JP6463370B2 - Photosensitive resin composition, dry film and cured film thereof, and printed wiring board using them - Google Patents

Description

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

  In recent years, solder resists for consumer printed wiring boards and industrial printed wiring boards are used to form images by developing after UV irradiation and finishing with either heat or light irradiation from the viewpoint of high accuracy and high density. A liquid development type solder resist that cures (mainly cures) is used. In addition, there is a demand for improved solder resist workability and higher performance in response to the increase in the density of printed wiring boards accompanying the reduction in size and size of electronic equipment.

  For example, Patent Document 1 discloses a carboxyl group having an aromatic ring as a resin composition that satisfies the required characteristics and suppresses the resist film from turning yellow when the resist film is exposed to high temperatures. A photosensitive composition containing a group-containing resin is disclosed. Further, Patent Document 2 discloses a white photocurable / thermosetting solder resist containing a carboxyl group-containing resin having no aromatic ring, which is one of the purposes for suppressing deterioration (yellowing) of the resin due to light. A composition is disclosed.

JP 2011-081410 A JP 2007-322546 A

  However, when resin compositions such as those described in Patent Documents 1 and 2 are used, improvement is still achieved in terms of touch dryness (tack-free performance) and prevention of sagging after application to a substrate. There was room. In this regard, it is known that the effect of preventing dripping can be obtained by using specially modified urea or saturated fatty acid in the composition, but there is a problem that the resin is discolored.

  Therefore, the object of the present invention is a photosensitivity excellent in sensitivity and developability, excellent in light irradiation of a cured product, and in suppressing reduction in reflectance due to heat, and also excellent in dryness to touch, suppression of discoloration, and anti-sagging effect. It is in providing a conductive resin composition, its dry film and cured film, and a printed wiring board using them.

  That is, the photosensitive resin composition of the present invention comprises (A) a carboxyl group-containing resin having a styrene skeleton, (B) a photopolymerization initiator, and (C) an inorganic filler. The (A) carboxyl group-containing resin 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. is there.

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

  Furthermore, 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 one of the above photosensitive resin compositions is applied to a film and dried.

  The cured coating film of the present invention is obtained by curing a photosensitive film composition described above or a dry film obtained by applying and drying any one of the photosensitive resin compositions described above to a film. It is what.

  The printed wiring board of the present invention is characterized by comprising the above-mentioned cured film.

  According to the present invention, a photosensitive resin composition that has good sensitivity and developability, is excellent in light irradiation of a cured product, is excellent in suppressing a decrease in reflectance due to heat, and is also excellent in dryness to touch, suppression of discoloration, and anti-sagging effect. Products, dry films and cured coatings thereof, and printed wiring boards using them can be provided.

Hereinafter, embodiments of the present invention will be specifically described.
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. The (A) carboxyl group-containing resin 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.
Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated in detail.

<(A) Carboxyl group-containing resin having a styrene skeleton>
(A) A carboxyl group-containing resin having a styrene skeleton is a resin having a carboxyl group in the molecule and no photosensitive group such as an ethylenically unsaturated bond, having a styrene skeleton in the molecule, and a weight. The average molecular weight is 10,000 to 50,000, and the acid value is 80 to 200 mg KOH / g. The carboxyl group-containing resin having such 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 touch-drying property and anti-sagging effect of the cured film made of the photosensitive resin composition of the present invention are improved.

  (A) Specific examples of the carboxyl group-containing resin having a styrene skeleton are selected from, for example, unsaturated carboxylic acids such as (meth) acrylic acid, styrene, α-methylstyrene, lower alkyl (meth) acrylate, isobutylene, and the like. And a carboxyl group-containing resin (either an oligomer or a polymer) obtained by copolymerization with an unsaturated group-containing compound. The 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 (A) carboxyl group-containing resin having a styrene skeleton varies depending on the resin skeleton, but from 10,000 to 50, 000 or less. When the weight average molecular weight is 10,000 or more, in addition to the above-mentioned sag-preventing effect, the touch drying property (tack-free performance) becomes better, the moisture resistance of the coated film after exposure is good, and the film during development Reduction can be suppressed, and reduction in resolution can be suppressed. Further, when the weight average molecular weight is 50,000 or less, in addition to the anti-sag effect, the developability is good and the storage stability is also excellent. More preferably, it is 10,000 or more and 25,000 or less, More preferably, it is 10,000 or more and 15,000 or less.

  In the photosensitive resin composition of the present invention, the acid value of (A) the carboxyl group-containing resin having a styrene skeleton is 80 to 200 mgKOH / g. More preferably, it is 100-160 mgKOH / g. (A) By setting the acid value of the carboxyl group-containing resin having a styrene skeleton to 80 mgKOH / g or more, a high softening point is obtained, the tack-free performance is excellent, and the developability is also excellent. On the other hand, (A) By setting the acid value of the carboxyl group-containing resin having a styrene skeleton to 200 mgKOH / g or less, the crosslinking density becomes appropriate, and no stress is generated during curing, and a good coating film is obtained. .

  In the photosensitive resin composition of the present invention, (A) the carboxyl group-containing resin having a styrene skeleton has a styrene skeleton, so that the cured product is irradiated with light unexpectedly despite having an aromatic ring. It is excellent in developability and dryness to touch while suppressing a decrease in reflectance due to heat and suppressing discoloration. The ratio of the styrene skeleton is preferably 10 to 80 mol%, more preferably 10 to 60 mol%, and still more preferably 10 to 50 mol% in the molecule. That is, it is preferable to use 30 to 60 mol% of styrene with respect to the total amount of monomers when synthesizing (A) a carboxyl group-containing resin having a styrene skeleton. (A) The compatibility with other components becomes favorable because the ratio of the styrene skeleton of the carboxyl group-containing resin having a styrene skeleton is 10 mol% or more in the molecule. Moreover, developability becomes more favorable by setting it as 80 mol% or less in a molecule | numerator.

  (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 is excellent in dryness to touch (tack-free performance). In general, when (A) a carboxyl group-containing resin having a styrene skeleton is produced by suspension polymerization, the polymer has a high molecular weight. However, in consideration of characteristics such as screen printing suitability, touch-drying property, and developability, the weight average molecular weight is 10, It is necessary to keep it in the range of 000 to 50,000. Therefore, in controlling the molecular weight, it is preferable to use a chain transfer agent during the synthesis of (A) a carboxyl group-containing resin having a styrene skeleton.

  As the chain transfer agent used in the synthesis of such a resin, known and commonly used ones can be used. Among them, MSD (α-methylstyrene dimer) and n-DM (n-dodecyl mercaptan) are preferable.

  Moreover, in order to accelerate | stimulate superposition | polymerization, it is preferable to use a polymerization initiator at the time of (A) carboxyl group-containing resin synthesis | combination which has a styrene skeleton. Examples of the polymerization initiator include BPO (benzoyl peroxide), t-butylperoxy-2-ethylhexanate, AMBN (2,2′-azobis (2-methylbutyronitrile)) and the like. Of these, 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 when synthesizing (A) a carboxyl group-containing resin having a styrene skeleton, It is more preferable that it is 0.1-4 mass parts in 100 mass parts of resin.

  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.

