KR102389115B1 - Curable composition, dry film, cured product, printed wiring board, and method for producing printed wiring board - Google Patents

Abstract

(Project) To provide a curable composition excellent in resolution and blackness of the cured product.
(Solutions) (A) carboxyl group-containing resin, (B) photoinitiator, (C) diluent, (D) polyfunctional epoxy compound having at least two epoxy groups in one molecule, (E) black colorant, and (F) other than black It is a composition containing a coloring agent, wherein the absorbance at a wavelength of 365 nm per 25 µm of the dry coating film is 1.5 or less, the absorbance at 385 nm is 1.0 or less, and the absorbance at a wavelength of 405 nm is 1.0 or less It is a printed wiring board provided with the curable composition characterized by the above-mentioned, the dry film using the same, its hardened|cured material, and its hardened|cured material.

Description

A curable composition, a dry film, hardened|cured material, a printed wiring board, and the manufacturing method of a printed wiring board {CURABLE COMPOSITION, DRY FILM, CURED PRODUCT, PRINTED WIRING BOARD, AND METHOD FOR PRODUCING PRINTED WIRING BOARD}

The present invention relates to a curable composition, a dry film, a cured product, a printed wiring board, a method for manufacturing a dry film, a method for manufacturing a cured product, and a method for manufacturing a printed wiring board.

Generally, in printed wiring boards used for electronic devices, etc., when mounting electronic components, a resin composition is applied or a dry coating film on a dry film is laminated on the area except for the connection hole on the board on which the circuit pattern is formed, and then cured The solder resist which consists of is formed. This soldering resist protects the conductor of a circuit while preventing adhesion of the solder to an unnecessary part.

Moreover, in a soldering resist, the discoloration by heat, moisture, etc. of a circuit pattern, an electrical discoloration, a flaw, a contamination, etc. are concealed, and it also has a role which prevents the deterioration of the external appearance of a printed wiring board. Therefore, in order to improve concealability, a coloring agent is normally added to the resin composition and dry film used in order to form a soldering resist (for example, refer patent document 1).

In recent years, based on the request|requirement of size reduction and high functionalization of an electronic device, refinement|miniaturization of a circuit pattern is advancing also about a printed wiring board, and thin film formation is progressing further also about a soldering resist with this. As a result, the concealability of a soldering resist fell, the discoloration of the circuit which is a lower layer, etc. were seen through a soldering resist, and the problem that it led to an external appearance defect had arisen. Therefore, in order to improve concealability, a black dark soldering resist is calculated|required. Moreover, a black soldering resist is calculated|required from a viewpoint of design. Moreover, conventionally, carbon black is used as a black coloring agent.

Photolithography has been conventionally used as one of the solder resist pattern formation methods. However, when carbon black is blended with solder resist ink to produce black, carbon black absorbs a wide range of light from the ultraviolet region to the visible region. Since the light transmittance worsened, problems, such as a fall of resolution, had arisen.

As a means to solve such a problem, the composition characterized by containing a black coloring agent and coloring agents other than a black coloring agent in patent document 2 is described. Moreover, in patent document 3, combining colorants other than a black colorant and blackening, The composition characterized by the above-mentioned is described. However, there was room for improvement in terms of resolution.

Japanese Patent Laid-Open No. 2009-258613 Japanese Patent Laid-Open No. 2008-257045 Japanese Patent Laid-Open No. 2010-091876

Accordingly, an object of the present invention is to provide a curable composition excellent in resolution and blackness of the cured product, a dry film formed by coating and drying the composition, a cured product of the composition or the dry film, a printed wiring board having the cured product, and the composition It is to provide the manufacturing method of the dry film to be used, the manufacturing method of the hardened|cured material using the said composition or the said dry film, and the manufacturing method of the printed wiring board using the said composition or the said dry film.

As a result of intensive studies, the present inventors found that the above problems can be solved by blending a black colorant and a colorant other than black, and further setting the absorbance at a specific wavelength per 25 µm of the dry coating film into a specific range. , came to complete the present invention.

That is, the curable composition of the present invention comprises (A) a carboxyl group-containing resin, (B) a photoinitiator, (C) a diluent, (D) a polyfunctional epoxy compound having at least two epoxy groups in one molecule, (E) a black colorant, and (F) a composition containing a colorant other than black, wherein the absorbance at a wavelength of 365 nm per 25 µm of the dry coating film is 1.5 or less, the absorbance at 385 nm is 1.0 or less, and the absorbance at a wavelength of 405 nm It is characterized in that the absorbance is 1.0 or less.

It is preferable that the curable composition of this invention contains a purple coloring agent as a coloring agent other than the said (F) black.

It is preferable that the curable composition of this invention contains an orange coloring agent as a coloring agent other than the said (F) black.

It is preferable that the curable composition of this invention contains at least 1 sort(s) of a red coloring agent, a blue coloring agent, and a yellow coloring agent as coloring agents other than the said (F) black.

It is preferable that the curable composition of this invention contains an oxime ester type photoinitiator as said (B) photoinitiator.

As for the curable composition of this invention, it is preferable that the said oxime ester type photoinitiator is a dimer oxime ester type photoinitiator.

The dry film of this invention has a resin layer obtained by apply|coating and drying the said curable composition on a film, It is characterized by the above-mentioned.

The hardened|cured material of this invention is obtained by hardening at least any one of the resin layer of the said curable composition and the said dry film, It is characterized by the above-mentioned.

The printed wiring board of this invention is provided with the said hardened|cured material, It is characterized by the above-mentioned.

The manufacturing method of the dry film of this invention is characterized by using the said curable composition.

The method for producing a cured product of the present invention is characterized in that the curable composition is used.

The manufacturing method of the printed wiring board of this invention uses at least any one of the said curable composition and the said dry film, It is characterized by the above-mentioned.

According to the present invention, a curable composition excellent in resolution and blackness of a cured product, a dry film having a resin layer obtained by coating and drying the composition, a cured product of the resin layer of the composition or the dry film, and a print having the cured product It becomes possible to provide a wiring board and the manufacturing method of the printed wiring board using the said composition.

1 is a photograph showing a cross section of a 50 µm line portion formed by exposure and development to a curable composition of Example 2. FIG.
FIG. 2 is a photograph showing a cross-section of a 50 μm line portion formed by exposing and developing the curable composition of Comparative Example 2. FIG.

The curable composition of the present invention comprises (A) a carboxyl group-containing resin, (B) a photoinitiator, (C) a diluent, (D) a polyfunctional epoxy compound having at least two epoxy groups in one molecule, (E) a black colorant, and (F) ) a composition containing a colorant other than black, wherein the absorbance at a wavelength of 365 nm per 25 µm of the dried coating film is 1.5 or less, the absorbance at 385 nm is 1.0 or less, and the absorbance at a wavelength of 405 nm is It is characterized in that it is 1.0 or less.

