JP2001254002A - Resin composition, its film and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having a low dielectric constant, excellent in patterning precision and adhesion to a substrate, developable with water or a diluted alkali solution, and suitable for forming a solder resist for a printed wiring board or an IC package, or an interlayer insulating layer or the like, and to provide a photosensitive film using this resin composition. SOLUTION: The photosensitive resin composition comprises an unsaturated group-containing resin (A) comprising an epoxy (meth)acrylate, which is a reaction product of an epoxy resin (a) bearing at least two epoxy groups in the molecule with a compound (b) having in one molecule one unsaturated double bond and one carboxylic group and a saturated monocarboxylic acid (c) as an optional component, and, if necessary, can be further reacted with a polybasic acid anhydride (d), a diluent (B), a photopolymerization initiator (C) and a surface-modified powder (D) having a dielectric constant of 3.5 or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low dielectric constant photosensitive resin composition useful as a solder resist or an interlayer insulating layer used for a multilayer substrate, a build-up substrate, an IC package, and the like, and a film and a cured product thereof.

[0002]

2. Description of the Related Art In recent years, high speed and high frequency of electronic devices such as computers and mobile phones have been strongly desired, and electronic components such as printed wiring boards and IC packages used for such devices have been demanded for high speed and high frequency. The demands are getting stronger. To meet this demand, it is necessary to lower the dielectric constant and the dielectric loss tangent of electronic components, and various studies have been made, but they satisfy all of the low dielectric constant, low dielectric loss tangent, patterning accuracy, and heat resistance. There is no resin composition.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition which solves the above problems of low dielectric constant, low dielectric loss tangent, patterning accuracy and heat resistance.

[0004]

That is, the present invention provides:
(1) An epoxy resin (a) having at least two epoxy groups in a molecule, a compound (b) having one unsaturated double bond and one carboxyl group in one molecule, and a saturated monocarboxylic acid as an optional component Unsaturated group-containing resin (A) obtained by reacting an epoxy (meth) acrylate which is a reaction product with (c) with polybasic anhydride (d) if necessary, diluent (B), photopolymerization initiator (C) and a photosensitive resin composition comprising a surface-modified powder (D) having a dielectric constant of 3.5 or less, (2) a surface-modified powder having a dielectric constant of 3.5 or less The above (1), wherein the particle diameter of the powder (D) is 30 μm or less.
(3) The photosensitive resin composition as described in (1) or (2), wherein (3) the surface-modified powder (D) having a dielectric constant of 3.5 or less and a melting point of 100 ° C. or more. (4) The photosensitive resin composition according to any one of the above (1) to (3), wherein the powder (D) has a dielectric constant of 3.0 or less.
(5) A film comprising the photosensitive resin composition according to (1) to (4), and (6) a photosensitive resin composition according to (1) to (5) and a cured product of the film.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The photosensitive resin composition of the present invention is applied on a substrate, dried as necessary with an organic solvent, exposed to ultraviolet light with a negative mask, developed with a diluted alkaline aqueous solution, and then, if necessary, thermally cured. To use.

The resin (A) used in the present invention comprises a compound (a) having two or more epoxy groups in one molecule and a compound (b) having one unsaturated double bond and one carboxyl group in one molecule. ) And a saturated carboxylic acid (c) as an optional component, and if necessary, a polybasic acid anhydride (d).

Specific examples of the compound (a) having two or more epoxy groups in one molecule include, for example, a bisphenol A type epoxy resin (for example, Epicoat 828, Epicoat 1001, manufactured by Yuka Shell Epoxy Co., Ltd.) Epicoat 1002, Epicoat 1004, etc.), an epoxy resin obtained by reacting an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (eg,
Nippon Kayaku Co., Ltd., NER-1302, epoxy equivalent 3
23, softening point 76 ° C), bisphenol F type resin (eg,
Yuka Shell Epoxy Co., Ltd., Epicoat 807, EP
-4001, EP-4002, EP-4004, etc.), an epoxy resin obtained by reacting an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin (eg, NER-7406, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 350, Softening point 66 ° C.), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg, Yuka Shell Epoxy Co., Ltd., YX-4000), phenol novolak type epoxy resin (eg, Nippon Kayaku Co., Ltd.), E
EP-201, manufactured by Yuka Shell Epoxy Co., Ltd., EP-
152, EP-154, manufactured by Dow Chemical Co., Ltd., DEN
-438), cresol novolak type epoxy resin (eg, Nippon Kayaku Co., Ltd., EOCN-102S, EOCN
-1020, EOCN-104S), triglycidyl isocyanurate (manufactured by Nissan Chemical Co., Ltd., TEPIC), trisphenolmethane epoxy resin (Nippon Kayaku Co., Ltd.)
, EPPN-501, EPN-502, EPPN-5
03), fluorene epoxy resin (eg, Nippon Steel Chemical Co., Ltd., Cardo epoxy resin, ESF-300), alicyclic epoxy resin (Daicel Chemical Industries, Ltd., Celloxide 2021P, Celloxide EHPE) and the like. Can be

