JP2920324B2 - Modifier for composite materials - Google Patents

Description

The present invention relates to a composite obtained by treating a glass fiber product or a mica product as a modifier for a composite material, particularly a reinforcing agent, with a matrix resin such as an epoxy resin or a polyimide resin. The present invention relates to a modifier for a composite material for improving the mechanical strength, electrical properties, heat resistance, chemical resistance and the like of the material.

[Prior art] Glass fiber products and mica products such as glass cloth, glass tape, glass mat and glass paper as reinforcing materials are converted into matrices such as epoxy resin, phenol resin, acrylic resin, polyimide resin, polyamide resin and polyester resin. Composite materials treated with resins are widely used in various applications.

Thus, for this type of composite material, the γ-aminopropyltriethoxysilane, N-β (aminoethyl γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, Preliminary treatment with a silane coupling agent such as glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc., improves the adhesion with the matrix resin, and is thus produced. It is also known that composite materials, such as laminates, have improved physical properties such as mechanical strength, electrical properties, water resistance, boiling resistance, and chemical resistance. Recently, printed circuit board laminates have been remarkably growing.

[Problems to be Solved by the Invention] However, since this printed board laminate is immersed in molten solder during the wiring process or processed by a reflow method, particularly strong heat resistance is required. When molded with a known silane coupling agent as described above, the interface between the inorganic material and the resin has a large curing strain, and since the heat resistance of the silane itself is poor, the solder heat resistance is reduced. There is a disadvantage that sex is bad.

Therefore, for this, A hydrochloride of a silane compound represented by There has been proposed a method of treating with a silane compound represented by (see JP-B-48-20609 and JP-B-57-41771).
Also the formula (Where R ¹ is a methyl group or an ethyl group, and R ² is
There has also been proposed a method of treating with a silane compound represented by the formula (6), a divalent hydrocarbon group of 6, and n is an integer of 4 to 8) or a hydrochloride thereof (see JP-A-1-48832). Although the heat resistance of silane itself has been improved, the solder heat resistance of this composite material has also been improved to some extent.However, since these materials are highly reactive, the curing speed of the resin is increased, and the Hardening distortion easily occurs,
There is a disadvantage that a sufficient effect cannot be obtained.

[Means for Solving the Problems] The present invention relates to a modifier for a composite material which has solved such disadvantages, and has a general formula (Where R ¹ is a monovalent hydrocarbon group having 1 to 2 carbon atoms, R ² is a divalent hydrocarbon group having 1 to 9 carbon atoms, x is 2 or 3, and y is 2 to 2.
An integer of 6, m is 0 to 1, n is 0 to 2 and m + n = 1.2 to 2.
5, wherein p is an organic acid salt or an inorganic acid salt of an amino group-containing silicon compound represented by the following formula: 0.8 to 2.0).

That is, the present inventors have conducted various studies to develop a modifier for a composite material for obtaining a composite material having particularly excellent heat resistance, and as a result, the amino group-containing compound represented by the general formula (I) described above was used as the modifier. Benzyl group as a substituent of amino group in silicon compounds Is introduced, or 0.8 to 2.0 mol of a benzyl group as a substituent of an amino group in the amino group-containing silicon compound of the general formula (II) is introduced. Since the number of aromatic rings in the molecule is increased, the heat resistance of the silane itself is improved, and when this amino group is used as an organic acid salt or an inorganic acid salt, the nucleophilicity of the nitrogen atom decreases, and the --NH group The curing speed when curing the composite material is reduced because the number of the composite materials is reduced, and as a result, the curing strain at the interface between a reinforcing agent such as a glass fiber product and a mica product and a matrix resin such as an epoxy resin and a polyimide resin is reduced. The present inventors have found that the heat resistance of the composite material is improved, and studied the molecular structure, type, and the like of the modified material, and completed the present invention.

 This will be described in more detail below.

[Function] The present invention relates to a modifier for improving the physical properties of a composite material obtained by treating a glass fiber product or mica product as a reinforcing agent with a matrix resin such as an epoxy resin or a polyimide resin.

The composite material which is a target of the composite material modifier of the present invention is a matland (glass yarn) in which glass filaments obtained by spinning alkali glass, alkali-free glass, low induction glass, high elasticity glass, E glass for electricity, and the like are bundled. ), Glass fiber products such as non-woven glass mats, glass papers, and even yarn-woven glass cloths, glass tapes, or soft or hard laminated mica sheets formed from mica flakes or fired products of these. Mica products are used as reinforcements, and these are treated with matrix resins such as epoxy resins and polyimide resins.This includes laminated boards, etc., but the composite material modifier of the present invention is used here. The above-mentioned reinforcing agent is preliminarily treated before being treated with the matrix resin.

The modifier for a composite material of the present invention has a general formula Wherein R ¹ is a methyl group or an ethyl group having 1 to 1 carbon atoms.
2 monovalent hydrocarbon groups, R ² is a divalent hydrocarbon group having 1 to 9 carbon atoms, for example, —CH ₂ —, —CH ₂ CH ₂ —, X is 2 or 3, y is an integer of 2 to 6, m is 0
-1 and n are values of 0-2, and the sum of m and n, m + n, is
If it is smaller than 1.2, the number of NH groups increases and the curing speed of this material increases, so the curing strain at the interface between the matrix resin and the reinforcing agent increases, and the solder heat resistance when using a laminated material becomes poor, which is less than 2.5 If it becomes large, it becomes difficult to complete the reaction at the time of synthesis, and the raw materials for synthesis remain, so that stains such as oil spots are generated on the surface of the reinforcing material, and the adhesiveness is deteriorated. Therefore, this m + n value is preferably in the range of 1.2 to 2.5. Is in the range of 1.2 to 2.0. The above (I
When the p-value in the formula (I) is smaller than 0.8, the NH group increases and the active group becomes active due to the increased number of NH groups, the curing speed increases, the curing strain at the interface between the reinforcing agent and the matrix resin increases, and The heat resistance of the solder becomes poor when it is used, and when it exceeds 2.0, the amino group part partially takes a quaternary ammonium salt structure, so the reactivity to the epoxy group is further reduced and the reinforcing property in the composite material is reduced. This needs to be in the range of 0.8 to 2.0 as it will be insufficient.

As the amino group-containing silicon compound represented by the general formula (I), And the like. Examples of the amino group-containing silicon compound represented by the above general formula (II) include And the like.

These amino group-containing silicon compounds can be synthesized by various methods, and the amino group-containing silicon compound represented by the general formula (I) is, for example, of the formula (Wherein R ¹ , R ² , x and y are the same as above) (Where A represents a halogen atom)
2 to 2.0 moles are reacted in an appropriate alcohol or hydrocarbon solvent or a tertiary amine such as pyridine or triethylamine or a halogen acid trapping agent such as sodium alkoxide as a catalyst. And according to this Can be reacted up to 1.2 to 2.5 moles, and this reaction is preferably performed at a temperature of 50 to 150 ° C. for 5 to 100 hours. This is also the formula (R ¹ , R ² , x are the same as above, A is a halogen atom) and 1 mole of a halogenoalkylsilane compound represented by the following formula: (M, n, y are the same as described above), and can be synthesized by reacting with 1 mol of an amine compound represented by the above-mentioned solvent or in the presence of the above-mentioned catalyst. Also the formula (R ¹ , R ² , x, y are the same as above). Can also be synthesized by reacting 0.5 to 1.5 moles of the compound represented by

The amino-containing silicon compound represented by the general formula (II) is, for example, a compound represented by the formula (R ¹ , R ² , and x are the same as described above). (A is a halogen atom) can be synthesized by reacting 0.8 to 2.0 moles of a compound represented by the formula (1) in the presence of the above-mentioned catalyst. (Wherein R ¹ , R ² , x, and A are the same as above) and 1 mole of a halogenoalkylsilane represented by the following formula: (N is 1.2 to 2.0) by reacting an amine compound represented by the formula (R ¹ , R ² , and x are the same as above) and 1 mol of an organic silicon compound represented by the formula: (A is a halogen atom).

In addition, the amino group-containing silicon compound represented by the general formula (I) or (II) produced in this manner reduces nucleophilicity to some extent, slows down the reactivity at the time of curing, and consequently reduces curing strain. Is used as a modifier for composite materials as a halogenate to improve heat resistance. Examples of the halogenate include hydrochloride, bromate, hydrofluoride, hydroiodide and the like. Is done. Also, after filtering the salt of this halogenate as sodium halide or the like with a halogen acid capturing agent such as sodium alkoxide,
The compound can be obtained by re-neutralizing with an organic acid or an inorganic acid.

Treatment of reinforcing agents such as glass fiber products and mica products with the organic acid salt or inorganic acid salt of this amino group-containing silicon compound can be carried out using water, an organic acid aqueous solution, alcohol, ether, or a mixture thereof. The reinforcing agent may be diluted with such a suitable solvent, and the diluent may be used to treat the reinforcing agent. The solvent is preferably a 0.1 to 2.0% by weight aqueous solution of acetic acid. The organic acid salt or inorganic acid salt of the elemental compound has a concentration of 0.1 to 2.0.
It may be diluted so as to be 0.2% by weight, preferably 0.2% to 1.0% by weight, and it is optional to add a dye, a pigment, an antistatic agent, a lubricant and the like as needed.

The treatment of the reinforcing material with the treatment liquid may be performed by immersing the reinforcement in the treatment liquid. In this case, the solution retention of the treatment liquid may be made constant using a squeeze roll or the like. For example, this treatment liquid may be applied by spraying. When the reinforcing agent thus treated is dried at 60 to 120 ° C. after this treatment, the silanol groups of the amino group-containing silicon compound are condensed on the surface of the reinforcing agent together with the removal of the solvent. The advantage of being better is given.

Examples Next, a synthesis example of an amino group-containing silicon compound for producing the modifier for a composite material of the present invention, and an example of the present invention,
Comparative examples will be described. In the examples, parts indicate parts by weight, and various physical property values in the examples indicate measurement results described below.

(Boiling water absorption) According to the test method of JIS C-6481, a 50 × 50 mm test piece from which a copper foil was removed from a copper-clad laminate by etching was cut out, and the water absorption after boiling for 4 to 14 hours was measured.

(Solder Heat Resistance) When the test piece after the above measurement of boiling water absorption was floated in a 260 ° C. solder bath for 45 seconds, a portion where the test piece had blistered was indicated as a fracture area (%).

(Heat shock property) Immediately after immersing the copper-clad laminate in liquid nitrogen for 1 minute,
Was immersed in a solder bath for 1 minute, then the copper foil was removed by etching, and the damage of the test piece was observed.

…: Good,…: slight spot-like defect, Δ: spot-like defect, ×: destruction as a whole

(Slow curing) Bisphenol type epoxy resin / Epicoat 1001 [trade name of Yuka Shell Epoxy Co., Ltd.] 80 parts, novolak type epoxy resin / Epicoat 154 [trade name of Yuka Shell Epoxy Co., Ltd.] 20 parts, dicyandiamide Resin varnish made by mixing 4.0 parts, 0.2 parts of benzyldimethylamine, 20 parts of methyl ethyl ketone and 45 parts of methyl cellosolve
Two parts of silane was added to 50 parts, and the gelation time at 150 ° C. was measured using a gelation tester (manufactured by Nissin Kagaku Co., Ltd.) to evaluate the slow curing property.

(Bubble removing property) The test piece from which the copper foil was removed from the copper-clad laminate by etching was observed to evaluate the bubble removing property.

Synthesis Example 1 2L equipped with a cooler, stirrer, dropping funnel and thermometer
N-β aminoethyl γ-
Aminopropyltrimethoxysilane H ₂ NCH _{2 2} NHCH _2
3 Si (OCH ₃ ) ₃ 222 g (1.0 mol) and 475 g of methanol were charged and heated to 60 ° C. under a nitrogen stream. 253 g (2.0 mol) was slowly added dropwise at 60 to 67 ° C.

After the completion of the dropwise addition, the reaction was carried out at 67 ° C. for 70 hours, and the chloro content was measured by potentiometric titration. As a result, it was 7.5% (theoretical value: 7.5%).
g (yield 98.5%) of a methanol solution of the product was obtained. The product was subjected to H-NMR spectrum analysis and IR spectrum analysis. The amino group-containing silicon compound (hereinafter referred to as silane-I)
(Abbreviated as).

Synthesis Examples 2 to 10 Synthesis Example 1 was the same as Synthesis Example 1 except that N-βaminoethyl γ-aminopropyltrimethoxysilane (component A) and benzyl chloride (component B) were as shown in Table 1 below. As a result, amino group-containing silicon compounds (silanes II to X) shown in Table 1 were obtained.

Example 1 A glass cloth WE18W105 (trade name, manufactured by Nitto Boseki Co., Ltd.) whose surface was cleaned by heat cleaning was prepared by adding 5 g of the hydrochloride of silane-I obtained in Synthesis Example 1 to a 1% by weight aqueous acetic acid solution. The solution was immersed in a treatment solution dissolved so as to be / l, squeezed with a squeeze roll, and then dried under conditions of 110 ° C for 15 minutes.

Then, according to the NEMA standard G-10 method, 80 parts of bisphenol-type epoxy resin / Epicoat 1001 (described above), 20 parts of novolak-type epoxy resin / Epicoat 154 (described above), 4.0 parts of dicyandiamide, 0.2 parts of benzyldimeasamine,
A resin varnish made by mixing 20 parts of methyl ethyl ketone and 45 parts of methyl cellosolve was impregnated with the above-mentioned silane-treated glass cloth, and then cured at 160 ° C. for 6 minutes to prepare a prepreg in a B-stage state. Then, copper foil is laid on the top and bottom of the eight prepregs and press-molded under the condition of 170 ° C x 35 kg / cm ² x 60 minutes to make a double-sided copper-clad epoxy laminate, which has boiling water absorption and solder heat resistance. The properties (260 ° C. × 45 seconds), heat shock properties, slow curing properties, and foam removal properties were examined, and the results shown in Table 2 below were obtained.

Examples 2 to 5 and Comparative Examples 1 to 5 Instead of silane-I in Example 1, halogenated salts of amino group-containing silicon compounds as silanes II to V obtained in Synthesis Examples 2 to 5 were used. Others were treated in the same manner as in Example 1 to produce a silane-treated glass cloth and a double-sided copper-clad epoxy resin laminate, and for comparison, the following five types of silane-XI to XV were used in place of silane-I in Example 1. The silane-treated glass cloth was treated in the same manner as in Example 1 except that silane-XI and XII were soluble in pure water, and pure water was used instead of the acetic acid aqueous solution. Making double-sided copper-clad epoxy laminates, boiling water absorption of these, solder heat resistance (260 ° C x 45 seconds),
When the heat shock property, the slow curing property, and the foam release property were examined, the results shown in Table 2 were obtained.

Examples 6-7, Comparative Examples 6-7 In addition to using the hydrochloride of the amino group-containing silicon compound as silane-VI, VII obtained in Synthesis Examples 6-7 in place of silane-I in Example 1, Was treated in the same manner as in Example 1 to produce a silane-treated glass cloth, and for comparison, the following two silanes were used in place of silane-I in Example 1.
X VI and X VII, A silane-treated glass cloth was prepared in the same manner as in Example 1 except that the hydrochloride was used.

Then, according to NEMA standard FR-4 prescription, 100 parts of brominated epoxy resin, Epicoat 5046-B-8 [trade name of Yuka Shell Epoxy Co., Ltd.], novolak type epoxy resin
Epicoat 154 (supra) 20 parts, dicyandiamide 4 parts,
A resin varnish obtained by mixing 0.2 parts of 2-ethyl-4-methylimidazole, 15 parts of methyl ethyl ketone and 30 parts of dimethylformamide is impregnated with these silane-treated glass cloths, and then the boiling water absorption, solder heat resistance, When the heat shock property, the slow curing property and the defoaming property were examined, the results shown in Table 3 were obtained.

Examples 8 to 10, Comparative Example 8 In place of silane-I in Example 1, halogenated salts of amino group-containing silicon compounds as silanes VIII, IX, and X obtained in Synthesis Examples 8 to 10 were used. Others were treated in the same manner as in Example 1 to produce a silane-treated glass cloth and a double-sided copper-clad epoxy resin laminate, and for comparison, the following formula was used in place of silane-I in Example 1. The silane-treated glass cloth and the double-sided copper-clad epoxy resin laminate were prepared in the same manner as in Example 1 except that the hydrochloride of the amino group-containing silicon compound XVIII represented by the following formula was used, and the physical properties of these were examined. However, the results as shown in Table 4 were obtained.

[Effects of the Invention] The present invention relates to a modifier for a composite material obtained by treating a reinforcing agent such as a glass fiber product or a mica product with a matrix resin such as an epoxy resin or a polyimide resin. General formula The main material is a halogen acid of an amino group-containing silicon compound represented by, but a composite material obtained by treating a reinforcing agent with this composite material modifier cures slowly when cured as a laminate. Therefore, the curing distortion at the interface between the reinforcing agent and the resin is reduced, and thus the heat resistance of the laminate is improved, and the defoaming property upon curing due to the slow curing property is excellent. Gender.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yoshiharu Suzuki 1-3-10 Minamimudaidai, Fukushima City, Fukushima Prefecture (72) Inventor Junichi Saito 2-2 Hino, Toriya, Fukushima City, Fukushima Prefecture (56) References JP Showa 64-48832 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08J 5/06-5/08 C08K 9/06

Claims (4)

(57) [Claims] (1) General formula Or general formula (Where R ¹ is a monovalent hydrocarbon group having 1 to ² carbon atoms, R ² is a divalent hydrocarbon group having 1 to 9 carbon atoms, x is 2 or 3, and y is 2 to 2.
An integer of 6, m is 0 to 1, n is 0 to 2 and m + n = 1.2 to 2.
5. A modifier for a composite material comprising, as a main component, an organic acid salt or an inorganic acid salt of an amino group-containing silicon compound represented by the formula 0.8 to 2.0). 2. The composite material modifier according to claim 1, wherein the composite material is a composite of glass fiber or mica and an epoxy resin or a polyimide resin. 3. The organic acid salt is a hydrochloride or a bromate.
The modifier for a composite material as described in 1 above. 4. The composite material modifier according to claim 1, wherein the inorganic acid salt is an acetate.