JP5422319B2 - Photosensitive resin composition, dry film and cured product thereof, and printed wiring board using them - Google Patents

Description

  The present invention relates to a photosensitive resin composition that can be developed with an aqueous alkaline solution, in particular a composition for a solder resist that is photocured by ultraviolet exposure or laser exposure, a dry film and a cured product thereof, and a cured film formed using them. The present invention relates to a printed wiring board.

  At present, some consumer printed wiring boards and most industrial printed wiring board solder resists are imaged by developing after irradiation with ultraviolet rays from the viewpoint of high accuracy and high density, and heat and / or light. Liquid development type solder resist that is final-cured (main-cured) by irradiation is used. In consideration of environmental problems, alkali development type photo solder resists that use an alkaline aqueous solution as the developer are the mainstream. Used in large quantities in the manufacture of plates. In addition, solder resists are also required to have improved workability and high performance in response to the recent increase in the density of printed wiring boards as electronic devices become lighter, thinner and shorter.

  However, the current alkali development type photo solder resist still has problems in terms of durability. That is, the alkali resistance, water resistance, heat resistance and the like are inferior to those of conventional thermosetting type and solvent developing type. This is because the alkali-developable photo solder resist is mainly composed of a hydrophilic group in order to enable alkali development, and it is easy for chemicals, water, water vapor, etc. to permeate, resulting in reduced chemical resistance and resist film. This is thought to reduce the adhesion between copper and copper. As a result, the alkali resistance as chemical resistance is weak, and especially in semiconductor packages such as BGA (ball grid array) and CSP (chip scale package), PCT resistance (pressure cooker Test resistance) is necessary, but under such severe conditions, it is only several hours to several tens of hours. Further, in the HAST test (highly accelerated life test) in a state where a voltage is applied under humidification conditions, in most cases, a defect due to the occurrence of migration is confirmed within a few hours.

  In recent years, there is a tendency for the temperature applied to the package to become very high, such as the shift to surface mounting and the use of lead-free solder in consideration of environmental problems. Along with this, the reached temperature inside and outside of the package is remarkably high, and in the conventional liquid photosensitive resist, there is a problem that the coating film is cracked by thermal shock or peels off from the substrate and the sealing material, There is a need for improvement.

  On the other hand, as a carboxyl group-containing resin used for a conventional solder resist, an epoxy acrylate-modified resin derived by modification of an epoxy resin is generally used. For example, Japanese Patent Application Laid-Open No. 61-243869 (Patent Document 1) discloses a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, and a diluent. And a solder resist composition comprising an epoxy compound has been reported. Japanese Patent Laid-Open No. 3-250012 (Patent Document 2) adds (meth) acrylic acid to an epoxy resin obtained by reacting a reaction product of salicylaldehyde with a monohydric phenol with epichlorohydrin. Furthermore, a solder resist composition comprising a photosensitive resin obtained by reacting a polybasic carboxylic acid or an anhydride thereof, a photopolymerization initiator, an organic solvent and the like is disclosed. However, the carboxyl group-containing resins used in conventional solder resists have poor electrical characteristics.

JP 61-243869 (Claims) Japanese Patent Laid-Open No. 3-250012 (Claims)

The present invention has been made in view of the problems of the prior art as described above, and its main purpose is to have PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance, which are important as solder resists for semiconductor packages. It is providing the photosensitive resin composition which can form a cured film.
Furthermore, an object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a photosensitive resin composition, and a cured film such as a solder resist using the dry film and the cured product. It is in providing the printed wiring board formed by.

In order to achieve the above object, according to the present invention, one or more acrylamide groups or methacrylamide groups per molecule are added to a reaction product obtained by reacting a phenol resin with an alkylene oxide or a cyclocarbonate compound. A photosensitive resin capable of alkali development, comprising a carboxyl group-containing photosensitive resin obtained by reacting an isocyanate compound having a polybasic acid anhydride with the obtained reaction product, and a photopolymerization initiator. A functional resin composition is provided.
In a preferred embodiment, the alkylene oxide is ethylene oxide and / or propylene oxide, and the cyclocarbonate is preferably ethylene carbonate and / or propylene carbonate. The carboxyl group-containing resin preferably does not contain a hydroxyl group. In a preferred embodiment, the photosensitive resin composition of the present invention further contains a thermosetting component, preferably for a solder resist containing a colorant.

Furthermore, according to the present invention, a photosensitive dry film obtained by applying and drying the photosensitive resin composition on a carrier film, and the photosensitive resin composition or the dry film are photocured, preferably a wavelength of 350 nm. A cured product obtained by photocuring in a pattern with a light source of ˜410 nm is provided.
Furthermore, according to the present invention, the photosensitive resin composition or dry film is photocured in a pattern by irradiation with active energy rays, preferably by direct drawing of ultraviolet rays, and then cured by heat curing. Also provided is a printed wiring board having:

  The photosensitive resin composition of the present invention comprises, as a main component curable resin, a reaction product obtained by reacting a phenol resin and an alkylene oxide or a cyclocarbonate compound with one or more acrylamide groups or 1 molecule. It contains a carboxyl group-containing photosensitive resin obtained by reacting an isocyanate compound having a methacrylamide group (hereinafter collectively referred to as a (meth) acrylamide group) and reacting the resulting reaction product with a polybasic acid anhydride. Therefore, it is excellent in workability and developability, and the cured product can have high reliability when used for, for example, a printed wiring board or a semiconductor package. In the carboxyl group-containing photosensitive resin, the unsaturated group and the carboxyl group do not exist on the same chain and are located at the end of the side chain, so they have excellent reactivity and excellent alkali developability. it can.

In the suitable aspect of this invention, heat resistance is further provided to the cured coating film obtained by containing a thermosetting component further.
In a preferred embodiment of the carboxyl group-containing photosensitive resin of the present invention, the alkylene oxide is ethylene oxide and / or propylene oxide, or the cyclocarbonate is ethylene carbonate and / or propylene carbonate. The chain | strand of the containing photosensitive resin is extended, the flexibility of the cured coating film obtained can improve, and it can improve thermal shock resistance. Furthermore, in another preferred embodiment of the present invention, since the carboxyl group-containing photosensitive resin does not contain a hydroxyl group, the carboxyl group-containing photosensitive resin is excellent in moisture absorption resistance, and excellent cured PCT resistance can be obtained.

In addition, by using a dry film obtained by applying and drying the above-described photosensitive resin composition of the present invention on a carrier film, a resist layer can be easily formed on a substrate without applying a curable resin composition. can do.
Furthermore, the above-described photosensitive resin composition is applied on a substrate and cured by active energy ray irradiation and / or heating, or the above-described dry film is attached to the substrate, and activated energy ray irradiation and / or heating. By curing, a cured film having PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance, which is important as a solder resist for semiconductor packages, can be formed. For example, when used in electronic parts, it has high reliability. Can be obtained.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used the carboxyl group-containing photosensitive resin having a phenol resin as a starting material as the curable resin as the main component of the composition. The inventors have found that the object can be achieved and have completed the present invention. The carboxyl group-containing photosensitive resin used in the present invention is excellent in flexibility and elongation due to chain extension by addition reaction of a phenol resin and an alkylene oxide or cyclocarbonate compound, and is generated by addition reaction of an alkylene oxide or cyclocarbonate compound. The addition of an isocyanate compound having one or more (meth) acrylamide groups in one molecule to the terminal hydroxyl group and the addition of a polybasic acid anhydride are performed, and there is no unsaturated group or carboxyl group on the same side chain. And since it is located at the end of each side chain, it has excellent reactivity, and has excellent alkali developability due to the presence of a terminal carboxyl group away from the main chain. Furthermore, the (meth) acrylamide group generally has a feature that it is excellent in hydrolysis resistance as compared with the (meth) acrylate group. In addition, the resin is excellent in moisture absorption resistance because it is easy to design a molecule that does not have a hydrophilic alcoholic hydroxyl group with low reactivity. It is speculated that this point leads to an improvement in PCT resistance required for the IC package. Therefore, the photosensitive resin composition of the present invention containing a carboxyl group-containing photosensitive resin derived from the phenol resin obtained by the present invention, a photopolymerization initiator, or a thermosetting component, a colorant, etc., is used for semiconductor packages. It is possible to provide a solder resist film having PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance, which are important as a solder resist.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail.
First, the carboxyl group-containing photosensitive resin constituting the curable resin of the photosensitive resin composition of the present invention can be easily obtained by the following method.
(1) A reaction product obtained by reacting a phenol resin with an alkylene oxide is reacted with an isocyanate compound having one or more (meth) acrylamide groups in one molecule, and the resulting reaction product is polybasic. A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride.
(2) A reaction product obtained by reacting a phenol resin with a cyclocarbonate compound is reacted with an isocyanate compound having one or more (meth) acrylamide groups in one molecule, and the reaction product obtained is A carboxyl group-containing photosensitive resin obtained by reacting a basic acid anhydride.

  The carboxyl group-containing photosensitive resin used in the present invention uses a phenol resin as a starting material. A phenolic resin having almost no chloride ion impurities can be easily obtained. Therefore, the chlorine ion impurity content of the carboxyl group-containing photosensitive resin used in the present invention is 0 to 100 ppm, more preferably 0 to 50 ppm, and still more preferably 0 to 30 ppm.

  The carboxyl group-containing photosensitive resin used in the present invention is also characterized in that it is a resin that does not contain a hydroxyl group. In general, the presence of a hydroxyl group has excellent characteristics such as improved adhesion by hydrogen bonding, but it is known to significantly reduce moisture resistance. Since the carboxyl group-containing photosensitive resin of the present invention is a resin not containing a hydroxyl group, it is presumed that it exhibits excellent insulation reliability and PCT resistance.

  Furthermore, a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule may be reacted with the carboxyl group-containing photosensitive resin obtained by the methods (1) and (2). Examples of such compounds include glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, which has no reactivity or supply surface, further contains no chloride ion impurities, or has a very low content. 4-epoxycyclohexylmethyl methacrylate is preferred. In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  The addition amount of the compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule is preferably 5% equivalent to 40% equivalent to the carboxyl group of the carboxyl group-containing photosensitive resin. When the added amount is less than 5% equivalent, sufficient sensitivity increase and improvement in solder resist characteristics cannot be obtained. On the other hand, when it exceeds 40% equivalent, the maximum development life is shortened and the dry coating is touch-dried. This is not preferable because the properties deteriorate. A more preferable addition amount is 10% equivalent to 30% equivalent.

  Since the carboxyl group-containing photosensitive resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible. Moreover, the acid value of the said carboxyl group-containing photosensitive resin is the range of 30-150 mgKOH / g, More preferably, it is the range of 40-130 mgKOH / g. If the acid value of the carboxyl group-containing photosensitive resin is less than 30 mgKOH / g, alkali development becomes difficult. On the other hand, if it exceeds 150 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line may be thinner than necessary. In some cases, the exposed portion and the unexposed portion are not distinguished because they are dissolved and peeled off with a developer, and it becomes difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group-containing photosensitive resin changes with resin frame | skeleton, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  The blending amount of such a carboxyl group-containing photosensitive resin is desirably in the range of 20 to 60% by mass and preferably in the range of 30 to 50% by mass in the entire composition. When the amount is less than the above range, the coating strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity of the composition is increased or the coating property is lowered, which is not preferable.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran. Among these, ethylene oxide and propylene oxide are preferable from the viewpoints of price and supply system. Moreover, as a cyclocarbonate compound, a well-known and usual carbonate compound can be used, For example, ethylene carbonate, propylene carbonate, butylene carbonate, 2, 3-carbonate propyl methacrylate, etc. are mentioned. Among these, 5-membered ethylene carbonate and propylene carbonate are preferable from the viewpoints of reactivity and supply system. These alkylene oxides or cyclocarbonate compounds can be used alone or in admixture of two or more.

  The alkylene oxide or cyclocarbonate compound can be modified from a phenolic hydroxyl group to a resin having an alcoholic hydroxyl group by addition reaction with the phenolic hydroxyl group of the phenol resin using a basic catalyst. The addition amount at this time is desirably in the range of 0.3 to 10 mol, preferably in the range of 0.8 to 5 mol, more preferably in the range of 1.0 to 3 mol, per equivalent of the phenolic hydroxyl group. It is. When the addition amount is less than the above range, reaction with an isocyanate compound or polybasic acid anhydride having one or more (meth) acrylamide groups in one molecule, which will be described later, is difficult to occur, and it is soluble in photosensitivity and dilute alkaline aqueous solution. This is not preferable because the properties are lowered. On the other hand, when the addition amount exceeds the above range, the water resistance of the cured coating film is lowered due to the generated ether bond, which is not preferable because the electrical insulation property, HAST resistance and the like are lowered.

  The isocyanate compound having one or more (meth) acrylamide groups in one molecule may be a compound having one isocyanate group and one or more (meth) acrylamide groups in one molecule, and is particularly limited. Not. The isocyanate compound having a (meth) acrylamide group used in the present invention is excellent in adhesion and hydrolysis resistance, and further has excellent reactivity with respect to photopolymerization as in the case of (meth) acrylate. The isocyanate compound having one or more (meth) acrylamide groups in one molecule used in the present invention is composed of one hydroxyl group and one or more (meth) acrylamide groups in one molecule such as hydroxyalkyl (meth) acrylamide. The desired compound can be easily obtained by half-urethane formation using a compound having a diisocyanate such as isophorone diisocyanate, toluylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate or the like having no or very little chloride ion impurities. be able to. Examples of the compound having one hydroxyl group and one or more (meth) acrylamide groups in one molecule include hydroxyethyl acrylamide. These compounds can be used alone or in combination of two or more.

  Examples of the polybasic acid anhydride include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylene Alicyclic dibasic acid anhydrides such as tetrahydrophthalic anhydride and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride Aliphatic or aromatic dibasic acid anhydrides such as biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride Acid, benzophenone Aliphatic or aromatic tetrabasic acid dianhydrides such as tetracarboxylic dianhydride can be mentioned, and one or more of these can be used.

  The photopolymerization initiator is one or more selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. A photopolymerization initiator can be used.

（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、なしか、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、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。 Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, N-1919, NCI-831 manufactured by Adeka, and the like as commercially available products. 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, for example, alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, 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 methyl or phenyl, n is 0, and Ar is preferably phenylene, naphthylene or thienylene. .

  It is preferable that the compounding quantity of such an oxime ester photoinitiator shall be 0.01-5 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resin. When it is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated. On the other hand, when it exceeds 5 parts by mass, light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. 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. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

  The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. If it is less than 0.01 parts by mass, the photo-curability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5-10 mass parts.

  In addition, as a photopolymerization initiator, a photoinitiator assistant, and a sensitizer that can be suitably used for the photocurable resin composition of the present embodiment, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, Examples include benzophenone compounds, tertiary amine compounds, and xanthone compounds.

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

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

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

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

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

  Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.

  Specifically, as the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenone such as 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4- Dialkylamino group-containing coumarin compounds such as methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics) 4 Dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamylethyl ester (Nippon Kayaku Co., Ltd. Kayacure DMBI), 4-dimethylaminobenzoic acid Examples thereof include 2-ethylhexyl (Esolol 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like.

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability. Among them, it is preferable to include a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

  As a compounding quantity of such a thioxanthone compound, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of carboxyl group-containing photosensitive resin. When the blending amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.

  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 provide 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.

  As a compounding quantity of such a tertiary amine compound, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resin. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. When the amount exceeds 20 parts by mass, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1-10 mass parts.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. When it exceeds 35 parts by mass, the deep curability tends to decrease 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 initiators, photoinitiator assistants, and sensitizers may function as ultraviolet absorbers. 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 enhance the photoreactivity of the surface, and changes the resist line shape and opening to vertical, tapered, and inversely tapered, and processing accuracy of line width and opening diameter Can be improved.

  Furthermore, a conventionally known carboxyl group-containing photosensitive resin may be added to the photosensitive resin composition of the present invention for the purpose of improving photosensitivity, developability, heat resistance, and electrical characteristics. As specific examples of the carboxyl group-containing photosensitive resin, the following compounds (any of oligomers and polymers) are preferable.

  (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. A carboxyl group-containing photosensitive resin obtained by reacting a compound having one or more ethylenically unsaturated groups and one epoxy group in a molecule.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin obtained by polyaddition reaction of diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups. During synthesis, a compound having one hydroxyl group and one or more (meth) acryl groups in the molecule such as hydroxyalkyl (meth) acrylate is added. (Meth) acrylated carboxyl group-containing photosensitive urethane resin.

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

  (4) During the synthesis of the resin of (3) above, a compound having one hydroxyl group and one or more (meth) acrylic groups in the molecule such as hydroxyalkyl (meth) acrylate is added, and terminal (meth) acrylated Carboxyl group-containing photosensitive urethane resin.

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

  (6) Carboxyl group-containing photosensitivity in which (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later and a dibasic acid anhydride is added to the hydroxyl group present in the side chain. Resin.

  (7) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added carboxyl group-containing photosensitive resin.

  (8) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and a polybasic acid is added to the remaining hydroxyl group. A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.

  (9) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resins (1) to (8).

Since the carboxyl group-containing photosensitive resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
Moreover, the acid value of the said carboxyl group-containing photosensitive resin is the range of 40-200 mgKOH / g, More preferably, it is the range of 45-120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group-containing photosensitive resin changes with resin frame | skeleton, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

The compounding amount of such a carboxyl group-containing photosensitive resin is suitably in the range of 0 to 50% by mass, preferably 10 to 40% by mass in the total composition.
These carboxyl group-containing photosensitive resins are not limited to those listed above, and can be used singly or in combination of two or more.

  Furthermore, a thermosetting component can be added to the photosensitive resin composition of the present invention in order to impart heat resistance. As the thermosetting component used in the present invention, known conventional heat such as blocked isocyanate compound, amino resin, maleimide compound, benzoxazine resin, carbodiimide resin, cyclocarbonate compound, polyfunctional epoxy compound, polyfunctional oxetane compound, episulfide resin, etc. A curable resin can be used. Among these, a preferable thermosetting component is a thermosetting component having a plurality of cyclic ether groups and / or 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 cyclic thioether groups or two types of groups in the molecule. A compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, and a plurality of thioether groups in the molecule. A compound having the same, that is, an episulfide resin.

  Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, and Epoto manufactured by Tohto Kasei Co., Ltd. YD-011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Industries Sumi-Epoxy ESCN- 195X, ESCN-220, A.A. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink and Chemicals, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., Ltd., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, etc. (both trade names); Epototo ST-2004, ST-2007, ST-3000 (trade names, manufactured by Toto Kasei) Hydrogenated bisphenol A type epoxy resin such as JER604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-Epoxy ELM manufactured by Sumitomo Chemical Co., Ltd. -120 etc. (both Product name) Glycidylamine type epoxy resin; Ardandide type epoxy resin such as araldide CY-350 (trade name) made by Ciba Specialty Chemicals; Celoxide 2021 made by Daicel Chemical Industries, Araldide made by Ciba Specialty Chemicals CY175, CY179, etc. (both trade names); YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. Trihydroxyphenylmethane type epoxy resins such as EPPN-501 and EPPN-502 manufactured by Nippon Kayaku Co., Ltd. (all trade names); YL-6056, YX-4000 and YL-6121 manufactured by Japan Epoxy Resin Co., Ltd. Bixylenol type or biphenol type epoxy resins such as (trade name) or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc. Bisphenol S type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc. (All are trade names) Tetraphenylol ester Type epoxy resins; heterocyclic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); diglycidyl phthalate resins such as Bremer DGT manufactured by Nippon Oil &Fats; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc. Naphthalene group-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; glycidyl methacrylate copolymer such as CP-50S and CP-50M manufactured by NOF Corporation Epoxy resin; cyclohexylmaleimide and group Glycidyl methacrylate copolymer epoxy resins; but CTBN modified epoxy resin (e.g., Tohto Kasei Co. YR-102, YR-450, etc.) and the like, not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bixylenol type epoxy resin or a mixture thereof is particularly preferable.

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo-type bisphenol Le ethers, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the episulfide resin having a plurality of cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin, YSLV-120TE manufactured by Tohto Kasei Co., Ltd., and the like. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the carboxyl group-containing photosensitive resin. More preferably, it is the range used as 0.8-2.0 equivalent. When the compounding amount of thermosetting components having multiple cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in decreased heat resistance, alkali resistance, electrical insulation, etc. Therefore, it is not preferable. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.

  Moreover, amino resins, such as a melamine derivative and a benzoguanamine derivative, are mentioned as another thermosetting component which can be used suitably. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, 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.

Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), 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 (above, manufactured by Sanwa Chemical Co., Ltd.).
The said thermosetting component can be used individually or in combination of 2 or more types.

  In addition, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is added to the photosensitive resin composition of the present invention in order to improve the curability of the composition and the toughness of the resulting cured film. Can do. 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 can be used singly or in combination of two or more.
The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass, more preferably 2 to 100 parts by mass of the carboxyl group-containing photosensitive resin. A proportion of 70 parts by weight is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, since the storage stability of a composition falls, it is unpreferable.

  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 possible 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 / or amine salts. preferable.

  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 sufficient at a normal quantitative ratio, for example, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 100 parts by mass of the carboxyl group-containing photosensitive resin. -10.0 parts by mass.

  When using a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, 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, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can 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 blending amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin or thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. The amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

  The photosensitive resin composition of this invention can mix | blend a coloring agent. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. 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. -Index (CI; issued by The Society of Dyers and Colorists) number.
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-based and anthraquinone-based pigments, and pigment-based compounds such as Pigment Blue 15 and Pigment Blue 15 are listed below. : 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, and 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.

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.
Specifically, 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 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 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 ratio of the colorant as described above is not particularly limited, but is preferably 0 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the carboxyl group-containing photosensitive resin. A proportion is sufficient.

  A compound having a plurality of ethylenically unsaturated groups in the molecule can be added to the photosensitive resin composition of the present invention. A compound having a plurality of ethylenically unsaturated groups in the molecule is photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the carboxyl group-containing photosensitive resin in an alkaline aqueous solution. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like can be used. Hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide Acrylamides such as N, N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl Aminoalkyl acrylates such as acrylates; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone Polyvalent acrylates such as adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, tri Multivalent acrylate of glycidyl ethers such as methylolpropane triglycidyl ether and triglycidyl isocyanurate Not limited to the above, but also acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, and / or the above acrylates And methacrylates corresponding to the above.

  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. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  As for the compounding quantity of the compound which has several ethylenically unsaturated groups in such a molecule | numerator, the ratio of 5-100 mass parts is desirable with respect to 100 mass parts of said carboxyl group-containing photosensitive resin, More preferably, 1- The ratio is 70 parts by mass. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.

  The photosensitive resin composition of the present invention can contain a filler as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide can be used as extender pigment fillers. The amount of these fillers is preferably 200 parts by mass or less, more preferably 0.1 to 150 parts by mass, and particularly preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. . When the blending amount of the filler exceeds 200 parts by mass, the viscosity of the composition becomes high, the printability is lowered, and the cured product becomes brittle.

  The photosensitive resin composition of the present invention can use a mercapto compound as a chain transfer agent and / or an adhesion imparting agent. Examples of the mercapto compound include mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercapto Propionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, Examples thereof include thioglycerol and 4,4-thiobisbenzenethiol. Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, Karenz-NR1 (above, Showa Denko Co., Ltd.) etc. can be mentioned.

  Further, examples of the mercapto compound having a heterocyclic ring 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-mer Pto-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, 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 (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet DB) , 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name DISNET AF) and the like. In addition, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (manufactured by Kawaguchi Chemical Industry Co., Ltd .: trade name Accel M), 3-mercapto-4-methyl-4H-1,2,4- Triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole and the like can be suitably used. These mercapto compounds can be used alone or in combination of two or more.

  The blending amount of such a mercapto compound is suitably 0.01 parts by weight or more and 10.0 parts by weight or less, more preferably 0.05 parts by weight with respect to 100 parts by weight of the carboxyl group-containing photosensitive resin. The amount is 5 parts by mass or less. If the amount is less than 0.01 parts by mass, the effect of adding the mercapto compound is not confirmed. On the other hand, if the amount exceeds 10.0 parts by mass, the photosensitive resin composition may be poorly developed and the drying control width may be reduced. It is not preferable.

  Furthermore, the photosensitive resin composition of the present invention can use a binder polymer for the purpose of improving dryness to touch and improving handling properties. For example, polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like can be used. These binder polymers can be used alone or as a mixture of two or more.

  Furthermore, the photosensitive resin composition of the present invention can use an elastomer for the purpose of imparting flexibility and improving brittleness of a cured product. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or the like can be used. These elastomers can be used alone or as a mixture of two or more.

Furthermore, the photosensitive resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing photosensitive resin and the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. Can do.
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 is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  Generally, in many polymer materials, once oxidation starts, oxidative degradation successively occurs one after another, resulting in a decrease in the function of the polymer material. Therefore, the photosensitive resin composition of the present invention prevents oxidation. (1) A radical scavenger that invalidates the generated radicals and / or (2) a peroxide decomposer that decomposes the generated peroxide into harmless substances and prevents the generation of new radicals. An antioxidant can be added. In particular, when an antioxidant is used in a composition that uses a butadiene-based elastomer used in the present invention, PCT resistance is improved, and peeling and discoloration during HAST are reduced, which is effective.

  Specific compounds of antioxidants that act as radical scavengers 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-hydroxy) Benzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone-based compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetra Chill 4-piperidyl) - sebacate, and the like amine compounds such as phenothiazine.

  The radical scavenger may be commercially available, for example, 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 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 152, TINUVIN 152, TINUVIN 292, TINUVIN 5100 Special Product name).

  Specific examples of the antioxidant acting as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.

The peroxide decomposing agent may be a commercially available one. For example, ADK STAB TPP (manufactured by Asahi Denka Co., Ltd., trade name), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), Sumilyzer TPS (Sumitomo Chemical) Company name, product name).
Said antioxidant can be used individually by 1 type or in combination of 2 or more types.

  In general, since the polymer material absorbs light and thereby decomposes and deteriorates, 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.

Ultraviolet absorbers may be commercially available, 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 (above, manufactured by Ciba Specialty Chemicals, Inc., trade name).
Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, By using together with the said antioxidant, the molding obtained from the photosensitive resin composition of this invention can be stabilized. I can plan.

  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. Specific examples include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Industry Co., Ltd.). 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazol-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzo Examples include triazole, amino group-containing benzotriazole, and silane coupling agent.

  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. Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics. In addition, thermal polymerization inhibitors, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, and bisphenols Known and conventional additives such as copper damage prevention agents such as those based on triazine and triazine thiols 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 adjusted to a viscosity suitable for the coating method with, 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 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. by volatile drying (preliminary drying) at a temperature of about 60 to 100 ° C. Thereafter, the contact pattern (or non-contact pattern) is selectively exposed with an active energy ray through a photomask on which a pattern is formed, or directly exposed with a pattern using a laser direct exposure machine. A resist pattern is formed by development with a 3 to 3% sodium carbonate aqueous solution. Further, in the case of a composition containing a thermosetting component, for example, by heating and curing at a temperature of about 140 to 180 ° C., a plurality of carboxyl groups in the carboxyl group-containing photosensitive resin, A thermosetting component having a cyclic ether group and / or a cyclic thioether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. Can do. In addition, even when it does not contain a thermosetting component, by performing heat treatment, the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Therefore, heat treatment (thermosetting) may be performed depending on the purpose and application.

  As the substrate, in addition to a printed circuit board and a flexible printed circuit board in which circuits are formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminate of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

  Volatile drying performed after applying the photosensitive resin composition of the present invention is performed in a dryer using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven or the like (equipped with a heat source of an air heating method using steam). It is possible to use a method in which hot air is brought into countercurrent contact and a method in which a hot air is blown onto a support.

After applying the photosensitive resin composition of the present invention and evaporating and drying as follows, the obtained coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.
As the exposure apparatus used for the active energy ray irradiation, 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), an exposure apparatus equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp. , An exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp. As the active energy ray, 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. Further, the exposure amount varies depending the thickness or the like, typically 5 to 200 mJ / cm ^2, preferably from 5 to 100 mJ / cm ^2, more preferably be in the range of 5~50mJ / cm ^2. As the direct drawing device, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

  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.

  The photosensitive resin composition of the present invention is in the form of a dry film having a solder resist layer formed by previously applying and drying a solder resist on a film of polyethylene terephthalate or the like, in addition to the method of directly applying to the base material in liquid It can also be used. The case where the photosensitive resin composition of this invention is used as a dry film is shown below.

  The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order. The solder resist layer is a layer obtained by applying and drying an alkali-developable photosensitive resin composition on a carrier film or a cover film. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
The solder resist layer is formed by uniformly applying an alkali-developable photosensitive resin composition to a carrier film or a cover film with a thickness of 10 to 150 μm using a blade coater, lip coater, comma coater, film coater, and the like, and then drying. .
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

  To produce a protective film (permanent protective film) on a printed wiring board using a dry film, peel off the cover film, layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc. A solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off either before exposure or after exposure.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

Resin synthesis example 1
120 parts of a novolac type cresol resin (Dainippon Ink Chemical Co., Ltd., OH equivalent: 120), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate were charged into a reaction kettle and stirred at 150 to 160 ° C. The reaction was started by heating and raising temperature, and then the reaction was continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system. Then, it cooled to room temperature and a hydroxyl group equivalent was 182.2 g / eq. A novolak cresol resin propylene carbonate reaction product was obtained. This was equivalent to an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
The above reaction product was dissolved in 270 parts of diethylene glycol monoethyl ether acetate, and 135.0 parts of half urethane obtained by reacting isophorone diisocyanate and hydroxyethyl acrylamide in a 1: 1 molar ratio at 75 ° C. for 4 hours. Further, 91.2 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 ° C. for about 5 hours. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 61% and a solid content acid value of 81.3 mgKOH / g. This is designated as resin solution A-1.

Resin synthesis example 2
A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 parts, 1.19 parts of potassium hydroxide and 119.4 parts of toluene were charged, the system was purged with nitrogen while stirring, and the temperature was raised. Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
293.0 parts of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer and a temperature. A reactor equipped with a meter and an air blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min. While blowing and stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. This is designated as resin solution A-2.

Comparative Synthesis Example 1
Orthocresol novolak type epoxy resin (Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 parts (number of glycidyl groups) (Total number of aromatic rings): 5.0 moles), 360 parts (5.0 moles) of acrylic acid, and 1.5 parts of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 parts of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction liquid, 415 parts of aromatic hydrocarbon (Sorvesso 150) and 456.0 parts (3.0 mol) of tetrahydrophthalic anhydride were reacted, and reacted at 110 ° C. for 4 hours. After cooling, solid acid A resin solution having a value of 89 mg KOH / g and a solid content of 65% was obtained. This is designated as resin solution R-1.

Comparative Synthesis Example 2
After dissolving 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide in 400 parts of bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C., 81.2 parts of 98.5% NaOH at 70 ° C. with stirring. Added over 100 minutes. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, the reaction product containing the by-product salt and dimethyl sulfoxide is dissolved in 750 parts of methyl isobutyl ketone, and 10 parts of 30% NaOH is further added. The reaction was carried out at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was recovered from the oil layer by distillation to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 ° C.
2900 parts (10 equivalents) of epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone, and 1950 parts of carbitol acetate are heated and stirred at 90 ° C. to dissolve the reaction mixture. did. Next, the reaction solution was cooled to 60 ° C., charged with 16.7 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, solid content acid value 100 mg KOH / g, solid content 65% A resin solution was obtained. This is designated as resin solution R-2.

Examples 1 to 6 and Comparative Examples 1 and 2
Using the resin solution of the above synthesis example, the various components shown in Table 1 are blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and photosensitive for a solder resist. A functional resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

Performance evaluation:
<Optimum exposure amount>
Each photosensitive resin composition of the above-mentioned examples and comparative examples was coated with a screen printing method on the whole surface after buffing a circuit pattern substrate having a copper thickness of 35 μm, buffed, dried, and dried at 80 ° C. with hot air circulation. Dry in an oven for 60 minutes. After drying, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and remains when developed (30 ° C., 0.2 MPa, 1 wt% sodium carbonate aqueous solution) in 90 seconds. When the step tablet pattern is 7 steps, the optimum exposure was set.

<Developability>
Each of the photosensitive resin compositions of Examples and Comparative Examples was applied on a copper solid substrate by a screen printing method so that the film thickness after drying was about 25 μm, and 30 minutes in a hot air circulation drying oven at 80 ° C. Dried. After drying, development was performed with a 1 wt% sodium carbonate aqueous solution, and the time until the dried coating film was removed was measured with a stopwatch.

<Maximum development life>
Each photosensitive resin composition of the Example and Comparative Example was applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C., and the substrate was taken out every 10 minutes from 20 to 80 minutes to room temperature. Allowed to cool. This substrate was developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 90 seconds, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.

<Tackiness>
Each of the photosensitive resin compositions of Examples and Comparative Examples was applied on the entire surface of a patterned copper foil substrate by screen printing, dried in a hot air circulating drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. A negative film made of PET was applied to this substrate, and the film was pressure-bonded under a reduced pressure condition with ORC (HMW-GW20) for 1 minute, and then the sticking state of the film when the negative film was peeled was evaluated according to the following criteria.
○: When peeling off the film, there is no resistance at all and no mark is left on the coating film.
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When the film is peeled off, there is resistance and the coating film is clearly marked.

Characteristic test:
Each photosensitive resin composition of the Examples and Comparative Examples was applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Using this exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the solder resist pattern is exposed at an optimal exposure amount, and developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. for 90 seconds under the condition of a spray pressure of 0.2 MPa. Obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Acid resistance>
The evaluation substrate was immersed in a 10 wt% HCl aqueous solution at room temperature for 30 minutes, and the infiltration and dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed. The judgment criteria are as follows.
○: No change is observed.
Δ: Slightly changed.
X: The coating film has swelling or swelling dropping.

<Alkali resistance>
The evaluation substrate was immersed in a 10 wt% NaOH aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed. The judgment criteria are as follows.
○: No change is observed.
Δ: Slightly changed.
X: The coating film has swelling or swelling dropping.

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.

<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 5μm and gold 0.05μm, and tape peeling is used to check for resist layer peeling and plating penetration. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
A: No soaking or peeling is observed.
○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.
Δ: Slight penetration after plating and peeling after tape peel.
X: There is peeling after plating.

<PCT resistance>
The evaluation board | substrate which formed the soldering resist cured coating film was processed for 168 hours on the conditions of 121 degreeC, saturation, and 0.2 MPa using a PCT apparatus (Espec Co., Ltd. HAST SYSTEM TPC-412MD). evaluated. Judgment criteria are as follows.
○: No swelling, peeling, discoloration or elution.
Δ: Some swelling, peeling, discoloration, and elution.
X: Swelling, peeling, discoloration, and elution are often observed.

<Cold shock resistance>
The evaluation board | substrate which has a soldering resist cured coating film in which (square) extraction and (circle) extraction pattern were formed was produced. The obtained evaluation substrate was subjected to a 1000 cycle durability test using a thermal shock tester (manufactured by ETAC Co., Ltd.) with -55 ° C / 30 minutes to 150 ° C / 30 minutes as one cycle. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged according to the following criteria.
A: Crack generation rate is less than 20%.
○: Crack occurrence rate of 20 to 40%.
Δ: Crack occurrence rate of 40 to 60%.
X: Crack occurrence rate of 60% or more.

<HAST characteristics>
A solder resist cured coating film was formed on a BT substrate on which comb-type electrodes (line / space = 30 μm / 30 μm) were formed, and an evaluation substrate was prepared. This evaluation board | substrate was put into the high-temperature, high-humidity tank of the atmosphere of 130 degreeC and humidity 85%, the voltage 5V was charged, and the in-chamber HAST test was done for 168 hours. The insulation resistance value in the tank when 168 hours passed was evaluated according to the following criteria.
○: 10 ⁸ Ω or more △: 10 ⁶ to 10 ⁸ Ω
×: 10 ⁶ Ω or less

The results of the evaluation test are shown in Table 2 below.

Examples 7-12 and Comparative Examples 3, 4
The photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 and 2 prepared according to the formulations shown in Table 1 were diluted with methyl ethyl ketone, applied onto a PET film, dried at 80 ° C. for 30 minutes, and the thickness. A 20 μm photosensitive resin composition layer was formed. Furthermore, the cover film was bonded together and the dry film was produced, and it was set as Examples 7-12 and Comparative Examples 3 and 4, respectively.

<Dry film evaluation>
The cover film of the dry film obtained as described above is peeled off, the film is thermally laminated on the patterned copper foil substrate, and then the same as the substrate used for the coating film property evaluation of Examples 1 to 6 above. The exposure was performed under the following conditions. After the exposure, the carrier film was peeled off, and a 1 wt% sodium carbonate aqueous solution at 30 ° C. was developed for 90 seconds under a spray pressure of 0.2 MPa to obtain a resist pattern. Thereafter, UV irradiation was performed in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ / cm ² , and this substrate was further heated and cured with a hot air dryer at 150 ° C. for 60 minutes to prepare a test substrate. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Table 3.

  From the results of Table 2 and Table 3, the photosensitive resin composition of the present invention is a photosensitive resin composition having both PCT resistance, thermal shock resistance, and electrical characteristics (HAST characteristics) required for a solder resist for IC packages. It became clear to give.

Claims (4)

A reaction product obtained by reacting a phenol resin with an alkylene oxide or a cyclocarbonate compound is reacted with an isocyanate compound having one or more acrylamide groups or methacrylamide groups in one molecule, and the resulting reaction product A photosensitive resin composition capable of alkali development, comprising: a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride; and a photopolymerization initiator.   The photosensitive dry film obtained by apply | coating and drying the photosensitive resin composition of the said Claim 1 to a film.   A cured product obtained by photocuring and thermosetting the photosensitive resin composition according to claim 1 or a dry film obtained by applying and drying the photosensitive resin composition on a film.   A printed wiring board having the cured product according to claim 3.