KR20090047367A - Photocurable resin composition, cured product pattern, and printed wiring board - Google Patents

Abstract

The present invention is highly sensitive to active energy rays, in particular, excellent in exposure curing by direct drawing of laser light, developability, dry touch, solder heat resistance, electroless gold plating resistance, alkali resistance, PCT and PCBT resistance, and solder An object of the present invention is to provide an alkali developing photocurable resin composition useful as a resist.

The present invention is characterized by containing (A) a carboxylic acid-containing photosensitive resin comprising a structure represented by the following formula (I), (B) a photopolymerization initiator, and (C) a compound having two or more ethylenically unsaturated groups in one molecule. The present invention relates to an alkali developable photocurable resin composition.

<Formula I>

(In Formula I, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, and R ³ represents a hydrogen atom or an organic acid ester residue.)

 Carboxylic acid-containing photosensitive resin, photoinitiator, alkali-developable photocurable resin composition

Description

Photocurable resin composition, cured product pattern and printed wiring board {PHOTOCURABLE RESIN COMPOSITION, CURED PRODUCT PATTERN, AND PRINTED WIRING BOARD}

The present invention relates to an alkali developing photocurable resin composition which is excellent in sensitivity to active energy rays and useful as a soldering resist.

BACKGROUND OF THE INVENTION In recent years, laser scanning exposure has been widespread in terms of excellent alignment accuracy as an exposure means for soldering resists for printed wiring boards. Laser exposure is an image formation while scanning a solder resist on a patterned wiring board without using a photomask. Conventionally, some solder resists have a drawback in that exposure is very time consuming because the appropriate exposure amount is 200 mJ / cm 2 or more. Therefore, very high sensitivity is required for the solder resist corresponding to laser exposure.

From this background, the proposal of the photosensitive composition which can exhibit high photopolymerization ability has been made (for example, refer patent document 1 and patent document 2). However, some of the photosensitive compositions that have been proposed so far can exhibit a high photopolymerization ability, but the sensitivity is not necessarily sufficient for laser direct exposure, and various special properties other than the sensitivity required for the photosensitive composition can be achieved. Even sex is not necessarily enough. Specifically, in the composition disclosed in Patent Document 1, only glycidyl methacrylate is exemplified as a compound having a cyclic ether group and an ethylenically unsaturated group in one molecule used for formation of the carboxyl group-containing photosensitive resin, but the sensitivity is insufficient. In addition, when the addition amount was increased, the developability tended to be deteriorated. On the other hand, in the case of using caprolactone modified acrylates which have been molecularly elongated by reacting ε-caprolactone in series with acrylates proposed in Patent Document 2, the sensitivity is high, but the touch-drying property is very poor, and the solder The heat resistance was also insufficient.

In addition, alkali developing photo solder resists still have problems in terms of durability. That is, the alkali solder type photo solder resist is inferior in chemical resistance, water resistance, heat resistance, etc. compared with the conventional thermosetting type and solvent developing type. This is because alkali developing type photo solder resist has a hydrophilic group as a main component in order to enable alkali developing. Thereby, chemical liquid, water, water vapor, etc. permeate easily, and fall of chemical-resistance and the adhesiveness of a resist film and copper are reduced. As a result, alkali resistance as chemical resistance is weak, and in particular, in semiconductor packages such as BGA and CSP, PCT resistance (pressure cooker test resistance), which is particularly moist and heat resistant, is required. What is impossible is reality. In addition, in the PCBT test under voltage applied under the PCT condition, it is a fact that in most cases, defects due to migration are confirmed in several hours.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2007-41502 (Patent Claims)

[Patent Document 2] Japanese Patent Application Laid-Open No. 2007-3590 (claims)

The present invention was developed in view of the above problems, and has high sensitivity to active energy rays, excellent exposure hardenability by direct drawing thereof, developability, dry touch, solder heat resistance, electroless gold plating resistance, alkali resistance, PCT Another object is to provide an alkali developing photocurable resin composition which is excellent in PCBT resistance and useful as a soldering resist.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, this subject uses the carboxylic acid containing photosensitive resin containing a specific structure as photosensitive resin, and the said subject by the photocurable resin composition which combines another component here. It has been found that to solve the problem has come to complete the present invention.

That is, this invention contains the thing containing the compound which has two or more ethylenically unsaturated groups in (A) carboxylic acid containing photosensitive resin containing the structure represented by following formula (I), (B) photoinitiator, and (C) 1 molecule. It is an alkali developable photocurable resin composition characterized by the above-mentioned.

<Formula I>

In general formula (I), R <^1> is a hydrogen atom or a methyl group, R <^2> is a C2-C6 linear, branched or cyclic alkyl group, R <^3> represents a hydrogen atom or an organic acid ester residue.

Here, in formula (I), R ³ may be an acid anhydride residue, or may be a (meth) acrylic acid residue.

Further, (B) the photopolymerization initiator is an oxime ester photopolymerization initiator comprising a structure represented by the following formula (II), an aminoacetophenone photopolymerization initiator comprising a structure represented by the following formula (III), and a structure represented by the following formula (IV) It may be one or a mixture of two or more selected from the group consisting of acylphosphine oxide-based photopolymerization initiator comprising a.

<Formula II>

<Formula III>

<Formula IV>

In formulas (II) to (IV), R ¹ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (one or more) May be substituted with a hydroxyl group, and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (alkyl group having 1 to 6 carbon atoms) Or may be substituted with a phenyl group),

R ² may be substituted with a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, or an alkyl chain May have one or more oxygen atoms in the middle), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms) ,

R ³ and R ⁴ each independently represent a linear, branched or cyclic alkyl group or an arylalkyl group having 1 to 12 carbon atoms,

R ⁵ and R ⁶ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ⁵ and R ⁶ may be bonded to form a cyclic alkyl ether group,

R ⁷ and R ⁸ are each independently a linear, branched or cyclic alkyl, alkoxy, cyclohexyl, cyclopentyl, or aryl group having 1 to 10 carbon atoms (which may be substituted with a halogen atom, an alkyl group, or an alkoxy group). Present), or RC (= O)-group, wherein R represents a hydrocarbon group of 1 to 20 carbon atoms. Except that both R ⁷ and R ⁸ are RC (═O) — groups.

In addition, the resin composition of the present invention may further include (D) a thermosetting component.

Moreover, the resin composition of this invention can be a soldering resist which further contains the (E) coloring agent.

This invention is a photocurable dry film obtained by apply | coating and drying the photocurable resin composition of the said invention to a carrier film in another aspect.

Moreover, in another aspect, this invention is a hardened | cured material pattern formed using the resin layer containing the said photocurable resin composition, and is a hardened | cured material pattern in which pattern formation is performed by active energy ray irradiation. Here, pattern formation by active energy ray irradiation may be by direct drawing using active energy rays having a wavelength of 350 nm to 410 nm.

Moreover, in another aspect, this invention is a printed wiring board provided with the said hardened | cured material pattern on a copper layer.

In addition, in this specification, (meth) acrylic acid is used as a term which shows acrylic acid and / or methacrylic acid, and it is the same about other similar expression.

According to the present invention, it has high sensitivity to active energy rays, and in particular, has excellent exposure hardenability by direct drawing of laser light, developability, dry touch, solder heat resistance, electroless gold plating resistance, alkali resistance, PCT and PCBT resistance. An alkali developing photocurable resin composition useful as a solder resist is provided.

Hereinafter, each structural component of the photocurable resin composition of this invention is demonstrated in detail.

The carboxylic acid containing photosensitive resin (A) contained in the photocurable resin composition of this invention contains the structure represented by following General formula (I), and contains the carboxylic acid in a molecule | numerator.

<Formula I>

In formula, R <^1> is a hydrogen atom or a methyl group, R <^2> is a C2-C6 linear, branched or cyclic alkyl group, R <^3> represents a hydrogen atom or an organic acid ester residue.

Here, as an organic acid ester residue represented by R <^3> , an acid anhydride residue or a (meth) acrylic acid residue is mentioned, As a specific example of an acid anhydride residue, (b) unsaturated group containing acid anhydride and (d) polybasic acid mentioned later Anhydrides etc. are mentioned.

The carboxylic acid-containing photosensitive resin (A) of the present invention is (a) a compound having two or more hydroxyl groups and one carboxyl group in one molecule, (b) an unsaturated group-containing acid anhydride, and (c) at least two molecules in one molecule. Although it can obtain according to the procedure (1)-(3) shown below using the epoxy compound which has the above epoxy group, and (d) polybasic acid anhydride, it is not limited to this.

In other words,

(1) An unsaturated group-containing acid anhydride (b) is reacted with a compound (a) having two or more hydroxyl groups and one carboxyl group in one molecule, and having two (meth) acryl groups and one carboxyl group in one molecule. Synthesize the compound. After reacting the epoxy compound (c) which has at least 2 or more epoxy group in 1 molecule with respect to the obtained compound, it is obtained by making polybasic acid anhydride (d) react further.

As a characteristic of the system of (1), what is effective for high sensitivity by increasing the density | concentration of a photosensitive group is mentioned. Although the detail is not clear, the improvement of developability was also confirmed. It is thought that this is because the emulsion effect was increased by the affinity with the other component which does not contain a carboxyl group as the acryl group concentration in resin improved. In addition, the improvement of the PCT and PCBT resistance by the alkali resistance and hydrophobicity improvement with the increase of the crosslinking density was also confirmed.

(2) A compound having two (meth) acryl groups and one carboxyl group in one molecule by reacting an unsaturated group-containing acid anhydride (b) with a compound (a) having two or more hydroxyl groups and one carboxyl group in one molecule. Synthesize The epoxy compound (c) which has at least 2 or more epoxy groups in 1 molecule is made to react with the obtained compound. It is obtained by making the compound obtained further react the compound (a) which has two or more hydroxyl groups and one carboxyl group in 1 molecule, and then makes polybasic acid anhydride react.

As a characteristic of the system of (2), the thing effective for high sensitivity by increasing the density | concentration of the photosensitive group like (1) is mentioned. Moreover, as a characteristic of the system of (2), the thing of the photosensitive unit (acryl group) and the developable unit (carboxyl group) completely completely is mentioned separately. This effect confirmed that the maximum developing life was extended from (1) with the same sensitivity as (1). In addition, as shown in (1), improvement of developability and improvement of PCT and PCBT resistance were also confirmed.

(3) An epoxy compound (c) having at least two or more epoxy groups in one molecule and a compound (a) having two or more hydroxyl groups and one carboxyl group in one molecule are reacted. It is obtained by making a unsaturated group containing acid anhydride (b) react with the compound obtained, and then making polybasic acid anhydride (d) react.

As a characteristic in the system of (3), what is effective for high sensitivity by increasing the density | concentration of the photosensitive group like (1) and (2) is mentioned. Moreover, also regarding (3), the improvement of developability was also confirmed similarly to (1) and (2). However, unlike (2), the photosensitive unit (acryl group) and the developable unit (carboxyl group) become random, and as a result, it becomes difficult to fully control the resin structure.

These systems (1) to (3) each have excellent characteristics, but it is considered that (2) or (1) is particularly preferable from the balance of photosensitivity, developability, and properties of the obtained cured product.

As a specific example of the compound which has two or more hydroxyl groups and one carboxyl group in (a) 1 molecule used for the synthesis | combination of (A) carboxylic acid containing photosensitive resin as described in said (1)-(3), Dimethylolpropionic acid And polyhydroxy containing monocarboxylic acids such as dimethylol acetic acid, dimethylol butyric acid, dimethylol valeric acid and dimethylol caproic acid. As an especially preferable thing, dimethylol propionic acid etc. are mentioned, for example.

(b) As an unsaturated group containing acid anhydride, acrylic anhydride and methacrylic anhydride are mentioned, These can be used individually or in combination of 2 or more types.

(c) As an epoxy compound which has two or more epoxy groups in 1 molecule, various epoxy resins for well-known tubes, for example, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, brominated bisphenol A-type epoxy resin , Hydrogenated bisphenol A epoxy resin, biphenol epoxy resin, bixylenol epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, brominated phenol novolak epoxy resin, novolac epoxy of bisphenol A Glycidyl ether compounds such as resins; Glycidyl ester compounds such as terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, and dimer acid diglycidyl ester; Triglycidyl isocyanurate, N, N, N ', N'- tetraglycidyl methacrylatenamine, N, N, N', N'- tetraglycidylbisaminomethylcyclohexane, N, N- Glycidyl amine compounds, such as diglycidyl aniline, are used. Especially, since a phenol novolak-type epoxy resin and a cresol novolak-type epoxy resin can provide the cured coating film which was highly sensitive and excellent in heat resistance, it is preferable. Moreover, the cresol novolak-type epoxy resin whose softening point is 60 degreeC or more is more preferable because it is excellent also in touch drying property. These polyfunctional epoxy compounds can also be used individually or in combination of 2 or more types.

(d) As the polybasic acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, itaconic anhydride, methyl end methylene tetrahydrophthalic anhydride, trimellitic anhydride, Pyromellitic anhydride etc. can be mentioned, These can be used individually or in combination of 2 or more types.

Moreover, about the carboxylic acid containing photosensitive resin (A) obtained by (1)-(3), resin obtained by making the compound which has a cyclic ether group and ethylenically unsaturated group react in (e) 1 molecule further can also be used. .

As a compound which has a cyclic ether group and ethylenically unsaturated group in said (e) molecule | numerator, 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3 -Hydroxypropyl (meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxypentyl ( Epoxy-group containing ethylenically unsaturated monomers, such as a meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl ether, or a glycidyl (meth) acrylate, These can be mentioned individually or It can be used in combination of 2 or more type. Among these epoxy group-containing ethylenically unsaturated monomers, 4-hydroxybutyl (meth) acrylate glycidyl ether and glycidyl (meth) acrylate are particularly preferable because they have appropriate productivity and photocurability.

The amount of the compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule of (e) is preferably 5% to 40% equivalents, more preferably 10% to 30% equivalents relative to the acid anhydride residue. to be. The addition amount of 5% equivalent or more is preferable in terms of increasing the sensitivity or improving the electroless gold plating resistance, while exceeding 40% equivalent may shorten the maximum developing life or deteriorate the touch drying property. Modification by these compounds (e) further confirmed a synergistic effect on higher sensitivity, alkali resistance, PCT and PCBT resistance by improving the crosslinking density.

The acid value of the said carboxylic acid containing photosensitive resin (A) becomes like this. Preferably it is the range of 40-200 mgKOH / g, More preferably, it is the range of 80-120 mgKOH / g. If the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, if it exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary or in some cases. It is not preferable because it dissolves and peels off with a developer without distinguishing between the exposed portion and the unexposed portion, and it becomes difficult to draw a normal resist pattern.

Moreover, although the weight average molecular weight of the said carboxylic acid containing photosensitive resin (A) changes with resin frame | skeleton, it is preferable to exist in the range of 2000-50000, Furthermore, it is 5000-20000. If the weight average molecular weight is less than 2000, the tack-free performance may be inferior, the moisture resistance of the coating film after exposure is bad, and a film reduction may occur at the time of image development, and the resolution may fall large. On the other hand, when a weight average molecular weight exceeds 50000, developability may become remarkably bad and storage stability may be inferior.

The compounding ratio of such carboxylic acid containing photosensitive resin (A) becomes like this. Preferably it is 20-60 mass% with respect to the total mass of a resin composition, More preferably, it is 30-50 mass%. When it is less than the said range, since coating film strength may fall, it is not preferable. On the other hand, when more than the said range, since viscosity may become high, or a resist coating property etc. may fall, it is not preferable.

In this invention, in addition to the said carboxylic acid containing photosensitive resin (A), carboxylic acid resin for a well-known pipe | tube, Especially preferably, photosensitive carboxylic acid resin can be added.

Next, a photoinitiator (B) is demonstrated.

As a photoinitiator (B), the oxime ester system photoinitiator (B-1) containing the structure represented by following formula (II), the (alpha)-aminoacetophenone type photoinitiator containing the structure represented by following formula (III) It is preferable to use 1 type, or 2 or more types of photoinitiators selected from the group which consists of 2) and the acylphosphine oxide type photoinitiator (B-3) containing the structure represented by following formula (IV).

<Formula II>

<Formula III>

<Formula IV>

In Formulas II to IV,

R ¹ may be substituted with a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, which may be substituted with one or more hydroxyl groups. And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (alkyl group having 1 to 6 carbon atoms or a phenyl group). Present),

R ² may be substituted with a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, or an alkyl chain May have one or more oxygen atoms in the middle), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms) ,

R ³ and R ⁴ each independently represent a linear, branched or cyclic alkyl group or an arylalkyl group having 1 to 12 carbon atoms,

R ⁵ and R ⁶ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ⁵ and R ⁶ may be bonded to each other to form a cyclic alkyl ether group,

R ⁷ and R ⁸ are each independently a linear, branched or cyclic alkyl, alkoxy, cyclohexyl, cyclopentyl, or aryl group having 1 to 10 carbon atoms (which may be substituted with a halogen atom, an alkyl group, or an alkoxy group). Present), or RC (= O)-group, wherein R represents a hydrocarbon group of 1 to 20 carbon atoms. Except that both R ⁷ and R ⁸ are RC (═O) — groups.

As an oxime ester type photoinitiator (B-1) which has a group represented by the said Formula (II), Preferably, 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by following formula (V):

<Formula V>

Compound represented by the following formula (VI):

<Formula VI>

(In the meal,

R ⁹ is a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, and a carbon number An alkoxycarbonyl group of 2 to 12 (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups or may have one or more oxygen atoms in the middle of the alkyl chain),

Or a phenoxycarbonyl group,

R ¹⁰ and R ¹² are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms substituted with one or more hydroxyl groups. May have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (alkyl group having 1 to 6 carbon atoms or phenyl group) May be substituted)

R ¹¹ may be substituted with a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, or may be substituted with one or more hydroxyl groups, May have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group) )); And

The compound represented by following formula (VII) is mentioned.

<Formula VII>

(In the meal,

R ¹³ , R ¹⁴ and R ¹⁹ each independently represent a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms,

R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms,

M represents O, S or NH,

m and n each independently represent an integer of 0 to 5)

Especially, the compound represented by 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by general formula (V), and general formula (VI) is more preferable. As a commercial item, CGI-325, Irgacure-OXE01, Irgacure-OXE02, etc. made by Ciba Specialty Chemicals, etc. are mentioned. These oxime ester photoinitiators can be used individually or in combination of 2 or more types.

Examples of the α-aminoacetophenone-based photopolymerization initiator (B-2) containing the structure represented by the formula (III) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4 -(4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, etc. are mentioned. Examples of commercially available products include Irgacure-907, Irgacure-369 and Irgacure-379 manufactured by Ciba Specialty Chemicals.

As an acylphosphine oxide type photoinitiator (B-3) containing the structure represented by General formula (IV), 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Examples of commercially available products include Lucirin TPO manufactured by BASF Corporation, Irgacure-819 manufactured by BASA Specialty Chemicals, Inc., and the like.

The blending ratio of such a photopolymerization initiator (B) is preferably 0.01 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). If it is less than 0.01 mass part, since the photocurability on copper is inferior and a coating film peels or coating film properties, such as chemical resistance, fall, it is unpreferable. On the other hand, when it exceeds 30 mass parts, since the light absorption in the soldering resist coating-film surface of a photoinitiator (B) becomes deep and core part hardenability tends to fall, it is unpreferable.

On the other hand, in the case of the oxime ester type photoinitiator containing the structure represented by the said Formula (II), the compounding quantity becomes like this. Preferably it is 0.01-20 mass parts with respect to 100 mass parts of said carboxylic acid containing photosensitive resin (A). It is preferable to select in the range of 0.01-5 mass parts preferably.

In the composition of this invention, photoinitiators other than the compound mentioned above, a photoinitiator, and a sensitizer can be used, For example, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, benzo A phenone compound, a xanthone compound, a tertiary amine compound, etc. are mentioned.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.

Specific examples of the thioxanthone compound include 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, and 2,4-diisopropyl thioxanthone.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4'-methyldiphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4-benzoyl- 4'-propyldiphenylsulfide.

Specific examples of the tertiary amine compound include ethanolamine compounds and compounds having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (Nissocure MABP manufactured by Nippon Soda Co., Ltd.), 4,4 ' Dialkylaminobenzophenones such as -diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- ( Dialkylamino group-containing coumarin compounds such as diethylamino) -4-methylcoumarin), 4-dimethylaminobenzoic acid ethyl (kayakure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (International Bio-Synthetics Co., Ltd.) Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Shincetics Co., Ltd.), isoamylethyl ester of p-dimethylaminobenzoic acid (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.) ), 4-dimethylaminobenzoic acid 2-ethylhexyl (Esolol 507 by Van Dyck), 4 And 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

Among the above, thioxanthone compounds and tertiary amine compounds are preferable. The thioxanthone compound is preferably contained in terms of core hardenability, and in particular, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, and 2,4- Thioxanthone compounds, such as diisopropyl thioxanthone, are preferable.

As a compounding ratio of such a thioxanthone compound, Preferably it is 20 mass parts or less, More preferably, it is 10 mass parts or less with respect to 100 mass parts of said carboxylic acid containing photosensitive resin (A). When the compounding ratio of a thioxanthone compound is too large, since thick film sclerosis | hardenability will fall and it will lead to the cost increase of a product, it is unpreferable.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As a dialkylamino benzophenone compound, 4,4'- diethylamino benzophenone is preferable because it is low in toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a small coloration because the maximum absorption wavelength is in the ultraviolet region, and of course, the colorless transparent photosensitive composition can be used as a color pigment. It becomes possible to provide the coloring soldering resist film which reflected the color. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

As a compounding ratio of such a tertiary amine compound, Preferably it is 0.1-20 mass parts, More preferably, it is the ratio of 0.1-10 mass parts with respect to 100 mass parts of said carboxylic acid containing photosensitive resin (A). When the compounding ratio of the tertiary amine compound is less than 0.1 part by mass, there is a tendency that sufficient sensitization effect cannot be obtained. When it exceeds 20 mass parts, the light absorption in the surface of the dry solder resist coating film by a tertiary amine compound becomes severe, and there exists a tendency for deep-part sclerosis | hardenability to fall.

These photoinitiators, photoinitiator adjuvant, and a sensitizer can be used individually or as a mixture of 2 or more types.

It is preferable that the total amount of such a photoinitiator (B), a photoinitiator, and a sensitizer are a range which becomes 35 mass parts or less with respect to 100 mass parts of said carboxylic acid containing photosensitive resin (A). When it exceeds 35 mass parts, there exists a tendency for deep-part sclerosis | hardenability to fall by these light absorption.

Next, the compound (C) which has two or more ethylenically unsaturated groups in a molecule | numerator is demonstrated.

