WO2010113478A1

WO2010113478A1 - Curable resin composition and printed wiring board

Info

Publication number: WO2010113478A1
Application number: PCT/JP2010/002305
Authority: WO
Inventors: 伊藤信人; 有馬聖夫
Original assignee: 太陽インキ製造株式会社
Priority date: 2009-03-31
Filing date: 2010-03-30
Publication date: 2010-10-07
Also published as: KR101690811B1; TW201107355A; KR20120000074A; CN102369482B; TWI532756B; CN102369482A

Abstract

Disclosed is a curable resin composition which has good workability and high sensitivity, and is capable of providing a cured product thereof with high reliability when the cured product is used, for example, in a printed wiring board or a semiconductor package. Also disclosed is a cured product of the curable resin composition. The curable resin composition contains a photopolymerization initiator and a carboxyl group-containing photosensitive resin which is obtained by reacting a polybasic acid anhydride with a reaction product that is obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product that is obtained by reacting a phenol resin having a specific skeleton with an alkylene oxide or a cyclocarbonate compound.

Description

Curable resin composition and printed wiring board

The present invention relates to a curable resin composition used as a solder resist for printed wiring boards.

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. A liquid development type solder resist that undergoes final curing (main curing) by irradiation is used, and in consideration of environmental problems, an alkali development type photo solder resist using an alkaline aqueous solution as a developing solution has become the mainstream and widely used (for example, , See Patent Document 1).

In such a liquid development type solder resist, a carboxyl group-containing photosensitive resin, generally an epoxy acrylate modified resin derived by modification of an epoxy resin is used.
For example, a solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound is disclosed (patent) Reference 1). In addition, (meth) acrylic acid is added to the epoxy resin obtained by reacting the reaction product of salicylaldehyde and monohydric phenol with epichlorohydrin, and polybasic carboxylic acid or its anhydride is further reacted. A solder resist composition composed of a photosensitive resin, a photopolymerization initiator, an organic solvent, and the like is disclosed (see Patent Document 2).

Thus, in an epoxy resin used for an epoxy acrylate-modified resin, an epoxy skeleton is generally introduced by reacting epichlorohydrin containing chlorine or the like. At this time, chlorine ion impurities that cause a decrease in insulation reliability are by-produced, and it is very difficult to remove them. Therefore, the epoxy resin used as a raw material contains a large amount of chlorine ion impurities. Is almost. Also, it is very difficult to remove this chloride ion impurity after the epoxy acrylate modification.

On the other hand, solder resists are also required to have high performance such as excellent developability and high workability in response to the recent increase in the density of printed wiring boards as electronic devices become lighter and thinner. Recently, along with the downsizing, lightening, and high performance of electronic devices, downsizing of semiconductor packages and increasing the number of pins have been put into practical use, and mass production is progressing. For example, in order to obtain high reliability in semiconductor packages such as BGA (ball grid array) and CSP (chip size package), PCT (pressure cooker test) resistance, which is also referred to as moisture heat resistance, is required. Furthermore, from the viewpoint of productivity, the solder resist is also required to have reactivity with ultraviolet rays used for patterning, that is, high exposure sensitivity.

However, the conventional liquid development type solder resist has only a few hours to a few dozen hours in the PCT resistance test and does not have sufficient wet heat resistance. Also, when the package is mounted, moisture absorbed by the solder resist boils the moisture absorbed inside the package during reflow, causing cracks in the solder resist film inside the package and its surroundings, and sufficient crack resistance cannot be obtained. is there.

Japanese Patent Laid-Open No. 61-243869 Japanese Patent Laid-Open No. 3-250012

The present invention has been made to solve the above-mentioned problems, has good workability, high sensitivity and excellent developability, and the cured product thereof is used, for example, in a printed wiring board or a semiconductor package. Another object of the present invention is to provide a curable resin composition capable of obtaining excellent PCT resistance and high insulation reliability.

In order to achieve such an object, the curable resin composition of the present invention reacts a phenol resin having at least one skeleton of general formulas (I) to (VI) with an alkylene oxide or a cyclocarbonate. Containing a carboxyl group-containing photosensitive resin obtained by reacting an unsaturated group-containing monocarboxylic acid with the reaction product obtained and reacting the resulting reaction product with a polybasic acid anhydride, and a photopolymerization initiator. A curable resin composition is provided.

(R in the general formulas (III), (IV), and (VI) represents hydrogen or a methyl group.)

With such a configuration, workability and developability are excellent, and the cured product has high reliability such as excellent PCT resistance and high insulation reliability when used for, for example, a printed wiring board or a semiconductor package. It becomes possible. Also, 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, respectively, so that the reactivity is high (high sensitivity) and the alkali development is excellent. Can be realized.

In the curable resin composition of the present invention, the acid value of the carboxyl group-containing photosensitive resin is preferably 30 to 150 mgKOH / g. By setting the acid value within this range, alkali development is possible and sufficient development resistance can be obtained.

In the curable resin composition of the present invention, the alkylene oxide is preferably ethylene oxide and propylene oxide or ethylene oxide or propylene oxide, and the cyclocarbonate compound is preferably ethylene carbonate and propylene carbonate or ethylene carbonate or propylene carbonate. .
With such a configuration, the chain of the carboxyl group-containing resin is extended, the flexibility is improved, and the thermal shock resistance can be improved.

In the curable resin composition of the present invention, the unsaturated group-containing monocarboxylic acid is preferably acrylic acid and methacrylic acid or acrylic acid or methacrylic acid.
With such a configuration, it can be used as a highly sensitive photocurable resin composition.
Moreover, in the curable resin composition of this invention, it is preferable that carboxyl group-containing photosensitive resin does not contain a hydroxyl group.
With such a configuration, the moisture absorption resistance is excellent, and excellent PCT resistance can be obtained in the cured product.

Further, the curable resin composition of the present invention preferably contains a thermosetting component. With such a configuration, it can be used as a thermosetting resin composition capable of main curing by heat, and heat resistance is further imparted to the curable resin composition.

The curable resin composition of the present invention preferably contains a colorant. By containing a colorant, when used as a solder resist for a printed wiring board, it is possible to obtain a concealing property such as a circuit.

Furthermore, such a curable resin composition can be applied to a substrate and cured by irradiation with active energy rays and heating or irradiation with active energy rays or heating to obtain a cured product. In such a cured product, for example, when used for a printed wiring board or a semiconductor package, it is possible to obtain high reliability such as excellent PCT resistance and high insulation reliability.

Further, such a curable resin composition can be applied to a film and dried to be used as a curable dry film. By using such a dry film, a resist layer can be easily formed without coating. Furthermore, this dry film can be affixed to a substrate and cured by active energy ray irradiation and heating or active energy ray irradiation or heating to obtain a cured product. In such a cured product, for example, when used for a printed wiring board or a semiconductor package, it is possible to obtain high reliability such as excellent PCT resistance and high insulation reliability.

And by using these hardened | cured material for a printed wiring board, it becomes possible to obtain high reliability, such as the outstanding PCT tolerance and high insulation reliability.

According to the present invention, the curable resin composition has good workability, high sensitivity and excellent developability, and in the cured product, for example, when used for a printed wiring board or a semiconductor package, Excellent PCT resistance and high insulation reliability can be obtained.

As a result of intensive studies to solve such problems, the present inventors have started a phenol resin having at least one skeleton of the general formulas (I) to (VI) as an essential component of the composition. The inventors have found that the above object can be achieved by using a carboxyl group-containing photosensitive resin as a raw material, and have completed the present invention.

This carboxyl group-containing photosensitive resin is excellent in flexibility by chain extension by addition reaction between a phenol resin having at least one skeleton of general formulas (I) to (VI) and alkylene oxide or cyclocarbonate, Elongation can be obtained. In addition, unsaturated group-containing monocarboxylic acid and polybasic acid anhydride are added to the terminal hydroxyl group generated by the addition reaction of alkylene oxide or cyclocarbonate, and the unsaturated group or carboxyl group is on the same side chain. Since it does not exist and is located at the end of each side chain, it has excellent reactivity. Furthermore, it has excellent alkali developability due to the presence of a terminal carboxyl group away from the main chain.

In addition, this carboxyl group-containing photosensitive resin is excellent in moisture absorption resistance because it has no or only a slightly reactive hydrophilic alcoholic hydroxyl group. The presence of a hydroxyl group has excellent characteristics such as improved adhesion by hydrogen bonding, but significantly reduces moisture resistance. In this respect, the carboxyl group-containing photosensitive resin in the present invention can improve moisture resistance by substantially not containing a hydroxyl group. And the improvement of the moisture resistance makes it possible to improve the PCT resistance required for the IC package.

In addition, the phenol resin having at least one skeleton of the general formulas (I) to (VI) used in the present invention is characterized in that the hydroxyl equivalent is larger than that of normal phenol or cresol type novolac resin. Can be mentioned. That is, a cured product using a carboxyl group-containing resin derived from the phenols has better flexibility than general novolak resins. Accordingly, compared to conventional novolak resins, a solder resist composition using a carboxylic acid-containing resin derived from a phenol resin having at least one skeleton of general formulas (I) to (VI) It is possible to improve the thermal shock resistance and PCT resistance of the resulting cured product. Among them, the carboxyl group-containing photosensitive resin derived from the general formula (III) can obtain very excellent insulation reliability and PCT resistance.

Hereinafter, the curable resin composition of the present invention will be described in detail.
First, specifically, the carboxyl group-containing photosensitive resin constituting the curable resin composition of the present invention can be easily obtained by the following method.
(1) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a phenol resin having at least one skeleton of general formulas (I) to (VI) with an alkylene oxide, A carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride.
(2) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a phenol resin having at least one skeleton of general formulas (I) to (VI) with a cyclocarbonate compound. A carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride.

Thus, the carboxyl group-containing photosensitive resin in the present invention is obtained using phenol resins having various skeletons as starting materials. Since the phenol resin containing almost no chloride ion impurities can be easily obtained, the chloride ion impurity concentration in the resulting carboxyl group-containing photosensitive resin can be greatly suppressed. The chloride ion content of such a carboxyl group-containing photosensitive resin is preferably 100 ppm or less. More preferably, it is 50 ppm or less, More preferably, it is 30 ppm or less.

Further, such a carboxyl group-containing photosensitive resin is also characterized in that it is a resin that does not substantially contain a hydroxyl group. Note that “substantially free of hydroxyl groups” means that a trace amount of hydroxyl groups is allowed.
As described above, it is possible to exhibit excellent insulation reliability and PCT resistance by suppressing chlorine ion impurities in the carboxyl group-containing photosensitive resin and substantially not including a hydroxyl group.

In addition, the carboxyl group-containing resin in the present invention can greatly reduce the number of ester bonds to the aromatic ring per repeating unit depending on the phenol resin raw material used.

For solder resists that require excellent insulation reliability, a cured resist coating is formed on a copper-clad laminate with very fine pitch lines / spaces, and voltage is applied to judge the insulation reliability. . In general, when a voltage is applied, the absorbed water causes electrolysis between the electrodes. At this time, it becomes alkaline on the cathode side and acidic on the anode side.

Due to this phenomenon, in conventional solder resists, it is confirmed that the ester film has undergone alkali hydrolysis on the cathode side, resulting in a decrease in resist film thickness. The mode is confirmed. Furthermore, since the hydrolyzed molecule has high hydrophilicity, it was considered that the water absorption of the coating film was increased and the electrical properties were deteriorated. The inventors focused on such a phenomenon and thought that reducing the ester bond per repeating unit is a very effective means for suppressing alkali hydrolysis on the cathode side. .

Hereinafter, the difference between the conventional phenol novolac resin and the carboxyl group-containing resin used in the present invention will be described by focusing on the number of ester bonds to the aromatic ring per one repeating unit.

A conventional phenol novolac type epoxy acrylate is obtained by adding acrylic acid to an epoxy resin synthesized from a phenol novolac resin and adding an acid anhydride to the hydroxyl group to be produced. Therefore, the number of ester bonds to the aromatic ring per repeating unit is 2. On the other hand, the carboxyl group-containing resin according to the present invention derived from a phenol resin reacts with an acrylic acid or an acid anhydride after reacting an alkylene oxide or a cyclocarbonate compound with a phenol resin having various skeletons. Therefore, the number of ester bonds per aromatic ring per repeating unit is theoretically never greater than 1.0. In the general formulas (I) and (II), the number of ester bonds to the aromatic ring per repeating unit is 1, 0.5 in the general formula (IV), 0.66 in the general formula (VI), and the general formula In (III), it is possible to reduce to 0.33, and therefore it is possible to exhibit excellent insulation reliability. The number of ester bonds to the aromatic ring per repeating unit of the carboxyl group-containing resin used in the present invention is 1 or less, preferably 0.75 or less, more preferably 0.5 or less.

In addition, a cured product obtained from a carboxyl group-containing resin derived from a phenol resin having various skeletons used in the present invention is compared with a cured product obtained from a carboxyl group-containing resin derived from a conventional phenol novolac resin. It is possible to develop excellent characteristics derived from the phenol resin raw material used. For example, various properties such as improvement of glass transition temperature (Tg), improvement of breaking strength of cured coating film and provision of toughness, improvement of thermal shock resistance, improvement of hydrolysis resistance, and further improvement of flame retardancy Can be granted.

Moreover, you may make the compound which has both a cyclic ether group and an ethylenically unsaturated group in 1 molecule react with the carboxyl group-containing photosensitive resin obtained by these (1) and (2). As such a compound, glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, or 3,4-epoxycyclohexylmethyl methacrylate is preferable from the viewpoint of reactivity and supply.
(Meth) acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

The addition amount of such a 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. When the added amount is less than 5% equivalent, sufficient sensitivity increase and improvement of the solder resist characteristics cannot be obtained, and when it exceeds 40% equivalent, the maximum development life is shortened and the dryness to the touch is deteriorated. More preferably, it is 10% equivalent to 30% equivalent.

By using such a carboxyl group-containing photosensitive resin, since it has a number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible. The acid value of the carboxyl group-containing photosensitive resin is preferably in the range of 30 to 150 mgKOH / g. When it is lower than 30 mgKOH / g, the solubility in an aqueous alkali solution is lowered, and development of the formed coating film becomes difficult. On the other hand, if the concentration is higher than 150 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line fades more than necessary, or dissolution and peeling occurs with the developer without distinction between the exposed portion and the unexposed portion. It may be difficult to draw a resist pattern. And it causes the appearance defect and the deterioration of electrical characteristics. More preferably, it is in the range of 40 to 130 mgKOH / g.

In addition, the weight average molecular weight of such a carboxyl group-containing photosensitive resin varies depending on the resin skeleton, but is generally preferably in the range of 2,000 to 150,000. When the weight average molecular weight is less than 2,000, tack-free performance is deteriorated, the moisture resistance of the coated film after exposure is poor, film loss occurs during development, and resolution may be greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated and the storage stability may be inferior. More preferably, it is 5,000 to 100,000.

The blending amount of such a carboxyl group-containing photosensitive resin is preferably 20 to 60% by mass in the entire composition. When it is less than 20% by mass, the coating film strength is lowered. On the other hand, when it is more than 60% by mass, the viscosity becomes high, and the coating property and the like are lowered. More preferably, it is 30 to 50% by mass.

The carboxyl-containing resin used in the present invention is not particularly limited as long as it is derived from a phenol resin having a structure of general formulas (I) to (VI).
(R in the general formulas (III), (IV), and (VI) represents hydrogen or a methyl group.)

Examples of the phenol resin used in the present invention include bisphenol A-formaldehyde type phenol resin, salicylaldehyde type phenol resin, phenyl aralkyl type phenol resin, biphenyl aralkyl type phenol resin, phenylene aralkyl type phenol resin, α-naphthol, β-naphthol and the like. A naphthol aralkyl type phenol resin, a dicyclopentadiene skeleton-containing phenol resin, or the like can be used.
As the resin having a skeleton of the general formula (I), for example, BPA-D manufactured by Meiwa Kasei Co., Ltd. can be used.
As the resin having the skeleton of the general formula (II), for example, MEH-7500 manufactured by Meiwa Kasei Co., Ltd. can be used.
As the resin having the skeleton of the general formula (III), for example, MEH-851 manufactured by Meiwa Kasei Co., Ltd. can be used.
As the resin having a skeleton of the general formula (IV), for example, MEH-7800 manufactured by Meiwa Kasei Co., Ltd. can be used.
As the resin having a skeleton of the general formula (V), for example, DPP-6115H manufactured by Shin Nippon Oil Co., Ltd. can be used.
As the resin having a skeleton of the general formula (VI), for example, Kayahard CBN manufactured by Nippon Kayaku Co., Ltd. can be used.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and the like, and ethylene oxide and propylene oxide are preferable from the viewpoint of price and supply system. As the cyclocarbonate compound, known carbonate compounds can be used, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate. Among these, 5-membered ethylene carbonate and propylene carbonate are preferable from the viewpoint of reactivity and supply system. These alkylene oxides and cyclocarbonate compounds can be used alone or in admixture of two or more.

An alkylene oxide or a cyclocarbonate compound is obtained by adding an alcoholic hydroxyl group from a phenolic hydroxyl group by an addition reaction using a basic catalyst to the phenolic hydroxyl group of a phenol resin having a structure of general formulas (I) to (VI). It can be modified to have a resin. The addition amount at this time is preferably in the range of 0.3 to 10 mol per equivalent of phenolic hydroxyl group. When the addition amount is less than 0.3 mol, a reaction with an unsaturated group-containing monocarboxylic acid or polybasic acid anhydride described later hardly occurs, and the photosensitivity and solubility in a dilute alkaline aqueous solution are lowered. On the other hand, when the addition amount exceeds 10 moles, water resistance decreases due to the ether bond to be generated, and electrical insulation, PCT resistance and the like decrease. The range is more preferably 0.8 to 5 mol, and still more preferably 1.0 to 3 mol.

Examples of unsaturated group-containing monocarboxylic acids include acrylic acid, methacrylic acid, or even hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples include unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, and (meth) acrylic acid caprolactone adducts. More preferred are acrylic acid and / or soot or methacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in combination of two or more.

Polybasic acid anhydrides include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydroanhydride Alicyclic dibasic acid anhydrides such as phthalic acid and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride, etc. Aliphatic or aromatic dibasic acid anhydride, or biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride, Benzophenone Tet Aliphatic or aromatic tetrabasic acid dianhydride such as dianhydrides may be mentioned, it is possible to use one or more of them.

Next, the photopolymerization initiator constituting the curable resin composition of the present invention includes an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. One or more photopolymerization initiators selected from the group consisting of initiators can be used.
Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Japan, N-1919 manufactured by Adeka, and Adeka Arcles NCI-831. 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.

(Wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) 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), and substituted with an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group. Alkyl group having 8 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) Or substituted with 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 alkyl group having 1 to 8 carbon atoms, or a dialkyl group) Anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar represents an alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene , Furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl). n is represented by an integer of 0 or 1.
In particular, in the chemical 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, thiophene or thienylene. )

The blending amount of such oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing 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 to 3 parts by mass.

Specific examples of α-aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.

Specific examples of acylphosphine oxide photopolymerization initiators 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. Commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by Ciba Japan.

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 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 to 10 parts by mass.

In addition, examples of the photopolymerization initiator, photoinitiator assistant, and sensitizer that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones. 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, 2,4-diisopropylthioxanthone, and the like.
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.

Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenones such as 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compounds, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure® DMB manufactured by International Bio-Synthetics), 4-dimethyl Minobenzoic acid (n-butoxy) ethyl (Quantacure® BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylhexyl 4-dimethylaminobenzoic acid (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. The composition of the present embodiment preferably contains a thioxanthone compound from the viewpoint of deep curability, and in particular, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl. Thioxanthone compounds such as thioxanthone are preferred.

The compounding amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When the compounding quantity of a thioxanthone compound exceeds 20 mass parts, thick film sclerosis | hardenability will fall and it will lead to the cost increase of a product. More preferably, the ratio 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. The dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, so it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition, and reflects the color of the colored pigment itself. It becomes possible to provide a solder resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing 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 to 10 parts by mass.
These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.

The total amount of the photopolymerization initiator, the photoinitiator assistant, and the sensitizer as described above is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing 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, the sensitivity may be lowered in some cases, and they may work 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.

In the curable resin composition of the present invention, optional components described below can be blended.

In the curable resin composition of this invention, in order to provide heat resistance, a thermosetting component can be mix | blended.
Examples of the thermosetting component used in the present invention include known and commonly used blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, and the like. A thermosetting resin can be used. Such thermosetting components can be used alone or in combination of two or more.
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, Epototo YD-011 manufactured by Tohto Kasei Co., Ltd. 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 Japan's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo A . E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical D. E. R. 542, Araldide 8011 manufactured by Ciba Japan, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd. 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 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd. Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epotote YDF-170, YDF-175, YDF-175 manufactured by Toto Kasei 2004, Bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd. (all trade names); Hydrogenated bisphenol such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Tohto Kasei Co., Ltd. Type A epoxy resin: jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Japan, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. ) Glycidylamine type epoxy resin; Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Bread; Celoxide 2021 manufactured by Daicel Chemical Industries, and alicyclic epoxy such as Araldide CY175 and CY179 manufactured by Ciba Japan Resin; 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; bisphenols such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC (trade name) S-type epoxy resin; bisphenol A novolac 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 Japan (all trade names) Tetraphenylolethane type epoxy resin; Chiba Japan Heterocyclic epoxy resin such as Araldide PT810 manufactured by Nihon Kagaku Kogyo Co., Ltd. (both trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Tetra such as ZX-1063 manufactured by Tohto Kasei Co., Ltd. Glycidyl xylenoyl ethane resin; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 manufactured by DIC; HP-7200 manufactured by DIC Epoxy resin having a dicyclopentadiene skeleton such as HP-7200H; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by NOF Corporation; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; CTBN Modified epoxy resin (for example, YR-102 City Chemical Co., YR-450, etc.) and the like, but not limited thereto. These epoxy resins can be used alone or in combination of two or more.

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 bisphe Lumpur acids, 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. 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 in the range of 0.8 to 2 equivalents. 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.

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. 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 / isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / 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 parts by mass.

Moreover, amino resins, such as a melamine derivative and a benzoguanamine derivative, are mentioned as another thermosetting component which can be used suitably.
Examples of the amino resin include a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, and a methylol urea compound. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound, and alkoxymethylated urea compound are each methylol melamine compound, methylol benzoguanamine compound, methylol glycoluril compound, methylol group of methylol urea 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 friendly to the human body and the environment of 0.2% or less is preferable.

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, Mx-100 Mw-750LM (manufactured by Sanwa Chemical Co., Ltd.).

In addition, the photosensitive resin composition of the present invention contains a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule 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 the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- 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 such a 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 Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxime, methylethyl 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 done.

The blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module 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 (Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (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 with respect 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.

In the photosensitive resin composition of the present invention, a urethanization catalyst can be blended in order to promote the curing reaction between a hydroxyl group or a carboxyl group and an isocyanate group.
As this urethanization catalyst, it is preferable to use one or more urethanization catalysts selected from tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and / or amine salts. .

Examples of the tin catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.
The metal chloride is a metal chloride composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, ferrous nickel chloride, and ferric chloride.
The metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, etc. Is mentioned.
The metal sulfate is a metal sulfate composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include copper sulfate.
Examples of the amine salt include an organic acid salt amine salt of DBU (1,8-diaza-bicyclo [5.4.0] undecene-7).

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-hydroxy Chill) -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) imi Sol, 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′-amino) Propyl) -2-methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxyethyl) ) 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 ′ , N'-bis (2-hydroxypropyl) amine, melamine or / and benzoguanamine.

The compounding amount of the urethanization catalyst is sufficient in an ordinary quantitative ratio. For example, it is preferably 0.1 to 20 parts by mass, more preferably 0.1 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. 5 to 10 parts by mass.

Moreover, in the photosensitive resin composition of this invention, a bismaleimide compound can be mix | blended as another thermosetting component.
Examples of the bismaleimide compound include polyfunctional aliphatic / alicyclic maleimide and polyfunctional aromatic maleimide.
Examples of the polyfunctional aliphatic / alicyclic maleimide include N, N′-methylene bismaleimide, N, N′-ethylene bismaleimide, tris (hydroxyethyl) isocyanurate, and aliphatic / alicyclic maleimide carboxylic acid. Isocyanurate skeletal polymide compounds such as isocyanurate skeleton maleimide urethane compounds obtained by urethanization of tris (carbamate hexyl) isocyanurate and aliphatic / alicyclic maleimide alcohol Maleimides; isophorone bisurethane bis (N-ethylmaleimide), triethylene glycol bis (maleimidoethyl carbonate), aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic polyols dehydrated or esterified Family / alicyclic Aliphatic / alicyclic polymaleimide ester compounds obtained by transesterification of maleimide carboxylic acid ester with various aliphatic / alicyclic polyols; aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic Aliphatic / alicyclic polymaleimide ester compounds obtained by ether ring-opening reaction with aliphatic polyepoxides, obtained by urethanization reaction between aliphatic / alicyclic maleimide alcohol and various aliphatic / alicyclic polyisocyanates Aliphatic / alicyclic polymaleimide urethane compounds and the like.

As the polyfunctional aromatic maleimide, aromatic polymaleimide ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols, or transesterification reaction of maleimide carboxylic acid ester and various aromatic polyols, maleimide Of aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of carboxylic acid and various aromatic polyepoxides, and aromatic polymaleimide urethane compounds obtained by urethanization reaction of maleimide alcohol and various aromatic polyisocyanates And aromatic polyfunctional maleimides.

Specific examples of the polyfunctional aromatic maleimide include, for example, N, N ′-(4,4′-diphenylmethane) bismaleimide, N, N′-2,4-tolylene bismaleimide, N, N′-2, 6-tolylene bismaleimide, 1-methyl-2,4-bismaleimide benzene, N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N, N′-m-toluylene Bismaleimide, N, N′-4,4′-biphenylenebismaleimide, N, N′-4,4 ′-[3,3′-dimethyl-biphenylene] bismaleimide, N, N′-4,4′- [3,3′-dimethyldiphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, N, N′-4,4′-diphenylmethane bismale N, N′-4,4′-diphenylpropane bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N′-3,3′-diphenylsulfone bismaleimide, N, N ′ -4,4'-diphenylsulfone bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-tert-butyl-4- (4-maleimidophenoxy) phenyl ] Propane, 2,2-bis [3-s-butyl-4- (4-maleimidophenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-bis [2-Methyl-4- (4-maleimidophenoxy) -5-t-butylphenyl] -2-methylpropane, 4,4′-cyclohexylidene-bis [1- ( -Maleimidophenoxy) -2- (1,1-dimethylethyl) benzene], 4,4'-methylene-bis [1- (4-maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene 4,4′-methylene-bis [1- (4-maleimidophenoxy) -2,6-di-s-butylbenzene], 4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) ) -2-cyclohexylbenzene, 4,4′-methylenebis [1- (maleimidophenoxy) -2-nonylbenzene], 4,4 ′-(1-methylethylidene) -bis [1- (maleimidophenoxy) -2, 6-bis (1,1-dimethylethyl) benzene], 4,4 ′-(2-ethylhexylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4 ′-( 1-methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4′-cyclohexylidene-bis [1- (maleimidophenoxy) -3-methylbenzene], 2,2-bis [ 4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4 -Maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4 -Maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] pro 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, bis [3-methyl- (4-maleimidophenoxy) phenyl] methane, bis [3,5-dimethyl- (4-Maleimidophenoxy) phenyl] methane, bis [3-ethyl- (4-maleimidophenoxy) phenyl] methane, 3,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1 .02,6] decane, 4,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 3,9-bis [4- (4-maleimide) Phenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 4,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [ 2.1.2,6] decane, 1,8-bis [4- (4-maleimidophenoxy) phenyl] menthane, 1,8-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] menthane 1,8-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] menthane and the like.

Examples of these commercially available products include BMI-1000, BMI-1000H, BMI-1000S, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI- 5100, BMI-7000, BMI-7000H, BMI-TMH (manufactured by Daiwa Kasei Kogyo Co., Ltd.), MIA-200 (manufactured by DIC), and the like.

These bismaleimide compounds may be synthesized by a conventional method, or commercially available products may be used. Particularly, among the bismaleimide compounds, those that do not contain a halogen atom in the molecule are preferable from the viewpoint of not placing a burden on the environment. These can be used individually by 1 type or in combination of 2 or more types.

Moreover, in the photosensitive resin composition of this invention, a benzoxazine compound, an oxazoline compound, and a carbodiimide compound can be mix | blended as another thermosetting component.
Examples of the benzoxazine compound include bisphenol A type benzoxazine, bisphenol F type benzoxazine, and bisphenol S type benzoxazine. Examples of commercially available products include “Fa” (manufactured by Shikoku Kasei Co., Ltd.).
The oxazoline compound is not particularly limited as long as it contains an oxazoline group. Examples of commercially available products include K-2010E, K-2020E, K-2030E, WS-500, WS-700, and RPS-1005 from Epocross (manufactured by Nippon Shokubai Co., Ltd.).
The cyclocarbonate compound is not particularly limited as long as it is a cyclic compound and has a carbonate bond. For example, the alkylene carbonate compound which has a polyfunctional structure is mentioned.
Examples of the carbodiimide compound include dicyclohexylcarbodiimide and diisopropylcarbodiimide.

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

Polyfunctional mercaptan compounds can be used and are not particularly limited. For example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide Aliphatic thiols such as xylylene dimercaptan, 4,4'-dimercaptodiphenyl sulfide, and aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythrito Poly (mercaptoacetate) s of polyhydric alcohols such as tetrakis (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) of polyhydric alcohols such as erythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H) , 3H, 5H) -trione, and poly (mercaptobutyrate) s such as pentaerythritol tetrakis (3-mertabutbutyrate).

Furthermore, examples of the heterocyclic compound having a mercapto group that functions as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 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-mercapto-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-mercapto-6-hexanolactam and the like.

In particular, as a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable resin composition, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4- Triazole, 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred. These chain transfer agents 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 parts by weight or less, more preferably 0.05 parts by weight or more, with respect to 100 parts by weight of the carboxyl group-containing photosensitive resin. 5 parts by mass or less. If it is less than 0.01 parts by mass, the effect of adding a mercapto compound is not confirmed. On the other hand, if it exceeds 10 parts by mass, it may cause development failure of the photosensitive resin composition, a decrease in the dry management width, etc., which is not preferable. .

In the photosensitive resin composition of the present invention, a reactive diluent is blended in order to incur or insolubilize the carboxyl group-containing photosensitive resin in an alkaline aqueous solution by photocuring by irradiation with active energy rays. be able to.
Examples of such reactive diluents include compounds having a plurality of ethylenically unsaturated groups in the molecule, and commonly known polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates. , Carbonate (meth) acrylate, epoxy (meth) acrylate, and the like. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol Diacrylates of glycols such as propylene glycol; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate; Multivalent acrylates such as these ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols Multivalent acrylates; glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether Polyglycerides of glycidyl ethers such as triglycidyl isocyanurate; not limited to the above, polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes and polyester polyols may be directly acrylated or urethane acrylated via diisocyanate Acrylates and melamine acrylates and / or methacrylates corresponding to the above acrylates.

Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, 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.

The compounding amount of the compound having a plurality of ethylenically unsaturated groups in the molecule is desirably 5 to 100 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. 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.

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.

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 the red colorant include monoazo, disazo, monoazo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and the like.
Specifically, those having the following color index numbers (CI; issued by The Society of Dyers and Colorists) can be used.
Monoazo series includes 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, etc. are used.
Pigment Red 37, 38, 41 etc. are used as the disazo system.
Monoazo lakes include 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 etc. are used.
Examples of benzimidazolone-based compounds include Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, and Pigment Red 208.
Examples of perylene systems include 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, and the like.
Examples of the diketopyrrolopyrrole include Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, and Pigment Red 272.
Examples of condensed azo compounds include Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, and Pigment Red 242.
Examples of anthraquinone include Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207, and the like.
As the quinacridone series, Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209 and the like are used.

Blue colorant:
Examples of blue colorants include phthalocyanine and anthraquinone.
Among these, in the pigment system, compounds classified as Pigment, specifically, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4 Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60, etc. are used.
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 67 70 etc. are used.
Besides these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Green colorant:
Similarly, examples of the green colorant include phthalocyanine series, anthraquinone series, and perylene series. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used. 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, and anthraquinone. In particular,
As an anthraquinone series, Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202, and the like are used.
Examples of isoindolinone compounds include Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, and Pigment Yellow 185.
Examples of condensed azo compounds include Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, and Pigment Yellow 180.
As the benzimidazolone series, Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181 and the like are used.
As monoazo series, 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, etc. are used.
As the disazo group, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 and the like are used.

Other colorants such as purple, orange, brown and black may be added for the purpose of adjusting the color tone. Examples of such colorants include Pigment® Violet® 19, 23, 29, 32, 36, 38, 42, Solvent® Violet® 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, and CI Pigment Orange. 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 2 , C.I. Pigment Black 1, there is a C.I. Pigment Black 7 and the like.

The blending ratio of the colorant as described above is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. Is enough.

In the photosensitive resin composition of the present invention, a filler can be blended 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.

Furthermore, in the photosensitive resin composition of the present invention, a binder polymer can be used for the purpose of improving the touch drying property and the handling property. 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 the 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. In addition, an elastomer in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with a carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used. These elastomers can be 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 compounds such as methaquinone and benzoquinone, bis (2,2,6,6-teto Methyl-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 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, TINUVIN 5100 Japan) 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 (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Sumilizer 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 benzophenone derivatives 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'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-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 Japan, trade name) and the like.
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 order to improve the adhesiveness between layers or the adhesiveness between the photosensitive resin layer and the substrate, the photosensitive resin composition of the present invention can be used.
Specific examples of adhesion promoters include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi Chemical Industry Co., Ltd.) Axel M), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzo Examples include triazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agents.

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 curable resin composition of the present invention configured as described above is adjusted to a viscosity suitable for a coating method using, for example, an organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method It is applied by a method such as screen printing or curtain coating.

Then, a tack-free coating film is formed by volatilizing and drying (preliminary drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. At this time, the volatile drying is supported by a hot air circulation drying furnace, IR furnace, hot plate, convection oven or the like (a method equipped with an air heating type heat source by steam and contacting the hot air in the dryer countercurrently and the nozzle. Can be performed using a method of spraying on the body).

In addition, the curable resin composition of the present invention is applied on a carrier film, dried and wound up as a film to form a dry film, and this is laminated on a substrate to form a resin insulation layer May be.

At this time, as a base material on which a coating film is formed or a dry film is laminated, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy All grades (FR-4, etc.) of copper clad laminates, such as copper clad laminates for high frequency circuits using fluorine, polyethylene, PPO, cyanate esters, etc., other polyimide films, PET films, A glass substrate, a ceramic substrate, a wafer board, etc. can be mentioned.

Next, by a contact method (or non-contact method), pattern exposure (irradiation of active energy rays) is selectively performed by an active energy ray through a photomask on which a pattern is formed, or by exposure or a laser direct exposure machine.

As an exposure machine used for 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) can be used. For example, devices manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device that oscillates laser light having a maximum wavelength of 350 to 410 nm may be used.

As the active energy ray, either a gas laser or a solid-state laser may be used as long as it has a maximum wavelength in the range of 350 to 410 nm. The exposure amount varies depending on the film thickness and the like, but can generally be in the range of 5 to 1000 mJ / cm ² , preferably 10 to 500 mJ / cm ² , more preferably 20 to 400 mJ / cm ² .

By exposing in this way, the exposed portion (the portion irradiated by the active energy ray) is cured, and then the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution). Thus, a resist pattern is formed.

At this time, the developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and the developer is potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, silicic acid. Alkaline aqueous solutions such as sodium, ammonia and amines can be used.

Further, when a thermosetting component is added, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing photosensitive resin and a plurality of cyclic ether groups in the molecule and A thermosetting component having 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.

Thus, in the curable resin composition of the present invention, by containing a carboxyl group-containing photosensitive resin, a photopolymerization initiator, and, if necessary, a diluent, a thermosetting component, a colorant, etc., it is excellent. Alkali developability, and excellent workability and mass productivity can be obtained. Furthermore, the coating film obtained by applying this is selectively exposed, developed, and finish-cured as necessary, so that adhesion, chemical resistance, electroless gold plating resistance, thermal shock resistance, PCT A cured product excellent in resistance, electrical insulation and the like can be obtained, and high reliability can be provided by using the cured product for a printed wiring board.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, it cannot be overemphasized that this invention is not limited to a following example.
(Resin synthesis example 1)
Into an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, a bisphenol A-formaldehyde type phenol resin (Maywa Kasei Co., Ltd., trade name “BPA-D”, OH equivalent: 120) 0 g, 1.20 g of potassium hydroxide and 120.0 g of toluene were charged, and the system was purged with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped 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 g 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 propylene oxide reaction solution of bisphenol A-formaldehyde type phenol resin was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
293.0 g of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, a thermometer and an air blowing tube. The reaction vessel was charged with air at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring.
12.6 g of water produced by the reaction was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71%. . This is designated as resin solution A-1.

(Resin synthesis example 2)
120 parts of bisphenol A-formaldehyde type phenolic resin (Maywa Kasei Co., Ltd., trade name “BPA-D”, OH equivalent: 120), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate are charged into a reaction kettle and stirred. The reaction was started by heating to 150 to 160 ° C., and then 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 propylene carbonate reaction product of bisphenol A-formaldehyde type phenol resin was obtained. This was equivalent to an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After the obtained reaction product was dissolved in 120 parts of toluene, 43.2 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid, and 0.04 part of methylhydroquinone were charged therein, and air was supplied at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 11.6 parts of water produced by the reaction was distilled as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with diethylene glycol monoethyl ether acetate 118.1 parts, and the acrylate resin solution was obtained.
Next, 332.5 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride is gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71%. Obtained. This is designated as resin solution A-2.

(Resin synthesis example 3)
A reaction kettle is charged with 120 parts of bisphenol A-formaldehyde type phenol resin (Maywa Kasei Co., Ltd., trade name “BPA-D”, OH equivalent: 120), 0.6 part of triphenylphosphine and 96.9 parts of ethylene carbonate. While stirring, the temperature was raised to 150 to 160 ° C. to start the reaction, 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 propylene carbonate reaction product of bisphenol A-formaldehyde type phenol resin was obtained. This was equivalent to an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After the obtained reaction product was dissolved in 120 parts of toluene, 43.2 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid, and 0.04 part of methylhydroquinone were charged therein, and air was supplied at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 11.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with diethylene glycol monoethyl ether acetate 118.1 parts, and the acrylate resin solution was obtained.
Next, 332.5 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 89 mgKOH / g and a nonvolatile content of 72%. Obtained. This is designated as Resin Solution A-3.

(Resin synthesis example 4)
While charging 98 kg of salicylaldehyde type phenol resin (Maywa Kasei Co., Ltd., trade name “MEH-7500”, OH equivalent: 98), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate, stirring them. The reaction was started by heating to 150 to 160 ° C. and then 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.
Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 159 g / eq. A propylene carbonate reaction product of salicylaldehyde type phenol resin was obtained. This was equivalent to an average of 1.05 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After the obtained reaction product was dissolved in 120 parts of toluene, 43.2 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid and 0.04 part of methylhydroquinone were charged therein, and air was supplied at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 11.8 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with diethylene glycol monoethyl ether acetate 118.1 parts, and the acrylate resin solution was obtained.
Next, 332.5 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride is gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 92 mgKOH / g and a nonvolatile content of 72%. Obtained. This is designated as Resin Solution A-4.

(Resin synthesis example 5)
A reaction vessel was charged with 205 parts of a phenol resin of the general formula (III) (Maywa Kasei Co., Ltd., trade name “MEH-7851”, OH equivalent: 205), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate, and stirred. The reaction was started by heating to 150 to 160 ° C., 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. Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 269 g / eq. A propylene carbonate reaction product of a phenol resin of the general formula (III) was obtained. This was equivalent to an average of 1.1 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After the above reactants were dissolved in 150 parts of toluene, 36.0 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid and 0.04 part of methylhydroquinone were charged therein, and air was blown at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 9.6 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, and the resulting reaction solution was washed with water and distilled off while replacing toluene with 150 parts of diethylene glycol monoethyl ether acetate by an evaporator to obtain an acrylate resin solution.
Next, 442 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min and stirred. Then, 76.0 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 79 mgKOH / g and a nonvolatile content of 71%. . This is designated as Resin Solution A-5.

(Resin synthesis example 6)
A reaction vessel was charged with 180 parts of a phenol resin of general formula (IV) (Maywa Kasei Co., Ltd., trade name “MEH-7800”, OH equivalent: 180), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate, and stirred. The reaction was started by heating to 150 to 160 ° C., 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. Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 244 g / eq. A propylene carbonate reaction product of a phenol resin of the general formula (IV) was obtained. This was equivalent to an average of 1.1 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After dissolving the above reactants in 120 parts of toluene, 36.0 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid and 0.04 part of methylhydroquinone are charged into it, and air is blown at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. The water produced | generated by reaction distills 9.7 parts of water as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with 120 parts of diethylene glycol monoethyl ether acetate, and the acrylate resin solution was obtained. Next, 388 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min and stirred. Then, 76.0 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 83 mg KOH / g and a nonvolatile content of 74%. . This is designated as Resin Solution A-6.

(Resin synthesis example 7)
A reaction kettle was charged with 180 parts of a phenol resin of the general formula (V) (trade name “DPP-6115H”, OH equivalent: 180, manufactured by Nippon Oil Corporation), 0.6 part of triphenylphosphine, and 112 parts of propylene carbonate. The reaction was started by heating to 150 to 160 ° C. and then 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. Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 243 g / eq. A propylene carbonate reaction product of a phenol resin of the general formula (V) was obtained. This was equivalent to an average of 1.1 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After dissolving the above reactants in 120 parts of toluene, 36.0 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid and 0.04 part of methylhydroquinone are charged into it, and air is blown at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 9.8 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with 120 parts of diethylene glycol monoethyl ether acetate, and the acrylate resin solution was obtained.
Next, 388 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min and stirred. Then, 76.0 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 82 mgKOH / g and a nonvolatile content of 73%. . This is designated as Resin Solution A-7.

(Resin synthesis example 8)
Charge 140 parts of phenolic resin of general formula (VI) (Nippon Kayaku Co., Ltd., trade name “Kayahard CBN”, OH equivalent: 140), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate to a reaction kettle and stir. The reaction was started by heating to 150 to 160 ° C., 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. Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 204 g / eq. A propylene carbonate reaction product of a phenol resin of the general formula (VI) was obtained. This was equivalent to an average of 1.1 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After dissolving the above reactants in 120 parts of toluene, 39.6 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid and 0.04 part of methylhydroquinone are charged into it, and air is blown at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 10.5 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with 120 parts of diethylene glycol monoethyl ether acetate, and the acrylate resin solution was obtained.
Next, 312 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min and stirred. Then, 68.4 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 85 mgKOH / g and a non-volatile content of 73%. . This is designated as Resin Solution A-8.

(Comparative resin synthesis example 1)
Orthocresol novolac type epoxy resin (produced by DIC, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average number of functional groups 7.6) to 1070 g of diethylene glycol monoethyl ether acetate (number of glycidyl groups (total number of aromatic rings): 5) 0.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. This is designated as resin solution R-1.

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

Using these resin solutions, the various components shown in Tables 1 and 2 are blended in the proportions (parts by mass) shown in Tables 1 and 2, premixed with a stirrer, kneaded with a three-roll mill, and solder resist A photocurable resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photocurable resin composition was evaluated by the particle size measurement by the grindometer made from an Eriksen company.

* 1 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907: Ciba Japan)
* 2 2,4-Diethylthioxanthone (KAYACURE DETX-S: Nippon Kayaku Co., Ltd.)
* 3 2- (Acetyloxyiminomethyl) thioxanthen-9-one * 4 Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0 -Acetyloxime)
(Irgacure OXE 02: made by Ciba Japan)
* 5 Adeka Arcles NCI-831 (manufactured by ADEKA Corporation)
* 6 Modified novolac epoxy resin (EPICLON N-865: manufactured by DIC)
* 7 Bixylenol type epoxy resin (YX-4000: manufactured by Japan Epoxy Resin Co., Ltd.)
* 8 Epoxidized polybutadiene (Epolide PB3600: manufactured by Daicel Chemical Industries)
* 9 Methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd.)
* 10 Block isocyanate (Asahi Kasei Chemicals)
* 11 Dipentaerythritol hexaacrylate (DPHA: Nippon Kayaku Co., Ltd.)
* 12 CIPigment Blue 15: 3
* 13 CIPigment Yellow147
* 14 2-mercaptobenzothiazole * 15 Antioxidant (Ciba Japan)
* 16 B-30 (manufactured by Sakai Chemical Co., Ltd.)
* 17 Hydrotalcite (Kyowa Chemical Industry Co., Ltd.)
* 18 Diethylene glycol monoethyl ether acetate

* 1 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907: manufactured by Ciba Japan)
* 2 2,4-Diethylthioxanthone (KAYACURE DETX-S: Nippon Kayaku Co., Ltd.)
* 3 2- (Acetyloxyiminomethyl) thioxanthen-9-one * 4 Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O -Acetyloxime)
(Irgacure OXE 02: Ciba Japan)
* 5 Adeka Arkles NCI-831 (manufactured by ADEKA Corporation)
* 6 Biphenyl novolac modified epoxy resin (NC3000: Nippon Kayaku Co., Ltd.)
* 7 Bixylenol type epoxy resin (YX-4000: manufactured by Japan Epoxy Resin)
* 8 Epoxidized polybutadiene (Epolide PB3600: manufactured by Daicel Chemical Industries)
* 9 Methylated melamine resin (MW-100LM: manufactured by Sanwa Chemical Co., Ltd.)
* 10 Block isocyanate (TPA-B80E: Asahi Kasei Chemicals)
* 11 Dipentaerythritol hexaacrylate (DPHA: Nippon Kayaku Co., Ltd.)
* 12 CIPigment Blue 15: 3
* 13 CIPigment Yellow147
* 14 2-mercaptobenzothiazole * 15 Antioxidant (Ciba Japan)
* 16 B-30 (manufactured by Sakai Chemical)
* 17 Hydrotalcite (Kyowa Chemical Industry Co., Ltd.)
* 18 Diethylene glycol monoethyl ether acetate

Examples 1 to 27 and Comparative Examples 1 to 4 thus obtained were evaluated as follows. These evaluation results are shown in Tables 3 and 4.
(Performance evaluation)
<Optimal exposure>
The obtained curable resin compositions of Examples and Comparative Examples were subjected to circuit printing with a copper thickness of 35 μm after buffing, washed with water, dried and then applied to the entire surface by a screen printing method. It was dried for 60 minutes in a drying furnace. After drying, the step tablet remaining after exposure through a step tablet (Kodak No. 2) using an exposure device equipped with a high-pressure mercury lamp and development (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) in 90 seconds. The optimal exposure amount was obtained when the pattern was 7 steps.
<Developability>
The curable resin compositions of each Example and Comparative Example were applied to a copper solid substrate by screen printing so that the thickness was about 25 μm after drying, and was dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. After drying, development was performed with a 1% by mass aqueous sodium carbonate solution, and the time until the dried coating film was removed was measured with a stopwatch.
<Maximum development life>
The composition of each example and comparative example was applied onto the patterned copper foil substrate by screen printing, dried at 80 ° C., taken out every 20 minutes from 20 to 80 minutes, and allowed to cool to room temperature. . The substrate was developed with a 1% by weight aqueous sodium carbonate solution at 30 ° C. for 90 seconds under the condition of a spray pressure of 0.2 MPa, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.
<Tackiness>
The composition of each Example and Comparative Example 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 with ORC (HMW-GW20) under reduced pressure conditions for 1 minute. Thereafter, the state of the film when it was peeled off was evaluated.
○: When the film is peeled off, there is no resistance, but the coating film has a slight mark. (Including the case where there is no resistance and no mark is left on the coating.)
(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 composition of 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 optimum exposure amount, and a 1% by weight sodium carbonate aqueous solution at 30 ° C. is developed for 90 seconds under a spray pressure of 0.2 MPa / cm ^2. A resist pattern was 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 vol% H ₂ SO ₄ aqueous solution at room temperature for 30 minutes, and the penetration and dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed.
Examples 15 to 27 and Comparative Examples 3 and 4 were evaluated in the same manner except that a 10% by mass HCl aqueous solution was used.
○: No change is observed Δ: Only a slight change ×: The coating film is swollen or swelled off <Alkali resistance>
The evaluation substrate was immersed in a 10 vol% 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.
Examples 15 to 27 and Comparative Examples 3 and 4 were evaluated in the same manner except that a 10% by mass NaOH aqueous solution was used.
○: No change is observed Δ: Only a slight change ×: The coating film is swollen or swelled off <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 substrate on which the solder resist cured coating film was formed was treated for 168 hours under the conditions of 121 ° C., saturation, 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Corporation), and the state of the coating film was determined. evaluated. Judgment criteria are as follows.
○: No swelling, peeling, discoloration, or elution △: Some swelling, peeling, discoloration, or elution ×: Many swelling, peeling, discoloration, or elution <Resistance to thermal shock>
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 resistance test with a thermal shock tester (manufactured by ETAC Co., Ltd.) at a cycle of −55 ° C./30 minutes to 150 ° C./30 minutes. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged according to the following criteria.
○: Crack generation rate of less than 30% △: Crack generation rate of 30-50%
×: Crack occurrence rate of 50% or more Note that Examples 15 to 27 and Comparative Examples 3 and 4 were judged according to the following criteria.
◎: Crack generation rate less than 20% ○: Crack generation rate 20 to 40%
Δ: Crack generation rate 40-60%
×: Crack generation 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 = 50 microns / 50 microns) were formed, and an evaluation substrate was prepared. This evaluation substrate was placed in a high-temperature and high-humidity tank under an atmosphere of 130 ° C. and humidity 85%, charged with a voltage of 5 V, and subjected to an in-chamber HAST test for 168 hours. The insulation resistance value in the tank when 168 hours passed was evaluated according to the following criteria. The evaluation results are shown in Table 2.
○: 10 ⁸ Ω or more △: 10 ⁶ to 10 ⁸ Ω
×: 10 ⁶ Ω or less

[Supplement under rule 26 12.05.2010]

As is apparent from the results shown in Table 3, the curable resin composition of the present embodiment is excellent in PCT resistance, thermal shock resistance, electrical characteristics, and solder required for use as a solder resist for IC packages. It was found that it has sufficient characteristics in heat resistance and electroless gold plating resistance. On the other hand, Comparative Examples 1 and 2 had good characteristics such as acid resistance and alkali resistance, but sufficient characteristics such as PCT resistance, thermal shock resistance, and electrical characteristics could not be obtained.

As is clear from the results shown in Table 4, Comparative Examples 3 and 4 did not give good results in terms of PCT resistance, thermal shock resistance, and electrical characteristics. However, in Examples 15 to 27, it was revealed that the use of a carboxyl group-containing photosensitive resin derived from various phenol skeletons has excellent PCT resistance, thermal shock resistance, and electrical characteristics.

<Evaluation with dry film>
The curable resin compositions of Examples 1 to 7, Example 14, Example 15, Examples 18 to 24, Example 27 and Comparative Examples 1 to 4 were diluted with methyl ethyl ketone and applied onto a PET film. A photosensitive resin composition layer having a thickness of 20 μm was formed by drying at 80 ° C. for 30 minutes. Further, a dry film was prepared by laminating a cover film thereon, and the dry films using the compositions of Examples 1 to 7 and Example 14 were designated as Examples 28 to 35, respectively, Examples 15 and 18 to 24, dry films using the compositions of Example 27 were designated as Examples 36 to 44, respectively, and dry films using the compositions of Comparative Examples 1 to 4 were designated as Comparative Examples 5 to 8, respectively.
Then, the cover film was peeled off, the film was heat-laminated on the patterned copper foil substrate, and then exposed under the same conditions as the substrate used for the evaluation of the coating film properties of the above-mentioned composition.
After the exposure, the carrier film was peeled off, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was developed for 90 seconds under the condition of a spray pressure of 0.2 MPa / cm ² to obtain a resist pattern.
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 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 Tables 5 and 6.

[Supplement under rule 26 12.05.2010]

As is clear from the results shown in Table 5, in the evaluations of the dry films of Examples 28 to 35 using the resin compositions of Examples 1 to 7 and Example 14, both were the same as the results shown in Table 3. Good evaluation results were obtained for PCT resistance, thermal shock resistance, and electrical characteristics. On the other hand, in the dry films of Comparative Examples 5 and 6 using the resin compositions of Comparative Examples 1 and 2, good results were obtained with respect to acid resistance, alkali resistance, and solder heat resistance, but sufficient PCT resistance, cold heat Impact resistance and electrical characteristics could not be obtained.

From the results shown in Table 6, as in Table 5, resist cured products using carboxyl group-containing photosensitive resins derived from various phenol skeletons are required to have PCT resistance when used for electronic components such as semiconductor packages, It can be seen that it has excellent thermal characteristics as well as excellent thermal shock resistance.

<Evaluation of flame retardancy>
The various components and ratios (parts by mass) shown in Table 7 were blended, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a photocurable resin composition for a solder resist. The prepared composition was applied onto the entire surface of a 0.1 mm thick FR-4 material by screen printing and dried at 80 ° C. for 30 minutes. Using this exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the entire surface was exposed at an optimum exposure amount, and development with a 1 mass% sodium carbonate aqueous solution at 30 ° C. was performed for 90 seconds under the condition of a spray pressure of 0.2 MPa / cm ² . 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 obtained evaluation substrate was evaluated for flame retardancy by a method and apparatus conforming to the flame retardant test standard UL94 of a polymer material of United States Underwriters Laboratories Inc. (abbreviated as UL). The evaluation results are shown in Table 8.
The evaluation criteria are as follows.
○: Flame resistance equivalent to UL94V-0 ×: Not equivalent to UL94V-0

* 1 Irgacure OXE 02: Ciba Japan * 2 Biphenyl novolak modified epoxy resin (NC3000: Nippon Kayaku)
* 3 Dipentaerythritol pentaacrylate (DPHA: Nippon Kayaku Co., Ltd.)
* 4 CIPigment Blue 15: 3
* 5 CIPigment Yellow147
* 6 2-Mercaptobenzothiazole * 7 Antioxidant (Ciba Japan)
* 8 Spherical silica (manufactured by Admatechs)
* 9 Barium sulfate # 100 (manufactured by Sakai Chemical Co., Ltd.)
* 10 Hydrotalcite compound (Kyowa Chemical Industry Co., Ltd.)

As is clear from the results shown in Table 8, the curable resin composition of the present invention also has excellent flame retardancy.

Claims

An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a phenol resin having at least one skeleton of general formulas (I) to (VI) with an alkylene oxide or a cyclocarbonate compound, A carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride;
A curable resin composition comprising a photopolymerization initiator.

(R in the general formulas (III), (IV), and (VI) represents hydrogen or a methyl group.)
A cured product obtained by applying the curable resin composition according to claim 1 to a substrate and curing the composition by irradiation with active energy rays and heating or irradiation with active energy rays or heating.
A dry film obtained by applying the curable resin composition according to claim 1 onto a film and drying it.
A cured product obtained by attaching the dry film according to claim 3 to a substrate and curing it by irradiation with active energy rays and heating or irradiation with active energy rays or heating.
A printed wiring board comprising the cured product according to claim 2.