KR100787341B1 - A resin composition, cured material therefrom, and printing wiring boards using the same - Google Patents

Abstract

It is possible to exhibit high photopolymerization ability with respect to laser light of 400 to 420 nm, at the same time obtain sufficient surface curability and deep curability, and also excellent photocurable or photocurable thermosetting resin composition excellent in thermal stability, and cured product thereof and Using this, a patterned printed wiring board is provided.

(A) carboxylic acid containing resin, (B) oxime ester type photoinitiator containing the oxime ester group represented by General formula (1), (C) aminoacetophenone type photoinitiator which has a structure represented by General formula (2), (D ) A composition containing one or more ethylenically unsaturated groups in a molecule and (E) a blue pigment, which can be developed by a dilute alkali solution, and the absorbance of the coating film at a wavelength of 400 to 420 nm of 0.5 to 25 µm. 1.2.

Printed wiring boards, photocurable resins, thermosetting resins, oxime esters, aminoacetophenones

Description

A resin composition, its hardened | cured material, and the printed wiring board obtained using the same {A RESIN COMPOSITION, CURED MATERIAL THEREFROM, AND PRINTING WIRING BOARDS USING THE SAME}

1 is a schematic diagram of a cross-sectional shape of a resin composition obtained by exposure and development

Description of the main parts of the drawing

1a line width design value

1b Resin composition after exposure and development

1c substrate

[Patent Document 1] Japanese Unexamined Patent Application Publication No. 2001-235858 (Patent Claims)

[Patent Document 2] International Publication WO02 / 096969 (Patent Claims)

 The present invention is a photocurable or photocurable and thermosetting resin composition useful as an etching resist or solder resist used in the manufacture of a printed wiring board and as an insulating resin layer of various electronic components, and a cured product thereof and a printed wiring board obtained using the same. The present invention relates to a photocurable or photocurable and thermosetting resin composition which can be cured by a blue violet laser oscillation light source having a maximum wavelength of 400 to 420 nm, a cured product thereof, and a printed wiring board obtained using the same. .

The solder resist film is formed in the outermost layer of the conventional printed wiring board. A soldering resist is a protective coating material which covers the surface of a printed wiring board and prevents unnecessary solder from adhering to the circuit surface at the time of coating | covering by a solder and component mounting. In addition, as a permanent protective mask, it protects the copper foil circuit of the printed wiring board from humidity and dust and also protects the circuit from electrical troubles. It has excellent chemical resistance and heat resistance, and can withstand high heat and gold plating when soldering. It is a protective film. Generally, the photolithographic method of forming a pattern by irradiating an active energy ray through a mask pattern is used for the formation method of a soldering resist.

In recent years, as a photolithography method that considers an environment such as resource saving or energy saving, a direct drawing method (laser direct imaging) using laser light as a light source has been put into practical use. A direct drawing apparatus is an apparatus which draws pattern data by direct laser light at high speed in the printed wiring board in which the film | membrane of the photocurable resin composition which photosensitizes a laser beam is already formed. Characterized by the need for a mask pattern, it is possible to shorten the manufacturing process and to significantly reduce the cost, and it is a method suitable for small lots and short delivery times of various kinds.

Since the direct drawing apparatus cannot simultaneously expose the entire exposed part surface such as the conventional mask pattern exposure, it is necessary to expose at high speed in order to obtain an exposure time equivalent to that of the conventional mask pattern exposure. In addition, the light source used for the conventional mask pattern exposure has a wide wavelength of 300 to 420 nm, such as a metal halide lamp, whereas the wavelength of the direct drawing device varies depending on the light source used, but is usually a single light ray. For example, the wavelength of a blue violet laser is around 405 nm.

However, even if a conventional solder resist is exposed using a direct drawing apparatus near a wavelength of 405 nm, a coating film which can obtain heat resistance and insulation required for the solder resist cannot be formed. For this reason, the photopolymerization initiator contained in the conventional solder resist is an α-acetophenone-based initiator, has a low absorption for 400 to 420 nm, and a single wavelength light ray having a photopolymerization initiation ability of 405 nm is not sufficient. , Very much exposure time was required. Therefore, the use of the photopolymerizable composition containing the conventional photoinitiator was remarkably limited.

Moreover, the photoinitiator which can exhibit high photopolymerization ability only by single wavelength light of 405 nm, and the composition using the photoinitiator were proposed (for example, refer patent document 1 and patent document 2). However, these techniques can certainly exhibit sufficient photopolymerization ability with only a single light beam of 405 nm, but the core hardenability and the surface hardenability cannot be obtained at the same time, and the sensitivity is due to the loss of activity of the photopolymerization initiator on the circuit after heat treatment. It is remarkably lowered and has the problem that peeling generate | occur | produces on a copper circuit.

In addition, since the straight line image formation by laser light is generally performed in an air atmosphere, reaction inhibition by oxygen is likely to occur, and in the developing step of removing unnecessary portions after exposure, the resist surface portion of a necessary portion is removed, and as a result, There is a problem that it is easy to cause gloss defects. In addition, in soldering resists for the purpose of protecting printed wiring boards, the poor glossiness is not only a problem of appearance defects, but also the reaction of the part to be reacted is not sufficient enough, so that the surface of the coating has poor chemical resistance and electrical characteristics. It also caused the problem of poor.

The present invention is a photocurable or photocurable and thermosetting resin composition which can exhibit high photopolymerization ability with respect to laser light of 400 to 420 nm, at the same time obtain sufficient surface curability and deep curability, and is excellent in thermal stability. It is an object of the present invention to provide a photocurable or photocurable, thermally curable resin composition, and a cured product thereof, and a patterned printed wiring board using the same, which are suitable for use in direct drawing by laser light of 400 to 420 nm as a solder resist use. do.

Means for solving the problem

As a result of earnestly researching the inventors in order to achieve the said objective, (A) carboxylic acid containing resin,

(B) An oxime ester type photoinitiator containing the oxime ester group represented by following General formula (1),

(C) an aminoacetophenone series photoinitiator having a structure represented by formula (2),

(D) a compound having at least one ethylenically unsaturated group in the molecule, except for the carboxylic acid-containing compound,

(E) It is a composition which contains a blue pigment and is developable by a dilute alkali solution, and the light absorbency in 400-420 nm wavelength of the coating film is 0.5-1.2 per 25 micrometers, The photocurable resin composition is 400 It was found that the composition can exhibit high photopolymerization ability with respect to the laser light of 420 nm and at the same time obtain sufficient surface curability and deep curability, and also exhibit excellent thermal stability.