Compound (C) which has two or more ethylenically unsaturated groups in the molecule | numerator used for the photocurable resin composition of this invention is photocured by active energy ray irradiation, and the said ethylene unsaturated group containing carboxylic acid containing photosensitive resin (A ) To insolubilize or insolubilize the aqueous alkali solution. As such a compound, Diacrylates of glycol, such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, propylene glycol; Polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts or propylene oxide adducts thereof; Polyhydric acrylates, such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; And melamine acrylate, and / or each methacrylate corresponding to the acrylate.

Moreover, hydroxyacrylates, such as pentaerythritol triacrylate, and isohydride are used for the epoxy acrylate resin which made acrylic acid react with polyfunctional epoxy resins, such as a cresol novolak-type epoxy resin, and the hydroxyl group of this epoxy acrylate resin. Epoxyurethane acrylate compounds etc. which reacted the half urethane compound of diisocyanate, such as phorone diisocyanate, are mentioned. Such epoxy acrylate-based resin can improve photocurability without deteriorating the touch dryness.

The compounding ratio of the compound (C) which has two or more ethylenically unsaturated groups in such a molecule | numerator becomes like this. Preferably it is 1-100 mass parts with respect to 100 mass parts of said carboxylic acid containing photosensitive resin (A), More preferably, it is 5- 70 parts by mass. When the said compounding rate is less than 1 mass part, since photocurability falls and pattern formation by alkali image development after active energy ray irradiation becomes difficult, it is unpreferable. On the other hand, when it exceeds 100 mass parts, since solubility to aqueous alkali solution falls and a coating film tends to become weak, it is unpreferable.

Next, a thermosetting component (D) is demonstrated.

A thermosetting component (D) can be added to the photocurable resin composition of this invention in order to provide heat resistance. Especially preferred are thermosetting components (D) having at least two cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule.

As the thermosetting component (D) having two or more cyclic (thio) ether groups in such a molecule, a molecule having two or more of any one or two of three, four or five member cyclic cyclic ether groups, or cyclic thioether groups A compound is mentioned, For example, the compound which has at least 2 or more epoxy groups in a molecule | numerator, ie, a polyfunctional epoxy compound (D-1), the compound which has at least 2 or more oxetanyl groups in a molecule | numerator, ie, a polyfunctional oxetane compound (D-2), the compound which has a 2 or more cyclic thioether group in a molecule | numerator, ie, an episulfide compound (D-3), etc. are mentioned.

Examples of the polyfunctional epoxy compound (D-1) include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, and Dinibon Ink Co., Ltd. Epiclone 840, manufactured by Japan Epoxy Resin Co., Ltd. Epiclone 850, Epiclone 1050, Epiclone 2055, Etoto YD-011, YD-013, YD-127, YD-128 manufactured by Toto Kasei Co., Ltd., DER317, DER331, DER661, manufactured by Dow Chemical Co., Ltd. DER664, Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumiepoxy ESA-011, ESA-014, ELA-115, ELA made by Sumitomo Chemical Co., Ltd. Bisphenol-A epoxy resins, such as -128, AER330, AER331, AER661, and AER664 by Asahi Kasei Kogyo Co., Ltd .; Epicoat YL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclone 152, Epiclone 165, manufactured by Dainippon Ink & Chemicals Co., Ltd., Efototo YDB-400, YDB-500, manufactured by Toto Kasei Co., Ltd., DER542 by Dow Chemical Co., Ltd. Brominated epoxy resins, such as Araldide 8011 by Shiba Specialty Chemicals, Sumitomo Chemical Co., Ltd., Sumiepoxy ESB-400, ESB-700, Asahi Kasei Kogyo AER711, and AER714 (all brand names); Epicoat 152, Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., Epiclone N-730, Epiclone N-770, Epiclone N- 865, Efototo YDCN-701, YDCN-704, Arodaide ECN1235, Araldide ECN1273, Araldide ECN1299, Araldide XPY307 by Nippon Kayaku Co., Ltd. -201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Kagaku Kogyo Co., Ltd. Sumier epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo AERECN-235, ECN-299 Novolak-type epoxy resins, such as (all are brand names); Epiclone 830, manufactured by Dainippon Ink Industries, Inc., Epicoat 807, manufactured by Japan Epoxy Resin Co., Ltd., Efototo YDF-170, YDF-175, YDF-2004, manufactured by Tohto Kasei Co., Ltd., Aral, manufactured by Ciba Specialty Chemicals, Inc. Bisphenol F-type epoxy resins such as DID XPY306 and the like (all trade names); Hydrogenated bisphenol A type epoxy resins such as Efototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; Epicoat 604, manufactured by Japan Epoxy Resin Co., Ltd., Efototo YH-434, manufactured by Toto Kasei Co., Ltd., Araldide MY720, manufactured by Ciba Specialty Chemicals, Sumitomo Chemical Co., Ltd., Sumiepoxy ELM-120, etc. (all brand names) Glycidyl amine epoxy resins; Hydantoin type epoxy resins, such as Araldide CY-350 (brand name) by the Ciba Specialty Chemicals company; Alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd., Araldide CY175 manufactured by Ciba Specialty Chemicals, Inc. (CY179), and the like; Trihydroxyphenyl methane type epoxy resins such as YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T.E.N., EPPN-501, EPPN-502, etc. manufactured by Dow Chemical Company; Bixylenol type or biphenol type epoxy resins, such as YL-6056, YX-4000, and YL-6121 (all are brand names) by the Japan epoxy resin company, or mixtures thereof; Bisphenol S-type epoxy resins, such as EBPS-200 by Nippon Kayaku Co., Ltd., EPX-30 by Asahi Denka Kogyo Co., Ltd., and EXA-1514 (brand name) by Dainippon Ink & Chemicals Co., Ltd .; Bisphenol A novolak-type epoxy resins, such as Epicoat 157S (brand name) by the Japan epoxy resin company; Tetraphenylolethane type epoxy resins, such as Epicoat YL-931 by the Japan epoxy resin company, Araldide 163 by Ciba Specialty Chemicals, Inc. (all are brand names); Heterocyclic epoxy resins, such as Araldide PT810 by Ciba Specialty Chemicals Co., Ltd. and TEPIC by Nissan Chemical Industries, Ltd. (all are brand names); Diglycidyl phthalate resins such as Bremmer DGT manufactured by Nippon Yushi Corporation; Tetraglycidyl xylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; Naphthalene group-containing epoxy resins such as ESN-190, ESN-360 manufactured by Shinnitetsu Chemical Co., Ltd., HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink & Chemicals Co., Ltd .; Epoxy resins having dicyclopentadiene skeletons such as HP-7200 and HP-7200H manufactured by Dainippon Ink & Chemicals Co., Ltd .; Glycidyl methacrylate copolymer type epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Corporation; Furthermore, copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (e.g., YR-102, YR-450, manufactured by Toto Kasei Co., Ltd.), and the like. However, it is not limited to these. These epoxy resins can be used individually or in combination of 2 or more types. Especially among these, a novolak-type epoxy resin, a heterocyclic epoxy resin, a bisphenol-A epoxy resin, or a mixture thereof is preferable.

Examples of the polyfunctional oxetane compound (D-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1 , 4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3- Oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl methacrylate and oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly (p-hydroxystyrene), cardo-type bisphenols, calix arenes and calyx rezos The etherified substance with resin which has hydroxyl groups, such as lecinarene or silsesquioxane, etc. are mentioned. In addition, the copolymer of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate etc. are mentioned.

As said episulfide compound (D-3), bisphenol-A episulfide resin YL7000 by a Japan epoxy resin company, etc. are mentioned, for example. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used using the same synthesis method.

The compounding ratio of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents, more preferably relative to 1 equivalent of the carboxyl group of the carboxylic acid-containing photosensitive resin (A). Is a range of 0.8 to 2.0 equivalents. When the compounding quantity of the thermosetting component (D) which has two or more cyclic (thio) ether groups in a molecule | numerator is less than 0.6 equivalent, it will cause a carboxyl group to remain in a soldering resist film, and in that case, heat resistance, alkali resistance, electrical insulation, etc. will fall. Therefore, it is not preferable. On the other hand, when it exceeds 2.5 equivalent, since the low molecular weight cyclic (thio) ether group remains in a dry coating film, since the strength etc. of a coating film may fall, it is not preferable.

When using a thermosetting component (D) for the photocurable resin composition of this invention, it is preferable to use a thermosetting catalyst together. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenyl are Imidazole derivatives such as midazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic dihydrazide and sebacic acid dihydrazide; As commercially available things, such as phosphorus compounds, such as a triphenylphosphine, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole type compound), acid by Shikoku Kasei Kogyo Co., Ltd. Aprosa-made U-CAT3503N, U-CAT3502T (all are brand names of the block isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compound and its salt), etc. are mentioned. In particular, it is not limited to these, What is necessary is just to accelerate the reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, and can also be used individually or in mixture of 2 or more types. . Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid It is also possible to use S-triazine derivatives such as adducts. Preferably, compounds which also function as these adhesion imparting agents are used in combination with the thermosetting catalyst.

The compounding ratio of these thermosetting catalysts is sufficient in a normal quantitative ratio, For example, Preferably it is 0.1-20 mass parts with respect to 100 mass parts of carboxylic acid containing photosensitive resin (A) or a thermosetting component (D). Preferably it is 0.5-15.0 mass parts.

Next, the coloring agent (E) which can be used in the photocurable resin composition of this invention is demonstrated.

A coloring agent can be mix | blended with the photocurable resin composition of this invention. As a coloring agent, common known coloring agents, such as red, blue, green, yellow, and black, can be used, and any of a pigment, dye, and a pigment may be used. However, it is preferable that it does not contain a halogen and an azo compound from the point of environmental load reduction and an effect on a human body.

Blue colorant:

As the blue colorant, there are phthalocyanine-based and anthraquinone-based compounds, and the pigment-based compound is classified as Pigment, specifically, the color index as described below (CI The Society of Diaries and Colorists (The Society) numbered: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue. 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

As a dye system, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 122, solvent blue 136, solvent blue 67, solvent blue 70 and the like can be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:

Examples of the green colorant include phthalocyanine series and anthraquinone series, and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, and Solvent Green 28 Etc. can be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone and the like. Specific examples include the following.

Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Condensation azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Monoazo series: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 , 116, 167, 168, 169, 182, 183.

Disazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

Red colorant:

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone and quinacridone. It can be mentioned.

Monoazo series: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114 , 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.

Disazo meter: Pigment Red 37, 38, 41.

Monoazo Lake system: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.

Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.

Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensation azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, I Pigment Red 207, Pigment Red 209.

In addition, coloring agents such as purple, orange, brown, and black may be added for the purpose of adjusting the color tone.

Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C.I. Pigment Orange 1, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 16, C.I. Pigment Orange 17, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 51, C.I. Pigment Orange 61, C.I. Pigment Orange 63, C.I. Pigment Orange 64, C.I. Pigment Orange 71, C.I. Pigment Orange 73, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Black 1, C.I. Pigment black 7 and the like.

Although the specific compounding ratio of a coloring agent is not influenced uniformly since it is influenced also by the kind of coloring agent to be used, the kind of other additives, etc., it is 0 mass part-100 mass parts with respect to 100 mass parts of carboxylic acid containing photosensitive resin of the photosensitive resin composition of this invention. It is preferable to mix | blend 5 mass parts. Particularly preferred colorants which can be used more preferably from 0.05 parts by mass to 3 parts by mass are blue and green phthalocyanine, anthraquinone, yellow anthraquinone, red diketopyrrolopyrrole and anthraquinone. It does not contain a halogen atom. In addition, blue and green pigments are preferred in terms of heat resistance, and blue, green and red colorants in dyes are preferred in terms of sensitivity and resolution.

The filler of the photocurable resin composition of this invention can be mix | blended as needed in order to raise the physical strength of the coating film, etc. As such a filler, an inorganic or organic filler for a known tube can be used, and barium sulfate, spherical silica and talc are particularly preferably used. Further, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733, XP 0746, manufactured by Hanse-Khemisa, in which nanosilica is dispersed in a compound having at least one ethylenically unsaturated group or the polyfunctional epoxy resin (D-1). XP 0765, XP 0768, XP 0953, XP 0954, XP1045 (all product grade names), Hanse Chemical Co., Ltd. NANOPOX (brand name) XP 0516, XP 0525, XP 0314 (all product grade names), etc. can also be used. These can be used individually or in mixture of 2 or more types.

The blending ratio of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, particularly preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). to be. When the compounding ratio of a filler exceeds 300 mass parts, since the viscosity of a photosensitive composition may become high and printability may fall, hardened | cured material may become weak, and it is unpreferable.

Moreover, the organic solvent can be used for the photocurable resin composition of this invention for the synthesis | combination of the said carboxylic acid containing photosensitive resin (A), manufacture of a composition, or viscosity adjustment for apply | coating to a board | substrate or a carrier film.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, Ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as these; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha and the like. These organic solvents are used alone or as a mixture of two or more thereof.

The photocurable resin composition of the present invention may further contain, if necessary, thermal polymerization inhibitors for known pipes such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol and phenothiazine, finely divided silica and organic bentonite. Known additives such as thickeners for known tubes such as montmorillonite, antifoaming agents and / or leveling agents such as silicone, fluorine, polymers, silane coupling agents such as imidazoles, thiazoles, and triazoles, antioxidants, and rust inhibitors. Can be blended.

The photocurable resin composition of this invention is adjusted to the viscosity suitable for the method of apply | coating with the said organic solvent, for example, and it is an immersion coating method, a flow coating method, a roll coating method, a bar coater method, the screen printing method, on a base material, After apply | coating by a curtain coating method etc., it forms in the tack free coating film by carrying out volatilization (temporary drying) of the organic solvent contained in a composition at the temperature of about 60-100 degreeC. Moreover, the resin insulating layer can be formed by apply | coating the resin composition of this invention on a carrier film, making it dry, and making it into a dry film, and bonding what wound this up on a base material.

The coating film obtained as mentioned above or the resin layer on a carrier film (it calls these "resin layer" with the said "coating film") is exposed by irradiation of an active energy ray, and it exposed by the exposure part (active energy ray Part).

Specifically, pattern exposure is performed by contact type (or non-contact method) by direct drawing of active energy rays through exposure using an active energy ray or by using a laser direct exposure machine or the like selectively through a photomask on which a pattern is formed. The miner is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% aqueous sodium carbonate solution) to form a resist pattern. Further, for example, by thermosetting by heating to a temperature of about 140 to 180 ℃, the thermosetting having a carboxyl group of the carboxylic acid-containing photosensitive resin (A) and two or more cyclic ether groups and / or cyclic thioether groups in the molecule The components react to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, hygroscopicity, adhesiveness, and electrical properties.

As said base material, the copper field for high frequency circuits using paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven fabric epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine polyethylene PPO cyanate ester etc. Copper laminates of all grades (FR-4, etc.), other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, etc. may be used as materials using laminates and the like.

As the volatilization drying performed after applying the photocurable resin composition of the present invention, hot air in the dryer is used in a hot air circulation drying furnace, using an IR plate, a hot plate, a convection oven, or the like (having a heat source of air heating method by steam). And a method of spraying the support from the nozzle).

