JP2003306591A - Curable resin composition and interlayer insulation material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition excellent in various characteristics such as dielectric characteristics and heat resistance and also excellent in flame retardancy, and to provide a substrate, prepreg and resin-clad copper foil having an interlayer insulation material using the same. <P>SOLUTION: The curable resin composition is characterized by containing a curable resin (A) in which at least one kind of the hydroxyl groups selected from the group consisting of a phenol aralkyl resin, naphthol aralkyl resin, biphenyl type phenol novolak resin, and biphenyl type naphthol novolak resin is etherified into a vinylbenzyl ether. There are also provided the substrate, prepreg, and resin-clad copper foil having the interlayer insulation material using this composition. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition and an interlayer insulating material using the same. More specifically, multi-layer laminated boards such as build-up multi-layer boards, insulating materials,
The present invention relates to a curable resin composition that is preferably used for dielectrics such as high frequency antennas and capacitors, a substrate having an interlayer insulating material using the same, a prepreg, and a copper foil with resin.

[0002]

2. Description of the Related Art In recent years, the required performance of electric / electronic materials has become higher as the performance, size and density of equipment have increased. As the performance of equipment becomes higher, the signal speed is getting faster, but in order to cope with this, it is necessary to increase the signal propagation speed, that is, the signal propagation delay time. here,
The delay of signal propagation is closely related to the dielectric constant of the material,
The lower the dielectric constant, the more advantageous it is to shorten the delay time. In addition, although the frequencies used are becoming higher, in the high frequency region, a material with low transmission loss is required to efficiently transmit electric signals. The transmission loss is closely related to the dielectric constant and the dielectric loss tangent, and the lower these are, the smaller the transmission loss becomes. From such a background, there is a strong demand for a material having a low dielectric constant and a low dielectric loss tangent.

In order to reduce the size and increase the density of equipment, a build-up multilayer substrate in which insulating layers and conductive layers are alternately stacked and each layer is electrically connected by a via hole has been used. Conventionally, an epoxy resin, which is a thermosetting resin, has been widely used as a resin for an interlayer insulating material of a build-up multilayer substrate. However, with respect to the recently required dielectric properties, epoxy resins cannot provide satisfactory properties. Further, a resin that sufficiently satisfies various required properties such as a fluorocarbon resin having excellent dielectric properties has poor processability has not yet been obtained.

On the other hand, frequencies used in information communication fields such as mobile phones, PHS, and digital TV broadcasting are shifting to higher frequencies. For dielectrics used for antennas, capacitors, etc. in the field of information and communications, materials with low dielectric loss characteristics have been used in order to respond to the transition to the high frequency range of such frequencies used, downsizing, and high density. Is being sought after.

Further, in electronic parts, electric equipment, etc., flame retardancy such as prevention and delay of fire is strongly required from the viewpoint of safety depending on the intended use. Further, from the viewpoint of global environmental problems, various flame-retardant materials that do not use halides are required.

To meet such requirements, for example, polybenzocyclobutene (RA Kirchhoff et al., Macromol. Sym.
54/55, 531 (1992)), fluorinated polybiphenylene ether (JP-A-10-74751), polyphenylene compound having a heterocyclic side chain (JP-A-9-278879), polyfumaric acid ester ( JP-A-9-208697), polynorbornene (JP-A-5-214079),
Polyquinoxaline (Japanese Patent No. 2705799), Fluorinated polyquinoline (Japanese Patent Publication No. 6-500591), Side chain allyl group-substituted polyphenylene ether (Japanese Patent Application Laid-Open No. 64-69628, Japanese Patent Application Laid-Open No. 4-183707, the same). 6-2007096), polyphenylene ether end-capped with an allyl group or a propargyl group (Japanese Patent Publication No. 7-51625), and the like. However, the materials proposed in these prior arts have a low crosslink density, a large linear expansion coefficient, a poor chemical resistance, a poor toughness, a complicated manufacturing process, and a multi-step process. Actually, there are various problems such as the need for a special solvent for shaping.