In the curable composition of the present invention, it is essential to satisfy the above three absorbances. By satisfying the above absorbance, it is cured to a deep part when exposed, particularly when exposed to LDI (laser direct imaging), and a fine pattern can be formed. Although the detailed mechanism of this is not certain, when examining the irradiated wavelength, in the case of LDI exposure, the irradiated wavelength is about 350 to 420 nm, and the peak wavelengths are I-line (365 nm) and h-line (405 nm). Alternatively, depending on the light source, since it is in the range of 370 to 400 nm, it is considered that the light transmittance in the range of 350 to 420 nm centering on the peak wavelength becomes important. It is preferable that the absorbance in wavelength 365nm per 25 micrometers of film thickness of a dry coating film is 1.0-1.5. When it is 1.0 or more, top hypertrophy becomes difficult to generate|occur|produce. Moreover, it is preferable that the absorbance in wavelength 385nm per 25 micrometers of film thickness of a dry coating film is 0.5-1.0. When it is 0.5 or more, top hypertrophy becomes difficult to generate|occur|produce. It is preferable that the absorbance in wavelength 405nm per 25 micrometers of film thickness of a dry coating film is 0-1.0.

The method for adjusting the absorbance is not particularly limited, but it is preferable to adjust according to the type or blending ratio of (E) a black colorant and (F) a colorant other than black. (B) It is also possible to adjust according to the kind or blending ratio of the photopolymerization initiator. Absorbance can be measured using an ultraviolet visible spectrophotometer.

(F) a colorant other than black, from the viewpoint of resolution, (F) as a colorant other than black, it is preferable to contain at least one of a purple colorant, an orange colorant and a red colorant, and at least one of a purple colorant and an orange colorant It is more preferable to contain, and it is still more preferable to contain a purple colorant and an orange colorant. Moreover, from a viewpoint of blackness, as a coloring agent other than (F) black, it is preferable to contain at least 1 sort(s) of a purple coloring agent and a blue coloring agent, and it is more preferable to contain a purple coloring agent. Moreover, when it contains a blue coloring agent, it is more preferable to contain a yellow coloring agent further. From the viewpoints of resolution and blackness, (F) as a colorant other than black, it is particularly preferable to contain a purple colorant, an orange colorant, a blue colorant and a yellow colorant.

Hereinafter, each component will be described in detail.

[(A) Carboxyl group-containing resin]

(A) As the carboxyl group-containing resin, in particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoint of photocurability and developability as a photosensitive composition for alkali development. And the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.

(A) As a specific example of carboxyl group-containing resin, the compound (any of an oligomer and a polymer may be sufficient) listed below is preferable.

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate or isobutylene.

(2) diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid; and polycarbonate-based polyols and polyethers Diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups, and, if necessary, one alcoholic hydroxyl group A carboxyl group-containing urethane resin by polyaddition reaction of a compound having a hydroxyl group.

(3) Diisocyanate and a bifunctional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bixylenol type epoxy resin, or a biphenol type epoxy resin of (meth)acrylate or a partial acid anhydride-modified product thereof, a carboxyl group-containing photosensitive urethane resin by polyaddition reaction of a carboxyl group-containing dialcohol compound and a diol compound.

(4) During the synthesis of the resin of (2) or (3) above, a compound having one hydroxyl group and one or more (meth)acryloyl group is added to a molecule such as hydroxyalkyl (meth) acrylate to end ( Meth) acrylated carboxyl group-containing photosensitive urethane resin.

(5) During the synthesis of the resin of (2) or (3), an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, having one isocyanate group and one or more (meth)acryloyl groups in the molecule A carboxyl group-containing photosensitive urethane resin obtained by adding a compound to (meth)acrylated terminal.

(6) A carboxyl group-containing photosensitive resin in which (meth)acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin, and dibasic acid anhydride is added to a hydroxyl group present in a side chain. Hereinafter, this is referred to as carboxylic acid-modified epoxy acrylate. In addition, as a specific example of a polyfunctional epoxy resin, the thing illustrated by paragraph [0039] of Unexamined-Japanese-Patent No. 2011-213828 is mentioned, for example.

(7) A carboxyl group-containing photosensitive resin in which (meth)acrylic acid is further reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and dibasic acid anhydride is added to the generated hydroxyl group.

(8) A dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid is reacted with a bifunctional oxetane resin, and a primary hydroxyl group generated is a dibasic acid such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride A polyester resin containing a carboxyl group to which an acid anhydride is added.

(9) Bisphenol A, bisphenol F, bisphenol S, novolak-type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, etc. in one molecule A carboxyl group obtained by reacting a compound having a phenolic hydroxyl group of containing photosensitive resin.

(10) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

(11) In an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and unsaturation such as (meth)acrylic acid Carboxyl group-containing obtained by reacting a group-containing monocarboxylic acid and reacting a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid with the alcoholic hydroxyl group of the obtained reaction product photosensitive resin.

(12) In the resin of (1) to (11) above, one epoxy group and one or more (meth) A carboxyl group-containing photosensitive resin formed by further adding a compound having an acryloyl group.

In addition, in this specification, (meth)acrylate is a general term for an acrylate, a methacrylate, and mixtures thereof, and the same applies to other similar expressions.

In the curable composition of the present invention, (A) the carboxyl group-containing resin is preferably a resin combining the above (6) and (12), specifically, a carboxylic acid-modified epoxy acrylate, an epoxy group and a radically polymerizable unsaturated group It is preferable that it is (A1) carboxyl group containing photosensitive resin obtained by making the compound which has it react.

Since the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone/polymer, development with a diluted aqueous alkali solution becomes possible.

In addition, the acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH/g, more preferably in the range of 40 to 150 mgKOH/g. When the acid value of carboxyl group-containing resin is 20 mgKOH/g or more, the adhesiveness of a coating film becomes favorable and alkali image development becomes favorable. On the other hand, when the acid value is 200 mgKOH/g or less, since dissolution of the exposed part by the developer can be suppressed, the line becomes thinner than necessary or, in some cases, it is suppressed from dissolving and peeling with the developer without distinguishing between the exposed part and the unexposed part Therefore, a resist pattern can be drawn favorably.

Moreover, although the weight average molecular weight of the carboxyl group-containing resin used by this invention changes with resin frame|skeleton, the range of 2,000-150,000, and further 5,000-100,000 is preferable. When the weight average molecular weight is 2,000 or more, the adhesion-free performance is good and the moisture resistance of the coating film after exposure is good, and it is possible to suppress a decrease in the film during development to suppress a decrease in resolution. On the other hand, when a weight average molecular weight is 150,000 or less, developability is favorable and it is excellent also in storage stability.

The curable composition of this invention may contain (A) carboxyl group-containing resin individually by 1 type, and may contain 2 or more types. When the curable composition of this invention contains 2 or more types of (A) carboxyl group-containing resin, it is preferable to contain the above-mentioned (A1) carboxyl group-containing photosensitive resin, for example.