As an exposure machine used for the said active energy ray irradiation, an ultraviolet irradiation apparatus and a direct drawing apparatus (for example, the laser direct imaging apparatus which draws an image directly with a laser by CAD data from a computer) can be used. As an active energy ray, a gas laser or a solid state laser may be sufficient as long as the laser beam in the range whose maximum wavelength is 350-410 nm is used. Moreover, although the exposure amount changes with film thickness etc., it can generally be in the range of 5-200 mJ / cm <2>, Preferably it is 5-100 mJ / cm <2>, More preferably, it is 5-50 mJ / cm <2>. As the direct drawing device, for example, Nippon Orbotec Co., Ltd., Pantax Co., Ltd., etc. can be used, and any device may be used as long as it is a device for oscillating laser light having a maximum wavelength of 350 to 410 nm.

The developing method may be a dipping method, a showering method, a spraying method, a brush method, or the like. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia or amines may be used. Can be.

Although an Example is described to the following and this invention is concretely demonstrated, it cannot be overemphasized that this invention is not limited to the following Example.

<Synthesis of carboxylic acid-containing photosensitive resin (A)>

Resin Synthesis Example 1 (A-1)

To 600 g of diethylene glycol monoethyl ether acetate, 442.2 parts (3.3 mol) of dimethylol propionic acid, 1031.8 parts (6.7 mol) of methacrylic anhydride, 3.0 parts of methylhydroquinone and 8.5 parts of triphenylphosphine were added and reacted at 95 ° C for 8 hours. Was performed. 2,200 g of diethylene glycol monoethyl ether acetate, ortho cresol novolak type epoxy resin (manufactured by Dainippon Ink Chemical Industries, Ltd., EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average functional number 7.6) (Glycidyl group number (aromatic ring total number): 10.0 mol), 3.0 parts of methylhydroquinones, and 1000 parts of carbitol acetates were thrown in, and it heated at 90 degreeC, stirring, and dissolved the reaction mixture. Subsequently, the reaction liquid was cooled to 60 degreeC, 10.0 parts of triphenylphosphines were thrown in, it heated at 100 degreeC, and reaction was performed for about 30 hours. Next, 912 parts (6.0 mol) of tetrahydro phthalic anhydrides were put into this, it heated at 95 degreeC, and after reacting for about 6 hours, it was cooled, solid content concentration 65% whose acid value of solid content is 74 mgKOH / g. Carboxylic acid-containing photosensitive resin (varnish A-1) was obtained.

Resin Synthesis Example 2 (A-2)

To 800 g of diethylene glycol monoethyl ether acetate, 442.2 parts (3.3 mol) of dimethylol propionic acid, 1031.8 parts (6.7 mol) of methacrylic anhydride, 3.0 parts of methylhydroquinone and 8.5 parts of triphenylphosphine were added and reacted at 95 ° C for 8 hours. Was performed. Subsequently, 1000 g of diethylene glycol monoethyl ether acetate and orthocresol novolac type epoxy resin (manufactured by Dainippon Ink & Chemical Co., Ltd., EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 2846.2 g (glycidyl group number (aromatic ring total number): 13.3 mol), 442.2 parts (3.3 mol) of dimethylolpropionic acid, 3.0 parts of methylhydroquinone, 1300 parts of carbitol acetate were added, and it heated at 90 degreeC, stirring, and the reaction mixture Was dissolved. Subsequently, the reaction liquid was cooled to 60 degreeC, 12.0 parts of triphenylphosphines were thrown in, it heated at 100 degreeC, and reaction was performed for about 25 hours. Next, 1064 parts (7.0 mol) of tetrahydro phthalic anhydrides were put into this, and it heated at 95 degreeC, and after reacting for about 6 hours, it was cooled, solid content concentration 65% whose acid value of solid content is 67 mgKOH / g. Carboxylic acid-containing photosensitive resin (varnish A-2) was obtained.

Resin Synthesis Example 3 (A-3)

To 600 g of diethylene glycol monoethyl ether acetate, 670 parts (5.0 moles) of dimethylol propionic acid, 1.5 parts of methylhydroquinone and 7.5 parts of triphenylphosphine were added, and the mixture was heated and dissolved at 80 ° C while stirring. 770 parts (5.0 mol) of methacrylic anhydride melt | dissolved in 750 g of diethylene glycol monoethyl ether acetates were dripped slowly over 2 hours, and reaction was performed for 5 hours after that. Subsequently, orthocresol novolak-type epoxy resin (the Dainippon ink Kagaku Kogyo Co., Ltd. make, EPICLON N-695, softening point 95 degreeC, epoxy equivalent 214, average functional group number 7.6) 2140 g (glycidyl number (aromatic ring total number)) : 10.0 mol), 3.5 parts of methyl hydroquinones, and 1100 parts of carbitol acetates were added, and it heated at 90 degreeC, stirring, and dissolved the reaction mixture. Subsequently, the reaction solution was cooled to 60 ° C, 12.0 parts of triphenylphosphine were added, heated to 100 ° C, and reacted for about 25 hours. Next, 1064 parts (7.0 mol) of tetrahydro phthalic anhydrides were put into this, it heated at 95 degreeC, reaction was performed for about 6 hours, it was cooled, solid content concentration 65% whose acid value of solid content is 85 mgKOH / g. Carboxylic acid-containing photosensitive resin (varnish A-3) was obtained.

Resin Synthesis Example 4 (A-4)

After dissolving 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide, 400 parts of bisphenol F-type solid epoxy resins of epoxy equivalent 800 and softening point of 79 degreeC were added, and 88.5 parts of 98.5% NaOH over 70 minutes were stirred at 100 degreeC under stirring. After addition, reaction was further performed at 70 degreeC for 3 hours. Subsequently, the majority of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further 30% NaOH 10 Part was added and reacted at 70 ° C for 1 hour. After completion of the reaction, water washing was performed twice with 200 parts of water. After the separation of oil and water, methyl isobutyl ketone was distilled off from the oil layer to obtain epoxy equivalent 290 and 370 parts of epoxy resin (a-1) having a softening point of 62 ° C.

Next, to 600 g of diethylene glycol monoethyl ether acetate, 442.2 parts (3.3 moles) of dimethylol propionic acid, 1031.8 parts (6.7 moles) of methacrylic anhydride, 3.0 parts of methylhydroquinone and 8.5 parts of triphenylphosphine were added, Time reaction was performed. Subsequently, 700 g of diethylene glycol monoethyl ether acetate, 2900 parts (10 mol) of an epoxy resin (a-1), 3.0 parts of methylhydroquinone, and 1000 parts of carbitol acetate were added thereto, heated to 90 ° C., and the mixture was stirred. Dissolved. Subsequently, the reaction solution was cooled to 60 ° C, 16.7 parts of triphenyl phosphine were added, heated to 100 ° C, and reacted for about 32 hours. Next, 786 parts (7.86 mol) of succinic anhydride and 450 parts of carbitol acetates were put into this, and it heated at 95 degreeC, reacted for about 6 hours, cooled, and after concentration, solid content whose solid acid value was 85 mgKOH / g. 65% of carboxylic acid-containing photosensitive resin (varnish A-4) was obtained.