Further, Japanese Patent Laid-Open No. 9-31006 discloses that
We have proposed vinyl benzyl ether compounds, which have the characteristics of low dielectric constant and low dielectric loss tangent in a wide frequency range, and can be materials that meet the strict requirements for current electronic materials. However, the compound alone does not have flame retardancy. Further, JP-A-2001-253992 proposes a curable flame-retardant polyvinyl benzyl ether resin composition having a low dielectric constant, a low dielectric loss tangent, and a flame retardancy. As a reactive flame retardant for the composition, a compound in which at least one of the phenolic hydroxyl groups of the halogenated phenol compound is a vinylbenzyloxy group is mentioned. However, since the composition contains a halogen atom in the skeleton, it is not preferable in view of the above environmental problems.

[0008]

[Non-Patent Document 1] R, A, Kirkoff and others (RA Kirc
hhoff et al.), Macromolecular Symposium (Ma
cromol. Symp.) 54/55, 531 (1992)

[Patent Document 1] Japanese Patent Laid-Open No. 10-74751

[Patent Document 2] JP-A-9-278879

[Patent Document 3] Japanese Patent Laid-Open No. 9-208697

[Patent Document 4] JP-A-5-214079

[Patent Document 5] Japanese Patent No. 2705799

[Patent Document 6] Japanese Patent Publication No. 6-500591

[Patent Document 7] Japanese Patent Laid-Open No. 64-69628

[Patent Document 8] Japanese Patent Laid-Open No. 4-183707

[Patent Document 9] JP-A-6-2007096

[Patent Document 10] Japanese Patent Publication No. 7-51625

[Patent Document 11] Japanese Patent Laid-Open No. 9-31006

[Patent Document 12] Japanese Patent Laid-Open No. 2001-253992

[0009]

In view of such a background, the present invention provides a thermosetting resin composition having excellent properties such as dielectric properties and heat resistance as well as flame retardancy. It is an object of the present invention to provide a substrate, a prepreg, and a resin-coated copper foil having the above-mentioned interlayer insulating material.

[0010]

As a result of intensive studies, the inventors of the present invention have found that the above-mentioned conventional problems can be solved by the following constitution of the present invention, and the present invention has been made. It came to completion. The invention of claim 1 is at least one selected from the group consisting of a phenol aralkyl resin, a naphthol aralkyl resin, a biphenyl type phenol novolac resin and a biphenyl type naphthol novolac resin.
A curable resin composition comprising a curable resin (A) in which a certain type of hydroxyl group is vinylbenzyl etherified. The invention of claim 2 is a curable resin composition comprising the curable resin (A) of claim 1 and a compound (B) having one or more maleimide groups in the molecule. The invention of claim 3 is a curable resin composition comprising the curable resin (A) according to claim 1 and a reactive diluent (C). The invention of claim 4 is characterized by containing the curable resin (A) according to claim 1, a compound (B) having at least one maleimide group in the molecule and a reactive diluent (C). It is a curable resin composition. According to the invention of claim 5, the equivalent of the double bond of the maleimide group of the compound (B) having at least one maleimide group in the molecule is equivalent to the equivalent of the double bond of the vinylbenzyl group of the curable resin (A). The curable resin composition according to claim 2 or 4, wherein the ratio is 1 or less. In the invention of claim 6, the amount of the reactive diluent (C) is 100 parts by weight or less with respect to 100 parts by weight of the curable resin (A), and the curability according to claim 3 or 4. It is a resin composition. The invention of claim 7 is a substrate having an interlayer insulating material using the curable resin composition according to any one of claims 1 to 6. The invention of claim 8 is a prepreg having an interlayer insulating material using the curable resin composition according to any one of claims 1 to 6. The invention according to claim 9 is a resin-coated copper foil having an interlayer insulating material, which uses the curable resin composition according to any one of claims 1 to 6.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The curable resin (A) used in the present invention is obtained by converting at least one hydroxyl group selected from the group consisting of phenol aralkyl resin, naphthol aralkyl resin, biphenyl type phenol novolac resin and biphenyl type naphthol novolac resin into vinylbenzyl ether. Obtained.

As the phenol aralkyl resin, for example, one having the following general formula can be used.

[0013]

[Chemical 1]

As the naphthol aralkyl resin, for example, one having the following general formula can be used.

[0015]

[Chemical 2]

As the biphenyl type phenol novolac resin, for example, those having the following general formula can be used.

[0017]

[Chemical 3]

As the biphenyl type naphthol novolac resin, for example, those having the following general formula can be used.

[0019]

[Chemical 4]

As the phenol aralkyl resin, naphthol aralkyl resin, biphenyl type phenol novolac resin and biphenyl type naphthol novolac resin,
A commercially available product can be used. For example, as the phenol aralkyl resin, Mitsui Chemicals Co., Ltd., trade name Milex XLC-LL, XLC-3L, XLC-4L and Sumikin Chemical Co., Ltd. trade name SK Resin HE100-10, HE.
Examples include 100C-15 and HE100C-30. Examples of the naphthol aralkyl resin include SN170 and SN1 manufactured by Nippon Steel Chemical Co., Ltd.
80, SN190, SN475, SN485 and the like. Examples of the biphenyl type phenol novolac resin and the biphenyl type naphthol novolac resin include MEH-7851SS, MEH7851S, MEH7851M, MEH7851H manufactured by Meiwa Kasei Co., Ltd.

Further, the phenol aralkyl resin, naphthol aralkyl resin, biphenyl type phenol novolac resin and biphenyl type naphthol novolak resin can be produced by a known method. The method is
For example, JP 2001-213946 A, JP 11-A11.
-255868, JP-A-11-228673, JP-A-08-073570, and JP-A-08-0.
It is described in JP-A-48755, JP-A-10-310634 and JP-A-11-116647. The phenol aralkyl resin, naphthol aralkyl resin, biphenyl type phenol novolac resin and biphenyl type naphthol novolac resin may be used alone or in combination of two or more kinds.

As a method for converting the hydroxyl groups of these phenol aralkyl resins, naphthol aralkyl resins, biphenyl type phenol novolac resins and biphenyl type naphthol novolac resins into vinylbenzyl ethers, as described in JP-A-9-31006, A known conventional etherification reaction may be used, for example, m-vinylbenzyl chloride, p-vinylbenzyl chloride, m-vinylbenzyl bromide, vinylbenzyl halide such as p-vinylbenzyl bromide in a polar solvent in the presence of an alkali, or In the presence of a phase transfer catalyst, water /
It can be synthesized by a method of reacting in an organic solvent mixture. Examples of the polar solvent include dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxypropane, 1,2-dimethoxypropane, tetramethylene sulfone and hexa. Examples include aprotic polar solvents such as methylphosphoamide, methylethylketone, methylisobutylketone, acetone, cyclohexanone, and mixtures thereof. Examples of the alkali include alkoxides, hydrides and hydroxides of alkali metals or alkaline earth metals, such as sodium methoxide, sodium ethoxide, sodium hydride, sodium borohydride, potassium hydride and potassium hydroxide. . As the phase transfer catalyst, various onium salts, for example, quaternary ammonium compounds such as tetra-N-butylammonium bromide, tetra-N-butylammonium hydrogensulfate, benzyltrimethylammonium chloride, tricaprylmethylammonium chloride, tetra-N. -A quaternary phosphonium compound such as -butylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium chloride and tetraphenylphosphonium bromide, a tertiary sulfonium compound such as benzyltetramethylenesulfonium bromide and a mixture thereof.

It is also possible to use a compound having a halomethyl group such as allyl chloride, allyl bromide, propargyl chloride, propargyl bromide, benzyl chloride, benzyl bromide and p-xylylene dichloride in combination with the above vinylbenzyl halide. . The vinylbenzyl halide / halomethyl compound is preferably 1.0 / 0 to 0.1 / 0.9 equivalent. If the amount of vinylbenzyl halide is less than this range, the curability will be poor and the physical properties such as heat resistance of the cured product will be reduced. Further, the proportion of these phenol aralkyl resins, naphthol aralkyl resins, biphenyl-type phenol novolac resins, biphenyl-type naphthol novolac resins that are etherified with hydroxyl groups of vinylbenzyl halide and optionally a halomethyl compound is preferably 70 mol% of the hydroxyl groups. The above is desirable. If the reaction rate is 70 mol% or less, good dielectric properties cannot be obtained.
The reaction temperature and the reaction time are, for example, 30 to 100 ° C. and 0.5 to 20 hours.

