JP2013182174A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having excellent photosensitivity to active energy rays, allowing formation of a fine pattern, exhibiting excellent developability, insulating property, heat resistance and folding resistance in a cured coating film of the composition, and suitably used for a photosolder resist.SOLUTION: The photosensitive resin composition comprises: a photosensitive resin (A) having a double bond equivalent of 200 to 5000 g/eq, an acid value of 10 to 200 mgKOH/g and a weight average molecular weight of 1000 to 100000; at least one curing agent (B) selected from a non-blocked isocyanate compound and a blocked isocyanate compound; a photopolymerization initiator (C); and a fatty acid alkanolamide (D).

Description

  The present invention relates to a photosensitive resin composition useful for printed wiring boards and the like and a cured product thereof. More specifically, it is useful as a solder resist for flexible printed wiring boards and an interlayer electrical insulation material for multilayer printed wiring boards. It has excellent developability, and its cured film has flexibility (fold resistance), solder heat resistance, electrical The present invention relates to a photosensitive resin composition and a cured product thereof that give a cured product excellent in insulation and the like.

  In the soldering process that is performed when protecting the wiring (circuit) pattern formed on the board from the external environment or when mounting electronic components on the printed wiring board, solder does not adhere to unnecessary parts. In order to protect the printed wiring board, a protective layer called a coverlay or a solder mask is coated on the printed wiring board. Until now, since hard printed wiring boards have been the mainstream, the resist coating after curing mainly requires adhesion to the substrate and heat resistance in addition to pattern accuracy. However, in recent years, the use of flexible printed wiring boards has greatly increased, and the protective layer used for the wiring pattern formed on the polyimide film has adhesiveness with polyimide, flexibility, folding resistance, flame resistance, etc. Is required.

Conventionally, as a protective layer for flexible printed wiring boards, a polyimide film called a coverlay film is made by punching a mold that matches the pattern and then pasted using an adhesive, or by thermosetting applied by screen printing There are various types of inks, but for high density and high definition accompanying recent advances in electronics, UV curable photoresist type solder resist ink or dry film type solder resist that can be patterned with higher precision is available. It is being considered.

  In general, in the photo solder resist for flexible printed wiring boards, the photo solder resist conventionally used for rigid substrates can provide pattern accuracy, but the cured coating film is hard and has good adhesion to polyimide. Since it was bad, there existed a problem that sufficient flexibility, flexibility, and folding resistance were not obtained.

In recent years, many proposals have been made as flexible photo solder resists. For example, a resist ink composition is disclosed that includes a resin obtained by reacting succinic anhydride with an addition product of an epoxy resin having a bisphenol A skeleton in the main chain and an unsaturated group-containing monocarboxylic acid (Patent Document 1). ). Although this is excellent in developability, photosensitivity, adhesion, heat resistance, etc., there is a problem that flexibility and folding resistance are still insufficient. In addition, as a photosensitive thermosetting composition, a reaction product of a secondary hydroxyl group generated by an esterification reaction of a cresol novolak type epoxy compound and an unsaturated monocarboxylic acid, and a saturated or unsaturated polybasic acid anhydride, A reaction product of the secondary hydroxyl group and an unsaturated group-containing isocyanate compound has been proposed (Patent Document 2). Although these are very excellent in adhesion, solder heat resistance, and coating film resistance, there is a problem that flexibility and folding resistance are still insufficient.

There has also been proposed a photosensitive element containing a polymer obtained by copolymerizing a monomer containing (meth) acrylic acid and (meth) acrylic acid ester as a binder component (Patent Document 3). These are excellent in developability and resolution, but when used in flexible printed wiring board applications, sufficient adhesion, flexibility and folding resistance cannot be obtained.

In addition, a polymer obtained by reacting a polyol compound, a polybasic acid anhydride having two acid anhydride groups in the molecule, and a polyisocyanate compound further has one epoxy group in the molecule (meta ) A photosensitive resin composition containing a carboxyl group-containing urethane oligomer obtained by reacting an acrylate has been proposed (Patent Document 4). Although these have sufficient flexibility, they have an ester bond derived from half-esterification with a dibasic acid anhydride in the main chain, so that dehydration occurs at high temperatures and the main chain is easily cleaved. In addition, because the carboxyl group is directly linked to the main chain, the mobility of the carboxyl group is suppressed, so that the developability, various coating film resistance, and solder heat resistance It was not enough.

Moreover, the photosensitive resin composition which added the phosphorus type flame retardant is disclosed (patent document 5). In order to reduce the burden on the environment, these are made flame retardant by using a non-halogen flame retardant. However, in order to impart sufficient flame retardancy with a non-halogen flame retardant, it is necessary to add a large amount of flame retardant. In terms of coating film resistance and solder heat resistance, it was not sufficient. In other words, physical properties other than the flame retardancy required for the resist are deteriorated, so that it is not sufficient to achieve both the flame retardancy and other physical properties.

Further, as with the photosensitive resin of the present invention, a resin whose main chain is synthesized from an epoxy compound and a phenol compound is also disclosed. For example, after adding an alkylene oxide to a hydroxyl group in a polyhydroxy ether resin synthesized from a bisphenol type epoxy compound and a bisphenol compound, an acid anhydride and a (meth) acrylate having one epoxy group in the molecule are added. A carboxyl group-containing unsaturated polyhydroxy ether compound obtained by reaction is disclosed (Patent Document 6). This is due to the addition of alkylene oxide, which develops good developability and resolution with an alkaline aqueous solution and has excellent flexibility and flexibility, but tends to decrease solder heat resistance and chemical resistance. there were.

In addition, acid-modified vinyl obtained by acid-modifying vinyl ester synthesized from bisphenol-type epoxy compound, bisphenol compound and unsaturated carboxylic acid or (meth) acrylate having one epoxy group in the molecule with polybasic acid anhydride Esters are disclosed. (Patent Document 7). This is because the double bond is introduced at the end of the main chain, so the distance between the double bonds is large, and the flexibility and folding resistance of the cured coating film are excellent, but the solubility in an alkaline developer is poor and the developability is high. There was a problem that the resolution was still insufficient. As a similar example, an acid-modified vinyl ester synthesized from a phenol compound, an epoxy compound, an unsaturated carboxylic acid, and a polybasic acid anhydride has also been reported (Patent Document 8). This also has a large distance between double bonds, so it can give flexibility to the cured coating film and has excellent flexibility and cold cycle crack resistance, but has conflicting properties such as tack-free properties, developability, and resolution. I was not satisfied with the balance.

It contains a photopolymerizable unsaturated compound obtained by reacting a compound having a phenolic hydroxyl group, a (meth) acrylate having one epoxy group in the molecule and an acid anhydride, and a polyfunctional dihydroxybenzoxazine. A photosensitive resin composition is disclosed (Patent Document 9). This is because the main chain is composed of a compound having a phenolic hydroxyl group, and the cured coating film has a benzoxazine skeleton. Due to the lack of properties, cracks due to thermal shock are likely to occur.

As described above, the conventional technology has both sufficient flexibility and folding resistance required as a protective layer for a flexible printed wiring board and developability and solder heat resistance capable of realizing high-precision patterning, and A resin composition that can satisfy all physical properties such as electrical insulation, chemical resistance, and flame retardancy necessary as a protective layer for a circuit and a cured product thereof have not been obtained.

Printed wiring boards are required to have high precision and high density in order to reduce the size and weight of portable devices and improve communication speed. Flexible printed wiring used mainly in the bent and connected areas of devices. The trend is the same for boards. Against this background, demands for protective layers for flexible printed wiring boards are becoming more and more advanced, and developability that can achieve higher definition of resist patterns and higher flexibility than conventional requirements. Performance that satisfies solder heat resistance, substrate adhesion, high insulation, coating film resistance, flame retardancy, etc. is required while maintaining the properties and folding resistance. Currently, commercially available photo solder resists cannot sufficiently meet these requirements.
Japanese Patent No. 3281473 Japanese Patent No. 2707495 JP 2004-279479 A JP 2001-159815 A JP 2006-251715 A Japanese Patent No. 3125424 JP 2003-73450 A Japanese Patent No. 4376290 JP 2006-343384 A

  The present invention improves the developability with a dilute alkaline aqueous solution without impairing the photosensitivity to active energy rays, can form a finer pattern, and the cured coating obtained through a post-curing (post-cure) step is flexible. Providing a photosensitive resin composition suitably used for a photo solder resist having excellent properties, insulating properties, adhesion, solder heat resistance, coating film resistance, and the like, and a cured product thereof, as well as a method for producing a photosensitive resin. Objective.

As a result of intensive studies, the present inventors have found that a specific photosensitive resin composition can solve the above problems, and have completed the present invention.
That is, a photosensitive resin (A) having a double bond equivalent of 200 to 5000 g / eq, an acid value of 10 to 200 mg KOH / g, and a weight average molecular weight of 1,000 to 100,000, an epoxy group-containing compound, an isocyanate group-containing compound, and blocking The present invention relates to a photosensitive resin composition containing at least one compound (B) selected from the group consisting of isocyanate group-containing compounds, a photopolymerization initiator (C), and a fatty acid alkanolamide (D).

Moreover, 2nd invention is related with said photosensitive resin composition whose melting | fusing point of fatty-acid alkanolamide (D) is -10-80 degreeC.
Moreover, 3rd invention is related with said photosensitive resin composition containing 1-30 weight part of fatty acid alkanolamides (D) with respect to 100 weight part of solid content of the photosensitive resin (A).
Moreover, 4th invention is related with said photosensitive resin composition containing 1-50 weight part of hardening | curing agents (B) with respect to 100 weight part of solid content of the photosensitive resin (A).

Moreover, 5th invention is photosensitive resin (A),
Resin (c) containing a side chain hydroxyl group by reacting an epoxy compound (a) having at least two epoxy groups in one molecule with a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule. Produces
Reacting the side chain hydroxyl group-containing resin (c) with the polybasic acid anhydride (d) to produce a carboxyl group-containing resin (e);
Hydroxyl group-containing photosensitive resin (A) obtained by reacting the carboxyl group-containing resin (e) with an epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group -1) or
It is a carboxyl group-containing photosensitive resin (A-2) obtained by reacting the hydroxyl group in the hydroxyl group-containing resin (A-1) with the acid anhydride group in the polybasic acid anhydride (d). The above-mentioned photosensitive resin composition characterized by the above.

Moreover, 6th invention is related with said photosensitive resin composition which contains a flame retardant (E) further.
Moreover, 7th invention is related with the hardened | cured material formed by hardening | curing said photosensitive resin composition.
Moreover, 8th invention is related with the photosensitive soldering resist ink containing said photosensitive resin composition and a solvent.
Moreover, 9th invention is related with the dry film type photosensitive soldering resist containing said photosensitive resin composition.

  According to the present invention, it has excellent photosensitivity to active energy rays, and can form a fine pattern by development with a dilute alkaline aqueous solution, and a cured coating film obtained through a post-curing (post-cure) process is flexible, insulating, and adhesive. It is excellent in solder heat resistance, coating film resistance, etc., and can now provide a photosensitive resin composition suitably used for a photo solder resist and its cured product, and further a method for producing a photosensitive resin. It was. The photosensitive resin composition of the present invention includes a solder resist for flexible printed wiring boards, a photosensitive coverlay film, a plating resist, an interlayer electrical insulating material for wiring boards, a photosensitive optical waveguide, and a silver paste on a polyethylene terephthalate film. It can be suitably used as a coverlay resist for a flexible printed circuit board formed with a circuit by printing a conductive ink such as carbon paste.

The photosensitive resin composition of the present invention comprises the photosensitive resin (A), a compound (B) that is at least one selected from an epoxy group-containing compound, a non-blocked isocyanate compound, and a blocked isocyanate compound, and photopolymerization initiation. In addition to the agent (C), a fatty acid alkanolamide (D) is included as an additive.
First, the fatty acid alkanolamide (D) will be described. The fatty acid alkanolamide (D) is added for the purpose of improving developability and folding resistance.
Alkanol is a non-cyclic saturated hydrocarbon in which one or more hydrogens are replaced by a hydroxyl group, and is also called a saturated alcohol, paraffin alcohol, or the like. Amide is obtained by replacing hydrogen of ammonia (NH ₃ ) with R ₁ —CO—. Therefore, the fatty acid alkanolamide (D) of the present invention has a structure in which hydrogen is substituted with at least R ₁ —CO— and —R ₂ —OH centering on N ₁ , and R ₁ —CON (—R ₂ —OH). ₂ or an amphiphilic compound having a hydrophilic group and a hydrophobic group, represented by a chemical formula of R ₁ —CONH (—R ₂ —OH). These are usually used as surfactants in cosmetics, detergents, shampoos and the like.