Resin Synthesis Example 5 (A-5)

To 700 g of diethylene glycol monoethyl ether acetate, 442.2 parts (3.3 moles) of dimethylol propionic acid, 1031.8 parts (6.7 moles) of methacrylic anhydride, 3.0 parts of methylhydroquinone, and 8.5 parts of triphenylphosphine were added, followed by 8 hours at 95 ° C. The reaction was carried out. Subsequently, 950 g of diethylene glycol monoethyl ether acetate and orthocresol novolak type epoxy resin (Dini Nippon Ink Chemical Co., Ltd. make, EPICLON N-695, softening point 95 degreeC, epoxy equivalent 214, average functional group 7.6) 2140 g (Glycidyl group number (aromatic ring total number): 10.0 mol), 3.0 parts of methylhydroquinones, and 1000 parts of carbitol acetate were thrown in, and it heated and stirred at 90 degreeC, and dissolved the reaction mixture. Subsequently, the reaction liquid was cooled to 60 degreeC, 10.0 parts of triphenylphosphines were thrown in, it heated at 100 degreeC, and reaction was performed for about 30 hours. Next, 1140.0 parts (7.5 mol) of tetrahydro phthalic anhydrides were put into this, it heated at 95 degreeC, and it reacted for about 6 hours. Furthermore, 213.0 g (1.5 mol) of glycidyl methacrylates were thrown into the obtained reaction liquid, and it reacts at 115 degreeC for 4 hours, and the carboxylic acid containing photosensitive of 65% of solid content concentration whose acid value of solid content is 68 mgKOH / g. Resin (varnish A-5) was obtained.

Comparative Synthesis Example 1 (R-1)

1070 g (for ditoglycol monoethyl ether acetate orthocresol novolak-type epoxy resin (Dini Nippon Ink Chemical Co., Ltd. make, EPICLON N-695, softening point 95 degreeC, epoxy equivalent 214, average functional number 7.6) 1070 g ( Glycidyl group number (5.0 mol) of aromatic rings, 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were thrown in, and it heated and stirred at 100 degreeC, and obtained the uniform solution. Subsequently, 4.3 g of triphenylphosphines were thrown in, and it heated at 110 degreeC, after reaction for 2 hours, it heated up at 120 degreeC and reacted for 12 hours further. 415 g of aromatic hydrocarbon (sorbetso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction solution, and the reaction was performed at 110 ° C for 4 hours, and after cooling, a solid acid value of 89 mgKOH / g and a solid content 65% of a resin solution was obtained. Let this be varnish R-1.

Comparative Synthesis Example 2 (R-2)

650 g of diethylene glycol monoethyl ether acetate orthocresol novolak-type epoxy resins (the Dainippon ink Kagaku Kogyo Co., Ltd. make, EPICLON N-695, softening point 95 degreeC, epoxy equivalent 214, average functional number 7.6) 1070 g ( Glycidyl group number (5.0 mol) of aromatic rings, 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were thrown in, and it heated and stirred at 100 degreeC, and obtained the uniform solution. Subsequently, 4.3 g of triphenylphosphines were thrown in, and it heated at 110 degreeC, and after reaction for 2 hours, 1.6 g of triphenylphosphines were added, it heated up at 120 degreeC, and reaction was further performed for 12 hours. 525 g of aromatic hydrocarbon (sorbetso 150) and 608 g (4.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction liquid, and reaction was performed at 110 degreeC for 4 hours. Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylates were thrown into the obtained reaction liquid, and it reacted at 115 degreeC for 4 hours, and obtained the resin solution of 77 mgKOH / g of solid content acid value, and 65% of solid content. Let this be varnish R-2.

Comparative Synthesis Example 3 (R-3)

After dissolving 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide, 400 parts of bisphenol F-type solid epoxy resins of epoxy equivalent 800 and softening point of 79 degreeC were added, and 88.5 parts of 98.5% NaOH over 70 minutes were stirred at 100 degreeC under stirring. After addition, reaction was further performed at 70 degreeC for 3 hours. Subsequently, the majority of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further 30% NaOH 10 Part was added and reacted at 70 ° C for 1 hour. After completion of the reaction, water washing was performed twice with 200 parts of water. After the separation of oil and water, methyl isobutyl ketone was distilled off from the oil layer to obtain epoxy equivalent 290 and 370 parts of epoxy resin (a-1) having a softening point of 62 ° C. 2900 parts (10 equivalents) of epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone, and 1950 parts of carbitol acetate were added, heated to 90 ° C, and stirred to dissolve the reaction mixture. Subsequently, the reaction solution was cooled to 60 ° C, 16.7 parts of triphenylphosphine was added, heated to 100 ° C, and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetates were put into this, it heated at 95 degreeC, and it reacted for about 6 hours, and obtained the resin solution of 100 mgKOH / g of solid content acidity 65% of solid content. . Let this be varnish R-3.

Example 1

Using the resin solution of the said synthesis example, the various components shown in Table 1 were mix | blended in each ratio (mass part), pre-mixed with the stirrer, and kneaded with the triaxial roll mill, and the photocurable resin composition was manufactured. The dispersion degree of the photocurable resin composition obtained here was 15 micrometers or less when it evaluated by the particle size measurement by the grindmeter by Eriksen company.

Performance rating:

<Optimal exposure amount>

Each of the prepared photocurable resin compositions was subjected to buff roll polishing of the substrate on a circuit pattern substrate having a copper thickness of 35 µm, washed with water, dried, and then applied to the entire surface by a screen printing method. Dry for 30 minutes in a hot air circulating drying furnace. After drying, direct drawing apparatus (paragon8000 made by Orbotec Co., Ltd.), direct drawing exposure machine equipped with semiconductor laser of maximum wavelength 355nm, high pressure mercury lamp (straight line exposure machine mounted with ultra high pressure mercury lamp lamp Marculex by Dainippon screen company) or high pressure When exposure was carried out through a step tablet (KodakNo2) using a mercury lamp-mounted exposure device (ORC company equipped with a mercury short arc lamp), and development (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) was performed for 60 seconds. The optimal exposure amount was set when the pattern of the remaining step tablet was seven steps.

<Touch dryness>

Each of the prepared photocurable resin compositions is applied to the entire surface by screen printing on a patterned copper foil substrate, dried at 80 ° C. for 20 minutes, and cooled to room temperature. The negative film made from PET was put on this board | substrate, and it crimped | bonded by ORC company (HMW680-GW20) for 1 minute under reduced pressure conditions, and the adhesive state of the film at the time of peeling a negative film after that was evaluated.

○: The film is peeled off without resistance.

(Triangle | delta): Although a film peels, a trace adheres to a coating film.

X: When peeling a film, there exists resistance and a trace adheres clearly to a coating film.

<Maximum developing life>

Each of the prepared photocurable resin compositions is coated on the patterned copper foil substrate by screen printing, and dried at 80 ° C. During 20 minutes to 80 minutes after the start of drying, the substrate is taken out at 10 minute intervals and allowed to cool to room temperature. Performing development for 60 seconds with 1% Na ₂ CO ₃ aqueous solution conditions of the spray pressure 2 kg / ㎠ of 30 ℃ on the substrate, and the maximum permitted drying time does not leave residues of up to life phenomena.

Characteristic test:

(Manufacture of coating film characteristic evaluation board | substrate)

Each said photocurable resin composition is apply | coated whole surface by screen printing on the patterned copper foil board | substrate, it is dried at 80 degreeC for 20 minutes, and it cools to room temperature. Using a direct drawing device equipped with a semiconductor laser having a maximum wavelength of 355 nm, the substrate was exposed to a solder resist pattern at an optimum exposure dose, and a 30% 1% Na ₂ CO ₃ aqueous solution was sprayed under a spray pressure of 2 kg / cm 2. It developed for the second time and obtained the resist pattern. This board | substrate was irradiated with the ultraviolet-ray on the conditions of accumulated exposure amount 1000mJ / cm <2> by a UV conveyor, and it heated at 150 degreeC for 60 minutes, and hardened | cured.

The characteristic was evaluated as follows about the obtained printed circuit board (evaluation board | substrate).

Solder Heat Resistance

The evaluation board | substrate which apply | coated rosin-type flux was immersed in the solder bath previously set to 260 degreeC, and after wash | cleaning the flux with denatured alcohol, it evaluated about swelling and peeling of the resist layer by visual observation. Judgment criteria are as follows.