Examples of the compound (B) having one or more maleimide groups in the molecule include maleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide and N- (2,6-
Diethylphenyl) maleimide, N- (4-bromophenyl) maleimide, N- (4-acetylphenyl) maleimide, N- (4-carboxy-3-hydroxyphenyl) maleimide, N- [p- (2-benzimidazolyl) Phenyl] maleimide, 4- (maleimidomethyl)
-1-Cyclohexanecarboxylic acid N-hydroxysuccinimide ester, 3-maleimidopropionic acid N-hydroxysuccinimide ester, 4,4'-diphenylmethane bismaleimide, bis (3-ethyl-5-methyl-
4-maleimidophenyl) methane, 2,2-bis [4-
(4-maleimidophenoxy) phenyl] propane,
N, N'-hexamethylene bismaleimide, N, N'-
Ethylene bismaleimide, N, N '-(1,2-phenylene) bismaleimide, N, N'-(1,3-phenylene) bismaleimide, N, N '-(1,4-phenylene) bismaleimide, N , N '-(4-methyl-1,3
-Phenylene) bismaleimide, bisallyl nadimide, amine-modified maleimide and the like. These can be used in combination.

The amount of the compound (B) having at least one maleimide group in the molecule is arbitrary, but one maleimide group is included in the molecule with respect to the equivalent of the double bond of the vinylbenzyl group of the curable resin (A). It is desirable that the ratio of the equivalents of the double bond of the maleimide group of the compound (B) having one or more is 1 or less. If this ratio exceeds 1, there is a possibility that it may cause deterioration of the dielectric properties.

The reactive diluent (C) may be any compound capable of reacting with the curable resin (A), and examples thereof include vinyl groups such as styrene, vinyltoluene, divinylbenzene, vinylbenzyl ether and acetoxystyrene. Compounds having an allyl group such as allylphenol, allyloxybenzene, diallylphthalate; methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-acryloylmorpholine, N, N-
Dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-
Dimethylaminopropyl acrylate, methoxy polyethylene glycol acrylate, ethoxy polyethylene glycol acrylate, melamine acrylate, phenoxyethyl acrylate, phenoxypropyl acrylate, ethylene glycol diacrylate, dipropylene glycol diacrylate, polydipropylene glycol diacrylate, trimethylolpropane triacrylate, penta Erythritol triacrylate,
Pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, glycerin diacrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, methyl methacrylate,
Ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-methacryloylmorpholine, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N, N-dimethylaminoethylmethacrylate, N, N- Dimethylaminopropyl methacrylate, methoxy polyethylene glycol methacrylate, ethoxy polyethylene glycol methacrylate, melamine methacrylate, phenoxyethyl methacrylate, phenoxypropyl methacrylate, ethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polydipropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, penta Erythritol trimethacrylate, pentaery Lithol tetramethacrylate, dipentaerythritol hexamethacrylate, glycerol dimethacrylate, isobornyl methacrylate, (meth) acrylic acid esters such as dicyclopentenyl oxyethyl methacrylate; vinyl pyrrolidone,
Liquid polybutadiene and the like, and examples thereof include one kind and a mixture thereof. Further, other curable resins can be used as the reactive diluent (C), and examples thereof include vinylbenzyl ether resin, vinylbenzyl resin, unsaturated polyester resin, vinyl ester resin, cyanate ester resin, and these. A mixture of

The amount of the reactive diluent (C) is about 100 parts by weight or less based on 100 parts by weight of the curable resin (A). If it exceeds 100 parts by weight, the workability of the composition and the heat resistance of the cured product may decrease.

The composition of the present invention includes the following four aspects, and any of the aspects can achieve desired effects. (1) A composition containing a curable resin (A). (2) A composition containing a curable resin (A) and a compound (B) having at least one maleimide group in the molecule. (3) A composition containing a curable resin (A) and a reactive diluent (C). (4) A composition containing a curable resin (A), a compound (B) having one or more maleimide groups in the molecule, and a reactive diluent (C).

Further, a flame retardant may be used in combination with the composition of the present invention depending on the application. The flame retardant may be a commonly used and commonly used one, and is not particularly limited, and examples thereof include phosphoric acid ester, phosphazene, phospholine oxide, phosphorus compounds such as melamine polyphosphate, and antimony trioxide. The flame retardant can be used in combination. The amount of the flame retardant used is preferably 150 parts by weight or less with respect to 100 parts by weight of the curable resin (A). 1
If the amount is more than 50 parts by weight, the dielectric property is deteriorated, which is not preferable.

Further, the composition of the present invention may be used in combination with a known and commonly used thermoplastic resin within a range not impairing the object of the present invention. For example, polyphenylene ether, polyamide, polyimide, silicone resin, polyethylene, polypropylene, polystyrene, polybutadiene, phenoxy resin, and the like, and mixtures thereof are not particularly limited.

Further, the composition of the present invention may contain known and commonly used additives such as a release agent, a surface treatment agent and a filler depending on the use. Examples of the release agent include waxes, examples of the surface treatment agent include a silane coupling agent, and examples of the filler include silica, talc, glass fiber, and the like.

Further, in order to accelerate curing, benzoyl peroxide, t-butylperoxybenzoate, t-butylhydroperoxide, di-t-butylperoxide, t-butylhydroperoxide, dicumyl peroxide, cation. It is also possible to use a known and commonly used curing agent such as a system thermal polymerization initiator (for example, Asahi Denka product name Adeka Opton CP-66, CP-77).

The method for producing an interlayer insulating material using the composition of the present invention is not particularly limited, but the following method may be mentioned. (1) Methyl ethyl ketone, methyl isobutyl ketone, 1,4-dioxane, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, toluene A method of dissolving in an organic solvent such as, coating on a substrate, drying the solvent, and then heating and curing to form an insulating film, (2) the composition is methyl ethyl ketone, methyl isobutyl ketone, 1,4-dioxane, ethylene glycol monomethyl ether, Diethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether Tate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, is dissolved in an organic solvent such as toluene, a method by coating and dried by heating on a copper foil or on a film to a resin-coated copper foil or a dry filming, (3)
Thermosetting resin composition methyl ethyl ketone, methyl isobutyl ketone, 1,4-dioxane, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, Dissolve in an organic solvent such as toluene, glass cloth,
A method of impregnating aramid fibers, etc. and drying with a solvent to form a prepreg.

Further, since the composition of the present invention is excellent in dielectric properties and flame retardance, it is possible to use a known filler having a high dielectric constant such as ceramics in combination with a dielectric for a high frequency antenna or a capacitor. And the like can be suitably used.

[0035]

EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples. All parts and% are based on weight unless otherwise specified.

Production Example 1 HE100C-15 (phenol aralkyl resin manufactured by Sumikin Chemical Co., Ltd.) 170 parts (1.0 equivalent) and CMS-AM were placed in a four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel. (Seimi Chemical Co. vinyl benzyl chloride) 160.1 parts (1.05 equivalents), tetra-n-butylammonium bromide 9.
6 parts, 2,4-dinitrophenol 0.152 parts, and methyl ethyl ketone 255 parts were charged and dissolved with stirring to a liquid temperature of 7
The temperature was raised to 5 ° C., 160 parts (2.0 equivalents) of 50% aqueous sodium hydroxide solution was added dropwise over 20 minutes, and stirring was continued at 75 ° C. for 4 hours. Next, after neutralizing the inside of the flask with a 10% aqueous hydrochloric acid solution, 400 parts of toluene was added, and the organic layer was added to 15
It was washed 3 times with 00 ml of water. The organic layer was precipitated in methanol to obtain the objective curable resin (A), vinylbenzyl ether (VBE-1). The ¹ H nuclear magnetic resonance spectrum (NMR) of the obtained product confirmed a signal indicating a vinylbenzyl group at around 5 to 6 ppm. In addition, it was confirmed from the infrared spectrum (IR) and the hydroxyl equivalent based on JIS K0770 that no phenolic hydroxyl group was present in the product.

Production Example 2 195 parts of SN180 (Naphthol aralkyl resin manufactured by Nippon Steel Chemical Co., Ltd.) (1.0 equivalent) in a four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel, CMS-AM. (Vinylbenzyl chloride manufactured by Seimi Chemical Co., Ltd.) 160.1 parts (1.05 equivalents), tetra-n-butylammonium bromide 9.6 parts, 2,4
-Prepare 0.152 parts of dinitrophenol and 255 parts of methyl ethyl ketone and dissolve with stirring to bring the liquid temperature to 75 ° C., and 5
160 parts (2.0 equivalents) of 0% aqueous sodium hydroxide solution was added dropwise over 20 minutes, and stirring was continued at 75 ° C. for 4 hours.
Next, after neutralizing the inside of the flask with a 10% aqueous hydrochloric acid solution, 400 parts of toluene was added, and the organic layer was mixed with 1500 ml of water to 3 times.
Washed twice. The organic layer is precipitated in methanol, which is the target curable resin (A), vinyl benzyl ether (VBE-
2) was obtained. In the same manner as in Production Example 1, the obtained product was confirmed by NMR for the presence of a vinylbenzyl group, and was confirmed by IR and hydroxyl equivalent to the absence of a phenolic hydroxyl group in the product.

Production Example 3 MEH7851H (biphenyl type phenol novolac resin manufactured by Meiwa Kasei Co. Ltd., hydroxyl equivalent 218) 218 parts (1.0 equivalent) in a four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel. ), CMS-AM (vinyl benzyl chloride manufactured by Seimi Chemical Co., Ltd.) 1
60.1 parts (1.05 equivalents), tetra-n-butylammonium bromide 9.6 parts, 2,4-dinitrophenol 0.152 parts, and methyl ethyl ketone 255 parts were charged and dissolved by stirring to bring the liquid temperature to 75 ° C. 160 parts (2.0 equivalents) of 50% aqueous sodium hydroxide solution was added dropwise over 20 minutes, and stirring was continued at 75 ° C. for 4 hours. Next, after neutralizing the inside of the flask with a 10% aqueous hydrochloric acid solution, 400 parts of toluene was added, and the organic layer was washed 3 times with 1500 ml of water. The organic layer was precipitated in methanol to obtain the desired vinyl benzyl ether (VBE-3). The ¹ H nuclear magnetic resonance spectrum (NMR) of the obtained product confirmed a signal indicating a vinylbenzyl group at around 5 to 6 ppm. In addition, it was confirmed from the infrared spectrum (IR) and the hydroxyl group equivalent by JIS K0770 that the phenolic hydroxyl group was not present in the product.

Comparative Production Example 1 BRG555 (Showa Polymer Co., Ltd., hydroxyl equivalent 102) 102 parts (1.0 equivalent), C in a four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel.
MS-AM (Seimi Chemical Co., Ltd. vinylbenzyl chloride) 160.1 parts (1.05 equivalents), tetra-
n-Butyl ammonium bromide 9.6 parts, 2,4-
Dinitrophenol 0.152 parts and methyl ethyl ketone 255 parts were charged and dissolved by stirring, and the liquid temperature was raised to 75 ° C., and 50
% Aqueous sodium hydroxide solution (160 parts, 2.0 equivalents)
The mixture was added dropwise over 0 minutes, and stirring was continued at 75 ° C. for 4 hours. Next, after neutralizing the inside of the flask with a 10% aqueous hydrochloric acid solution, 400 parts of toluene was added, and the organic layer was washed 3 times with 1500 ml of water. The organic layer was precipitated in methanol to obtain the desired vinyl benzyl ether (VBE-4). The obtained product has a ¹ H nuclear magnetic resonance spectrum (NMR) of 5 to 6 ppm.
A signal indicating a vinylbenzyl group was confirmed in the vicinity. In addition, it was confirmed from the infrared spectrum (IR) and the hydroxyl group equivalent by JIS K0770 that the phenolic hydroxyl group was not present in the product.

Examples 1-10 and Comparative Examples 1-3 Varnishes are made by blending each component according to the formulation shown in Table 1.
did. Apply this on a tetrafluoroethylene sheet
Solvent drying was performed at 110 ° C. for 2 hours to obtain a dried product. This dry
The product is crushed and pressed at 150 ° C for 2 hours and 180 ° C for 4 hours.
Mold (40kg / cm ²) Is performed and a cured product with a thickness of about 1.5 mm is
Created.