(In formula, R <^1> represents a hydrogen atom, a C1-C7 alkyl group, or a phenyl group, and R <^2> represents a C1-C7 alkyl group or a phenyl group.)

(In formula, R <^3> , R <^4> represents a C1-C12 alkyl group or an arylalkyl group, and R <^5> , R <^6> represents a hydrogen atom, a C1-C6 alkyl group, or the cyclic alkylether group which two couple | bonded.)

As a provision form of the photocurable, photocurable, thermosetting resin composition of this invention, a liquid form may be sufficient and the photosensitive dry film form may be sufficient.

Moreover, according to this invention, the printed wiring board which forms the hardened | cured material of the photocurable or photocurable thermosetting resin composition of this invention, and the pattern of the said hardened | cured material is provided.

Best Mode for Carrying Out the Invention

The photocurable or photocurable and thermosetting resin composition of this invention is represented by (A) carboxylic acid containing resin, (B) oxime ester photoinitiator containing the oxime ester group represented by General formula (1), (C) represented by General formula (2) Aminoacetophenone-based photopolymerization initiator, (D) a compound having at least one ethylenically unsaturated group in the molecule (excluding the carboxylic acid-containing compound), (E) blue pigment, containing a dilute alkali solution It is a developable composition, and the absorbance in the 400-420 nm wavelength of the coating film is 0.5-1.2 per 25 micrometers, It is a composition characterized by the above-mentioned.

That is, in the said carboxylic acid containing resin (A), the oxime ester type photoinitiator (B) containing the oxime ester group represented by General formula (1), the aminoacetophenone type photoinitiator (C) represented by General formula (2), and a molecule | numerator By including the compound which has one or more ethylenically unsaturated groups (except a carboxylic acid containing compound) (D), it becomes a composition which can be developed by a diluted alkali aqueous solution, and also an oxime ester system photoinitiator (B), amino The acetophenone-based photopolymerization initiator (C) and the blue pigment (E) make it possible to adjust the absorbance at a wavelength of 400 to 420 nm of the coating film to 0.5 to 1.2 per 25 μm. It has been found that an excellent coating film can be formed.

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

As carboxylic acid containing resin (A) contained in the photocurable, photocurable, thermosetting resin composition of this invention, the well-known conventional resin compound which contains a carboxyl group in a molecule | numerator can be used. Carboxylic acid containing photosensitive resin (A ') which has an ethylenically unsaturated double bond in a molecule | numerator is more preferable at the point of photocurability and developability.

Specifically, resin listed below is mentioned.

(1) Carboxylic acid containing resin obtained by copolymerizing one or more types of unsaturated carboxylic acids, such as (meth) acrylic acid, and the compound which has an unsaturated double bond other than that,

(2) Glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acryl to one or more types of copolymers of unsaturated carboxylic acids such as (meth) acrylic acid and compounds having other unsaturated double bonds Carboxylic acid containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant by the compound which has an unsaturated double bond, such as an acrylate, and an unsaturated double bond, (meth) acrylic acid chloride, etc.,

(3) to a copolymer of a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate and a compound having other unsaturated secondary bonds; Carboxylic acid containing photosensitive resin obtained by reacting unsaturated carboxylic acids, such as (meth) acrylic acid, and making polybasic acid anhydride react with the produced | generated secondary hydroxyl group,

(4) Compounds having an unsaturated double bond, such as 2-hydroxyethyl (meth) acrylate, in a copolymer of an acid anhydride having an unsaturated mobile bond such as maleic anhydride and a compound having an unsaturated double bond other than that Carboxylic acid-containing photosensitive resin obtained by reacting

(5) Carboxylic acid containing photosensitive resin obtained by making a polyfunctional epoxy compound react unsaturated monocarboxylic acids, such as (meth) acrylic acid, and making a hydroxyl group react with saturated or unsaturated polybasic anhydride,

(6) A hydroxyl group-containing carboxylic acid obtained by reacting a saturated or unsaturated polybasic anhydride with a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative, and then reacting the resulting carboxylic acid with a compound having an epoxy group and an unsaturated double bond in one molecule. Containing photosensitive resin,

(7) Compounds having at least one alcoholic hydroxyl group in one molecule with unsaturated monocarboxylic acids such as a polyfunctional epoxy compound and (meth) acrylic acid and an alcoholic hydroxyl group reacting with the epoxy group (for example, dimethylol Carboxylic acid-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic anhydride with a reaction product with propionic acid)

(8) A saturated or unsaturated polybasic acid relative to the primary hydroxyl group in the modified oxetane resin obtained by reacting an unsaturated monocarboxylic acid such as (meth) acrylic acid with a polyfunctional oxetane compound having two or more oxetane rings in one molecule. Carboxylic acid-containing photosensitive resin obtained by reacting anhydride, and

(9) After reacting an unsaturated monocarboxylic acid (for example, (meth) acrylic acid, etc.) to a polyfunctional epoxy resin (for example, cresol novolak-type epoxy resin, etc.), polybasic acid anhydride (for example, tetra To the carboxylic acid-containing photosensitive resin obtained by reacting hydrophthalic anhydride, etc.), a compound (eg, glycidyl (meth) acrylate, etc.) having one oxirane ring and one or more ethylenically unsaturated groups in the molecule is further added. Although carboxylic acid containing photosensitive resin etc. which are obtained by making it react are mentioned, It is not limited to these.

Preferred among these examples are the carboxylic acid-containing photosensitive resins of the above (2), (5), (7) and (9), and particularly the carboxylic acid-containing photosensitive resin of the above (9) is photocurable and cured coating film. It is preferable at the point of a characteristic.

In addition, in this specification, (meth) acrylate is a term which generically mentions acrylate, methacrylate, and mixtures thereof, and is the same also about another similar expression.

Since the carboxylic acid-containing resin (A) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development by a thin alkaline aqueous solution is possible.