Further, in another aspect, the curable composition of the present invention may contain (A) as the carboxyl group-containing resin, the above-described (A1) carboxyl group-containing photosensitive resin and a carboxyl group-containing acrylic copolymer having no alicyclic skeleton. . As a carboxyl group-containing acrylic copolymer which does not have an alicyclic skeleton, the carboxyl group-containing resin of the (1) styrene copolymerization type mentioned as a specific example of the said (A) carboxyl group-containing resin is mentioned. As a compounding ratio in the case of mix|blending the carboxyl group-containing acrylic copolymer which does not have an alicyclic skeleton, when (A) the whole carboxyl group-containing resin is 100 mass parts, it is 10-95 mass parts, for example, Preferably it is 10-80 mass is wealth

[(B) Photoinitiator]

The curable composition of this invention contains (B) a photoinitiator. (B) As a photoinitiator, a benzophenone type, acetophenone type, aminoacetophenone type, benzoin ether type, benzyl ketal type, acylphosphine oxide type, oxime ether type, oxime ester type, titanocene type, etc. well-known and common compounds can be heard

(B) As a photoinitiator, the oxime ester type photoinitiator containing the structural moiety represented by General formula (I) shown below is preferable. It is more preferable that the said oxime ester-type photoinitiator is a dimer oxime ester-type photoinitiator. In addition, the oxime ester-based photopolymerization initiator preferably has a carbazole structure, more preferably a dimer oxime ester-based photopolymerization initiator having a carbazole structure. Moreover, as an aminoacetophenone type|system|group photoinitiator, the (alpha)-aminoacetophenone type|system|group photoinitiator containing the structural moiety represented by the following general formula (II) is mentioned. As an acylphosphine oxide type|system|group photoinitiator, the acylphosphine oxide type photoinitiator containing the structural moiety represented by general formula (III) is mentioned. As a titanocene-type photoinitiator, the titanocene-type photoinitiator represented by General formula (IV) is mentioned.

In general formula (I), R< ¹ > represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group, or a benzoyl group. R ² represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.

The phenyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.

The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms, and may contain one or more oxygen atoms in the alkyl chain. It may also be substituted with one or more hydroxyl groups.

As the cycloalkyl group represented by R ¹ and R ² , a cycloalkyl group having 5 to 8 carbon atoms is preferable.

As the alkanoyl group represented by R ¹ and R ² , an alkanoyl group having 2 to 20 carbon atoms is preferable.

The benzoyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like.

In the general formula (II), R ³ and R ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or an arylalkyl group, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Or two may be combined to form a cyclic alkyl ether group.

In the general formula (III), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, or an aryl group having 1 to 10 carbon atoms A carbonyl group of 20 (however, except the case where both are a C1-C20 carbonyl group) is shown.

In the general formula (IV), R ⁹ and R ¹⁰ each independently represent a halogen atom, an aryl group, a halogenated aryl group, or a heterocycle-containing halogenated aryl group.

As an oxime ester type photoinitiator containing the structural moiety represented by general formula (I), 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], following formula ( The compound represented by I-1), 2-(acetyloxyiminomethyl)thioxanthen-9-one, and ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- The oxime ester type compound etc. which have carbazole skeletons, such as a compound represented by 3-yl]-,1-(O-acetyloxime) and the following general formula (I-2), etc. are mentioned.

In the general formula (I-2), R ¹¹ has the same meaning as R ¹ in the general formula (I), and R ¹² and R ¹⁴ each independently have the same meaning as R ² in the general formula (I). . R ¹³ is a hydrogen atom, a halogen atom, an 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, an alkoxycarbonyl group having 2 to 12 carbon atoms (alkoxy When the number of carbon atoms of the alkyl group constituting the actual group is 2 or more, the alkyl group may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain) or a phenoxycarboxyl group.

Such an oxime ester-type photoinitiator can make the sensitivity of the curable composition of this invention high with respect to exposure for direct imaging, for example, and since it is excellent in resolution, it is preferable. Moreover, it is especially preferable that an oxime ester type photoinitiator is a dimer.

As a dimer oxime ester type|system|group photoinitiator, it is more preferable that it is a compound represented by the following general formula (I-3).

In general formula (I-3), R ²³ represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, or a naphthyl group. R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a benzofuryl group, or a benzothienyl group.

Ar is a single bond, or an alkylene group having 1 to 10 carbon atoms, a vinylene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthrylene group, a thienylene group, a furylene group, 2,5-pyrrole-di diyl, 4,4'-stilbene-diyl group, and 4,2'-styrene-diyl group.

n represents the integer of 0-1.

As the alkyl group represented by R ²³ , an alkyl group having 1 to 17 carbon atoms is preferable.

As the alkoxy group represented by R ²³ , an alkoxy group having 1 to 8 carbon atoms is preferable.

The phenyl group represented by R ²³ may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, an alkylamino group ( Preferably, an alkyl group has 1 to 8 carbon atoms) or a dialkylamino group (preferably an alkyl group has 1 to 8 carbon atoms).

The naphthyl group represented by R ²³ may have a substituent, and examples of the substituent include the same groups as the substituents that the phenyl group represented by R ²³ may have.

As the alkyl group represented by R ²¹ and R ²² , an alkyl group having 1 to 17 carbon atoms is preferable.

As the alkoxy group represented by R ²¹ and R ²² , an alkoxy group having 1 to 8 carbon atoms is preferable.

The phenyl group represented by R ²¹ and R ²² may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, and an alkylamino group (preferably an alkyl group having 1 to 8 carbon atoms) or a dialkylamino group (preferably an alkyl group having 1 to 8 carbon atoms).

The naphthyl group represented by R ²¹ and R ²² may have a substituent, and examples of the substituent include the same groups as the substituents that the phenyl group represented by R ²¹ and R ²² may have.

Further, in the general formula (I-3), R ²¹ , R ²³ are each independently a methyl group or an ethyl group, R ²² is methyl or phenyl, Ar is a single bond, or a phenylene group, a naphthylene group, or a thienylene group and n is preferably 0.

As a compound represented by general formula (I-3), following compound No. 1 is more preferable.

When using such an oxime ester type photoinitiator, in order to improve the sensitivity to exposure, it is preferable to use together with the alpha-aminoacetophenone type photoinitiator containing the structural moiety represented by general formula (II), etc.

Examples of the α-aminoacetophenone-based photopolymerization initiator containing a structural moiety represented by the general formula (II) 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, and the like.

Examples of the acylphosphine oxide-based photopolymerization initiator containing a structural moiety represented by the general formula (III) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine. Pinoxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. are mentioned.

As the titanocene-based photopolymerization initiator represented by the general formula (IV), bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl) yl)-phenyl)titanium.

(B) Preferably the compounding quantity of a photoinitiator is 0.01-100 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin, More preferably, it is a ratio of 0.5-80 mass parts. (B) When the compounding quantity of a photoinitiator is 0.01 mass part or more with respect to 100 mass parts of (A) carboxyl group-containing resin, the photocurability on copper becomes favorable, the coating film becomes difficult to peel, and coating-film characteristics, such as chemical-resistance, become favorable. On the other hand, when the compounding quantity of a photoinitiator (B) is 100 mass parts or less with respect to 100 mass parts of (A) carboxyl group-containing resin, the light absorption of (B) photoinitiator becomes favorable and deep part sclerosis|hardenability improves.

[(C) Diluent]

(C) As a diluent, at least any one of an organic solvent and a photopolymerizable monomer can be used.

(C) As an organic solvent used as a diluent, For example, 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 (DPM), dipropylene glycol diethyl ether, tripropylene glycol glycol ethers such as monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; Petroleum solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, etc. can be used. These organic solvents can be used individually or in combination of 2 or more types.

The purpose of using the organic solvent is to dissolve and dilute the (A) carboxyl group-containing resin, thereby apply as a liquid, and then form a film by temporary drying to enable contact exposure. The usage-amount of the organic solvent is not limited to a specific ratio, According to the coating method etc. to be selected, it can set suitably.

On the other hand, (C) as representative examples of the photopolymerizable monomer used as the diluent, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinyl pyrrolidone, acryloyl morph Pauline, methoxytetraethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N,N-dimethyl (meth) acrylamide, N-methylol (meth) Acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, melamine (meth)acrylate, di Ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene Glycol di (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, glycerin diglycidyl ether di (meth) acrylate, glycerin triglyceride cydyl ether tri(meth)acrylate, isobornyl(meth)acrylate, cyclopentadiene mono- or di-(meth)acrylate; Polyhydric (meth)acrylates of polyhydric alcohols, such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or ethylene oxide of these polyhydric alcohols or polyvalent (meth)acrylates of propylene oxide adducts; and mono-, di-, tri- or higher polyesters of polybasic acids and hydroxyalkyl (meth)acrylates. These photopolymerizable monomers can be used individually or in combination of plurality.

The purpose of using the photopolymerizable monomer is to impart photopolymerizability while diluting the (A) carboxyl group-containing resin to make it easy to apply.

(C) When using a photopolymerizable monomer as a diluent, as for the compounding quantity of a photopolymerizable monomer, the range of 5-40 mass parts per 100 mass parts of total amounts of said (A) carboxyl group-containing resin is suitable. When the compounding quantity of a photopolymerizable monomer is 5 mass parts or more, the photocurability provision effect becomes more favorable. On the other hand, when it is 40 mass parts or less, the dry-to-touch property of a coating film becomes favorable.

[(D) polyfunctional epoxy compound having at least two epoxy groups in one molecule]

(D) It has been confirmed that the polyfunctional epoxy compound having at least two epoxy groups in one molecule not only imparts heat resistance to the composition but also improves adhesion to the underlying substrate.

(D) As a polyfunctional epoxy compound which has at least two epoxy groups in 1 molecule, For example, Mitsubishi Chemical Corporation Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, DIC Corporation Epiclone 840, Epiclone 850, Epiclone 1050, Epiclone 2055, Ephototo YD-011, YD-013, YD-127, YD-128 manufactured by Toto Chemical Co., Ltd. D.E.R. 317, D.E.R. 331, D.E.R. 661, D.E.R. 664, Sumitomo Chemical Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Industries, Ltd., A.E.R. 330, A.E.R. 331, A.E.R. 661, A.E.R. bisphenol A epoxy resins such as 664 (all are brand names); Epicoat YL903 by Mitsubishi Chemical Corporation, EpiClone 152, EpiClone 165 by DIC, EPTOTO YDB-400, YDB-500 by Toto Chemicals, D.E.R. by Dow Chemical. 542, Sumitomo Chemical ESB-400, ESB-700 manufactured by Sumitomo Chemical Industries, A.E.R. 711, A.E.R. Brominated epoxy resins, such as 714 (all are brand names); Epicoat 152, Epicoat 154, manufactured by Mitsubishi Chemical, D.E.N. 431, D.E.N. 438, Epiclone N-730, Epiclone N-770, Epiclone N-865 manufactured by DIC, Epotto YDCN-701, YDCN-704 manufactured by Nippon Kayaku, EPPN-201, EOCN manufactured by Toto Chemical Corporation -1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. A.E.R. novolac-type epoxy resins such as ECN-235 and ECN-299 (all are trade names); Bisphenol F-type epoxy resins, such as Epiclon 830 by DIC, Epicoat 807 by Mitsubishi Chemical, and Epotto YDF-170, YDF-175, YDF-2004 by Toto Chemical Company (all are brand names); Hydrogenated bisphenol-A epoxy resins, such as the Toto Chemicals company EPOTTO ST-2004, ST-2007, and ST-3000 (brand name); glycidylamine-type epoxy resins such as Epicoat 604 by Mitsubishi Chemical Co., Ltd., Epotto YH-434 by Toto Chemical Co., Ltd., and Sumitomo Chemical ELM-120 by Sumitomo Chemical Co., Ltd. (all are trade names); hydantoin-type epoxy resin; alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd. (all are brand names); Trihydroxyphenylmethane type epoxy resins, such as YL-933 by Mitsubishi Chemical Corporation, T.E.N. by Dow Chemical, EPPN-501, EPPN-502 (all are brand names); Bixylenol-type or biphenol-type epoxy resins, such as Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all are brand names), or mixtures thereof; bisphenol S-type epoxy resins such as EBPS-200 by Nippon Kayaku, EPX-30 by ADEKA, EXA-1514 (trade name) by DIC; Bisphenol A novolak-type epoxy resins, such as Mitsubishi Chemical's Epicoat 157S (brand name); Tetraphenylolethane-type epoxy resins, such as Mitsubishi Chemical's Epicoat YL-931 (all are brand names); Heterocyclic epoxy resins, such as TEPIC by the Nissan Chemical Industry Co., Ltd. (all are brand names); diglycidyl phthalate resins such as Blemmer DGT manufactured by Nichiyu Corporation; Tetraglycidyl xylenoylethane resin, such as ZX-1063 by Toto Chemical Co., Ltd.; Naphthalene group-containing epoxy resins, such as ESN-190, ESN-360 by Nippon-Steel Chemicals, HP-4032 by DIC, EXA-4750, EXA-4700; Epoxy resin which has dicyclopentadiene frame|skeleton, such as HP-7200 by DIC and HP-7200H; Glycidyl methacrylate copolymerization type epoxy resins, such as CP-50S and CP-50M by Nichiyo Corporation; Further, a copolymerized epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (eg, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (eg, YR-102 and YR-450 manufactured by Toto Chemical Co., Ltd.), etc. , but is not limited thereto. These epoxy resins can be used individually or in combination of 2 or more type. Among these, a novolak-type epoxy resin, a heterocyclic epoxy resin, a bisphenol A-type epoxy resin, or a mixture thereof is especially preferable.