(Circle) *: Peeling is not seen even if it repeats immersion 6 times or more for 10 second.

(Circle): Peeling is not seen even if immersion is repeated 3 times or more for 10 second.

(Triangle | delta): When it immerses 3 times or more for 10 second, it peels a little.

X: There exists swelling and peeling in a resist layer within 3 times of immersion for 10 second.

Electroless Gold Plating Resistant

After plating on the conditions of nickel 0.5 micrometer and gold 0.03 micrometer using the electroless nickel plating bath and the electroless gold plating bath of a commercial item, after visually evaluating the presence or absence of peeling of the resist layer and the seepage of plating, Tape peeling evaluated the presence or absence of peeling of a resist layer. Judgment criteria are as follows.

○ *: No seepage or peeling is observed.

(Circle): Although it penetrates a little after plating, it does not peel after tape peeling.

(Triangle | delta): A very slight soaking is seen after plating, and peeling is seen after tape peeling.

X: There is peeling after plating.

<Alkali resistance>

The evaluation board | substrate was immersed in 10 vol% NaOH aqueous solution for 30 minutes at room temperature, the seepage and the elution of the coating film were visually confirmed, and peeling by tape peeling was also confirmed.

(Circle): There is no seepage and elution, and peeling is not confirmed after tape peeling.

(Triangle | delta): There is no infiltration and elution, and peeling is seen a little after tape peeling.

X: There is peeling after infiltration eluting or tape peeling.

<PCT resistant>

The evaluation board | substrate was processed for 50 hours on 121 degreeC, saturation, and 0.2 MPa conditions using a PCT apparatus (HAST SYSTEM TPC-412MD by the specification of SPEC), and visually confirmed the state of a coating film, Peeling by tape peeling was confirmed. Judgment criteria are as follows.

(Circle): There is no seepage and elution, and peeling is not confirmed after tape peeling.

(Triangle | delta): There is no infiltration and elution, and peeling is seen a little after tape peeling.

X: There is peeling after infiltration eluting or tape peeling.

<PCBT immunity>

The evaluation board | substrate was manufactured on the said conditions using the comb-shaped electrode B coupon of IPC B-25 instead of the copper foil board | substrate, the bias voltage of DC30V was applied to this comb-shaped electrode, and the PCT apparatus (HAST made by SPECK Corporation) SYSTEM TPC-412 MD) was used for 96 hours under conditions of 121 ° C and a humidity of 97% to evaluate the presence or absence of discoloration and migration. Judgment criteria are as follows.

○ *: No discoloration or migration.

○: very little discoloration, migration occurred.

(Triangle | delta): Discoloration and migration generate | occur | produced.

X: Discoloration is remarkable, and migration reaches from one electrode to another.

<Electrical characteristic>

The evaluation board | substrate was manufactured on the said conditions using the comb-shaped electrode B coupon of IPC B-25 instead of the copper foil board | substrate, the bias voltage of DC100V was applied to this comb-shaped electrode, and it was made in the constant temperature and humidity chamber of 85 degreeC, and 85% of humidity. The presence of migration after 1,000 hours was confirmed. Judgment criteria are as follows.

○: no change at all.

(Triangle | delta): A very slight change.

×: The migration occurred.

<Color of coating>

The color of the cured product was visually judged.

The results are shown in Table 2.

Example 2

<Dry Film Evaluation>

The composition example 1 used in Example 1 was diluted with methyl ethyl ketone, apply | coated on PET film, it dried at 80 degreeC for 30 minutes, and formed the 20-micrometer-thick photosensitive resin composition layer. Furthermore, the cover film was bonded together on it and the dry film was obtained. Then, the cover film was peeled off, the film was heat-laminated to the patterned copper foil board | substrate, and then it exposed on the conditions similar to the board | substrate used for the coating-film characteristic evaluation of Example 1. The carrier film was peeled off after exposure, heat-hardened for 60 minutes with the 150 degreeC hot air dryer, and the test board | substrate was manufactured. About the test board | substrate which has the obtained hardened film, the evaluation test of each characteristic was done by the above-mentioned test method and evaluation method. The results are shown in Table 3.

As can be seen from the results shown in Tables 2 and 3 in Examples 1 and 2, the photocurable resin composition containing the carboxylic acid-containing photosensitive resin (A) of the present invention is compared with conventional resins. It is highly sensitive, and is excellent in developability, dry touch, solder heat resistance, electroless gold plating resistance, alkali resistance, PCT resistance and PCBT resistance, and is useful as a resist ink. Moreover, it turns out that the photocurable resin composition of this invention can respond with high sensitivity also to monochromatic light, such as i line | wire, h line | wire, or laser beam, and ultraviolet light sources, such as a high pressure mercury lamp.

Claims (10)

(A) Alkaline development characterized by containing the carboxylic acid containing photosensitive resin containing the structure represented by following formula (I), (B) photoinitiator, (C) compound which has two or more ethylenically unsaturated groups in 1 molecule. Possible photocurable resin composition. <Formula I>

(In Formula I, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, and R ³ represents a hydrogen atom or an organic acid ester residue.) The alkali developable photocurable resin composition according to claim 1, wherein R ³ in formula (I) is an acid anhydride residue. The alkali developable photocurable resin composition according to claim 1, wherein R ³ in formula (I) is a (meth) acrylic acid residue. The photopolymerization initiator according to claim 1, wherein An oxime ester photoinitiator containing the structure represented by following formula (II), An aminoacetophenone-based photopolymerization initiator comprising a structure represented by the following formula (III), and Alkali-developable photocurable resin composition, characterized in that the mixture is one or two or more selected from the group consisting of acylphosphine oxide-based photopolymerization initiator comprising a structure represented by the formula (IV). <Formula II>

<Formula III>

<Formula IV>

(In Formula II-IV, R <^1> is a hydrogen atom, a phenyl group (it may be substituted by a C1-C6 alkyl group, a phenyl group, or a halogen atom.), C1-C20 linear, branched or cyclic alkyl group (one. May be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (with 1 to 6 carbon atoms) May be substituted with an alkyl group or a phenyl group), R ² may be substituted with a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, or an alkyl chain May have one or more oxygen atoms in the middle), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms) , R ³ and R ⁴ each independently represent a linear, branched or cyclic alkyl group or an arylalkyl group having 1 to 12 carbon atoms, R ⁵ and R ⁶ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ⁵ and R ⁶ may be bonded to form a cyclic alkyl ether group, R ⁷ and R ⁸ are each independently a linear, branched or cyclic alkyl, alkoxy, cyclohexyl, cyclopentyl, or aryl group having 1 to 10 carbon atoms (which may be substituted with a halogen atom, an alkyl group, or an alkoxy group). Present), or RC (= O)-group, wherein R represents a hydrocarbon group of 1 to 20 carbon atoms. Except that both R ⁷ and R ⁸ are RC (= O)-groups) The alkali-developable photocurable resin composition according to claim 1, further comprising (D) a thermosetting component. The alkali-developable photocurable resin composition according to claim 1, which is a soldering resist containing (E) colorant. The photocurable dry film obtained by apply | coating the photocurable resin composition in any one of Claims 1-6 to a carrier film, and drying it. It is a hardened | cured material pattern formed using the resin layer containing the photocurable resin composition of any one of Claims 1-6, and hardened | cured material pattern in which pattern formation was performed by active energy ray irradiation. The hardened | cured material pattern whose pattern formation by active energy ray irradiation of Claim 8 is by direct drawing using active energy ray of wavelength 350nm -410nm. The printed wiring board provided with the hardened | cured material pattern of Claim 8 on a copper layer.