The acid value of the carboxylic acid-containing resin (A) is in the range of 40 to 200 mg KOH / g, more preferably in the range of 45 to 120 mg KOH / g. When the acid value of the carboxylic acid-containing resin is less than 40 mg KOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mg KOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes weaker than necessary, In some cases, it is not preferable because it can be dissolved and peeled off by a developer without distinction between the exposed portion and the unexposed portion, which makes it difficult to draw a normal resist pattern.

Moreover, although the weight average molecular weight of the said carboxylic acid containing resin (A) changes with resin frame | skeleton, it is preferable that it is generally 2,000-150,000, and also the range of 5,000-100,000. When the weight average molecular weight is less than 2,000, the tact free performance may be poor, the moisture resistance of the coating film after exposure is poor, the film decreases at the time of development, and the resolution may be largely poor. On the other hand, when a weight average molecular weight exceeds 150,000, developability may become remarkably bad and storage stability may be inferior.

The compounding quantity of such carboxylic acid containing resin (A) and / or carboxylic acid containing photosensitive resin (A ') is 20-60 mass% in the whole composition, Preferably it is 30-50 mass%. When it is less than the said range, since coating film strength falls, it is unpreferable. On the other hand, when more than the said range, since viscosity increases, applicability | paintability, etc. fall, it is unpreferable.

An oxime ester photoinitiator (B) used for this invention is an oxime ester photoinitiator containing the oxime ester group represented by following General formula (1),

<Formula 1>

(In formula, R <^1> represents a hydrogen atom, a C1-C7 alkyl group, or a phenyl group, and R <^2> represents a C1-C7 alkyl group or a phenyl group.)

For example, what was described in the said patent document 1 is mentioned. Preferred examples of the oxime ester photopolymerization initiator (B) include a photopolymerization initiator (2- (acetyloxyiminomethyl) thioxanthene-9-one) represented by the following general formula (3) and a structure represented by the following general formula (4). The photoinitiator which has and the photoinitiator which has a structure represented by following General formula (5) are mentioned. As a commercial item, CGI-325, Irugacure OXE01, and Irugacure OXE02 by Ciba Specialty Chemicals Co., Ltd. are mentioned. These oxime ester photoinitiators can be used individually or in combination of 2 or more types.

(In formula, R <^7> , R <^8> represents a C1-C12 alkyl group each independently, R <^9> , R <^10> , R <^11> , R <^12> represents a hydrogen atom or a C1-C6 alkyl group each independently, n Represents an integer of 0 to 5. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ¹⁴ and R ¹⁵ represent an alkyl group having 1 to 12 carbon atoms. M represents -S-.

When the photocurable or photocurable and thermosetting resin composition containing such an oxime ester photoinitiator (B) is apply | coated independently on copper, such as a printed wiring board, it reacts with a copper atom at the interface with copper, and serves as a photoinitiator. There exists a problem that a function loses activity, and it needs to use together with the aminoacetophenone system photoinitiator (C) mentioned later.

As a compounding quantity of such an oxime ester type photoinitiator (B), it is 0.01-10 mass parts with respect to 100 mass parts of said carboxylic acid containing resins (A), Preferably it is the ratio of 0.01-5 mass parts. If the compounding quantity of an oxime ester system photoinitiator (B) is 0.01 mass part with respect to 100 mass parts of said carboxylic acid containing resins (A), the compound (D) and carr which have one or more ethylenically unsaturated groups in the molecule | numerator by light. The curing of the acid-containing resin (A) is not sufficient, the hygroscopicity of the cured film is increased, the PCT resistance is easily lowered, and the solder heat resistance and the electroless plating resistance are also low. On the other hand, when the compounding quantity of an oxime ester system photoinitiator (B) exceeds 10 mass parts with respect to 100 mass parts of said carboxylic acid containing resins (A), the shape of a cured coating film will be larger than the part irradiated by laser irradiation (Hull Phenomena) is not preferable because the phenomenon is likely to occur, and the hardening depth is also difficult to obtain.

As aminoacetophenone type photoinitiator (C) which has a structure represented by following General formula (2) used by this invention, it is 2-methyl-1- [4- (methylthio) phenyl] -2- morpholino, for example. Aminopropanone-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 Irugacure 907, Irugacure 369, Irugacure 379, and the like manufactured by Ciba Specialty Chemicals.

<Formula 2>

(In formula, R <^3> , R <^4> represents a C1-C12 alkyl group or an arylalkyl group, and R <^5> , R <^6> represents a hydrogen atom, a C1-C6 alkyl group, or the cyclic alkylether group which two couple | bonded.)

Such aminoacetophenone-based photoinitiator (C) does not inhibit the polymerization of the oxime ester-based photoinitiator (B), and the oxime ester-based photoinitiator (B) is deactivated by heat on copper. Function to supplement

As a compounding quantity of such an aminoacetophenone system photoinitiator (C), it is 0.1-30 mass parts with respect to 100 mass parts of said carboxylic acid containing resins (A), Preferably it is the ratio of 0.5-15 mass parts. When the compounding quantity of an aminoacetophenone type photoinitiator (C) is less than 0.1 mass part with respect to 100 mass parts of said carboxylic acid containing resins (A), the photocurability on copper will run short, and a coating film will peel or a coating film, such as chemical-resistance, It is not preferable because the property is degraded. On the other hand, when the compounding quantity of an aminoacetophenone type photoinitiator (C) exceeds 30 mass parts with respect to 100 mass parts of said carboxylic acid containing resins (A), since heat resistance and an electrical property fall, it is unpreferable.

Moreover, the photocurable, photocurable, thermosetting resin composition of this invention can contain a tertiary amine compound and a benzophenone compound as a photoinitiator. Examples of such tertiary amines include ethanolamines, 4,4'-dimethylaminobenzophenone (Nissocure MABP manufactured by Nippon Soda Co., Ltd.), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 4 Ethyl dimethylaminobenzoate (Gayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (International Bio-Shinsei Ethics Quantacure BEA), p-dimethylaminobenzoic acid isoamyl ethyl ester (Naybon Kayaku Co., Ltd. Kayacure DMBI), 4-dimethylaminobenzoic acid 2-ethylhexyl (Esolol 507 by Van Dyk), etc. are mentioned. These known conventional tertiary amine compounds can be used alone or as a mixture of two or more thereof.

Among them, dialkylaminobenzophenones (F) such as 4,4'-dimethylaminobenzophenone and 4,4'-diethylaminobenzophenone are particularly preferable. In particular, 4.4'-diethylaminobenzophenone has a low toxicity and is preferably used. The reason is that it has a large absorption in the region having a wavelength of 400 to 420 nm, and has a great influence on the absorbance described later to achieve the surface curability and the depth of cure which are the objects of the present invention.

As a compounding quantity of such dialkylamino benzophenone (F), it is 5 mass parts or less with respect to 100 mass parts of said carboxylic acid containing resins (A), Preferably it is 0.01-5 mass parts, More preferably, the ratio of 0.1-2 mass parts to be. When the compounding quantity of dialkylamino benzophenone (F) exceeds 5 mass parts with respect to 100 mass parts of said carboxylic acid containing resins (A), since an electrical property falls, it is unpreferable.

The photocurable or photocurable thermosetting resin composition of this invention further contains benzoin and benzoin alkyl ether, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, if necessary; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Thioxanthones, such as 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, and 2, 4- diisopropyl thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Such as benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4-methyldiphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4-benzoyl-4'-propyldiphenyl sulfide Benzophenones or xanthones; Known common photoinitiators, such as phosphine oxides, such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide, can also be used together.

Especially preferable among these is 4-benzoyl-4'-methyldiphenyl sulfide, More preferably, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, 2 It is preferable from the viewpoint of high sensitivity to use together thioxanthone type photoinitiators, such as a 4-4-isoiso thioxanthone. As for the compounding quantity of such a photoinitiator and a photoinitiator, the total amount of the said oxime ester system photoinitiator (B), the amino acetophenone system photoinitiator (C), and the alkylamino benzophenone (F) is the said carboxylic acid containing resin ( A) It is a range used as 20 mass parts or less with respect to 100 mass parts. When more than the said range, since an electrical property falls, it is unpreferable.

Compound (D) which has one or more ethylenically unsaturated groups in the molecule | numerator used for the photocurable or photocurable thermosetting resin composition of this invention (however, the said carboxylic acid containing photosensitive resin (A ') is a carboxylic acid containing compound) Is photocured by active energy ray irradiation to aid insolubilization or insolubilization of the carboxylic acid-containing resin (A) in an aqueous alkali solution.

As such a compound (D), Hydroxyalkyl acrylates, such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Mono or diacrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N.N-dimethylaminopropyl acrylate; Polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts or propylene oxide adducts thereof; Acrylates such as phenoxyacrylate, bisphenol A diacrylate and ethylene oxide adducts or propylene oxide adducts of these phenols; 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 said acrylate etc. are mentioned. Among these, the polyfunctional (meth) acrylate compound which is a compound which has two or more ethylenically unsaturated groups in a molecule | numerator is especially preferable because it is excellent in photocurability.

Moreover, pentaerythritol triacryl is epoxy acrylate resin which made acrylic acid react with polyfunctional epoxy resins, such as bisphenol A, bisphenol F-type epoxy resin, a phenol, and a cresol novolak-type epoxy resin, and the hydroxyl group of this epoxy acrylate resin. Epoxy urethane acrylate compounds etc. which made the half urethane compounds of hydroxyacrylates, such as a late, and diisocyanate, such as isophorone diisocyanate react, are mentioned. Such epoxy acrylate resin can improve photocurability without deteriorating a touch drying property.

The compounding quantity of the compound (D) which has one or more ethylenically unsaturated group in such a molecule | numerator is 5-100 mass parts with respect to 100 mass parts of said carboxylic acid containing resins (A), More preferably, it is the ratio of 10-70 mass parts. . When the said compounding quantity is less than 5 mass parts, since photocurability falls and pattern formation becomes difficult by alkali image development after active energy ray irradiation, it is unpreferable. On the other hand, when it exceeds 100 mass parts, since solubility to aqueous alkali solution falls or a coating film becomes weak, it is not preferable.

Although the blue pigment (E) which is one of the characteristics of this invention is used normally as a blue pigment, when using the 400-420 nm laser light in this invention, a blue pigment (for example, phthalocyanine blue) is added. It was found that glossiness was obtained at a lower exposure dose.

Although the reason for the sensitization effect of this blue pigment (for example, a phthalocyanine blue pigment) is not clear, For example, phthalocyanine blue is added to the resin composition whose absorbance per 25 micrometers of the scope of this invention is 0.5 or less, and absorbance is carried out. It became clear that sufficient surface hardening property and hardening depth are simultaneously obtained by low exposure amount only by making 0.5 or more. Moreover, this sensitization effect is effective in surface reactivity (gloss improvement), and hardening depth worsens on the contrary. That is, it functions to reflect laser light. This function is also effective in stabilizing the resist shape.

For example, in the case where the cross-sectional shape of the resist is seen, when the absorbance is less than 0.5 without containing phthalocyanine blue, the cross-sectional shape of the resist is a shape in which the bottom portion is greatly widened, and there is no gloss of the coating surface. In addition, when it does not contain phthalocyanine blue and absorbance is larger than 0.5, it is a situation where a surface layer part becomes large and the bottom part becomes thin. However, further containing an oxime ester photoinitiator (B), an aminoacetophenone type photoinitiator (C) and a blue pigment (E), or dialkyl benzophenone (F) within the appropriate range of the absorbance of this invention. In the case, it was found that a resist shape having a resist film thickness in the range of 5 to 100 µm and having a bottom portion of a dimension substantially the same as the irradiation dimension of the laser light source was obtained, and that the surface gloss was obtained.

The appropriate addition amount of such a blue pigment (E) can be added arbitrarily as long as the absorbance in 400-420 nm wavelength of a dry coating film becomes 0.5-1.2 per 25 micrometers.

As such a blue pigment (E), such as (alpha) type copper phthalocyanine blue, (alpha) type monochloro copper phthalocyanine blue, (beta) copper phthalocyanine blue, (epsilon) copper phthalocyanine blue, cobalt phthalocyanine blue, metal-free phthalocyanine blue, etc. Inorganic pigments, such as a phthalocyanine blue pigment and a blue-green color, are mentioned, but a phthalocyanine blue pigment is especially preferable.

