JP4501736B2 - Phenolic resin molding material - Google Patents

Description

  The present invention relates to a phenol resin molding material.

Phenolic resin molding materials are excellent in mechanical strength, heat resistance, dimensional stability, moldability, etc., and have a track record of being used for a long time in key industries such as automobiles, electricity, and electronics. In recent years, replacement of metal parts with high-strength phenolic resin products reinforced with glass fibers has made it possible to significantly reduce costs, so active replacement studies have been conducted. Therefore, in recent years, the level of demand for phenolic resin molding materials has become increasingly sophisticated, and one of them is the ease of treatment of burrs that adhere to the copper surface during copper insert molding.
The burrs adhering to the copper surface must be completely removed depending on the application of the product, but if the adhesion between the copper and the resin is high and cannot be easily removed, there is a problem that the removal work is costly. is there.

  Although many studies have not been made on the method for facilitating the treatment of burrs adhered to the copper surface, it is generally necessary to remove factors that increase the adhesion to copper. . For example, it should be noted that a resin having an epoxy group and a melamine derivative, which are considered to improve adhesion to copper, are not blended. In addition, a technique has been disclosed that can easily remove burrs by applying a mold release agent used to improve mold releasability (see, for example, Patent Document 1). However, no studies have been made to find out among these release agent types, particularly those that relieve the adhesion between the copper and the resin.

JP 2002-317100 A

  An object of the present invention is to maintain the mechanical strength of a molded product, which is an originally required characteristic, while maintaining low adhesion between copper and resin, and facilitating removal of burrs attached to the copper surface after molding. The object is to provide a resin molding material.

Such an object is achieved by the following present inventions (1) to ( 2 ).
(1) A phenolic resin containing a resol type phenolic resin, a fatty acid aluminum selected from aluminum stearate, 12 hydroxyaluminum stearate, aluminum behenate and aluminum montanate , and glass fibers and powdered inorganic fillers as inorganic fillers A phenolic resin molding material comprising:
(2) The phenol resin molding material as described in (1) whose content of the said fatty-acid aluminum is 0.1-10 weight part with respect to 100 weight part of said phenol resins.

According to the present invention, while maintaining the mechanical strength of the obtained molded product, the adhesion between the copper and the resin is low, and the phenol resin molding material that can easily remove the burrs attached to the copper surface after molding. Can be provided.
Moreover, content of fatty acid aluminum is 0.1-1 with respect to 100 parts by weight of phenol resin.
In the case of 0 part by weight, the adhesion between the copper and the resin can be further lowered.
Further, by including resole phenolic resin in at least a part of phenolic resin, further copper - it is possible to lower the adhesion between the resin.

Hereinafter, the phenol resin molding material of the present invention (hereinafter sometimes simply referred to as “molding material”) will be described.
The molding material of the present invention is characterized by containing a phenol resin and fatty acid aluminum.

In the molding material of the present invention, a phenol resin containing a resol type phenol resin is used as the phenol resin.
When a novolac type phenol resin is used, hexamethylenetetramine is usually used as a curing agent. When hexamethylenetetramine is used, its content is not particularly limited, but it is preferably 10-30 parts by weight, more preferably 15-25 parts by weight, with respect to 100 parts by weight of the novolak type phenol resin. preferable. If the content of hexamethylenetetramine exceeds the above upper limit, the mechanical strength of the molded product may be reduced. If the content is less than the lower limit, the amount of molding shrinkage cannot be sufficiently reduced. Mechanical strength may decrease. In addition, when using a novolak type phenol resin and a resol type phenol resin together as a phenol resin, it can also be set as the composition which does not use a hexamethylenetetramine depending on the use ratio of a resol type phenol resin.

In the molding material of the present invention, at least a part of the phenol resin is a resol type phenol resin .
By using at least a part of the phenol resin as a resol type phenol resin, the adhesion between the copper and the resin can be lowered. The reason is not clear, but because the methylol group of the resol type phenolic resin acts on the copper surface, when hexamethylenetetramine is used, it suppresses the binding between the nitrogen compound and the copper surface caused by its decomposition. Conceivable.

  As the above-mentioned resol type phenol resin, any of a normal methylol type resol type phenol resin and a dimethylene ether type resol type phenol resin can be used.

  In the molding material of the present invention, when a resol type phenol resin is used, the content of the resol type phenol resin is not particularly limited, but the adhesion between the copper resin and the resin tends to decrease as the proportion of the resol type phenol resin increases. . However, since the resol type phenolic resin is more expensive than the novolac type phenolic resin, the total amount of the phenolic resin (including hexamethylenetetramine, if used) is 10 to 40 parts by weight. The part is preferably a resol type phenol resin.

  The content of the above phenol resin (including hexamethylenetetramine when a novolak type phenol resin is used) is not particularly limited, but is preferably 20 to 50% by weight, more preferably 25 to 40% by weight based on the entire molding material. Is preferred. If the content of the above components is less than the above lower limit value, the productivity at the time of molding material production and the mechanical strength of the molded product may decrease.If the above upper limit value is exceeded, the heat resistance, dimensional stability, etc. of the molded product may be reduced. The characteristics may be degraded.

The molding material of the present invention contains a fatty acid aluminum selected from aluminum stearate, aluminum 12 hydroxystearate, aluminum behenate, and aluminum montanate . Thereby, the adhesiveness between copper-resin falls and the removal removal of the burr | flash adhering to the copper surface after shaping | molding becomes easy. The reason is not clear, but some chemical action occurs between the aluminum part of fatty acid aluminum and the phenolic hydroxyl group of the phenolic resin, and it has the function of weakening the interaction between the phenolic hydroxyl group and copper. Guessed.