(D) The blending amount of the polyfunctional epoxy compound having at least two epoxy groups in one molecule is preferably 0.6 to 2.8 equivalents, more preferably 0.8 to 2.5 equivalents in terms of epoxy equivalent to 100 parts by mass of the (A) carboxyl group-containing resin to the range of (D) By making the compounding quantity of the polyfunctional epoxy compound which has at least 2 epoxy groups in 1 molecule into the said range, favorable heat resistance can be provided to a composition.

[(E) Black Colorant]

(E) The black coloring agent may be an organic type coloring agent, or an inorganic type coloring agent may be sufficient as it. For example, carbon black pigments, such as C.I. Pigment black 6, 7, 9, 18, Graphite pigments, such as C. I. pigment black 8 and 10, C. I. Pigment black 11, 12, 27, iron oxide-based pigments such as Pigment Brown 35; For example, iron oxide of KN-370 manufactured by Toda Kogyo Co., Ltd., titanium black of 13M-T manufactured by Mitsubishi Materials, anthraquinone pigments such as C.I. Pigment Black 20, C.I. Pigment Black 13, 25, 29 Cobalt oxide pigments, copper oxide pigments such as C.I. Pigment Black 15 and 28, manganese pigments such as C.I. Pigment Black 14 and 26, antimony oxide pigments such as C.I. Pigment Black 23, C.I. Pig Nickel oxide pigments such as pigment black 30, C.I. Pigment Black 31 and 32, BASF Japan Lumogen Black FK4280 perylene pigments, Pigment Black 1 An aniline-based pigment and molybdenum sulfide and bismuth sulfide can also be exemplified as suitable pigments. Particularly preferred are carbon black-based and perylene-based pigments. In the case of a carbon black-based pigment and a perylene-based pigment, the absolute value of the ab value is closer to 0, so it tends to blacken and is preferable. These colorants are used individually or in appropriate combination.

(E) It is preferable that it is 0.01-5 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin from a viewpoint of resolution, and, as for the compounding quantity of a black coloring agent, it is more preferable that it is 0.05-1 mass part. In the case of 0.01 mass part or more, it is easy to blacken. In the case of 5 parts by mass or less, the light transmittance hardly deteriorates.

[(F) Colorants other than black]

The curable composition of this invention contains (F) coloring agents other than black. As a coloring agent to be used, commonly known coloring agents, such as red, blue, green, yellow, and white, can be used, Any of a pigment, dye, and a pigment|dye may be sufficient. As a specific example, the thing to which the following color index (C.I.; published by The Society of Dyers and Colorists) number was attached is mentioned. However, it is preferable not to contain a halogen from a viewpoint of environmental load reduction and an influence on a human body.

(red colorant)

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and the like. For example, those with the same color index number are attached.

Monoazo: 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: Pigment Red 37, 38, 41;

Monoazolakes: 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;

Benzimidazolones: Pigment Red 171, 175, 176, 185, 208;

Perylene-based: Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224;

Diketopyrrolopyrrole type: Pigment Red 254, 255, 264, 270, 272;

Condensed Azo: Pigment Red 144, 166, 214, 220, 221, 242;

Anthraquinones: Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207;

Quinacridone: Pigment Red 122, 202, 206, 207, 209

It is preferable that it is 0-1 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin, as for the compounding quantity of a red coloring agent, it is more preferable that it is 0.1-1 mass, It is more preferable that it is 0.1-0.8 mass parts. In the case of 1 mass part or less, the light transmittance hardly deteriorates. Moreover, in the case of 0.1 mass part or more, it is easy to blacken.

(blue colorant)

As the blue colorant, there are compounds classified as phthalocyanine-based, anthraquinone-based, dioxazine-based, cobalt-based, pigment-based, and dye-based, solvent-based compounds, and specifically, the following colors There are those with index numbers attached. In addition to these, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Pigmentation system: Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60;

Dye-based: Solvent Blue 35, 45, 63, 67, 68, 70, 83, 87, 94, 97, 104, 122, 136

It is preferable that it is 0.1-2.5 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin, and, as for the compounding quantity of a blue coloring agent, it is more preferable that it is 0.2-1.5 mass parts. In the case of 0.1 mass part or more, it is easy to blacken. In the case of 2.5 parts by mass or less, the light transmittance hardly deteriorates.

(yellow colorant)

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone and the like, and specifically, the following colorants are exemplified.

Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 101 , 104, 105, 111, 116, 167, 168, 169, 182, 183;

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

Condensed Azo: Pigment Yellow 93, 94, 95, 128, 155, 166, 180;

Benzimidazolones: Pigment Yellow 120, 151, 154, 156, 175, 181;

isoindolinones: Pigment Yellow 109, 110, 139, 179, 185;

Anthraquinones: Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202;

It is preferable that the compounding quantity of a yellow coloring agent is 0.1-1.5 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin. In the case of 0.1 mass part or more, it is easy to blacken. In the case of 1.5 parts by mass or less, the light transmittance hardly deteriorates. Moreover, it is preferable that the compounding quantity of a yellow coloring agent is 0.1-2.5 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin of the total compounding quantity with a red coloring agent. In the case of 0.1 mass part or more, it is easy to blacken. In the case of 2.5 parts by mass or less, the light transmittance hardly deteriorates.

(Green Colorant)

As the green colorant, there are phthalocyanine-based and anthraquinone-based, and specifically, Pigment Green 7, 36, Solvent Green 3, 5, 20, 28, and the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound may also be used. It is preferable that the compounding quantity of a green coloring agent is 0.2-2.0 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin. In the case of 0.2 mass part or more, it is easy to blacken. In the case of 2.0 mass parts or less, the light transmittance hardly deteriorates.

(purple colorant)

Specific examples of the purple colorant include Pigment Violet 19, 29, 32, 36, 38, 42; Solvent Violet 13, 36, etc. are mentioned.

It is preferable that it is 0.1-2.5 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin, and, as for the compounding quantity of a purple coloring agent, it is more preferable that it is 0.2-2.5 mass parts. In the case of 0.1 mass part or more, it is easy to blacken. In the case of 2.5 parts by mass or less, the light transmittance hardly deteriorates.

(orange colorant)

Specific examples of the orange colorant include Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, etc. are mentioned.

It is preferable that it is 0.05-1 mass part with respect to 100 mass parts of (A) carboxyl group-containing resin, and, as for the compounding quantity of an orange coloring agent, it is more preferable that it is 0.1-0.8 mass part. In the case of 0.05 mass part or more, it is easy to blacken. In the case of 1 mass part or less, the light transmittance hardly deteriorates.

(browning)

As a brown coloring agent, Pigment Brown 23, 25 etc. are mentioned specifically,.

(white colorant)

Examples of the white colorant include zinc oxide represented by Pigment White 4, titanium oxide represented by Pigment White 6, and zinc sulfide represented by Pigment White 7, and titanium oxide is particularly preferable from the viewpoint of coloring power and non-toxicity. and, for example, TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titan Kogyo, R-550, R-580, R-630, R-820, CR- manufactured by Ishihara Sangyo. 50, CR-60, CR-90, rutile-type titanium oxide such as KR-270, KR-310, KR-380 manufactured by Titan Industries, TA-100, TA-200, TA-300 manufactured by Fuji Titan Industries, Ltd. and anatase-type titanium oxide such as TA-500, A100 and A220 by Ishihara Sangyo, KA-15, KA-20, KA-35, and KA-90 by Titan Kogyo. When a white coloring agent is added so that it may become a small amount, for example, in the curable composition of this invention so that it may become 0.1-3 mass %, the effect of raising blackness may be expectable.

(F) Coloring agents other than black may combine 2 or more types. (F) As for the total amount of the compounding quantity of coloring agents other than black, 0.35-9.5 mass parts is preferable with respect to 100 mass parts of (A) carboxyl group-containing resin. In the case of 0.35 mass part or more, it is easy to blacken. In the case of 9.5 parts by mass or less, the light transmittance hardly deteriorates.

(thermosetting catalyst)

It is preferable to further contain a thermosetting catalyst in the curable composition of this invention. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, imidazole derivatives such as 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, and 4-methyl-N,N-dimethylbenzylamine hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. Moreover, as what is marketed, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are the brand names of an imidazole type compound) by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U-CAT3503N by San Apro Corporation, for example, are commercially available, for example. CAT3502T (all are the brand names of the block isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and its salt), etc. are mentioned. It is not limited to these, and can be used as long as it promotes a thermosetting catalyst of an epoxy resin or an oxetane compound, or a reaction between an epoxy group and/or an oxetanyl group and a carboxyl group, and these can be used alone or in mixture of two or more can Also guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine , 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid addition product, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid addition product S-triazine derivatives, such as water, can also be used, Preferably, the compound which functions also as these adhesion-imparting agents is used together with a thermosetting catalyst.

The compounding amount of the thermosetting catalyst is sufficient in a ratio normally used, for example, (A) a carboxyl group-containing resin or (D) preferably 0.1 to 100 parts by mass of a polyfunctional epoxy compound having at least two epoxy groups in one molecule. -20 mass parts, More preferably, it is 0.5-15.0 mass parts.

(filler)

In addition, an inorganic filler or an organic filler can be further mix|blended with the curable composition of this invention for the purpose of improving characteristics, such as the adhesiveness of hardened|cured material, mechanical strength, and a coefficient of linear expansion. Examples of such fillers include known and customary fillers such as barium sulfate, barium titanate, silicon oxide powder, fine silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. can be used

(Other optional ingredients)

In the curable composition of the present invention, if necessary, well-known and usual polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine; finely divided silica, organic bentonite, montmorillonite, etc. At least any one of antifoaming agents and leveling agents such as thickeners, silicones, fluorines, and polymers, silane coupling agents such as imidazoles, thiazoles, and triazoles, antioxidants, photopolymerization sensitizers, light stabilizers, dispersants, curing accelerators, A flame retardant, a flame-retardant auxiliary agent, (D) a thermosetting component other than a polyfunctional epoxy compound, etc. well-known and usual additives can be mix|blended further.

It is preferable that the curable composition of this invention is black. Moreover, it is preferable that the L* value of the hardened|cured material by the colorimeter which is a reference|standard which shows blackness is 35 or less by SCI method. Further, from the viewpoint of blackness, the a* value is preferably -1.0 to 2.0, and the b* value is preferably -3.0 to 1.1. More preferably, the a* value is -0.5 to 0.5, and the b* value is -2.0 to 0.5.

Moreover, it is preferable that the curable composition of this invention contains a purple coloring agent as a coloring agent other than (F) black from a viewpoint of blackness. In particular, as for the curable composition of this invention, it is more preferable to contain 0.05-1.0 mass part of black coloring agents with respect to 100 mass parts of (A) carboxyl group-containing resin, and also contain 0.2-2.0 mass parts of purple coloring agents. As for the (F) curable composition containing a purple colorant as a colorant other than black, it is especially preferable that a* value is 0.07-1.55 and b* value is -1.0-1.1.

The curable composition of this invention is suitable for formation of hardened films, such as a soldering resist and an interlayer insulating layer of a printed wiring board or a flexible printed wiring board, Especially in the printed wiring board of densification and high fineness WHEREIN: Density-ized and a high black resist pattern suitable for the formation of The curable composition of the present invention, in addition to printing ink, inkjet ink, photomask manufacturing material, printing proof manufacturing material, etching resist, solder resist, barrier ribs of plasma display panel (PDP), dielectric pattern, electrode (conductor circuit) pattern, It can be used for production of shielding images, such as wiring patterns of electronic components, electrically conductive pastes, a conductive film, and a black matrix.

The curable composition of this invention can be made into the form of a dry film obtained by apply|coating and drying on a carrier film (support body). In the case of dry film formation, the curable composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity, followed by a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, It can be applied to a uniform thickness on a carrier film with a spray coater or the like, and usually dried at a temperature of 50 to 130° C. for 1 to 30 minutes to obtain a dry coating film. Although there is no restriction|limiting in particular about the coating film thickness, Usually, it is 0.1-100 micrometers as a film thickness after drying, Preferably it selects suitably in the range of 0.5-50 micrometers.

A plastic film is used as the carrier film, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film. Although there is no restriction|limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 0.1-150 micrometers.

In this case, after the coating film is formed on the carrier film, it is preferable to further laminate a peelable cover film on the surface of the coating film for the purpose of preventing dust from adhering to the surface of the coating film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used. When the cover film is peeled off, the adhesive force between the coating film and the cover film is determined by the coating film and the carrier. What is necessary is just to be smaller than the adhesive force of a film.

In addition, after adjusting the curable composition of the present invention to a viscosity suitable for the coating method using the above organic solvent, dip coating method, flow coating method, roll coating method, bar coater method, screen printing method, curtain coating method on a substrate A non-stick dry coating film can be formed by applying by a method such as a method, a die coater method, or the like, and volatilizing and drying (temporarily drying) the organic solvent contained in the composition at a temperature of about 50°C to 90°C. In addition, in the case of a dry film wound up as a film by applying the curable composition of the present invention on a carrier film, drying it, and bonding it on a substrate so that the coating film of the composition is in contact with the substrate by a laminator, etc., by peeling the carrier film, on the substrate A layer of a coating film can be formed.

Hardened|cured material can be obtained by making these coating films photocuring by active energy ray irradiation, for example, or heating to the temperature of 100 degreeC - 250 degreeC and thermosetting.

Examples of the substrate include printed wiring boards and flexible printed wiring boards with circuits formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluorine/polyethylene/poly Copper-clad laminates of all grades (FR-4, etc.), as well as polyimide films, PET films, glass substrates, A ceramic substrate, a wafer plate, etc. are mentioned.

The volatilization drying performed after application of the curable composition of the present invention is performed using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. equipped with a heat source of an air heating method by steam, and the hot air in the dryer is counter-current. It can carry out using the method of making contact, and the method of injecting into a support body from a nozzle.

As an exposure machine used for active energy ray irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc. are mounted and it is a device that irradiates ultraviolet rays in the range of 350 to 450 nm, and further a direct drawing device (For example, a direct imaging device that draws an image by irradiating an active energy ray directly with CAD data from a computer) can also be used. As a light source of a straight drawing machine, what is necessary is just to use the light which has a maximum wavelength in the range of 350-410 nm. The exposure amount for image formation varies depending on the film thickness and the like, but can be generally within the range of 20 to 800 mJ/cm 2 , preferably 20 to 600 mJ/cm 2 .

In addition, as a developing method, a dipping method, a shower method, a spraying method, a brush method, etc. can be used. As a developing solution, aqueous alkali solutions, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, are used. can

[Example]

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. In addition, in the following, what is referred to as "part" and "%" is a mass basis, unless there is particular notice.

[Synthesis of carboxyl group-containing resin A-1]

Orthocresol novolac type epoxy resin in 600 g of diethylene glycol monoethyl ether acetate [Dainippon Ink Chemical Chemicals Co., Ltd., EPICLON N-695, softening point 95°C, epoxy equivalent 214, average number of functional groups 7.6] 1070 g (the number of glycidyl groups (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were added and stirred at 100° C. to uniformly dissolve.

Then, 4.3 g of triphenylphosphine was added, and after heating at 110° C. for 2 hours, the temperature was raised to 120° C. and reaction was performed for 12 hours. 415 g of aromatic hydrocarbons (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction solution, reacted at 110° C. for 4 hours, cooled, and a photosensitive carboxyl group-containing resin solution (solid content acid value 89 mgKOH/ g, solid content 65%) was obtained. Let this be resin solution A-1.

[Synthesis of carboxyl group-containing resin A-2]

In an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, 119.4 g of novolac cresol resin (manufactured by Showa Denko, trade name “Shonol CRG951”, OH equivalent: 119.4), potassium hydroxide 1.19 g and 119.4 g of toluene were added, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating.

Next, 63.8 g of propylene oxide was dripped gradually, and it was made to react at 125-132 degreeC and 0-4.8 kg/cm<2> for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide, and propylene oxide of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. A reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl groups.

293.0 g of the obtained novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air intake tube, and air It was blown at a rate of 10ml/min and reacted at 110°C for 12 hours while stirring. Water produced by the reaction was an azeotrope with toluene, and 12.6 g of water was discharged.

Thereafter, the reaction solution was cooled to room temperature and neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, followed by washing with water. Then, it distilled off, substituting 118.1 g of diethylene glycol monoethyl ether acetate for toluene with an evaporator, and the novolak-type acrylate resin solution was obtained.

Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were put into a reactor equipped with a stirrer, a thermometer and an air suction tube, and air was blown in at a rate of 10 ml/min and stirred while tetrahydrogen 60.8 g of phthalic anhydride was gradually added, and it was made to react at 95-101 degreeC for 6 hours, and the photosensitive carboxyl group-containing resin solution (solid content acid value 88 mgKOH/g, solid content 71%) was obtained. Let this be resin solution A-2.

[Preparation of carboxyl group-containing resin A-3]

Cyclomer ACA Z320 (solid content, acid value 135 gKOH/g, solid content 39%) manufactured by Daicel Corporation was used. Let this be resin solution A-3.

According to the formulation shown in Table 1 below, each component was blended, stirred, and dispersed with a triaxial roll to prepare a curable composition, respectively. In addition, the compounding quantity in Table 1 shows a mass part.

Carboxyl group-containing resin solution A-1: Varnish A-1 (solid content: 65%, acid value: 89 mgKOH/g)

Carboxyl group-containing resin solution A-2: Varnish A-2 (solid content: 71%, acid value: 88 mgKOH/g)

Carboxyl group-containing resin solution A-3: Varnish A-3 (Cyclomer (ACA) Z320 (solid content: 39%, acid value: 135 mgKOH/g) manufactured by Daicel Corporation))

Photoinitiator B-1: Irgacure 907 by BASF Japan (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one)

Photoinitiator B-2: Dimeric oxime ester-based photopolymerization initiator having a carbazole structure (compound No. 1 above)

Photoinitiator B-3: oxime ester-based photoinitiator

Diluent C-1: dipropylene glycol monomethyl ether (DPM)

Diluent C-2: NK ester A-9550 (polyfunctional acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.

Polyfunctional epoxy compound D-1: N870-75EA (bisphenol A epoxy resin) by DIC Corporation

Polyfunctional Epoxy Compound D-2: TEPIC-HP

Black colorant E-1: CKT-7198 (carbon black) manufactured by Regino Color

Blue colorant F-1: ε-phthalocyanine blue

Red Colorant F-2: PY8025

Violet Colorant F-3: Dioxazine Violet Violet B

Yellow Colorant F-4: Chromophthal Yellow AGR

Orange Colorant F-5: Diketopyrrolopyrrole Orange Orange TR

Curing Catalyst G-1: Melamine

Curing catalyst G-2: dicyandiamide

Additive H-1: KS-66 (silicone-based antifoaming agent) manufactured by Shin-Etsu Silicone

Filler I-1: B-30 (barium sulfate) manufactured by Sakai Chemical Co., Ltd.

Filler I-2: SiO ₂

(Assessment Methods)

<a*value and b*value>

The curable composition of each Example and each comparative example was applied to the entire surface by screen printing on each cleaned copper front substrate, dried in a hot air circulation drying furnace at 80° C. for 10 minutes to form a dry coating film, and then, Oak Seisaku It exposed with the exposure amount used as 7 sensitivities with the exposure machine which mounted the metal halide lamp|lamp by the Sho Corporation. Then, the cured coating film was obtained by developing for 1 minute with a spray pressure of 0.1 MPa with ₁ wt% _Na2CO3 aqueous solution, then thermosetting at 150 degreeC for 60 minutes using a hot-air circulation drying furnace. With respect to the obtained cured coating film, the value of the L*a*b* colorimetric system on the coating film was measured in accordance with JIS Z 8729 using a spectrophotometer (manufactured by Konica Minolta, CM-2600d), and L*a which is an index indicating the brightness The *b* value was evaluated as an index of blackness. The closer the a* and b* values are to 0, the better the blackness is. The obtained results are shown in Table 2 below.

<Absorbance>

An ultraviolet-visible spectrophotometer (Ubest-V-570DS manufactured by Nippon Bunko) and an integrating sphere device (ISN-470 manufactured by Nippon Bunko) were used for the measurement of the absorbance. The curable composition of each of the above Examples and each comparative example was applied to a glass plate using an applicator, and then dried at 80° C. for 30 minutes using a hot air circulation drying furnace to prepare a dry coating film of the curable composition on the glass plate. The absorbance baseline in 500-300 nm was measured with the same glass plate as the glass plate to which the curable composition was apply|coated using the ultraviolet-visible spectrophotometer and the integrating sphere apparatus. The absorbance of the prepared glass plate with a dry coating film was measured, the absorbance of the dry coating film was computed from the base line, and the absorbance in wavelength 355 nm of desired light was obtained. In order to prevent the shift in absorbance due to shift in the thickness of the coating film, this operation is performed by changing the application thickness by the applicator to four steps, and a graph of the application thickness and the absorbance at 355 nm is created, and from the approximate formula The absorbance of the dry coating film with a film thickness of 25 micrometers was computed, and it was set as each absorbance. The obtained results are shown in Table 2 below.

<Sensitivity>

The curable compositions of Examples and Comparative Examples were applied over the entire surface to a thickness of 10 μm after drying by screen printing on a washed copper front substrate, and dried at 80° C. for 10 minutes in a hot air circulation drying furnace. A step tablet (41 steps) manufactured by Stouffer was brought into contact on this coating film, and exposed at an exposure dose of 300 mJ/cm 2 in an exposure machine equipped with a metal halide lamp manufactured by Oak Seisakusho, 1 wt% Na ₂ CO ₃ The residual number of plates after developing for 1 minute by the spray pressure of 0.1 MPa with the aqueous solution was investigated. The more the number of remaining stages, the better the sensitivity, which is preferable. The obtained results are shown in Table 2 below.

<Resolution>

The curable resin composition of each Example and Comparative Example was applied over the entire surface by screen printing on a copper front substrate and dried at 80° C. for 30 minutes. Using a negative film of L/S=50/500, exposure was performed at an optimal exposure dose, and a 30°C 1% Na ₂ CO ₃ aqueous solution was developed for 60 seconds under a spray pressure of 2 kg/cm 2 to obtain a pattern. After development, the relief shape was observed under an optical microscope and evaluated as follows. The obtained results are shown in Table 2 below. The relief shapes of Example 2 and Comparative Example 2 are shown in FIGS. 1 and 2, respectively.

(double-circle): None of the wrinkles, hypertrophy, and undercut (dimension difference between top and bottom) of a pattern could be confirmed.

○: Any one of slight pattern wrinkles, hypertrophy, and undercut (dimension difference between top and bottom) was confirmed.

x: Any one of wrinkles, hypertrophy, and undercut (dimension difference between top and bottom) of a clear pattern was confirmed.

<Gold Plating Resistance (Adhesiveness)>

The curable compositions of Examples and Comparative Examples were applied over the entire surface by screen printing to a dry film thickness of 20 µm on a pattern-formed copper foil substrate, dried at 80°C for 30 minutes, and allowed to cool to room temperature. After exposing the pattern at the optimal exposure amount using the exposure apparatus which mounted the high pressure mercury lamp on this board|substrate, it developed for 60 second under the conditions of spray pressure 0.2 MPa with 30 degreeC 1wt% sodium carbonate aqueous solution, and obtained the pattern. This board|substrate was post-cured at 150 degreeC and 60 minutes, and the evaluation board|substrate in which the hardened|cured material pattern was formed was obtained.

With respect to the evaluation substrate, using a commercially available electroless nickel plating bath and an electroless gold plating bath, plating was performed at 80 to 90° C. under conditions of 5 µm of nickel and 0.05 µm of gold. The plated evaluation substrate WHEREIN: After visually evaluating the presence or absence of penetration of plating, the presence or absence of peeling of a resist layer was evaluated by tape peeling. Each judgment criterion is as follows. The obtained results are shown in Table 2 below.

(double-circle): After plating, seepage was not seen at all, and there was no peeling after tape peeling.

(circle): Slight permeation was seen after plating, but there was no peeling after tape peeling.

(triangle|delta): Slight permeation was confirmed after plating, and it peeled slightly after tape peeling.

×: Seepage is confirmed after plating, and peeling is also seen after peeling the tape.

It was confirmed that the curable composition of any Example was also excellent in resolution and blackness of the cured product. On the other hand, it was confirmed that the curable compositions of Comparative Examples 1 to 3 that do not satisfy the absorbance have poor resolution. In addition, it was confirmed that Comparative Example 4, which does not satisfy the absorbance, has inferior resolution compared to Example 2, which has a similar composition.

Claims (12)

(A) a carboxyl group-containing resin, (B) a photoinitiator, (C) a diluent, (D) a polyfunctional epoxy compound having at least two epoxy groups in one molecule, (E) a black colorant, and (F) a colorant other than black. is a composition that
(F) As a colorant other than black, a purple colorant is contained, and the mixing amount of the purple colorant is 0.1 to 2.5 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin,
The dry coating film has an absorbance of 1.5 or less at a wavelength of 365 nm, an absorbance of at 385 nm of 1.0 or less, and an absorbance of at a wavelength of 405 nm of 1.0 or less per 25 µm of the thickness of the dry coating film. (A) a carboxyl group-containing resin, (B) a photoinitiator, (C) a diluent, (D) a polyfunctional epoxy compound having at least two epoxy groups in one molecule, (E) a black colorant, and (F) a colorant other than black. is a composition that
(F) As a colorant other than black, an orange colorant is contained, and the blending amount of the orange colorant is 0.05 to 1 part by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin,
The dry coating film has an absorbance of 1.5 or less at a wavelength of 365 nm, an absorbance of at 385 nm of 1.0 or less, and an absorbance of at a wavelength of 405 nm of 1.0 or less per 25 µm of the thickness of the dry coating film. The curable composition according to claim 1 or 2, further comprising (F) at least one of a red colorant, a blue colorant and a yellow colorant as a colorant other than black. The curable composition according to claim 1 or 2, wherein the (B) photoinitiator contains an oxime ester-based photopolymerization initiator. The curable composition according to claim 4, wherein the oxime ester-based photopolymerization initiator is a dimer oxime ester-based photopolymerization initiator. It has a resin layer obtained by apply|coating and drying the curable composition of Claim 1 on a film, The dry film characterized by the above-mentioned. A cured product obtained by curing at least any one of the curable composition according to claim 1 or 2 and the resin layer of the dry film according to claim 6 . A printed wiring board comprising the cured product according to claim 7. The manufacturing method of the dry film characterized by using the curable composition of Claim 1 or 2 characterized by the above-mentioned. A method for producing a cured product, wherein the curable composition according to claim 1 or 2 is used. At least any one of the curable composition of Claim 1 or 2, and the dry film of Claim 6 is used, The manufacturing method of the printed wiring board characterized by the above-mentioned. delete

Images