 ° C. and reacted for about 18 hours. Once the reaction product was cooled to room temperature, 222 parts (1.5 mol) of dimethylolbutanoic acid, 555 parts (2.5 mol) of isophorone diisocyanate, 1.0 part of dibutyltin dilaurate were charged and heated to 70 ° C. The reaction was carried out for about 6 hours. The reaction mixture was cooled to room temperature, charged with 312 parts (2.05 mol) of tetrahydrophthalic anhydride,
The mixture was heated to 110 ° C. and reacted for about 5 hours. Solid content acid value 9
A photosensitive resin (8) having a concentration of 1.0 KOH mg / g and a solid content concentration of 66.7% was obtained.

Comparative Synthesis Example 2 Isophorone diisocyanate 8 under a nitrogen stream atmosphere
88 parts (4.0 mol), 296 parts of dimethylolbutanoic acid (2.0 mol), polyether polyol [Actcor 22-110, manufactured by Mitsui Takeda Chemicals, Inc.] 102
0 part (1.0 mol), carbitol acetate 1312
Part, 1.0 part of dibutyltin dilaurate was charged, and
The mixture was heated to 0 ° C. and reacted for about 6 hours. The reaction mixture is cooled to room temperature and 2-hydroxyethyl acrylate 232
(2.0 mol) was added, the nitrogen flow was stopped, and then 80
Heat to ℃, react for about 2 hours, solid content acid value 46.0K
A photosensitive resin (9) having an OH mg / g and a solid content concentration of 65% was obtained.

Comparative Synthesis Example 3 Cresol novolac type epoxy resin [Epotote YD
CN-704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 21
0, softening point 90 ° C.] 210 parts, acrylic acid 72 parts (1 mol), methyl hydroquinone 0.28 parts, carbitol acetate 232.6 parts were charged and heated to 95 ° C. to uniformly dissolve the above mixture. After confirming the above, 1.4 parts of triphenylphosphine was charged and heated to 100 ° C.
The reaction was carried out for 0 hours to obtain a reaction product having an acid value of 0.5 mgKOH / g. This was charged with 66.9 parts (0.44 mol) of tetrahydrophthalic anhydride, heated to 90 ° C. and reacted for about 6 hours to obtain a photosensitive resin having a solid content acid value of 70.0 KOHmg / g and a solid content concentration of 60%. (10) was obtained.

Examples 1 to 7 and Comparative Examples 1 to 3 Using the photosensitive resins obtained from the above-mentioned synthetic examples and comparative synthetic examples, a photosensitive resist was kneaded in a three-roll mill in accordance with the compounding ratio shown in Table 1. An ink composition was prepared. Next, the composition is applied to a pre-degreased printed circuit board by a screen printing method so as to have a dry film thickness of 30 to 40 μm, pre-dried at 80 ° C. for 20 minutes, and then cooled to room temperature to form a dried coating film. Obtained. A negative film having a resist pattern is brought into close contact with this coating film, exposed to 350 mJ / cm ² using an ultraviolet exposure device, the negative film is removed, and then a 1% sodium carbonate aqueous solution is used to spray pressure 2.0 kgf / cm 2. ^It was developed at ² for 60 seconds to dissolve and remove the unexposed portion. Then, using a hot air dryer, 150
After heat-curing at 30 ° C. for 30 minutes, a test piece for the following adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance test, etc. was obtained. The resulting coating film was evaluated for various physical properties according to the test methods described below. The evaluation results of these tests are shown in Tables 2 and 3. However, the developability was evaluated by using coating films with different predrying times at 80 ° C. as test samples.

[0047]

[Table 1]

* 1: 1,3,5-triglycidyl isocyanurate [manufactured by Nissan Kagaku Co., Ltd.] * 2: Irgacure 907, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropane-
1-one [Ciba Geigy] * 3: Kayacure DETX-S, 2,4-diethylthioxanthone [Nippon Kayaku Co., Ltd.] * 4: Light acrylate TMP-A, trimethylolpropane triacrylate [Kyoeisha Chemical Co., Ltd.] * 5: NK ester APG-200, tripropylene glycol diacrylate [Shin-Nakamura Chemical Co., Ltd.] * 6: Aerosil 300, [Japan Aerosil Co., Ltd.]

(Developability) Predrying time is 20 minutes, 40
Minutes, 60 minutes, 80 minutes, 100 minutes, 140 minutes, the dry coating film was developed with a 1% sodium carbonate aqueous solution at a spraying pressure of 2.0 kgf / cm ² for 60 seconds, and the presence or absence of the coating film after development. Was observed and evaluated according to the following criteria. ◯: Ink was completely removed during development and development was possible. X: Some parts cannot be developed during development.

(Adhesion) According to the test method of JIS D 0202, cross-cuts were put on the cured film in a grid pattern, and then the state of peeling after a peeling test with cellophane tape was visually judged. The evaluation was performed based on the following criteria. ◯: No peeling at all. Δ: The cross cut part was slightly peeled off. X: The coating film is peeled off.

(Solder Heat Resistance) In accordance with the test method of JIS C 6481, the test piece was immersed in a solder bath at 260 ° C. for 10 seconds three times, taken out, and then observed for change in appearance. The evaluation was performed based on the following criteria. ○: No change in appearance. Δ: Discoloration of the cured film was observed. X: The cured film has floating, peeling, and solder submergence.

(Electroless Gold Plating Resistance) As a pretreatment of a test piece, it is immersed in an acidic degreasing solution at 30 ° C. → immersion water washing → soft etching treatment → immersion water washing → catalyst (immersion in nickel plating catalyst solution at 30 ° C. for 7 minutes ) → The immersion washing process was performed. Next, in the electroless nickel plating step, the test piece is dipped in a nickel plating solution (85 ° C., PH = 4.6) for 20 minutes → acid dipped for 1 minute (10 vol% sulfuric acid aqueous solution at room temperature) →
Immersion water washing is performed, and finally, as an electroless gold plating step, the test piece is immersed in a gold plating solution (95 ° C., PH = 6, 3% by volume of potassium gold cyanide for 3 minutes) → immersion water washing → 6
Immersion in hot water at 0 ° C Washing with water → After thoroughly washing with water → Drain the water well →
Electroless gold plating was performed in the drying step, and the test piece was observed for changes in appearance and peeling test using cellophane tape. The evaluation was performed based on the following criteria. Good: No change in appearance and no peeling of the resist. Δ: There is no change in appearance, but slight peeling of the resist is seen. X: The resist floated or the plating diving was observed, and the peeling of the resist was large in the peeling test.

(PCT resistance) A test piece was tested at 121 ° C. for 2 at.
m, the appearance of the coating film after standing for 100 hours in a saturated steam atmosphere was judged. The evaluation was performed based on the following criteria. ○: The coating film does not swell or peel off. X: Swelling or peeling.

(Flexible) polyimide film (thickness: 10
0 μm) and the composition is applied to a film thickness of 15 μm and dried.
The resist film was exposed to light, developed, and heated, and the obtained test piece was bent 180 ° from the back surface so that the cured surface of the resist was on the outside, and the appearance of the resist film was observed. The evaluation was performed based on the following criteria. ⊚: No change. ◯: Slight streaks remain. Δ: Streaks remain. X: A crack occurs.

(Tensile Test) A cured film of the above composition (film thickness: 50) according to the test method of JIS K 7127.
μm) was pulled at room temperature at a speed of 1 mm / min to measure the tensile elongation of the film.

[0056]

[Table 2]

[0057]

[Table 3]

As is clear from the evaluation results of Tables 2 and 3, the composition of the present invention has excellent alkali developability, and the cured product thereof has adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance, It can be seen that it has excellent flexibility.

[0059]

According to the present invention, in the field of electronic materials such as printed wiring board solder resists, semiconductor package solder resists, flexible printed wiring board resist inks, and high-density multilayer board interlayer insulating films, dilute alkaline aqueous solutions can be used. It has excellent developability, and the coating film after curing, especially when applied on a film, has little warpage when cured and has excellent flex resistance, and also flexibility, heat resistance, solder heat resistance, and adhesion. Provided are a photosensitive resin and a photosensitive resist ink composition which are excellent in water resistance and chemical resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G03F 7/027 502 G03F 7/027 502 513 513 515 515 (56) Reference JP-A-9-52925 (JP, A) 2000-137325 (JP, A) JP 60-90211 (JP, A) JP 2001-100410 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 18/00- 18/87

Claims (4)

(57) [Claims] 1. A compound (a) having at least one carboxyl group and two hydroxyl groups in one molecule, a diol compound (b), and a polyisocyanate compound having at least two isocyanate groups in one molecule ( A photosensitive resin obtained by reacting the terminal isocyanate compound (X) of the reaction product with c) with a compound (d) having a polymerizable unsaturated group, a carboxyl group and at least one hydroxyl group in one molecule ( Y). 2. The photosensitive resin (Y) according to claim 1,
Further, a photosensitive resin (Z) obtained by reacting a polybasic acid anhydride (e). 3. The photosensitive resin (Y) according to claim 1,
A photosensitive resist ink composition comprising (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a polymerizable unsaturated compound and / or a solvent. 4. The photosensitive resin (Z) according to claim 2,
A photosensitive resist ink composition comprising (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a polymerizable unsaturated compound and / or a solvent.