JP3391067B2 - Epoxy resin composition and epoxy resin composition for laminated board - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel epoxy resin composition having excellent heat resistance, water resistance and electrical characteristics.
More specifically, laminated resin materials, electrical insulation materials, semiconductor encapsulation materials, fiber reinforced composite materials, coating materials, molding materials,
The present invention relates to an epoxy resin composition having excellent heat resistance, water resistance, and toughness, which is extremely useful as an adhesive material.

[0002]

2. Description of the Related Art Epoxy resins, when cured with various curing agents, generally become cured products having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc. It is used in a wide range of fields such as laminates, molding materials, and casting materials. Particularly in the fields of electricity and electronics, there are more stringent requirements for higher density and higher precision of electronic parts, and more excellent epoxy resins are desired.

Up to now, a polyfunctional epoxy resin has been often used in combination as an epoxy resin for printed wiring boards for the purpose of improving heat resistance, and specifically, a phenol novolac type epoxy resin and Cresol-novolak type epoxy resins and the like have been used, but high heat resistance and low water absorption, which are desirable characteristics in electric and electronic applications such as electric laminates, have not been sufficient.

Therefore, for example, Japanese Patent Application Laid-Open No. 4-103616 discloses a technique of using a dicyclopentadiene-phenol cross-linking epoxy resin as an epoxy resin excellent in high heat resistance and low water absorption.

[0005]

However, the above-mentioned Japanese Patent Application Laid-Open No. 4-
Although the dicyclopentadiene-phenol cross-linking epoxy resin disclosed in Japanese Patent No. 103616 is excellent in high heat resistance and low water absorption, it has a trifluorocarbon structure as a catalyst during the production method described in the publication, i.e., a raw material phenol resin is produced. Epoxy resin obtained by the production method using boron trifluoride, boron trifluoride ether, phenol, boron trifluoride complex such as alcohol complex, aluminum trichloride, sulfuric acid and the like has a blackish brown color and is laminated. There is a problem that the appearance of the plate when processed is significantly impaired.

[0006] The problem to be solved by the present invention is to provide an excellent appearance when processed in various applications such as electric laminates, insulating powder paints, paints, and the like, and to have excellent high heat resistance and low water absorption. An object of the present invention is to provide a combined epoxy resin composition.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have found that an aromatic hydrocarbon group as a main component is bound to a cycloaliphatic hydrocarbon group as a knotting group , and the glycidyloxy group is present on the aromatic hydrocarbon group. It was found that the above problems can be solved by using, as an epoxy resin having a structure having ## STR3 ## as a substituent, one having a Gardner color number of 10 or less in a non-volatile content of 50% by weight in dioxane, and the present invention has been completed. It was

That is, according to the present invention, an aromatic hydrocarbon group is bonded with a cycloaliphatic hydrocarbon group as a knotting group,
An epoxy resin having a structure having a glycidyloxy group as a substituent on a hydrocarbon group , and having a non-volatile content of 50% by weight in a dioxane solution having a Gardener color number of 1
The present invention relates to an epoxy resin composition comprising an epoxy resin (A) of 0 or less, a curing agent (B), and a curing accelerator (C) as essential components.

The epoxy resin (A) used in the present invention has a structure in which an aromatic hydrocarbon group is bonded with a cycloaliphatic hydrocarbon group as a knotting group, and a glycidyloxy group is a substituent on the aromatic group. It has a guardian color number of 10 or less, but is usually represented by epichlorohydrin as a polyaddition reaction product of a phenol and an unsaturated alicyclic hydrocarbon compound. It is obtained by reacting epihalohydrin. In addition, the color tone of the epoxy resin is light yellow, and the color tone of the epoxy resin itself is considerably improved as compared with the conventional color tone.

The cycloaliphatic hydrocarbon group in the epoxy resin (A) is not particularly limited, but for example, a hydrocarbon group having a cyclohexane ring or a cyclohexene ring has high heat resistance and low water absorption. It is preferable from the viewpoint of excellent properties, among which 4-vinylcyclohexene, 5-vinylnorbona-2-ene, 3a, 4,7,7a-tetrahydroindene, dicyclopentadiene, α-pinene,
A divalent hydrocarbon group derived from β-pinene or limonene is preferable because this effect is more remarkable.

[0011] The aromatic hydrocarbon group attached to the nodules based on the cyclic aliphatic hydrocarbon group is not particularly limited, for example, benzene nucleus, naphthalene nucleus, etc. These aromatic The group hydrocarbon group may be substituted with an alkyl group, and the aromatic hydrocarbon groups may be linked with each other by an alkylene group or an alkylidene group other than the cycloaliphatic hydrocarbon group.

The epoxy equivalent of the epoxy resin (A) is not particularly limited, but usually 200 to 3
From the viewpoint that the effect of the present invention is remarkable, it is preferably 00 g / eq, and particularly preferably 220 to 280 g / eq.

The epoxy resin (A) used in the present invention may have a Gardner color number of 10 or less, and the method for adjusting the Gardner color number of the epoxy resin (A) to the range is not particularly limited. However, for example, a preferred method is a method of producing a raw material phenol resin by polyaddition reaction of a phenol with an unsaturated alicyclic hydrocarbon compound in the presence of an acidic ion exchange resin, and then reacting with epihalohydrin. Can be mentioned.

The reaction conditions for producing the raw material phenol resin differ depending on the type of acidic ion exchange resin used, and can be set arbitrarily, but in order to obtain a favorable color epoxy resin, it is usually at 40 to 80 ° C. for 2 hours. ~ 60 hours range,
Specifically, for example, in the case of using a strongly acidic ion exchange resin having a sulfonic acid group, which will be described in detail below, 60 to 80
It is preferable to carry out the reaction in the range of ° C.

After completion of the reaction, the desired raw material phenol resin can be obtained by removing the catalyst by centrifugation and filtration and then concentrating the reaction solution.

The acidic ion exchange resin used here is not particularly limited, and examples thereof include a strong acidic ion exchange resin having a sulfonic acid group. As the strongly acidic ion exchange resin having a sulfonic acid group, specifically, a resin obtained by copolymerizing an olefinic hydrocarbon monomer and a crosslinking agent is usually used. The olefin hydrocarbon monomer is, for example, an olefin containing a functional group such as an acrylic acid derivative, or an olefin having no functional group such as styrene, and the cross-linking agent is divinylbenzene, or at least a terminal thereof. Aliphatic compounds with two double bonds are mentioned. In order to smoothly carry out the reaction and obtain a raw material phenol resin having a favorable hue, the acidic ion-exchange resin has a crosslinking degree of 5 to 30%, divinylbenzene is used as a crosslinking agent, and its porosity is 20%. ~ 60
%, And the average pore size is preferably 60 to 500 angstrom. Specific examples that satisfy these conditions include "K2411" manufactured by Bayer and "K2611" manufactured by Bayer.

Although the phenols are not particularly limited, for example, phenol compounds such as phenol, cresol, catechol, mononaphthol, dinaphthol, etc.,
Bisphenol-based compounds such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD,
Novolak resins such as phenol novolac, cresol novolac, mononaphthol novolac, dinaphthol novolac, bisphenol A novolac and bisphenol F novolac, or bis- (2,7-dihydroxynaphthyl) -1,1-methane, (2-hydroxynaphthyl) ) -1- (2,7-Dihydroxynaphthyl) -1
-Methane, bis- (2-hydroxynaphthyl) -1,1
-A polyfunctional phenol compound such as methane can be used. Among them, a bisphenol compound is preferable because it has excellent heat resistance and low water absorption, which are particularly excellent in semiconductor encapsulation applications.

The unsaturated alicyclic hydrocarbon compound is not particularly limited, but is preferably one having a cyclohexane ring or a cyclohexene ring, for example, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, 3a,
Mention may be made of 4,7,7a-tetrahydroindene, dicyclopentadiene, α-pinene, β-pinene or limonene.

The molecular weight and the molecular weight of the raw material phenol resin thus obtained are not particularly limited, but the number average molecular weight is preferably 320 to 800, particularly preferably 320 to 600. Is desirable.

Next, the method for producing an epoxy resin from the starting phenols will be described in detail, but the method for producing the epoxy resin used in the present invention is not limited to these. That is,
For example, 0.5 to 1 with respect to the hydroxyl group in the raw material phenols
Add 5 equivalents of epihalohydrin and dissolve. At this time, epichlorohydrin is most commonly used as epihalohydrin, but epiyohydrin, epibromhydrin, β-methylepichlorohydrin and the like may be used, and the epihalohydrin is not limited thereto. Also,
Then 0.8 to 1.2 equivalents to hydroxyl groups of 10 to 50
% NaOH aqueous solution is added dropwise at a temperature of 50 to 80 ° C. over 3 to 5 hours. After the dropping, stirring is continued for 0.5 to 2 hours at that temperature, and after standing, the lower layer saline is discarded. Then, excess epihalohydrin is recovered by distillation to obtain a crude resin. To this, an organic solvent such as toluene or MIBK is added, and washed with water-dehydration-
The desired epoxy resin can be obtained through the filtration-desolvation step. The epoxy equivalent of the epoxy resin thus obtained is not particularly limited, but is preferably 200 to 300 g / eq, and particularly 230 to 28.
It is preferably 0 g / eq.

In the above reaction, a solvent such as dioxane or DMSO may be used in combination during the reaction for the purpose of reducing the amount of impurity chlorine.

As the curing agent used as the component (b) in the epoxy resin composition of the present invention, all compounds which are commonly used as curing agents for epoxy resins can be used, and fats such as diethylenetriamine and triethylenetetramine can be used. Aromatic amines such as group amines, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, phenol novolac resins, orthocresol novolac resins, bisphenol A novolac resins, bisphenol F novolac resins, phenols-dicyclopentadiene addition type resins,
Dihydroxynaphthalene novolak resin, xylidene-bonded phenols, naphthol resins, polyamide resins and modified products thereof, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride and other acid anhydrides Examples include latent hardeners such as system hardeners, dicyandiamide, imidazole, BF3 -amine complexes, guanidine derivatives and the like.

Among these, in laminated plate applications,
Dicyandiamide, phenol novolac resin, and bisphenol A novolac resin are preferred.

The amount of these curing agents used may be any amount as long as it cures the epoxy resin, and is not particularly limited, but preferably the number of epoxy groups contained in one molecule of the epoxy resin used and the curing agent. It is an amount in which the number of active hydrogens in the vicinity is equivalent.

When each of the compounds listed above is used as a curing agent, a curing accelerator can be used appropriately.

The curing accelerator of the component (c) used in the epoxy resin composition of the present invention may be any one that promotes the reaction between the epoxy group and the phenolic hydroxyl group, and examples thereof include tertiary phosphines and imidazole. , Tertiary amines and the like can be used. Specifically, examples of the tertiary phosphines include triethylphosphine,
Preferable examples include tributylphosphine and triphenylphosphine. Preferred examples of the tertiary amine include dimethylethanolamine, dimethylbenzylamine, 2,4,6-tris (dimethylamino) phenol, and 1,8-diazabicyclo [5.4.0] undecene. it can.

Examples of the imidazoles include 2-
Ethyl-4-methylimidazole, 2,4-dimethylimidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2 -Isopropylimidazole, 1
-Cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 1-benzyl-2 -Methylimidazole, 2
-Phenyl-4-methylimidazole, 2-phenyl-
Examples include 4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Particularly preferable examples of the component (c) include 2-methylimidazole, diazabicycloundecene (DBU), triphenylphosphine, dimethylbenzylamine, and mixtures thereof.

In the epoxy resin composition of the present invention, it goes without saying that the above epoxy resin (A) may be used alone as the epoxy resin component, but it may be used in combination with other epoxy resins. Good. In particular, in laminated plate applications, it is usually used in combination with other epoxy resins, and the proportion of the other epoxy resins used is usually in the range of 10 to 50% by weight with respect to the total of the epoxy resin (A). Is mentioned.

Other epoxy resins include, for example,
Bisphenol type epoxy resin, halogenated bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, or a mixture thereof, or bisphenol type epoxy resin or halogenated bisphenol type epoxy resin,
Examples thereof include a copolymer type epoxy resin obtained by reacting a phenol novolac type epoxy resin or a cresol novolac type epoxy resin with bisphenol.

[0030]

The present invention will be described in detail below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these.

[Synthesis Example 1] 500 m equipped with a condenser
Dry sulfonic acid group-containing strongly acidic ion exchange resin (“K2411” manufactured by Bayer Co., degree of crosslinking: 7-1)
3, porosity: 25%, average pore size: 400 angstrom, surface area: 25 m ² / g), 8 g was charged, and 80 ° C.
At several times, the solution was washed several times with a several head volume phenol until the effluent was clean. Next, 320 g of phenol was added to the washed ion exchange resin, and 45 g of dicyclopentadiene was added dropwise at 60 ° C. for 6 hours. Then, the temperature was raised to 80 ° C. and the mixture was heated and stirred for 20 hours. After the reaction was completed, the catalyst was filtered. The obtained clear filtrate was distilled under reduced pressure to obtain 102 g of phenol resin.

100 g of the obtained solid was dissolved in 235 g of epichlorohydrin and 20% NaOH 1 was added at 70 ° C.
27 g was added over 3 hours. Then, the mixture was stirred at the same temperature for 1 hour, allowed to stand still for liquid separation, and the saline layer was discarded. Then, excess epichlorohydrin was recovered by distillation, and MIBK1
It was dissolved in 50 g, washed with water, dehydrated and filtered to obtain 130 g of a pale yellow epoxy resin A.

The softening point of the obtained epoxy resin was 54 ° C. The epoxy equivalent determined by perchloric acid titration was 251 g / eq. Also, the gadner color of the resin was measured and found to be 4-5. Further gel
Mation chromatography (hereinafter referred to as GPC)
The number average molecular weight of this resin was found by analysis to be 48
It was 3.

[Synthesis Example 2] The brown epoxy resin B132 was reacted in the same manner as in Synthesis Example 1 except that the reaction temperature of phenol and dicyclopentadiene was changed to 100 ° C.
g was obtained.

The softening point of the obtained epoxy resin B is 54 ° C.
Met. The epoxy equivalent determined by perchloric acid titration was 252 g / eq. Also, resin guard
The color was measured and found to be 8-9. Further GPC
The number average molecular weight of this resin was found by analysis to be 49
It was 5.

[Synthesis Example 3] Sulfonic acid group-containing strongly acidic ion
Containing sulfonic acid groups instead of the resin K2411
Strongly acidic ion exchange resin (Bayer's "K2611",
Crosslinking degree: 14 to 25, porosity: 50%, average pore diameter:
650 Å, surface area: 40 m ²/ G)
The reaction was carried out by the same method as in Synthesis Example 1 except that
130 g of Poxy resin C was obtained.

The softening point of the obtained epoxy resin was 54 ° C. The epoxy equivalent C determined by perchloric acid titration was 251 g / eq. Also, resin guard
The color was measured and found to be 9-10. Further GP
When the number average molecular weight of this resin was determined by C analysis, it was 4
It was 87.

[Synthesis Example 4] The reaction was carried out in the same manner as in Example 1 except that a boron trifluoride phenol complex was used in place of the ion exchange resin and the water in the system was removed by azeotropic distillation with toluene. This was performed to obtain 128 g of a blackish brown epoxy resin D.

The softening point of the obtained epoxy resin D is 59 ° C.
Met. The epoxy equivalent determined by perchloric acid titration was 268 g / eq. Also, resin guard
The color was measured and found to be 16-17. Furthermore G
It was 604 when the number average molecular weight of this resin was calculated | required by PC analysis.

Examples 1 to 4 and Comparative Examples 1 to 2 Epoxy resins A to D shown in Tables 1 and 2 were separately dissolved in methyl ethyl ketone and then hardener dicyandiamide dissolved in methyl cellosolve in advance. Then, a curing accelerator 2-ethyl-4-methylimidazole was added to obtain an epoxy resin composition having a nonvolatile content (NV) of 55%. At this time, the amount of the curing agent was set to be 0.5 equivalent to the epoxy group in the polyfunctional epoxy resin.

The Gardner color number of this epoxy resin composition was measured. The results are shown in Tables 1 and 2. After that, each of the epoxy resin compositions was used to impregnate a glass cloth WE-18K-104-BZ2 (manufactured by Nitto Boseki Co., Ltd.) as a base material, and dried at 160 ° C. for 3 minutes to obtain a resin content of 40%. A prepreg was produced. Next, nine obtained prepregs were stacked and cured under the conditions of a pressure of 40 Kg / cm ² , a heating temperature of 170 ° C. and a heating time of 120 minutes to produce a laminated plate.

[0042]

[Table 1]

[0043]

[Table 2] (In Tables 1 and 2, "epoxy resin E" has an epoxy equivalent of 545 g / eq and a bromine content of 23%. Each evaluation test is as follows.

Glass transition temperature: measured by the DMA method. Water absorption treatment conditions: Conditions where (time / temperature / humidity) is (6/120/100). Solder resistance test condition: 260 ° C., 20 seconds Color tone: The appearance of the obtained laminated plate was visually evaluated. ◎:
It has a yellowish tinge, but has no blackness and has an excellent transparency. ◯: There is a slight brownness, but there is a transparent feeling. X: Dark brown and completely transparent. )

[0045]

EFFECTS OF THE INVENTION According to the present invention, it has an excellent appearance when processed in various applications such as electric laminates, insulating powder coatings and coatings, and has both excellent high heat resistance and low water absorption. An epoxy resin composition can be provided. In addition, the epoxy resin composition of the present invention is excellent in appearance, high heat resistance and low water absorption, especially in electric laminate applications.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 59/08 C08G 59/24 C08G 61/02 C08J 5/24

Claims (5)

(57) [Claims] 1. An epoxy resin having a structure in which an aromatic hydrocarbon group is bonded with a cycloaliphatic hydrocarbon group as a knot group, and the aromatic hydrocarbon group has a glycidyloxy group as a substituent on the aromatic hydrocarbon group. And an epoxy resin (A) having a Gardner color number of 10 or less in a 50 wt% non-volatile dioxane solution, a curing agent (B), and a curing accelerator (C) as essential components. And an epoxy resin composition. 2. The composition according to claim 1, wherein the cyclic aliphatic hydrocarbon group has a cyclohexane ring or a cyclohexene ring in its skeleton. 3. An epoxy resin (A) obtained by reacting a hydroxyl group-containing compound with an unsaturated cyclic hydrocarbon compound in the presence of an acidic ion exchange resin, and a phenol resin obtained by reacting epihalohydrin. Claim 1
The composition as described. 4. The composition according to claim 3, wherein the unsaturated cyclic hydrocarbon compound has a cyclohexane ring or a cyclohexene ring. 5. An epoxy resin composition for a laminated board, which further comprises a halogenated epoxy resin in the composition according to any one of claims 1 to 4.