KR20170063859A - Photosensitive resin composition, dry film of same, cured coating film of same, and printed wiring board using said cured coating film - Google Patents

Abstract

A photosensitive resin composition which is excellent in sensitivity and developability, excellent in suppression of light irradiation of a cured product and suppressed in reduction of reflectance due to heat, and also excellent in touch-to-dryness, inhibition of discoloration and prevention of spillage, its dry film and cured film, A printed wiring board is provided. (A) a photosensitive resin composition comprising a carboxyl group-containing resin having (A) a styrene skeleton, (B) a photopolymerization initiator, and (C) an inorganic filler, wherein the weight average molecular weight of the carboxyl group- 50,000, and an acid value of 80 to 200 mgKOH / g.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a dry film thereof, a cured film thereof, and a printed circuit board using the same. BACKGROUND OF THE INVENTION [0001]

The present invention relates to a photosensitive resin composition, a dry film thereof, a cured coating film, and a printed wiring board using the same.

BACKGROUND ART In recent years, in solder resists for commercial printed wiring boards and industrial printed wiring boards, there has been proposed a method of forming an image by irradiating ultraviolet light and developing it, and performing a liquid phase phenomenon (final curing) Type solder resist is used. Further, in response to the increase in density of printed wiring boards accompanied by the shortening of length of electronic devices, there has been a demand for improvement in workability and high performance of solder resists.

For example, in Patent Document 1, a photosensitive composition containing a carboxyl group-containing resin having an aromatic ring is proposed as a resin composition which satisfies the above-mentioned demand characteristics while suppressing discoloration of the resist film to yellow when the resist film is exposed at a high temperature. . Patent Document 2 discloses a white photo-curable and thermosetting solder resist composition containing a carboxyl group-containing resin having no aromatic ring, whose purpose is to suppress the deterioration (yellowing) of resin by light.

Japanese Patent Application Laid-Open No. 2011-081410 Japanese Patent Application Laid-Open No. 2007-322546

However, when the resin compositions described in the above Patent Documents 1 and 2 are used, there is room for improvement in terms of prevention of touch formation (tack-and-dry performance) and prevention of shed after coating on a substrate. In this respect, it has been known that by using a specially modified urea or a saturated fatty acid in the composition, an anti-shedding effect is obtained, but there has been a problem that discoloration of the resin occurs.

Accordingly, an object of the present invention is to provide a photosensitive resin composition which is excellent in sensitivity and developability, excellent in suppression of light irradiation of a cured product, suppression of a decrease in reflectance due to heat, A film and a cured coating, and a printed wiring board using the same.

That is, the photosensitive resin composition of the present invention is a photosensitive resin composition containing (A) a carboxyl group-containing resin having a styrene skeleton, (B) a photopolymerization initiator, and (C) an inorganic filler, wherein (A) Wherein the carboxyl group-containing resin has a weight average molecular weight of 10,000 to 50,000 and an acid value of 80 to 200 mgKOH / g.

In the photosensitive resin composition of the present invention, (C) is preferably titanium oxide, and (C) is more preferably rutile-type titanium oxide.

The photosensitive resin composition of the present invention preferably contains a thermosetting component.

The dry film of the present invention is characterized in that any of the above photosensitive resin compositions is applied to a film and dried.

The cured coating film of the present invention is characterized in that it is obtained by curing a dry film obtained by applying any of the above photosensitive resin compositions or any of the above photosensitive resin compositions to a film and drying the film.

The printed wiring board of the present invention is characterized by comprising the cured coating.

According to the present invention, there is provided a photosensitive resin composition which is excellent in sensitivity and developability, excellent in suppression of light irradiation of a cured product and suppressed in reduction of reflectance due to heat, Cured coating films and printed wiring boards using them.

Hereinafter, embodiments of the present invention will be described in detail.

The photosensitive resin composition of the present invention is a photosensitive resin composition containing (A) a carboxyl group-containing resin having a styrene skeleton, (B) a photopolymerization initiator and (C) an inorganic filler, wherein the content of the carboxyl group The resin has a weight average molecular weight of 10,000 to 50,000 and an acid value of 80 to 200 mgKOH / g.

Each component of the photosensitive resin composition of the present invention will be described in detail below.

≪ (A) Carboxyl group-containing resin having styrene skeleton >

(A) The carboxyl group-containing resin having a styrene skeleton is a resin having a carboxyl group in the molecule and not having a photosensitive group such as an ethylenically unsaturated bond, having a styrene skeleton in the molecule, a weight average molecular weight of 10,000 to 50,000, an acid value of 80 To 200 mg KOH / g. Such a carboxyl group-containing resin having a styrene skeleton can be synthesized by copolymerization using styrene as an essential monomer. By using a carboxyl group-containing resin having such physical properties, the effect of preventing drying of the cured coating film containing the photosensitive resin composition of the present invention and the prevention of bleeding can be improved.

(A) Specific examples of the carboxyl group-containing resin having a styrene skeleton include unsaturated carboxylic acids such as (meth) acrylic acid and unsaturated carboxylic acids such as styrene,? -Methylstyrene, lower alkyl (meth) acrylate and isobutylene And a carboxyl group-containing resin (any of an oligomer and a polymer may be used) obtained by copolymerization of a group-containing compound. Further, lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.

In the photosensitive resin composition of the present invention, the weight average molecular weight of the carboxyl group-containing resin (A) having a styrene skeleton differs depending on the resin skeleton, but is 10,000 or more and 50,000 or less, By setting the weight average molecular weight to 10,000 or more, in addition to the above-mentioned effect of preventing the spillage, the touch-drying dryness (touch-dry performance) becomes better and the wettability in the coated film after exposure is good, Can be suppressed. In addition, when the weight average molecular weight is 50,000 or less, the development property is improved and the storage stability is excellent in addition to the above-mentioned spill prevention effect. More preferably 10,000 or more and 25,000 or less, and still more preferably 10,000 or more and 15,000 or less.

In the photosensitive resin composition of the present invention, the acid value of the carboxyl group-containing resin (A) having a styrene skeleton is 80 to 200 mg KOH / g. More preferably, it is 100 to 160 mg KOH / g. When the acid value of the carboxyl group-containing resin (A) having a styrene skeleton is 80 mgKOH / g or more, a high softening point is obtained, and the touch-drying performance is excellent and the developing property is also excellent. On the other hand, when the acid value of the carboxyl group-containing resin (A) having a styrene skeleton is 200 mgKOH / g or less, the cross-linking density becomes appropriate, and no stress is generated during curing.

In the photosensitive resin composition of the present invention, the carboxyl group-containing resin (A) having a styrene skeleton has a styrene skeleton, so that it is possible to suppress the decrease of the reflectance due to light irradiation and heat of the cured product unexpectedly, While suppressing discoloration, is excellent in developability and touch and dryness. The proportion of the styrene skeleton in the molecule is preferably from 10 to 80 mol%, more preferably from 10 to 60 mol%, and even more preferably from 10 to 50 mol%. That is, it is preferable to use 30 to 60 mol% of styrene relative to the total amount of the monomers when synthesizing the carboxyl group-containing resin (A) having a styrene skeleton. When the proportion of the styrene skeleton of the carboxyl group-containing resin (A) having a styrene skeleton is 10 mol% or more in the molecule, compatibility with the other component improves. In addition, when the content is 80 mol% or less in the molecule, the developing property is better.

(A) The carboxyl group-containing resin having a styrene skeleton is a resin having a high molecular weight when produced by suspension polymerization. As a result, the composition using the resin is preferable in that it has excellent touch-drying properties (tack-and-dry performance). Generally, when a carboxyl group-containing resin having (A) a styrene skeleton is prepared by suspension polymerization, a high molecular weight is obtained. However, considering the characteristics such as screen printability, touch dryness and developability, the weight average molecular weight is preferably in the range of 10,000 to 50,000 . Therefore, in controlling the molecular weight, it is preferable to use a chain transfer agent in synthesizing the carboxyl group-containing resin (A) having a styrene skeleton.

As the chain transfer agent used in the synthesis of such a resin, those known in the art can be used. Of these, MSD (alpha -methylstyrene dimer) and n-DM (n-dodecylmercaptan) are preferable.

In order to accelerate the polymerization, it is preferable to use a polymerization initiator in the synthesis of the carboxyl group-containing resin (A) having a styrene skeleton. Examples of the polymerization initiator include BPO (benzoyl peroxide), t-butylperoxy-2-ethylhexanonate, and AMBN (2,2'-azobis (2-methylbutyronitrile)). Among them, BPO (benzoyl peroxide) is preferable. The blending amount of the polymerization initiator is preferably 0.1 to 10 parts by mass in 100 parts by mass of the resin in terms of solid content in the case of (A) a carboxyl group-containing resin having a styrene skeleton, and 0.1 to 4 parts by mass It is more desirable to be negative.

In the photosensitive resin composition of the present invention, a mixture of (A) a carboxyl group-containing resin having a styrene skeleton and a carboxyl group-containing resin other than (A) can be used.

(A carboxyl group-containing resin other than (A)

The carboxyl group-containing resin other than the component (A) used in the photosensitive resin composition of the present invention is preferably a carboxyl group-containing resin having no aromatic ring because it is excellent in touch-drying performance under particularly stringent conditions. In this case, if the resin contains a carboxyl group having no aromatic ring, both a photosensitive carboxyl group-containing resin having at least one photosensitive unsaturated double bond and a carboxyl group-containing resin having no photosensitive unsaturated double bond can be used, But is not limited to a specific one. Particularly, resins having no aromatic ring (any of an oligomer or a polymer) among the resins listed below can be suitably used.

(2) a method in which a compound having an oxirane ring and an ethylenically unsaturated group in one molecule is reacted with a carboxyl group-containing (meth) acrylic copolymer resin by reacting a carboxyl group-containing resin obtained by copolymerization of a compound having an unsaturated carboxylic acid and an unsaturated double bond; (3) an unsaturated monocarboxylic acid is allowed to react with a copolymer of a compound having an epoxy group and an unsaturated double bond in each molecule and a compound having an unsaturated double bond to produce a photosensitive carboxyl group-containing resin A photosensitive carboxyl group-containing resin obtained by reacting a secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride, (4) a method of reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, A compound having an epoxy group and an unsaturated double bond in each molecule By reaction of a hydroxyl group and a carboxyl group-containing photosensitive resin obtained.

Among them, a carboxyl group-containing (meth) acrylic copolymer resin (a) which is the photosensitive carboxyl group-containing resin of the above (2) and a carboxyl group obtained by the reaction of a compound having an oxirane ring and an ethylenically unsaturated group in one molecule Is preferred.

The (meth) acrylic copolymer resin containing a carboxyl group of (a) is obtained by copolymerizing a (meth) acrylic acid ester with a compound having one unsaturated group and at least one carboxyl group in one molecule. Examples of the (meth) acrylic acid ester constituting the copolymer resin (a) include acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (Meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone- (Meth) acrylates such as methoxyethyleneglycol (meth) acrylate, ethoxydiethyleneglycol (meth) acrylate, isooctyloxydiethyleneglycol (meth) acrylate, Modified with glycols such as phenoxy triethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, and methoxy polyethylene glycol (meth) (Meth) acrylates, and the like. Of these, methyl (meth) acrylate and caprolactone-modified 2-hydroxyethyl (meth) acrylate are preferable. These may be used alone or in combination of two or more. In the present specification, (meth) acrylate is a generic term for acrylate and methacrylate, and the same applies to other similar expressions.

Examples of the compound having one unsaturated group and at least one carboxyl group in one molecule of the copolymer resin (a) include acrylic acid, methacrylic acid, a modified unsaturated monocarboxylic acid having a chain extending between the unsaturated group and the carboxylic acid, Unsaturated monocarboxylic acid having an ester bond by β-carboxyethyl (meth) acrylate, 2-acryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, lactone modification or the like, Modified unsaturated monocarboxylic acids, and further maleic acid, which have at least two carboxyl groups in the molecule. Among them, methacrylic acid is preferable. These may be used alone or in combination of two or more.

(b) a compound having an oxirane ring and an ethylenically unsaturated group in one molecule may be any compound having an ethylenically unsaturated group and an oxirane ring in one molecule, and examples thereof include glycidyl (meth) acrylate, Epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) , 4-epoxycyclohexylmethylaminoacrylate, and the like. Among them, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferable. These (b) compounds having an oxirane ring and an ethylenic unsaturated group in one molecule may be used alone or in combination of two or more.

The acid value of the carboxyl group-containing resin other than the above (A) is preferably in the range of 50 to 200 mg KOH / g. When the acid value is not less than 50 mgKOH / g, the unexposed portion of the coating film of the composition in the weakly alkaline aqueous solution can be easily removed. When the acid value is 200 mgKOH / g or less, the cured coating film is excellent in water resistance and electrical properties. The weight average molecular weight of the carboxyl group-containing resin other than the above (A) is preferably in the range of 5,000 to 100,000. If the weight average molecular weight is 5,000 or more, the dry adhesion of the coating film of the photosensitive resin composition tends to remarkably improve. When the weight average molecular weight is 100,000 or less, development and storage stability of the photosensitive resin composition tends to be remarkably improved, which is preferable.

<(B) Photopolymerization initiator>

In the photosensitive resin composition of the present invention, any known photopolymerization initiator can be used as the photopolymerization initiator (B). Among these, oxime ester photopolymerization initiators having oxime ester groups,? -Aminoacetophenone photopolymerization initiators, acylphosphine oxides Based photopolymerization initiator is preferable, and an acylphosphine oxide-based photopolymerization initiator is more preferable. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

As the oxime ester-based photopolymerization initiator, CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02, Adeka-made N-1919, Adeka Ariz (registered trademark) NCI- 831 and the like.

Further, a photopolymerization initiation system having two oxime ester groups in the molecule can be suitably used. Specifically, an oxime ester compound having a carbazole structure represented by the following formula can be given.

(Wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, (Having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms), a naphthyl group Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms or an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group or a benzothienyl group, Ar represents a group having 1 to 10 carbon atoms Alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'- Styrene-diyl, and n is an integer of 0 or 1)

Especially preferred is an oxime ester photopolymerization initiator wherein X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, and Ar is phenylene, naphthylene, thiophene or thienylene Do.

When the oxime ester-based photopolymerization initiator is used, the blending amount is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) in terms of solid content. When the amount is 0.01 parts by mass or more, the photocurability on copper is good, the coating film is difficult to peel off, and the coating film properties such as chemical resistance become good. On the other hand, when the amount is 5 parts by mass or less, the light absorption at the surface of the coating film becomes satisfactory, and the deep portion curing property is improved. More preferably 0.5 to 3 parts by mass.

Specific examples of the? -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone, N, N-dimethylaminoacetophenone, and the like. Commercial products include Irgacure 907, Irgacure 369 and Irgacure 379 manufactured by BASF Japan.

Specific examples of the acylphosphine oxide photopolymerization initiator include monoacylphosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine And bis-acylphosphine oxide-based photopolymerization initiators such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Among them, a bisacylphosphine oxide-based photopolymerization initiator is preferable from the standpoint of suppressing discoloration. Commercially available products include Irgacure TPO as a monoacylphosphine oxide-based photopolymerization initiator manufactured by BASF Japan, Irgacure 819 as a bisacylphosphine oxide-based photopolymerization initiator, and the like.

The amount of the α-aminoacetophenone-based photopolymerization initiator or the acylphosphine oxide-based photopolymerization initiator is preferably from 0.01 to 25 parts by weight, based on 100 parts by weight of the resin having a styrene skeleton, Mass part is preferable. When the amount is 0.01 parts by mass or more, as in the case of using an oxime ester-based photopolymerization initiator, the photocurability on copper is good, the coating film is difficult to peel off, and deterioration of coating film properties such as chemical resistance can be suppressed. On the other hand, when it is 25 parts by mass or less, the outgas is reduced and the light absorption on the surface of the coating film becomes good, and the deep portion curing property is improved. More preferably 0.5 to 20 parts by mass.

&Lt; (C) Inorganic filler >

Examples of the inorganic filler (C) used in the photosensitive resin composition of the present invention include inorganic fillers such as titanium oxide, zinc oxide, basic carbonate carbonate, basic sulfuric acid lead, lead sulfate, zinc sulfide, antimony oxide, aluminum hydroxide, . As the titanium oxide, rutile titanium oxide or anatase titanium oxide may be used, but rutile titanium oxide is preferably used. Anatase type titanium oxide which is the same titanium oxide has higher whiteness than rutile type titanium oxide and is often used as a white pigment. However, since anatase type titanium oxide has a photocatalytic activity, Which may cause discoloration of the resin in the resin composition. On the other hand, although the rutile titanium oxide has a slightly lower degree of whiteness compared with the anatase type, the rutile titanium oxide exhibits a remarkably suppressed deterioration (yellowing) of the resin due to light caused by the photoactivity of titanium oxide, And is also stable against heat. Thus, when the LED is used as a white coloring agent in the insulating layer of the printed wiring board on which the LED is mounted, high reflectance can be maintained for a long period of time.