  Although content of the said fatty-acid aluminum is not specifically limited, 0.1-10 weight part is preferable with respect to 100 weight part of phenol resins (when it uses hexamethylenetetramine), 1-5 weight part is preferable. Is more preferable. If the content of fatty acid aluminum is less than the above lower limit value, the effect of removing burrs adhering to the copper surface after molding may be reduced, and if it exceeds the upper limit value, mechanical strength and formability may be reduced. .

  An inorganic filler can be further blended in the molding material of the present invention. Thereby, the mechanical characteristics, dimensional characteristics, etc. of the molded product can be improved.

The inorganic filler used in the molding material of the present invention is preferably a glass fiber and a powdery inorganic filler in combination. By blending glass fiber, high mechanical strength can be imparted to the molded product. Moreover, the dimensional accuracy of a molded product can be improved by mix | blending a powdery inorganic filler.
When the glass fiber and the powdery inorganic filler are used in combination, the respective characteristics can be improved in a balanced manner. The reason is presumed that the anisotropy generated in the molded product due to the orientation of the glass fibers is alleviated due to the influence of the powdery inorganic filler.

  Although it does not specifically limit as glass fiber used for the molding material of this invention, A thing with an average fiber diameter of 5-15 micrometers is preferable. The average fiber length is preferably 1 to 3 mm. By using the glass fiber in this range, workability at the stage of forming a molding material can be improved, and the mechanical strength of the obtained molded product can be improved. If the average fiber diameter is less than the lower limit, the effect of improving the mechanical strength may be reduced. When the above upper limit is exceeded, when a kneading roll is used during the production of the molding material, the followability to the roll is lowered, and kneading may not be performed sufficiently. When the average fiber length is less than the above lower limit value, the mechanical strength improvement effect may be reduced, and when the upper limit value is exceeded, the fiber is likely to break during roll kneading, and the mechanical strength improvement effect cannot be further expected. There is.

  Although content of the said glass fiber is not specifically limited, 25 to 60 weight% is preferable with respect to the whole molding material, and also 30 to 50 weight% is preferable. When the content is less than the lower limit, the effect of improving the mechanical strength may not be sufficient, and when the content exceeds the upper limit, workability at the molding material stage may be deteriorated.

Moreover, a powdery inorganic filler can be used for the molding material of this invention. The powdered inorganic filler is not particularly limited. For example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, calcined clay, unfired clay, wollastonite, talc, silica, diatomaceous earth, alumina, magnesium oxide, sulfuric acid Examples include barium and rock wool.
Among these, it is preferable to include at least one selected from fired clay, unfired clay, calcium carbonate, wollastonite, talc, and rock wool, and it is particularly preferable to use fired clay. Thereby, the said effect can be improved more.

  Although content of the said powdery inorganic filler is not specifically limited, 5 to 50 weight% is preferable with respect to the whole molding material, and also 10 to 35 weight% is preferable. If the content is less than the above lower limit value, the heat resistance and dimensional stability of the molded product may not be sufficient, and if the content exceeds the above upper limit value, the workability during the production of the molding material and the mechanical strength of the molded product may be insufficient. The improvement effect may be reduced.

  When the glass fiber and the powdery inorganic filler are used in combination, the total content is not particularly limited, but is preferably 50 to 80% by weight, more preferably 55 to 75% by weight based on the entire molding material. preferable. When the content of the glass fiber and the powdered inorganic filler is less than the lower limit, the effect of improving the mechanical strength may not be sufficient, and the dimensional change may be large. On the other hand, when the above upper limit is exceeded, workability at the molding material stage is lowered, and the resin content is relatively lowered, so that the effect of improving the mechanical strength may be lowered.

  In addition to the components described above, additives such as mold release agents, curing aids, and pigments can be added to the molding material of the present invention as long as the object of the present invention is not impaired.

A normal kneading method can be applied to the method for producing the molding material of the present invention.
For example, it can be obtained by adding phenol resin, fatty acid aluminum, hexamethylenetetramine, glass fiber, powdered inorganic filler, curing aid, pigment, mold release agent, mixing, melting and kneading, cooling and grinding. it can. The melt kneading can be performed by a kneading apparatus such as a kneading roll, a kneader, or a twin screw extruder alone or in combination with a kneading roll and another mixing apparatus.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

  Table 1 shows the composition and characteristics of Examples and Comparative Examples. All contents shown in Table 1 represent% by weight.

(Note to Table 1)
1. Ingredients (1) Novolac-type phenolic resin: “A-1082” (number average molecular weight 850) manufactured by Sumitomo Bakelite Co., Ltd.
(2) dimethylene ether type resol type phenol resin: “R-25” manufactured by Sumitomo Bakelite Co., Ltd.
(3) Glass fiber: “RES03-BM38” manufactured by Nippon Sheet Glass Co., Ltd. (chopped strand having an average fiber diameter of 11 μm and an average fiber length of 3 mm)
(4) Fired clay: “Pellstar 501” manufactured by Imeris
(5) Curing aid: “Kyowa Mug 30” manufactured by Kyowa Chemical
(6) Aluminum stearate (monosubstituted salt): Nitto Kasei Co., Ltd. “Al-St103”
(7) Aluminum stearate (disubstituted salt): Nitto Kasei Co., Ltd. “Al-St102”
(8) Aluminum 12-hydroxystearate (monosubstituted salt): “AS-6” manufactured by Nitto Kasei Co., Ltd.
(9) Aluminum behenate (monosubstituted salt): “AS-7” manufactured by Nitto Kasei Co., Ltd.
(10) Aluminum montanate (monosubstituted salt): “AS-8” manufactured by Nitto Kasei Co., Ltd.
(11) Release agent (stearic acid): manufactured by NOF Corporation “Stearic acid”
(12) Pigment: “Carbon Black # 750B” manufactured by Mitsubishi Chemical Corporation

2. