JPH06212056A - Tough phenol resin - Google Patents

Abstract

PURPOSE:To obtain the subject composition useful as a curing agent, having excellent fluidity and toughness by blending a novolak type phenol resin with an acrylonitrile-butadiene copolymer rubber, a silicone compound and a cross- linking catalyst in a specific ratio in a molten state. CONSTITUTION:(A) 99-50 pts.wt. of a novolak type phenol resin is blended with (B) 1-50 pts.wt. of acrylonitrile-butadiene copolymer rubber, (C) 0.1-20 pts.wt. of a silicon compound (e.g. cyclic polysiloxane) containing two or more SiH groups in the molecule, its derivative compound or a polymer derived from the silicone compound, (D) 0.0001-3 pts.wt. of a cross-linking catalyst and preferably (E) 0.1-10 pts.wt. of one or more compatibilizing agents selected from an epoxy-containing modified polyethylene-based resin, a hydrogenated epoxy-containing modified styrene-butadiene-styrene block copolymer, etc., in a molten state and the rubber part is dynamically cross-linked to give the objective composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenolic resin molding material, a base resin for a phenolic resin laminate, or a tough phenolic resin preferably used as a curing agent for epoxy resin molding materials and epoxy powder coatings.

[0002]

2. Description of the Related Art Phenolic resin has various characteristics such as good electric insulation, sufficient mechanical strength, good heat resistance, low coefficient of thermal expansion, flame retardancy, and low cost. Therefore, it is widely used for electrical or mechanical parts, but it has the drawback of being brittle. In order to improve this drawback, polysulfone, polycarbonate, polyester-
IPNs of an amorphous thermoplastic resin such as polycarbonate and a certain type of modified phenolic resin have been investigated, but these products are not sufficiently improved in toughness, resulting in poor fluidity and extremely unsatisfactory. It was a thing. In addition, blending with a rubber such as NBR, which has a good compatibility with the phenol resin, is being studied. With this method, although the toughness of the phenol resin can be achieved, if the rubber is added to such an extent that the toughness is effective, the fluidity is improved. However, there has been no problem in the prior art in which fluidity and toughness are compatible with each other.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a tough phenol resin having good fluidity, which is not available in the prior art and which is useful for molding materials or laminated plates.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have found that silicone compounds having two or more SiH groups in the molecule have a function of selectively crosslinking a rubber having an unsaturated double bond. Focusing on this point, a silicone compound having two or more SiH groups in the molecule is used as a cross-linking agent, and a specific compatibilizer is preferably added to the novolac type phenol resin and acrylonitrile-butadiene copolymer rubber, and the mixture is melt-kneaded. By using the dynamic vulcanization method, a blended product in which vulcanized rubber is uniformly dispersed is obtained, and the blended product is used as a phenol resin molding material, a base resin of a phenol resin laminate, an epoxy resin molding material, or an epoxy powder. It was found that when used as a curing agent for paints, tough properties can be obtained without impairing fluidity, and the present invention has been completed.

That is, the present invention comprises: (a) a novolac type phenolic resin 99 to 50 parts by weight (b) an acrylonitrile-butadiene copolymer rubber 1 to 50 parts by weight (c) a silicone compound having two or more SiH groups in the molecule. And / or a derivative compound thereof and / or a polymer derived from the silicone compound 0.1 to 20 parts by weight (d) a crosslinking catalyst 0.001 to 3 parts by weight, or (a) a novolac type phenol resin 99 to 50 parts by weight ( b) Acrylonitrile-butadiene copolymer rubber 1 to 50 parts by weight (c) Silicone compound having two or more SiH groups in the molecule and / or a derivative compound thereof and / or a polymer derived from the silicone compound 0.1 to 20 (D) Modified polyethylene resin having an epoxy group and modified styrene-butadiene-styrene block having an epoxy group It is selected from a combined hydrogenated product, a modified ethylene-α-olefin-non-conjugated diene copolymer rubber having an epoxy group or an amino group, and an acrylonitrile-butadiene copolymer rubber having an epoxy group or an amino group. At least one compatibilizing agent 0.1 to 10 parts by weight (e) crosslinking catalyst 0.001 to 3 parts by weight are blended, and the rubber portion is dynamically crosslinked by melt kneading. The present invention relates to a tough phenol resin having good fluidity, which is useful for applications such as molding materials and laminated plates.