As the rutile type titanium oxide, known ones can be used. There are two methods for producing the rutile-type titanium oxide, namely, the sulfuric acid method and the chlorine method. In the present invention, those produced by any production method can be suitably used. Here, in the sulfuric acid method, a precipitate of hydroxide is obtained by using an aluminate or titanium slag as a raw material, dissolving it in concentrated sulfuric acid, separating the iron content as iron sulfate, and hydrolyzing the solution to obtain precipitates of hydroxides, And the like. On the other hand, the chlorination method refers to a process in which synthetic rutile or natural rutile is used as a raw material, which is reacted with chlorine gas and carbon at a high temperature of about 1000 ° C to synthesize titanium tetrachloride and oxidize the rutile titanium oxide. Among them, the rutile type titanium oxide produced by the chlorine method has a remarkable effect of suppressing deterioration (yellowing) of the resin due to heat, and is more suitably used in the present invention.

In addition, titanium oxide whose surface is treated with hydrated alumina or aluminum hydroxide may be used.

Although titanium oxide may contain sulfur in some cases, its sulfur content is preferably 100 ppm or less, more preferably 60 ppm or less. When the sulfur content is 100 ppm or less, discoloration of the peripheral portion due to the generated sulfur gas does not occur.

In addition, it is preferable to use barium sulfate because of the suppression of discoloration, the touch-drying performance, the anti-sagging effect, and the developability. However, it is preferably added as an extender pigment, not as a color pigment.

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

The amount of the inorganic filler to be incorporated is not particularly limited, but is preferably 50 to 300 parts by mass, more preferably 70 to 250 parts by mass, per 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) to be.

The present invention can also add a fluorescent whitening agent. The fluorescent brightener may be added to the white portion of the cured product of the composition so that it appears as if it is not discolored. In the present invention, by using a fluorescent whitening agent in combination with titanium oxide, particularly rutile type titanium oxide, among the inorganic fillers in the photosensitive resin composition, it becomes possible to realize a high reflectance in the cured coating film.

The fluorescent whitening agent absorbs light having a wavelength of 200 to 400 nm and emits light having a wavelength of 400 to 500 nm. As such a fluorescent whitening agent, benzooxazole derivatives, coumarin derivatives, styrene biphenyl derivatives, pyrazolone derivatives, bis (triazinylamino) stilbenylsulfonic acid derivatives and the like can be given. Among them, benzoxazole derivatives are preferable. The substituent of the benzoxazole derivative is preferably butyl, octyl, naphthalene, thiophene or stilbene.

(Thermosetting component)

A thermosetting component may be added to the photosensitive resin composition of the present invention. Examples of the thermosetting component used in the present invention include a polyfunctional epoxy compound, a block isocyanate compound, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, a polyfunctional oxetane compound, And thermosetting resins for publicly known thermoplastic resins. Among them, the preferred thermosetting component is a thermosetting component having at least one of a plurality of cyclic ether groups and cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule.

The thermosetting component having a cyclic (thio) ether group has many kinds of commercially available products and can impart various properties depending on the structure thereof.

The thermosetting component having a plurality of cyclic (thio) ether groups in such a molecule is a compound having at least two, three or four or five membered cyclic ether groups or cyclic thioether groups in the molecule, For example, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, and a compound having a plurality of thioether groups in the molecule, that is, an episulfide resin.

In the photosensitive resin composition of the present invention, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be added as a thermosetting component in order to improve the curability of the composition and the toughness of the resulting cured coating film. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a compound having a plurality of blocked isocyanate groups in one molecule, i.e., a block isocyanate compound. .

As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Examples of the isocyanate compound adduct, burette and isocyanurate include the isocyanate compounds described above.

The blocked isocyanate group contained in the block isocyanate compound is a group in which the isocyanate group is protected by a reaction with the blocking agent and is temporarily inactivated. When heated to a predetermined temperature, the block agent dissociates to form an isocyanate group.

As the block isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent is used. Examples of the isocyanate compound capable of reacting with the blocking agent include isocyanurate type, buret type, and adduct type. As the isocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate block agent include phenolic block agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam-based blocking agents such as? -caprolactam,? -flareolactam,? -butyrolactam and? -propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; But are not limited to, methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Alcohol-based blocking agents such as butyl acetate, diacetone alcohol, methyl lactate and ethyl lactate; Oxime-based blocking agents such as formaldehyde scouring, acetal decyl, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol and ethylthiophenol; Acid amide type block agents such as acetic acid amide, benzamide and the like; Imide block agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine blockers such as methylene imine and propylene imine, and the like.

Block isocyanate compounds may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS- B-815 (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.), Coronate 2512, Coronate 2513, Coronate 2520 (manufactured by NIPPON POLYURETHANE INC.), Desmotherm 2170 and Desmotherm 2265 TPA-B80E, 17B-60PX and E402-B80T (trade names, manufactured by Asahi Kasei Chemicals Co., Ltd.), B- And the like. Further, SMILDUR BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a block agent.

The compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be used singly or in combination of two or more.

The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in the molecule is preferably from 1 to 100 parts by mass, more preferably from 1 to 100 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) 2 to 70 parts by mass. When the blending amount is 1 part by mass or more, sufficient toughness of the coating film is obtained. On the other hand, when it is 100 parts by mass or less, storage stability is good.

As the thermosetting component, an amino resin such as a melamine derivative or a benzoguanamine derivative may be added to the photosensitive resin composition of the present invention. Examples of such thermosetting components include, for example, methylolmelamine compounds, methylolbenzoguanamine compounds, methylol glycol uril compounds, methylol urea compounds, alkoxymethylated melamine compounds, alkoxymethylated benzoguanamine compounds, alkoxymethylated glycoluril compounds, Alkoxymethylated urea compounds, and the like. The kind of the alkoxymethyl group is not particularly limited, and for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group and the like can be used. In particular, a melamine derivative having a human or environmentally friendly formalin concentration of 0.2% or less is preferable. These thermosetting components may be used alone or in combination of two or more.

Examples of commercially available products of these thermosetting components include Cymel 300, Copper 301, Copper 303, Copper 370, Copper 325, Copper 327, Copper 701, Copper 266, Copper Copper 267, Copper Copper 238, Copper Copper 1141, Copper Copper Copper 272 202, copper 1156, copper 1158, copper 1123, copper 1170, copper 1174, copper UFR 65, copper 300 (manufactured by Mitsui Cyanamid Co., Ltd.), Nigalak Mx-750, copper Mx-032 copper copper Mx-270 copper Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM and Mw-390 Mw-100LM, and Mw-750LM (manufactured by Sanwa Chemical Co., Ltd.).

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, epiclon 840 manufactured by DIC, epiclon 850, epiclon 1050, epiclon 2055, DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Sumi-epoxy ESA-011 manufactured by Sumitomo Chemical Co., Ltd., ESA -204, ELA-115, ELA-128, AER330, AER331, AER661, AER664 (all trade names) manufactured by Asahi Kasei Kogyo Co., Ltd., bisphenol A type epoxy resin; JERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152 manufactured by DIC Corporation, Epiclon 165, Epitoto YDB-400 manufactured by Toto Kasei Co., Ltd., YDB-500, DER542 manufactured by Dow Chemical Co., Sumitomo Chemical Co., Brominated epoxy resin of Sumi-epoxy ESB-400, ESB-700 manufactured by Asahi Chemical Industry Co., Ltd., AER711 and AER714 (all trade names) manufactured by Asahi Kasei Corporation; JER152, jER154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438 manufactured by Dow Chemical Company, Epiclon N-730 manufactured by DIC, Epiclon N-770, Epiclon N-865, Epoxy ESCN manufactured by Sumitomo Chemical Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 manufactured by Nippon Kayaku Co., Ltd., YDCN- AERECN-235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, and YDCN-700-E manufactured by Asahi Kasei Kogyo Co., 7, YDCN-700-10, YDCN-704, YDCN-704A, Epiclon N-680, N-690 and N-695 (all trade names) manufactured by DIC; Bisphenol F type epoxy resins such as Epiclon 830 manufactured by DIC Corporation, jER 807 manufactured by Mitsubishi Chemical Corporation, and Epototo YDF-170, YDF-175 and YDF-2004 manufactured by Toto Kasei Co., Hydrogenated bisphenol A type epoxy resins such as Epitoto ST-2004, ST-2007 and ST-3000 (trade name) manufactured by Toto Kasei; JER604 manufactured by Mitsubishi Kagaku Co., Ltd., EGPOTTO YH-434 manufactured by Toto Kasei Corporation, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all trade names), glycidylamine type epoxy resin; Hidanto dolphin epoxy resin; Alicyclic epoxy resins such as Celloxide 2021 (all trade names) manufactured by Daicel Chemical Industries, Ltd.; YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501 and EPPN-502 manufactured by Dow Chemical Co., Ltd. (all trade names), trihydroxyphenylmethane type epoxy resin; Biscylenol-type or biphenol-type epoxy resins such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation or a mixture thereof; Bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., EPX-30 manufactured by Adeka Co., and EXA-1514 (trade name) manufactured by DIC Corporation; Bisphenol A novolak type epoxy resins such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Tetraphenylol ethane type epoxy resins such as jERYL-931 (all trade names) manufactured by Mitsubishi Chemical Corporation; A heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); Diglycidyl phthalate resins such as Blemmer DGT manufactured by Nippon Utsunomiya; Tetraglycidylsilane ethyl resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd.; Epoxy resin containing naphthalene group such as ESN-190, ESN-360 manufactured by Shinnittsu Kagaku KK, HP-4032, EXA-4750 and EXA-4700 manufactured by DIC Corporation; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; Glycidyl methacrylate copolymer-based epoxy resins such as Nicot-like manufactured CP-50S and CP-50M; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; And CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Tohto Kasei Co., Ltd.). However, the present invention is not limited thereto. Of these, bisphenol A type epoxy resins, heterocyclic epoxy resins, biquileneol type epoxy resins or mixtures thereof are particularly preferable.

These epoxy resins may be used singly or in combination of two or more kinds.

The blending amount of the epoxy resin is in the range of preferably 0.3 to 2.5 equivalents, more preferably 0.5 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the carboxyl group-containing resin having the styrene skeleton (A). When the amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule, in particular, the blending amount of the epoxy resin is 0.3 or more, the carboxyl group is hardly left in the solder resist film and the heat resistance, alkali resistance and electric insulation property are improved. On the other hand, when the amount is 2.5 equivalents or less, a cyclic (thio) ether group having a low molecular weight is less likely to remain in the dried coating film, and the strength or the like of the coated film is improved.

(Antioxidant)

The photosensitive resin composition of the present invention may contain an antioxidant such as a radical scavenger for neutralizing radicals generated and a peroxide decomposition agent for decomposing the generated peroxide into a harmless substance and preventing generation of new radicals have. The antioxidant used in the present invention can prevent oxidation deterioration of resins and the like and further suppress yellowing. In addition to the above effect, addition of the antioxidant makes it possible to improve the process margin in the production of the photosensitive resin composition, such as prevention of halation due to the photo-curing reaction of the photosensitive resin composition and stabilization of the opening shape . The antioxidant may be used singly or in combination of two or more kinds.

Examples of the antioxidant serving as the radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6- , 2-methylene-bis (4-methyl-6-t-butylphenol), 1,1,3-tris -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'- (1H, 3H, 5H) trione, quinone compounds such as methoquinone and benzoquinone, bis (2,2,6,6-tetramethylpiperidine) , 6-tetramethyl-4-piperidyl) sebacate, phenothiazine, and the like. Examples of commercially available products include Adeka Staff AO-30, Adeka Staff AO-330, Adeka Staff AO-20, Adeka Staff LA-77, Adeka Staff LA-57, Adeka Staff LA-67, TANUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, BASF (registered trademark of BASKA)), LA-68 (manufactured by Adeka Corporation), LA- Japan), and the like.

Examples of the antioxidant which acts as a release agent for peroxide include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetra lauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3'-t- And sulfur compounds such as octyl propionate. Examples of commercially available products include Adekastab TPP (trade name, manufactured by Adeka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Co., Ltd.), and Smilylizer TPS (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

When the antioxidant is used, the blending amount is preferably 0.01 part by mass to 10 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) . When the blending amount of the antioxidant is 0.01 parts by mass or more, the effect of adding the above-mentioned antioxidant tends to be obtained easily. On the other hand, when the amount is 10 parts by mass or less, it is possible to suppress the inhibition of the photoreaction, the defective development of the alkali aqueous solution, the deterioration of tackiness and the deterioration of physical properties of the coating film.

In addition, the above antioxidant, particularly the phenol antioxidant, may exhibit the effect of a far-off layer by being used in combination with the heat-resistant stabilizer. Therefore, a heat-resistant stabilizer may be added to the photosensitive resin composition of the present invention.

Examples of the heat-resistant stabilizer include phosphorus-based, hydroxylamine-based, and sulfur-based heat stabilizers. As the commercial products of these heat stabilizers, IRGAFOX168, IRGAFOX12, IRGAFOX38, IRGASTAB PUR68, IRGASTAB PVC76, IRGASTAB FS301FF, IRGASTAB FS110, IRGASTAB FS210FF, IRGASTAB FS410FF, IRGANOX PS800FD, IRGANOX PS802FD, RECYCLOSTAB 411, RECYCLOSTAB 451AR, RECYCLOSSORB 550, RECYCLOBLEND 660 , Trade name, manufactured by BASF Japan), and the like. The heat stabilizer may be used alone or in combination of two or more.

When the heat-resistant stabilizer is used, the amount is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.01 parts by mass to 5 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) in terms of solid content.

(Photoinitiator or sensitizer)

In addition to the photopolymerization initiator, in the photosensitive resin composition of the present invention, a photoinitiator may be suitably used. Examples of the photoinitiator or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds and xanthone compounds. These compounds may be used as a photopolymerization initiator, but they are preferably used in combination with a photopolymerization initiator. The photoinitiator or sensitizer may be used alone or in combination of two or more.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.

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

Examples of the anthraquinone compound include 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 1-chloro anthraquinone and the like.

Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone. .

Examples of the ketal compound include acetophenone dimethyl ketal, benzyl dimethyl ketal and the like.

Examples of the benzophenone compound include benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl- '-Propyldiphenyl sulfide and the like.

Examples of tertiary amine compounds include 4,4'-dimethylaminobenzophenone (NISO Cure (registered trademark) MABP manufactured by Nippon Soda Co., Ltd.) in the case of commercial products such as ethanolamine compounds and compounds having a dialkylaminobenzene structure, , Dialkylaminobenzophenones such as 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran- Dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd., Kaya Cure (registered trademark) EPA), 2-dimethylaminobenzoate ((ethylamino) (Quantacure DMB manufactured by International Bio-Synthics Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (QuantacureBEA manufactured by International Bio-Synthics), p-dimethylaminobenzoic acid isoamylethylester (Kayacure DMBI ), 2-ethylhexyl 4-dimethylaminobenzoate (Es of VanDyk) olol507). As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, Particularly preferred.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of low toxicity. Since the dialkylamino group-containing coumarin compound has a maximum absorption wavelength in the range of 350 to 410 nm and an ultraviolet ray region, it is possible to obtain a colored solder resist which reflects the color of the colored pigment itself by using a coloring pigment as well as a colorless transparent photosensitive composition, It becomes possible to obtain a film. Particularly, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable in that it exhibits an excellent increase / decrease effect on laser light having a wavelength of 400 to 410 nm.

Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the incorporation of a thioxanthone compound can improve deep curing properties.

When the photoinitiator is used, it is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) in terms of solid content. When the blending amount of the photoinitiator or the sensitizer is 0.1 part by mass or more, a good increase / decrease effect can be obtained. On the other hand, when the amount is 20 parts by mass or less, the light absorption at the surface of the coating film by the tertiary amine compound does not become too large, and the deep curing property becomes good. More preferably, it is 0.1 to 10 parts by mass.

It is preferable that the total amount of the photopolymerization initiator, photoinitiator and sensitizer is 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) in terms of solid content. When the amount is 35 parts by mass or less, the lowering of the deep portion curing property due to the light absorption can be suppressed.

Further, these photopolymerization initiators, photoinitiator, and sensitizer may have a low sensitivity in some cases in order to absorb a specific wavelength, and may act as an ultraviolet absorber. However, they are not used for the purpose of improving the sensitivity of the composition. It is possible to increase the photoreactivity of the surface by changing the line shape and the opening of the resist to a vertical, tapered, or reverse tapered shape, and to improve the processing accuracy of the line width and the opening diameter .

(Chain transfer agent)

In the photosensitive resin composition of the present invention, N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like can be used as a chain transfer agent in order to improve the sensitivity. Examples of the chain transfer agent include a chain transfer agent having a carboxyl group such as mercapto succinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; Chain transfer agents having a hydroxyl group such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropane diol, mercaptobutanediol, hydroxybenzene thiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylene dioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, Pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

A multifunctional mercaptan-based compound as a chain transfer agent may also be used. Examples of the multifunctional mercaptan compounds include aliphatic thiols such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether and dimercaptodiethyl sulfide, Aromatic thiols such as mercaptane, 4,4'-dimercaptodiphenylsulfide and 1,4-benzenedithiol; (Mercaptoacetate), ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylol ethane tris Poly (mercaptoacetates) of polyhydric alcohols such as mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), dipentaerythritol hexakis (mercaptoacetate); (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate) , Trimethylol ethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis - mercapto propionate); poly (3-mercaptopropionates) of polyhydric alcohols; 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- 3H, 5H) -triene, and poly (mercaptobutyrates) such as pentaerythritol tetrakis (3-mercaptobutyrate).

Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEMPIC (manufactured by SAKAI KAGAKU KOGYO K.K.), car lens MT-PE1, car lens MT- (Trade name, manufactured by Showa Denko K.K.), and the like.

A heterocyclic compound having a mercapto group as a chain transfer agent may also be used. Examples of the heterocyclic compound having a mercapto group include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanololide), 2-mercapto- 4-butyrolactone, 2-mercapto-4-butyrolactone, 2-mercapto-4-butyrolactone, N-methoxy- Methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-valerolactam 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2- mercaptobenzothiazole, 2- Methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl- 5-mercapto-1H-tetrazole, 2- Mercapto-6-hexanolactam, 2,4,6-trimercapto-s-triazine (manufactured by Sankyo Gosei Co., Ltd., trade name Gisunet F), 2-dibutylamino-4,6-dimercapto- Azine (manufactured by Sankyo Chemical Industry Co., Ltd., Jisnet DB) and 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Industry Co., Ltd., trade name: Jisnet AF).

Particularly, from the viewpoint of not impairing the developability of the photosensitive resin composition, it is preferable to use mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, , 4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferable. These chain transfer agents may be used singly or in combination of two or more kinds.

(Urethanization catalyst)

In the photosensitive resin composition of the present invention, an urethane formation catalyst may be added to accelerate the curing reaction of the hydroxyl group, the carboxyl group and the isocyanate group. As the urethanization catalyst, it is preferable to use at least one urethane-forming catalyst selected from the group consisting of a tin catalyst, a metal chloride, a metal acetylacetonate salt, a metal sulfate, an amine compound and an amine salt.

Examples of the tin catalyst include organotin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

Examples of the metal chloride include chlorides of metals including Cr, Mn, Co, Ni, Fe, Cu or Al, and examples thereof include dicarboxylic chloride, nickel chloride and ferric chloride.

The metal acetylacetonate salt is an acetylacetonate salt of a metal containing Cr, Mn, Co, Ni, Fe, Cu or Al, and examples thereof include cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate .

Examples of the metal sulfate include metal sulfates such as Cr, Mn, Co, Ni, Fe, Cu, or Al, and copper sulfate, for example.

Examples of the amine compound include triethylenediamine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) N, N &quot;, N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, Aminopyridine, triazine, N'- (2-hydroxyethyl) -N, N'-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, (2-hydroxyethyl) -N, N ', N ", N" -tetramethyldiamine, N- N, N'-trimethyl-N '- (2-hydroxyethyl) -N, N'-tetramethyldiethylenetriamine, N- ) Propane diamine, N, N'-bis (N, N-dimethylaminopropyl) amine, bis Aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1- (2'-hydroxy Propyl imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole, 1- Imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (3'-aminopropyl) imidazole, 1- , N, N-dimethylaminopropyl-N '- (2-hydroxyethyl) imidazole, 1- (3'- (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ', N'-bis (2-hydroxypropyl) amine, (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ', N'-bis (2-hydroxypropyl) amine, melamine or / And benzoguanamine.

Examples of the amine salt include an organic acid salt-based amine salt of DBU (1,8-diaza-bicyclo [5.4.0] undecene-7).

The blending amount of the urethanization catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10.0 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) in terms of solid content.

(Thermosetting catalyst)

When the above-mentioned epoxy resin or a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-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- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Chemicals, Inc., U-CAT DBT, U-CATSA102, and U-CAT5002 (all of bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, and it may be any one that accelerates the reaction of a thermal curing catalyst of an epoxy resin or an oxetane compound or a carboxyl group with at least one of an epoxy group and an oxetanyl group, It may be used. Further, it is also possible to use at least one selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid Triazine derivatives such as adducts may be used. Preferably, a compound that also functions as such an adhesion-imparting agent is used in combination with the above-mentioned thermosetting catalyst.

The blending amount of these thermosetting catalysts is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) in terms of solid content.

(Adhesion promoter)

In the photosensitive resin composition of the present invention, an adhesion promoter may be used to improve the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate. As the adhesion promoter, for example, benzoimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi Chemical Co., 3-morpholinomethyl-thiazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2- -Thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agent.

(coloring agent)

The photosensitive resin composition of the present invention may contain a coloring agent. As the coloring agent to be used, publicly known coloring agents such as red, blue, green, sulfur, and white can be used, and any of pigments, dyes and pigments may be used. As a specific example, a color index (published by C. I. Society of Dyers and Colors) issued by the following number is attached. However, from the viewpoint of reducing the environmental burden and influencing the human body, it is preferable not to contain a halogen.

Red colorant:

Examples of the red colorant include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. &Lt; / RTI &gt;

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

Disazo system: Pigment Red 37, 38, 41.

50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 48: 3, 48: , 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.

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

Solvent Red 135, Solvent Red 179, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.

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

Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

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

Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 2, and Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

Examples of the dye system include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, 70 may be used. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Also, a blue inorganic pigment can be suitably used. As examples of the blue inorganic pigment,

(Color Index Generic Name: Pigment Blue 29), French Ultramarine, Lapis Lazuli, Azurite, Prussian Blue (Prussian Blue; Color Index Name: Pigment Blue 27);

Blue composite oxide pigments such as aluminum-cobalt oxide, aluminum-zinc-cobalt oxide, silicon-cobalt oxide and silicon-zinc-cobalt oxide;

(Color Index Name: Pigment Blue 32), cobalt blue (cobalt aluminate; Pigment Blue 28), cobalt stannate (color index name: Pigment Blue 35), cobalt chrome blue Cobalt pigment such as cobalt-aluminum-silicon oxide, cobalt silicate zinc (color index name: Pigment Blue 74), and cobalt-zinc-silicon oxide (composition formula: spinel of CoO.Al ₂ O ₃ .SiO ₂ ) .

In addition, pigments containing silicates such as particles in which natural mica is coated with titanium oxide can also be used. The natural mica formulas are generally IM _{2-3 1-0} T ₄ O ₁₀ A ₂ where I is K, Na, Ca, optionally Ba, Rb, Cs, NH ₄ and M is Al, is Mg, Fe, Li, Ti, as desired, and Mn, Cr, Zn, V, □ is a public (空孔), T is Si, Al, Fe ^{3 +,} and Be, B, as desired, a Is OH, F and is Cl, O, S as desired.

Green colorant:

Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. may be used as the green colorant. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Yellow colorant:

Examples of the yellow colorant include a monoazo system, a disazo system, a condensed azo system, a benzimidazolone system, an isoindolinone system, and an anthraquinone system, and specific examples include the following.

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

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

Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

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

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

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

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

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

The blending amount of the coloring agent (excluding the white coloring agent) is not particularly limited, but it is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass based on 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) Is 0.1 to 5 parts by mass.

(Compound having an ethylenic unsaturated group (photosensitive monomer))

In the photosensitive resin composition of the present invention, a compound (photosensitive monomer) having at least one ethylenic unsaturated group in the molecule may be used. The compound having at least one ethylenically unsaturated group in the molecule is photo-cured by irradiation with active energy rays to help insolubilize or insolubilize the carboxyl group-containing resin having the styrene skeleton (A) in the aqueous alkaline solution. In particular, in the case of a carboxyl group-containing resin, use of a non-photosensitive one is preferable from the viewpoint of photo-curability.

Examples of the compound used as the photosensitive monomer include polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy ) Acrylate, and the like. Specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol, and tris-hydroxyethylisocyanurate, or ethylene oxide adducts thereof, propylene oxide adducts, or? -Caprolactone adducts Polyhydric acrylates; Polyfunctional acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; The present invention is not limited to the above, and it is also possible to use a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene or a polyester polyol directly acrylated or acrylated with a urethane acrylate through a diisocyanate, And at least one of the methacrylates corresponding to the acrylate and the like.

In addition, epoxy acrylate resins obtained by reacting acrylic acid with polyfunctional epoxy resins such as cresol novolak type epoxy resins, and epoxy acrylate resins obtained by reacting hydroxy acrylates such as pentaerythritol triacrylate with iso An epoxy urethane acrylate compound obtained by reacting a half urethane compound of diisocyanate such as phthalone diisocyanate or the like may be used as a photosensitive monomer. Such an epoxy acrylate resin can improve the photo-curability without lowering the touch-dry composition.

The compounding amount of the compound having at least one ethylenic unsaturated group in the molecule used as the photosensitive monomer is preferably from 5 to 100 parts by mass based on 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) , And more preferably from 5 to 70 parts by mass. When the blending amount is 5 parts by mass or more, the photocurability is good and the patterning is facilitated by the alkali development after irradiation with active energy rays. On the other hand, when the amount is 100 parts by mass or less, the touch dryness (tack-and-dry performance) is improved and the resolution is also good.

(Organic solvent)

Further, the photosensitive resin composition of the present invention can use an organic solvent for the synthesis of the carboxyl group-containing resin having the styrene skeleton (A), for the production of the composition, or for the viscosity production for application to the substrate or the carrier film .

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; 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 And the like; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents may be used singly or as a mixture of two or more kinds.

(Ultraviolet absorber)

In general, the ultraviolet absorber can be used in the photosensitive resin composition of the present invention in addition to the antioxidant in order to take measures against stabilization of ultraviolet rays, because the polymer material absorbs light and causes decomposition and deterioration thereof .

Examples of ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives and the like. Specific examples of benzophenone derivatives include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy- , 4-dihydroxybenzophenone, and the like. Specific examples of the benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di- -Hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- 5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di- Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, and the like . Specific examples of the triazine derivatives include hydroxyphenyltriazine, bisethylhexyphenol methoxyphenyltriazine, and the like.

Examples of commercially available ultraviolet absorbers include TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460 and TINUVIN 479 Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

The ultraviolet absorber may be used singly or in combination of two or more. By using this antioxidant in combination, the cured product obtained from the photosensitive resin composition of the present invention can be stabilized.

(additive)

In the photosensitive resin composition of the present invention, a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, and hydrotalcite may be added as needed. As the thixotropic agent, organic bentonite and hydrotalcite are preferred because of their excellent stability over time, and hydrotalcite is particularly preferred because of its excellent electrical properties. It is also possible to blend known additives such as heat polymerization inhibitors, antifoaming agents such as silicone, fluorine, and high molecular weight, and leveling agents, anti-rust agents, and antioxidants such as bisphenol and triazine thiol have.

The thermal polymerization inhibitor may be used to prevent thermal polymerization or polymerization over time of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy- Benzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine,? -Naphthol, 2,6-di-t-butyl-4-cresol, 2,2'- butylphenol), reactants such as pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agents, methyl salicylate and phenothiazine, nitroso compounds, nitroso compounds and chelates of Al And the like.

The photosensitive resin composition of the present invention is useful for forming a pattern layer of a printed wiring board, and is useful as a material of a solder resist or an interlayer insulating layer.

The photosensitive resin composition of the present invention may be used as a dry film or as a liquid phase. When it is used as a liquid phase, it may be one-liquid or two-liquid or more. In particular, from the viewpoint of storage stability, it is preferable to use two liquids. (A) a carboxyl group-containing resin having (A) a styrene skeleton used in the present invention, (B) a photopolymerization initiator and (C) Or may be blended with other preparations. Particularly, it is preferable to blend the photopolymerization initiator (B) in the same preparation.

The dry film of the present invention is obtained by applying and drying the photosensitive resin composition of the present invention onto a film (carrier film) and comprises a carrier film and a layer containing a photosensitive resin composition formed on the carrier film.

In the case of dry film formation, the photosensitive resin composition of the present invention is diluted with the above-mentioned organic solvent to an appropriate viscosity, and the resultant mixture is applied to a substrate by a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, Coater or the like to a uniform thickness on a support and dried at a temperature of usually 50 to 130 DEG C for 1 to 30 minutes to obtain a film. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 占 퐉, preferably 20 to 60 占 퐉 in film thickness after drying.

As the carrier film, a plastic film is used, 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, and a polystyrene film. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 mu m.

It is preferable to laminate a peelable cover film on the surface of the film for the purpose of preventing the adherence of dust to the surface of the film after the film is formed on the carrier film.

As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface treated paper, or the like can be used. When peeling the cover film, The adhesive force may be smaller.

The cured coating film of the present invention can be formed by a method such as dip coating method, flow coating method, roll coating method, bar coater method, screen printing method, curtain coating method , And the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 60 to 100 占 폚 to form a touch-dried coating film. In the case of a dry film obtained by applying the above composition onto a carrier film and drying the film, the photosensitive resin composition layer is brought into contact with the base material by a laminator or the like so as to come into contact with the base material, Can be formed.

Thereafter, the resist pattern is selectively exposed to light by an active energy ray through a photomask having a pattern formed thereon by a contact type (or noncontact type), or directly pattern-exposed by a laser direct exposure apparatus, and the unexposed portion is exposed to a dilute alkali aqueous solution 0.3 to 3 wt% aqueous sodium carbonate solution) to form a resist pattern. In the case of a composition containing a thermosetting component, for example, by heating to a temperature of about 140 to 180 ° C to thermoset, the carboxyl group of the carboxyl group-containing resin having the styrene skeleton (A) and the epoxy group, And can form a cured coating film excellent in various properties such as heat resistance, chemical resistance, hygroscopicity, adhesion, and electrical characteristics. In addition, even when the thermosetting component is not contained, since the ethylenic unsaturated bonds remaining in the unreacted state during exposure are thermally radically polymerized by the heat treatment, the film properties are improved. Therefore, Curing).

As the above substrate, it is possible to use a substrate such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluororesin, polyethylene (FR-4 and the like), other polyimide films, PET films, glass substrates (for example, FR-4), and the like, using a material such as a copper clad laminate for high frequency circuit using polyphenylene ether, polyphenylene oxide, cyanate ester, , A ceramic substrate, a wafer plate, and the like.

The volatile drying performed after the application of the photosensitive resin composition of the present invention can be carried out by a hot-air circulating drying furnace, a hot plate, a convection oven or the like (a furnace equipped with a heat source of air heating by steam, A method of bringing into contact with a support by a nozzle, and the like).

The exposed portions (portions irradiated with active energy rays) of the photosensitive resin composition are cured by performing exposure (irradiation with an active energy ray) on the coating film obtained by applying and evaporating and drying the solvent.

As the exposure device used for the irradiation of the active energy ray, any device that irradiates ultraviolet rays in a range of from 350 to 450 nm by mounting a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, A device (e.g., a laser direct imaging device that draws a laser image directly with CAD data from a computer) can also be used. As the laser light source of the direct shot, a gas laser or a solid laser may be used if laser light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure dose for image formation varies depending on the film thickness and the like, but may be generally within the range of 20 to 1000 mJ / cm 2, preferably 20 to 800 mJ / cm 2.

Examples of the developing method include a dipping method, a shower method, a spraying method, a brushing method and the like. As the developing solution, an alkali aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, Can be used.

Example

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following, &quot; part &quot; and &quot;% &quot; are on a mass basis unless otherwise specified.

[Synthesis of Resin Solution 1]

200 parts by mass of deionized water and 0.3 parts by mass of sodium sulfate were put into a pressure-resistant container equipped with a thermometer, a cooling tube and a stirrer to confirm dissolution.

Then, 5 parts by mass of BPO (benzoyl peroxide) as a polymerization initiator and 5 parts by mass of MSD (? -Methylstyrene dimer) as a chain transfer agent were mixed with 10.4 parts by mass of MMA (methyl methacrylate) Butyl acrylate): 5 parts by mass, MAA (methacrylic acid): 24.6 parts by mass, and St (styrene): 60 parts by mass.

Thereafter, the dispersant was added so as to have a concentration of 300 ppm, sufficiently stirred, and the interior of the kiln was replaced with nitrogen, and the temperature was elevated to perform suspension polymerization.

After completion of the polymerization, the obtained suspension was filtered with a mesh having an eye size of 30 탆 and dried with warm air at 40 캜 to obtain a particulate resin. The thus obtained granular resin (copolymerized resin) was sufficiently dissolved by using an organic solvent DPM (dipropylene glycol methyl ether) so that the solid concentration became 50% by mass. The solid content was 160 mgKOH / g.

[Synthesis of Resin Solution 2]

A particulate resin was obtained in the same manner as in Resin Solution 1 except that 5 parts by mass of BPO was changed to 4.0 parts by mass and MSD: 5 parts by mass was changed to 4.0 parts by mass. A resin solution 2 obtained by sufficiently dissolving the granular resin (copolymer resin) thus obtained so as to have a solid content concentration of 50 mass% using an organic solvent DPM (dipropylene glycol methyl ether) is used. The solid content was 160 mgKOH / g.

[Synthesis of Resin Solution 3]

A particulate resin was obtained in the same manner as in Resin Solution 1 except that 5 parts by mass of BPO was replaced by 1.5 parts by mass and MSD: 5 parts by mass was replaced by 1.0 part by mass. A resin solution 3 obtained by sufficiently dissolving the granular resin (copolymer resin) thus obtained so as to have a solid concentration of 50 mass% using an organic solvent DPM (dipropylene glycol methyl ether) is used. The solid content was 160 mgKOH / g.

[Synthesis of resin solution 4]

145 parts by mass of deionized water and 0.3 parts by mass of sodium sulfate were put into a pressure-resistant container equipped with a thermometer, a cooling tube and a stirrer to confirm dissolution.

Thereafter, 5 parts by mass of t-butylperoxy-2-ethylhexanonate (Nitin-like perbutyl O) as a polymerization initiator and 4.5 parts by mass of MSD (α-methylstyrene dimer) as a chain transfer agent were added to MMA 45.5 parts by mass of styrene (methyl methacrylate), 45.5 parts by mass of n-BA (n-butyl acrylate), 6 parts by mass of MAA (methacrylic acid), and 30 parts by mass of styrene did.

Thereafter, the dispersant was allowed to have a concentration of 500 ppm. The suspension was sufficiently stirred, the inside of the flask was replaced with nitrogen, and the temperature was elevated to perform suspension polymerization.

After completion of the polymerization, the obtained suspension was filtered with a mesh having an eye size of 30 탆 and dried with warm air at 40 캜 to obtain a particulate resin. A resin solution 4 obtained by sufficiently dissolving the granular resin (copolymer resin) thus obtained so as to have a solid concentration of 50 mass% using an organic solvent DPM (dipropylene glycol methyl ether) is used. The solid content was 120 mgKOH / g.

[Synthesis of Resin Solution 5]

A granular resin was obtained in the same manner as in the case of the resin solution 4 except that 45.5 parts by mass of MMA was changed to 33.3 parts by mass and that of MAA: 18.5 parts by mass was changed to 30.7 parts by mass. A resin solution 5 obtained by sufficiently dissolving the granular resin (copolymer resin) thus obtained so as to have a solid concentration of 50 mass% using an organic solvent DPM (dipropylene glycol methyl ether) is used. The solid content was 200 mgKOH / g.

[Synthesis of Resin Solution 6]

145 parts by mass of deionized water and 0.3 parts by mass of sodium sulfate were put into a separable flask equipped with a thermometer, a cooling tube and a stirrer to confirm dissolution.

Thereafter, 0.3 part by mass of AMBN (2,2'-azobis (2-methylbutyronitrile)) as a polymerization initiator and 4 parts by mass of n-DM (n-dodecylmercaptan) as a chain transfer agent were added to MMA 55.5 parts by mass of styrene (methyl methacrylate), 55.5 parts by mass of n-BA (n-butyl acrylate), 6 parts by mass of MAA (methacrylic acid), and 20 parts by mass of styrene did.

Thereafter, the dispersant was allowed to have a concentration of 500 ppm. The suspension was sufficiently stirred, the inside of the flask was replaced with nitrogen, and the temperature was elevated to perform suspension polymerization.

After completion of the polymerization, the obtained suspension was filtered with a mesh having an eye size of 30 탆 and dried with warm air at 40 캜 to obtain a particulate resin. The thus obtained granular resin (copolymerized resin) is sufficiently dissolved in an organic solvent DPM (dipropylene glycol methyl ether) so that the solid content concentration becomes 50 mass%. The solid content was 120 mgKOH / g.

[Synthesis of resin solution 7]

42 parts by mass of MAA (methacrylic acid), 43 parts by mass of MMA (methyl methacrylate), 35 parts by mass of styrene, and 50 parts by mass of benzyl acrylate were added to a four-necked flask equipped with a reflux condenser, a thermometer, , 35 parts by mass of carbitol acetate, 100 parts by mass of carbitol acetate, 0.5 parts by mass of MSD (? -Methylstyrene dimer) as chain transfer agent, and 4 parts by mass of azobisisobutyronitrile were added, Deg.] C for 5 hours to carry out the polymerization reaction to obtain a copolymer solution (solid concentration of 50 mass%). Then, 0.05 parts by mass of hydroquinone, 23 parts by mass of glycidyl methacrylate, and 2.0 parts by mass of dimethylbenzylamine were added and the addition reaction was carried out at 80 ° C for 24 hours. Then, 35 parts by mass of carbitol acetate was added To obtain a copolymer resin solution (resin solution 7) having an aromatic ring. The solid content concentration of the copolymer resin solution (resin solution 7) thus obtained was 50 mass% and the acid value of the solid content was 80 mg KOH / g.

[Synthesis of resin solution 8]

50 parts by mass of DPM (dipropylene glycol methyl ether) was put into a pressure-resistant container equipped with a thermometer, a cooling tube and a stirrer, and the temperature was raised.

Thereafter, 5 parts by mass of t-butylperoxyisopropyl monocarbonate (perbutyl I manufactured by Nichia Corporation) as a polymerization initiator was added to 10.4 parts by mass of MMA (methyl methacrylate), n-BA (n-butyl acrylate) (Meth) acrylic acid), 24.6 parts by mass of MAA (methacrylic acid), and 60 parts by mass of St (styrene), the monomer mixture was sufficiently dissolved and the pressure vessel was heated to a predetermined temperature. , And solution polymerization was carried out.

After completion of the polymerization, the solution was filtered through a mesh having an eye size of 5 탆 to obtain a resin solution. A resin solution 8 obtained by sufficiently dissolving the resin solution (copolymer resin) thus obtained so as to have a solid concentration of 50 mass% using an organic solvent DPM (dipropylene glycol methyl ether) is used. The solid content was 160 mgKOH / g.

[Synthesis of resin solution 9]

A granular resin was obtained in the same manner as in the case of the resin solution 1 except that 5 parts by mass of BPO was changed to 1.0 part by mass and MSD: 5 parts by mass was changed to 1.0 part by mass. A resin solution 9 obtained by sufficiently dissolving the resin solution (copolymer resin) thus obtained in an organic solvent DPM (dipropylene glycol methyl ether) to a solid content concentration of 50% by mass is used. The solid content was 160 mgKOH / g.

[Synthesis of Resin Solution 10]

A granular resin was obtained in the same manner as in the case of the resin solution 4 except that 45.5 parts by mass of MMA was changed to 48.6 parts by mass and that of MAA: 18.5 parts by mass was changed to 15.4 parts by mass. The resin solution 10 obtained by sufficiently dissolving the resin solution (copolymer resin) thus obtained so as to have a solid content concentration of 50 mass% using an organic solvent DPM (dipropylene glycol methyl ether). The solid content was 70 mgKOH / g.

[Synthesis of Resin Solution 11]

145 parts by mass of deionized water and 0.3 parts by mass of sodium sulfate were put into a separable flask equipped with a thermometer, a cooling tube and a stirrer to confirm dissolution.

Thereafter, 0.5 part by mass of AMBN (2,2'-azobis (2-methylbutyronitrile)) as a polymerization initiator and 3 parts by mass of MSD (α-methylstyrene dimer) as a chain transfer agent were added to MMA (methyl methacrylate ): 75.5 parts by mass, n-BA (n-butyl acrylate): 6 parts by mass, and MAA (methacrylic acid): 18.5 parts by mass.

Thereafter, the dispersant was allowed to have a concentration of 400 ppm. The suspension was sufficiently stirred, the inside of the kiln was replaced with nitrogen, and the temperature was elevated to perform suspension polymerization.

After completion of the polymerization, the obtained suspension was filtered with a mesh having an eye size of 30 탆 and dried with warm air at 40 캜 to obtain a particulate resin. Resin solution 11 obtained by sufficiently dissolving the resin solution (copolymer resin) thus obtained so as to have a solid concentration of 50 mass% using an organic solvent DPM (dipropylene glycol methyl ether) is used. The solid content was 120 mgKOH / g.

[Synthesis of resin solution 12]

Liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen-introducing tube was charged with 900 g of diethylene glycol dimethyl ether as a solvent and 200 g of t-butylperoxy-2-ethylhexanonate 21.4 g of perbutyl O (manufactured by Healing Co.) was added and heated to 90 占 폚. After heating, 309.9 g of MAA (methacrylic acid), 116.4 g of MMA (methyl methacrylate) and 109.8 g of caprolactone-modified 2-hydroxyethyl methacrylate (Daicel Flaxel FM1) g was added dropwise over 3 hours together with 21.4 g of bis (4-t-butylcyclohexyl) peroxydicarbonate as a polymerization initiator (Perillo TCP manufactured by Nichiyu Co., Ltd.) To obtain a carboxyl group-containing copolymer resin. The reaction was carried out in a nitrogen atmosphere.

Subsequently, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (Daicel Cychroma M100), dimethylbenzylamine as a ring opening catalyst (3.6 g), and hydroquinone monomethyl ether as a polymerization inhibitor were added to the obtained carboxyl group- : 1.80 g, and the mixture was heated to 100 占 폚 and stirred to effect a ring-opening addition reaction of epoxy. After 16 hours, a resin solution 12 having an acid value of solid content of 108.9 mgKOH / g and a weight average molecular weight of 25,000 and containing 50% by mass (nonvolatile content) of a carboxyl group-containing resin having no aromatic ring was obtained.

&Lt; Preparation of Photosensitive Resin Composition of Examples 1 to 12 and Comparative Examples 1 to 5 >

The components shown in Tables 1 and 2 were compounded in the ratios (parts by mass) described in the table, preliminarily mixed with a stirrer, and kneaded with a three roll mill to prepare a photosensitive resin composition.

* 1: Resin solution 1

(Unit: styrene skeleton content / acid value / weight average molecular weight = 60 (mol%) / 160 (mgKOH / g) / 10000)

* 2: Resin solution 2

(Styrene skeleton content / acid value / weight average molecular weight = 60/160/15000)

* 3: Resin solution 3

(Styrene skeleton content / acid value / weight average molecular weight = 60/160/50000)

* 4: Resin solution 4

(Styrene skeleton content / acid value / weight average molecular weight = 30/120/20000)

* 5: Resin solution 5

(Styrene skeleton content / acid value / weight average molecular weight = 30/200/20000)

* 6: Resin solution 6

(Styrene skeleton content / acid value / weight average molecular weight = 20/120/15000)

* 7: Resin solution 7

(Styrene skeleton content / acid value / weight average molecular weight = 20/80/15000)

* 8: Resin solution 8

(Content of styrene skeleton / acid value / weight average molecular weight = 60/160/8000)

* 9: Resin solution 9

(Styrene skeleton content / acid value / weight average molecular weight = 60/160/65000)

* 10: Resin solution 10

(Styrene skeleton content / acid value / weight average molecular weight = 30/70/20000)

* 11: Resin solution 11

(Styrene skeleton content / acid value / weight average molecular weight = 0/120/15000)

* 12: Resin solution 12

(Styrene skeleton content / acid value / weight average molecular weight = (0 / 108.9 / 25000)

* 13: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, BASF Japan)

* 14: Alpha-aminoacetophenone-based photopolymerization initiator (Irgacure 907 manufactured by BASF Japan)

* 15: 2,4,6-Trimethylbenzoyldiphenylphosphine oxide (Irgacure TPO manufactured by BASF Japan)

* 16: C-1 rutile type titanium oxide (Taipure R-931 manufactured by DuPont)

* 17: C-2 aluminum hydroxide (H-42M (specific gravity: 2.4) manufactured by Showa Denko K.K.)

* 18: C-3 Barium sulfate (B-30 manufactured by SAKAI KAGAKU KOGYO CO., LTD.)

* 19: Antifoaming agent (KS-66 manufactured by Shinetsu Chemical Industry Co., Ltd.)

* 20: Thermal curing catalyst (melamine)

* 21: Thermal curing catalyst (DICY (dicyandiamide))

* 22: jER828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation)

* 23: IRGANOX1010 (phenolic antioxidant, BASF Japan)

* 24: DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

* 25: Organic solvent (DPM (dipropylene glycol methyl ether))

(Assessment Methods)

<Touch-up Drying>

The photosensitive resin compositions of the examples and comparative examples were coated on a copper foil substrate by pattern printing, screen printing was applied on the entire surface, and each was dried with a hot air circulating type drying furnace (1) for 15 minutes and then for 30 minutes, Lt; / RTI &gt; A PET film was pressed against the substrate, and then the film adhering state was evaluated when the negative film was peeled off. The obtained results are shown in Tables 3 and 4.

◎: There is no stickiness at all.

○: There is no stickiness.

△: Slightly sticky.

X: Sticky.

&Lt; Change in reflectance and discoloration >

The entire surface of the photosensitive resin composition of each of Examples and Comparative Examples was applied by screen printing to a dry copper film substrate having a dry film thickness of 20 占 퐉, dried at 80 占 폚 for 30 minutes, and cooled to room temperature. The pattern was exposed at an optimum exposure dose using an exposure apparatus equipped with a high pressure mercury lamp mounted on this substrate and then developed with a 1 mass% sodium carbonate aqueous solution at 30 DEG C under a spray pressure of 0.2 MPa for 90 seconds, . This substrate was cured by heating at 150 DEG C for 60 minutes to obtain an evaluation substrate on which a cured pattern was formed.

The obtained evaluation substrate was evaluated for the initial value of the Y value of the XYZ color system and the L ^* , a ^* , and b ^* values of the L ^* a ^* b ^* table colorimeter at a wavelength of 360 to 740 nm using a color color system CR-400 manufactured by Konica Minolta Co., The initial value of b ^* was measured. Thereafter, the evaluation substrate was subjected to a light irradiation treatment or a heat treatment as described below, and then each value was measured with a color chromaticity meter CR-400 manufactured by Konica Minolta Co. Then, from the change in Y value and ΔE ^* ab, And discoloration were evaluated. The criteria are as follows. The obtained results are shown in the following Tables 3 and 4.

Change in Reflectivity:

◎: Reduction rate of Y value is less than 5%

○: Reduction ratio of Y value is 5% or more and less than 10%

×: Reduction rate of Y value is 10% or more

discoloration:

?:? E ^* ab is less than 3

○: ΔE ^* ab is 3 or more and less than 5

×: ΔE ^* ab is 5 or more

Also, the higher the Y value, the higher the reflectance. ΔE ^* ab is the L ^* a ^* b ^* colorimetric system in which the difference between the initial value and each treatment is calculated. The larger the value, the greater the discoloration. The calculation formula of? E ^* ab is as follows.

^{ΔE * ab = [(L *} 2 -L * 1) 2 + (a * 2 -a * 1) 2 + (b * 2 -b * 1) 2] 1/2

Wherein, L ^{* 1,} a ^{* 1,} b ^{* 1} are each L ^*, a ^*, b ^* represents the initial value of, L ^{* 2,} a ^{* 2,} b ^{* 2} are each L after each treatment ^* , a ^* , and b ^* .

Light irradiation treatment:

The evaluation substrate thus obtained was subjected to accelerated deterioration by irradiation with light of 100 J / cm 2 using a UV conveyor (output: 150 W / cm, metal halide lamp, cold mirror).

Heat treatment:

The evaluation substrate obtained above was set to a heating temperature of 260 占 폚 in accordance with the standard of IPC / JETEC J-STD-020 and subjected to five reflow operations. Here, it means that the operation of reflowing 5 times, passing through the infrared ray at 260 DEG C for 10 seconds, and returning the temperature to room temperature was repeated 5 times.

<Spillability>

The evaluation of the shedding property was measured and evaluated as follows.

1. The photosensitive resin compositions of each of the examples and comparative examples were dropped into a copper clad laminate using a syringe.

2. The laminated board is set up against the substrate rack, and a dummy substrate is provided on the front face of the laminated plate so that the wind of the hot air circulating type drying furnace does not directly touch it.

3. With the laminate standing up against the substrate rack, it is dried for 30 minutes in a hot-air circulation type drying furnace set at 80 ° C.

4. After drying, measure the length from the center to the lowermost part of the dried photosensitive resin composition.

◎: The length of the shed is 0 cm or more and less than 2 cm

○: The length of the shed is 2 cm or more and less than 4 cm

?: The length of the shed is 4 cm or more and less than 6 cm

X: The length of the shed is 6 cm or more

The obtained results are shown in Tables 3 and 4.

<Developability>

The entire surface of the photosensitive resin composition of each of Examples and Comparative Examples was applied by screen printing to a dry copper film substrate having a dry film thickness of 20 占 퐉, dried at 80 占 폚 for 30 minutes, and cooled to room temperature. This substrate was developed with a 1 mass% sodium carbonate aqueous solution at 30 占 폚 under a spraying pressure of 0.2 MPa, and the state of the residue was visually observed to measure and evaluate the developing time at which no residue remained. The obtained results are shown in Tables 3 and 4.

◎: Within 30 seconds

○: 30 seconds or more and less than 60 seconds

△: 60 seconds or more and less than 120 seconds

×: 120 seconds or more

As shown in the above table, the composition of each Example containing a carboxyl group-containing resin having a styrene skeleton and a weight average molecular weight of 10,000 to 50,000 and an acid value of 80 to 200 mgKOH / g, a photopolymerization initiator and an inorganic filler It was confirmed that all of the comparative examples were excellent in sensitivity and developability, excellent in suppression of the light irradiation of the cured product and suppressed in lowering of the reflectance due to heat, and also excellent in touch-drying dryness, suppression of discoloration and prevention of bleeding.

Claims (7)

(A) a photosensitive resin composition containing a carboxyl group-containing resin having a styrene skeleton, (B) a photopolymerization initiator, and (C) an inorganic filler,
Wherein the carboxyl group-containing resin (A) having a styrene skeleton has a weight average molecular weight of 10,000 to 50,000 and an acid value of 80 to 200 mgKOH / g. The photosensitive resin composition according to claim 1, wherein the component (C) is titanium oxide. The photosensitive resin composition according to claim 1, wherein (C) is rutile-type titanium oxide. The photosensitive resin composition according to claim 1, further comprising a thermosetting component. A dry film obtained by applying and drying the photosensitive resin composition according to claim 1 to a film. A cured coating film characterized by being obtained by curing the photosensitive resin composition according to claim 1 or a dry film obtained by applying and drying the photosensitive resin composition according to claim 1 to a film. A printed wiring board comprising the cured coating film according to claim 6.