Since fatty acid alkanolamide (D) has a hydrophilic group, the developability of the photosensitive resin composition can be improved. Furthermore, since it has the effect of plasticizing the photosensitive resin composition, folding resistance can be imparted and the performance of less warping after crosslinking can be imparted.
In addition to imparting developability and folding resistance, it is important not to adversely affect other physical properties. For example, the fatty acid alkanolamide (D) is not easily left in the photosensitive resin composition after development because excess fatty acid alkanolamide (D) is washed away with a developer during development. Moreover, even if it remains in the photosensitive resin composition after development, because it has an alcohol site that reacts with the blocked isocyanate or isocyanate compounded as the curing agent (B), it can be incorporated into the composition by thermal curing, There is little bleed out after heat curing.

Although it does not specifically limit as a fatty acid which forms the hydrophobic group of fatty acid alkanolamide (D), As a suitable example, lauric acid, myristic acid, palmitic acid, oleic acid, isostearic acid, etc. are mentioned. From the viewpoint of developability and folding resistance, those having 8 to 18 carbon atoms in the fatty acid moiety are preferred.
The alcohol that forms the hydrophilic group of the fatty acid alkanolamide (D) is not particularly limited, and preferred examples include methanol, ethanol, propanol, propanol, butanol, and pentanol. From the viewpoints of developability and folding resistance, those having 2 to 4 carbon atoms in the alcohol moiety are preferred. Those having a carbon number greater than 4 tend to be inferior in developability because of less hydrophilic effect.

Preferable examples of the fatty acid alkanolamide (D) include coconut oil fatty acid monoethanolamide, coconut oil fatty acid diethanolamide, coconut fatty acid isopropanolamide, lauric acid monoethanolamide, lauric acid diethanolamide, lauric acid isopropanolamide, oleic acid diethanolamide. And isostearic acid diethanolamide.
Commercially available products include Dainol 300 (coconut oil fatty acid diethanolamide), Dainoru CDE (coconut oil fatty acid diethanolamide), Nihon Yushi Co., Ltd. StarDL (lauric acid diethanolamide), Stahome DF-4. (Coconut oil fatty acid diethanolamide), stahome DO (oleic acid diethanolamide), stahome DOS (oleic acid diethanolamide), stahome MF (coconut oil fatty acid monoethanolamide), stahome LIPA (lauric acid isopropanolamide), etc. Can be illustrated.

The fatty acid alkanolamide (D) preferably has a melting point of -10 to 80 ° C. When the temperature is lower than -10 ° C, the tack before thermosetting tends to be strong, resulting in problems such as poor handling when formed into a dry film and poor bubble removal when embedded in a circuit by vacuum lamination. There is a case. When the temperature is 80 ° C. or higher, the embedding property in the circuit tends to deteriorate. More preferably, it is 25-75 degreeC.
The addition amount of the fatty acid alkanolamide (D) is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solid content of the photosensitive resin (A). If the amount is less than 1 part by weight, the developability and folding resistance may be insufficiently improved. If the amount is more than 30 parts by weight, the insulation reliability and heat resistance may be lowered. More preferably, it is 1-10 weight part.

<Photosensitive resin (A)>
The photosensitive resin (A) having a double bond equivalent of 200 to 5000 g / eq, an acid value of 10 to 200 mg KOH / g, and a weight average molecular weight of 1,000 to 100,000 is not particularly limited. For example, an acrylic resin, a polyester resin, Examples of the resin include urethane resin, urea resin, urethane urea resin, epoxy resin, polyamide resin, and polyimide resin. These can be used alone or in combination.

  The acid value of the photosensitive resin (A) of the present invention is 10 to 200 mgKOH / g, preferably 30 to 150 mgKOH / g. When the acid value is less than 10 mg KOH / g, sufficient developability may be difficult to obtain. For example, the film may remain as a residue in a portion where the film is dissolved and removed during development. On the other hand, when the acid value exceeds 200 mgKOH / g, the solubility of the coating film in the developer increases, and even the portion that is desired to be photocured and left as a pattern is dissolved, and the shape of the pattern may deteriorate.

  The acid value in the present invention is an acid value (mgKOH / g) measured according to the potentiometric titration method of JIS K 0070.

The ethylenically unsaturated group equivalent of the photosensitive resin (A) of the present invention is 200 to 5000 g / eq, preferably 300 to 3000 g / eq. When the ethylenically unsaturated group equivalent is less than 200 g / eq, the photosensitivity may be too high, and even the part to be removed by dissolving the film during development is cured by light, and a good pattern shape is obtained. There may not be. When the ethylenically unsaturated group equivalent exceeds 5000 g / eq, the photosensitivity may be too low, the portion to be photocured may not be sufficiently cured, and the pattern dissolves during development, thereby obtaining a good pattern shape. There may not be.

The “ethylenically unsaturated group equivalent” in the present invention is a theoretical value calculated from the weight of the material constituting the photosensitive resin (A), and the weight of the photosensitive resin (A) is the photosensitive resin (A). It is divided by the number of ethylenically unsaturated groups present in (A) and corresponds to the weight of the resin per mole of ethylenically unsaturated groups, that is, the reciprocal of the ethylenically unsaturated group concentration. .

The weight average molecular weight of the photosensitive resin (A) of this invention is 1000-100000, Preferably, it is 3000-60000. If the weight average molecular weight is less than 1000, sufficient solder heat resistance and flexibility may not be obtained. On the other hand, when the weight average molecular weight exceeds 100,000, the solder heat resistance is excellent, but the developability may be deteriorated, and the viscosity and handling at the time of coating may be problems.

  The weight average molecular weight as used in the field of this invention is a polystyrene conversion molecular weight in a gel permeation chromatography (GPC) measurement.

The photosensitive resin (A) is preferably the following hydroxyl group-containing photosensitive resin (A-1) or carboxyl group-containing photosensitive resin (A-2).
The hydroxyl group-containing photosensitive resin (A-1) has, as a first step, an epoxy compound (a) having at least two epoxy groups in one molecule and at least two phenolic hydroxyl groups in one molecule. A phenol compound (b) is reacted to prepare a side chain hydroxyl group-containing resin (c). Next, as a second step, the side chain hydroxyl group-containing resin (c) and the polybasic acid anhydride (d) are reacted to produce a carboxyl group-containing resin (e). Furthermore, as a third step, the carboxyl group-containing resin (e) is obtained by reacting the epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. be able to.
Furthermore, the carboxyl group-containing photosensitive resin (A-2) of the present invention comprises, as the fourth step, an acid anhydride in the hydroxyl group polybasic acid anhydride (d) in the hydroxyl group-containing resin (A-1). It can be obtained by the group.

Since the photosensitive resins (A-1) and (A-2) do not have an ester bond derived from half esterification with a dibasic acid anhydride or a urethane bond derived from the reaction of an isocyanate group and a hydroxyl group in the main chain, Since the chain is chemically stable, the resulting cured coating has excellent resistance to various coatings, exhibits excellent heat resistance even when exposed to high temperature conditions such as a solder bath, and is also hot and humid. It is further preferable in order to exhibit excellent electric insulation even under the above. Furthermore, since the photosensitive resins (A-1) and (A-2) have a photosensitive group and a carboxyl group in the side chain, even when the amount of the photosensitive group and the carboxyl group is small, Very good resolution and developability. The functional groups introduced into these side chains are more reactive than when directly connected to the main chain, and the amount of introduction can be adjusted arbitrarily compared to the case where they are introduced only at the ends of the main chain. Curability, developability, resolution and coating film resistance can be exhibited.
Below, the manufacturing method of hydroxyl group containing photosensitive resin (A-1) or carboxyl group-containing photosensitive resin (A-2) is demonstrated in detail.

First, the side chain hydroxyl group-containing resin (c) obtained in the first step will be described. The side chain hydroxyl group-containing resin (c) reacts an epoxy compound (a) having at least two epoxy groups in one molecule with a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule. In the epoxy compound (a) having at least two epoxy groups in one molecule and in the phenol compound (b) having at least two phenolic hydroxyl groups in one molecule. It is preferable to prepare a phenolic hydroxyl group by reacting with a molar ratio of epoxy group / phenolic hydroxyl group = 1/1 to 1 / 2.5. If the phenolic hydroxyl group is less than the above molar ratio range, the remaining excess epoxy group may react and gel in the subsequent synthesis step. Moreover, when there are more phenolic hydroxyl groups than the range of the said molar ratio, the molecular weight of the photosensitive resin (A) finally obtained becomes low, and it becomes difficult to obtain desired coating-film resistance and film formability. Furthermore, the phenol compound (b) having at least two phenolic hydroxyl groups in one excess molecule may adversely affect physical properties such as solder heat resistance and electrical insulation.

In addition, the molar ratio as used in the field of this invention is a molar ratio with which functional groups actually react, and various starting materials use the quantity which enables reaction by the said molar ratio. Therefore, for example, in the reaction of “epoxy compound (a) having at least two epoxy groups in one molecule” and “phenol compound (b) having at least two phenolic hydroxyl groups in one molecule”, When the starting material is charged, “having at least two phenolic hydroxyl groups in one molecule” with respect to 1.0 mol of epoxy groups in “epoxy compound (a) having at least two epoxy groups in one molecule”. The phenolic hydroxyl group in the “phenolic compound (b)” may be charged in an amount exceeding 2.5 mol (preferably charged at an upper limit of 2.7 mol).

The epoxy compound (a) having at least two epoxy groups in one molecule used in the present invention is not particularly limited as long as it is preferably a compound containing two epoxy groups in the molecule. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, bisphenol F / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, polyglycidyl ether of glycerin / epichlorohydrin adduct , Resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneope Tyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, dihydroxyanthracene type epoxy resin, polypropylene glycol diglycidyl ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone Diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluorenediglycidyl ether, biscresol fluorenediglycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane N, N-diglycidylaniline, N, N-dig Ricidyl toluidine, an epoxy compound having excellent flexibility disclosed in JP-A No. 2004-156024, JP-A No. 2004-315595, and JP-A No. 2004-323777, and the following formulas (1) to (3) An epoxy compound having a structure represented by:

Formula (1)

Formula (2)

Formula (3)

Among them, polyethylene glycol diglycidyl ether is preferable in the case where the finally obtained hydroxyl group-containing photosensitive resin (A-1) is provided with flexibility and solubility in an alkaline developer, and is preferably a bisphenol A / epichlorohydrin type. The epoxy resin is preferable in the case where heat resistance is imparted to the finally obtained carboxyl group-containing modified ester resin (A). Thus, in the present invention, the epoxy compound (d) having at least two epoxy groups in one molecule can be selected according to the purpose, and these may be used alone or in combination. Use in combination is also preferred.