The novolac type phenolic resin used as the raw material of the present invention is not particularly limited and is commercially available. For example, the ratio of phenols to formalin is 0.5 to phenol.
The mixture was charged into a reaction kettle at a compounding ratio of 1.0, and a catalyst such as oxalic acid, hydrochloric acid, sulfuric acid, and toluenesulfonic acid was added, and the mixture was heated and refluxed for an appropriate time. For removal, it can be obtained by vacuum dehydration or static dehydration, and further removing remaining water and unreacted phenols. The co-condensed phenol resin obtained by using these resins or a plurality of raw material components may be used alone or in combination of two or more kinds.

The acrylonitrile / butadiene copolymer rubber used as a raw material of the present invention is not specified, but is generally commercially available. It is obtained by emulsion polymerization of a mixture of an acrylonitrile monomer and a butadiene monomer. can get. Acrylonitrile-butadiene copolymer rubber used in the present invention is preferably a polymer rubber having an acrylonitrile content of 15 to 50%.

S in the molecule used as the raw material of the present invention
A silicone compound having two or more iH groups and / or a derivative compound thereof and / or a polymer derived from the silicone compound is used as a crosslinking agent for rubber. This utilizes a selective addition reaction of SiH groups to unsaturated hydrocarbons. In order to be a cross-linking agent, addition to two or more molecules of rubber is a necessary condition, so it is necessary to have two or more SiH groups in the molecule. Specific examples of compounds include cyclic polysiloxanes (1), linear polysiloxanes (2), and tetrahedral siloxanes (3) as shown below.
A compound having the structure of is typical. Moreover, you may use the compound and / or polymer derived from this compound.

[0009]

[Chemical 1]

M is an integer of 0 to 20, n is an integer of 0 to 50, R is hydrogen, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, and at least one of which is bonded to a silicon atom. There are two or more silicon atoms in which R is hydrogen in the molecule.

The cross-linking catalyst used as the raw material of the present invention refers to all catalysts that accelerate the hydrosilylation reaction.
As the catalyst, a noble metal catalyst or a peroxide is often used. Chloroplatinic acid is the most popular catalyst. The compatibilizing agent used as the raw material of the present invention is not particularly limited and is commercially available, and the novolac type phenol resin and acrylonitrile
It has the function of lowering the interfacial tension with the butadiene copolymer rubber and making the dispersed particle size of the acrylonitrile-butadiene copolymer rubber, which is an island component, finer. The compatibilizer of the present invention is obtained by copolymerizing or grafting a compound having an epoxy group or an amino group.

The modified phenol resin of the present invention comprises 99 to 50 parts by weight of a novolac type phenol resin, 1 to 50 parts by weight of an acrylonitrile-butadiene copolymer rubber, a silicone compound having two or more SiH groups in the molecule and / or a derivative thereof. Compound and / or polymer derived from the silicone compound 0.1 to 20 parts by weight, crosslinking catalyst 0.001
To 3 parts by weight, more preferably, a modified polyethylene resin having an epoxy group, a hydrogenated product of a modified styrene-butadiene-styrene block copolymer having an epoxy group, a modified ethylene-α having an epoxy group or an amino group.
A pressure kneader containing 0.1 to 10 parts by weight of at least one compatibilizing agent selected from olefin-non-conjugated diene copolymer rubber and acrylonitrile-butadiene copolymer rubber having an epoxy group or an amino group. , A Banbury mixer or a twin-screw kneader. In the modified phenol resin of the present invention, the novolac type phenol resin and the acrylonitrile / butadiene copolymer rubber are 99: 1 to 50:50 parts by weight, preferably 90:10 to 70:30 parts by weight, and more preferably 85:15. It is compounded in the range of 75:25 parts by weight. When the compounding ratio of the acrylonitrile / butadiene copolymer rubber is less than 1 part by weight, the effect of improving the properties such as bending strength and impact resistance becomes insufficient, and when it exceeds 50 parts by weight, the fluidity is lowered. Further, a silicone compound having two or more SiH groups in the molecule and / or a derivative compound thereof and / or a polymer derived from the silicone compound is 0.1
-20 parts by weight, preferably 0.5-10 parts by weight.

The mixing ratio of the silicone compound having two or more SiH groups in the molecule and / or its derivative compound and / or the polymer derived from the silicone compound is
If it is less than 0.1 parts by weight or more than 20 parts by weight, crosslinking of the acrylonitrile-butadiene copolymer rubber will be insufficient and the effect of improving properties such as bending strength and impact resistance will be insufficient. Further, the crosslinking catalyst can be optionally added within the range of 0.001 to 3 parts by weight. If it is less than 0.001, the crosslinking does not proceed at a practical speed. Further, if it exceeds 5 parts, there is no effect of increasing the amount. Here, the degree of cross-linking is 1 g of the modified phenolic resin with a Soxhlet extractor using boiling xylene.
Reflux for 0 hours, filter the residue through a wire mesh of 80 mesh, and dry weight (g) of insoluble matter remaining on the mesh /
It can be determined by multiplying the weight ratio of the acrylonitrile-butadiene copolymer rubber contained in 1 g of the modified phenolic resin by 100 times, and this value is 30%, preferably 50% or more (however, insoluble inorganic fillers and the like are insoluble. It is preferable to vulcanize so that the components are not included in this).

In addition to the above-mentioned components, a modified polyethylene resin having an epoxy group, a hydrogenated product of a modified styrene-butadiene-styrene block copolymer having an epoxy group, a modified ethylene-α · having an epoxy group or an amino group. 0.1 to 10 parts by weight of at least one compatibilizer selected from olefin-non-conjugated diene copolymer rubber and acrylonitrile-butadiene copolymer rubber having an epoxy group or an amino group may be blended. preferable. By adding the compatibilizer, the acrylonitrile-butadiene copolymer rubber, which is an island component, becomes more finely dispersed, and the effect of improving properties such as bending strength and impact resistance becomes remarkable. If the compounding amount of the compatibilizer is less than 0.1 part by weight, the effect of improving properties such as bending strength and impact resistance tends to be small, and if it exceeds 10 parts, the effect of increasing the amount is not obtained.

[0015]

【Example】

<< Example 1 >> Novolac-type phenol resin (Sumilite Resin R PR-51470, manufactured by Sumitomo Dures Co., Ltd.) 8
After sufficiently dry blending 0 part by weight and 20 parts by weight of an acrylonitrile / butadiene copolymer rubber (JSR N230S [bonded acrylonitrile content: 35% by weight] manufactured by Japan Synthetic Rubber Co., Ltd.), the resin was dried using a biaxial kneader. Warm 8
A thermoplastic composition before melt-kneading under extrusion and dynamic vulcanization under conditions of 0 to 120 ° C. was obtained and pelletized. As a cross-linking agent A, 1,3,5,7-
0.5 parts by weight of tetramethylcyclotetrasiloxane (manufactured by Toray Dow Corning Silicone Co., Ltd.) and 0.05 parts by weight of chloroplatinic acid (H ₂ PtCl ₂ .6H ₂ O) as a crosslinking catalyst were added and blended again. Resin temperature 80-120 using shaft kneader
A modified phenolic resin A which was kneaded at a temperature of ℃ and dynamically vulcanized was obtained. 40 parts by weight of the modified phenolic resin A thus obtained, 7 parts by weight of hexamine as a curing agent, and 53 parts by weight of glass fiber as a reinforcing material were mixed and roll-kneaded to obtain a molding material. After that, molding was carried out under the condition of 175 ° C. for 3 minutes to evaluate the moldability and the bending strength and the Charpy impact strength of the obtained test piece. The evaluation results are shown in Table 1.

Example 2 Cashew-modified phenolic resin (Sumilite Resin R PR-1 manufactured by Sumitomo Dures Co., Ltd.)
2687) 80 parts by weight, acrylonitrile-butadiene copolymer rubber (manufactured by Japan Synthetic Rubber Co., Ltd., JSR N23)
0S [bound acrylonitrile content: 35% by weight]) 2
After sufficiently dry blending 0 part by weight, a thermoplastic composition before melt-kneading and extrusion dynamic vulcanization is obtained by using a twin-screw kneader under conditions such that the resin temperature is 80 to 120 ° C. and pelletizing this. did. As a cross-linking agent to this pellet 1,
1,3,3-Tetramethylditetrasiloxane (Toray
0.5 parts by weight of Dow Corning Silicone Co., Ltd.,
Chloroplatinic acid (H ₂ PtCl ₂ · 6H ₂ O) 0.05 as crosslinking catalyst B
Add 2 parts by weight of the mixture and use the twin-screw kneader again to make the resin temperature 8
A modified phenolic resin B which was kneaded at 0 to 120 ° C. and dynamically vulcanized was obtained. 40 parts by weight of the modified phenolic resin B thus obtained, 7 parts by weight of hexamine as a curing agent, and 53 parts by weight of glass fiber as a reinforcing material are blended,
A molding material was obtained by roll kneading. Then 17
Molding was carried out under the conditions of 5 ° C. for 3 minutes, and the moldability was evaluated, and the bending strength and the Charpy impact strength of the obtained test pieces were evaluated. The evaluation results are shown in Table 1.

Example 3 Novolac-type phenol resin (Sumilite Resin R PR-5 manufactured by Sumitomo Dures Co., Ltd.)
1470) 80 parts by weight, acrylonitrile / butadiene copolymer rubber (manufactured by Japan Synthetic Rubber Co., Ltd., JSR N23)
0S [bound acrylonitrile content: 35% by weight]) 2
After sufficiently dry blending 0 part by weight and 3 parts by weight of an epoxy-modified styrene-ethylene / butylene-styrene block copolymer (Tuftec R Z-514 manufactured by Asahi Kasei Co., Ltd.), a resin temperature of 80 to 80 was obtained using a biaxial kneader. A thermoplastic composition before melt-kneading and extrusion dynamic vulcanization under conditions of 120 ° C. was obtained and pelletized. 0.5 parts by weight of 1,3,5,7-tetramethylcyclotetrasiloxane (manufactured by Toray Dow Corning Silicone Co., Ltd.) as a crosslinking agent A, and chloroplatinic acid (H ₂ PtCl ₂ 6H ₂ O) (0.05 parts by weight) was added and blended again, and the mixture was kneaded again using a twin-screw kneader to a resin temperature of 80 to 120 ° C. to obtain a dynamically vulcanized modified phenolic resin C. 40 parts by weight of the modified phenolic resin C thus obtained, 7 parts by weight of hexamine as a curing agent, and 53 parts by weight of glass fiber as a reinforcing material were mixed and roll-kneaded to obtain a molding material. After that, molding was carried out under the condition of 175 ° C. for 3 minutes to evaluate the moldability and the bending strength and the Charpy impact strength of the obtained test piece. The evaluation results are shown in Table 1.

Comparative Example 1 Novolak type phenolic resin (Sumilite Resin R PR-5 manufactured by Sumitomo Dures Co., Ltd.)
1470) 40 parts by weight, 7 parts by weight of hexamine as a curing agent, and 53 parts by weight of glass fiber as a reinforcing material were blended, roll-kneaded in the same manner as in Example 1, and the characteristics were evaluated after molding. The evaluation results are shown in Table 1. << Comparative Example 2 >> Novolac-type phenol resin (Sumilite Resin R PR-51470, manufactured by Sumitomo Dures Co., Ltd.) 8
0 parts by weight, 20 parts by weight of acrylonitrile-butadiene copolymer rubber (manufactured by Japan Synthetic Rubber Co., Ltd., JSR N230S [bound acrylonitrile content: 35% by weight]), epoxy-modified styrene-ethylene / butylene-styrene block copolymer ( Asahi Kasei Corporation Tuftec R Z-5
14) After sufficiently dry blending 3 parts by weight, melt kneading is carried out using a twin-screw kneader under conditions such that the resin temperature is 80 to 120 ° C., and this is pelletized and modified phenol resin D
Got Modified phenol resin D thus obtained
40 parts by weight, 7 parts by weight of hexamine as a curing agent and 53 parts by weight of glass fiber as a reinforcing material were blended, roll-kneaded in the same manner as in Example 1, and the characteristics were evaluated after molding.
The evaluation results are shown in Table 1. << Comparative Example 3 >> Novolak type phenolic resin (Sumilite Resin R PR-51470, manufactured by Sumitomo Dures Co., Ltd.) 4
After sufficiently dry blending 0 part by weight and 60 parts by weight of acrylonitrile-butadiene copolymer rubber (manufactured by Japan Synthetic Rubber Co., Ltd., JSR N230S [bound acrylonitrile content: 35% by weight]), the resin was dried using a biaxial kneader. Warm 8
A thermoplastic composition before melt-kneading under extrusion and dynamic vulcanization under conditions of 0 to 120 ° C. was obtained and pelletized. As a cross-linking agent A, 1,3,5,7-
0.5 parts by weight of tetramethylcyclotetrasiloxane (manufactured by Toray Dow Corning Silicone Co., Ltd.) and 0.05 parts by weight of chloroplatinic acid (H ₂ PtCl ₂ .6H ₂ O) as a crosslinking catalyst were added and blended again. Resin temperature 80-120 using shaft kneader
A modified phenolic resin E was obtained which was kneaded at a temperature of ℃ and dynamically vulcanized. 40 parts by weight of the modified phenolic resin E thus obtained, 7 parts by weight of hexamine as a curing agent and 53 parts by weight of glass fiber as a reinforcing material were blended, roll-kneaded in the same manner as in Example 1, and evaluated for its characteristics after molding. I went. The evaluation results are shown in Table 1.

[0019]

* 1 Moldability: The surface condition of the test piece after molding and the filling condition of the molding material into the test piece mold were visually observed and evaluated. ◯: Appearance of test piece: Good. Filling state in the mold: Good Δ: Appearance of test piece: somewhat uneven. Filling state into mold: last minute ×: Appearance of test piece: unevenness. Filling state in mold: occurrence of non-filling * 2 Bending strength: Measured according to JIS K6911. * 3 Charpy impact strength: Measured according to JIS K6911.

[0021]

As is apparent from Tables 1 and 2, when the modified phenolic resin of the present invention is used as a phenolic resin molding material, a base resin of a phenolic resin laminate, an epoxy resin molding material, or a curing agent for an epoxy powder coating material. A composition having tough properties is obtained.

Claims (2)

[Claims] 1. A novolac type phenol resin 99 to 50 parts by weight (b) 1 to 50 parts by weight of an acrylonylolyl-butadiene copolymer rubber (c) A silicone compound having two or more SiH groups in the molecule, and / or the same. Derivative compound and / or polymer derived from the silicone compound 0.1 to 20 parts by weight (d) Crosslinking catalyst 0.001 to 3 parts by weight were blended and melt-kneaded to dynamically crosslink the rubber part. A tough phenolic resin characterized by 2. (a) Novolac type phenolic resin 99 to 50 parts by weight (b) Acrylonitrile-butadiene copolymer rubber 1 to 50 parts by weight (c) Silicone compound having two or more SiH groups in the molecule and / or the same. Derivative compound and / or polymer derived from the silicone compound 0.1 to 20 parts by weight (d) Hydrogenation of modified polyethylene resin having epoxy group, modified styrene-butadiene-styrene block copolymer having epoxy group , A modified ethylene-α-olefin-non-conjugated diene copolymer rubber having an epoxy group or an amino group, and a modified acrylonitrile-butadiene copolymer rubber having an epoxy group or an amino group. The above compatibilizing agent 0.1 to 10 parts by weight (e) crosslinking catalyst 0.001 to 3 parts by weight should be blended and melt-kneaded. A tough phenolic resin whose rubber part is dynamically cross-linked.