JPH11181060A - Resin composition and semiconductor encapsulant and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in curability, sufficiently curable even by molding in a short time, excellent in preservation stability at about normal temperatures, making the curability consistent with the shelf life and useful as electrical and electronic materials. SOLUTION: This resin composition consists essentially of (A) an epoxy resin, (B) a curing agent, (C) an onium salt free of a halide ion in a counter anion and (D) a tri-substituted boron in which the boron is not directly substituted with a halogen or a product obtained by previously reacting (A) the epoxy resin with (B) the curing agent, (C) the onium salt free of the halide ion in the counter anion and (D) the tri-substituted boron in which the boron is not directly substituted with the halogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having good curability and preservability and useful in the fields of electric and electronic materials, and a semiconductor sealing material and a laminate using the same.

[0002]

2. Description of the Related Art In recent years, electric and electronic materials, particularly materials used for encapsulation of ICs and copper-clad laminates, have been required to have rapid curability in order to improve production efficiency. Even better storage stability has been required.

[0003] Until now, Japanese Patent Application Laid-Open No. 8-41290 and Japanese Patent Application Laid-open No.
As seen in JP-A No. 2355, quaternary phosphonium salts and bicyclic amidinium salts have been studied as curing accelerators (hereinafter also referred to as catalysts) for epoxy resins, and it has been found that some performance is exhibited. . However, at present, it is not always satisfactory with respect to the required performance that has become increasingly severe.

On the other hand, the present inventors have made intensive studies in view of such a situation, and as a result, added a tri-substituted boron compound to a conventional onium salt such as a quaternary phosphonium salt or a bicyclic amidinium salt. It has been found that a catalyst that gives unprecedented good curability and preservability can be obtained by performing the above-mentioned method and further positively contacting the onium salt with the trisubstituted boron compound.

[0005]

SUMMARY OF THE INVENTION Based on this new knowledge, the present invention provides a resin composition which has good curability and storage properties and is useful in the fields of electric and electronic materials, and a semiconductor encapsulant using the same. And a copper-clad laminate.

[0006]

That is, the present invention provides an epoxy resin (A), a curing agent (B), an onium salt (C) containing no halogen ion in the counter anion, and a method in which boron is not directly substituted with halogen. Tri-substituted boron (D)
And an onium salt (C) containing no halogen ion in the counter anion, and further comprising an epoxy resin (A), a curing agent (B),
It is a resin composition containing a pre-reacted product obtained by preliminarily reacting boron with a tri-substituted boron (D) in which halogen is not directly substituted with halogen.

Furthermore, a semiconductor encapsulating material obtained by mixing and kneading components such as a filler with these resin compositions, and a varnish obtained by dissolving the resin composition in a solvent are used, or A laminate obtained by impregnating a substrate with no solvent and drying, laminating a predetermined number of the substrates, heating and pressing.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The epoxy resin (A) used in the present invention is not particularly limited as long as it is known to those skilled in the art in the field of IC encapsulating materials and copper-clad laminates. Epoxy resin, novolak type epoxy resin,
Bisphenol type epoxy resin, naphthalene type epoxy resin, etc., epoxy resin manufactured by reacting epichlorohydrin with hydroxyl groups such as phenolic resin and naphthols, and olefin using peracid such as alicyclic epoxy resin Although epoxy resins that are oxidized and epoxidized are also included, orthocresol novolak epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, bisphenol type epoxy Resins are preferred.

The curing agent (B) used in the present invention is not particularly limited as long as the functional group of the curing agent reacts with the epoxy group of the epoxy resin to form a cured product. Anhydrides and the like are known to those skilled in the art. However, in consideration of heat resistance and moisture resistance, a phenol resin, an amine compound, or a combination thereof is preferable. Specific examples of such a curing agent include, as a phenol resin, a phenol novolak resin, a cresol novolak resin, an alkyl-modified novolak resin, a phenol aralkyl resin, a resin obtained by co-condensing naphthols and phenols with a carbonyl group-containing compound. Examples thereof include a compound in which a hydrogen atom bonded to an aromatic ring such as phenol or naphthol is substituted with a hydroxyl group, and any compound that reacts with an epoxy group of an epoxy resin to form a cured product. . As amine-based curing agents,
Examples thereof include aromatic diamines such as diaminodiphenylmethane, aniline resin, dicyandiamide, guanidine and derivatives thereof, but are not limited as long as they are known to those skilled in the art.

The onium salt (C) which does not contain a halogen ion in the counter anion is a compound which forms an ion pair with the counter anion and causes a curing reaction and the counter anion is not a halogen ion. Tetraalkylphosphonium salts such as butylphosphonium salts, tetraarylphosphonium salts such as tetraphenylphosphonium salts, trisubstituted sulfonium salts such as trialkylsulfonium salts, triarylsulfonium salts, acyclic ammonium salts, iminium salts, guanidinium salts, amidinium 1,4-diazabicyclo [2,2,2] which is a salt or a cyclic ammonium salt
Octanium salts, 1,8- which are bicyclic amidinium salts
Diazabicyclo [5,4,0] undecenium salt,
Examples thereof include nitrogen cations such as 5-diazabicyclo [4,3,0] nonenium salt, imidazolium monocyclic amidinium salt, and pyridinium salt. Among them, preferred are tetra-substituted phosphonium salts, tri-substituted sulfonium salts, tetra-substituted ammonium salts, bicyclic amidinium salts, imidazolium salts, and guanidinium salts. But,
A counter anion, an oxygen anion generated by ring opening of an epoxy group during a curing reaction, and a carbonium ion such as tritium can be used if they do not have recombination properties.

The counter anion of these onium salts (C) is not particularly limited as long as it is an anion other than a halogen ion which can be formed by the onium salt. Is preferred. Organic acid anions (roots) are also defined in the Chemical Dictionary, Vol. 9, p. 339 (Kyoritsu Shuppan) as an organic acid, which is a generic term for all acidic organic compounds. As is evident, there is no particular limitation as long as the acidic organic compound emits a proton and is an anion. However, carboxylic acids, phenols and naphthols are compounds in which a hydrogen atom bonded to an aromatic ring is substituted with a hydroxyl group. And oxocarbons such as squaric acid, croconic acid, and tetronic acid. Also suitable are the alkoxy anions which are the corresponding proton emitters of alcohols such as methanol, ethanol and butanol.

It is not preferable that the trisubstituted boron (D) is present in an easily hydrolyzed form in which a halogen which has a bad influence on electric and electronic materials is directly substituted by boron.
Therefore, trialkylboron, triphenylboron,
Tritolylboron, triarylboron such as trispentafluorophenylboron, tribenzoyloxyboron, triaryloyloxyboron such as trinaphthoyloxyboron, triethylborate, borate such as triphenylborate are preferred. There is
A tri-substituted boron in which boron is not directly substituted with halogen includes one in which a polyfunctional phenolate and boron are bonded between multiple molecules to form an oligomer.

[0013] An onium salt (C) containing no halogen ion in the counter anion and a trisubstituted boron (D) in which boron is not directly substituted with halogen are preliminarily reacted and mixed with other components. It is also an important technique in the present invention to make a resin composition. By performing such a preliminary reaction, the interaction between the counter anion of the onium salt contributing to the curing reaction and the trisubstituted boron functions more efficiently, and the storage stability is further improved.

In the present invention, additives and auxiliary materials known to those skilled in the art, such as an inorganic filler, a release agent and a coupling agent, are added to the resin composition described above, if necessary. Then, a semiconductor sealing material or a semiconductor sealing liquid resin is prepared. Further, it is used for manufacturing a semiconductor device by a method of molding or enclosing an electronic device such as low-pressure transfer molding or potting.

A prepreg is prepared by dissolving the resin composition in a solvent, if necessary, or preparing a varnish without a solvent, impregnating a substrate such as a glass cloth and drying. By laminating a predetermined number of them, or by laminating press molding with copper foil or the like, or by continuous hot roll molding, a laminated board or a copper-clad laminated board for a printed wiring board is manufactured. It is needless to say that a printed wiring board by the additive method is included in the technical scope of the present invention.

[0016]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the present invention. First, a preliminary reaction example of an onium salt (C) containing no halogen ion in the counter anion and a trisubstituted boron (D) in which boron is not directly substituted with halogen will be described. Examples 1 to 10 and Comparative Examples 1 to 6 in which an onium salt (C) and a trisubstituted boron (D) are blended to prepare a molding material for sealing and a laminate.

(Preliminary Reaction Example) In a 50 ml round bottom flask, 10 ml of N, N-dimethylformamide, 4.6 g of tetraphenylphosphonium benzoate (K-1), and triphenyl borate (TB-1) 2 .9g
, And the mixture was stirred and reacted at room temperature for 1 hour. Then, the external temperature was raised to 100 ° C. over 1 hour, and the reaction was continued at 100 ° C. for 1 hour. Thereafter, the solvent was distilled off under reduced pressure to stop the reaction, and a product was obtained. The chemical structures of tetraphenylphosphonium benzoate (K-1) and triphenylborate (TB-1) are represented by the formulas (1) and (9).
It was shown to.

All of the pre-reactants of the onium salt (C) and the trisubstituted boron (D) used in the examples were prepared in the same manner as in this example. In Tables 1 and 2, in the examples using the pre-reactant, X was described in the treatment column, while the pre-reaction was not performed, and the onium salt (C) and the trisubstituted boron (D) were used as they were. In Examples, Y was described in the processing column. Further, the symbols described in Tables 1 and 2 and K-2
To K-8, and TB-2 to TB-4 represent an onium salt and a trisubstituted boron, respectively, and their chemical structures are represented by formulas (2) to (8) and formulas (10) to (1).
This is as shown in 2).

(Examples 1 to 8 and Comparative Examples 1 to 4) For the purpose of preparing a molding material and evaluating its properties, the hot hardness immediately after heat molding, the spiral flow of the molding material, and the flow residual ratio after storage were measured. It measured and evaluated the hardenability and the preservability. Each evaluation method was as follows.

1. Barcol hardness After molding for 50 seconds at 175 ° C using a water-absorbing disk-forming mold according to JIS-K6911, immediately take out
The molded product was allowed to stand on a hot plate heated to 75 ° C. for 10 seconds, and immediately measured for its hot hardness using a Barcol hardness meter. The larger the value, the higher the curability.

2. Spiral flow Using a mold for spiral flow measurement according to EMMI-I-66, mold temperature 175 ° C, injection pressure 70 kg / cm
^2. Measure with a curing time of 2 minutes. Spiral flow (c
m) is a parameter of fluidity, and a larger value indicates better fluidity.

3. Remaining flow rate Spiral flow immediately after molding material preparation, and 4
Measure spiral flow after storage at 0 ° C for 3 days,
The percentage of the spiral flow (cm) after storage with respect to the spiral flow (cm) immediately after the material preparation was calculated.
The larger the residual flow rate, the better the storage stability.

(Example 1) A polyfunctional epoxy resin,
To 67 parts by weight (hereinafter simply referred to as "parts") of orthocresol novolak epoxy resin (EOCN102065) manufactured by Nippon Kayaku, 33 parts of phenol novolak having a softening point of 105 ° C and a hydroxyl equivalent of 104, 300 parts of crushed fused silica,
Two parts of carnauba wax, 2.9 parts of a pre-reaction product from onium salt K-1 and trisubstituted boron TB-1 were blended and kneaded with a hot roll at 90 ° C. for 5 minutes to obtain a molding material.

Example 2 Polyfunctional, epoxy equivalent of 2
60 parts of dicyclopentadiene-type epoxy resin (HP-7200) manufactured by Dainippon Ink and 29 parts of phenol novolak having a softening point of 105 ° C. and a hydroxyl equivalent of 104, 500 parts of spherical fused silica, 2 parts of carnauba wax, onium salt K And 2.9 parts of an equimolar mixture of tri-substituted boron TB-1 (without preliminary reaction) were mixed at 90 ° C. with a hot roll.
The mixture was kneaded for minutes to obtain a molding material.

Example 3 Bifunctional epoxy resin biphenyl type epoxy resin (YX4000H) 52 made of bifunctional oiled shell epoxy
, An aralkyl-modified phenolic resin manufactured by Mitsui Toatsu Chemicals (X
L225-3L) 48 parts, 800 parts of spherical fused silica, 2 parts of carnauba wax, 3 parts of a pre-reaction product from onium salt K-2 and trisubstituted boron TB-2, and kneading with a hot roll at 90 ° C. for 5 minutes. Thus, a molding material was obtained.

(Examples 4 to 8, Comparative Examples 1 to 4) By the formulations shown in Table 1, the same operations as in Examples 1 to 3 were carried out to prepare molding materials. The evaluation results are shown in Table 1 together with Examples 1 to 3.

[0027]

[Table 1] 1) Orthocresol novolak epoxy resin manufactured by Nippon Kayaku 2) Dicyclopentadiene type epoxy resin manufactured by Dai Nippon Ink 3) Biphenyl type epoxy resin manufactured by Yuka Shell Epoxy 4) Phenol novolak resin having a softening point of 105 ° C. and a hydroxyl equivalent of 104 5 ) Aralkyl-modified phenolic resin manufactured by Mitsui Toatsu Chemicals 6) 1,8-diazabicyclo [5,4,0] undecene 7) Treatment X: Equimolar pre-reaction of onium salt and trisubstituted boron as described in Pre-reaction example Y: Preliminary reaction was not carried out, and an equimolar mixture of onium salt and trisubstituted boron was mixed with other components. 8) Soft and unmeasurable

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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(Examples 9 to 10 and Comparative Examples 5 to 6)
A copper-clad laminate was prepared, and for the property evaluation, the glass transition temperature of the resin of the obtained laminate and the gel time remaining ratio of the resin after storage of the prepreg were measured, and the curability and the storage stability were evaluated. . Each evaluation method was as follows.

4. Glass transition temperature The copper foil was removed by etching from the obtained double-sided copper-clad laminate, only the cured prepreg layer was cut out, and the glass transition temperature was measured at a heating rate of 5 ° C./min with a dynamic viscoelasticity measuring device. It was measured. If not sufficiently cured, the glass transition temperature will be low.

5. Residual gel time The resin content is dropped from the prepreg, and the gel time is measured on a hot plate heated to 170 ° C. The gel time immediately after preparation of the prepreg and after storage at 40 ° C. and 35% RH for 7 days were measured, and the percentage of the gel time (second) after storage relative to the gel time (second) immediately after preparation was calculated. The larger the value of the residual gel time, the better the storage stability.

Example 9 50 parts of a biphenol A type epoxy resin having an epoxy equivalent of 925, 50 parts of a bisphenol A type epoxy resin having an epoxy equivalent of 475, 3 parts of diaminodiphenylmethane, 0.8 part of dicyandiamide, and 0.8 parts of onium salt K-6 A varnish was prepared by mixing 2.8 parts of the pre-reaction product from the substituted boron TB-3 and dissolving it in 100 parts of a 1: 1 mixed solvent of N, N-dimethylformamide and methyl ethyl ketone. Using this varnish, a glass cloth having a thickness of 100 μm was impregnated, and dried at 150 ° C. for 4 minutes to obtain a prepreg. The 16 prepregs are stacked, and a copper foil having a thickness of 35 microns is stacked on both sides thereof.
170 ° C, 40kg / cm sandwiched between two stainless steel plates
² was pressed for 50 minutes to obtain a double-sided copper-clad laminate having a thickness of 1.6 mm.

(Example 10, Comparative Examples 5 to 6) Using the formulations shown in Table 2, the same operation as in Example 9 was carried out to prepare double-sided copper-clad laminates. The evaluation results are shown in Table 2 together with the results of Example 9.

[0045]

[Table 2]

As is clear from the results of Tables 1 and 2, both the Barcol hardness (Table 1) in the short-time molding of the molding material and the glass transition temperature (Table 2) in the short-time lamination molding of the prepreg were all used. The examples show generally superior values, indicating that the curability of the resin composition according to the present invention is high. In addition, the residual flow rate after storage (Table 1) and the residual gel time (Table 2) after storage are all higher in the examples, and the resin composition according to the present invention is also superior in storage stability, The effect of the combination of the onium salt and the trisubstituted boron as a neutral catalyst is apparent.

[0047]

The resin composition of the present invention has excellent curability and can be sufficiently cured even in a short molding time.
In addition, it has excellent storage stability at around normal temperature, can be suitably used for electric and electronic materials, and can provide a product having good curability and preservability, and has great merits in the electric and electronic industries.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akiko Okubo 2-58-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. (72) Inventor Minoru Kobayashi 2-5-2-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd.

Claims (9)

[Claims] An essential component is an epoxy resin (A), a curing agent (B), an onium salt (C) containing no halogen ion in the counter anion, and a trisubstituted boron (D) in which boron is not directly substituted with halogen. A resin composition characterized by the following. 2. An epoxy resin (A), a curing agent (B), an onium salt (C) containing no halogen ion in the counter anion, and a trisubstituted boron (D) in which boron is not directly substituted with halogen. Wherein the product obtained by preliminarily reacting is used as an essential component. 3. The epoxy resin (A) is one selected from orthocresol novolak epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin and bisphenol type epoxy resin, or The resin composition according to claim 1, wherein the resin composition comprises two or more types. 4. The resin composition according to claim 1, wherein the curing agent (B) is a phenol resin and / or an amine compound. 5. The onium salt (C) containing no halogen ion in the counter anion is selected from tetra-substituted phosphonium salts, tri-substituted sulfonium salts, tetra-substituted ammonium salts, bicyclic amidinium salts, imidazolium salts, and guanidinium salts. The resin composition according to claim 1, wherein the resin composition is at least one selected from the group consisting of: 6. The counter anion of the onium salt (C) containing no halogen ion in the counter anion is at least one selected from organic acid anions and proton emitters of alcohols. The resin composition according to claim 1. 7. The method according to claim 1, wherein the trisubstituted boron (D) in which boron is not directly substituted with halogen is at least one selected from triarylboron, triarylloyloxyboron, and borate ester. The resin composition according to claim 1 or 2, wherein 8. A semiconductor encapsulating material, which is basically composed of the resin composition according to claim 1 and a filler. 9. A laminate comprising a resin composition according to any one of claims 1 to 7 and a base material.