JP2018151628A - Photosensitive resin composition and cured product of the same, and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is excellent in photosensitivity to active energy rays, can form a pattern by development of a dilute alkali aqueous solution to form a fine image, obtains a cured film with sufficient flexible property by thermosetting in a post-curing (postcure) step, and is suitable for solder resist ink having high insulating property and excellent adhesion, developing property, heat resistance and electroless gold plating resistance, and to provide a cured product of the same.SOLUTION: A photosensitive resin composition contains a carboxyl group-containing resin (A), a crosslinking agent (B), a photopolymerization initiator (C) and a liquid epoxy resin (D) obtained by reaction of an epoxy group-containing alkoxy silicon compound represented by the following formula (1a) and a substituted alkoxy silicon compound represented by the following formula (1b). In formula (1a), Rrepresents a substituent having a glycidyl group. Rrepresents an alkyl group having 4 or less carbon atoms. In formula (1b), Rrepresents an alkyl group having 10 or less carbon atoms, an aryl group or an unsaturated aliphatic residue group. Rrepresents an alkyl group having 4 or less carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition containing a liquid epoxy resin or the like and a cured product thereof.

  A photosensitive resin composition using a photosensitive epoxycarboxylate compound has an excellent balance of various properties such as environmental, thermal, and mechanical properties and adhesion to a substrate. For this reason, it has been used for a long time in the fields of paints, coatings, adhesives and the like. Recently, it is well known that it is used in a wide range of industrial fields, such as electrical / electronic component manufacturing applications and printed circuit board manufacturing applications, and its application range is expanding. However, along with the expansion of this application field, the addition of high functions such as flexibility, low warpage and low water absorption to the photosensitive resin composition using the epoxy carboxylate compound has been required. Development of various photosensitive resin compositions has been actively promoted mainly for parts manufacturing applications and printed circuit board manufacturing applications. Conventionally, Patent Document 1 discloses a photosensitive thermosetting resin composition for a solder resist that can be applied to a flexible substrate in addition to a rigid substrate.

  In recent years, there is a tendency for the temperature applied to the package to become very high, such as the transition to surface mounting and the use of lead-free solder in consideration of environmental problems. Along with this, the temperature reached inside and outside of the package is remarkably increased, and the conventional liquid photosensitive resist is improved due to the problem that the coating film cracks due to thermal shock or peels off from the substrate or sealing material. It has been demanded.

  In order to solve such a problem, Patent Document 2 includes (A) a carboxy group-containing resin, (B) a photopolymerization initiator, and (D) a dilute alkaline aqueous solution containing epoxidized polybutadiene. A developable photocurable thermosetting resin composition has been proposed (for example, Patent Document 2).

JP 2000-109541 A JP 2010-256728 A JP 2007-332211 A

  The present invention is excellent in photosensitivity to active energy rays, can form a pattern of a fine image by developing with a dilute alkaline aqueous solution, and has a sufficiently flexible cured film obtained by heat curing in a subsequent curing (post-cure) step. It is to provide a resin composition suitable for a solder resist ink having high insulation, excellent adhesion, developability, heat resistance, and electroless gold plating resistance, and a cured product thereof.

In order to solve the above-mentioned problems, the present inventors have completed the present invention as a result of intensive studies on the photosensitive resin composition.
That is, the present invention
[1]
Carboxy group-containing resin (A), crosslinking agent (B), photopolymerization initiator (C), epoxy group-containing alkoxysilicon compound represented by the following formula (1a) and substituted alkoxysilicon represented by the following formula (1b) A photosensitive resin composition containing a liquid epoxy resin (D) obtained by reacting a compound;

(In the formula, R _1a represents a substituent having a glycidyl group. R ₂ represents an alkyl group having 4 or less carbon atoms.)

(In the formula, R _1b represents an alkyl group having 10 or less carbon atoms, an aryl group, or an unsaturated aliphatic residue. R ₃ represents an alkyl group having 4 or less carbon atoms.)
[2]
The said liquid epoxy resin (D) contains the structure represented by following formula (2), The photosensitive resin composition of the preceding clause [1],

(A plurality of R _{4 in the} formula represents R _1a or R _1b , and R ₅ represents an alkyl group having 4 or less carbon atoms. P, q, and r each represents an integer of 0 to 50, provided that None of p, q, and r is 0.)
[3]
In the liquid epoxy resin (D), R _1a in the formula (1a) is an alkyl group substituted with a glycidoxyalkyl group having 3 or less carbon atoms, and R _1b in the formula (1b) has 6 carbon atoms. The photosensitive resin composition according to the above item [1], which is the following alkyl group or aryl group:
[4]
The photosensitive resin composition according to any one of [1] to [3], wherein the total chlorine content of the liquid epoxy resin (D) is 100 ppm or less,
[5]
The photosensitive resin composition according to any one of [1] to [4], wherein the liquid epoxy resin (D) has a melt viscosity at 25 ° C. of 50 mPa · s to 10 Pa · s,
[6]
In the liquid epoxy resin (D), when the higher-order structure ratio is defined as x = p / (p + q + r), the value of x is in the range of 0.5 to 0.9 [1] to [5] Photosensitive resin composition according to any one of
[7]
The carboxy group-containing resin (A) is obtained by reacting an epoxy compound (a) having two or more epoxy groups in the molecule with a monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule. The photosensitive resin composition according to any one of [1] to [6], which is a reaction product of an epoxycarboxylate compound and a polybasic acid anhydride (c);
[8]
Epoxy obtained by reacting the carboxy group-containing resin (A) with an epoxy compound (d) having two epoxy groups in the molecule and a monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule Any of [1] to [6] above, which is a reaction product of a carboxylate compound, a diisocyanate compound (e), a carboxylic acid (f) having two hydroxyl groups in the molecule and / or a diol compound (g). The photosensitive resin composition according to claim 1,
[9]
A cured product of the photosensitive resin composition according to any one of [1] to [8] above,
[10]
A substrate having a layer of the cured product as described in [9] above;
[11]
An article having the base material according to [10] above;
About.

  The photosensitive resin composition of the present invention has no tackiness and high photosensitivity. In addition, the cured product of the present invention is excellent in solder heat resistance, chemical resistance, gold plating resistance, etc., and the surface of the cured product does not crack, and even when a thin substrate is used, there is little warping on the substrate. Therefore, it is particularly suitable for a photosensitive resin composition for printed circuit boards.

  Suitably, for example, it can be used for applications such as solder resists for printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, photosensitive optical waveguides and the like that require particularly high reliability. I can do it.

The NMR chart of the liquid epoxy resin (D1) of the synthesis example 4 is shown.

  The liquid epoxy resin (D) used in the present invention is obtained by condensing an epoxy group-containing alkoxysilicon compound represented by the following formula (1a) and a substituted alkoxysilicon compound represented by the following formula (1b).

(In the formula, R _1a represents a substituent having a glycidyl group. R ₂ represents an alkyl group having 4 or less carbon atoms.)

(In the formula, R _1b represents an alkyl group having 10 or less carbon atoms, an aryl group, or an unsaturated aliphatic residue. R ₃ represents an alkyl group having 4 or less carbon atoms.)

  The condensation reaction can be obtained by (co) condensation in the presence of a basic catalyst or an acidic catalyst.