(Carboxyl group-containing resins other than (A))
As the carboxyl group-containing resin other than (A) used in the photosensitive resin composition of the present invention, a carboxyl group-containing resin having no aromatic ring is particularly preferable because of excellent tack-free performance under severe conditions. . In this case, if it is a resin containing a carboxyl group that does not have an aromatic ring, the photosensitive carboxyl group-containing resin having one or more photosensitive unsaturated double bonds in itself, and a photosensitive unsaturated double bond. Any of the carboxyl group-containing resins having no heavy bond can be used, and is not limited to a specific one. In particular, among the resins listed below, those having no aromatic ring (which may be either oligomers or polymers) can be preferably used.

  That is, (1) a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having an unsaturated double bond, (2) a carboxyl group-containing (meth) acrylic copolymer resin with an oxirane ring in one molecule A photosensitive carboxyl group-containing resin obtained by reacting a compound having an ethylenically unsaturated group, and (3) a compound having one epoxy group and an unsaturated double bond in each molecule and an unsaturated double A photosensitive carboxyl group obtained by reacting a copolymer with a compound having a bond with an unsaturated monocarboxylic acid and reacting a secondary hydroxyl group produced by this reaction with a saturated or unsaturated polybasic acid anhydride. Containing resin, (4) a hydroxyl group-containing polymer is reacted with a saturated or unsaturated polybasic acid anhydride, and then one carboxylic acid produced by this reaction is included in each molecule. A photosensitive hydroxyl and carboxyl group-containing resin obtained by reacting a compound having an epoxy group and an unsaturated double bond.

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

  The carboxyl group-containing (meth) acrylic copolymer resin (a) is obtained by copolymerizing a (meth) acrylic acid ester and a compound having one unsaturated group and at least one carboxyl group in one molecule. Obtained. Examples of the (meth) acrylic acid ester constituting the copolymer resin (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl ( Hydroxyl groups such as (meth) acrylic acid alkyl esters such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate Containing (meth) acrylic acid esters, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxy Triethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, glycol-modified (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate. 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 addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.

  In addition, as a compound having one unsaturated group and at least one carboxyl group in one molecule constituting the copolymer resin (a), acrylic acid, methacrylic acid, a chain between the unsaturated group and the carboxylic acid is a chain. Extended modified unsaturated monocarboxylic acid, for example, β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acid having ester bond by lactone modification, etc. Examples thereof include acids, modified unsaturated monocarboxylic acids having an ether bond, and those containing two or more carboxyl groups in the molecule such as maleic acid. Of these, methacrylic acid is preferred. These may be used alone or in combination of two or more.

  (B) The compound having an oxirane ring and an ethylenically unsaturated group in one molecule may be a compound having an ethylenically unsaturated group and an oxirane ring in one molecule. For example, glycidyl (meth) acrylate, α -Methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexyl Examples include methylamino acrylate. Of these, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferable. These (b) compounds having an oxirane ring and an ethylenically unsaturated group in one molecule may be used alone or in admixture of two or more.

  The carboxyl group-containing resin other than the above (A) preferably has an acid value in the range of 50 to 200 mgKOH / g. When the acid value is 50 mgKOH / g or more, it becomes easy to remove the unexposed portion of the coating film of the composition with a weak alkaline aqueous solution. When the acid value is 200 mgKOH / g or less, the cured film has excellent water resistance and electrical characteristics. Moreover, it is preferable that the weight average molecular weights of carboxyl group-containing resin other than said (A) exist in the range of 5,000-100,000. When the weight average molecular weight is 5,000 or more, the dryness to touch of the coating film of the photosensitive resin composition tends to be remarkably improved. Moreover, since it exists in the tendency for the developability and storage stability of the photosensitive resin composition to become remarkably favorable as a weight average molecular weight is 100,000 or less, it is preferable.

<(B) Photopolymerization initiator>
In the photosensitive resin composition of the present invention, any known photopolymerization initiator (B) can be used, and among them, an oxime ester photopolymerization initiator having an oxime ester group, α-amino An acetophenone photopolymerization initiator and an acylphosphine oxide photopolymerization initiator are preferred, and an acylphosphine oxide photopolymerization initiator is more preferred. A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.

  As oxime ester photopolymerization initiators, commercially available products such as CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919 manufactured by ADEKA, Adeka Arcles (registered trademark) NCI-831 Etc.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０又は１の整数である。）Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

(In the formula, X is 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). A group, an amino group, an alkylamino group having 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 alkoxy group having 1 to 8 carbon atoms), And Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number 1). Alkyl group having 1 to 8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Group or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or Substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, Thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1)

  In particular, in the above formula, 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. An ester photopolymerization initiator is preferred.

  The blending amount when using the oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass in terms of solid content with respect to 100 parts by mass of the carboxyl group-containing resin having the (A) styrene skeleton. It is. When the amount is 0.01 parts by mass or more, the photocurability on copper is good, the coating film is hardly peeled off, and the coating properties such as chemical resistance are good. On the other hand, in the case of 5 parts by mass or less, light absorption on the coating film surface becomes good, and deep part curability is improved. More preferably, it is 0.5-3 mass parts.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like can be mentioned. Examples of commercially available 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)- Examples thereof include bisacylphosphine oxide photopolymerization initiators such as phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Among these, a bisacylphosphine oxide photopolymerization initiator is preferable in that it is excellent in suppressing discoloration. Examples of commercially available products include Irgacure TPO as a monoacylphosphine oxide photopolymerization initiator manufactured by BASF Japan, and Irgacure 819 as a bisacylphosphine oxide photopolymerization initiator.

  Each compounding amount in the case of using an α-aminoacetophenone photopolymerization initiator or an acylphosphine oxide photopolymerization initiator is calculated in terms of solid content with respect to 100 parts by mass of the carboxyl group-containing resin having the (A) styrene skeleton. The content is preferably 0.01 to 25 parts by mass. In the case of 0.01 parts by mass or more, the photocurability on copper is good as in the case of using an oxime ester photopolymerization initiator, the coating film is difficult to peel off, and the coating properties such as chemical resistance Can be suppressed. On the other hand, in the case of 25 parts by mass or less, outgas is reduced, light absorption on the coating film surface is improved, and deep part curability is improved. More preferably, it is 0.5-20 mass parts.

<(C) Inorganic filler>
Examples of the inorganic filler (C) used in the photosensitive resin composition of the present invention include titanium oxide, zinc oxide, basic lead carbonate, basic lead sulfate, lead sulfate, zinc sulfide, antimony oxide, aluminum hydroxide, Examples thereof include barium sulfate. Titanium oxide may be rutile titanium oxide or anatase titanium oxide, but rutile titanium oxide is preferably used. Anatase-type titanium oxide, which is the same titanium oxide, has higher whiteness compared to rutile-type titanium oxide and is often used as a white pigment. The emitted light may cause discoloration of the resin in the insulating resin composition. In contrast, rutile-type titanium oxide is slightly inferior to anatase-type in whiteness, but has almost no photoactivity, so that the resin is deteriorated by light due to the photoactivity of titanium oxide (yellowing). Is remarkably suppressed and is stable against heat. For this reason, when used as a white colorant in the insulating layer of the printed wiring board on which the LED is mounted, a high reflectance can be maintained for a long period of time.

  A well-known thing can be used as a rutile type titanium oxide. There are two types of production methods for rutile titanium oxide, a sulfuric acid method and a chlorine method. In the present invention, those produced by any of the production methods can be suitably used. Here, the sulfuric acid method uses ilmenite ore or titanium slag as a raw material, dissolves this in concentrated sulfuric acid, separates iron as iron sulfate, and hydrolyzes the solution to obtain a hydroxide precipitate. A production method in which rutile titanium oxide is taken out by baking at a high temperature. On the other hand, the chlorine method uses synthetic rutile or natural rutile as a raw material, reacts with chlorine gas and carbon at a high temperature of about 1000 ° C to synthesize titanium tetrachloride, and oxidizes this to extract rutile titanium oxide. Say. Among them, rutile-type titanium oxide produced by the chlorine method is particularly effective in suppressing the deterioration (yellowing) of the resin due to heat, and is more preferably used in the present invention.

  Further, titanium oxide whose surface is treated with hydrous alumina or aluminum hydroxide can also be used.

  Furthermore, although the titanium oxide may contain sulfur, the amount of sulfur is preferably 100 ppm or less, and more preferably 60 ppm or less. This is because when the sulfur amount is 100 ppm or less, discoloration of the peripheral portion due to the generated sulfur gas does not occur.

  Moreover, it is preferable to use barium sulfate from the viewpoints of suppressing discoloration, tack-free performance, anti-sagging effect, and excellent developability. However, it is preferable to add as an extender rather than as a colored pigment.

  The said inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the inorganic filler is not particularly limited, but is preferably 50 to 300 parts by mass, more preferably 70, based on 100 parts by mass of the carboxyl group-containing resin (A) having a styrene skeleton in terms of solid content. -250 parts by mass.

  In the present invention, an optical brightener can be further added. A fluorescent whitening agent is one that can increase the whiteness of the cured product of the composition and make it appear as if it is not discolored. In the present invention, in the photosensitive resin composition, it is possible to achieve high reflectance in the cured coating film by using a fluorescent whitening agent together with titanium oxide, particularly rutile type titanium oxide, among inorganic fillers. It becomes.

  The optical brightener absorbs light having a wavelength of 200 to 400 nm and emits light having a wavelength of 400 to 500 nm. Examples of such optical brighteners include benzoxazoyl derivatives, coumarin derivatives, styrene biphenyl derivatives, pyrazolone derivatives, bis (triazinylamino) stilbene disulfonic acid derivatives, and the like. Of these, benzoxazoyl derivatives are preferred. Moreover, as a substituent which a benzoxazoyl derivative has, butyl, octyl, naphthalene, thiophene, and stilbene are preferable.

(Thermosetting component)
Furthermore, a thermosetting component can be added to the photosensitive resin composition of the present invention. Examples of the thermosetting component used in the present invention include known and commonly used thermosetting resins such as polyfunctional epoxy compounds, blocked isocyanate compounds, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional oxetane compounds, and episulfide resins. Etc. Among these, a preferable 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.

There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.
Such a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule contains either one of the three-, four- or five-membered cyclic ether groups, or the cyclic thioether group or two kinds of groups in the molecule. A compound having two or more compounds includes, for example, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, that is, an episulfide resin.

  Further, the photosensitive resin composition of the present invention includes a plurality of isocyanate groups or blocked isocyanates in one molecule as a thermosetting component in order to improve the curability of the composition and the toughness of the resulting cured coating film. Compounds having groups can be added. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule. The compound which has, ie, a blocked isocyanate compound, etc. are mentioned.

  As said polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. 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- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; 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, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is.

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B- 846, B-870, B-874, B-882 (above, Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (above, Asahi Kasei Chemicals, trade name), etc. Can be mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be used alone or in combination of two or more.
The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass in terms of solid content with respect to 100 parts by mass of the carboxyl group-containing resin having the (A) styrene skeleton. 100 parts by mass, more preferably 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, the storage stability is good.

  Moreover, amino resins, such as a melamine derivative and a benzoguanamine derivative, can be added to the photosensitive resin composition of the present invention as a thermosetting component. Examples of such thermosetting components include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, methylol urea compounds, alkoxymethylated melamine compounds, alkoxymethylated benzoguanamine compounds, alkoxymethylated glycoluril compounds, and alkoxymethylated ureas. Compound etc. are mentioned. The type of the alkoxymethyl group is not particularly limited, and for example, it can be a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less. The said thermosetting component may be used individually by 1 type, and may be used in combination of 2 or more type.

  Commercially available products of these thermosetting components include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202. 1156, 1158, 1123, 1170, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw-750LM (made by Sanwa Chemical Co., Ltd.).

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epoto YD-011, YD- manufactured by Tohto Kasei Co., Ltd. 013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Mitsubishi Chemical, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., manufactured by Dow Chemical Of D. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, NC-3000, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd., A.C. E. R. ECN-235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704 YDCN- manufactured by Nippon Steel Chemical Co., Ltd. Novolak type epoxy resins such as 704A, Epicron N-680, N-690, N-695 (all trade names) manufactured by DIC; Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd. Bisphenol F type epoxy resin such as YDF-170, YDF-175, YDF-2004, etc. (all trade names); Hydrogenation of Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Toto Kasei Co., Ltd. Bisphenol A type epoxy resin; jER604 manufactured by Mitsubishi Chemical Co., Ltd. Epototo YH-434 manufactured by Toto Kasei Co., Ltd. Glycidylamine type epoxy resin such as Sumi-epoxy ELM-120 manufactured by Tomo Chemical Industry Co., Ltd. (all trade names); Hydantoin type epoxy resin; Cycloside 2021 manufactured by Daicel Co., Ltd. (all trade names) and alicyclic epoxy resins YL-933 manufactured by Mitsubishi Chemical Corporation, T.M. manufactured by Dow Chemical Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name) and other bisphenol S type epoxy resins; Bisphenol A novolac type epoxy resin such as jER157S (trade name); tetraphenylolethane type epoxy resin such as jERYL-931 (all trade name) made by Mitsubishi Chemical; TEPIC made by Nissan Chemical Industries (all) Product name) heterocyclic epoxy resin; Niguri such as Bremer DGT manufactured by NOF Corporation Zylphthalate resin; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Naphthalene group-containing epoxy resin; epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by NOF Corporation; Further, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; a CTBN-modified epoxy resin (for example, YR-102, YR-450, etc., manufactured by Tohto Kasei Co., Ltd.), and the like, are not limited thereto. Among these, bisphenol A type epoxy resin, heterocyclic epoxy resin, bixylenol type epoxy resin or a mixture thereof is particularly preferable.
These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The compounding amount of the epoxy resin is preferably 0.3 to 2.5 equivalents, more preferably 0.5 to 2.1, with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin having the (A) styrene skeleton. It is a range that becomes 0 equivalent. When the compounding amount of thermosetting component having two or more cyclic (thio) ether groups in the molecule, especially epoxy resin is 0.3 or more, the carboxyl group hardly remains in the solder resist film, and the heat resistance, alkali resistance, electricity Insulation properties are improved. On the other hand, when the amount is 2.5 equivalents or less, the low molecular weight cyclic (thio) ether group hardly remains in the dry coating film, and the strength of the coating film is improved.

(Antioxidant)
In order to prevent oxidation, the photosensitive resin composition of the present invention decomposes the generated radical scavenger or the generated peroxide into a harmless substance so as not to generate new radicals. Antioxidants such as peroxide decomposers can be included. The antioxidant used in the present invention can prevent oxidative deterioration of a resin or the like and further suppress yellowing. In addition to the above effects, addition of an antioxidant improves the process margin in the preparation of the photosensitive resin composition, such as prevention of halation due to the photocuring reaction of the photosensitive resin composition and stabilization of the opening shape. Is possible. An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of the antioxidant acting as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2 -Methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2 , 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4-hydroxybenzyl)- Phenol compounds such as S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetrame -4-piperidyl) - sebacate, and the like amine compounds such as phenothiazine. Examples of commercially available products include ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (and above, ADEKA). IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (trade name, manufactured by BASF Japan) and the like.

  Examples of the antioxidant acting as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3′-thiodipro Sulfur compounds such as pionate can be mentioned. Examples of commercially available products include ADK STAB TPP (trade name, manufactured by ADEKA), Mark AO-412S (trade name, manufactured by ADEKA), and Sumilizer TPS (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

  The blending amount when the antioxidant is used is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin having the styrene skeleton (A) in terms of solid content. 01-5 mass parts is more preferable. When the blending amount of the antioxidant is 0.01 parts by mass or more, the above-described effect of adding the antioxidant is easily obtained. On the other hand, when the amount is 10 parts by mass or less, inhibition of photoreaction, poor development with respect to an alkaline aqueous solution, deterioration of dryness to touch and deterioration of physical properties of the coating film can be suppressed.

  In addition, since the above-mentioned antioxidants, particularly phenolic antioxidants, may exhibit further effects when used in combination with a heat stabilizer, a heat stabilizer is added to the photosensitive resin composition of the present invention. May be.

  Examples of the heat stabilizer include phosphorus, hydroxylamine, and sulfur heat stabilizers. Examples of commercially available 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 (above, manufactured by BASF Japan Ltd., trade name). The said heat stabilizer may be used individually by 1 type, and may use 2 or more types together.

  The blending amount in the case of using a heat resistance stabilizer is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin having a styrene skeleton in terms of solid content. -5 mass parts is more preferable.

(Photoinitiator or sensitizer)
In addition to the photopolymerization initiator, in the photosensitive resin composition of the present invention, a photoinitiator assistant or a sensitizer can 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 in some cases, but are preferably used in combination with a photopolymerization initiator. Moreover, a photoinitiator auxiliary or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

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

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

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

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

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

  Examples of the benzophenone compound include benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4′-methyl diphenyl sulfide, 4-benzoyl-4′-ethyl diphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide, and the like. .

Examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nissoure (registered trademark) MABP manufactured by Nippon Soda Co., Ltd.), 4,4 Dialkylaminobenzophenone such as' -diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethyl Aminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Nippon Kayaku Co., Ltd. Kayacure DMBI), 4-dimethylaminobenzoic acid 2-ethylhexyl ( Examples include Esolol 507) manufactured by VanDyk. As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.
As the dialkylaminobenzophenone compound, 4,4′-diethylaminobenzophenone is preferable because of its low toxicity. Dialkylamino group-containing coumarin compounds have a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, so they are less colored, and use colored pigments as well as colorless and transparent photosensitive compositions, and colors that reflect the color of the colored pigments themselves It becomes possible to obtain a solder resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, by including a thioxanthone compound, it is possible to improve deep curability.

  As a compounding quantity when using a photoinitiator adjuvant or a sensitizer, it is 0.1-20 mass parts with respect to 100 mass parts of carboxyl group-containing resin which has the said (A) styrene skeleton in conversion of solid content. It is preferable. When the blending amount of the photoinitiator auxiliary or sensitizer is 0.1 parts by mass or more, a good sensitizing effect can be obtained. On the other hand, in the case of 20 parts by mass or less, light absorption on the surface of the coating film by the tertiary amine compound does not become too large, and the deep part curability is improved. More preferably, it is 0.1-10 mass parts.

  The total amount of the photopolymerization initiator, photoinitiator assistant, and sensitizer may be 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. preferable. In the case of 35 parts by mass or less, it is possible to suppress a decrease in deep part curability due to light absorption.

  In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, in some cases, the sensitivity is lowered, and the photopolymerization initiator, the photoinitiator assistant, and the sensitizer may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.

(Chain transfer agent)
In the photosensitive resin composition of the present invention, known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as chain transfer agents in order to improve sensitivity. Examples of chain transfer agents include chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol Chain transfer agents having a hydroxyl group such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylenediene), mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; Oxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanthi Lumpur, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

A polyfunctional mercaptan-based compound can also be used as a chain transfer agent. Examples of the polyfunctional mercaptan compound include aliphatic thiols such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide, xylylene dimercaptan, 4,4. Aromatic thiols such as' -dimercaptodiphenyl sulfide, 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate) , Trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), dipenta Poly (mercaptoacetate) polyhydric alcohols such as erythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3- Mercaptopropionate), glycerol tris (3-mercaptopropionate), trimethylol ethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) And poly (3-mercaptopropionate) of polyhydric alcohols such as dipentaerythritol hexakis (3-mercaptopropionate); 1,4-bis (3-mercaptobutyryl) Xyl) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-merta And poly (mercaptobutyrate) such as ptobutyrate).
Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, and Karenz -NR1 (above, Showa Denko Co., Ltd.) etc. can be mentioned.

  Moreover, the heterocyclic compound which has a mercapto group as a chain transfer agent can also be used. Examples of the heterocyclic compound having a mercapto group include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto-4-ethyl-4. -Butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl- 2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto- 4-butyrolactam, 2-mercapto-5-valerolactone, 2-mercap -5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 3-mercapto-4-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 Kasei Co., Ltd .: trade name Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (Sankyo Kasei Co., Ltd .: trade name Gisnet DB) and 2-anilino-4,6-dimercapto-s-triazine (Sankyo Kasei Co., Ltd .: trade name Gisnet AF).

  In particular, since the developability of the photosensitive resin composition is not impaired, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4- Thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole is preferred. These chain transfer agents may be used individually by 1 type, and may use 2 or more types together.

(Urethane catalyst)
A urethanization catalyst can be added to the photosensitive resin composition of the present invention in order to accelerate the curing reaction of hydroxyl groups, carboxyl groups and isocyanate groups. As the urethanization catalyst, it is preferable to use one or more urethanization catalysts selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and amine salts.

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

  The metal chloride is a metal chloride composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, ferrous nickel chloride, and ferric chloride.

  The metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, etc. Is mentioned.

  The metal sulfate is a metal sulfate composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include copper sulfate.

  Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′. , N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N'- (2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) ) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N', N ", N" -tetramethyldiethylenetriamine, N, N, N'-trimethyl -N '-(2-hydroxyethyl) propanediamine, N-methyl-N'-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) Isopropanolamine, 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1 -(2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imida 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′- Aminopropyl) -2-methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxy) Ethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ′, Examples thereof include N'-bis (2-hydroxypropyl) amine, melamine and / or benzoguanamine.

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

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

(Thermosetting catalyst)
When using the said epoxy resin and the thermosetting component which has a some cyclic | annular (thio) ether group in a molecule | numerator, 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, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, the present invention is not limited to these, and any epoxy resin or oxetane compound thermosetting catalyst, or any one that promotes the reaction of a carboxyl group with at least one of an epoxy group and an oxetanyl group, alone or 2 A mixture of seeds or more may be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

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

(Adhesion promoter)
In the photosensitive resin composition of the present invention, an adhesion promoter can be used to improve adhesion between layers or adhesion between the photosensitive resin layer and the substrate. Examples of the adhesion promoter include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Co., Ltd.), 3-morpholino. Methyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group Examples thereof include benzotriazole and silane coupling agents.

(Coloring agent)
The photosensitive resin composition of the present invention can contain a colorant. As the colorant to be used, conventionally known colorants such as red, blue, green, yellow, and white can be used, and any of pigments, dyes, and pigments may be used. As a specific example, the following color index (CI; issued by The Society of Dyers and Colorists) numbers can be given. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

Red colorant:
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and 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.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:
Blue colorants include phthalocyanine and anthraquinone, and pigments are compounds classified as Pigment, specifically: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.
The dye systems 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, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
Moreover, a blue inorganic pigment can also be used suitably. Examples of blue inorganic pigments include
Ultramarine Blue (Color Index Generic Name: Pigment Blue 29), French Ultramarine, Lapis Lazuli, Azurite, Prussian Blue (Prussia Blue; Color Index Name: Pigment Blue 27);
Blue complex oxide pigments such as aluminum-cobalt oxide, aluminum-zinc-cobalt oxide, silicon-cobalt oxide and silicon-zinc-cobalt oxide;
Smalto (color index name: Pigment Blue 32), cobalt blue (cobalt aluminate; color index name: Pigment Blue 28), cobalt stannate (color index name: Pigment Blue 35), cobalt chrome blue (color index name: Pigment Blue) 36), cobalt-aluminum-silicon oxide, cobalt zinc silicate (color index name: Pigment Blue 74), cobalt-zinc-silicon oxide (composition formula: CoO.Al ₂ O ₃ .SiO ₂ spinel), etc. A cobalt pigment etc. can be mentioned.
In addition, pigments containing silicate such as particles in which natural mica is coated with titanium oxide can also be used. The chemical formula of natural mica is generally IM _2-3 □ _1-0 T ₄ O ₁₀ A ₂ (I is K, Na, Ca, optionally Ba, Rb, Cs, NH ₄ , M Are Al, Mg, Fe, Li, Ti, optionally Mn, Cr, Zn, V, □ are vacancies, T is Si, Al, Fe ³⁺ , optionally Be, B And A is OH, F, optionally Cl, O, S).

Green colorant:
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
Monoazo: 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: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
For example, 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, CI 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 And the like.

  The blending amount of the colorant (excluding the white colorant) is not particularly limited, but is preferably 0.01 to 100 parts by mass of the carboxyl group-containing resin having the (A) styrene skeleton in terms of solid content. 10 parts by mass, particularly preferably 0.1 to 5 parts by mass.

(Compound having an ethylenically unsaturated group (photosensitive monomer))
The photosensitive resin composition of the present invention may use a compound (photosensitive monomer) having one or more ethylenically unsaturated groups in the molecule. A compound having one or more ethylenically unsaturated groups in the molecule is photocured by irradiation with active energy rays to insolubilize or insolubilize the (A) carboxyl group-containing resin having a styrene skeleton in an alkaline aqueous solution. It will help. In particular, when a non-photosensitive carboxyl group-containing resin is used, it is preferable from the viewpoint of photocurability.

  Examples of the compound used as the photosensitive monomer include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like. . Specifically, 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; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like; Multivalent acrylates such as a peroxide adduct, a propylene oxide adduct, or an ε-caprolactone adduct; a polyvalent such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols Acrylates: glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; not limited to the above, polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, Polyacrylate polyol and other polyols are directly acrylated or urethane acrylated via diisocyanate Acrylates and melamine acrylates, and at least any one of each methacrylate corresponding to the acrylate.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. An epoxy urethane acrylate compound obtained by reacting a half urethane compound may be used as a photosensitive monomer. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding amount of the compound having one or more ethylenically unsaturated groups in the molecule used as the photosensitive monomer is preferably 100 parts by mass of the carboxyl group-containing resin having the (A) styrene skeleton in terms of solid content. The proportion is 5 to 100 parts by mass, more preferably 5 to 70 parts by mass. When the said compounding quantity is 5 mass parts or more, photocurability is favorable and pattern formation becomes easy by the alkali image development after active energy ray irradiation. On the other hand, when the amount is 100 parts by mass or less, the dryness to touch (tack-free performance) is good, and the resolution is also good.

(Organic solvent)
Furthermore, the photosensitive resin composition of the present invention is organic for the synthesis of the carboxyl group-containing resin having the styrene skeleton and the preparation of the composition, or for the preparation of the viscosity for application to a substrate or a carrier film. Solvents can be used.
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; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.

(UV absorber)
In general, the polymer material absorbs light and thereby decomposes and deteriorates. Therefore, the photosensitive resin composition of the present invention includes, in addition to the above antioxidant, in order to take a countermeasure against stabilization against ultraviolet rays. UV absorbers can be used.

  Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone. Is mentioned. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

Commercially available UV absorbers include, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, BASF Japan, product name) and the like.
Said ultraviolet absorber may be used individually by 1 type, and may be used in combination of 2 or more type. By using together with the antioxidant, the cured product obtained from the photosensitive resin composition of the present invention can be stabilized.

(Additive)
The photosensitive resin composition of the present invention may further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc., if necessary. As the thixotropic agent, organic bentonite and hydrotalcite are preferable because of excellent stability over time, and hydrotalcite is particularly preferable because of excellent electrical characteristics. Also, thermal polymerization inhibitors, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, rust-preventing agents, and bisphenol-based, triazinethiol-based copper damage preventing agents, etc. The known and conventional additives such as can be blended.

  The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization 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-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and 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 particularly useful as a material for 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. When used as a liquid, it may be one-component or two-component or more. In particular, it is preferable to use two liquids from the viewpoint of storage stability. When two liquids are used, when (A) a carboxyl group-containing resin having a styrene skeleton used in the present invention is used, (B) a photopolymerization initiator and (C) an inorganic filler are combined with (A) a carboxyl having a styrene skeleton. You may mix | blend with the same formulation as group-containing resin, or you may mix | blend with a different formulation. In particular, it is preferable to blend (B) a photopolymerization initiator in the same preparation.

The dry film of the present invention is obtained by coating and drying the photosensitive resin composition of the present invention on a film (carrier film), and comprises a carrier film and a photosensitive resin composition formed on the carrier film. A layer.
In forming a dry film, the photosensitive resin composition of the present invention is diluted with the above organic solvent to an appropriate viscosity, and then a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater. The film can be obtained by applying a uniform thickness on a support with a spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

  As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

After the film is formed on the carrier film, it is desirable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the 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, and when the cover film is peeled off, the adhesive strength between the film and the support is more than What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

  The cured film of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method. A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. and performing volatile drying (temporary drying). In the case of a dry film obtained by applying the above composition on a carrier film and drying and winding it as a film, after laminating the photosensitive resin composition layer on the base material so as to come into contact with the base material The resin insulating layer can be formed by peeling off the carrier film.

  Thereafter, by a contact method (or non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3). The resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution. Further, in the case of a composition containing a thermosetting component, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the above-mentioned (A) carboxyl group-containing resin having a styrene skeleton, and epoxy A cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics can be formed by reaction with a resin and a thermosetting component. Even if it does not contain a thermosetting component, the heat treatment causes the ethylenically unsaturated bond remaining in an unreacted state to undergo thermal radical polymerization, improving the coating film characteristics. Further, heat treatment (thermosetting) may be performed.

  Examples of the base material include printed circuit boards and flexible printed circuit boards in which circuits are formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber. Copper graded laminates of all grades (FR-4 etc.) using materials such as epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc. Examples thereof include a polyimide film, a PET film, a glass substrate, a ceramic substrate, and a wafer plate.

Volatile drying performed after the photosensitive resin composition of the present invention is applied may be performed by using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a steam-heated heat source in the dryer. Can be carried out by using a counter-current contact method and a method of spraying a nozzle on a support.
The photosensitive resin composition is applied and exposed (active energy ray irradiation) to the coating film obtained after volatilizing and drying the solvent, so that an exposed portion (a portion irradiated with the active energy ray) is obtained. Harden.

As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, and the like may be used as long as the apparatus irradiates ultraviolet rays in a range of 350 to 450 nm. Furthermore, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. As a laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure amount for image formation varies depending on the film thickness and the like, but is generally 20 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .

  The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In the following, “parts” and “%” are based on mass unless otherwise specified.

[Synthesis of Resin Solution 1]
A pressure vessel equipped with a thermometer, a condenser, and a stirrer was charged with 200 parts by mass of deionized water and 0.3 parts by mass of sodium sulfate, and dissolution was confirmed.
Thereafter, BPO (benzoyl peroxide) as a polymerization initiator: 5 parts by mass and MSD (α-methylstyrene dimer) as a chain transfer agent: 5 parts by mass MMA (methyl methacrylate): 10.4 parts by mass, n-BA ( Normal-butyl acrylate): 5 parts by mass, MAA (methacrylic acid): 24.6 parts by mass, and St (styrene): 60 parts by mass The monomer mixture was sufficiently dissolved.
Thereafter, a dispersant was added to a concentration of 300 ppm, and the mixture was sufficiently stirred. After replacing the inside of the kettle with nitrogen, the temperature was raised and suspension polymerization was performed.
After completion of the polymerization, the obtained suspension was filtered with a mesh having an opening of 30 μm and dried with hot air at 40 ° C. to obtain a granular resin. Resin solution 1 is obtained by sufficiently dissolving the granular resin (copolymer resin) thus obtained using an organic solvent DPM (dipropylene glycol methyl ether) so that the solid concentration is 50% by mass. To do. The solid content acid value was 160 mgKOH / g.

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

[Synthesis of Resin Solution 3]
A granular resin was obtained in the same manner as in the resin solution 1 except that 5 parts by mass of BPO was changed to 1.5 parts by mass and 5 parts by mass of MSD was changed to 1.0 parts by mass. Resin solution 3 is obtained by sufficiently dissolving the granular resin (copolymer resin) thus obtained using an organic solvent DPM (dipropylene glycol methyl ether) so that the solid concentration is 50% by mass. To do. The solid content acid value was 160 mgKOH / g.

[Synthesis of Resin Solution 4]
Deionized water: 145 parts by mass and sodium sulfate: 0.3 parts by mass were charged in a pressure vessel equipped with a thermometer, a condenser, and a stirrer, and dissolution was confirmed.
Thereafter, t-butyl peroxy-2-ethylhexanate (Perbutyl O manufactured by NOF Corporation) as a polymerization initiator: 5 parts by mass and MSD (α-methylstyrene dimer) as a chain transfer agent: 4.5 parts by mass (Methyl methacrylate): 45.5 parts by mass, n-BA (normal-butyl acrylate): 6 parts by mass, MAA (methacrylic acid): 18.5 parts by mass and St (styrene): 30 parts by mass Added to the monomer mixture and fully dissolved.
Thereafter, a dispersant was added so as to have a concentration of 500 ppm, the mixture was sufficiently stirred, the inside of the kettle was replaced with nitrogen, the temperature was raised, and suspension polymerization was performed.
After completion of the polymerization, the obtained suspension was filtered with a mesh having an opening of 30 μm and dried with hot air at 40 ° C. to obtain a granular resin. Resin solution 4 is obtained by sufficiently dissolving the granular resin (copolymer resin) thus obtained using an organic solvent DPM (dipropylene glycol methyl ether) so that the solid concentration is 50% by mass. To do. The solid content acid value was 120 mgKOH / g.

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

[Synthesis of Resin Solution 6]
A thermometer, a condenser, and a stirrer were charged into a separable flask with 145 parts by mass of deionized water and 0.3 part by mass of sodium sulfate, and dissolution was confirmed.
Thereafter, AMBN (2,2′-azobis (2-methylbutyronitrile)): 0.3 parts by mass as a polymerization initiator and n-DM (n-dodecyl mercaptan): 4 parts by mass as MMA (methacrylic acid) as a chain transfer agent. Methyl acid): 55.5 parts by mass, n-BA (normal butyl acrylate): 6 parts by mass, MAA (methacrylic acid): 18.5 parts by mass and St (styrene): 20 parts by mass Added to the mixture and dissolved well.
Thereafter, a dispersant was added so as to have a concentration of 500 ppm, the mixture was sufficiently stirred, the inside of the kettle was replaced with nitrogen, the temperature was raised, and suspension polymerization was performed.
After completion of the polymerization, the obtained suspension was filtered with a mesh having an opening of 30 μm and dried with hot air at 40 ° C. to obtain a granular resin. Resin solution 6 is obtained by sufficiently dissolving the granular resin (copolymer resin) thus obtained using an organic solvent DPM (dipropylene glycol methyl ether) so that the solid content concentration becomes 50 mass%. To do. The solid content acid value was 120 mgKOH / g.

[Synthesis of Resin Solution 7]
In a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution and a stirrer, MAA (methacrylic acid): 42 parts by mass, MMA (methyl methacrylate): 43 parts by mass, styrene: 35 parts by mass, Benzyl acrylate: 35 parts by mass, carbitol acetate: 100 parts by mass, MSD (α-methylstyrene dimer): 0.5 part by mass as a chain transfer agent and azobisisobutyronitrile: 4 parts by mass are added under nitrogen flow The polymerization reaction was allowed to proceed by heating at 75 ° C. for 5 hours to obtain a copolymer solution (solid content concentration 50 mass%). Hydroquinone: 0.05 parts by mass, glycidyl methacrylate: 23 parts by mass, and dimethylbenzylamine: 2.0 parts by mass were added thereto, and after addition reaction at 80 ° C. for 24 hours, carbitol acetate: 35 parts by mass was added. In addition, a copolymer resin solution (resin solution 7) having an aromatic ring was obtained. The copolymer resin solution (resin solution 7) thus obtained had a solid content concentration of 50 mass% and an acid value of solid content of 80 mgKOH / g.

[Synthesis of Resin Solution 8]
A pressure vessel equipped with a thermometer, a condenser tube, and a stirrer was charged with 50 parts by mass of DPM (dipropylene glycol methyl ether) and heated.
Thereafter, t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by NOF Corporation) as a polymerization initiator: 5 parts by mass of MMA (methyl methacrylate): 10.4 parts by mass, n-BA (normal-butyl acrylate): In addition to the monomer mixture consisting of 5 parts by mass, MAA (methacrylic acid): 24.6 parts by mass and St (styrene): 60 parts by mass, the mixture is sufficiently dissolved and the pressure vessel is heated to a predetermined temperature, and then a single amount The body mixture was dropped into the container to perform solution polymerization.
After completion of the polymerization, the mixture was filtered through a mesh having an opening of 5 μm to obtain a resin solution. The resin solution (copolymer resin) thus obtained was sufficiently dissolved using an organic solvent DPM (dipropylene glycol methyl ether) so as to have a solid content concentration of 50% by mass. To do. The solid content acid value was 160 mgKOH / g.

[Synthesis of Resin Solution 9]
A granular resin was obtained in the same manner as the resin solution 1 except that 5 parts by mass of BPO was changed to 1.0 part by mass and 5 parts by mass of MSD was changed to 1.0 part by mass. The resin solution (copolymer resin) thus obtained was sufficiently dissolved using an organic solvent DPM (dipropylene glycol methyl ether) so as to have a solid content concentration of 50% by mass. To do. The solid content acid value was 160 mgKOH / g.

[Synthesis of Resin Solution 10]
A granular resin was obtained in the same manner as the resin solution 4 except that MMA: 45.5 parts by mass was changed to 48.6 parts by mass, and MAA: 18.5 parts by mass was changed to 15.4 parts by mass. The resin solution (copolymer resin) thus obtained was sufficiently dissolved using an organic solvent DPM (dipropylene glycol methyl ether) so that the solid content concentration was 50% by mass. To do. The solid content acid value was 70 mgKOH / g.

[Synthesis of Resin Solution 11]
A separable flask equipped with a thermometer, a condenser, and a stirrer was charged with 145 parts by weight of deionized water and 0.3 parts by weight of sodium sulfate, and dissolution was confirmed.
Thereafter, AMBN (2,2′-azobis (2-methylbutyronitrile)): 0.5 part by mass as a polymerization initiator and MSD (α-methylstyrene dimer): 3 parts by mass of MMA (methacrylic acid) as a chain transfer agent Methyl): 75.5 parts by mass, n-BA (normal-butyl acrylate): 6 parts by mass, MAA (methacrylic acid): 18.5 parts by mass.
Thereafter, a dispersant was added so as to have a concentration of 400 ppm, the mixture was sufficiently stirred, the inside of the kettle was replaced with nitrogen, the temperature was raised, and suspension polymerization was performed.
After completion of the polymerization, the obtained suspension was filtered with a mesh having an opening of 30 μm and dried with hot air at 40 ° C. to obtain a granular resin. The resin solution (copolymer resin) thus obtained was sufficiently dissolved using an organic solvent DPM (dipropylene glycol methyl ether) so as to have a solid content concentration of 50% by mass. To do. The solid content acid value was 120 mgKOH / g.

[Synthesis of Resin Solution 12]
In a 2 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy-2-ethylhexanate (as a polymerization initiator) 21.4 g of NOF Corporation Perbutyl O) was added and heated to 90 ° C. After heating, MAA (methacrylic acid): 309.9 g, MMA (methyl methacrylate): 116.4 g, and caprolactone-modified 2-hydroxyethyl methacrylate (Placcel FM1 manufactured by Daicel Corporation): 109.8 g Bis (4-t-butylcyclohexyl) peroxydicarbonate as a polymerization initiator (Perroyl TCP manufactured by NOF Corporation): 21.4 g added dropwise over 3 hours, and further aged for 6 hours, A carboxyl group-containing copolymer resin was obtained. The reaction was performed under a nitrogen atmosphere.
Next, to the obtained carboxyl group-containing copolymer resin, 3,4-epoxycyclohexylmethyl acrylate (Cyclomer M100 manufactured by Daicel Corporation): 363.9 g, dimethylbenzylamine: 3.6 g as a ring-opening catalyst, polymerization Hydroquinone monomethyl ether: 1.80 g was added as an inhibitor, heated to 100 ° C., and stirred to carry out epoxy ring-opening addition reaction. After 16 hours, a resin solution 12 containing 50% by mass (non-volatile content) of a carboxyl group-containing resin having no aromatic ring and having an acid value of solid content of 108.9 mgKOH / g and a weight average molecular weight of 25,000 was obtained. .

<Preparation of photosensitive resin compositions of Examples 1 to 4, Comparative Examples 1 to 5 and Reference Examples 1 to 8>
The components shown in Tables 1 and 2 below were blended in the proportions (parts by mass) shown in the tables, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a photosensitive resin composition.

＊１：樹脂溶液１
（スチレン骨格含有量／酸価／重量平均分子量＝６０（モル％）／１６０（ｍｇＫＯＨ／ｇ）／１００００）（以下、単位は略する）
＊２：樹脂溶液２
（スチレン骨格含有量／酸価／重量平均分子量＝６０／１６０／１５０００）
＊３：樹脂溶液３
（スチレン骨格含有量／酸価／重量平均分子量＝６０／１６０／５００００）
＊４：樹脂溶液４
（スチレン骨格含有量／酸価／重量平均分子量＝３０／１２０／２００００）
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（スチレン骨格含有量／酸価／重量平均分子量＝３０／２００／２００００）
＊６：樹脂溶液６
（スチレン骨格含有量／酸価／重量平均分子量＝２０／１２０／１５０００）
＊７：樹脂溶液７
（スチレン骨格含有量／酸価／重量平均分子量＝２０／８０／１５０００）
＊８：樹脂溶液８
（スチレン骨格含有量／酸価／重量平均分子量＝６０／１６０／８０００）
＊９：樹脂溶液９
（スチレン骨格含有量／酸価／重量平均分子量＝６０／１６０／６５０００）
＊１０：樹脂溶液１０
（スチレン骨格含有量／酸価／重量平均分子量＝３０／７０／２００００）
＊１１：樹脂溶液１１
（スチレン骨格含有量／酸価／重量平均分子量＝０／１２０／１５０００）
＊１２：樹脂溶液１２
（スチレン骨格含有量／酸価／重量平均分子量＝（０／１０８．９／２５０００）
＊１３：ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド（ＢＡＳＦジャパン社製イルガキュア８１９）
＊１４：α−アミノアセトフェノン系光重合開始剤（ＢＡＳＦジャパン社製イルガキュア９０７）
＊１５：２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド（ＢＡＳＦジャパン社製イルガキュアＴＰＯ）
＊１６：Ｃ−１ ルチル型酸化チタン（デュポン（株）社製タイピュアＲ−９３１）
＊１７：Ｃ−２ 水酸化アルミニウム（昭和電工（株）社製Ｈ−４２Ｍ（比重：２．４））
＊１８：Ｃ−３ 硫酸バリウム（堺化学工業（株）社製Ｂ−３０）
＊１９：消泡剤（信越化学工業（株）社製ＫＳ−６６）
＊２０：熱硬化触媒（メラミン）
＊２１：熱硬化触媒（ＤＩＣＹ（ジシアンジアミド））
＊２２：ｊＥＲ８２８（ビスフェノールＡ型エポキシ樹脂、三菱化学（株）社製）
＊２３：ＩＲＧＡＮＯＸ１０１０（フェノール系酸化防止剤、ＢＡＳＦジャパン社製）
＊２４：ＤＰＨＡ（ジペンタエリスリトールヘキサアクリレート、日本化薬（株）社製）
＊２５：有機溶剤（ＤＰＭ（ジプロピレングリコールメチルエーテル））

* 1: Resin solution 1
(Styrene skeleton content / acid value / weight average molecular weight = 60 (mol%) / 160 (mg KOH / g) / 10000) (hereinafter, units are omitted)
* 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
(Styrene skeleton content / 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 manufactured by BASF Japan)
* 14: α-aminoacetophenone 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 (Typure R-931, manufactured by DuPont)
* 17: C-2 aluminum hydroxide (H-42M (specific gravity: 2.4) manufactured by Showa Denko KK)
* 18: C-3 barium sulfate (B-30 manufactured by Sakai Chemical Industry Co., Ltd.)
* 19: Antifoaming agent (KS-66 manufactured by Shin-Etsu Chemical Co., Ltd.)
* 20: Thermosetting catalyst (melamine)
* 21: Thermosetting catalyst (DICY (dicyandiamide))
* 22: jER828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation)
* 23: IRGANOX 1010 (phenolic antioxidant, manufactured by BASF Japan)
* 24: DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
* 25: Organic solvent (DPM (dipropylene glycol methyl ether))

(Evaluation method)
<Dry touch dryness>
The photosensitive resin compositions of Examples and Comparative Examples were each coated on a patterned copper foil substrate by screen printing, and (1) 15 minutes and (2) 30 minutes in an 80 ° C. hot air circulation drying oven. Each was dried and allowed to cool to room temperature. A PET film was pressed against this substrate, and then the sticking state of the film when the negative film was peeled off was evaluated. The obtained results are shown in Tables 3 and 4 below.
A: There is no stickiness.
○: There is no stickiness.
Δ: Some stickiness.
X: There is stickiness.

<Change in reflectance and discoloration>
The photosensitive resin composition of each example and comparative example was applied on the entire surface of the patterned copper foil substrate by screen printing so that the dry film thickness was 20 μm, dried at 80 ° C. for 30 minutes, and brought to room temperature. Allowed to cool. After exposing the pattern with an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp on this substrate, development was performed for 90 seconds under a spray pressure of 0.2 MPa with a 1 mass% sodium carbonate aqueous solution at 30 ° C. Got a pattern. This substrate was cured by heating at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a cured product pattern was formed.

About the obtained evaluation board, using Konica Minolta Co. color difference meter CR-400, the initial value of the Y value of the XYZ color system at a wavelength of 360 to 740 nm, and L ^* a ^* b ^* L ^{* of the} color system , A ^* , b ^* initial values were measured. Thereafter, the evaluation substrate was subjected to light irradiation treatment or heat treatment as described below, and then each value was measured again with a color difference meter CR-400 manufactured by Konica Minolta Co., Ltd., and the change in Y value and ΔE ^* ab From the above, changes in reflectance and discoloration were evaluated. The judgment criteria are as follows. The obtained results are shown in Tables 3 and 4 below.
Change in reflectance:
A: Y value reduction rate is less than 5% B: Y value reduction rate is 5% or more and less than 10% X: Y value reduction rate is 10% or more
◎: ΔE ^* ab is less than 3 ○: ΔE ^* ab is 3 or more and less than 5 ×: ΔE ^* ab is 5 or more

In addition, Y value shows a high reflectance, so that a numerical value is large. ΔE ^* ab is the difference between the initial value and each processed value in the L ^* a ^* b ^* color system, and the larger the value, the greater the color change. The calculation formula of ΔE ^* 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 is, after each treatment, respectively L ^* , A ^* , b ^* values are represented.

Light irradiation treatment:
The evaluation substrate obtained above was accelerated and deteriorated by irradiating with 100 J / cm ² of light in a UV conveyor furnace (output 150 W / cm, metal halide lamp cold mirror).

Heat treatment:
The evaluation board | substrate obtained above was set to 260 degreeC in accordance with the specification of IPC / JETEC J-STD-020, and 5 reflows were implemented. Here, 5 reflows means that the operation of passing through an infrared furnace at 260 ° C. for 10 seconds and returning to normal temperature was repeated 5 times.

<Sagging>
The sagging property was measured and evaluated as follows.
1. The photosensitive resin composition of each Example and a comparative example is dripped at a copper clad laminated board using a syringe.
2. The laminated board is leaned against the board rack, and a dummy board is installed on the front face of the laminated board so that the wind of the hot air circulation type drying furnace does not directly hit.
3. The laminated sheet is dried for 30 minutes in a hot air circulation drying oven set at 80 ° C. while standing on the substrate rack.
4). After drying, the length from the center to the bottom of the dried photosensitive resin composition is measured.
◎: Sagging length of 0 cm or more and less than 2 cm ○: Sagging length of 2 cm or more and less than 4 cm △: Sagging length of 4 cm or more and less than 6 cm ×: Sagging length of 6 cm or more The results obtained are shown in Table 3 below. 4 shows.

<Developability>
The photosensitive resin composition of each example and comparative example was applied on the entire surface of the patterned copper foil substrate by screen printing so that the dry film thickness was 20 μm, dried at 80 ° C. for 30 minutes, and brought to room temperature. Allowed to cool. This substrate was developed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. under the condition of a spray pressure of 0.2 MPa, the state of the residue was visually confirmed, and the development time during which no residue was produced was measured and evaluated. The obtained results are shown in Tables 3 and 4 below.
◎: 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, it has a styrene skeleton, a weight average molecular weight of 10,000 to 50,000, an acid value of 100 to 160 mgKOH / g, and a styrene skeleton ratio of 10 to 50 mol% in the molecule. In the composition of each example containing a carboxyl group-containing resin, a photopolymerization initiator, and a titanium oxide having a sulfur content of 100 ppm or less, the sensitivity and development are all compared to the comparative example. It was confirmed that the cured product was excellent in light irradiation of the cured product and excellent in suppression of a decrease in reflectance due to heat, and also excellent in dryness to touch, suppression of discoloration, and anti-sagging effect.

Claims (6)

(A) a photosensitive resin composition containing a carboxyl group-containing resin having a styrene skeleton, (B) a photopolymerization initiator, and (C) titanium oxide,
The weight average molecular weight of the (A) carboxyl group-containing resin having a styrene skeleton is 10,000 to 50,000, the acid value is 100 to 160 mgKOH / g, and the ratio of the styrene skeleton is 10 to 50 mol% in the molecule. ,
(C) the amount of sulfur contained in the titanium oxide is 100 ppm or less ,
(C) The photosensitive resin composition, wherein the titanium oxide is rutile titanium oxide .   2. The photosensitive resin composition according to claim 1, wherein the (A) carboxyl group-containing resin having a styrene skeleton has a weight average molecular weight of 10,000 to 15,000.   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 on a film.   A cured coating obtained by curing a photosensitive resin composition according to claim 1 or a dry film obtained by applying and drying the photosensitive resin composition according to claim 1 on a film. A printed wiring board comprising the cured film according to claim 5 .