Another example of (a) is a copolymerizable epoxy resin. As a copolymer type epoxy resin,
For example, glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide, and other monofunctional ethylenically unsaturated group-containing compounds (eg, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate,
(Meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α
-Methylstyrene, glycerin mono (meth) acrylate, general formula (1)

[0009]

Embedded image

Wherein R 1 is hydrogen or an ethyl group, R 2
Is hydrogen or a C1-C6 alkyl group, and n is 2-23
Is an integer, and copolymers obtained by reacting one or two or more selected from the group consisting of: Specifically, Nippon Oil & Fats Co., Ltd., CP-15, CP-30, CP-50,
CP-20SA, CP-510SA, CP-50S, C
P-50M, CP-20MA, etc.). Examples of the compound of the formula (1) include polyethylene glycol mono (meth) acrylate such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate, and methoxydiethylene glycol mono (meth) acrylate. Alkoxy polyethylene glycol (meth) acrylates such as acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate;

The molecular weight of the copolymer type epoxy resin is about 1
000 to 200,000 is preferred. Glycidyl (meta)
The use amount of the acrylate is preferably from 10 to 70% by weight, particularly preferably from 20 to 50% by weight, based on the total amount of unsaturated monomers used in the copolymerizable epoxy resin.

When a copolymerizable epoxy resin which can be developed with water is obtained, glycerin mono (meth) acrylate and / or the compound of the general formula (1) is added to the total amount of unsaturated monomers used in the polymer. On the other hand, it is desirable to add 30% by weight or more, particularly preferably 50% by weight or more.

The above-mentioned copolymerizable epoxy resin can be obtained by a known polymerization method, for example, solution polymerization or emulsion polymerization. To explain the case of using solution polymerization,
The ethylenically unsaturated monomer mixture is added to a polymerization initiator in an applicable organic solvent, and is preferably added under a nitrogen stream under a nitrogen stream.
The polymerization is carried out by heating and stirring at 00 ° C. Examples of the organic solvent include ethanol, propanol,
Isopropanol, butanol, isobutanol, 2-
Alcohols such as butanol, hexanol and ethylene glycol, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve,
Carbitols such as carbitol and butyl carbitol; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol Examples thereof include acetic esters such as monomethyl acetate, lactic esters such as ethyl lactate and butyl lactate, and dialkyl glycol ethers. These organic solvents can be used alone or in combination.

As the polymerization initiator, for example, a peroxide such as benzoyl peroxide and an azo compound such as azobisisobutyronitrile can be used.

The compound (b) having one unsaturated double bond and one carboxyl group in one molecule includes (meth) acrylic acid and a hydroxyl group-containing (meth) acrylate (for example,
Acid anhydrides of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.) and polycarboxylic acid compounds (for example, succinic anhydride, maleic anhydride) Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.).

Specific examples of the saturated monocarboxylic acid (c) include, for example, acetic acid, propionic acid, pivalic acid, hydroxypivalic acid, dimethylolpropionic acid, benzoic acid and hydroxybenzoic acid.

It is preferable that 0.5 to 1.1 equivalents of the compound (b) and the saturated monocarboxylic acid (c) as an optional component are reacted with 1 equivalent of the epoxy group of the epoxy resin (a). Also, a reaction solvent may be used if necessary,
For example, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, alcohols such as ethylene glycol, methyl ethyl ketone, ketones such as cyclohexanone, toluene, aromatic hydrocarbons such as xylene, cellosolve,
Cellosolves such as butyl cellosolve, carbitols such as carbitol and butyl carbitol, propylene glycol alkyl ethers such as propylene glycol methyl ether, polypropylene pyrene glycol alkyl ethers such as dipropylene glycol methyl ether, ethyl acetate, butyl acetate And acetates such as cellosolve acetate and propylene glycol monomethyl acetate, lactates such as ethyl lactate and butyl lactate, and dialkyl glycol ethers. These organic solvents can be used alone or as a mixture.

In order to promote the reaction, a basic compound such as triphenylphosphine, triphenylstibine, triethylamine, triethanolamine, tetramethylammonium chloride, benzyltriethylammonium chloride or the like is added to the reaction solution as a reaction catalyst in an amount of 0.1 to 0.1%. 1
% Is preferably added. During the reaction, it is preferable to add a polymerization inhibitor (for example, methoxyphenol, methylhydroquinone, hydroquinone, phenothiazine, etc.) in the reaction solution in an amount of 0.05 to 0.5% in order to prevent polymerization.
The reaction temperature is preferably 90 to 150 ° C, and the reaction time is preferably 5 to 40 hours.

If necessary, an acid anhydride (d) of a polycarboxylic acid compound (for example, succinic anhydride, maleic anhydride, anhydride, etc.) is added to one equivalent of the hydroxyl group of the epoxy (meth) acrylate thus obtained. Phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) can be reacted preferably in an amount of from 0.2 to 1.0 equivalent of an anhydride group.
The reaction temperature is preferably 90 to 150 ° C, and the reaction time is preferably 3 to 30 hours.

In the present invention, a diluent (B) is used.
Specific examples of the component (B) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol (meth) acrylate, acryloyl Acid anhydride of morpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.) and polycarboxylic acid compound (Eg, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) half ester, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) Acrylate, Methylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycene polypropoxytri (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of neopyrene glycol hydroxybivalate (for example, KAY manufactured by Nippon Kayaku Co., Ltd.
ARAD HX-220, HX-620, etc.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, mono or polyglycidyl Compounds (for example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Epoxy which is a reaction product of (meth) acrylic acid with hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, etc. Reactive diluents (B-1) such as meth) acrylates, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers,
Diethylene glycol monoalkyl ether acetates, ethylene glycol monoaryl ethers, polyethylene glycol monoaryl ethers, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetates, esters such as butyl acetate,
Toluene, xylene, aromatic hydrocarbons such as benzyl alcohol, propylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, ethylene carbonate, propylene carbonate,
Organic solvents (B-2) such as γ-butyrolactone and solvent naphtha can be exemplified. The diluents may be used alone or as a mixture of two or more.

Specific examples of the photopolymerization initiator (C) include, for example, 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholino-propane-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 4-benzoyl-4'-methyldiphenylsulfide, 2,4,6-trimethylbenzoyldiphenylphosphine Oxides, Michler's ketone, benzyldimethyl ketal, 2-ethylanthraquinone and the like can be mentioned. Further, a photopolymerization accelerator (for example, amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester) as an accelerator of the photopolymerization initiator (B) is used in combination. You can also.

Specific examples of the powder (D) having a dielectric constant of 3.5 or less and surface-modified include low-density polyethylene powder, high-density polyethylene powder, ethylene / acrylic acid copolymer powder, polyphenylene ether powder, and polyphenylene ether powder. Ether sulfone powder, polytetrafluoroethylene powder, silicone powder, polyimide powder, Teflon powder and the like can be mentioned, and two or more kinds can be mixed. The particle size of these powders is preferably 30 μm or less. If the thickness is 30 μm or more, the pattern accuracy deteriorates, which is not preferable. Melting point is 10
If the temperature is lower than 0 ° C., the heat resistance of the cured product deteriorates.
0 ° C. or higher is preferred.

The surface modification is performed to improve the dispersion stability of the powder (D) in the resin. Surface modification methods include coating modification such as rosin treatment, topochemical modification such as low-temperature plasma treatment, modification by mechanochemical reaction, in-situ method, modification by encapsulation such as phase separation method, and radiation. And the like, and reforming by a precipitation reaction such as a CVD method. These may be combined, or the modified layer may be further modified by a chemical reaction.

The resin composition of the present invention comprises (A), (B),
It can be prepared by dissolving, mixing and kneading the components (C) and (D). In the resin composition of the present invention,
The use ratio of each component can be as follows (%
Is% by weight). The total amount of (A) + (B-1) + (C) used is preferably from 10 to 90%, particularly preferably from 30 to 80%, based on the composition. The component (D) preferably accounts for 10 to 90% of the composition, and particularly preferably 20 to 7%.
0%. The preferred amount of each component in the total amount of (A) + (B-1) + (C) is 30-90% of component (A), and the use of component (B-1). The amount is 5
The amount of the component (C) used is 5 to 30%. The amount of the organic solvent (B-2) can be used in any ratio for the purpose of adjusting the viscosity and the like suitable for using the composition of the present invention.

In the present invention, a thermosetting component (E) can be used. By using this, heat resistance and the like can be further improved. Examples of the thermosetting component (E) include an epoxy resin, a melamine compound, an oxazoline compound, and a phenol compound.
As the epoxy resin, specifically, bisphenol A
Glycidyl ethers such as epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, trisphenolmethane epoxy resin, brominated epoxy resin, biphenol epoxy resin, etc .; Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,
Alicyclic epoxy resins such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer Glycidyl esters such as esters; glycidylamines such as tetraglycidyl diaminodiphenylmethane; and heterocyclic epoxy resins such as triglycidyl isocyanurate. Above all, melting point is 50 ℃
The above epoxy resin is preferable because it can form a tack-free photopolymerizable film after drying.

Examples of the melamine compound include melamine and a melamine resin which is a polycondensate of melamine and formalin. Examples of the urea compound include urea and urea resins which are polycondensates of urea and formalin.

Examples of the oxazoline compound include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 5-methyl-2-phenyl-2-oxazoline,
2,4-diphenyloxazoline and the like.

Examples of the phenol compound include phenol, cresol, chilenol, catechol, resorcin, hydroquinone, pyrogallol, resol and the like.

When an epoxy resin is used as the thermosetting component (E), a curing accelerator is preferably used. Specific examples of the curing accelerator for the epoxy resin include 2-methylimidazole and 2-methylimidazole. Imidazole compounds such as ethyl-3-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, etc .; melamine, guanamine, acetoguanamine, benzoguanamine , Ethyldiaminotriazine, 2,4-diaminotriazine, 2,4
Triazine derivatives such as -diamino-6-tolyltriazine and 2,4-diamino-6-xylyltriazine; tertiary amines such as trimethylamine, triethanolamine, N, N-dimethyloctylamine, pyridine and m-aminophenol Polyphenols and the like.
These curing accelerators can be used alone or in combination. These thermosetting components (E) and curing accelerators are:
It is preferable to use 5 to 100%, particularly preferably 10 to 60%, based on 100% of the total of (A) + (B) + (C) + (D).

In the present invention, various additives and the like can be further added as needed. As various additives,
For example, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay,
Thixotropic agents such as Aerosil, silicones, fluorine-based leveling agents and defoamers, dyes, polymerization inhibitors such as hydroquinone, P-methoxyphenol and hydroquinone monotyl ether, coupling agents, waxes and the like.

As described above, the resin composition of the present invention can be used as a composition for a solder resist, a composition for an interlayer insulating layer, and the like. These include spin coating, screen printing, curtain flow coating, and spray coating. By such a method, it is applied to the entire surface of various substrates (for example, glass, ceramic, metal, etc.). After the application, if necessary, pre-baking is performed at about 50 to 150 ° C. with far infrared rays or warm air to remove the organic solvent, and then the film is exposed to ultraviolet rays using a negative mask that allows only the portions to be patterned to pass ultraviolet rays. The exposure amount of ultraviolet rays is 10 to 10000
mJ / cm ² is preferred. Next, development is carried out by means of spraying or the like with water or a dilute aqueous alkali solution at a normal liquid temperature of 10 to 60 ° C.
Heat cured for 4 hours to form a pattern.

When used as a film, the resin composition of the present invention is applied to a release film or the like by using, for example, a wire bar system, a dipping system, a spin coating system, a gravure system, a doctor blade system or the like. It is dried at 50 to 150 ° C. by far infrared rays or warm air as needed, and a release film or the like is attached as needed. When using, peel off the release film and transfer it to the substrate,
A pattern is formed by exposure, development, and thermosetting as described above.

[0033]

The present invention will be described below with reference to Examples 1 to 5 and Comparative Examples. In the examples, “parts” means “parts by weight”. A photosensitive resin composition was prepared according to the composition shown in Table 1. The resulting resin composition was applied on the entire surface of the glass-epoxy copper-clad laminate with a thickness of 50 μm (dry film thickness) by screen printing, and prebaked at 80 ° C. for 20 minutes. −150 μm / 150 μm) and irradiated with 500 mJ / cm ² by an ultra-high pressure mercury lamp,
Next, the unexposed portion was treated with a 1.0% aqueous sodium carbonate solution (30%).
° C) at a spray pressure of 2 kg / cm ² for 2 minutes. After the development, the film was thermally cured at 150 ° C. for 1 hour in the air to form a resist pattern, and the developability, the state of the pattern after the development, the adhesion to the substrate, the solder heat resistance, the dielectric constant, and the dielectric loss tangent were evaluated.

Synthesis Example 1 (Synthesis Example of Reactant A) A trisphenolmethane-type epoxy resin (Nippon Kayaku Co., Ltd., EPPN-503, epoxy equivalent 200, (Softening point 83 ° C) 200 parts, acrylic acid 72
, 0.2 parts of methylhydroquinone and 169.1 parts of propylene glycol monomethyl ether acetate, and the mixture was heated to 90 ° C. and dissolved. Then, the mixture was cooled to 60 ° C. and charged with 1.2 parts of triphenylphosphine.
After reacting for 32 hours, tetrahydrophthalic anhydride 1
12.6 parts were charged and reacted at 95 ° C. for 15 hours to obtain an unsaturated group-containing polycarboxylic acid resin having a solid content acid value (mg KOH / g) of 100.

Synthesis Example 2 (Synthesis Example of Reactant (A)) A round-bottomed flask equipped with a stirrer and a condenser was charged with a copolymerizable epoxy resin (manufactured by NOF Corporation, Blenmer CP-50M, epoxy equivalent: 31).
0, average molecular weight 6000) 310 parts, acrylic acid 72
, 0.3 parts of methylhydroquinone and 244.5 parts of propylene glycol monomethyl ether acetate, and the mixture was heated to 60 ° C. and dissolved. Then, the mixture was cooled to 60 ° C., and 1.8 parts of triphenylphosphine was charged.
After reacting for 32 hours at 70 ° C., 70 parts of succinic anhydride was charged and reacted at 95 ° C. for 15 hours to obtain a solid acid value (mg KO).
H / g) 80 unsaturated group-containing polycarboxylic acid resin was obtained.

Table 1 Example Comparative Example 1 2 3 4 5 Polymer obtained in Synthesis Example 1 15.4 15.4 15.4 7.7 15.4 Polymer obtained in Synthesis Example 2 15.4 7.7 KAYARAD PEG400DA * 144 2 KAYARAD DPHA * 2 44 4 4 KAYARAD DPCA-60 * 3 24 KAYACURE DETX-S * 4 1 1 1 1 1 1 KAYACURE EPA * 5 1 1 1 1 1 1 EOCN-104S * 6 4 4 4 4 4 4 4 Hexamethylol melamine 0.4 0.4 Powder (D-1) * 714 Powder (D-2) * 8 10 14 Powder (D-3) * 914 14 Propylene glycol monomethyl ether acetate 35 35 35 35 35 35 35 Developability (1% carbonic acid (Aqueous sodium solution) ○ ○ ○ ○ ○ ○ State of pattern after development ○ ○ ○ ○ ○ ○ Adhesion ○ ○ ○ ○ ○ Soldering heat resistance ○ ○ ○ ○ ○ ○ dielectric constant 2.5 2.7 2.5 2.5 2.7 3.9 Dielectric dissipation factor 0.02 0.02 0.02 0.02 0.02 0.04

Note * 1 KAYARAD PEG400DA: polyethylene glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd.) * 2 KAYARAD DPHA: dipentaerythritol penta and hexaacrylate (Nippon Kayaku Co., Ltd.)
* 3 KAYARAD DPCA-60: caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) * 4 KAYACURE DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) * 5 KAYACURE EPA: manufactured by Nippon Kayaku Co., Ltd.
p-Dimethylaminobenzoic acid ethyl ester * 6 Cresol novolak type epoxy resin (Nippon Kayaku Co., Ltd.) * 7 Plasma-treated low-density polyethylene powder * 8 Plasma-treated ethylene-acrylic acid copolymer powder * 9 Plasma-treated Polytetrafluoroethylene beads

(Developability): Evaluated as follows: ○: Completely developed △: Slight residue ×: Undeveloped part-: Pattern Part or all of the pattern is peeled off (the state of the pattern after development): ○ ・ ・ ・ ・ ・ ・ The pattern is maintained accurately △ ・ ・ ・ ・ The width of the pattern is narrow ×× ・ ・ ・ Pattern Part or all of the part is peeled off (adhesion): Cellophane tape peeling test was performed ..... No peeling was observed. (Solder heat resistance): Rosin flux MH-820V
(Tamura Kaken Corp., trade name), soldered at 260 ° C. for 10 seconds, and observed for abnormalities such as peeling and swelling. ○ ・ ・ ・ ・ No peeling or swelling △ ・・ ・ ・ Partially peeled and swelled × ・ ・ ・ ・ ・ ・ Many peeled and swelled parts (Dielectric constant): Dielectric constant was measured at 1 MHz (Dielectric tangent): Dielectric tangent was measured at 1 MHz

Example 5 The resin composition of Example 2 was applied to a release film so that the film thickness after drying was 50 μm, and dried at 80 ° C. for 20 minutes to obtain a film. This film was transferred to a glass-epoxy copper-clad laminate, contacted with a negative film, irradiated with 500 mJ / cm ² using an ultra-high pressure mercury lamp, and then the unexposed portion was sprayed with a 1.0% aqueous sodium carbonate solution (30 ° C.). Development was performed at 2 kg / cm ² for 2 minutes. After development, in air, 1
Baking at 50 ° C. for 1 hour to form a resist pattern. The developability, the state of the pattern after development, the adhesion to the substrate, and the solder heat resistance are all ○, the dielectric constant is 2.7, and the dielectric loss tangent is 0. 0.02.

As is clear from the results of Examples 1 to 5 and Comparative Example, the resin composition, film and cured product of the present invention have excellent developability, good pattern accuracy after development, and
Excellent adhesion, low dielectric constant and low dielectric loss tangent.

[0041]

The resin composition and the film of the present invention can form a resist pattern by selectively exposing to ultraviolet light through a pattern-formed film and developing an unexposed portion, and a cured product after thermosetting. Has excellent solder heat resistance and low dielectric constant and dielectric loss tangent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 512 512 7/027 515 7/027 515 F term (Reference) 2H025 AA03 AA10 AA20 AB15 AB17 AC01 AD01 BC14 BC34 BC43 BC74 BJ00 CB28 CB30 CC17 CC20 FA17 FA43 4F071 AA15 AA16 AA18 AA27 AA39 AA42 AA51 AA60 AA67 AF40Y AH12 BB02 BB12 BC01 4J002 BB032 03032 BB082 BB083 FD207 GP03 4J027 AA02 AC03 AE01 AE02 AE03 AE04 AE05 AE07 BA02 BA04 BA08 BA19 BA23 BA26 BA27 CA01 CA04 CA31 CB10 CC03 CD06 CD10

Claims (6)

[Claims] 1. An epoxy resin (a) having at least two epoxy groups in a molecule, a compound (b) having one unsaturated double bond and one carboxyl group in one molecule, and a saturated monoamine as an optional component. An unsaturated group-containing resin (A) obtained by reacting an epoxy (meth) acrylate that is a reaction product with a carboxylic acid (c) and, if necessary, a polybasic anhydride (d);
Diluent (B), photopolymerization initiator (C) and dielectric constant of 3.5
A photosensitive resin composition comprising a powder (D) whose surface has been modified as follows. 2. The photosensitive resin composition according to claim 1, wherein the particle diameter of the surface-modified powder (D) having a dielectric constant of 3.5 or less is 30 μm or less. 3. The photosensitive resin composition according to claim 1, wherein the powder (D) having a dielectric constant of 3.5 or less and a surface modified powder has a melting point of 100 ° C. or more. 4. The photosensitive resin composition according to claim 1, wherein the dielectric constant of the powder (D) is 3.0 or less. 5. A film comprising the photosensitive resin composition according to claim 1. 6. A cured product of the photosensitive resin composition and the film according to claim 1.