The phenol compound (b) having at least two phenolic hydroxyl groups in one molecule used in the present invention is not particularly limited as long as it is a compound containing two phenolic hydroxyl groups in the molecule. For example, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A) is a representative example, and other examples include bis (4-hydroxyphenol) methane, 1,1-bis (4-hydroxyphenyl). ) Ethane, 1,1-bis (4-hydroxyphenyl) -n-propane, 1,1-bis (4-hydroxyphenyl) -n-butane, 1,1-bis (4-hydroxyphenyl) -n- Pentane, 1,1-bis (4-hydroxyphenyl) -n-hexane, 1,1-bis (4-hydroxyphenyl) -n-heptane, 1,1-bis (4-hydroxyphenyl) -n-octane, 1,1-bis (4-hydroxyphenyl) -n-nonane, 1,1-bis (4-hydroxyphenyl) -n-decane, bis (4-hydroxyphenyl) phenylmethane Bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl) toluylmethane, bis (4-hydroxyphenyl)-(4-ethylphenyl) methane, bis (4-hydroxyphenyl)-(4-n- Propylphenyl) methane, bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane, bis (4-hydroxyphenyl)-(4-n-butylphenyl) methane, bis (4-hydroxyphenyl)-(4 -Pentylphenyl) methane, bis (4-hydroxyphenyl)-(4-hexylphenyl) methane, bis (4-hydroxyphenyl)-(4-fluorophenyl) methane, bis (4-hydroxyphenyl)-(4-chlorophenyl) ) Methane, bis (4-hydroxyphenyl)-(2-fluoropheny) ) Methane, bis (4-hydroxyphenyl)-(2-chlorophenyl) methane, bis (4-hydroxyphenyl) tetrafluorophenylmethane, bis (4-hydroxyphenyl) tetrachlorophenylmethane, bis (3-methyl-4-) Hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-ethyl-4-hydroxyphenyl) methane, bis (3-isobutyl-4-hydroxyphenyl) methane, bis (3 -T-butyl-4-hydroxyphenyl) -1-phenylmethane, bis (3-phenyl-4-hydroxyphenyl) -1-phenylmethane, bis (3-fluoro-4-hydroxyphenyl) methane, bis (3 , 5-Difluoro-4-hydroxyphenyl) methane, bis (3-chloro- -Hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) ethane, 1,1-bis (3,5- Dimethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-ethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-isobutyl-4-hydroxyphenyl) ethane, 1,1-bis ( 3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,1-bis (3-chloro-4-hydroxyphenyl) ethane, 1, Bisphenols in which a hydrogen atom is bonded to a central carbon such as 1-bis (3,5-dichloro-4-hydroxyphenyl) ethane;
2,2-bis (4-hydroxyphenyl) -n-butane, 2,2-bis (4-hydroxyphenyl) -n-pentane, 2,2-bis (4-hydroxyphenyl) -n-hexane, 2 , 2-bis (4-hydroxyphenyl) -n-heptane, 2,2-bis (4-hydroxyphenyl) -n-octane, 2,2-bis (4-hydroxyphenyl) -n-nonane, 2,2 -Bis (4-hydroxyphenyl) -n-decane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (commonly called bisphenol P), 1,1-bis (4-hydroxyphenyl) -1-naphthyl Ethane, 1,1-bis (4-hydroxyphenyl) -1-toluyl ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-ethylphenyl) ethane, 1,1-bis ( 4-hydroxyphenyl) -1- (4-n-propylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-isopropylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) L) -1- (4-n-butylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-pentylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1 -(4-hexylphenyl) ethane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -1- Phenylethane, 1,1-bis (4-hydroxyphenyl) -1- (4-fluorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-chlorophene) L) ethane, 1,1-bis (4-hydroxyphenyl) -1- (2-fluorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (2-chlorophenyl) ethane, Bisphenols in which one methyl group is bonded to the central carbon such as 1-bis (4-hydroxyphenyl) -1-tetrafluorophenylethane and 1,1-bis (4-hydroxyphenyl) -1-tetrachlorophenylethane ;
2,2-bis (3-methyl-4-hydroxyphenyl) propane (commonly called bisphenol C), 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propan, 2,2-bis (3- Ethyl-4-hydroxyphenyl) propane, 2,2-bis (3-isobutyl-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3 , 5-Difluoro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, etc. Bisphenols with two methyl groups attached to the carbon;
Bis (4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-methyl-4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-t-butyl-4-hydroxyphenyl) -1,1 -Bisphenols that are diphenylmethane derivatives such as diphenylmethane, bis (3-phenyl-4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-chloro-4-hydroxyphenyl) -1,1-diphenylmethane;
1,1-bis (4-hydroxyphenyl) cyclohexane (commonly known as bisphenol Z), 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxy) Phenyl) cyclohexane, 1,1-bis (3-ethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-isobutyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-fluoro-4-) Hydroxyphenyl) cyclohexane, 1,1-bis (3,5-difluoro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5 -Bis, which is a cyclohexane derivative such as -dichloro-4-hydroxyphenyl) cyclohexane Phenols;
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1, 1-bis (3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-ethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-isobutyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-fluoro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, -3,3,5-trimethyl such as 1,1-bis (3,5-difluoro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane Bisphenols which are cyclohexane derivatives;
9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 9 , 9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-isobutyl-4-hydroxyphenyl) fluorene, 1,1-bis (3-fluoro-4-hydroxyphenyl) fluorene, Bisphenols which are fluorene derivatives such as 9,9-bis (3,5-difluoro-4-hydroxyphenyl) fluorene;
1,1-bis (4-hydroxyphenyl) -cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 1,1-bis ( Bisphenols which are cycloalkane derivatives such as 4-hydroxyphenyl) cyclononane and 1,1-bis (4-hydroxyphenyl) cyclodecane;
Biphenols directly linked with aromatic rings such as 4,4′-biphenol;
Bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-ethyl-4-hydroxyphenyl) sulfone Bisphenols which are sulfone derivatives such as bis (3-isobutyl-4-hydroxyphenyl) sulfone, bis (3-fluoro-4-hydroxyphenyl) sulfone, bis (3,5-difluoro-4-hydroxyphenyl) sulfone;
Bis (4-hydroxyphenyl) ether, bis (3-methyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3-ethyl-4-hydroxyphenyl) ether Bisphenols having an ether bond such as bis (3-isobutyl-4-hydroxyphenyl) ether, bis (3-fluoro-4-hydroxyphenyl) ether, bis (3,5-difluoro-4-hydroxyphenyl) ether;
Bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3-ethyl-4-hydroxyphenyl) sulfide, Bisphenols having a sulfide bond such as bis (3-isobutyl-4-hydroxyphenyl) sulfide, bis (3-fluoro-4-hydroxyphenyl) sulfide, bis (3,5-difluoro-4-hydroxyphenyl) sulfide;
Bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfoxide, bis (3-ethyl-4-hydroxyphenyl) sulfoxide Bisphenols which are sulfoxide derivatives such as bis (3-isobutyl-4-hydroxyphenyl) sulfoxide, bis (3-fluoro-4-hydroxyphenyl) sulfoxide, bis (3,5-difluoro-4-hydroxyphenyl) sulfoxide ;
Bisphenols having a heteroatom-containing aliphatic ring such as phenolphthalein;
Bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) difluoromethane, 1,1-bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) perfluoroethane, 2, Examples thereof include bisphenols having no carbon-hydrogen bond such as 2-bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) perfluoropropane.

And dihydroxybenzenes such as hydroquinone, resorcinol, catechol, methylhydroquinone;
Examples thereof include dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene.

In the present invention, the conditions for synthesizing the side chain hydroxyl group-containing resin (c) are not particularly limited, and can be performed under known conditions. For example, an epoxy compound (a) having at least two epoxy groups in one molecule, a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule, and a solvent are charged into a flask while stirring. The side chain hydroxyl group-containing resin (c) can be obtained by heating at 100 to 150 ° C. At this time, a catalyst such as triphenylphosphine or a tertiary amino group-containing compound may be used as necessary.

Next, the carboxyl group-containing resin (e) obtained in the second step will be described. The carboxyl group-containing resin (e) can be obtained by reacting the side chain hydroxyl group-containing resin (c) with the polybasic acid anhydride (d), and the hydroxyl group in the side chain hydroxyl group-containing resin (c). And an acid anhydride group in the polybasic acid anhydride (d) are preferably reacted at a molar ratio of hydroxyl group / acid anhydride group = 1 / 0.1 to 1/1. If there are less acid anhydride groups than the above molar ratio range, the concentration of carboxyl groups that function as crosslinking points in the finally obtained photosensitive resin (A) will decrease, so the desired heat resistance and solubility in alkaline developer Is difficult to obtain. In addition, when there are more acid anhydride groups than the above molar ratio range, excess polybasic acid anhydride (d) generates a by-product in a later synthesis step, so the flexibility and solder heat resistance of the final coating film, Insulation reliability tends to decrease.

The polybasic acid anhydride (d) used in the present invention is not particularly limited as long as it is a compound containing at least one acid anhydride group in the molecule. For example, phthalic anhydride, trimellitic anhydride, methyltetrahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylpentahydrophthalic anhydride, methyltrihydrophthalic anhydride, trialkyltetrahydro Examples thereof include compounds containing an acid anhydride group having an alicyclic structure such as phthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, het acid anhydride, tetrabromophthalic anhydride, or an aromatic ring structure. Other compounds include succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, butyl maleic anhydride, pentyl maleic acid Anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecylmaleic anhydride, butylglutamic anhydride, hexylglutamic anhydride, heptylglutamic anhydride, octylglutamic anhydride, decylglutamic anhydride Products, dodecylglutamic acid anhydride, and the like. In the present invention, the polybasic acid anhydride (d) may be used alone or in combination.

Of these, succinic anhydride, tetrahydrophthalic anhydride, and the like are particularly preferable in the present invention because of their excellent developability, pattern formability, and coating film resistance.

In the present invention, the synthesis conditions of the carboxyl group-containing resin (e) are not particularly limited, and can be performed under known conditions. For example, a side chain hydroxyl group-containing resin (c) is prepared by charging a flask with a side chain hydroxyl group-containing resin (c), a polybasic acid anhydride (d), and a solvent, and heating at 25 to 150 ° C. with stirring. Can be obtained. This reaction proceeds even in the absence of a catalyst, but a catalyst such as a tertiary amino group-containing compound may be used if necessary.

Next, the hydroxyl group-containing resin (A-1) obtained in the third step will be described. The hydroxyl group-containing resin (A-1) of the present invention can be obtained by reacting the carboxyl group-containing resin (e) with a compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. The carboxyl group in the carboxyl group-containing resin (e) and the epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group are converted into a carboxyl group / epoxy group or oxetane group. It is preferable to prepare it by reacting at a molar ratio of 1 / 0.1 to 1/1. When the epoxy group or oxetane group is less than the above molar ratio range, the double bond equivalent functioning as a photo-crosslinking point in the finally obtained photosensitive resin (A) becomes high. It becomes difficult to obtain resistance. Moreover, when there are more epoxy groups or oxetane groups than the range of the said molar ratio, it exists in the tendency for the flexibility of a final coating film to fall with the compound (f) which has an excess epoxy group or oxetane group, and an ethylenically unsaturated group. .

  The compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group used in the present invention may be any compound containing at least one epoxy group or oxetane group and an ethylenically unsaturated group in the molecule. There is no particular limitation. For example, glycidyl (meth) acrylate, glycidyl cinnamic acid, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl (meth) acrylate, (3,4-epoxycyclohexyl) Many hydroxyl-containing groups such as methyl (meth) acrylate, 4-vinyl-1-cyclohexene-1,2-epoxide, 1,3-butadiene monoepoxide, oxetanyl (meth) acrylate, oxetanylcinnamic acid, and pentaerythritol triacrylate Modification of most epoxide groups of polyfunctional acrylate groups by reacting epichlorohydrin with hydroxyl groups of functional acrylic monomers, and phenol novolac epoxy resins to acrylate groups with acrylic acid, etc. Epoxy of the compound which has two or more epoxy groups in the molecule to the carboxyl group of the polyfunctional acrylate group-containing monoepoxide and carboxyl group-containing polyfunctional acrylic monomer, in which one epoxy group remains in one molecule on average Polyfunctional acrylate group-containing monoepoxide obtained by reacting a part of the group, and the like. By reacting these epoxy group or oxetane group with the carboxyl group in the carboxyl group-containing resin (e), hydroxyl group is obtained. A group-containing resin (A-1) is obtained. In the present invention, the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group may be used alone or in combination.

Among them, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like are particularly preferable in the present invention because they are highly reactive with carboxyl groups and are very excellent in photosensitivity.

In the present invention, a compound having no ethylenically unsaturated group and having an epoxy group or oxetane group is used in combination with the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group. You can also. In this case, it is possible to control the photosensitivity of the carboxyl group-containing photosensitive urethane resin (A) of the present invention more broadly. Examples of the compound having no ethylenically unsaturated group and having an epoxy group or oxetane group of the present invention include styrene oxide, phenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, glycidyl cinnamon. Mate, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, glycidol, N-glycidyl phthalimide, 1,3-dibromophenyl glycidyl ether, Celoxide 2000 (Daicel Chemical Industries) And oxetane alcohol).

In the present invention, the synthesis conditions of the hydroxyl group-containing resin (A-1) are not particularly limited, and can be performed under known conditions. For example, in the presence of oxygen, the flask is charged with the carboxyl group-containing resin (e), the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group, and a solvent at 25 to 150 ° C. with stirring. The hydroxyl group-containing resin (A-1) can be obtained by heating. At this time, an ethylenically unsaturated group may be added so as not to add a reaction catalyst such as a tertiary amino group-containing compound or the like to promote the reaction, or to cause gelation due to polymerization reaction or progress of polymerization. It is also possible to use a polymerization inhibitor or molecular oxygen.

As the polymerization inhibitor, hydroquinone, methylhydroquinone, pt-butylcatechol, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, trimethylhydroquinone, methoxyhydroquinone, p-benzoquinone, 2,5- Di-t-butylbenzoquinone, naphthoquinone, phenothiazine, N-oxyl compound and the like can be used. Further, even if molecular oxygen is present in the reaction vessel, there is an effect of inhibiting polymerization. For example, air or a mixed gas of air and an inert gas such as nitrogen may be blown into the reaction vessel so-called bubbling. In order to enhance the polymerization inhibition effect, it is preferable to use a polymerization inhibitor and molecular oxygen in combination.

  Next, the carboxyl group-containing photosensitive resin (A-2) obtained in the fourth step of the present invention will be described. The carboxyl group-containing photosensitive resin (A-2) of the present invention can be obtained by reacting the hydroxyl group-containing resin (A-1) with the polybasic acid anhydride (d). Prepared by reacting the hydroxyl group in A-1) with the acid anhydride group in the polybasic acid anhydride (d) at a molar ratio of hydroxyl group / acid anhydride group = 1 / 0.01 to 1/1. It is preferable to do. If there are less acid anhydride groups than the above molar ratio range, the concentration of carboxyl groups that function as crosslinking points in the finally obtained photosensitive resin (A) will decrease, so the desired heat resistance and solubility in alkaline developer Is difficult to obtain. Moreover, when there are more acid anhydride groups than the said molar ratio range, it exists in the tendency for the flexibility of a final coating film, solder heat resistance, and insulation reliability to fall with an excess polybasic acid anhydride (d).

As described above, the polybasic acid anhydride (d) used in the present invention is not particularly limited as long as it is a compound containing at least one acid anhydride group in the molecule. You may use and you may use multiple together. Of these, succinic anhydride, tetrahydrophthalic anhydride, and the like are particularly preferable in the present invention because of their excellent developability, pattern formability, and coating film resistance.

In the present invention, the synthesis condition of the carboxyl group-containing photosensitive resin (A-2) is not particularly limited, and the hydroxyl group-containing resin (A-1) is added to the flask in the presence of oxygen in the same manner as in the third step. ), A polybasic acid anhydride (d), and a solvent are charged, and the reaction is preferably performed by heating and stirring at 25 to 150 ° C., and if necessary, a suitable reaction catalyst and an ethylenically unsaturated group A polymerization inhibitor can be newly added.

The solvent used for the synthesis of the photosensitive resin (A) can be appropriately selected according to the end use and the solubility of the reactant. For example, when a dry film type photosensitive solder resist is used as the final application, it is preferable to use a low-boiling solvent because the solvent needs to be quickly dried in the dry film preparation step. Examples of the low boiling point solvent in this case include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, isopropyl alcohol and the like. In addition, when liquid solder resist ink is used as the final application, it is necessary to suppress the volatilization of the solvent as much as possible in consideration of the process of kneading fillers and pigments with rolls in the ink preparation process and the storage stability as ink. Therefore, it is preferable to use a high boiling point solvent. Examples of the high boiling point solvent in this case include carbitol acetate, methoxypropyl acetate, cyclohexanone, diisobutyl ketone and the like.

In the present invention, these solvents may be used alone or in combination, if necessary, and may be used in combination. Or a solvent may be added.

The photosensitive resin (A) may further contain an ethylenically unsaturated group-containing compound. The ethylenically unsaturated group-containing compound is not particularly limited as long as it has an ethylenically unsaturated double bond in the structure. For example, alkyl (meth) acrylate, alkylene glycol (meth) acrylate , A compound having a carboxyl group and an ethylenically unsaturated group, a (meth) acrylate compound having a hydroxyl group, a nitrogen-containing (meth) acrylate compound, and the like. Monofunctional and polyfunctional compounds can be used as appropriate. From the viewpoint of photocurability and hard coat properties of the coating film, polyfunctional ones are preferred. These ethylenically unsaturated group-containing compounds can be used alone or in combination.

Alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) ) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate , Pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, There are alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms, such as kosyl (meth) acrylate, henycosyl (meth) acrylate, docosyl (meth) acrylate, and preferably carbon for the purpose of adjusting the polarity. Examples thereof include alkyl (meth) acrylates having an alkyl group of 2 to 10, more preferably 2 to 8 carbon atoms.

Examples of the alkylene glycol (meth) acrylate include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, and polyethylene glycol. Mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, etc .;
Mono (meth) acrylate having a hydroxyl group at the terminal and a polyoxyalkylene chain;
Methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate , N-butoxytetraethylene glycol (meth) acrylate, n-pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxy Tetrapropylene glycol (meth) acrylate, ethoxytetrapropyleneglycol (Meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetra Methylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, mono (meth) acrylate having an alkoxy group at the terminal and a polyoxyalkylene chain;
Phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, Examples thereof include polyoxyalkylene (meth) acrylates having a phenoxy group or an aryloxy group at the terminal, such as phenoxytetrapropylene glycol (meth) acrylate.

  Examples of the compound having a carboxyl group and an ethylenically unsaturated group include maleic acid, fumaric acid, itaconic acid, citraconic acid, alkyl or alkenyl monoesters thereof, and phthalic acid β- (meth) acryloxyethyl monoester. Ester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, Cinnamic acid and the like can be exemplified.

  Moreover, as a compound which has a hydroxyl group and an ethylenically unsaturated group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene and the like are listed.

Examples of the compound having a nitrogen atom and an ethylenically unsaturated group include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, Monoalkylol (meth) acrylamides such as N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxy Methyl-N-propoxy Tylmethacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) ) Acrylamide unsaturated compounds such as dialkyl (meth) acrylamides such as methacrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide, dimethylaminoethyl (meta ) Unsaturated compounds having dialkylamino groups such as acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene, and C as a counter ion ^{-, Br} -, I ^- a halogen ion or, QSO ^3-: having (Q alkyl group having 1 to 12 carbon atoms) can be exemplified by quaternary ammonium salts of dialkylamino group-containing unsaturated compound.

Further, other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2 -Perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) ) Acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. Perfluoroalkyl (meth) acrylates having Kill group;
Perfluoroalkyl group-containing vinyl monomers such as perfluoroalkyl, alkylenes such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene;
Alkoxysilyl group-containing vinyl compounds such as vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof;
Examples thereof include glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate, and one or more types can be appropriately selected from these groups and used.

Examples of fatty acid vinyl compounds include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, and vinyl stearate;
Examples of alkyl vinyl ether compounds include butyl vinyl ether and ethyl vinyl ether;
As the α-olefin compound, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like;
As vinyl compounds, allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene, etc .;
As an ethynyl compound, acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like;
Can also be used.

  Next, a polyfunctional compound having two or more ethylenically unsaturated groups is specifically exemplified.

  First, an aliphatic compound is illustrated among the compounds which have an ethylenically unsaturated group. Specifically, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Bis (acryloxy neopentyl glycol) adipate, bis (methacryloxy neopentyl glycol) adipate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate: Nippon Kayaku Kayrad R-167, hydroxypivalate neopentyl glycol di (Meth) acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate: Nippon Kayaku Kayrad HX series alkyl type (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -811, epichlorohydrin modified diethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -851, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified propylene Recall di (meth) acrylate: alkylene glycol type (meth) acrylate such as Nagase Sangyo Denacol DA (M) -911, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, neopentyl glycol modified trimethylolpropane Di (meth) acrylate: Nippon Kayaku Kayrad R-604, ethylene oxide modified trimethylolpropane tri (meth) acrylate: Sartomer SR-454, propylene oxide modified trimethylolpropane tri (meth) acrylate: Nippon Kayaku TPA- 310, trichlorohydrin-modified trimethylolpropane tri (meth) acrylate: trimethylolpropane type (meth) acrylate such as Nagase Sangyo DA (M) -321, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate: Toa Synthetic Aronix M-233, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meta ) Acrylate, alkyl-modified dipentaerythritol poly (meth) acrylates: Kayarad D-310, 320, 330 made by Nippon Kayaku, etc. Caprolactone-modified dipentaerythritol poly (meth) acrylates: Kayrad DPCA-20 made by Nippon Kayaku Pentaerythritol type (meth) acrylate such as 30, 60, 120, glycerol di (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate Rate: Nagase Sangyo Denacol DA (M) -314, glycerol type (meth) acrylate such as triglycerol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclopentanyl di (meth) acrylate, cyclohexyldi (Meth) acrylate, methoxylated cyclohexyl di (meth) acrylate: cycloaliphatic (meth) acrylate such as Sanyo Kokusaku Pulp CAM-200, tris (acryloxyethyl) isocyanurate: Toa Gosei Aronix M-315, Tris (methacryloxy) Isocyanurate type (meth) acrylates such as ethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (methacryloxyethyl) isocyanurate, etc. It is below.

  Of the compounds having an ethylenically unsaturated group, aromatic compounds are exemplified. For example, hydroquinone, resorcin, catechol, pyrogallol, bisphenol A di (meth) acrylate, ethi (propyrene) oxide-modified bisphenol A di (meth) acrylate [“ethi (propyrene) oxide” means “ethylene oxide” or “propylene” Means "oxide". The same applies below. ], Bisphenol F di (meth) acrylate, Ethi (propi) ylene oxide modified bisphenol F di (meth) acrylate, Bisphenol S di (meth) acrylate, Ethi (propi) lene oxide modified bisphenol S di (meth) acrylate, Epichlorohydrin modified (Meth) acrylate compounds having aromatic groups such as di (meth) acrylate phthalate, tetrachlorobisphenol S ethyl (propylene) oxide modified di (meth) acrylate, tetrabromobisphenol S ethyl (propylene) oxide modified di (meth) Examples thereof include styrenes having an aromatic group substituted with a halogen atom having an atomic weight of chlorine atom or more, such as acrylate, and (meth) acrylate compounds.

  Furthermore, polyfunctional (meth) acrylates such as urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate can be suitably used as compounds from the viewpoint of coating film strength and scratch resistance. . Epoxy (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid and converting the functional group to (meth) acrylate, and (meth) acrylic acid adduct to bisphenol A type epoxy resin. And (meth) acrylic acid adducts to novolac epoxy resins. Urethane (meth) acrylates are, for example, those obtained by reacting diisocyanates with (meth) acrylates having a hydroxyl group, and isocyanate group-containing urethane prepolymers obtained by reacting polyols and polyisocyanates under conditions of excess isocyanate groups. Some are obtained by reacting polymers with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group.

The following can be illustrated as a commercial item.
Toa Gosei Co., Ltd .: Aronix M-400, Aronix M-402, Aronix M-310, Aronix M-408, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060;
Osaka Organic Chemical Industry Co., Ltd .: Biscote # 400;
Kayaku Sartomer Co., Ltd .: SR-295;
Made by Daicel UCB Corporation: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602;
Shin-Nakamura Chemical Co., Ltd .: NK Ester A-TMMT, NK Oligo EA-1020, NK Oligo EMA-1020, NK Oligo EA-6310, NK Oligo EA-6320, NK Oligo EA-6340, NK Oligo MA-6, NK oligo U-4HA, NK oligo U-6HA, NK oligo U-324A;
Manufactured by BASF: LaromerEA81;
San Nopco Co., Ltd .: Photomer 3016;
Arakawa Chemical Industries, Ltd .: beam set 371, beam set 575, beam set 577, beam set 700, beam set 710;
Manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T, Art Resin HDP, Art Resin HDP- 3, Art Resin H61;
Nippon Synthetic Chemical Industry Co., Ltd .: Purple light UV-7600B, Purple light UV-7610B, Purple light UV-7620EA, Purple light UV-7630B, Purple light UV-1400B, Purple light UV-1700B, Purple light UV-6300B;
Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A, Light acrylate DPE-6A, UA-306H, UA-306T, UA-306I;
Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330, SR-35;
Etc.

Among them, those containing an ethylene oxide addition structure in the molecule, Aronix M-310 manufactured by Toagosei Co., Ltd., SR-355 manufactured by Nippon Kayaku Co., Ltd., etc. are particularly preferred because of their excellent developability in the present invention. .

<Curing agent (B)>
The photosensitive resin composition of the present invention is at least one curing selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, and a blocked isocyanate group-containing compound as a curing agent for the above-described photosensitive resin (A). Agent (B) [hereinafter also simply referred to as “curing agent (B)”. ] Is used.

The epoxy group-containing compound in the present invention is not particularly limited as long as it is a compound containing an epoxy group in the molecule. For example, examples of the compound having one epoxy group in the molecule include compounds such as N-glycidylphthalimide, glycidol, and glycidyl (meth) acrylate. These can be suitably used for the purpose of controlling the crosslink density of the cured product by using together with a compound having two or more epoxy groups in the molecule exemplified below as needed. Examples of the compound containing two or more epoxy groups in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, Bisphenol F / epichlorohydrin type epoxy resin, bisphenol S / epichlorohydrin type epoxy resin, bisphenol AD / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, ethylene oxide adduct of bisphenol A or Propylene oxide adduct epichlorohydrin type epoxy resin, glycerin / epichlorohydrin adduct polyglycidyl ether, naphthalenediol diglycidyl ether, resorcino Rudiglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, polypropylene glycol diglycidyl Ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol full orange glycidyl ether, biscresol full orange glycidyl ether, bisphenoxyethanol full orange glycidyl ether, 1,3-bis ( N, N-diglycidyl Minomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, Japanese Patent Application Laid-Open Nos. 2004-156024, 2004-315595, and 2004-323777. And an epoxy compound having a structure represented by the following formulas (4) to (6).

Formula (4)

Formula (5)

Formula (6)

Further, trishydroxyethyl isocyanurate triglycidyl ether, triglycidyl isocyanurate, “Epicoat 1031S”, “Epicoat 1032H60”, “Epicoat 604”, “Epicoat 630” manufactured by Mitsubishi Chemical Corporation, phenol novolac epoxy resin, cresol Novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, polyglycidyl ether of ethylene glycol / epichlorohydrin adduct, pentaerythritol polyglycidyl ether, trimethylol propane poly, disclosed in JP-A-2001-240654 Examples thereof include glycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, and the like. Moreover, the compound which has other thermosetting groups other than an epoxy group can also be used. For example, the silane modified epoxy resin currently disclosed by Unexamined-Japanese-Patent No. 2001-59011 and 2003-48953 is mentioned.

In particular, isocyanurate ring-containing epoxy compounds such as trishydroxyethyl isocyanurate triglycidyl ether and triglycidyl isocyanurate are preferred because they tend to improve the adhesion strength to polyimide and copper when used in the present invention. Also, “Epicoat 1031S”, “Epicoat 1032H60”, “Epicoat 604”, and “Epicoat 630” manufactured by Mitsubishi Chemical Corporation are highly functional in the present invention because they are multifunctional and have excellent heat resistance. Aliphatic epoxy compounds and epoxy compounds described in JP-A Nos. 2004-156024, 2004-315595, and 2004-323777 are preferable because they are excellent in flexibility of a cured coating film. In addition, the dicyclopentadiene type epoxy compound, the phenol novolak type epoxy resin, the cresol novolak type epoxy resin, the biphenol / epichlorohydrin type epoxy resin, etc. described in JP-A No. 2001-240654 are thermally cured in the present invention. It is excellent in terms of durability of a cured coating film including properties, hygroscopicity and heat resistance, and is preferable.

The isocyanate group-containing compound is not particularly limited as long as it is a compound having an isocyanate group in the molecule. Specific examples of the diisocyanate compound include aromatic diisocyanates having 4 to 50 carbon atoms, aliphatic diisocyanates, araliphatic diisocyanates, and alicyclic diisocyanates.

  Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-Triphenylmethane triisocyanate etc. can be mentioned.

  Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2 4,4-trimethylhexamethylene diisocyanate and the like.

  Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1 , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane diisocyanate. , Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanate methyl) A cyclohexane etc. can be mentioned.

Specific examples of the isocyanate group-containing compound having one or more isocyanate groups in the molecule include (meth) acryloyloxyethyl isocyanate, monofunctional isocyanate having one isocyanate group in one molecule, , 1-bis [(meth) acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. In addition, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nitrate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate and hydroxyl group, carboxyl group, and amide group-containing vinyl monomers are reacted in equimolar amounts. It can be used as an ester compound.

  Examples of the polyfunctional isocyanate having 3 or more isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanates and lysine triisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates. Examples thereof include trimethylolpropane adducts of diisocyanate described above, burettes reacted with water, and trimers having an isocyanurate ring.

The blocked isocyanate group-containing compound is not particularly limited as long as the isocyanate group is an isocyanate group-containing compound protected with ε-caprolactam, MEK oxime, or the like. Specific examples include those obtained by blocking the isocyanate group of the isocyanate group-containing compound with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol and the like.

In the present invention, the compound (B) may be used alone or in combination. The amount of the compound (B) used may be determined in consideration of the application of the curable resin composition of the present invention, and is not particularly limited, but is 100 parts by weight of the solid content of the photosensitive resin (A). The amount is preferably 0.5 to 100 parts by weight, more preferably 1 to 50 parts by weight. By using a compound (B), since the crosslinking density of the photosensitive resin composition of this invention can be adjusted to an appropriate value, the various physical properties of the coating film after hardening can be improved further. When the amount of the compound (B) used is less than 0.5 parts by weight, the crosslinking density of the coating film after heat curing becomes too low, and the desired adhesive strength and heat resistance may be insufficient. Further, if the amount used is more than 100 parts by weight, the crosslinking density after heat curing becomes too high, and as a result, the flexibility and flexibility of the coating film may be lowered, and the adhesive strength may be significantly deteriorated. is there.

<Photopolymerization initiator (C)>
Next, the photopolymerization initiator (C) will be described. The photopolymerization initiator (C) is added when the photosensitive compound is cured by ultraviolet rays. The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl A compound etc. can be used.

  Specific examples of monocarbonyl compounds include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl-enetanone. 3,3′-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, 3,3′4,4′-tetra ( t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethylbenzenemethammonium chloride, 2-hydroxy-3- (4-benzoyl-phenoxy) -N, N, N-trimethyl-1-propanamine Hydrochloride, 4-benzoyl-N, N-dimethyl-n- [2 (1-Oxo-2-propenyloxyethyl)] metaammonium bromide, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone 2-hydroxy-3- (3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1, 2-d) thiazoline and the like.

  Examples of the dicarbonyl compound include 1,7,7-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.

  Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ( 4-Isopropylphenyl) 2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymerization , Diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyla No-1- (4-morpholino-phenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2- Morpholino-propanonyl) -9-butylcarbazole and the like.

  Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide.

  Examples of aminocarbonyl compounds include methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-nbutoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-diethylaminobenzophenone, 2,5′-bis- (4-diethylaminobenzal) cyclopenta Non etc. are mentioned.

In particular, in the present invention, when 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and thioxanthones are used in combination, the photosensitivity is extremely low but the cost is very low. This is particularly preferable.

These are not limited to the above compounds, and any compounds can be used as long as they have the ability to initiate polymerization by ultraviolet rays. These can be used alone or in combination, and the amount used is not limited, but it is preferably added in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the solid content of the photosensitive resin (A). Moreover, a well-known organic amine can also be added as a sensitizer.

The photosensitive resin composition of the present invention may further contain a thermosetting aid.
The term “thermosetting aid” as used herein refers to a compound that contributes directly or catalytically to the curing reaction during thermosetting.

  Examples of the compound that directly contributes to the curing reaction during thermosetting include amino resins, phenol resins, polyfunctional polycarboxylic acid anhydrides, polyfunctional vinyl ether compounds, high molecular weight polycarbodiimides, and aziridine compounds.

Examples of amino resins and phenol resins include addition compounds of urea, melamine, benzoguanamine, phenol, cresols, bisphenols, and the like with formaldehyde, or partial condensates thereof.

The polyfunctional polycarboxylic acid anhydride is a compound having two or more carboxylic acid anhydride groups and is not particularly limited, but tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride And polyvalent carboxylic acid anhydrides such as maleic anhydride copolymer resins. In addition, polycarboxylic acid, polycarboxylic acid ester, polycarboxylic acid half ester, and the like that can be converted into an anhydride via a dehydration reaction during the reaction are “compounds having two or more carboxylic acid anhydride groups” in the present invention. "include.

More specifically, as tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, Diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, "Ricacid TMTA-C", "Ricacid MTA-" manufactured by Shin Nippon Chemical Co., Ltd. 10 ”,“ Licacid MTA-15 ”,“ Licacid TMEG series ”,“ Licacid TDA ”, and the like.

   Examples of maleic anhydride copolymer resins include SMA resin series manufactured by Sartomer, GSM series manufactured by Gifu Shellac Co., Ltd., styrene-maleic anhydride copolymer resins, p-phenylstyrene-maleic anhydride copolymer resins, polyethylene- Α-olefin-maleic anhydride copolymer resin such as maleic anhydride, “VEMA” (copolymer of methyl vinyl ether and maleic anhydride) manufactured by Daicel Chemical Industries, Ltd., and acrylic anhydride modified maleic anhydride (“Aurolen series”) ": Nippon Paper Chemical Co., Ltd.), maleic anhydride copolymer acrylic resin, and the like.

  Specific examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, and tripropylene glycol. Divinyl ether, neopentyl glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, glycerin divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxylcyclohexane divinyl ether, 1,4 -Dihydroxymethylcyclohexanedivinyl ether, Hyde Quinone divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified resorcin divinyl ether, ethylene oxide modified bisphenol A divinyl ether, ethylene oxide modified bisphenol S divinyl ether, glycerin trivinyl ether, sorbitol tetravinyl ether, trimethylolpropane trivinyl ether, pentaerythritol Examples include trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, ditrimethylolpropane tetravinyl ether, and ditrimethylolpropane polyvinyl ether.

Examples of the high molecular weight polycarbodiimides include Nisshinbo's Carbodilite series. Among these, Carbodilite V-01, 03, 05, 07, and 09 are preferable because of excellent compatibility with organic solvents.

Examples of the aziridine compound include 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane, and the like.

Other compounds that directly contribute to the curing reaction during thermal curing include benzoxazine compounds, benzocyclobutene compounds, maleimide compounds, nadiimide compounds, allyl nadiimide compounds, melamine compounds, and guanamine compounds, which are cured by heating. Any of them can be used effectively. These photopolymerizable groups, functional groups capable of reacting with carboxyl groups, and compounds having functional groups capable of reacting with hydroxyl groups can improve the heat resistance of the coating film after curing, and are therefore used more effectively. be able to.

Examples of compounds that contribute catalytically to the curing reaction during heat curing include tertiary amines such as triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, and N-methylpiperazine. And salts thereof;
2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl-1] -Imidazoles such as ethyl-S-triazine and salts thereof;
1,5-diazabicyclo [5,4,0] -7-undecane, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,4-diabicyclo [2,2,2,] octane, etc. Diazabicyclo compounds;
Phosphines such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine;
Phosphonium salts such as tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate;
In addition, dicyandiamide, carboxylic acid hydrazide, and the like can be cited as compounds that are catalytic and that directly contribute to the curing reaction. Examples of the carboxylic acid hydrazide include succinic acid hydrazide and adipic acid hydrazide.

Only one type of these thermosetting aids may be used, or two or more types may be used in combination. The amount of the thermosetting aid used may be determined in consideration of the use of the photosensitive resin composition, and is not particularly limited, but is 100 parts by weight based on the solid content of the photosensitive resin (A). In the range of 0.1 to 100 parts by weight, more preferably in the range of 0.5 to 80 parts by weight. Thereby, since the crosslinking density of the photosensitive resin composition can be adjusted to an appropriate value, various physical properties of the photosensitive resin composition can be further improved. If the amount of the thermosetting aid used is less than 0.1 parts by weight, the cross-linking density of the coating film after heat curing becomes too low, and the cohesive strength and durability may be insufficient. Also, if the amount used is more than 100 parts by weight, the crosslinking density after heat curing becomes too high, and as a result, the flexibility and flexibility of the coating film are lowered and the warpage of the substrate is remarkably deteriorated. There is.

In addition to the above, the photosensitive resin composition of the present invention may further include solvents, dyes, pigments, flame retardants, antioxidants, polymerization inhibitors, leveling agents, humectants, viscosity modifiers as optional components within a range not to impair the purpose. Preservatives, antibacterial agents, antistatic agents, anti-blocking agents, ultraviolet absorbers, infrared absorbers, electromagnetic shielding agents, fillers, and the like can be added. Especially used for insulating materials (such as circuit protection films, coverlay layers, interlayer insulating materials, etc.) that are in direct contact with the circuit for electronic materials, and for members that can become high heat around the circuit (printed wiring board adhesive, support substrate, etc.) When doing, it is preferable to use a flame retardant (E) together.
Generally, when a flame retardant is used, the folding resistance and developability tend to be inferior. However, in the present invention, even when the flame retardant (E) is contained, the photosensitivity is excellent in folding resistance and developability. A resin composition can be obtained.

 The flame retardant (E) is not particularly limited, but suitable examples include, for example, melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, polyphosphorus Phosphate compounds such as ammonium amidophosphate, carbamate phosphate, and carbamate polyphosphate, polyphosphate compounds, red phosphorus, organic phosphate compounds, phosphazene compounds, phosphonic acid compounds, diethyl diethylphosphinate, methylethylphosphinic acid Phosphinic acid compounds such as aluminum, aluminum diphenylphosphinate, aluminum ethylbutylphosphinate, aluminum methylbutylphosphinate, aluminum polyethylenephosphinate, phosphine oxide Phosphorus flame retardants such as compounds, phosphorane compounds, phosphoramide compounds, triazine compounds such as melamine, melam, melem, melon, melamine cyanurate, cyanuric acid compounds, isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, Nitrogen flame retardants such as urea, silicon flame retardants such as silicone compounds and silane compounds, low molecular halogen-containing compounds such as halogenated bisphenol A, halogenated epoxy compounds and halogenated phenoxy compounds, halogenated oligomers and polymers, etc. Halogen flame retardant, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, metal hydroxide such as calcium hydroxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, Zinc, molybdenum oxide, antimony oxide, nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and inorganic flame retardants such as hydrated glass. In the present invention, taking into consideration the influence on the environment, which has been recently taken into consideration, it is desirable to use a non-halogen flame retardant such as a phosphorus flame retardant or a nitrogen flame retardant, and in particular, the thermosetting resin composition of the present invention. It is preferable to use a phosphazene compound, a phosphine compound, melamine polyphosphate, ammonium polyphosphate, melamine cyanurate, or the like that is more effective in flame retardancy when used in combination. In the present invention, these flame retardants (E) can be used alone or in combination.

  Since the photosensitive resin composition of the present invention and its cured product are characterized by excellent alkali developability, they can be suitably used for applications in which a film forming process including photocuring, alkali development, and post-cure is used. . In addition, it is excellent in solder heat resistance and coating film resistance, and at the same time it is excellent in flexibility and flexibility, so it is particularly suitable for photosensitive solder resist ink for flexible printed wiring boards and dry film type photosensitive solder resist applications. Can be used.

  The photosensitive resin composition of the present invention can be applied to a metal, ceramics, glass, plastic, wood, slate or the like as a substrate, and is not particularly limited. Specific types of plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, melamine resin, and the like. Examples of the shape of the substrate include a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber shape, but are not particularly limited.

The photosensitive resin composition of the present invention can be cured by a known radiation curing method to obtain a cured product, and as active energy rays, electron beams, ultraviolet rays, and visible light of 400 to 500 nm can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) for ultraviolet light and visible light of 400 to 500 nm. Specifically, an ultra-high pressure mercury lamp, a xenon mercury lamp, or a metal halide lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated, can be set appropriately in the range of 5~2000mJ / cm ^2, it is preferably in the range on the easy of 50~1000mJ / cm ² management process. Further, these active energy rays can be used in combination with heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

  When used as a photosensitive solder resist, the photosensitive resin composition of the present invention can be used as a liquid resist ink dissolved in a solvent or as a dry film resist obtained by previously drying the solvent.

When used as a liquid resist ink, the photosensitive resin composition of the present invention may be subjected to radiation curing after the solvent is volatilized by natural or forced drying after coating on the base material. Although natural or forced drying may be performed after the radiation curing, it is preferable that the radiation curing is performed after natural or forced drying. In the case of a liquid resist ink, it is preferable that the solvent does not evaporate during handling until the application to the substrate is completed, such as the storage step and the coating step. As the dilution solvent at the time of ink preparation, those having a high boiling point are preferable. For example, it is particularly preferable to use carbitol acetate, methoxypropyl acetate, cyclohexanone, diisobutyl ketone or the like. In addition, in the case of liquid resist inks, there are also two-component types that are stored in advance separately from the curing agent in consideration of storage stability and handling, and mixed with a curing agent as necessary before coating. is there. In the case of the present invention, a compound (B) that is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, and a blocked isocyanate group-containing compound, and a photopolymerization initiator (C) are required. Accordingly, it can be used as a two-component type, for example, stored separately from the others.

On the other hand, when using as a dry film type resist, first, a dry film type is obtained by applying a photosensitive composition dissolved in a solvent to a film substrate having good releasability such as a separate film and then drying the solvent. Create a resist. In this case, unlike the above-described liquid resist ink, it is necessary to dry the solvent completely in a short time, and therefore a solvent having a low boiling point is preferable. For example, it is particularly preferable to use methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, isopropyl alcohol, or the like. The dry film formed on the separate film is laminated on a copper circuit or the like formed on polyimide, and thereafter, bubbles and the like are removed and adhered to the circuit by lamination or vacuum lamination. After this pasting step, there may be a case where the radiation curing is performed through a separate film, or a case where the development pattern is brought into contact after the separation film is peeled to perform the radiation curing. When radiation curing is performed by bringing a development pattern into contact, if the dry film has a tack, the development pattern may be contaminated. Therefore, a dry film type resist is required to have a low dry film tack. Since the photosensitive resin composition of this invention can reduce a tack as needed, it can be usefully used also as a dry film resist.

Furthermore, the photosensitive resin composition of the present invention forms a pattern by developing after radiation curing, and forms a film having excellent resistance by thermosetting as post-cure. The post cure is preferably 30 to 2 hours at 100 to 200 ° C. Further, in order to further improve the resistance of the coating film, an active energy ray can be irradiated as necessary after post-curing. By irradiating the active energy ray after the post cure, the solder heat resistance and the like can be further improved.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”.

  The measurement conditions for GPC are as follows.

<Measurement of weight average molecular weight (Mw)>
For measurement of Mw, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size. In the measurement of the present invention, “LF-604” (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) is connected in series to the column, the flow rate is 0.6 ml / min, and the column temperature is 40. It carried out on the conditions of (degreeC) and the determination of the weight average molecular weight (Mw) was performed in polystyrene conversion.

<Molecular weight distribution (Mw / Mn)>
The degree of dispersion of the molecular weight is expressed. In the present invention, the weight average molecular weight (Mw) / number average molecular weight (Mn) was determined from the molecular weight measurement result.

<Preparation of photosensitive resin (A)>
[Production Example 1]
A 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, bisphenol A type epoxy having an epoxy equivalent of 650, a softening point of 81.1 ° C, and a melt viscosity (150 ° C) of 12.5 poise 371 parts of resin, 925 parts of epichlorohydrin, and 463 parts of dimethyl sulfoxide were added and dissolved uniformly, and then 52.8 parts of 98.5% aqueous sodium hydroxide solution was added at 70 ° C. over 100 minutes with stirring. After the addition, the reaction was further performed at 70 ° C. for 3 hours. Subsequently, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, the reaction product containing by-product salt and dimethyl sulfoxide is dissolved in 750 parts of methyl isobutyl ketone, and further 10 parts of 30% aqueous sodium hydroxide solution. And reacted at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After separation of oil and water, methyl isobutyl ketone is recovered by distillation from the oil layer, and an epoxy resin having an epoxy equivalent of 287, a hydrolyzable chlorine content of 0.07%, a softening point of 64.2 ° C., and a melt viscosity (150 ° C.) of 7.1 poise. 340 parts were obtained.

287 parts of this epoxy resin was put into a four-necked flask equipped with another stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe and thermometer, and further 72 parts of acrylic acid, 0.3 part of methylhydroquinone, cyclohexanone 194 The reaction mixture was dissolved by heating and stirring at 90 ° C. Subsequently, the reaction liquid was cooled to 60 ° C., 1.7 parts of triphenylphosphine was added, and the reaction was performed at 100 ° C. for about 32 hours in the presence of oxygen to obtain a reaction product having an actually measured acid value of 1 mgKOH / g. Next, 78 parts of succinic anhydride and 42 parts of cyclohexanone were added thereto and reacted at 95 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin whose main skeleton was a bisphenol A type epoxy resin. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content by this design is 450 eq / g, the weight average molecular weight in terms of polystyrene is 7400, the molecular weight distribution is 2.23, and the acid value of the resin solid content by actual measurement is 100 mgKOH / g. It was.

[Production Example 2]
To a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 330 parts of a cresol novolac epoxy resin having an epoxy equivalent of 218 g / eq (manufactured by Toto Kasei Co., Ltd .: YDCN-702). The mixture was melted by heating at 90 to 100 ° C. and stirred. Next, 120 parts of acrylic acid, 0.6 part of hydroquinone, and 5 parts of dimethylbenzylamine were added, and the mixture was heated to 115 ° C. with stirring in the presence of oxygen and reacted for 12 hours. Next, 400 parts of cyclohexanone was added to this flask and dissolved by heating to 70 ° C. Next, 81 parts of succinic anhydride was added, the temperature was raised to 95 ° C., and the mixture was stirred and reacted for 8 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, the mixture was cooled to room temperature to obtain a carboxyl group-containing photosensitive resin whose main skeleton was a cresol novolak skeleton. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content by this design is 319 g / eq, the weight average molecular weight in terms of polystyrene is 11000, the molecular weight distribution is 2.90, and the acid value of the resin solid content by measurement is 85 mgKOH / g. It was.

[Production Example 3]
A dropping funnel was placed in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, and 400 parts of cyclohexanone was charged into the flask, and the temperature was raised to 90 ° C. with stirring in a nitrogen atmosphere. did. In a separate container, 15 parts of methacrylic acid, 30 parts of methyl methacrylate, 30 parts of butyl methacrylate, 25 parts of benzyl methacrylate, 20 parts of azobisisobutyronitrile as a polymerization initiator and 100 parts of cyclohexanone are stirred and dissolved uniformly. did. The monomer solution was charged into a dropping funnel installed in the flask, and the monomer solution in the dropping funnel was dropped into the flask over 2 hours while stirring the flask at 90 ° C. in a nitrogen atmosphere. Stirring was continued at 90 ° C. even after completion of the dropping, and 0.5 part of azobisisobutyronitrile was charged into the flask after 2 hours from the end of the dropping. After 1 hour, 0.5 part of azobisisobutyronitrile was again added to the flask, and stirring was continued for another 2 hours. Thereafter, the flask was cooled to stop the reaction. A small amount of sampling was performed to obtain a carboxyl group-containing acrylic prepolymer having a polystyrene-equivalent weight average molecular weight of 18700, a molecular weight distribution of 2.58, and an acid value of resin solid content of 98 mgKOH / g.

Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 111 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. , Reacted at 90 ° C. for 8 hours. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing acrylic prepolymer having a polystyrene-equivalent weight average molecular weight of 19,900, a molecular weight distribution of 2.72, and an actually measured acid value of resin solids of 5 mgKOH / g.

Next, 63 parts of succinic anhydride was added to the flask and reacted for 6 hours with stirring at 90 ° C. in a dry air atmosphere. After confirming that absorption of the acid anhydride group disappeared by FT-IR measurement, the mixture was cooled to room temperature to obtain a carboxyl group-containing photosensitive resin whose main skeleton was an acrylic resin. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content by this design is 863 g / eq, the weight average molecular weight in terms of polystyrene is 22000, the molecular weight distribution is 2.81, and the acid value of the resin solid content by measurement is 70 mgKOH / g. It was.

[Production Example 4]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 212 parts of PTG850 (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, hydroxyl value = 129 mgKOH / g), ethylene glycol 75 Part, pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.) 159 parts, dimethylbenzylamine 2 parts, cyclohexanone 375 parts as a solvent, stirred for 10 hours at 100 ° C. with stirring in a nitrogen stream, Reaction was performed. Subsequently, 54 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 15,200, a molecular weight distribution of 2.87, and an actually measured acid value of 170 mgKOH / g of resin solids.

Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, 110 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine, and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After cooling, a small amount of sampling was performed to obtain a carboxyl group-containing photosensitive urethane resin whose main skeleton is an acid anhydride-modified urethane skeleton. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content by this design was 896 g / eq, the weight average molecular weight in terms of polystyrene was 18,800, the molecular weight distribution was 3.12, and the acid value of the resin solid content was 72 mgKOH / g as measured.

[Production Example 5]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 218 parts of PTG850 (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, hydroxyl value = 129 mgKOH / g), ethylene glycol 47 Part, 125 parts of pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.), 2 parts of dimethylbenzylamine, and 375 parts of cyclohexanone as a solvent, stirred for 10 hours at 100 ° C. with stirring in a nitrogen stream, Reaction was performed. Subsequently, 111 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 17000, a molecular weight distribution of 2.60, and an actually measured acid value of 110 mgKOH / g of resin solids.

Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air. While stirring, 131 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine, and 0.3 part of hydroquinone as a polymerization inhibitor were added. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 19,200, a molecular weight distribution of 3.00, and an actually measured resin solid acid value of 4 mgKOH / g.

Next, 74 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that absorption of the acid anhydride group disappeared by FT-IR measurement, the mixture was cooled to room temperature to obtain a carboxyl group-containing urethane resin whose main skeleton was an acid anhydride-modified urethane resin. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content by this design is 765 g / eq, the weight average molecular weight in terms of polystyrene is 21400, the molecular weight distribution is 3.20, and the acid value of the resin solid content by measurement is 67 mgKOH / g. It was.

Table 1 shows a summary of the specifications of the resins obtained in Production Examples 1 to 5.

[Production Example 6]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 64.8 parts of bisphenol A, 57.1 parts of YD8125 (manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type epoxy compound) EX861 (manufactured by Nagase ChemteX Corporation: polyethylene glycol diglycidyl ether) 128.1 parts, 1.25 parts triphenylphosphine as catalyst, 1.25 parts N, N-dimethylbenzylamine, 250 parts toluene as solvent The mixture was heated to 110 ° C. with stirring under a nitrogen stream and reacted for 8 hours to obtain a hydroxyl group-containing resin. Next, 54.6 parts of Ricacid SA (manufactured by Shin Nippon Rika Co., Ltd .: succinic anhydride) was added as an acid anhydride and reacted at 110 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air. While stirring, 26.0 parts of GMA (manufactured by NOF Corporation: glycidyl methacrylate), hydroquinone 0.165 as a polymerization inhibitor. Part was added and reacted at 80 ° C. for 8 hours. After completion of the reaction, methyl ethyl ketone was added to this solution to adjust the solid content to 50.0%. The hydroxyl group-containing photosensitive resin (A-1) according to the present design has an ethylenically unsaturated group equivalent of 1803 g / eq, a polystyrene-equivalent weight average molecular weight of 23500, and an actually measured acid value of resin solids of 63 mgKOH / g. there were.

[Production Example 7]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 60.8 parts of bisphenol A, 43.4 parts of YD8125 (manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type epoxy compound) , EX861 (manufactured by Nagase ChemteX Corporation: polyethylene glycol diglycidyl ether) 145.8 parts, 1.25 parts triphenylphosphine as catalyst, 1.25 parts N, N-dimethylbenzylamine, 250 parts toluene as solvent The mixture was heated to 110 ° C. with stirring under a nitrogen stream and reacted for 8 hours to obtain a hydroxyl group-containing resin. Next, 49.8 parts of Ricacid SA (manufactured by Shin Nippon Rika Co., Ltd .: succinic anhydride) was added as an acid anhydride and reacted at 110 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air, while stirring, 41.1 parts of GMA (manufactured by NOF Corporation: glycidyl methacrylate), hydroquinone 0.17 as a polymerization inhibitor. Part was added and reacted at 80 ° C. for 8 hours. After completion of the reaction, 26.0 parts of Ricacid SA (manufactured by Shin Nippon Rika Co., Ltd .: succinic anhydride) was added as an acid anhydride to a flask in which dry air was introduced, and reacted at 80 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Methyl ethyl ketone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive resin (A-2) according to this design is 1269 g / eq, the polystyrene-equivalent weight average molecular weight is 20200, and the acid value of the resin solid content measured is 73 mgKOH / g. there were.

[Production Examples 8 to 9]
Using the raw materials shown in Table 2, the same operations as in Production Example 7 were performed to obtain carboxyl group-containing photosensitive resins (A-2) of Production Examples 8 to 9.

Table 2 shows the specifications of the photosensitive resins obtained in Production Examples 6 to 9.

BisA: Bisphenol A
YD8125: manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type epoxy compound EX861: manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether SA: manufactured by Nippon Nippon Chemical Co., Ltd., succinic anhydride GMA: manufactured by NOF Corporation, glycidyl Methacrylate EX830: manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether YL7410: manufactured by Mitsubishi Chemical Corporation, rubber elastic epoxy resin

A photosensitive resin composition was prepared by the following method and evaluated as a photosensitive dry film and a photosensitive resist ink.
<Preparation of photosensitive resin composition>
[Examples 1 to 25]
Epicoat 1031S (manufactured by Mitsubishi Chemical Corporation) as fatty acid alkanolamide (D) and curing agent (B) according to the solid content ratio shown in Table 4 with respect to 100 parts of the solid content of the photosensitive resin solution obtained in the production example. Multifunctional glycidyl ether type epoxy resin), BL3175 (manufactured by Sumika Bayer Urethane Co., Ltd .: isocyanurate type blocked isocyanate), aluminum phosphinate EXOLITOP-935 (made by Clariant Japan) and phosphazene SPB-10 (Otsuka) as flame retardant (E) Chemical Co., Ltd. and cyanophenoxyphosphazene FP-300 (manufactured by Fushimi Pharmaceutical Co., Ltd.), copper phthalocyanine pigment LIONOL BLUE FG7350 (Toyochem Co., Ltd.) as a colorant, and Irgacure 907 (C) as a photopolymerization initiator (C) Chiba Specialte -Chemicals Co., Ltd .: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane), DETX-S (manufactured by Nippon Kayaku Co., Ltd .: 2,4-) as a photosensitizer Diethylthioxanthone) is uniformly dissolved and mixed, dispersed with a horizontal sand mill DYNO-MILL (manufactured by Shinmaru Enterprise Co., Ltd.), and dispersed with a grind gauge until the coarse particles are less than 10 μm to obtain a photosensitive resin composition. It was.

Table 3 shows the melting point of the fatty acid alkanolamide (D) used. The melting point of the fatty acid alkanolamide (D) is a value measured with a differential thermal analyzer DSC (EXSTAR DSC220 manufactured by SII Nanotechnology Co., Ltd.).

[Comparative Examples 1 to 7]
Except having changed into the material and usage-amount shown in Table 5, the photosensitive resin composition was produced like the Example.

<Production and evaluation of photosensitive dry film>
The photosensitive resin compositions obtained in Examples 1 to 17 and Comparative Examples 4 to 7 were uniformly coated on a 12 μPET film (S-12 manufactured by Toray DuPont Co., Ltd.) so that the dry film thickness was 40 μm. The film was dried at 100 ° C. for 5 minutes, cooled to room temperature, and a biaxially stretched polypropylene film (OPP film) was laminated on the surface of the photosensitive resin composition to obtain a photosensitive dry film. The following evaluation was performed. . The evaluation results are shown in Table 4.

(1) Tack dry film was evaluated by tackiness when it was manually bonded to a polyimide film (Kapton 100H). The tackiness was evaluated based on whether or not a dry film remained on the polyimide film when peeled from the polyimide film.
◎ ・ ・ ・ No tack at all and peels off immediately ○ ・ ・ ・ Small tack and can be peeled off even if left for more than 10 seconds Δ ・ ・ ・ Tack is left, but if left for more than 10 seconds, it is partially transferred onto polyimide .
X: Cannot be removed.

(2) The substrate warpage is 5 cm × 5 cm, and a 3-layer copper-clad laminate (electrolytic Cu 18 μm / adhesive 20 μm / PI 25 μm) made by Nikkan Kogyo is bordered with 2 mm of copper, and the pattern: line width 125 μm / between lines A dry film resist was vacuum-laminated on a pattern having a 125 μm pattern. The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds.
The vacuum-laminated sample was exposed to 300 mJ with a mercury short arc amplifier (5 kW) over a 120 μm PET Mylar sheet on 12 μPET, and then the 12 μPET film was peeled off, followed by thermosetting (post-cure) for 1 hour with a 150 ° C. hot air dryer. After passing through a solder reflow furnace at 260 ° C. and a peak temperature of 10 seconds, it was allowed to stand for 12 hours on a flat table at 25 ° C. and a humidity of 50%. For the sample after standing, the height at which the four corners of the square were lifted from the table was measured, the average value was calculated, and evaluated according to the following criteria. The smaller this value, the less the sample warps, indicating better. Good substrate warpage indicates good adhesion to the substrate.
◎ ・ ・ ・ 2mm or less ○ ・ ・ ・ 5mm or less △ ・ ・ ・ 6mm or more-10mm or less × ・ ・ ・ 11mm or more

(3) The OPP film was peeled off from the developable photosensitive dry film and vacuum-laminated on a polyamide film (Toray DuPont Co., Ltd .; Kapton 100H). The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. The vacuum-laminated sample was exposed on 12 μPET over a 120 μm PET Mylar sheet / Stouffer step tablet 21 with a mercury short arc amplifier (5 kW), the 12 μPET film was peeled off, and the following development conditions (1 at 30 ° C. liquid temperature) % Na ₂ CO ₃ aqueous solution was developed at a spray pressure of 0.2 MPa for 40 seconds. After development, the film was heat-cured (post-cured) for 1 hour in a hot air dryer at 150 ° C. The obtained cured film was cooled to room temperature, and developability was evaluated.
The number of steps at which the coating film was washed away with the developer was defined as the number of peeling steps, and the exposure amount at which the number of peeling steps was 6 was determined and evaluated. The exposure amount was measured using an integrated exposure meter UV-351 manufactured by Oak Manufacturing Co., Ltd.
◎ ・ ・ ・ less than 200 mJ / cm ² ○ ・ ・ ・ 200 to 400 mJ / cm ²
Δ: 400-600 mJ / cm ²
× ・ ・ ・ greater than 600 mJ / cm ²

(4) Resolution The same cured film as that used in the evaluation of developability was evaluated. The number of steps where the coating film was swollen by the developer was taken as the number of swelling steps, and the resolution step was determined by the following formula for the number of peeling steps confirmed by evaluation of developability.
[Resolution step] = [Number of peeling steps]-[Number of swelling steps]
It can be said that the smaller the resolution step, the sharper the pattern can be formed in the actual pattern forming process, and the better the resolution. Using this resolution step, the resolution was judged according to the following criteria.
◎ ・ ・ ・ Resolution step ≦ 1
○ ・ ・ ・ Resolution step = 2 ～ 3
△ ・ ・ ・ Resolution step = 4-7
× ・ ・ ・ Resolution step ≧ 8

(5) The OPP film was peeled off from the folding-resistant photosensitive dry film, and the photosensitive dry film was vacuum-laminated on a 2 cm × 9 cm two-layer substrate (manufactured by Nippon Steel Chemical Co., Ltd .: Espanex MC-18-25-00FRM). . The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. The vacuum-laminated sample was irradiated with ultraviolet light of 300 mJ / cm ^{2 with} a UV exposure device with a mercury short arc amplifier (5 kW) through a 120 μm PET Mylar sheet on 12 μPET, and then heat-cured for 1 hour in a hot air dryer at 150 ° C. (Post cure).
This sample was bent 180 degrees at a portion of conductor pattern width / space width = 50/50, and a 500 g weight was placed on the bent portion for 5 seconds, and this was performed once.
Whether or not a crack was generated in the dry film provided on the copper side of the two-layer substrate was observed with a microscope “VHX-900” manufactured by Keyence Corporation, and the number of times of bending without cracks was evaluated.
◎ ・ ・ ・ 20 times or more ○ ・ ・ ・ 11 times or more Δ ・ ・ ・ 5-10 times × ・ ・ ・ less than 5 times

(6) Insulation reliability The OPP film is peeled off from the photosensitive dry film, and a 65 mm × 65 mm sheet is formed into a comb-shaped pattern in which a copper circuit is formed on a polyimide (conductor pattern width / space width = 50 μm / 50 μm). Vacuum laminated to the printed circuit board. The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. The vacuum-laminated sample was irradiated with ultraviolet light of 300 mJ / cm ^{2 with} a UV exposure device using a mercury short arc amplifier (5 kW) over a 120 μm PET Mylar sheet on 12 μPET, and then heat cured for 1 hour with a 150 ° C. hot air dryer. (Post-cure) to prepare a test piece for evaluation. The conductor circuit of this test piece was placed in a pressure cooker (PC-422R8 manufactured by Hiraoka Seisakusho), and a DC voltage of 50 V was continuously applied for 100 hours under an atmosphere of 130 ° C., 85% relative humidity and 2 atm. The insulation resistance value between the conductors was measured. The evaluation criteria are as follows.
○ ・ ・ ・ Insulation resistance value 10 ⁷ or more △ ・ ・ ・ Insulation resistance value 10 ⁶ or more and less than 10 ⁷ Ω × ・ ・ ・ Insulation resistance value less than 10 ⁶ Ω (7) Heat resistance 5 cm × 5 cm Nikkan Kogyo's 3-layer copper 2mm copper border is put on the laminated laminate (electrolytic Cu 18μm / adhesive 20μm / PI25μm), and the pattern: line width 125μm / line spacing 125μm pattern is formed on the inside. Laminated. The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds.
The vacuum-laminated sample was exposed to 300 mJ with a mercury short arc amplifier (5 kW) through a 120 μm PET Mylar sheet on 12 μPET, and then the 12 μPET film was peeled off, followed by thermosetting (post-cure) for 1 hour with a 150 ° C. hot air dryer. Thereafter, it was passed through a solder reflow furnace at 260 ° C. and a peak temperature of 10 seconds. The degree of discoloration after passing was evaluated.
○ ・ ・ ・ No discoloration △ ・ ・ ・ Slight discoloration × ・ ・ ・ Significant discoloration

<Evaluation of photosensitive resist ink>
The photosensitive resin compositions obtained in Examples 18 to 25 and Comparative Examples 1 to 3 were evaluated by the following methods. The evaluation results are shown in Table 5.

(1) A polyimide film (Kapton 100H) coated with a blade knife coater uniformly on a tack polyimide film so as to have a film thickness of 40 μm and allowed to stand for 5 minutes with a 100 ° C. hot air drier. Was evaluated by the tackiness when it was attached to the surface of the photosensitive resist ink by hand. The tackiness was evaluated based on whether or not a dry film remained on the polyimide film when peeled from the polyimide film.
◎ ・ ・ ・ No tack at all and peels off immediately ○ ・ ・ ・ Small tack and can be peeled off even if left for more than 10 seconds Δ ・ ・ ・ Tack is left, but if left for more than 10 seconds, it is partially transferred onto polyimide .
X: Cannot be removed.

(2) The substrate warpage is 5 cm × 5 cm, and a 3-layer copper-clad laminate (electrolytic Cu 18 μm / adhesive 20 μm / PI 25 μm) made by Nikkan Kogyo is bordered with 2 mm of copper, and the pattern: line width 125 μm / between lines A photosensitive resin composition is uniformly coated on a 125 μm pattern so that the dry film thickness is 40 μm, dried at 100 ° C. for 5 minutes, and then a mercury short arc amplifier over a 120 μm PET Mylar sheet on the sample. After 300 mJ exposure at (5 kW), heat curing (post-cure) was carried out with a hot air dryer at 150 ° C. for 1 hour. After passing through a solder reflow furnace at 260 ° C. and a peak temperature of 10 seconds, it was allowed to stand for 12 hours on a flat table at 25 ° C. and a humidity of 50%. For the sample after standing, the height at which the four corners of the square were lifted from the table was measured, the average value was calculated, and evaluated according to the following criteria. The smaller this value, the less the sample warps, indicating better. Good substrate warpage indicates good adhesion to the substrate.

◎ ・ ・ ・ 2mm or less ○ ・ ・ ・ 5mm or less △ ・ ・ ・ 6mm or more-10mm or less × ・ ・ ・ 11mm or more

(3) The photosensitive resin composition is uniformly coated on a developable polyimide film (Toray DuPont Co., Ltd .; Kapton 100H) so that the dry film thickness is 40 μm and dried at 100 ° C. for 5 minutes, and then on the sample. After exposure with a mercury short arc amplifier (5 kW) through 21 stages of 120 μm PET Mylar sheet / Stouffer step tablet, the following development conditions (1% Na ₂ CO ₃ aqueous solution with a liquid temperature of 30 ° C. of 0.2 MPa are applied with a developing machine. Development was performed at a spray pressure for 40 seconds.
After development, the film was heat-cured (post-cured) for 1 hour in a hot air dryer at 150 ° C. The obtained cured film was cooled to room temperature, and developability was evaluated. The number of steps at which the coating film was washed away with the developer was defined as the number of peeling steps, and the exposure amount at which the number of peeling steps was 6 was determined and evaluated. The exposure amount was measured using an integrated exposure meter UV-351 manufactured by Oak Manufacturing Co., Ltd.

◎ ・ ・ ・ less than 200 mJ / cm ² ○ ・ ・ ・ 200 to 400 mJ / cm ²
Δ: 400-600 mJ / cm ²
× ・ ・ ・ greater than 600 mJ / cm ²

(4) The same cured film as used in the evaluation of resolution developability was evaluated. The number of steps where the coating film was swollen by the developer was taken as the number of swelling steps, and the resolution step was determined by the following formula for the number of peeling steps confirmed by evaluation of developability.
[Resolution step] = [Number of peeling steps]-[Number of swelling steps]
It can be said that the smaller the resolution step, the sharper the pattern can be formed in the actual pattern forming process, and the better the resolution. Using this resolution step, the resolution was judged according to the following criteria.
◎ ・ ・ ・ Resolution step ≦ 1
○ ・ ・ ・ Resolution step = 2 ～ 3
△ ・ ・ ・ Resolution step = 4-7
× ・ ・ ・ Resolution step ≧ 8

(5) A photosensitive resin composition is uniformly coated on a two-layer substrate (Nippon Steel Chemical Co., Ltd .: Espanex MC-18-25-00FRM) having a folding resistance of 2 cm × 9 cm so that the dry film thickness is 40 μm. After drying at 100 ° C. for 5 minutes, the sample was exposed to 300 mJ through a 120 μm PET Mylar sheet with a mercury short arc amplifier (5 kW), and then heat cured (post-cure) for 1 hour with a hot air dryer at 150 ° C.
This sample was bent 180 degrees at a portion of conductor pattern width / space width = 50/50, and a 500 g weight was placed on the bent portion for 5 seconds, and this was performed once.
Whether or not a crack was generated in the dry film provided on the copper side of the two-layer substrate was observed with a microscope “VHX-900” manufactured by Keyence Corporation, and the number of times of bending without cracks was evaluated.
◎ ・ ・ ・ 20 times or more ○ ・ ・ ・ 11-19 times Δ ・ ・ ・ 5-10 times × ・ ・ ・ less than 5 times

(6) Insulation reliability 65 mm × 65 mm size sheet, comb-shaped pattern (conductor pattern width / space width = 50 μm / 50 μm) in which a copper circuit is formed on polyimide, a photosensitive resin composition on a printed circuit board After coating uniformly to a dry film thickness of 40 μm and drying at 100 ° C. for 5 minutes, the sample is exposed to 300 mJ through a 120 μm PET Mylar sheet with a mercury short arc amplifier (5 kW) and then dried with hot air at 150 ° C. It was heat-cured (post-cure) for 1 hour in a vessel. The conductor circuit of this test piece was placed in a pressure cooker (PC-422R8 manufactured by Hiraoka Seisakusho), and a DC voltage of 50 V was continuously applied for 100 hours under an atmosphere of 130 ° C., 85% relative humidity and 2 atm. The insulation resistance value between the conductors was measured. The evaluation criteria are as follows.
○ ・ ・ ・ Insulation resistance value 10 ⁷ or more △ ・ ・ ・ Insulation resistance value 10 ⁶ or more and less than 10 ⁷ Ω × ・ ・ ・ Insulation resistance value less than 10 ⁶ Ω (7) Heat resistance 5 cm × 5 cm Nikkan Kogyo's 3-layer copper A photosensitive resin composition is applied to a laminated laminate (electrolytic Cu 18 μm / adhesive 20 μm / PI 25 μm) with a copper border of 2 mm, and a pattern: line width 125 μm / line spacing 125 μm formed inside. After coating uniformly to a dry film thickness of 40 μm and drying at 100 ° C. for 5 minutes, the sample was exposed to 300 mJ through a 120 μm PET Mylar sheet with a mercury short arc amplifier (5 kW), and then a hot air dryer at 150 ° C. For 1 hour. The sample was passed through a solder reflow furnace at 260 ° C. and a peak temperature of 10 seconds. The degree of discoloration after passing was evaluated.
○ ・ ・ ・ No discoloration △ ・ ・ ・ Slight discoloration × ・ ・ ・ Significant discoloration

From the evaluation results of Examples and Comparative Examples, by adding a fatty acid alkanolamide to the photosensitive resin composition, developability, resolution, folding resistance and substrate warpage are improved, and resist performance is improved. In addition, fatty acid alkanolamide has a melting point higher than room temperature, and if a solid one is added at room temperature, the resist can be attached to the circuit without increasing the surface tack of the resist. Excellent.

Claims (9)

  Photosensitive resin (A) having a double bond equivalent of 200 to 5000 g / eq, an acid value of 10 to 200 mgKOH / g, and a weight average molecular weight of 1,000 to 100,000, an epoxy group-containing compound, an unblocked isocyanate compound, and a blocked A photosensitive resin composition comprising at least one curing agent (B) selected from isocyanate compounds, a photopolymerization initiator (C), and a fatty acid alkanolamide (D).   The photosensitive resin composition according to claim 1, wherein the fatty acid alkanolamide (D) has a melting point of -10 to 80 ° C.   The photosensitive resin composition of Claim 1 or 2 which contains 1-30 weight part of fatty acid alkanolamides (D) with respect to 100 weight part of solid content of the photosensitive resin (A).   The photosensitive resin composition in any one of Claims 1-3 which contain 1-50 weight part of hardening | curing agents (B) with respect to 100 weight part of solid content of the photosensitive resin (A). The photosensitive resin (A) is
Resin (c) containing a side chain hydroxyl group by reacting an epoxy compound (a) having at least two epoxy groups in one molecule with a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule. Produces
Reacting the side chain hydroxyl group-containing resin (c) with the polybasic acid anhydride (d) to produce a carboxyl group-containing resin (e);
Hydroxyl group-containing photosensitive resin (A) obtained by reacting the carboxyl group-containing resin (e) with an epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group -1) or
It is a carboxyl group-containing photosensitive resin (A-2) obtained by reacting the hydroxyl group in the hydroxyl group-containing resin (A-1) with the acid anhydride group in the polybasic acid anhydride (d). The photosensitive resin composition according to any one of claims 1 to 4.   Furthermore, the photosensitive resin composition in any one of Claims 1-5 containing a flame retardant (E).   Hardened | cured material formed by hardening | curing the photosensitive resin composition in any one of Claims 1-6.   A photosensitive solder resist ink comprising the photosensitive resin composition according to claim 1 and a solvent. A dry film type photosensitive solder resist comprising the photosensitive resin composition according to claim 1.