[0041]

[Table 1]

The compounds listed in Table 1 are as follows. BMI-70: Bis (3-ethyl-5-methyl-4-, manufactured by KAI KASEI CO., LTD.
Maleimidophenyl) methane YDCN703: Tohto Kasei Co., Ltd. cresol novolac type epoxy BRG555: Showa Polymer Co., Ltd. phenol novolac cure sol 2E4MZ: Shikoku Kasei 2-ethyl-4-methylimidazole

According to the evaluation test method shown below,
Various physical properties were evaluated. Regarding the flame retardancy, a cured product having a thickness of 3.0 mm was used. The results are shown in Table 2.

Dielectric constant and dielectric loss tangent A vector network analyzer HP8753E manufactured by Hewlett-Packard Co., Ltd. was used to measure by a cavity resonator perturbation method using a 1.5 mm × 1.5 mm × 75 mm prismatic test piece.

Solder heat resistance At 40 ° C. and 90% relative humidity, a cured product that had been moisture-absorbed for 96 hours was dipped in a solder bath at 260 ° C. for 10 seconds, and swelling and cracking were confirmed. ○: No swelling and cracks ×: Swelling and cracks

The flame retardant cured product having a thickness of 3.0 mm was evaluated according to UL-94 standard.

[0047]

[Table 2]

From the results of Table 2, Examples 1 to 10 have excellent dielectric constant, dielectric loss tangent, solder heat resistance and flame retardancy, whereas Comparative Examples have excellent solder heat resistance, It is understood that the ratio, the dielectric loss tangent and the heat resistance are not all satisfied.

[0049]

INDUSTRIAL APPLICABILITY According to the present invention, a thermosetting resin composition excellent in various properties such as dielectric properties and heat resistance and also excellent in flame retardancy, a substrate having an interlayer insulating material using the same, a prepreg, A resin-coated copper foil is provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/46 H05K 3/46 TF term (reference) 4F072 AA07 AD13 AD15 AD18 AD53 AG03 AK04 AK15 AL12 AL13 4F100 AB17B AB33B AK31A BA02 BA07 CA30A EJ08A GB43 JB12A JG05 JJ03 JJ07 YY00A 4J002 BL012 CC051 CC071 CC091 CH052 EA037 ED057 EH077 EH107 EH147 EJ027 EN027 EP017 EU026 EU027 EU187 EU237 GF00 GQ01 4J027 AH03 BA03 CC02 CD01 5E346 AA12 EE09 HH01 HH18

Claims (9)

[Claims] 1. A curable resin (A) in which at least one hydroxyl group selected from the group consisting of a phenol aralkyl resin, a naphthol aralkyl resin, a biphenyl type phenol novolac resin and a biphenyl type naphthol novolac resin is vinylbenzyl etherified. A curable resin composition comprising: 2. The curable resin (A) according to claim 1 and a compound (B) having one or more maleimide groups in the molecule.
A curable resin composition comprising: 3. A curable resin composition comprising the curable resin (A) according to claim 1 and a reactive diluent (C). 4. A curable resin comprising the curable resin (A) according to claim 1, a compound (B) having at least one maleimide group in the molecule, and a reactive diluent (C). Resin composition. 5. The ratio of the equivalent of the double bond of the vinylbenzyl group of the curable resin (A) to the equivalent of the double bond of the maleimide group of the compound (B) having at least one maleimide group in the molecule is It is 1 or less, The claim 2 or 4 characterized by the above-mentioned.
The curable resin composition according to. 6. The curable resin composition according to claim 3, wherein the amount of the reactive diluent (C) is 100 parts by weight or less based on 100 parts by weight of the curable resin (A). object. 7. A substrate having an interlayer insulating material using the curable resin composition according to any one of claims 1 to 6. 8. A prepreg having an interlayer insulating material using the curable resin composition according to any one of claims 1 to 6. 9. A resin-coated copper foil having an interlayer insulating material using the curable resin composition according to claim 1. Description: