JP2003141933A - Resin composition for electric insulation, insulation material for electronic material, and their manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a specific resin composition or the like for electric insulation excellent in thermal resistance, low thermal expansion property, insulation, and adhesion which, moreover, can produce a hybrid cured matter without fear of void, crack, or the like, and facilitate molding process in a semi-cured state. SOLUTION: The resin composition for electric insulation contains methoxy- group-containing silane-denatured novolac type epoxy resin obtained by demethanolic condensation reaction of oxyepoxy resin obtained by denaturation with ring opening of a part of epoxy group of novolac type epoxy resin (1) and methoxysilane partial condensation matter (2). Or, one containing methoxy- group-containing silane-denatured novolac type epoxy resin obtained by demethanolic condensation reaction of oxyepoxy resin obtained by denaturing a part of epoxy group of novolac type epoxy resin (1), a partial methoxysilane condensation product (2) and an epoxy compound having one hydroxy group in one molecule (3).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for electrical insulation containing a methoxy group-containing silane-modified epoxy resin. The present invention also relates to an insulating material for electronic materials, which is obtained by processing (coating, casting, bonding, laminating, impregnating, molding, etc.) the resin composition for electrical insulation and then curing it, and a method for producing the same. In the present specification, the “insulating material for electronic materials” refers to a resin composition containing a methoxy group-containing silane-modified epoxy resin, or a cured product (including a semi-cured product and a completely cured product) obtained from the resin composition. An insulating material suitable for use in electronic materials obtained by using, for example, a prepreg for a printed circuit board, a copper clad laminate for a printed circuit board, a printed wiring board or an interposer made by combining these, and further a build-up print. Interlayer insulating material for substrates, semiconductor interlayer insulating film, sealant for electronic parts and semiconductor chips, cured underfill resin, cured resist ink such as solder resist,
It means a conductive paste cured product, a molded product such as an IC tray, and an anisotropic conductive film.

[0002]

2. Description of the Related Art Epoxy resins have hitherto been generally used as a composition in combination with a curing agent, and the composition has been favored in the field of electronic materials. However, with the recent development of the electronic materials field,
Higher levels of heat resistance, low linear expansion, insulation, and high adhesion have been demanded for insulating materials used in this field. For example, when using lead-free solder, which is an environmentally friendly solder, the reflow temperature is higher than that of conventional lead-containing solder, so it is possible to use an insulating material with better heat resistance and longer life than conventional insulating materials. Development is coveted. In these fields, brominated epoxy resins have been traditionally nominated as highly flame-retardant insulating materials, but since the waste products of products using the resins generate toxic gas derived from bromine when incinerated, Recently, the use of halogenated resins such as brominated epoxy resins has been shunned.

In order to improve the heat resistance of a cured product of a non-halogenated epoxy resin composition, for example, a method of using a composition in which a filler such as glass fiber, glass particles, mica, etc. is mixed with an epoxy resin and a curing agent is used. Has been done. However, even with this method, sufficient heat resistance cannot be obtained.
In addition, the transparency of the cured product obtained by this method is lost,
Moreover, since the adhesiveness at the interface between the filler and the epoxy resin is poor, mechanical properties such as elongation are insufficient.

Further, as a method for improving the heat resistance of a cured product of an epoxy resin composition, a method using a composite of an epoxy resin and silica has been proposed (JP-A-8-10).
No. 0107). The complex is a solution of a partially cured epoxy resin, hydrolyzable alkoxysilane,
It can be obtained by further curing the cured product, hydrolyzing the alkoxysilane to form a sol, and further polycondensing to form a gel. However, the cured product obtained from such a composite has improved heat resistance to some extent as compared with the cured product of the epoxy resin alone, but due to water in the composite, water generated during curing, and alcohol, a cured product is obtained. Voids are generated inside. Further, when the amount of alkoxysilane is increased for the purpose of further improving heat resistance, transparency of the cured product obtained by aggregation of silica generated by the sol-gel curing reaction is lost and whitening occurs, and a large amount of alkoxysilane is added. A large amount of water is required to turn it into a sol, and as a result, warpage and cracks of the cured product are caused.

Further, a composition in which a silane-modified epoxy resin obtained by reacting an epoxy resin with a silicone compound and a phenol novolac resin as a curing agent are combined (Japanese Patent Laid-Open No. 3-201466), a bisphenol A type epoxy resin, A composition in which a silane-modified epoxy resin obtained by reacting tetrabisbromobisphenol A and a methoxy group-containing silicone intermediate is combined with a phenol novolac resin which is a curing agent (JP-A-61-27224).
No. 3, JP-A-61-272244, etc.) are also proposed. However, the cured products of these epoxy resin compositions have insufficient heat resistance because the main constituent units of the silicone compound and the methoxy group-containing silicone intermediate are diorganopolysiloxane units and cannot form silica. .

The applicant of the present invention has found that a cured product obtained by curing a methoxy group-containing silane-modified epoxy resin obtained by subjecting a bisphenol type epoxy resin and a methoxysilane partial condensate to a methanol removal reaction has a high glass transition point, It has been found that it can be used as a heat resistant material (Japanese Patent No. 3077765). In this method, in order to obtain a cured product, the solvent is volatilized from the resin composition and the methoxysilyl group is sol-formed.
Although gel curing and epoxy curing of an epoxy group are carried out to obtain an epoxy resin-silica hybrid cured product, there is a problem that it is difficult to perform molding processing in a semi-cured state, which is indispensable for applications related to electric / electronic materials.

In recent years, engineering plastics such as polyimide and polyphenylene ether have been used as highly heat resistant insulating materials. However, since these materials have weak adhesion to a metal (conductor) such as copper, there is a disadvantage that an epoxy adhesive having weak heat resistance must be used as an anchoring agent and that the cost is high.

[0008]

DISCLOSURE OF THE INVENTION The present invention is capable of obtaining a hybrid cured product which is excellent in heat resistance, low thermal expansion property, insulation property and adhesiveness and does not cause voids, cracks and the like, and is in a semi-cured state. It is an object of the present invention to provide a specific resin composition for electrical insulation, which is easy to mold and process, an insulating material for electronic materials obtained from the composition, and a method for producing the material.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a methoxy group-containing silane-modified epoxy resin containing a specific epoxy resin and a specific methoxysilane partial condensate is contained. A resin composition to
The inventors have found that an insulating material for electronic materials obtained from the resin composition meets the above-mentioned object, and completed the present invention.

That is, according to the present invention, a hydroxyl group-containing epoxy resin (1) obtained by ring-opening modification of a part of the epoxy groups of a novolac type epoxy resin and a methoxysilane partial condensate (2) are subjected to a methanol removal condensation reaction. The present invention relates to a resin composition for electrical insulation containing the silane-modified epoxy resin containing methoxy group obtained as described above. Further, the present invention is
Hydroxyl group-containing epoxy resin (1) obtained by ring-opening modification of a part of the epoxy groups of novolak type epoxy resin, methoxysilane partial condensate (2), and epoxy compound (3) having one hydroxyl group in one molecule And a methoxy group-containing silane-modified novolac type epoxy resin obtained by subjecting the above to a methanol removal condensation reaction. The present invention also relates to an insulating material for electronic materials obtained by curing the resin composition for electrical insulation and a method for producing the material.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a hydroxyl group-containing epoxy resin (1) obtained by ring-opening modification of a part of epoxy groups of a novolac type epoxy resin is essential as a constituent component of a methoxy group-containing silane modified epoxy resin. use. The novolak type epoxy resin, which is a constituent raw material of the hydroxyl group-containing epoxy resin (1), is a reaction product of a novolac phenol resin and a haloepoxide such as epichlorohydrin. Examples of the novolac phenolic resins include novolac phenolic resins, cresol novolac resins, bisphenol novolac resins, and poly-p-vinylphenol. Among these novolac phenol resins, a phenol novolac epoxy resin using a phenol novolac resin is particularly preferable because the cured product has low thermal expansion property.

In the present invention, the novolac type epoxy resin is used as the constituent raw material of the hydroxyl group-containing epoxy resin (1), as compared with the case where the bifunctional epoxy resin represented by the bisphenol type epoxy resin is used. This is because the resin-silica hybrid cured product has a low thermal expansion property.

The number average phenol nucleus number of the novolac type epoxy resin is preferably 3 to 10, and more preferably 3 to 6. If the average number of nuclear bodies is less than 3,
The thermal expansion property becomes high, and if it exceeds 10, the compatibility with the methoxysilane partial condensate (2) becomes low, which is not preferable.

The phenol novolac type epoxy resin is
General formula (a):

[0015]

[Chemical 1]

(Wherein, m represents an integer of 1 to 8).

Hydroxyl group-containing epoxy resin (1) which is a raw material for the methoxy group-containing silane-modified epoxy resin in the present invention
Is obtained by ring-opening modification of one or more epoxy groups of a novolac type epoxy resin so as to have a hydroxyl group capable of forming a silicate ester by a demethanol condensation reaction with a methoxysilane partial condensate (2). Examples of the compound that undergoes ring-opening modification include active hydrogen compounds such as phenols, amines, and carboxylic acids. Specifically, phenol, paratertiary butylphenol, paratertiary octylphenol, cresol, xylenol, catechol, bisphenol A, bisphenol F, phenols such as bisphenol S, quinones such as hydroquinone, ethylamine, isopropylamine, 2-ethylhexyl. Amine, primary amines such as 3-methoxypropylamine, allylamine, secondary amines such as diethylamine, diisopropylamine, diisobutylamine, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, benzoic acid, fumaric acid, maleic acid And carboxylic acids such as phosphoric acid, methylphosphonic acid, and dimethylphosphonic acid. Among these, a bifunctional compound having two active hydrogens is preferable because the epoxy resin-silica hybrid has a low thermal expansion property. More preferably, since the compatibility between the hydroxyl group-containing epoxy resin (1) and the methoxysilane partial condensate (2) is good and the reaction is easy, the ring-opening modification with a bisphenol is more preferable.

The amount of the active hydrogen compound used for ring-opening modification of the novolac type epoxy resin is not particularly limited, but the molar ratio of active hydrogen for ring-opening modification to 1 mol of the novolak type epoxy resin molecule is 0.2 to 3. It is preferable that the average number of ring-opening modified epoxy groups is 0.2 to 3 among the epoxy groups of the novolac type epoxy resin. If this numerical value is less than 0.2, the effect of the present invention cannot be obtained, and if it exceeds 3, there is a tendency that gelation occurs at the time of ring-opening modification and thermal expansion becomes high, which is not preferable.

Further, it is not necessary that all molecules of the novolac type epoxy resin are ring-opening modified. The unmodified novolac type epoxy resin promotes a demethanol reaction between the hydroxyl group-containing epoxy resin (1) and the methoxysilane partial condensate (2), and thus serves as a reaction medium for phase-dissolving both and sol- It plays the role of softening the semi-cured product that is gel-cured. Therefore, in particular, for applications that require processing in a semi-cured state such as adhesives, molding intermediate materials, prepregs, and encapsulants, in order to leave part of the novolac epoxy resin unmodified, novolac epoxy The molar ratio of active hydrogen for ring-opening modification to 1 mol of the resin is 0.
It is preferably 8 or less.

As the methoxysilane partial condensate (2) used in the present invention, an oligomer obtained by partially hydrolyzing and condensing methoxysilane which is generally used in the sol-gel method can be used. For example, the general formula: R _p Si (OC
H ₃ ) _4-p (In the formula, p represents an integer of 0 or 1, and R
Represents a lower alkyl group having 6 or less carbon atoms or a phenyl group. Examples of the partial condensate of the compound represented by
When p is 2 to 4, three-dimensional crosslinking does not occur, and it becomes difficult to impart desired high heat resistance to the finally obtained cured product.

Specific examples of the methoxysilane partial condensate (2) include tetramethoxysilane partial condensate; methyltrimethoxysilane, ethyltrimethoxysilane,
Partial condensates of trimethoxysilanes such as n-propyltrimethoxysilane, isopropyltrimethoxysilane, vinyltrimethoxysilane and phenyltrimethoxysilane can be mentioned. Among these, partial condensates such as tetramethoxysilane and methyltrimethoxysilane are preferable because they have high versatility and a high sol-gel curing rate.

As the methoxysilane partial condensate (2), one kind or two or more kinds may be appropriately selected from the above substances, but the average number of Si per molecule is preferably 3 to 12. When the average number of Si is less than 3, during the methanol removal reaction with the hydroxyl group-containing epoxy resin (1),
It is not preferable because the amount of toxic methoxysilanes flowing out of the system together with by-product methanol increases. Further, when it exceeds 12, the compatibility with the hydroxyl group-containing epoxy resin (1) deteriorates, the amount of the novolak epoxy resin (1) and the large amount of organic solvent exceeding the above weight ratio are required, and the desired methoxy group-containing silane modification is performed. Epoxy resin is difficult to obtain.

In particular, the general formula (b):

[0024]

[Chemical 2]

(In the formula, Me represents a methyl group, and the average number of repeating units of n is 3 to 12.) or a partial condensate of tetramethoxysilane represented by the general formula (c):

[0026]

[Chemical 3]

A partial condensate of methyltrimethoxysilane represented by the formula (wherein Me represents a methyl group and the average number of repeating units of n is 3 to 12) is preferred.

In the present invention, the methoxy group-containing silane-modified epoxy resin is obtained by subjecting the hydroxyl group-containing epoxy resin (1) and the methoxysilane partial condensate (2) to a demethanol reaction. An epoxy compound (3) having one hydroxyl group (hereinafter, simply referred to as epoxy compound (3)) may be used. The epoxy compound (3) also undergoes a demethanol reaction with the methoxysilane partial condensate (2) to form a methoxy group-containing silane-modified epoxy resin.

A hydroxyl group must be present in the hydroxyl group-containing epoxy resin (1). However, when the molar ratio of active hydrogen for ring-opening modification to 1 mol of the novolac type epoxy resin is less than 1, it has no hydroxyl group. No novolac type epoxy resin is present in the hydroxyl group-containing epoxy resin (1). Since such a novolac type epoxy resin does not react with the methoxysilane partial condensate (2), it is present in the methoxy group-containing silane-modified epoxy resin in an unreacted state. When the epoxy resin-silica hybrid semi-cured film is formed, the molecule effectively acts to impart flexibility and adhesion, and when the methoxy group-containing silane-modified epoxy resin contains a large amount of novolac type epoxy resin,
The heat resistance of the finally obtained cured film may be insufficient.

In the present invention, when the hydroxyl group-containing epoxy resin (1) containing a large amount of novolac type epoxy resin having no hydroxyl group is used, specifically, 1 mol of the novolac type epoxy resin is treated with active hydrogen that undergoes ring-opening modification. Even when the molar ratio is less than 1, it is preferable to use the epoxy compound (3) in order to impart sufficient heat resistance to the obtained epoxy resin-silica hybrid cured film. That is, the epoxy compound (3) has a function and effect of preventing a decrease in heat resistance of the epoxy resin-silica hybrid cured film by the novolac type epoxy resin having no hydroxyl group. In the production of the methoxy group-containing silane-modified epoxy resin, the amount of the epoxy compound (3) used is not particularly limited and may be appropriately determined depending on the content of the molecule having no hydroxyl group in the epoxy resin (1). .

From the viewpoint of heat resistance of the epoxy resin-silica hybrid cured product, when a hydroxyl group-containing epoxy resin (1) having a molar ratio of active hydrogen for ring-opening modification of 0.3 or less to 1 mol of a novolac type epoxy resin is used. In addition, the weight of the epoxy compound (3) / the weight of the hydroxyl group-containing epoxy resin (1) is 0.1 or more, and when the value is 0.5 or less, it is preferably 0.03 or more. Since many epoxy compounds (3) have some toxicity, it is preferable to minimize the residual amount of the epoxy compound (3) in the methoxy group-containing silane-modified epoxy resin. If the weight ratio exceeds 0.3, the production time of the methoxy group-containing silane-modified epoxy resin becomes long in order to reduce the unreacted epoxy compound (3), and the production efficiency decreases.

The number of epoxy groups is not particularly limited as long as the epoxy compound (3) is an epoxy compound having one hydroxyl group in one molecule. Further, as the epoxy compound (3), the smaller the molecular weight, the better the compatibility with the epoxy resin (1) and the methoxysilane partial condensate (3), and the higher the heat resistance imparting effect, the more the number of carbon atoms is 1.
Those of 5 or less are preferable. As a specific example thereof, monoglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting epichlorohydrin with water, dihydric alcohol or phenols having two hydroxyl groups; epichlorohydrin and Polyglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting a trihydric or higher polyhydric alcohol such as glycerin or pentaerythritol; a molecular end obtained by reacting epichlorohydrin and aminomonoalcohol Examples thereof include an epoxy compound having one hydroxyl group; and an alicyclic hydrocarbon monoepoxide having one hydroxyl group in the molecule (for example, epoxidized tetrahydrobenzyl alcohol). Of these epoxy compounds, glycidol is the most excellent in terms of the heat resistance imparting effect, and is also the most suitable because it has high reactivity with the methoxysilane partial condensate (2).

The methoxy group-containing silane-modified epoxy resin according to the present invention is obtained by removing a novolac type epoxy resin, a hydroxyl group-containing epoxy resin (1) and a methoxysilane partial condensate (2) in the presence or absence of a solvent. It is obtained by a methanol condensation reaction. The amount of the hydroxyl group-containing epoxy resin (1) and the methoxysilane partial condensate (2) used is not particularly limited, and the hydroxyl group equivalent of the hydroxyl group-containing epoxy resin (1) / the methoxy group equivalent of the methoxysilane partial condensate (2) is used. The (equivalent ratio) is usually about 0.02 to 0.6, preferably 0.03 to 0.5. The equivalence ratio is 0.
If it is less than 02, the amount of unreacted methoxysilane partial condensate (2) becomes too much, and if it exceeds 0.6 (stoichiometrically approaching the same amount), gelation tends to occur due to progress of the demethanol reaction. Not preferable.

When the hydroxyl group equivalent of the hydroxyl group-containing epoxy resin (1) / the methoxy group equivalent (equivalent ratio) of the methoxysilane partial condensate (2) is 0.2 or more, or the amount of Si per molecule is When the methoxysilane partial condensate (2) having an average number of 7 or more is used as a starting material, the hydroxyl group-containing epoxy resin (1), the novolac type epoxy resin and the novolac type epoxy resin are removed until the hydroxyl groups completely disappear. When the methanol condensation reaction is carried out, it tends to lead to high viscosity and gelation. In such a case, it is possible to prevent the increase in viscosity and gelation by a method such as stopping the demethanol reaction during the reaction. For example, it is possible to adopt a method of refluxing the methanol flowing out to adjust the amount of methanol distilled from the reaction system, or cooling the reaction system to terminate the reaction when the viscosity is increased.

The silane-modified epoxy resin containing a methoxy group can be produced in the presence or absence of a solvent as described above. In the demethanol condensation reaction in the present invention, the reaction temperature is about 50 to 130 ° C, preferably 70 ° C.
It is ~ 110 ° C, and the total reaction time is about 1 to 15 hours. This reaction is preferably carried out under substantially anhydrous conditions in order to prevent the polycondensation reaction of the methoxysilane partial condensate (2) itself. As the reaction solvent, any conventionally known solvent may be used as long as it does not react with an epoxy group and has a boiling point of at least the reaction temperature for demethanol and dissolves the hydroxyl group-containing resin (1) and the methoxysilane partial condensate (2). Can be used. Such organic solvents include methyl ethyl ketone, methyl isobutyl ketone, toluene,
Xylene, tetrahydrofuran, dimethyldiglycol, dimethyltriglycol, dimethylformamide,
Examples thereof include dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and the like. Among these, organic solvents having a boiling point of less than 120 ° C. and easily dried, such as methyl ethyl ketone and toluene, are preferable for applications requiring processing in a semi-cured state.

In the demethanol condensation reaction described above, a conventionally known catalyst that does not open the epoxy ring can be used to accelerate the reaction. Examples of the catalyst include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium,
Cobalt, germanium, tin, lead, antimony, arsenic,
Metals such as cerium, boron, cadmium, manganese;
Examples thereof include oxides, organic acid salts, halides and methoxides of these metals. Among these, especially organic tin,
Organic acid tin is preferable, and specifically, dibutyltin dilaurate, tin octylate and the like are effective.

The methoxy group-containing silane-modified epoxy resin of the present invention has a methoxy group derived from the methoxysilane partial condensate (2) in its molecule. The content of the methoxy group is necessary for the methoxy group to undergo a sol-gel reaction or a demethanol condensation by a heat treatment or a reaction with moisture (humidity) to form a hybrid cured product bonded to each other. Therefore, the methoxy group-containing silane-modified epoxy resin usually retains 40 to 95 mol%, preferably 50 to 90 mol%, of the methoxy group of the methoxysilane partial condensate (2) which is a reaction raw material in an unreacted state. It's good to leave. Such a hybrid cured product has a gelled fine silica site (a higher-order network structure of siloxane bonds). The methoxy group-containing silane-modified epoxy resin may contain the methoxysilane partial condensate (2) in an unreacted state. The unreacted methoxysilane partial condensate (2) becomes silica by hydrolysis and polycondensation during sol-gel curing, and bonds with the methoxy group-containing silane-modified epoxy resin.

In the present invention, the methoxy group-containing silane-modified epoxy resin is used as an electrical insulating resin composition in which a curing agent for a latent epoxy resin is combined. In the electrical insulation resin composition of the present invention, in addition to the methoxy group-containing silane-modified epoxy resin, various epoxy resins,
A curing agent for epoxy resin, a curing accelerator, an epoxy polymerization catalyst, etc. can be used in combination. In applying the resin composition for electrical insulation of the present invention to various applications, various epoxy resins and rubber components are used together in order to adjust the flexibility and mechanical strength of the epoxy resin-silica hybrid cured product and semi-cured product. You can also do it. As the epoxy resin which can be used in combination, the novolac type epoxy resin described as a constituent of the present invention; a bisphenol type epoxy resin obtained by reacting a bisphenol with epichlorohydrin;
Glycidyl ester type epoxy resin obtained by reacting polybasic acids such as phthalic acid and dimer acid and epichlorohydrin; glycidyl amine type obtained by reacting polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin Epoxy resin: linear aliphatic epoxy resin and alicyclic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid. Examples of the rubber component include polyisobutene, polybutylene, polybutadiene, butadiene-acrylonitrile rubber, chloroprene rubber, and silicone rubber.

As the latent epoxy resin curing agent, a conventionally known latent curing agent which is usually used as an epoxy resin curing agent can be used. Examples of the latent epoxy resin curing agent include a novolac resin-based curing agent, an imidazole-based curing agent, and an acid anhydride-based curing agent. Specifically, examples of novolac resin-based ones include phenol novolac resin, cresol novolac resin, bisphenol novolac resin, poly-p-vinylphenol, and the like, and imidazole-based curing agents include 2-methylimidazole and 2-ethyl. Hexyl imidazole, 2-undecyl imidazole, 2-phenyl imidazole, 1
-Cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazolium isocyanurate, and the like. Examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3, 6-endomethylenetetrahydrophthalic anhydride, hexachloroendmethylenetetrahydrophthalic anhydride, methyl-3,6-endmethylenetetrahydrophthalic anhydride, and other curing agents include dicyandiamide and ketimine compounds. Of these, novolac resin-based curing agents and imidazole-based curing agents are preferable in consideration of the storage stability of the electrical insulating resin composition.

The latent epoxy resin curing agent is usually used in an amount of 0.2 to 0.2% of the functional group having active hydrogen in the curing agent with respect to 1 equivalent of the epoxy group in the electrically insulating resin composition.
It is prepared by mixing in a ratio such that the amount becomes about 1.5 equivalents.

Further, the resin composition for electrical insulation may contain a curing accelerator for promoting the curing reaction between the epoxy resin and the curing agent. For example, tertiary amines such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2 −
Methylimidazole, 2-phenylimidazole, 2-
Imidazoles such as phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; tetraphenylphosphonium.
Examples thereof include tetraphenyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, and tetraphenyl boron salts such as N-methylmorpholine tetraphenyl borate. The curing accelerator is preferably used in a proportion of 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.

If necessary, the resin composition for electrical insulation may contain an organic solvent, a filler, a release agent, a surface treatment agent, a flame retardant, a viscosity modifier, and a plasticizer as long as the effects of the present invention are not impaired. Agent, antibacterial agent, antifungal agent, leveling agent, defoaming agent, coloring agent,
You may mix | blend a stabilizer, a coupling agent, etc.

The insulating material for electronic materials of the present invention is obtained from the electrical insulating resin composition as described above. That is, in order to directly obtain a hybrid cured product as an insulating material for electronic materials from the resin composition for electrical insulation, the composition is cured at room temperature to 250 ° C. When passing through a semi-cured product, the composition is volatilized with a solvent at 50 to 120 ° C. to be sol-gel cured, and then completely cured at 150 to 250 ° C. The curing temperature is appropriately determined depending on the type of curing agent for epoxy resin. When a phenol resin-based curing agent or an acid anhydride-based curing agent is used as the curing agent, 0.1% or more of a sol-gel curing catalyst is used in combination with the curing agent to perform processing such as coating or impregnation. After application, it is preferably cured at 150 to 250 ° C. Because methanol is generated in the sol-gel curing reaction at the methoxysilyl site, curing proceeds by ring-opening / crosslinking reaction of the epoxy group in the methoxy group-containing silane-modified epoxy resin and the epoxy resin curing agent. Later, when the alcohol is generated, foaming or cracking occurs. Therefore, it is necessary to adjust the sol-gel curing reaction rate by appropriately selecting the catalyst.

The method for obtaining various insulating materials from the electrical insulating resin composition of the present invention will be described below. To obtain a final cured product from the electrical insulating resin composition through a semi-cured sheet or an intermediate material for molding, the type of epoxy curing agent in the resin composition, and further the semi-curing condition, etc. Careful selection is important. As the epoxy curing agent, a phenol resin-based curing agent, an acid anhydride-based curing agent, a latent curing agent such as imidazole is used, and a tin-based sol-gel curing catalyst is added to the solid residue of the methoxy group-containing silane-modified epoxy resin. It is preferable to add about 0.05 to 5%. In order to produce a semi-cured film or an intermediate material for molding using the above-mentioned electrical insulating resin composition, preferably 5
When the solvent is contained, the solvent is evaporated by heating at 0 to 150 ° C., so that the methoxysilyl moiety of the methoxy group-containing silane-modified epoxy resin contained in the resin composition is sol-gel cured. It is necessary to proceed 70% or more, preferably 90% or more to form a siloxane bond. Because methanol is generated in the sol-gel curing reaction at the methoxysilyl site, if the progress of sol-gel curing during preparation of semi-cured product is small, curing shrinkage, cracks, and foaming may occur in the subsequent complete curing reaction. Because there is a nature. The semi-cured film and intermediate molding material thus obtained are softened by heating at 60 to 150 ° C., and operations such as molding, molding, and component mounting become possible. After that, the processed semi-cured film and the molding intermediate material are heated at 150 to 250 ° C., whereby the epoxy group and the epoxy curing agent are cured, and the intended insulating material for electronic material is obtained.

To obtain a prepreg for a printed circuit board from the resin composition for electric insulation of the present invention, for example, JP-A-9-14 is used.
As described in Japanese Patent No. 3286, a prepreg sheet can be obtained by varnishing a resin composition for electrical insulation with a solvent, impregnating the varnish into a reinforcing base material, and heating. At this time, the composition and production conditions of the epoxy resin composition may be determined in the same manner as the semi-cured film and the molding intermediate material. Examples of the solvent include polar solvents having a boiling point of 160 ° C. or less such as methyl ethyl ketone, acetone, ethyl cellosolve, dimethylformamide, methanol, ethanol and isopropyl alcohol, which are preferable because they do not remain in the prepreg. The heating temperature is determined in consideration of the type of solvent used, and is preferably 50 to 150 ° C. The type of the reinforcing base material is not particularly limited, and various examples such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth can be exemplified. The ratio of the resin component to the reinforcing base material is not particularly limited, but it is usually preferable to adjust the resin component in the prepreg to be 20 to 80% by weight.

In order to obtain a copper clad laminate from the resin composition for electrical insulation of the present invention, the above prepreg is used as described in, for example, JP-A-5-86215 and JP-A-6-100763. About 3 to 8 sheets are piled up, copper foils are further piled up and down, and 170 to 170 MPa under a pressure of 1 to 10 MPa.
It is thermocompression bonded at 250 ° C. for 10 minutes to 3 hours.

To obtain a printed wiring board or an interposer from the prepreg and the copper-clad laminate, the copper-clad laminate is resist-etched to form a circuit, and then the prepreg and the copper foil are laminated to form the copper-clad laminate. It suffices to perform thermocompression bonding under the same conditions as in the production of the plate to form a multilayer.

The method for obtaining the interlayer insulating material for the build-up substrate from the resin composition for electrical insulation of the present invention is not particularly limited, but for example, Japanese Patent Publication No. 4-6116, JP-A-7-.
304931, JP-A-8-64960, JP-A-9-
Various methods described in JP-A No. 71762, JP-A No. 9-298369, etc. can be adopted. More specifically, the epoxy resin composition containing rubber, a filler and the like,
The wiring substrate on which the circuit is formed is applied by a known method such as a spray coating method or a curtain coating method, and then cured according to the method for directly obtaining the hybrid body as described above. After that, a predetermined through-hole portion or the like is bored as needed, and then treated with a roughening agent, and the surface thereof is washed with hot water to form irregularities, and a metal such as copper is plated. The plating method is preferably electroless plating or electrolytic plating, and the roughening agent used is at least one selected from an oxidizing agent, an alkali and an organic solvent. Such an operation can be sequentially repeated as desired to build up the resin insulating layer and the conductor layer having a predetermined circuit pattern alternately. However, the through holes are formed after the outermost resin insulating layer is formed. Further, a semi-cured film or a semi-cured product obtained from the resin composition for electric insulation of the present invention can be used to produce an interlayer insulating material for build-up substrates. For example, on a wiring board on which a circuit is formed, the resin composition for electrical insulation is semi-cured under the same conditions as described above, and then, if necessary, a predetermined through-hole portion or the like is punched, and then roughened. A roughening treatment is carried out with an agent to form a good roughened surface having unevenness on the surface of the resin insulating layer and the through holes. Then, the surface of the resin insulating layer thus roughened is subjected to metal plating in the same manner as described above, and then the resin composition for electrical insulation is coated again.
Heat treatment is performed at 0 to 250 ° C. Such an operation may be sequentially repeated as desired to alternately build up the resin insulating layer and the conductor layer having a predetermined circuit pattern to form the resin layer. In addition, a resin-coated copper foil obtained by semi-curing the epoxy resin composition on a copper foil is heat-pressed at 170 to 250 ° C. onto a wiring board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to manufacture the build-up substrate by omitting the step.

Various types of sealants for electronic parts, such as mold type sealants, tape type sealants, potting type liquid sealants, etc., are known. When preparing, for example, a mold-type sealant from the resin composition for electrical insulation of the present invention, the method is not particularly limited, but a method using a powder of a cured product obtained by sol-gel curing the resin composition is preferable. . For example, a silane-modified epoxy resin containing a methoxy group and a tin-based sol-gel curing catalyst in an amount of 0.05 to 5% per resin content.
And, if necessary, an inorganic filler such as silica is blended to obtain the resin composition for electrical insulation of the present invention (without blending an epoxy resin curing agent), and then 10 on a Teflon (registered trademark) sheet.
There is a method of curing at 0 to 200 ° C. and further pulverizing the sol-gel cured product into a powder. In addition, the resin composition is diluted with a solvent to obtain 500 mPa · s at 25 ° C.
It is also possible to obtain a powder of a sol-gel cured product by adjusting the viscosity to the following and spraying it to react with moisture in the air. The solvent is the same as that described above, and a solvent having a boiling point of 100 ° C. or lower is particularly preferable. In the powder of the sol-gel cured product thus obtained,
A novolac phenol resin as an epoxy resin curing agent, an epoxy resin curing catalyst, and an inorganic filler are usually used.
The composition for a sealant is obtained by kneading at a temperature of 0 to 170 ° C. for 30 to 300 seconds. The semiconductor or electronic component is sealed by encapsulating the composition for a sealant in a mold and usually transfer molding at 170 to 250 ° C. and 5 to 20 MPa. Low water absorption is the most important performance because the use of a sealant is intended to prolong the life of electronic parts and semiconductors.
In the production of the methoxy group-containing silane-modified epoxy resin of the present patent, it is preferable to use a methyltrimethoxysilane partial condensate as the methoxysilane partial condensate (3), since the cured product shows a low water absorption.

When it is used as a tape-shaped sealant, a semi-cured sheet is prepared according to the above procedure using the resin composition for electrical insulation of the present invention containing an inorganic filler such as silica if necessary. , A sealant tape. This sealant tape is placed on a semiconductor chip, heated to 100 to 150 ° C. to be softened and molded, and then completely cured at 170 to 250 ° C.

Further, when it is used as a potting type liquid sealant, the resin composition for electrical insulation of the present invention containing an inorganic filler such as silica, if necessary, is applied on a semiconductor chip or an electronic component and directly applied. It may be cured.

The method of using the resin composition for electrical insulation of the present invention as an underfill resin is not particularly limited, but for example, JP-A-9-266221 and "Plastics in the field of electronics" (published by the Industrial Research Board,
The method as described in 1999, pp. 27-34) can be adopted. More specifically, the resin composition for electrical insulation of the present invention is provided in the gap between the semiconductor element with electrodes and the printed wiring board with solder during flip-chip mounting by a capillary flow method using capillary action. A method of injecting and curing by the method of directly obtaining the hybrid body, and a semi-cured resin is previously formed on the substrate or the semiconductor element according to the above procedure, and then heated to bring the semiconductor element and the substrate into close contact with the semi-cured resin. Then, an underfill resin layer is formed by a compression flow method or the like for completely curing. In this case, it is preferable to use the electrical insulating resin composition of the present invention in the form of a liquid resin composition containing no solvent. Especially when the capillary flow method is used, it is necessary to have a low viscosity, and the viscosity is 5000 mPa · s.
The following viscosities are preferred. When the epoxy resin composition has a viscosity exceeding this range, it can be heated at room temperature to 100 ° C. or lower and then injected. The purpose of the underfill resin is to relieve the stress around the solder caused by the difference in the linear expansion coefficient between the semiconductor element and the substrate, and to have a low linear expansion coefficient close to that of the solder that is the interface joint. Insulating materials are said to be preferred. Therefore, if the epoxy resin composition has a low viscosity, the coefficient of linear expansion can be further reduced by adding a filler such as silica.

When the resin composition for electric insulation of the present invention is used as a thermosetting resist ink such as a solder resist, it can be prepared by the method described in, for example, JP-A-5-186567 and JP-A-8-307041. According to the above, after the composition for resist ink, by the screen printing method,
A resist ink cured product is obtained by a method of directly obtaining a hybrid cured product after coating on a printed board. Preferably, as the composition for the resist ink, a methoxy group-containing silane-modified epoxy resin and an epoxy resin curing agent, and optionally a vinyl-based resin having an ethylenically unsaturated double bond such as an acrylic ester or a methacrylic ester. Monomers, various pigments such as phthalocyanine blue, fillers such as silica and alumina, and leveling agents are added.

When the resin composition for electrical insulation of the present invention is used as an interlayer insulating material for semiconductors, it is disclosed in, for example, JP-A-6-
The method described in 85091 publication can be adopted. Specifically, it can be obtained by a method in which the resin composition is spin-coated on a semiconductor to directly obtain a hybrid cured product. When it is used as an interlayer insulating film, it is in direct contact with the semiconductor, so the coefficient of linear expansion of the insulating material should be low so as to approach the coefficient of linear expansion of the semiconductor so that cracks due to the difference in coefficient of linear expansion do not occur in high temperature environments. Is required. Moreover, in order to cope with the problem of signal delay due to miniaturization, multi-layering, and high density of semiconductors, a technology for reducing the capacity of insulating materials is required,
This problem can be solved by reducing the dielectric constant of the insulating material. To meet these requirements, in the resin composition for electrical insulation of the present invention, when the novolac epoxy resin is modified to obtain the hydroxyl group-containing epoxy resin (1),
The molar ratio of active hydrogen for ring-opening modification to 1 mol of the novolak epoxy resin molecule is 0.8 to 3 mol, that is, the average of the epoxy groups to be ring-opened modified among the epoxy groups of the novolak epoxy resin. The number is 0.8
It is preferable to reduce the residual amount of the unmodified novolac type epoxy resin to 3 or less. Further, tetramethoxysilane partial condensate is used as methoxysilane partial condensate (2), and further, silica formed by sol-gel curing of methoxysilane partial condensate (2) in the solid residue of the epoxy resin composition. The content is preferably 10% by weight or more.

When the electrically insulating resin composition of the present invention is used as a conductive paste, it is disclosed in, for example, JP-A-9-355.
As described in Japanese Patent Laid-Open No. 30, a conductive powder such as a spherical or flake shaped silver or nickel must be mixed with the insulating material. The content of the conductive powder is preferably 50 to 80% by weight from the viewpoint of conductivity and economy with respect to the conductive paste. If the content is less than 50% by weight, the resistance tends to increase, and if it exceeds 80% by weight, there are disadvantages such as a decrease in adhesiveness and an increase in product price. The conductive paste is required to have a small change in resistivity after being exposed to severe conditions such as high temperature and high humidity. From the viewpoint of reducing water absorption, use of a partial condensate of methyltrimethoxysilane as the methoxysilane partial condensate (2) which is a component of the methoxy group-containing silane-modified epoxy resin in the resin composition for electrical insulation of the present invention. Further, it is particularly preferable to use a novolac phenol resin as an epoxy resin curing agent.

In the case of producing a container (molded product) for housing an electronic component such as an IC tray from the resin composition for electric insulation of the present invention, the semi-cured sheet or the molding intermediate material obtained by the above method. After obtaining these, they are remelted at 60 to 150 ° C and put in a mold, and 150 to 250 ° C, 1 to 30M.
It is obtained by molding under the condition of Pa.

[0057]

According to the present invention, heat resistance, low linear expansion,
It is possible to obtain an insulating material for electronic materials, which has excellent insulating properties and adhesion, and which is free from voids, cracks and the like.

[0058]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In each example,% is based on weight unless otherwise specified.

Production Example 1 (Production of methoxy group-containing silane-modified epoxy resin) A novolac type epoxy resin (Toto Kasei Co., Ltd.) was added to a reactor equipped with a stirrer, a water divider, a thermometer, and a nitrogen inlet.
Manufactured, product name "Epototo YDPN-638P", epoxy equivalent 177 g / eq, number average phenol nuclide number 5.
2) 150g of 400g and 21.2g of bisphenol A
It is a hydroxyl group-containing epoxy resin (hereinafter referred to as a ring-opening modified resin A-1) by dissolving at 0 ° C. and adding 0.1 g of N, N-dimethylbenzylamine as a catalyst for ring-opening modification and reacting for 2 hours. A bisphenol-modified novolac type epoxy resin was obtained. The number of moles of active hydrogen for ring-opening modification / the number of moles of a novolac type epoxy resin was 0.4. Further poly (methyltrimethoxysilane)
(Tama Chemical Co., Ltd., trade name "MTMS-A", average number of Si per molecule 3.5) 215.2 g, methyl ethyl ketone 350 g, glycidol 30.99 g and dibutyltin dilaurate 1 g as a catalyst were added, and nitrogen was added. A methoxy group-containing silane-modified epoxy resin (hereinafter, referred to as resin (A-1)) was obtained by performing a demethanol reaction using a water divider at 100 ° C. for 5 hours under an air stream.
In addition, at the time of charging, the hydroxyl group equivalent of the hydroxyl group-containing epoxy resin (1) / the methoxy group equivalent of the methoxysilane partial condensate (2) = 0.056, the weight of glycidol / the weight of the ring-opening modified resin = 0.17. there were. The epoxy equivalent of the resin (A-1) was 324 g / eq.

Production Example 2 A novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name "Epototo YDPN-" was added to the same reactor as in Production Example 1.
638P ", epoxy equivalent 177 g / eq number average phenol nucleus number 5.2) 500 g and bisphenol A3
Dissolve 3.14 g at 150 ° C., add 0.1 g of N, N-dimethylbenzylamine as a catalyst for ring-opening modification,
By reacting for 2 hours, a bisphenol-modified novolac type epoxy resin which is a hydroxyl group-containing epoxy resin (hereinafter referred to as ring-opening modified resin A-2) was obtained. The number of moles of active hydrogen for ring-opening modification / the number of moles of a novolac type epoxy resin was 0.5. Further, here, poly (tetramethoxysilane) (manufactured by Tama Chemical Co., Ltd., trade name "MS-5"
1 ”, average number of Si per molecule 4) 413.4
g, methyl ethyl ketone 350 g, glycidol 64.
53 g and 0.5 g of dibutyltin dilaurate as a catalyst were added, and a methoxy group-containing silane-modified epoxy resin (hereinafter, resin ( A-2)) was obtained. The ring-opening modified resin (A-
Hydroxyl equivalent of 2) / Methoxysilane partial condensate (2)
Of the methoxy group of 0.033, the weight of glycidol / the weight of the ring-opening modified resin (A-2) = 0.23.
The epoxy equivalent of the resin (A-2) was 329 g / eq.

Production Example 3 A novolac type epoxy resin (Toto Kasei Co., Ltd.) was added to a reactor equipped with a stirrer, a reflux pipe, a thermometer and a nitrogen blowing port.
Made by trade name "Epototo YDPN-638P", epoxy equivalent 177 g / eq number average phenol nucleus number 5.2)
1200 g and bisphenol A 159.07 g in 1
It was dissolved at 50 ° C., 0.5 g of N, N-dimethylbenzylamine was added as a catalyst for ring-opening modification, and a reaction was carried out for 2 hours to obtain a hydroxyl group-containing epoxy resin (hereinafter referred to as ring-opening modified resin A-3). A bisphenol-modified novolak type epoxy resin was obtained. The number of moles of active hydrogen for ring-opening modification / the number of moles of a novolac type epoxy resin was 1.0. Furthermore, here poly (tetramethoxysilane)
(Tama Chemical Co., Ltd., trade name "MS-51", average number of Si per molecule is 4) 1228.3 g, methyl ethyl ketone 2100 g, glycidol 191.8 g and dibutyltin dilaurate 1.5 g as a catalyst are added and refluxed. A methoxy group-containing silane-modified epoxy resin (hereinafter referred to as resin (A-3)) was obtained by performing a methanol removal reaction at 80 ° C. for 7 hours using a water divider. The equivalent of hydroxyl group of the ring-opening modified resin (A-3) at the time of charging / equivalent of methoxy group of the methoxysilane partial condensate (2) = 0.070, weight of glycidol / ring-opening modified resin (A)
The weight of -3) was 0.14. The epoxy equivalent of the resin (A-3) was 609 g / eq.

Comparative Production Example 1 Novolak type epoxy resin (manufactured by Tohto Kasei Co., Ltd., trade name "Epototo YDPN-638P", epoxy equivalent 17)
7 g / eq number average phenol nucleus number 5.2) was used as it was. Hereinafter, the resin composition will be referred to as resin (a-1).

Comparative Production Example 2 The ring-opening modified resin A obtained in Production Example 1 was used as it was. Hereinafter, the resin composition will be referred to as resin (a-2).

Comparative Production Example 3 200 g of the ring-opening modified resin A obtained in Production Example 1, poly (methyltrimethoxysilane) (manufactured by Tama Chemical Co., Ltd., trade name “MTMS-A”, average of Si per molecule) Number 3.
5) An epoxy resin composition was obtained by mixing 102.2 g and 200 g of methyl ethyl ketone. Hereinafter, the resin composition is referred to as a resin (a-3).

Comparative Production Example 4 A bisphenol A type epoxy resin (manufactured by Japan Epoxy Resins Co., Ltd., trade name "Epicoat 1001", epoxy equivalent 472 g / e, was placed in the same reactor as in Production Example 1.
q) 336.0 g and methyl ethyl ketone 268.8
g was added and melted at 70 ° C. Further, poly (tetramethoxysilane) (manufactured by Tama Chemical Co., Ltd., trade name "MS-5"
1 ”, average number of Si per molecule 4) 360.4 g
Then, 0.3 g of dibutyltin dilaurate as a catalyst was added, and the mixture was refluxed at 80 ° C. for 6 hours, cooled to 50 ° C., added with 33.6 g of methanol, and added with a methoxy group-containing silane-modified epoxy resin (hereinafter referred to as resin (a -4)) was obtained. Equivalent hydroxyl group of bisphenol epoxy resin /
Equivalent amount of methoxy group of methoxysilane partial condensate (2) =
0.1 and the epoxy equivalent were 1400 g / eq.

Examples 1 and 2 and Comparative Examples 1 to 4 (Preparation of Epoxy Resin Composition for Electrical Insulation and Preparation of Insulating Material for Electronic Material in Semi-Cured State) Production Examples 1 and 2 and Comparative Production Examples 1 to 4 Novolak type phenolic resin (Arakawa Chemical Industry Co., Ltd.)
(Trade name "Tamanor 759" manufactured by Mitsui Chemicals, Inc.) was diluted to 50% with methyl ethyl ketone at a ratio of epoxy equivalent / phenol equivalent of 1/1, and tin octylate was added at 2% per solid content to obtain an epoxy for electrical insulation. It was a resin composition.

(Evaluation of Insulating Material for Electronic Material in Semi-Cured State) The epoxy resin compositions for electrical insulation obtained in Examples 1 and 2 and Comparative Examples 1 to 4 were coated with a fluororesin container (length × width). × depth = 10 cm × 10 cm × 1.5
cm) and heated at 80 ° C. for 1 hour to volatilize the solvent and cure the sol-gel to obtain a semi-cured insulating material for electronic materials. The state (appearance, shrinkage, foaming, flexibility) of the obtained semi-cured product was evaluated according to the following criteria. The results are shown in Table 1.

(Evaluation of appearance) ○: Transparent. Δ: There is cloudiness. X: Whitened.

(Evaluation of shrinkage) ◯: The cured product has no cracks or warpage. B: Warp exists in the cured product. X: The cured product has cracks.

(Evaluation of foaming) ◯: There are no bubbles in the cured product. Δ: There are less than 5 bubbles in the cured product. X: Five or more bubbles are present in the cured product.

(Evaluation of flexibility) ◯: Flexible and rich in moldability. X: Breaks when deformed.

[0072]

[Table 1]

As is clear from Table 1, each of Examples 1 and 2
In each of Comparative Examples 1 and 2, a transparent semi-cured product was obtained. However, the semi-cured product obtained in Comparative Example 3 was whitened due to phase separation between the epoxy resin and silica, and was extremely brittle. The semi-cured product obtained in Comparative Example 4 was transparent, but cracked when deformed. Each of the semi-cured products of the examples is transparent, has no warpage, has little shrinkage, and is highly flexible, and is useful as a semi-cured product for electrical insulation such as a prepreg for a printed circuit board.

Examples 3 and 4 and Comparative Examples 5 to 8 (Preparation and Evaluation of Insulating Material for Electronic Material) The semi-cured product obtained above was further cured by heating at 200 ° C. for 1 hour to epoxy-cure it and completely cure it. I got a thing. The state (appearance, shrinkage, foaming, weight change from semi-cured product) of the obtained completely cured product was evaluated according to the following criteria. The results are shown in Table 2.

(Evaluation of appearance) ○: Transparent. Δ: There is cloudiness. X: Whitened.

(Evaluation of shrinkage) ◯: The cured product has no cracks or warpage. B: Warp exists in the cured product. X: The cured product has cracks.

(Evaluation of foaming) ◯: There are no bubbles in the cured product. Δ: There are less than 5 bubbles in the cured product. X: Five or more bubbles are present in the cured product.

[0078]

[Table 2]

In Examples 3 and 4 and Comparative Examples 5, 6 and 8,
In each case, a transparent completely cured product was obtained. The completely cured product obtained in Comparative Example 7 had unevenness, foaming, and cracks due to phase separation of the epoxy resin and silica, and was extremely brittle.

(Heat Resistance) Examples 3 and 4 and Comparative Examples 6 and 8
The cured film obtained in Step 5 was cut into 5 mm × 20 mm, and a viscoelasticity measuring instrument (Rheology Co., Ltd., trade name “DVE-V” was used.
4 ”, measurement conditions: amplitude 0.5 μm, frequency 10 Hz, slope 3 ° C./min) to measure the dynamic storage elastic modulus,
The heat resistance was evaluated. The measurement results are shown in FIG.

As is clear from FIG. 1, in Examples 3 and 4 and Comparative Example 8, the glass transition point of the cured film is higher than that of Comparative Example 6, and the elastic modulus is less decreased even at high temperatures. It has excellent heat resistance.

(Linear Expansion) Examples 3 and 4 and Comparative Example 6
Using the cured film obtained in step 1, a thermal stress strain measuring device (manufactured by Seiko Electronics Co., Ltd., trade name TMA120
In C), the coefficient of linear expansion of 40 to 100 ° C. was measured. The results are shown in Table 3.

[0083]

[Table 3]

As is clear from Table 3, Examples 3 and 4 are lower in the coefficient of linear expansion than Comparative Example 6 and can be highly reliable underfill resin cured material layers.

(Electrical Properties) Using the cured films obtained in Examples 3 and 4 and Comparative Examples 5, 6 and 8, frequency 1 was used.
Dielectric constant and dielectric loss were measured at MHz. The results are shown in Table 4.

[0086]

[Table 4]

As is clear from Table 4, it was confirmed that Examples 3 and 4 were superior to Comparative Examples 5, 6 and 8 in insulating property and there was no difference in dielectric loss. Each of the examples has high heat resistance, a low linear expansion coefficient, and a low dielectric constant. Therefore, a prepreg for a printed circuit board, a copper clad laminate for a printed circuit board, a printed wiring board, an interposer, an interlayer insulating material for a buildup printed circuit board, Semiconductor interlayer insulating film,
It is useful as a sealant for electronic parts, a sealant for semiconductor chips, a cured product of underfill resin, a cured product of resist ink, a cured product of conductive paste, a molded product for housing electronic components, and an anisotropic conductive film.

Example 5 (Preparation of prepreg and epoxy resin composition for copper-clad laminate) The resin obtained in Production Example 1 was diluted with methyl ethyl ketone, and the same 50% phenol resin methyl ethyl ketone solution as in Example 1 was added to the phenol resin. Hydroxyl equivalents / epoxy group equivalents in resin solution = 0.8, tin octylate was added at 2% per resin, methyl imidazole at 0.1% and methyl ethyl ketone to give a cured resin content of 6
A 0% epoxy resin composition was prepared. A 0.18 mm-thick glass woven fabric was impregnated with the epoxy resin composition so that the resin content was about 40%, followed by drying at 130 ° C. for 15 minutes and sol-gel curing to prepare a prepreg. Three pieces of this prepreg and 18 μm thick copper foil on both sides
A double-sided copper-clad laminate was produced by heating and pressurizing at 10 ° C. and 10 MPa for 120 minutes.

Example 6 A prepreg and a double-sided copper-clad laminate were obtained in the same manner as in Example 5, except that the resin obtained in Production Example 2 was used.

Comparative Example 9 A novolac type epoxy resin (manufactured by Tohto Kasei Co., Ltd., trade name “Epototo YDPN-638P”) dissolved in methyl ethyl ketone to 70% was used instead of the alkoxy group-containing silane-modified epoxy resin. The same operation as in Example 5 was carried out except that the double-sided copper-clad laminate was prepared.

(Heat resistance) Glass transition temperature: A copper-clad laminate was cut into 6 mm × 25 mm, and a viscoelasticity measuring instrument (Rheology Co., trade name “DVE-V4”, measuring condition amplitude 1 μm)
m, frequency 10 Hz, slope 3 ° C./min), the glass transition point was measured to evaluate heat resistance.

(Peeling strength of copper foil) JIS C-6481
It was measured according to.

[0093]

[Table 5]

As is clear from Table 5, the copper-clad laminate of the present invention is excellent in heat resistance and adhesion, and is suitable for the production of not only ordinary printed wiring boards but also multilayer printed wiring boards. .

Example 7 (Production of coating agent for build-up substrate, double-sided printed circuit board, interlayer insulating film (coating) for build-up substrate, build-up substrate) 70% phenol was added to the resin obtained in Production Example 1. Novolak resin (trade name "Tamanor 759") carbitol acetate solution was mixed in such a manner that the hydroxyl group equivalent of phenol novolac resin / the epoxy group equivalent of the resin solution = 0.8, and 100 g of 2-methyl Imidazole, barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., trade name "BA
10 g of RIFINE BF-10 ") and 1 g of phthalocyanine green were mixed and dispersed, and then kneaded with a three-roll mill. Further, it was diluted with carbitol acetate to the extent that screen printing was possible to obtain a coating agent for build-up substrate. The surface of the copper foil of the double-sided copper-clad laminate of Example 5 was mechanically surface-treated with a general brush and chemically surface-treated by pickling. Next, after forming a circuit by etching resist on the surface of the copper foil by screen printing, the surface was etched to form a conductor pattern to obtain a double-sided printed wiring board. This double-sided printed wiring board is used as a core substrate, and both surfaces are subjected to similar mechanical surface conditioning and chemical surface conditioning, and then the entire surface of both sides is covered with the above-mentioned build-up board so as to cover the conductor pattern. Apply the coating agent by screen printing so that the film thickness after curing will be 30 μm, and apply at 120 ° C. for 15
Min, and cured at 170 ° C. for 1 hour to produce a printed wiring board having an interlayer insulating film. Then, the printed wiring board is treated with an alkaline potassium permanganate solution at 60-80.
The surface of the electrically insulating coating film was roughened at 0 ° C., electroless copper plating was performed, and thin copper plating with a thickness of 0.3 μm was applied. Then, the electroless copper-plated printed wiring board was placed in a plating tank containing a copper electrolytic plating bath, and electrolytic copper plating with a thickness of 18 μm was performed to produce a target build-up substrate.

Example 8 (Preparation of coating agent for build-up board, double-sided printed board, interlayer insulating film for build-up board (by coating method), build-up board) Resin obtained in Production Example 2 and Example 6 A build-up substrate was prepared in the same manner as in Example 7, except that the double-sided copper-clad laminate was used.

Example 9 (Preparation of Interlayer Insulating Film for Buildup Substrate (by Method Using Semi-Cured Film), Buildup Substrate) Double-sided so as to cover the conductor pattern of the double-sided printed wiring board washed as in Example 7. Was coated with the epoxy resin composition used in Example 5 by screen printing so that the film thickness after curing was 40 μm, and the temperature was 100 ° C. for 10 minutes.
A printed wiring board was prepared which was dried and cured and laid with a semi-cured resin. A copper foil with a thickness of 18 μm is further placed on the semi-cured resin of this printed wiring board, and 170 ° C., 6 MPa
Was heated and pressed for 120 minutes to prepare a build-up substrate having an interlayer insulating film.

Example 10 (Preparation of interlayer insulating film for build-up substrate (by using resin-coated copper foil), build-up substrate) After curing the epoxy resin composition of Example 5 on a copper foil having a thickness of 18 μm Was coated with a roller coater to a thickness of 40 μm, dried, and dried and cured at 100 ° C. for 15 minutes to prepare a copper foil with a semi-cured resin. Next, the same copper foil with resin as described above was placed on the entire both surfaces so as to cover the conductor pattern of the same double-sided printed wiring board as in Example 7, so that the resin surface was in contact with the circuit surface. 6MP
It was heated and pressed for 120 minutes at a to produce a build-up substrate having an interlayer insulating film.

Comparative Example 10 A build-up substrate was prepared in the same manner as in Example 7, except that the epoxy resin composition used in Comparative Example 9 was used and the semi-curing condition was 150 ° C. for 15 minutes.

The performance of the build-up substrates obtained in Examples 7 to 10 and Comparative Example 10 was evaluated by the following method. The results are shown in Table 6.

(Hygroscopic solder heat resistance test) Moisture absorption conditions: Pressure cooker treatment, 125 ° C., 23
0 kPa, 30 minutes test condition: n = 5, all test pieces at 280 ° C., 120
When there was no swelling in a second, the result was ◯, and when swelling occurred, the result was x.

(Peeling Strength) The peeling strength between copper and the insulating substrate was measured according to JIS C-6481.

[0103]

[Table 6]

As is clear from Table 6, the interlayer insulating film for build-up substrate of the present invention is excellent in solder heat resistance and adhesion.

Example 11 (Preparation of Resin Composition for Semiconductor Interlayer Insulation and Semiconductor Interlayer Insulation Film) The resin obtained in Production Example 3 was diluted to 30% with dimethyldiethylene glycol to prepare 2-methyl-4-ethylimidazole, amino group. Equivalent weight / equivalent weight of epoxy group in resin solution =
The mixture was uniformly mixed so as to have a ratio of 0.2, and allowed to stand for 10 minutes to obtain a resin composition for semiconductor interlayer insulation. This resin composition was applied by spin coating, heated at 100 ° C. for 30 minutes, and then heat-cured at 150 ° C. for 1 hour to form an insulating film of 10 μm on a silicon substrate.

Comparative Example 11 A novolac type epoxy resin (trade name "Epototo YDPN-638P" manufactured by Tohto Kasei Co., Ltd.) was used, except that
The same operation as in Example 11 was performed to obtain a resin composition for semiconductor interlayer insulation and a semiconductor interlayer insulation film.

The performances of the resin compositions for semiconductor interlayer insulation and the semiconductor interlayer insulation films obtained in Example 11 and Comparative Example 11 were evaluated as follows. The results are shown in Table 7.

(Soldering Heat Resistance Test) Strips were cut out together with a silicon substrate and immersed in a solder bath at 280 ° C. for 30 seconds, and then the presence or absence of peeling of the surface was observed. ◯: There is no peeling ×: There is peeling

(Linear Expansion) Each of the resin compositions obtained in Example 11 and Comparative Example 11 was spin-coated on aluminum foil, heated at 150 ° C. for 30 minutes, and then heat-cured at 200 ° C. for 1 hour. Was repeated about 10 times and peeled from the aluminum foil to obtain a test piece having a thickness of about 400 μm. The coefficient of linear expansion of the thus obtained cured product (5 mm square) at 40 to 100 ° C. was measured by a thermal stress strain measuring device (Seiko Denshi Kogyo KK, trade name TMA120C).

(Electrical Properties) Each resin composition obtained in Example 11 and Comparative Example 11 was coated with a fluororesin-coated container (length × width × depth = 10 cm × 10 cm × 1.5 c).
m), heated at 150 ° C. for 30 minutes, and further heat-cured at 200 ° C. for 1 hour to obtain a test piece. Using the cured film thus obtained, the dielectric constant and the dielectric loss were measured at a frequency of 1 MHz.

[0111]

[Table 7]

As is clear from Table 7, the resin composition for semiconductor interlayer insulation of the present invention has a low linear expansion coefficient and a low dielectric constant, and is therefore useful as a semiconductor interlayer insulation film.

Example 12 (Preparation of sol-gel cured product, resin composition for encapsulant and encapsulant) 100 g of the resin obtained in Production Example 1 was melted with orthocresol novolac epoxy resin (Nippon Kayaku Ltd., trade name "EOCN1020", epoxy equivalent 200g / e
40 g of q) and 2% of tin octylate per solid residue are added, stirred at 80 ° C. for 30 minutes, mixed, cast on a Teflon (registered trademark) sheet, and cured at 150 ° C. for 30 minutes. Thus, a sol-gel cured product having a thickness of 200 μm was obtained. This sol-gel cured product, using a crusher,
After crushing to particles of 50 μm or less, sol-gel cured product 100
To g, 24 g of phenol novolac resin (trade name "Tamanor 759"), 0.3 of 2-methylimidazole
g and 15 g of styrene were added, and the mixture was kneaded with a three-roll mill at 100 ° C. to obtain an epoxy resin resin composition for a sealant. This epoxy resin composition is cast, 180 ° C
Then, it was cured for 2 hours to prepare a cured product for a sealing agent having a thickness of 300 μm.

Comparative Example 12 Orthocresol novolac epoxy resin (trade name "E
OCN1020 ") and phenol novolac resin (trade name" Tamanor 759 ") 43.2 g were melt-mixed, and then 2-methylimidazole 0.3 g and styrene 15 g were further mixed, and the same operation as in Example 12 was performed. An epoxy resin composition for a sealant and a cured product for a sealant having a thickness of 300 μm were prepared.

The performance of the cured products for sealants obtained in Example 12 and Comparative Example 12 was evaluated by the following methods.
The results are shown in Table 8.

(Heat resistance) Glass transition temperature: A cured product for a sealant was cut into 6 mm × 25 mm, and a viscoelasticity measuring instrument (Rheology Co., trade name “DVE-V4”, measurement condition amplitude 1 μm)
m, frequency 10 Hz, slope 3 ° C./min), the glass transition point was measured to evaluate heat resistance.

The (water-absorbing) cured product was dried in water at 100 ° C. for 24 hours.
After boiling for a period of time, the increased weight was measured to determine the water absorption.

[0118]

[Table 8]

As is clear from the results in Table 8, the resin composition for encapsulant of the present invention has good heat resistance and water resistance, so that the semiconductor element encapsulated with the composition has a long life. it can.

Example 13 (Preparation of Underfill Resin Composition and Underfill Resin Cured Product) A 370 μm thick, 1 cm square silicon chip was mounted on a single-sided printed wiring board by a Philip chip (gap 50 μm). Next, 4-methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name "Rikacid MH-700") was added to the resin obtained in Production Example 1 in the equivalent of carboxylic acid group / resin solution. Epoxy group equivalent = 0.8 and tin octylate were mixed so as to be 2% based on the solid residue to obtain a resin composition for underfill. Furthermore, this underfill resin composition was injected between the silicon chip and the printed circuit board by a capillary flow method, and the mixture was kept at 100 ° C. for 2 hours for 1 hour.
It was cured at 70 ° C. for 4 hours to prepare a cured underfill resin layer.

Example 14 (Preparation of underfill resin, cured product of underfill resin-compression flow method) The resin obtained in Production Example 1 was mixed with 4-methylhexahydrophthalic anhydride and tin octylate in the same manner as in Example 16. To obtain a resin composition for underfill. Further, 1c of the resin composition for underfill having a thickness of 60 μm is formed on a single-sided printed wiring board for mounting a Philip chip.
After being applied to the m-square, dried at 100 ° C. for 10 minutes and cured, a semi-cured resin-coated glass substrate was produced. After placing this printed circuit board with semi-cured resin in an oven heated to 110 ° C. for 10 minutes, a 370 μm thick, 1 cm square silicon chip was placed on the semi-cured resin at the same temperature, and a load of 300 g was applied to bump the board. After making contact with the electrode of the chip, 180 ℃
Was completely cured for 1 hour to prepare a cured underfill resin layer.

Example 15 (Preparation of resin composition for solder resist and cured solder resist film) 10 g of silica was further added to the coating agent for build-up substrate (epoxy resin composition) of Example 7, and three rolls were used. And uniformly dispersed to prepare a solder resist ink. After diluting with carbitol acetate to a viscosity suitable for screen printing, the solder resist ink is printed on a single-sided printed circuit board to a thickness of 15 μm,
C. and heat cured for 30 minutes to obtain a solder resist cured film.

Example 16 A resin composition for solder resist and a cured solder resist film were obtained by the same procedure as in Example 15 except that the resin composition of Example 8 was used.

Comparative Example 13 The same procedure as in Example 15 was carried out except that the epoxy resin composition of Comparative Example 9 was used to obtain a solder resist resin composition and a solder resist cured film.

The cured films obtained in Examples 15 and 16 and Comparative Example 13 were evaluated for performance by the following method. The results are shown in Table 9.

(Solder Heat Resistance) The cured film formed on the test substrate and the cured film after the rosin-based flux was applied and flowed on the molten solder at 260 ° C. for 10 seconds three times were used as JI.
According to SK-5400, a cellophane tape peeling test for goggle was performed, and the adhesion was evaluated according to the following criteria. ⊚: 100/100, ∘: 99 to 95/100,
Δ: 94 to 70/100, ×: 69 to 0/100

[0127]

[Table 9]

As is clear from Table 9, the solder resist cured film of the present invention has excellent adhesion and solder heat resistance.

[Brief description of drawings]

FIG. 1 shows the evaluation results of heat resistance of the cured films obtained in Examples 3 and 4 and Comparative Examples 6 and 8.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 63:00 C08L 63:00 ZF term (reference) 4F072 AA04 AA07 AB09 AB28 AD35 AG03 AG19 AL13 4J036 AF06 AF08 AF09 AF19 BA04 CA07 CA08 CA13 CA18 CA19 CA22 CA25 CB04 CC02 CC03 CD16 DA10 DB15 DC28 DC31 DC41 FB07 HA12 HA13 JA08 5G305 AA06 AA14 AB01 AB24 AB34 AB36 BA09 CA17 CA55 CD01 CD04 CD06 CD09 CD12 CD13 CD17 CD20

Claims (18)

[Claims] 1. A methoxy compound obtained by subjecting a hydroxyl group-containing epoxy resin (1) obtained by ring-opening modification of a part of an epoxy group of a novolac type epoxy resin and a methoxysilane partial condensate (2) to a methanol-free condensation reaction. A resin composition for electrical insulation comprising a group-containing silane-modified novolac type epoxy resin. 2. A hydroxyl group-containing epoxy resin (1) obtained by ring-opening modification of a part of epoxy groups of a novolac type epoxy resin, a methoxysilane partial condensate (2), and one hydroxyl group in one molecule. A resin composition for electrical insulation comprising a methoxy group-containing silane-modified novolac type epoxy resin obtained by subjecting an epoxy compound (3) to a demethanol condensation reaction. 3. The electrical insulating resin composition according to claim 1, wherein the novolac type epoxy resin is a phenol novolac type epoxy resin. 4. The resin composition for electrical insulation according to claim 1, wherein the hydroxyl group-containing epoxy resin (1) is a novolac type epoxy resin modified by ring-opening with a phenol. 5. The resin composition for electrical insulation according to claim 4, wherein the phenols are bisphenols. 6. The hydroxyl group-containing epoxy resin (1) has 0.2 to 10% of the epoxy groups contained in the novolac type epoxy resin.
The resin composition for electrical insulation according to any one of claims 1 to 5, which is obtained by ring-opening modification of three pieces. 7. The resin composition for electrical insulation according to claim 1, wherein the methoxysilane partial condensate (2) is a tetramethoxysilane partial condensate and / or methyltrimethoxysilane partial condensate. object. 8. The (hydroxyl group equivalent of the hydroxyl group-containing epoxy resin (1)) / (methoxy group equivalent of the methoxysilane partial condensate (2)) (equivalent ratio) is 0.02 to 0.6. Item 7. A resin composition for electrical insulation according to any one of items 1 to 7. 9. The resin composition for electrical insulation according to claim 1, which contains a latent epoxy resin curing agent. 10. The electrical insulating resin composition according to claim 9, wherein the latent epoxy resin curing agent is at least one selected from the group consisting of novolac resin curing agents and imidazole curing agents. 11. An insulating material for electronic materials, which is obtained by curing the resin composition for electrical insulation according to any one of claims 1 to 10. 12. A method for producing an insulating material for electronic materials, comprising curing the resin composition for electrical insulation according to claim 1 at room temperature to 250 ° C. 13. A semi-cured product is obtained by sol-gel curing the resin composition for electrical insulation according to claim 1 at 50 to 120 ° C., and then the semi-cured product is molded and processed. ,
Then, a method for producing an insulating material for electronic materials, which is completely cured at 150 to 250 ° C. 14. A resin composition for electrical insulation according to claim 1, wherein the resin composition does not contain an epoxy resin curing agent and is sol-gel cured. Production method. 15. A method for producing a resin composition for electrical insulation, which comprises the insulating material for electronic materials according to claim 14 and an epoxy resin curing agent. 16. A method for producing an insulating material for electronic materials, which is obtained by further curing the resin composition for electrical insulation according to claim 15. 17. A resin composition for a prepreg for a printed circuit board, a resin composition for a copper-clad laminate for a printed circuit board, a coating agent for an interlayer insulating material of a buildup printed circuit board,
Semiconductor interlayer insulating film resin composition, electronic component sealant resin composition, semiconductor chip sealant resin composition, underfill resin cured product, resist ink, conductive paste, electronic component storage molding The resin composition for electrical insulation according to any one of claims 1 to 10, which is used for at least one application selected from the group consisting of a resin composition for materials and a composition for anisotropic conductive films. 18. A prepreg for a printed circuit board, a copper clad laminate for a printed circuit board, a printed wiring board, an interposer, an interlayer insulating material for build-up printed circuit boards, a semiconductor interlayer insulating film, a sealant for electronic parts, and a semiconductor chip. Use for at least one application selected from the group consisting of a sealant, a cured product of an underfill resin, a cured product of a resist ink, a cured product of a conductive paste, a molded product for housing electronic parts, and an anisotropic conductive film. An insulating material for electronic materials as described.