The substituent R _1a having a glycidyl group in the epoxy group-containing alkoxysilicon compound of the formula (1a) is not particularly limited as long as it is a substituent having a glycidyl group, but β-glycidoxyethyl group, γ- Examples thereof include glycidoxyalkyl groups and glycidyl groups having 4 or less, preferably 3 or less carbon atoms such as glycidoxypropyl group and γ-glycidoxybutyl group. Of these, β-glycidoxyethyl group and γ-glycidoxypropyl group are preferable.
Preferable specific examples of compounds that can be used as the compound of the formula (1a) having these substituents R _1a include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and the like can be mentioned.

In addition, examples of the substituted alkoxysilicon compound represented by the formula (1b) include an alkyl group, aryl group or unsaturated aliphatic residue in which the substituent R _1b has 10 or less carbon atoms. From the viewpoints of compatibility and physical properties of the cured product, a compound having a combination of an alkyl group or aryl group having 6 or less carbon atoms and R ₃ being an alkyl group having 4 or less carbon atoms is preferable. Specifically, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-propyltrimethoxysilane , N-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane and other alkyltrialkoxysilanes, phenyltrimethoxysilane, phenyltriethoxysilane and other aryltrialkoxysilanes And the like.
In addition, as an alkoxy group in the said epoxy group containing alkoxy silicon compound and a substituted alkoxy silicon compound, a methoxy group or an ethoxy group is preferable at the point of reaction conditions, and a methoxy group is especially preferable.
In order to promote (co) condensation, water can be added as necessary. The amount of water added is usually 0.05 to 5.0 mol, preferably 0.5 to 3.0 mol, more preferably 0.8 to 1. mol, based on 1 mol of alkoxy groups in the entire reaction mixture. 5 moles. Here, the molecular weight can be influenced by adjusting the amount of water added. That is, 0.8 to 1.5 mol is preferable because it is possible to synthesize an epoxy resin having a desired viscosity width with good coatability and hardly causing dripping.

The reaction ratio between the epoxy group-containing alkoxysilicon compound represented by the formula (1a) and the substituted alkoxysilicon compound represented by the formula (1b) is preferably 1:10 to 500: 1 in molar ratio. 1: 1 to 500: 1 is more preferable, 1: 1 to 300: 1 is particularly preferable, and 1: 1 to 200: 1 is very preferable. As described above, by reacting a large amount of the epoxy group-containing alkoxysilicon compound of the formula (1a), it is possible to exhibit the effect of elastic modulus having a high crosslinking density.
The reaction temperature in the condensation reaction is usually 45 ° C. to 80 ° C. (for example, the reaction time is 1 hour or more, preferably 5 hours or more), preferably 45 ° C. to 60 ° C., more preferably 45 ° C. to 55 ° C. . If the reaction temperature is lower than 45 ° C, the reaction is difficult to proceed, and a large amount of monofunctional monomer remains, so that there is a possibility that a cured product with high hardness cannot be obtained. If the reaction temperature is higher than 80 ° C, the cleavage reaction of silicon-oxygen proceeds. As a result, the reaction may be difficult to proceed.

The catalyst used for the condensation reaction is not particularly limited, but sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia, triethylamine, diethylenetriamine, n -Uses basic catalysts such as butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide, and acidic catalysts such as acetic acid, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, and boron trifluoride. I can do it. Among these, an inorganic base or ammonia is preferable because the catalyst can be easily removed from the product. The addition amount of the catalyst is usually 5 × 10 ^{−4 to} 7.5% by weight, preferably 1 × 10 ^{−3 to} 5% by weight, based on the total of the epoxy group-containing alkoxysilicon compound and the substituted alkoxysilicon compound.

  The condensation reaction can be carried out without a solvent or in a solvent. The solvent is not particularly limited as long as it is a solvent that dissolves the epoxy group-containing alkoxysilicon compound and the substituted alkoxysilicon compound. Examples of such solvents include aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene.

After completion of the reaction, the excess catalyst can be quenched. The quench treatment is not particularly limited as long as it is a component that can neutralize the catalyst, and examples of the acidic compound include phosphoric acid, boric acid, citric acid, acetic acid, and sodium dihydrogen phosphate. Examples of the basic compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate and diethylenetriamine, Examples include organic amines such as triethylenetetramine, aniline, and phenylenediamine. Moreover, it is also preferable to use together with a reducing agent. As a preferable treatment method, there is a method of quenching the remaining catalyst using a reducing agent after neutralization adjustment to pH 6 to 10 with an acidic compound. When the pH is other than 6 to 10, there is a large amount of heat generated when reducing the excess catalyst, which may cause decomposition products, and the molecular weight may not be stable. Here, coloring of the liquid epoxy resin from which sodium dihydrogen phosphate is obtained can be suppressed, and a colorless and transparent liquid epoxy resin can be obtained, which is preferable. Furthermore, since it has a buffer region in the neutral region, it contributes to stabilization of the molecular weight.
Although it does not specifically limit as the usage-amount of a quenching agent, From a viewpoint of stabilizing molecular weight, it is preferable to set it as 3 mol or more (especially 5 mol or more) with respect to 1 mol of remaining catalysts. When the amount of the quenching agent used is less than 3 mol, silanol groups present in the epoxy resin act as a Lewis acid, and the quenching agent may be consumed, and neutralization may not be performed sufficiently.
As a form of the quenching agent, for example, an aqueous solution or a solid quenching agent having a constant concentration of 10% or the like can be used, but it is preferable to use a solid type from the viewpoint of stabilization of molecular weight.

  The liquid epoxy resin (D) thus obtained contains a structure represented by the following formula (2).

(A plurality of R _{4 in the} formula represents R _1a or R _1b , and R ₅ represents an alkyl group having 4 or less carbon atoms. P, q, and r each represents an integer of 0 to 50, provided that p, q, and r are all not 0)

The liquid epoxy resin (D) used in the present invention contains a higher-order structure that is higher-order crosslinked by silicon-oxygen-silicon. The higher the higher-order structure ratio, the higher the crosslink density, so that a cured product having a higher elastic modulus can be obtained.
The higher order structure ratio can be defined as x = p / (p + q + r). The x value used here can be calculated by identifying the progress rate of the sol-gel reaction around the silicon atom from ²⁹ Si-NMR. Specifically, it can be obtained by calculating the ratio of the peak observed at 62 to 72 ppm with respect to the peak area of all silicon atoms observed.
( ²⁹ Si-NMR measurement conditions)
Manufacturer: Agilent Company Equipment: 500MHz VNMR
Integration count: 5000 times Waiting time: 1 second Sample tube: Sample tube for quartz NMR manufactured by Shigemi Co., Ltd. (operation)
1 g of a sample, 6 mg of chromium (III) acetylacetonate as a relaxation reagent, 2 μl of tetramethylsilane as a standard reagent, and 600 μl of tetrahydrofuran as a solvent were mixed to obtain a resin solution. 500 μl was extracted from this resin solution, mixed with 100 μl of heavy tetrahydrofuran for locking, and charged into a sample tube to start measurement.
The x value is preferably in the range of 0.5 to 0.9, more preferably 0.55 to 0.85, and even more preferably 0.6 to 0.8. The value of x represents the progress rate of the sol-gel reaction in the product. That is, the higher the value of x, the higher the sol-gel reaction proceeds. When the value of x is lower than 0.5, a cured product having an insufficient elastic modulus is obtained. There is a concern about the conversion.

  The total amount of chlorine in the liquid epoxy resin (D) is preferably 100 ppm or less, more preferably 50 ppm or less, and further preferably 30 ppm or less. For example, if a chlorosilane body that is a precursor of formula (1a) or formula (1b) remains, the total chlorine amount is assumed to exceed 100 ppm, which may cause migration in the cured product. There is concern about deterioration of reliability. Further, the residual free sodium is preferably 1.2 ppm or less, and the residual free chlorine is preferably 0.5 ppm or less.

  The viscosity of the liquid epoxy resin (D) is preferably 50 mPa · s to 10 Pa · s, more preferably 500 mPa · s to 5 Pa · s, and further preferably 1.0 Pa · s to 3 Pa · s, as measured at 25 ° C. preferable. When the viscosity is lower than 50 mPa · s, dripping is caused in the composition, and the composition on the substrate is repelled, so that a uniform film may not be obtained. If it is higher than 10 Pa · s, the coating property is poor, the film is uneven, and the productivity may be deteriorated.

The molecular weight of the liquid epoxy resin (D) is preferably 400 to 50,000 in terms of weight average molecular weight, and more preferably 750 to 30,000. When the weight average molecular weight is less than 400, the effect of improving the elastic modulus is poor, and when it is greater than 50000, the physical properties of the composition such as a decrease in compatibility and an increase in viscosity are reduced, which is not preferable.
Moreover, as an epoxy equivalent, it is preferable that it is 150-250 g / eq, and it is preferable that it is 170-200 g / eq. By setting it as such an epoxy equivalent, the effect of a high elasticity modulus can be expressed suitably.

  Further, specific examples of the liquid epoxy resin (D) containing the structure represented by the formula (2) include compounds having a silsesquioxane skeleton represented by the following formula (3) as a repeating unit. . And the said liquid epoxy resin (D) takes well-known shapes, such as a chain | strand shape, ladder shape, and basket shape, as a skeleton of a silicone resin.

(R _1a in the formula represents a substituent having a glycidyl group, and R _{1b in} the formula represents an alkyl group, aryl group or unsaturated aliphatic residue having 10 or less carbon atoms, and R _{6 to} R ₉ are And each independently represents a hydrogen atom, a hydroxyl group or an alkoxy group having 4 or less carbon atoms, n represents an integer of 1 to 100.)

A preferred range of _{R 1a} and _{R 1b} in the formula (3) in is the same as _{R 1a} and _{R 1b} described by the formula (1a) and the formula (1b). 1-50 are preferable and, as for n in Formula (3), 1-20 are especially preferable.

The carboxy group-containing resin (A) used in the present invention comprises, for example, an epoxy compound (a) having two or more epoxy groups in the molecule and a monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule. It is a reaction product (A1) of the epoxycarboxylate compound obtained by making it react and a polybasic acid anhydride (c).
The carboxy group-containing resin (A) used in the present invention includes, for example, an epoxy compound (d) having two epoxy groups in the molecule and a monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule. A reaction product (A2) of an epoxy carboxylate compound obtained by reacting with a diisocyanate compound (e), a carboxylic acid (f) having two hydroxyl groups in the molecule, and an arbitrary diol compound (g) is there.

  In the present invention, the epoxy compound (a) having two or more epoxy groups in the molecule used for producing the carboxy group-containing resin (A) or the epoxy compound (d) having two epoxy groups in the molecule, Epoxy equivalent is 100-900 g / eq. It is desirable that Epoxy equivalent is 100 g / eq. If it is less than 1, the molecular weight of the resulting carboxy group-containing resin (A) is so small that film formation may be difficult and flexibility may not be sufficiently obtained, and an epoxy equivalent of 900 g / eq. If it exceeds 1, the introduction rate of the monocarboxylic acid (b) having an ethylenically unsaturated group is lowered, and the photosensitivity may be lowered.

  Examples of the epoxy compound (a) having two or more epoxy groups in the molecule include phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, and bisphenol. Type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, bisphenol-A novolac type epoxy resin, epoxy resin having naphthalene skeleton, alicyclic epoxy resin, heterocyclic epoxy resin and the like. These may be produced using known methods, or commercially available products may be used.

  Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by Dainippon Ink & Chemicals, Inc.), D.I. E. N438 (made by Dow Chemical Company), Epicoat 154 (made by Japan Epoxy Resin Co., Ltd.), RE-306 (made by Nippon Kayaku Co., Ltd.), etc. are mentioned.

  Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink & Chemicals, Inc.), EOCN-102S, EOCN-103S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 ( Union Carbide), ESCN-195 (Sumitomo Chemical Co., Ltd.) and the like.

  Examples of the trishydroxyphenylmethane type epoxy resin include, for example, EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Company), Epicoat E1032H60 (Japan Epoxy Resin ( Etc.).

  Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by Dainippon Ink & Chemicals, Inc.) and TACTIX-556 (manufactured by Dow Chemical Co., Ltd.).

  Examples of the bisphenol type epoxy resin include bisphenol-A type epoxy resin and bisphenol-F type epoxy resin. Examples of the bisphenol-A type epoxy resin include Epicoat 828, Epicoat 1001 (manufactured by Japan Epoxy Resin), UVR-6410 (manufactured by Union Carbide), D.I. E. R-331 (manufactured by Dow Chemical Company), YD-8125 (manufactured by Toto Kasei Co., Ltd.) and the like can be mentioned. Examples of the bisphenol-F type epoxy resin include UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Tohto Kasei) and the like.

  Examples of the biphenol type epoxy resin include NC-3000, NC-3000L, NC-3500 (manufactured by Nippon Kayaku Co., Ltd.), YL-6121H (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

  Examples of the bixylenol type epoxy resin include YX-4000 (manufactured by Japan Epoxy Resin Co., Ltd.).

  Examples of the bisphenol-A novolak type epoxy resin include Epicron N-880 (manufactured by Dainippon Ink & Chemicals, Inc.), Epicoat E157S75 (manufactured by Japan Epoxy Resin Co., Ltd.), and the like.

  Examples of the epoxy resin having a naphthalene skeleton include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by Dainippon Ink & Chemicals, Inc.).

  Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.).

  Examples of the heterocyclic epoxy resin include TEPIC-L, TEPIC-H, and TEPIC-S (all manufactured by Nissan Chemical Industries, Ltd.).

  In the present invention, the epoxy compound (a) having two or more epoxy groups in the molecule is preferably a biphenol type epoxy resin or a cresol novolac type epoxy resin, and particularly preferably a biphenol type epoxy resin.

  The epoxy compound (d) having two epoxy groups in the molecule only needs to have two epoxy groups. Among the epoxy compounds (a) having two or more epoxy groups in the molecule, the epoxy group It may have two. Specific examples include, for example, hydroquinone diglycidyl ether, catechol diglycidyl ether, phenyl diglycidyl ether such as resorcinol diglycidyl ether, bisphenol-A type epoxy resin, bifunctional bisphenol-A type epoxy resin {for example, described in Production Examples below Manufactured by Nippon Kayaku Co., Ltd. RE-310S}, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3 -Bisphenol type epoxy compound such as hexafluoropropane epoxy compound, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4 -Hydroxyphenyl)- , 1,1,3,3,3-Hexafluoropropane epoxy compounds such as hydrogenated bisphenol type epoxy compounds, brominated bisphenol-A type epoxy resins, brominated bisphenol-F type epoxy resins, etc. Compounds, alicyclic diglycidyl ether compounds such as cyclohexanedimethanol diglycidyl ether compound, aliphatic diglycidyl ethers such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether Examples thereof include polysulfide type diglycidyl ether compounds such as compounds, polysulfide diglycidyl ether, and biphenol type epoxy resins.

  Commercially available products of these epoxy compounds include, for example, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004 (all manufactured by Japan Epoxy Resin), Epomic R-140, Epomic R-301, and Epomic R-304 (all Mitsui Chemicals), DER-331, DER-332, DER-324 (all manufactured by Dow Chemical Company), Epicron 840, Epicron 850 (all manufactured by Dainippon Ink), UVR-6410 (manufactured by Union Carbide), Bisphenol-A type epoxy resin such as YD-8125 (manufactured by Tohto Kasei Co., Ltd.), UVR-6490 (manufactured by Union Carbide), YDF-2001, YDF-2004, YDF-8170 (all manufactured by Tohto Kasei Co., Ltd.), Epicron 830 , Epichrome Bisphenol-F type epoxy resin such as 835 (all manufactured by Dainippon Ink), hydrogenated bisphenol-A type epoxy resin such as HBPA-DGE (manufactured by Maruzen Petrochemical), Rica Resin HBE-100 (manufactured by Shin Nippon Chemical), DER -513, DER-514, DER-542 (all manufactured by Dow Chemical Co., Ltd.) and other brominated bisphenol-A type epoxy resins, Celoxide 2021 (manufactured by Daicel), Rica Resin DME-100 (manufactured by Shin Nippon Rika), EX- 216 (manufactured by Nagase Kasei), ED-503 (manufactured by Asahi Denka), Rikaresin W-100 (manufactured by Nippon Nippon Chemical Co., Ltd.), EX-212, EX-214, EX-850 (all Nagase Kasei) Aliphatic diglycidyl ether compounds, FLEP-50, FLEP-60 (both made by Toray Rethiocol) Polysulfide-type diglycidyl ether compound, biphenol type epoxy compounds such as YX-4000 (manufactured by Japan Epoxy Resins) and the like.

  In the present invention, the monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule used for producing the carboxy group-containing resin (A) can be used without particular limitation. For example, acrylic acid or crotonic acid , Α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated dibasic acid or an unsaturated dibasic acid and a monoglycidyl compound having an unsaturated group.

  Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, saturated dibasic acid anhydride or unsaturated dibasic acid anhydride and one hydroxyl group in one molecule. Half-esters that are equimolar reactants with (meth) acrylate derivatives, half-esters that are equimolar reactants of saturated dibasic acid or unsaturated dibasic acid and monoepoxy (meth) acrylate derivatives, etc. .

  Examples of the saturated dibasic acid anhydride include succinic anhydride and hexahydrophthalic anhydride. Examples of the unsaturated dibasic acid anhydride include maleic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Examples of the (meth) acrylate derivative having one hydroxyl group in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like. The half-esters which are equimolar reactants are, for example, reaction products of the above saturated dibasic acid anhydride or unsaturated dibasic acid anhydride and a (meth) acrylate derivative having one hydroxyl group in one molecule, etc. It is. Examples of the monoepoxy (meth) acrylate derivatives include a reaction product of phenyl glycidyl ether and (meth) acrylic acid, a reaction product of toluyl glycidyl ether and (meth) acrylic acid, naphthyl monoglycidyl ether and (meth) ) Reaction products with acrylic acid and the like.

  Examples of the saturated dibasic acid include succinic acid, glutaric acid, adipic acid, hexahydrophthalic acid and the like.

  Examples of the unsaturated dibasic acid include maleic acid, phthalic acid, and tetrahydrophthalic acid.

  Examples of the monoglycidyl compound having an unsaturated group include glycidyl (meth) acrylate, a reaction product of hydroxyethyl (meth) acrylate and epihalohydrin, a reaction product of hydroxypropyl (meth) acrylate and epihalohydrin, and the like.

  Monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule is a reaction product of (meth) acrylic acid, (meth) acrylic acid and ε-caprolactone in terms of sensitivity when a photosensitive resin composition is used. And cinnamic acid are particularly preferred.

  In the present invention, the polybasic acid anhydride (c) used for producing the carboxy group-containing resin (A) can be used without particular limitation, but has one or more acid anhydride structures in the molecule. Any can be used. Specifically, succinic anhydride, acetic anhydride, phthalic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, ethylene glycol-bis (anhydrotrimellitate), glycerin-bis (Anhydrotrimellitate) monoacetate, 1,2,3,4, -butanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′ , 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2-bis (3,4-anhydrodicarboxyphenyl) propane, 2,2-bis (3,4-anhydrodicarboxyphenyl) he Safluoropropane, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methylcyclohexene-1,2-dicarboxylic anhydride, 3a, 4,5,9b-tetrahydro-5- (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione is particularly preferred.

  In the present invention, the diisocyanate compound (e) used for producing the carboxy group-containing resin (A2) can be used without particular limitation as long as it has two isocyanate groups in the molecule. In addition, a plurality of diisocyanate compounds can be reacted at the same time. Among them, the diisocyanate compound (e) particularly excellent in flexibility and the like includes phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, Isophorone diisocyanate, arylene sulfone ether diisocyanate, allyl cyanide diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane or norbornane-diisocyanate methyl are preferred.

  In the present invention, the carboxylic acid (f) having two hydroxyl groups in the molecule used for producing the carboxy group-containing resin (A2) has both an alcoholic hydroxyl group or a phenolic hydroxyl group and a carboxy group in the molecule. Any diol compound can be used without particular limitation. The carboxylic acid (f) having two hydroxyl groups in the molecule is preferably a carboxylic acid having two alcoholic hydroxyl groups excellent in alkaline aqueous solution developability, such as dimethylolpropionic acid {for example, 2,2-bis (dimethylol). ) -Propionic acid}, dimethylolcarboxylic acid such as dimethylolbutanoic acid is more preferable.

  As an arbitrary diol compound (g) used for producing the carboxy group-containing resin (A2) in the present invention, an aliphatic or alicyclic compound in which two hydroxyl groups are bonded to two different carbon atoms If it can be used, there is no particular limitation. Specifically, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-heptanediol, 1,9-nonanediol, 1,10-decanediol, hydrobenzoin, benzpinacol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, cyclohexane-1,2 -Dimethanol, cyclohexane-1,4-dimethanol, butadiene-acrylonitrile copolymer having a terminal hydroxyl group (for example, AT × 013 manufactured by Ube Industries), spiroglycol having a terminal hydroxyl group {for example, 3,9-bis ( 2-hydroxy-1,1-dimethylethyl) -2, , 8,10-tetraoxaspiro [5,5] undecane}, dioxane glycol having a terminal hydroxyl group {for example, 2- (2-hydroxy-1,1-dimethylethyl) -5-ethyl-5-hydroxyl-1, 3-dioxane}, tricyclodecane-dimethanol having a hydroxyl group at the end, a macromonomer having a hydroxyl group at the end and polystyrene as a side chain (for example, HS-6 manufactured by Toagosei Co., Ltd.), a polystyrene having a hydroxyl group at the end -A diol compound such as a macromonomer having an acrylonitrile copolymer in the side chain (for example, HN-6 manufactured by Toagosei Co., Ltd.) or a reaction product of these diol compound and an oxide such as ethylene oxide or propylene oxide. .

  In the present invention, the production of the carboxy group-containing resin (A1) includes the epoxy compound (a) having two or more epoxy groups in the molecule and the monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule. By reacting the polycarboxylate (c) with an epoxycarboxylate compound in which an alcoholic hydroxyl group has been formed by the reaction (hereinafter referred to as “first reaction”) (hereinafter referred to as “second reaction”). Done.

  In the present invention, the carboxy group-containing resin (A2) is produced by the epoxy compound (d) having two epoxy groups in the molecule and the monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule. The urethanation reaction (hereinafter referred to as the epoxy carboxylate compound in which an alcoholic hydroxyl group is generated by the reaction with (i), the diisocyanate compound (e), and the carboxylic acid (f) having two hydroxyl groups in the molecule (Referred to as “fourth reaction”). At this time, the diol compound (g) can be reacted as an optional component.

  The first reaction is a solvent-free or solvent having no alcoholic hydroxyl group, specifically, for example, ketones such as acetone, ethylmethylketone, cyclohexanone, aromatic carbonization such as benzene, toluene, xylene, tetramethylbenzene, etc. Hydrogens, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and other glycol ethers, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl Cellosolve acetate, butyl cellosolve acetate, carbitol acetate (CA), propylene glycol monomethyl ether acetate, glutar Esters such as dialkyl, dialkyl succinate and dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, and the above-mentioned crosslinking agent (B ) Etc. alone or in a mixed organic solvent.

  The raw material charge ratio in this reaction is 80 to 120 equivalent% of the monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule with respect to 1 equivalent of the epoxy compound (a) or the epoxy compound (d). When deviating from this range, gelation may occur during the second reaction, and the thermal stability of the finally obtained carboxy group-containing resin (A) may be lowered.

  In the first reaction, a catalyst is preferably used to promote the reaction, and the amount of the catalyst used is 0.1 to 10% by mass with respect to the weight of the reaction product. The reaction temperature in that case is 60-150 degreeC, and reaction time is 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, Examples include zirconium octoate. Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-ditertiary butyl-4hydroxytoluene, etc. as a thermal polymerization inhibitor. The first reaction has an end point when the acid value of the sample is 1 mg · KOH / g or less, preferably 0.5 mg · KOH / g or less, while appropriately sampling.

  The second reaction is an esterification reaction in which the polybasic acid anhydride (c) is reacted with the reaction solution after completion of the first reaction. Although the reaction can be carried out without a catalyst, a basic catalyst can be used to promote the reaction, and the amount of the catalyst used is 10% by mass or less based on the weight of the reaction product. The reaction temperature at this time is 40 to 120 ° C., and the reaction time is 5 to 60 hours.

  As for the addition amount of the polybasic acid anhydride (c), a calculation amount is added so that the solid content acid value of the carboxy group-containing resin (A1) is 50 to 150 mg · KOH / g. If the solid content acid value is less than 50 mg · KOH / g, the solubility in an alkaline aqueous solution is insufficient, and if patterning is performed, a residue may be generated or patterning may not be possible. Moreover, when the solid content acid value exceeds 150 mg · KOH / g, the solubility in an alkaline aqueous solution is too high, and the photocured pattern may be peeled off, which is not preferable.

In the fourth reaction, after completion of the first reaction, a carboxylic acid (f) having two hydroxyl groups in the molecule and an arbitrary diol compound (g) are added to the reaction solution to obtain a dispersion or solution. Thereafter, the diisocyanate compound (e) is gradually added and reacted to cause urethanization. Although the reaction can be carried out without a catalyst, a basic catalyst can be used to promote the reaction, and the amount of the catalyst used is 10% by mass or less based on the weight of the reaction product. The reaction temperature at this time is 40 to 120 ° C., and the reaction time is 5 to 60 hours. In this case, a solvent or a thermal polymerization inhibitor as described above may be used. In the fourth reaction, the end point is the time point at which absorption in the vicinity of 2250 cm ⁻¹ in the infrared absorption spectrum of the sample disappears while sampling appropriately.

  The amount of carboxylic acid (f) having two hydroxyl groups in the molecule is calculated such that the solid content acid value of the carboxy group-containing resin (A2) is 50 to 150 mg · KOH / g. The amount of the diisocyanate compound (e) charged in the fourth reaction [[number of moles of epoxycarboxylate compound produced by the first reaction + number of moles of compound (f)) + mol of arbitrary diol compound (g) The ratio of [number] / (number of moles of compound (e)) is in the range of 1-5. When this value is less than 1, an isocyanate group remains at the terminal of the carboxy group-containing resin (A2), and the thermal stability is low, which may cause gelation during storage. On the other hand, when this value exceeds 5, the molecular weight of the carboxy group-containing resin (A2) is lowered, and the tackiness and sensitivity may be deteriorated. Further, when the solid content acid value is less than 50 mg · KOH / g, the solubility in an alkaline aqueous solution is insufficient, and when patterning is performed, a residue may be generated or patterning may not be possible. Moreover, when the solid content acid value exceeds 150 mg · KOH / g, the solubility in an alkaline aqueous solution is too high, and the photocured pattern may be peeled off, which is not preferable.

  When a solvent is used, the carboxy group-containing resin (A) can be isolated by removing it with an appropriate method. In the present invention, the carboxy group-containing resin (A) is usually soluble in an alkaline aqueous solution, but is also soluble in the above-described solvent. When used in a solder resist, a plating resist, etc., it can be developed with a solvent. It is.

  The content ratio of the carboxy group-containing resin (A) used in the photosensitive resin composition of the present invention is usually 15 to 70% by mass when the solid content of the photosensitive resin composition is 100% by mass. Preferably, it is 20-60 mass%.

  Examples of the crosslinking agent (B) used in the photosensitive resin composition of the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 1,4-butanediol mono (meth) acrylate. , Carbitol (meth) acrylate, acryloylmorpholine, (meth) acrylate having a hydroxyl group (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate) Etc.) and polycarboxylic acid anhydrides (for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) half ester, polyethylene glycol di (meth) Acrylate, tripropylene glycol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycerin polypropoxytri (meth) acrylate, and di- of ε-caprolactone adducts of hydroxybivalic acid neopenglycol (Meth) acrylate (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and ε-caprolactone , Dipentaerythritol poly (meth) acrylate, mono- or polyglycidyl compounds (eg, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, Lenglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether ) And the like, and epoxy (meth) acrylate which is a reaction product of (meth) acrylic acid. A crosslinking agent (B) can also be used independently, and may mix and use 2 or more types. The content of these crosslinking agents (B) is usually 2 to 40% by mass, preferably 3 to 30% by mass, when the solid content of the photosensitive resin composition is 100% by mass.

  The photopolymerization initiator (C) used in the photosensitive resin composition of the present invention can be used without particular limitation. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin. Benzoins such as isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl Acetophenones such as phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (for example, Irgacure-907 described in Examples below); 2-ethylanthraquinone, 2- Tarrive Anthraquinones such as luanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone (for example, DETX-S described in Examples below), 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide and 4,4′-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenyl And phosphine oxides such as phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. A photoinitiator (C) can also be used independently, and may mix and use 2 or more types. The content rate of these photoinitiators (C) is 1-30 mass% normally, when solid content of the photosensitive resin composition is 100 mass%, Preferably, it is 2-25 mass%.

  These photopolymerization initiators (C) can be used alone or as a mixture of two or more thereof, and further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N -It can be used in combination with accelerators such as benzoic acid derivatives such as dimethylaminobenzoic acid isoamyl ester. The addition amount of these accelerators is preferably 100% by mass or less with respect to the photopolymerization initiator (C).

  In the photosensitive resin composition of the present invention, the content of the liquid epoxy resin (D) is an amount of 200% or less of the equivalent calculated from the solid content acid value and the amount used of the carboxy group-containing resin (A). preferable. If this amount exceeds 200%, the developability of the photosensitive resin composition may be remarkably lowered, which is not preferable.

  The liquid epoxy resin (D) may be mixed in advance with the resin composition, but is preferably mixed before application to a printed circuit board. That is, it is blended into a two-pack type of a main agent solution mainly composed of the component (A) and containing an epoxy curing accelerator and the like, and an epoxy resin solution mainly composed of the epoxy resin (D). It is preferable to use a mixture.

  In obtaining the photosensitive resin composition of the present invention, various additives such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay and the like as necessary. Fillers (hereinafter also referred to as “fillers”), thixotropic agents such as Aerosil; colorants such as phthalocyanine blue, phthalocyanine green, and titanium oxide; silicone leveling agents (for example, KS-66 described in Examples below) ), Fluorine leveling agents and antifoaming agents (for example, BYK-354 described in Examples below); polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, thermosetting catalysts (for example, melamine described in Examples below) and the like. It can be added for the purpose of enhancing various performances of the composition.

  The photosensitive resin composition of the present invention can be obtained, for example, by mixing the carboxy group-containing resin (A) with a crosslinking agent (B), a photopolymerization initiator (C), and a liquid epoxy resin (D). it can.

  The photosensitive resin composition of the present invention can also be used as a dry film resist having a structure in which the resin composition is sandwiched between a support film and a protective film. The photosensitive resin composition of the present invention is preferably processed into a liquid or film form.

  The photosensitive resin composition of the present invention is useful as a resist material such as an insulating material between layers of electronic components, an optical waveguide connecting optical components, a solder resist for printed circuit boards, a coverlay, a color filter, It can also be used as printing ink, sealant, paint, coating agent, adhesive and the like.

  The cured product of the present invention is obtained by curing the above-described photosensitive resin composition of the present invention by irradiation with energy rays such as ultraviolet rays. Curing by irradiation with energy rays such as ultraviolet rays can be performed by a conventional method. For example, in the case of irradiating ultraviolet rays, an ultraviolet generator such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or an ultraviolet light emitting laser (such as an excimer laser) may be used.

  The cured product of the present invention is used, for example, as a resist film, an interlayer insulating material for a build-up method, or an optical waveguide as a substrate such as an electric / electronic / optical substrate such as a printed circuit board, an optoelectronic substrate or an optical substrate. Specific examples of these include articles such as computers, home appliances, and portable devices. The thickness of the cured product layer is usually about 0.5 to 160 μm, preferably about 1 to 100 μm.

The printed circuit board can be obtained, for example, as follows. That is, when a liquid resin composition is used, the present invention is applied to a printed wiring board with a film thickness of 5 to 160 μm by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, or the like. A coating film can be formed by applying the photosensitive resin composition and drying the coating film at 50 to 110 ° C., preferably 60 to 100 ° C. Thereafter, the coating film is directly or indirectly irradiated with high energy rays such as ultraviolet rays with an intensity of about 10 to 2000 mJ / cm ² through a photomask having an exposure pattern such as a negative film, and the unexposed portion is described later. Using the liquid, development is performed, for example, by spraying, rocking dipping, brushing, scrubbing, or the like. Thereafter, if necessary, further ultraviolet irradiation is performed, and then heat treatment is usually performed at a temperature of 100 to 200 ° C., preferably 140 to 180 ° C., so that the gold plating property is excellent, and heat resistance, solvent resistance, acid resistance, A printed circuit board having a permanent protective film that satisfies various properties such as adhesion and flexibility can be obtained.

  The alkaline aqueous solution used for development includes potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, and other inorganic alkaline solutions and tetramethylammonium hydroxide. Organic alkali aqueous solutions such as tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to the following Example. Moreover, unless otherwise indicated in an Example, a part shows a mass part. In addition, each physical property value in an Example was measured with the following method.

Weight average molecular weight: measured by GPC (gel permeation chromatography) method.
GPC measurement conditions Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC KF-802.5 (2) KF-802 KF-803
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
-Higher-order structure ratio x: Measured by ²⁹ Si-NMR.
²⁹ Si-NMR identifies the progress of sol-gel reaction around silicon atoms. The x value was calculated from the ratio of peaks observed at 62 to 72 ppm in all the observed silicon atoms.
( ²⁹ Si-NMR measurement conditions)
Manufacturer: Agilent Company Equipment: 500MHz VNMR
Integration count: 5000 times Waiting time: 1 second Sample tube: Sample tube for quartz NMR manufactured by Shigemi Co., Ltd. (operation)
1 g of a sample, 6 mg of chromium (III) acetylacetonate as a relaxation reagent, 2 μl of tetramethylsilane as a standard reagent, and 600 μl of tetrahydrofuran as a solvent were mixed to obtain a resin solution. 500 μl was extracted from this resin solution, mixed with 100 μl of heavy tetrahydrofuran for locking, and charged into a sample tube to start measurement.
・ Epoxy equivalent: measured in accordance with JIS K7236 ・ Oxidation: Measured in accordance with JIS K0070 (measured with a sodium hydroxide aqueous solution instead of a potassium hydroxide ethanol solution).

Synthesis example 1
In a 3 L flask equipped with a stirrer and a reflux tube, EOCN-103S (polyfunctional cresol novolac type epoxy resin, epoxy equivalent: 215.0 g / in) as an epoxy compound (a) having two or more epoxy groups in the molecule. Equivalent Nippon Kayaku Co., Ltd.) 860.0 g, acrylic acid (molecular weight: 72.06) 288.3 g as a monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule, and Calvi as a reaction solvent 492.1 g of tall acetate, 4.921 g of 2,6-di-tert-butyl-p-cresol as a polymerization inhibitor and 4.921 g of triphenylphosphine as a reaction catalyst were charged, and the acid value of the reaction solution at 98 ° C. Was reacted until 0.5 mg · KOH / g or less, to obtain an epoxycarboxylate compound. Next, 169.8 g of carbitol acetate as a solvent for reaction and 201.6 g of tetrahydrophthalic anhydride as a polybasic acid anhydride (c) were added to this reaction solution and reacted at 95 ° C. for 4 hours to obtain a carboxy group-containing resin (A1 ) A resin solution containing 65% by mass was obtained (this solution is referred to as “A1-1”). When the acid value was measured, it was 67.3 mg · KOH / g (solid content acid value: 103.6 mg · KOH / g).

Synthesis example 2
In a 1 L flask equipped with a stirrer and a reflux tube, NC-3000 (biphenol type epoxy resin, epoxy equivalent: 277.0 g / equivalent) as an epoxy compound (a) having two or more epoxy groups in the molecule 277.0 g of Yakuhin Co., Ltd., 72.06 g of acrylic acid (molecular weight: 72.06) as the monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule, and carbitol acetate as the reaction solvent 121.39 g, 0.850 g of 2,6-di-tert-butyl-p-cresol as a polymerization inhibitor and 0.850 g of triphenylphosphine as a reaction catalyst were charged, and the acid value of the reaction solution was 0.8 at 98 ° C. It was made to react until it became 5 mg * KOH / g or less, and the epoxy carboxylate compound was obtained. Next, 86.32 g of carbitol acetate as a solvent for reaction and 102.51 g of tetrahydrophthalic anhydride as a polybasic acid anhydride (c) were charged into this reaction solution, and reacted at 95 ° C. for 4 hours to obtain a carboxy group-containing resin (A1 ) A resin solution containing 65% by mass was obtained (this solution is referred to as “A1-2”). When the acid value was measured, it was 66.8 mg · KOH / g (solid content acid value: 102.7 mg · KOH / g).

Synthesis example 3
In an 3 L flask equipped with a stirrer and a reflux tube, as an epoxy compound (d) having two epoxy groups in the molecule, RE-310S (bifunctional bisphenol-A type epoxy resin, epoxy equivalent: 184.0 g / 368.0 g of Nippon Kayaku Co., Ltd.), 141.2 g of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule, as a thermal polymerization inhibitor 1.02 g of hydroquinone monomethyl ether and 1.53 g of triphenylphosphine as a reaction catalyst were charged and reacted at 98 ° C. until the acid value of the reaction solution became 0.5 mg · KOH / g or less, and an epoxycarboxylate compound (molecular weight) : 509.2). Next, 755.5 g of carbitol acetate was used as a reaction solvent in this reaction solution, and 2,2-bis (dimethylol) -propionic acid (molecular weight: 134.16) as a carboxylic acid (f) having two hydroxyl groups in the molecule. ), 268.3 g, 1.08 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 140.3 g of spiroglycol (molecular weight: 304.38) as an optional diol compound (g), and the temperature was raised to 45 ° C. . To this solution, 485.2 g of trimethylhexamethylene diisocyanate (molecular weight: 210.27) was gradually added dropwise as a diisocyanate compound (e) so that the reaction temperature did not exceed 65 ° C. After completion of the dropwise addition, the temperature is raised to 80 ° C., and the mixture is reacted for 6 hours until absorption near 2250 cm ⁻¹ disappears by an infrared absorption spectrum measurement method to obtain a resin solution containing 65% by mass of the carboxy group-containing resin (A2). (This solution is referred to as “A2-1”.) When the acid value was measured, it was 52.0 mg · KOH / g (solid content acid value: 80.0 mg · KOH / g).

Synthesis example 4
A reaction vessel was charged with 118.2 parts of γ-glycidoxypropyltrimethoxysilane, 0.7 parts of methyltrimethoxysilane, 178.3 parts of methyl isobutyl ketone, and 21.4 parts of methanol. 0.53 KOH 12.3 parts was continuously added dropwise over 30 minutes. The cloudiness phenomenon did not occur at the time of dropping. After dropping, the temperature was raised to 50 ° C. and reacted for 5 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. or lower, 0.4 parts of sodium dihydrogen phosphate dihydrate was added all at once, stirred for 30 minutes at 40 ° C. or lower, and then repeatedly washed with water until the washing solution became neutral. Subsequently, the liquid epoxy resin (D1) 112.9 parts was obtained by concentrating at 120 degreeC. The obtained compound had an epoxy equivalent of 175 g / eq, a total chlorine content of 18 ppm, and a viscosity of 2322 mPa · s. Was higher order structure ratio x was determined by ²⁹ Si-NMR of the obtained liquid epoxy resin (D1), from the integral value of the ²⁹ Si-NMR spectrum shown in FIG. 1, p = 192.78, q = 53 .33, r = 10.00, and the higher order structure ratio was x = 0.75.

Synthesis example 5
A reaction vessel was charged with 118.2 parts of γ-glycidoxypropyltrimethoxysilane, 0.7 parts of methyltrimethoxysilane, 178.3 parts of methyl isobutyl ketone, and 21.4 parts of methanol. 7.3 parts of 0.5% KOH was continuously added dropwise over 30 minutes. The cloudiness phenomenon did not occur at the time of dropping. After dropping, the temperature was raised to 50 ° C. and reacted for 5 hours. After completion of the reaction, the mixture was cooled to 40 ° C. or lower, 0.4 parts of sodium dihydrogen phosphate dihydrate was added all at once, stirred at 40 ° C. or lower for 30 minutes, and then repeatedly washed with water until the washing solution became neutral. . Subsequently, it concentrated at 120 degreeC, and obtained 111.7 parts of liquid epoxy resins (D2) of this invention. The epoxy equivalent of the obtained compound was 198 g / eq, the total chlorine content was 8.5 ppm, the viscosity was 2403 mPa · s, and the integrated value of ²⁹ Si-NMR spectrum was x = 0.43.

Synthesis Example 6
A reaction vessel was charged with 82.7 parts of γ-glycidoxypropyltrimethoxysilane, 29.7 parts of phenyltrimethoxysilane, 0.7 parts of methyltrimethoxysilane, 178.3 parts of methyl isobutyl ketone, and 21.4 parts of methanol. While stirring at 40 ° C. or lower, 12.3 parts of 0.5% KOH was continuously added dropwise over 30 minutes. The cloudiness phenomenon did not occur at the time of dropping. After dropping, the temperature was raised to 50 ° C. and reacted for 5 hours. After completion of the reaction, the mixture was cooled to 40 ° C. or lower, 0.4 parts of sodium dihydrogen phosphate dihydrate was added all at once, stirred at 40 ° C. or lower for 30 minutes, and then repeatedly washed with water until the washing solution became neutral. . Subsequently, the liquid epoxy resin (D3) 107.5 part of this invention was obtained by concentrating at 120 degreeC. The epoxy equivalent of the obtained compound was 236 g / eq, the total chlorine content was 9.1 ppm, the viscosity was 4913 mPa · s, and the integrated value of ²⁹ Si-NMR spectrum was x = 0.94.

Examples 1-3, Comparative Examples 1-3
Carboxy group-containing resins (A1-1), (A1-2), (A2-1) obtained in Synthesis Examples 1 to 3, and liquid epoxy resins (D1) obtained in Synthesis Examples 4, 5, and 6 ( Using D2) and (D3), the mixing ratios shown in Table 1 were obtained, and then kneaded with a three-roll mill to obtain the photosensitive resin composition of the present invention. This was applied to a printed circuit board by a screen printing method so that the dry film thickness was 15 to 25 μm, and the coating film was dried with a hot air dryer at 80 ° C. for 30 minutes. Next, ultraviolet rays were irradiated through a mask on which a circuit pattern was drawn using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW). Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin in the non-ultraviolet irradiated area. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction for 60 minutes in a hot air dryer at 150 ° C. to obtain a cured film (hereinafter also referred to as “cured product”).
About the obtained cured product, tackiness, developability, resolution, photosensitivity, surface gloss, substrate warpage, flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, resistance PCT (Pressure Cooker Test) property, thermal shock resistance, and storage elastic modulus were tested. The results are shown in Table 2. The test method and evaluation method are as follows.

(Tackiness)
Absorbent cotton was rubbed onto the dried film applied to the substrate to evaluate the tackiness of the film.
○: Absorbent cotton does not stick.
× ··· Absorbent cotton lint sticks to the membrane.

(Developability)
The following evaluation criteria were used.
○: The ink was completely removed during development and development was possible.
× ··· Some parts are not developed during development.

(Resolution)
A 50 μm negative pattern was brought into intimate contact with the dried coating film and irradiated with ultraviolet rays with an integrated light amount of 200 mJ / cm ² . Next, development was performed with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the transfer pattern was observed with a microscope. The following criteria were used:
○ The pattern edge is a straight line and is resolved.
X: Peeling or pattern edges are jagged.

(Light sensitivity)
Stepped tablet 21 steps (manufactured by Kodak Co., Ltd.) were brought into intimate contact with the dried coating film and irradiated with ultraviolet rays having an integrated light amount of 500 mJ / cm ² . Next, the film was developed with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the number of coating layers remaining without development was confirmed.

(Surface gloss)
The dried coating film was exposed to 500 mJ / cm ² of ultraviolet rays. Next, development is performed with a 1% sodium carbonate aqueous solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the dried cured film is observed. The following criteria were used:
○ ・ ・ ・ ・ No cloudiness is seen at all × ・ ・ ・ ・ Slight cloudiness is seen

(Board warpage)
The following criteria were used:
○ ········································································· •

(Flexibility)
The cured film is bent at 180 ° C. and the appearance is observed. The following criteria were used:
○ ···· No crack on the film surface × ··· The film surface breaks

(Adhesion)
In accordance with JIS K5400, 100 1 mm grids were made on the test piece, and a peeling test was performed using cello tape (registered trademark). The peeled state of the grid was observed and evaluated according to the following criteria.
○ ···········································

(Pencil hardness)
Evaluation was performed according to JIS K5400.

(Solvent resistance)
The specimen is immersed in isopropyl alcohol for 30 minutes at room temperature. After confirming that there was no abnormality in the external appearance, a peeling test with cello tape (registered trademark) was conducted, and evaluation was performed according to the following criteria.
○ ··· There is no abnormality in the appearance of the coating film, and there is no swelling or peeling × ·······

(Acid resistance)
The test piece is immersed in a 10% aqueous hydrochloric acid solution at room temperature for 30 minutes. After confirming that there was no abnormality in the external appearance, a peeling test with cello tape (registered trademark) was conducted, and evaluation was performed according to the following criteria.
○ ··· There is no abnormality in the appearance of the coating film, and there is no swelling or peeling × ·········

(Heat-resistant)
The test piece was coated with rosin-based plax and immersed in a solder bath at 270 ° C. for 30 seconds. This was defined as 1 cycle and repeated 3 cycles. After being allowed to cool to room temperature, a peeling test with Cellotape (registered trademark) was conducted, and the following criteria were evaluated.
○ ··· There is no abnormality in the appearance of the coating film and there is no swelling or peeling × ········

(PCT resistance)
The test substrate was allowed to stand in water at 121 ° C. and 2 atm for 96 hours, after which it was confirmed whether or not there was any abnormality in appearance, a peeling test was performed using cello tape (registered trademark), and evaluation was performed according to the following criteria.
○ ··· There is no abnormality in the appearance of the coating film, and there is no swelling or peeling × ·········

(Heat shock resistance)
The test piece was subjected to thermal history with one cycle of −40 ° C./30 minutes and 120 ° C./30 minutes. After 1000 cycles, the test piece was observed with a microscope and evaluated according to the following criteria.
○ ·············································································

(Storage modulus)
On the glossy surface side (copper foil), the resin layer is formed on the copper foil by the screen printing method so that the resin layer is in contact with the substrate of the photosensitive resin compositions according to Examples and Comparative Examples prepared above. did. This was irradiated with ultraviolet rays with an exposure machine under the condition of an integrated exposure of 1000 mJ / cm ² , and then cured by heating at 150 ° C. for 60 minutes. Then, after peeling a cured film from copper foil, the sample was cut out to measurement size (5 mm x 50 mm, 40 micrometers size). The sample was subjected to RSA G2 (manufactured by TA Instruments), and the storage elastic modulus at 25 ° C. was measured at a frequency of 10 Hz.

  As is clear from the above results, the photosensitive resin composition of the present invention obtained by using the epoxy group-containing alkoxysilicon resin of the epoxy resin (D1) as the liquid epoxy resin (D) has no tackiness and is light-resistant. It can be confirmed that the sensitivity is high. In addition, the cured product of the present invention is excellent in solder heat resistance, chemical resistance, gold plating resistance, etc., and the surface of the cured product does not crack, and even when a thin substrate is used, there is little warping on the substrate. It was a cured product having a sufficient elastic modulus.

The photosensitive resin composition of this invention is suitable for the photosensitive resin composition for printed circuit boards and the photosensitive resin composition for optical waveguide formation.

Claims (11)

Carboxy group-containing resin (A), crosslinking agent (B), photopolymerization initiator (C), epoxy group-containing alkoxysilicon compound represented by the following formula (1a) and substituted alkoxysilicon represented by the following formula (1b) The photosensitive resin composition containing the liquid epoxy resin (D) obtained by making a compound react.

(In the formula, R _1a represents a substituent having a glycidyl group. R ₂ represents an alkyl group having 4 or less carbon atoms.)

(In the formula, R _1b represents an alkyl group having 10 or less carbon atoms, an aryl group, or an unsaturated aliphatic residue. R ₃ represents an alkyl group having 4 or less carbon atoms.) The said liquid epoxy resin (D) is a photosensitive resin composition of Claim 1 containing the structure represented by following formula (2).

(A plurality of R _{4 in the} formula represents R _1a or R _1b , and R ₅ represents an alkyl group having 4 or less carbon atoms. P, q, and r each represents an integer of 0 to 50, provided that None of p, q, and r is 0.) In the liquid epoxy resin (D), R _1a in the formula (1a) is an alkyl group substituted with a glycidoxyalkyl group having 3 or less carbon atoms, and R _1b in the formula (1b) has 6 carbon atoms. The photosensitive resin composition of Claim 1 which is the following alkyl groups or aryl groups.   The photosensitive resin composition as described in any one of Claims 1 thru | or 3 whose total chlorine amount of the said liquid epoxy resin (D) is 100 ppm or less.   The photosensitive resin composition according to any one of claims 1 to 4, wherein the liquid epoxy resin (D) has a melt viscosity at 25 ° C of 50 mPa · s to 10 Pa · s.   In the liquid epoxy resin (D), when the higher order structure ratio is defined by x = p / (p + q + r), the value of x is in the range of 0.5 to 0.9. The photosensitive resin composition as described in any one.   The carboxy group-containing resin (A) is obtained by reacting an epoxy compound (a) having two or more epoxy groups in the molecule with a monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule. The photosensitive resin composition as described in any one of Claims 1 thru | or 6 which is a reaction product of an epoxycarboxylate compound and a polybasic acid anhydride (c).   An epoxy carboxy obtained by reacting a carboxy group-containing resin (A) with an epoxy compound (d) having two epoxy groups in the molecule and a monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule 7. The reaction product of a rate compound, a diisocyanate compound (e), a carboxylic acid (f) having two hydroxyl groups in the molecule and / or a diol compound (g). The photosensitive resin composition according to item.   Hardened | cured material of the photosensitive resin composition as described in any one of Claims 1-8.   A substrate having a layer of the cured product according to claim 9. An article comprising the substrate according to claim 10.

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