When using the photocurable resin composition of this invention as a resin composition which requires heat resistance, such as a soldering resist, the thermosetting component (henceforth cyclic (thio) which has two or more cyclic ether groups and / or cyclic thioether group in a molecule | numerator ) Ether compound) (G) can be mix | blended.

Such a cyclic (thio) ether compound is a compound having two or more of any one or two of three, four or five member cyclic cyclic ether groups or cyclic thioether groups in a molecule, for example, at least two or more in the molecule Compound having an epoxy group, ie, polyfunctional epoxy compound (G-1), compound having at least two or more oxetanyl groups in the molecule, ie polyfunctional oxetane compound (G-2), having two or more thioether groups in the molecule A compound, ie, episulfide resin, etc. are mentioned.

Examples of the polyfunctional epoxy compound (G-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, Doto Kasei Co., Ltd. EPOT YD-011, YD-013, YD-127, YD-128, DER317, DER331, manufactured by Dow Chemical Corporation, DER661, DER664, Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumiepoxy ESA-011, ESA-014, manufactured by Sumitomo Chemical Co., Ltd. Bisphenol-A epoxy resins such as ELA-115, ELA-128, and AER330, AER331, AER661, and AER664 manufactured by Asahi Kasei Kogyo Co., Ltd .; Epicoat YL903 manufactured by Japan Epoxy Resin Co., Ltd., Epikron 152, Epicron 165, manufactured by Dainippon Ink & Chemicals Co., Ltd., Efotot YDB-400, YDB-500, manufactured by Toto Kasei Co., Ltd., DER542, manufactured by Dow Chemical Corporation , Brominated epoxy such as Araldide 8011 manufactured by Shiba Specialty Chemicals, Sumitomo Chemical Co., Ltd., Semiepoxy ESB-400, ESB-700, and Asahi Kasei Kogyo Co., Ltd. Suzy; Epicoat 152, Epicoat 154 made by Japan Epoxy Resin Co., Ltd., DEN431, DEN438 made by Dow Chemical Co., Ltd., epicron N-730, epicron N-770, epicron N- by Kagaku Kogyo Co., Ltd. 865, Etotsu YDCN-701, YDCN-704 by Toto Kasei Co., Ltd. Araldide ECN1235 by Ciba Specialty Chemical Co., Ltd. Araldide ECN1273, Araldide ECN1299, Araldide XPY307, Nippon Kayakusa EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumiepoxy ESCN-195X, ESCN-220, AERECN-235, manufactured by Asamihi Kasei Kogyo Co., Ltd. Novolac-type epoxy resins such as ECN-299 (all trade names); Epiclon 830 manufactured by Dainippon Ink & Chemicals Co., Ltd., Epicoat 807 manufactured by Japan Epoxy Resin Co., Ltd., Efotot YDF-170, YDF-175, YDF-2004, manufactured by Tohto Kasei Co., Ltd., manufactured by Ciba Specialty Chemicals Co., Ltd. Bisphenol F-type epoxy resins, such as Araldide XPY306 (all are brand names); Hydrogenated bisphenol A epoxy resins, such as Efotot ST-2004, ST-2007, and ST-3000 (brand name) by a Toto Kasei company; Epicoat 604, manufactured by Japan Epoxy Resin Co., Ltd., Efotot YH-434, manufactured by Toto Kasei Co., Ltd., Araldide MY720, manufactured by Ciba Specialty Chemicals, and Sumiepoxy ELM-120, manufactured by Sumitomo Chemical Co., Ltd. Glycidyl amine type epoxy resin of the brand name); Hydantoin type epoxy resins, such as Araldide CY-350 (brand name) by Ciba Specialty Chemicals Co., Ltd .; Alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd., Araldide CY175 manufactured by Ciba Specialty Chemicals, and CY179 (both trade names); Trihydroxyphenylmethane type epoxy resins such as YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T.E.N., EPPN-501, EPPN-502 manufactured by Dow Chemical Co., Ltd. (both trade names); 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 Nippon Kayaku Co., Ltd. EBPS-200, Asahi Denka Kogyo Co., Ltd. EPX-30, and Dai Nippon Ink Chemical Co., Ltd. EXA-1514 (brand name); 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 manufactured by Ciba Specialty Chemicals Co., Ltd. and TEPIC manufactured by Nissan Chemical Industries, Ltd. (both trade names); Diglycidyl phthalate resins such as Blenmer DGT manufactured by Nippon Yushi Corporation; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .: ESN-190, ESN-360, manufactured by Shinnitetsu Chemical Co., Ltd., HP-4032, EXA-4750, EXA Naphthalene group-containing epoxy resins such as -4700; Epoxy resin which has dicyclopentadiene frame | skeleton, such as the Dai Nippon Ink Industries Co., Ltd. product HP-7200 and HP-7200H; Glycidyl methacrylate copolymer 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.), etc. 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 (G-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-jade Cetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) methyl In addition to polyfunctional oxetanes such as methacrylates and oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly (p-hydroxystyrenes), cardo-type bisphenols, calyx arenes and calyx resorcines And ethers with a resin having a hydroxyl group such as arene or silsesquioxane. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As a compound which has two or more cyclic thioether group in the said molecule | numerator, bisphenol A episulfide resin YL7000 by the 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 using the same synthesis method can also be used.

The compounding quantity at the time of providing heat resistance by such cyclic (thio) ether (G) is 0.6-2.0 equivalent, Preferably it is 0.8-1.5 equivalent with respect to 1 equivalent of carboxyl groups of the said carboxylic acid containing resin. When the compounding quantity of cyclic (thio) ether (G) is less than the said range, since a carboxyl group remains and heat resistance, alkali resistance, electrical insulation, etc. fall, it is unpreferable. On the other hand, when it exceeds the said range, since the low molecular weight cyclic (thio) ether (C) remains, the intensity | strength of a coating film, etc. fall, and it is unpreferable.

When using the said cyclic (thio) ether compound (G), it is preferable to contain a thermosetting catalyst. As such a thermosetting catalyst, for example, imidazole, 2-methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imida Imidazole derivatives such as sol, 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 dihydraside; As commercially available things, such as phosphorus compounds, such as a triphenyl phosphine, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole compound), and San Apro by Shikoku Kasei Kogyo Co., Ltd., for example. U-CAT3503N, U-CAT3502T (all are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof) and the like. It is not specifically limited to these, It may be what accelerates | stimulates reaction of the epoxy resin, the thermosetting catalyst of an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, and may also be used individually or in mixture of 2 or more types. have. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine and 2-vinyl-4,6-, which also function as an adhesion imparting agent Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-tri S-triazine derivatives, such as an azine and an isocyanuric acid adduct, can also be used. Preferably, the compound which also functions as these adhesiveness imparting agents is used together with the said thermosetting catalyst.

The compounding quantity of these thermosetting catalysts is sufficient in a normal quantitative ratio, For example, 0.1-20 mass parts with respect to 100 mass parts of carboxylic acid containing resin (A) or cyclic (thio) ether compound (G), Preferably It is the ratio of 0.5-15.0 mass parts.

In order to raise the physical strength of a coating film, etc., the photocurable or photocurable, thermosetting resin composition of this invention can mix | blend a filler as needed. As such a filler, well-known conventional inorganic or organic filler can be used, but especially barium sulfate, spherical silica, and talc are used preferably. Moreover, NANOCRYL (brand name) XP 0396 by Hanse-Chemie company which disperse | distributed nanosilica to the compound (D) which has one or more ethylenically unsaturated groups mentioned above, or the said polyfunctional epoxy resin (G-1). , XP 0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (both product name) or Hanse-Shemi manufactured by NANOPOX (brand name) XP 0516, XP 0525, XP 0314 ( All product grade names) can also be used.

These may be used alone or in combination of two or more thereof.

The compounding quantity of these fillers is 300 mass parts or less with respect to 100 mass parts of said carboxylic acid containing resins (A), Preferably it is 0.1-300 mass parts, More preferably, it is the ratio of 0.1-150 mass parts. When the compounding quantity of the said filler exceeds 300 mass parts, since the viscosity of a composition becomes high and printability falls or hardened | cured material becomes weak, it is unpreferable.

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

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; Ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate. Esters such as 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 and solvent naphtha. These organic solvents are used alone or as a mixture of two or more thereof.

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

Moreover, in the photocurable, photocurable, thermosetting resin composition of this invention, coloring pigments other than a blue pigment can be added within the range which does not adversely affect resolution.

The photocurable or photocurable and thermosetting resin composition of this invention is adjusted to the viscosity suitable for the application | coating method with the said organic solvent, for example, and it is immersion coating method, flow coating method, roll coating method, bar coating method, screen on a base material. An adhesive-free coating film can be formed by volatilizing (temporarily drying) the organic solvent contained in a composition by apply | coating by the printing method, the curtain coating method, etc. at the temperature of about 60-100 degreeC. Moreover, the resin insulating layer can be formed by apply | coating the said composition on a carrier film, drying, and bonding what wound up as a film on a base material. Thereafter, the pattern is drawn in a direct drawing device (laser direct imaging device), or selectively exposed to active energy rays through a photomask in which the pattern is formed by a contact or non-contact method, and the unexposed portion is diluted with alkali. It develops by aqueous solution (for example, 0.3-3% of sodium carbonate aqueous solution), and a resist pattern is formed. Moreover, when it contains a thermosetting component, it heats and hardens | cures to the temperature of about 140-180 degreeC, for example, the carboxyl group of the said carboxylic acid containing resin (A), and 2 or more cyclic ether groups in a molecule | numerator, and / or ) The thermosetting component (G) having a cyclic (thio) ether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, hygroscopicity, adhesiveness, and electrical properties.

Copper coating 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. The use of materials such as laminates includes copper coated laminates of all grades (such as FR-4), other polyimide films, PET films, glass substrates, ceramic substrates, and wafer plates.

Volatilization drying after apply | coating the photocurable or photocurable and thermosetting resin composition of this invention is hot air circulation type drying, using IR with a hotplate and a convection oven (The thing equipped with the heat source of the air heating system by steam | vapor) Or a method in which the hot air in the dryer is brought into countercurrent contact, or the method is blown from the nozzle to the support.

As the exposure apparatus used for the said active energy ray irradiation, as described above, 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 the active energy ray, laser light having a maximum wavelength in the range of 400 to 420 nm can be used. Moreover, although the exposure amount changes with film thickness, generally, it can be in the range of 2-100 mJ / cm <^2> , Preferably it is 5-60 mJ / cm <^2> , More preferably, it is 10-30 mJ / cm <^2> . . As the direct drawing apparatus, for example, a pentax manufactured product, a Hitachi Pia Mechanics manufactured product, a ball / semiconductor manufactured product, or the like can be used, and any apparatus can be used.

Examples of the developing method include an immersion method, a shower method, a spray method, a brush method, and the like. As a developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and tetramethylammonium hydroxide is used. Can be used.

<Example>

Although an Example and a comparative example are shown to the following and this invention is demonstrated concretely, of course, this invention is not limited to the following Example.

Synthesis Example 1

Cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent = 220) in a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube. g / equivalent) 660 g, carbitol acetate 421.3 g and solvent naphtha 180.6 g were added, and it heated and stirred at 90 degreeC and dissolved. Next, it cooled to 60 degreeC once, 216 g of acrylic acid, 4.0 g of triphenylphosphines, and 1.3 g of methylhydroquinone were added, it was made to react at 100 degreeC for 12 hours, and the reaction product which has an acid value of 0.2 mg KOH / g was obtained. 241.7 g of tetrahydrophthalic anhydride was put into this, it heated at 90 degreeC, and made it react for 6 hours. Thereby non-volatile content = 65 mass%, solid acid value = 77 mg KOH / g, double bond equivalent (g weight of resin per mol of unsaturated groups) = 400 g / equivalent, weight average molecular weight = carboxylic acid containing photosensitive resin ( A ') solution was obtained. Hereinafter, the solution of this carboxylic acid containing photosensitive resin is called A-1 varnish.

Synthesis Example 2

O-cresol novolac-type epoxy resin (epoxy equivalent = 215 g / equivalent, with an average of six phenol nuclei in one molecule) in a 2-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping lot and nitrogen introduction tube ) 430 g and 144 g (2 mol) of acrylic acid were added. It heated to 120 degreeC, stirring, and continued reaction for 10 hours, maintaining 120 degreeC. Once the reaction product was cooled to room temperature, 190 g (1.9 mol) of succinic anhydride were added and heated to 80 ° C to react for 4 hours. Again the reaction product was cooled to room temperature. The acid value of this product solid was 139 mg KOH / g.

85.2 g (0.6 mol) of glycidyl methacrylate and 45.9 g of propylene glycol methyl ether acetate were added to this solution, and it heated to 110 degreeC, stirring, and reaction was continued for 6 hours, maintaining 110 degreeC. As a result of cooling this reaction product to room temperature, a viscous solution was obtained. Thus, the solution of carboxylic acid containing photosensitive resin (A ') of non volatile matter = 65 mass% and solid content acid value = 86 mg KOH / g was obtained. Hereinafter, the solution of this carboxylic acid containing photosensitive resin is called A-2 varnish.

Synthesis Example 3

Epiclon N-680 (manufactured by Dainippon Ink & Chemicals Co., Ltd.) of cresol novolak type epoxy resin in a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube, epoxy equivalent = 215 g / equivalent) 215 parts were added, and 266.5 parts of carbitol acetate were added to dissolve by heating. To this resin solution, 0.05 part of hydroquinone as a polymerization inhibitor and 1.0 part of triphenylphosphine were added as a reaction catalyst. The mixture was heated to 85 to 95 ° C, 72 parts of acrylic acid was slowly added dropwise and reacted for 24 hours. 208 parts of half urethane which reacted isoboron diisocyanate and pentaerythritol triacrylate in 1: 1 mol previously was gradually dripped at this epoxy acrylate, and it was made to react at 60-70 degreeC for 4 hours. The epoxy urethane acrylate varnish (non-volatile content = 65 mass%) which is a compound (D) which has two or more ethylenically unsaturated groups in the molecule | numerator thus obtained is called D-1 varnish below.

Using the resin solutions of the above Synthesis Examples 1 to 3 together with the various components shown in Table 1 in the ratio (mass parts) shown in Table 1, pre-mixed in a stirrer, kneaded in three roll mill for solder resist The photocurable thermosetting resin composition was manufactured. The dispersion degree of the photocurable thermosetting resin composition obtained here was 15 micrometers or less as a result of evaluating by the particle size measurement by the grindmeter made from Eriksen.

Performance rating:

<Absorbance>

An ultraviolet visible spectrophotometer (Ubest-V-570DS manufactured by Nippon Bunko Co., Ltd.) and an integrating sphere apparatus (Nisbon Bunko Co., Ltd. ISN-470) were used for the measurement of absorbance. After apply | coating the photocurable thermosetting resin composition of Examples 1-7 and Comparative Examples 1-7 to a glass plate, it dried at 80 degreeC for 30 minutes using a hot air circulation type drying furnace, and dried the photocurable thermosetting resin composition. The coating film was produced on the glass plate. The absorbance baseline at 500-300 nm was measured with the glass plate which apply | coated the photocurable and thermosetting resin composition using the ultraviolet visible spectrophotometer and the integrating sphere apparatus. The absorbance of the manufactured glass plate with a dry coating film was measured, and the absorbance of the dry coating film was calculated from the baseline, and the absorbance in the wavelength of 405 nm of the desired light was obtained. In order to avoid variations in absorbance due to variations in the coating film thickness, this operation is carried out by changing the coating thickness by the applicator in four steps, creating a coating thickness and an absorbance graph at 405 nm, and from the approximation formula, the film thickness 25. The absorbance of the dry coating film of µm was calculated and taken as the respective absorbances.

The evaluation results are shown in Table 2.

<Optimal exposure amount>

The copper-clad laminated substrate was washed with puff rolls, washed with water and dried, and the photocurable and thermosetting resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 were applied by screen printing to circulate hot air at 80 ° C. It was dried in a drying furnace for 30 minutes. After drying, it exposed using the direct drawing apparatus which mounted the blue-violet laser of wavelength 405nm through the photomask (Eastman Kodak Corporation make, step tablet N0.2). After irradiating for 60 seconds with the developing solution (sodium carbonate aqueous solution) of spray pressure of 0.2 MPa using what was irradiated, the number of stages of a remaining coating film was visually determined. The exposure amount whose number of stages of a residual coating film becomes 6 steps was made into the appropriate exposure amount.

The evaluation results are shown in Table 2.

<Surface curability>

A substrate prepared in the same manner as the optimum exposure dose was exposed without a photomask and developed in the same manner as above to obtain a developing coating film. The exposure amount was taken as the exposure amount obtained by the said optimum exposure amount evaluation. The cured coating film was obtained by performing 150 degreeC and 60 minutes of thermosettings after ultraviolet-ray irradiation of 1000 mJ / cm <^2> with a high pressure mercury lamp with a developing coating film. Thus, the surface curability of the obtained cured coating film was evaluated about the glossiness at 60 degrees using the glossimeter micro trigloss (made by Big Gardner). Evaluation criteria made glossiness 50 or more after image development favorable, and glossiness less than 50 called defect.

The evaluation results are shown in Table 2.

<Section shape>

Screen-printing method of the photocurable and thermosetting resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 after puff roll polishing of a circuit pattern substrate having a line / space of 300/300 and a copper thickness of 50 µm, followed by washing with water It apply | coats and it dries for 30 minutes in 80 degreeC hot air circulation type drying furnace. After drying, it exposed using the direct drawing apparatus in which the blue-violet laser of wavelength 405nm was mounted. The exposure pattern used the pattern which draws the line of 20/30/40/50/60/70/80/90/100 micrometers in a space part. The exposure amount was taken as the exposure amount obtained by the said optimum exposure amount evaluation. After exposure, image development was performed with aqueous sodium carbonate solution to form a pattern, and a cured coating film was obtained by performing thermal curing at 150 ° C. for 60 minutes after ultraviolet irradiation of 1000 mJ / cm ^{2 with} a high pressure mercury lamp. The cross section of the 100-micrometer line part of the design value of the cured coating film was observed.

This shape was evaluated by dividing into five steps A to E as in the schematic diagram shown in the drawings. The figure shows a schematic diagram when the following phenomenon occurs. In particular, in the case of the A evaluation, the variation from the design value was assumed to be within 5 µm for both the upper and lower lines. The results are shown in Table 2.

A evaluation: abnormal state of design width

B evaluation: occurrence of surface layer feeding due to lack of developing resistance

C evaluation: Undercut status

D evaluation: line thickening caused by halation etc.

E evaluation: Line thickness and undercut of the surface layer occur

As can be seen from the results shown in Table 2, the photocurable or photocurable and thermosetting resin composition of the present invention can exhibit high photopolymerization ability with respect to 400-42 nm blue-violet laser light, and at the same time, sufficient deep-curability. Is obtained and is excellent in surface curability and thermal stability, and is particularly suitable for use in solder resist applications and for direct drawing by laser light of 400 to 420 nm, and a photocurable or photocurable, thermosetting resin composition, and It is possible to provide a patterned printed wiring board using it.

The photocurable or photocurable and thermosetting resin composition of the present invention is excellent in surface curability and deep curability, capable of pattern formation by a laser oscillation light source having a wavelength of 400 to 420 nm, and used as a solder resist for laser direct imaging. It becomes possible.

In addition, by using such a solder resist for laser direct imaging, a negative pattern becomes unnecessary, and can contribute to the improvement of initial stage productivity, and low cost.

Moreover, since the photocurable, photocurable, and thermosetting resin composition of this invention is excellent in surface curability and deep part curability, it is highly sensitive and high resolution, it becomes possible to provide a highly reliable printed wiring board.

Claims (15)

(A) carboxylic acid containing resin, (B) An oxime ester type photoinitiator containing the oxime ester group represented by following General formula (1), (C) an aminoacetophenone-based photoinitiator having a structure represented by the following formula (2), (D) a compound having at least one ethylenically unsaturated group in the molecule, except for the carboxylic acid-containing compound, and (E) blue pigment It is possible to develop by a dilute alkali solution, and the light absorbency in 400-420 nm wavelength of the coating film is 0.5-1.2 per 25 micrometers, The photocurable resin composition characterized by the above-mentioned. <Formula 1>

(In formula, R <^1> represents a hydrogen atom, a C1-C7 alkyl group, or a phenyl group, and R <^2> represents a C1-C7 alkyl group or a phenyl group.) <Formula 2>

(In formula, R <^3> , R <^4> represents a C1-C12 alkyl group or an arylalkyl group, and R <^5> , R <^6> represents a hydrogen atom, a C1-C6 alkyl group, or the cyclic alkylether group which two couple | bonded.) The carboxylic acid-containing resin according to claim 1, wherein the carboxylic acid-containing resin (A) is obtained by reacting (a) a polyfunctional epoxy resin with (b) an unsaturated monocarboxylic acid, followed by (c) a polybasic anhydride. It is carboxylic acid containing photosensitive resin (A ') obtained by making the resin (d) react with the compound which has one oxirane ring and one or more ethylenically unsaturated group further in a molecule | numerator, The photocurable resin composition characterized by the above-mentioned. The photocurable resin composition according to claim 1, wherein the oxime ester photopolymerization initiator (B) comprises a photopolymerization initiator represented by the following general formula (3). <Formula 3>

The method of claim 1, wherein the oxime ester photopolymerization initiator (B) comprises a photopolymerization initiator having a structure represented by the following formula (4) and / or a photopolymerization initiator having a structure represented by the following formula (5). Photocurable resin composition. <Formula 4>

<Formula 5>

(In formula, R <^7> , R <^8> represents a C1-C12 alkyl group each independently, R <^9> , R <^10> , R <^11> , R <^12> represents a hydrogen atom or a C1-C6 alkyl group each independently, n Represents an integer of 0 to 5. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ¹⁴ and R ¹⁵ represent an alkyl group having 1 to 12 carbon atoms. M represents -S-. The photocurable resin composition according to claim 1, wherein the compound (D) having at least one ethylenically unsaturated group in the molecule is an epoxy acrylate resin. The photocurable resin composition according to claim 1, wherein the blue pigment (E) is a phthalocyanine-blue pigment. The said carboxylic acid containing resin (A) is contained 20-60 mass% in the whole composition, The said oxime ester system photoinitiator (B) is contained with respect to 100 mass parts of said carboxylic acid containing resin (A). ) 0.01 to 10 parts by mass, the aminoacetophenone-based photopolymerization initiator (C) 0.1 to 30 parts by mass, the compound (D) in a proportion of 5 to 100 parts by mass, the blue pigment (E) is dried The photocurable resin composition containing the absorbance in 400-420 nm wavelength of a coating film in the range which becomes 0.5-1.2 per 25 micrometers. The photocurable resin composition of Claim 1 which further contains 5 mass parts or less of (F) dialkylamino benzophenone with respect to 100 mass parts of said carboxylic acid containing resins (A). The thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in the (G) molecule is further added in an amount of 0.6 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the carboxylic acid-containing resin (A). It includes a photocurable resin composition. The photocurable dry film obtained by apply | coating and drying the resin composition in any one of said Claims 1-9 to a carrier film. Hardened | cured material obtained by photocuring the resin composition of any one of the said Claims 1-9, or the photocurable dry film obtained by apply | coating and drying the said resin composition to a carrier film on copper. Hardened | cured material obtained by photocuring the resin composition of any one of the said Claims 1-9, or the photocurable dry film obtained by apply | coating and drying the said resin composition to a carrier film with a laser oscillation light source. Hardened | cured material whose cured film of the photocurable dry film obtained by apply | coating and drying the resin composition as described in any one of the said Claims 1-9, or the said resin composition to a carrier film is 5-100 micrometers. After photocuring the resin composition of any one of Claims 1-9, or the photocurable dry film obtained by apply | coating and drying the said resin composition to a carrier film with the laser beam whose wavelength is 350-420 nm. Printed wiring board obtained by thermosetting. The printed wiring board whose cured film of the photocurable dry film obtained by apply | coating and drying the resin composition of any one of the said Claims 1-9, or the said resin composition to a carrier film is 5-100 micrometers.

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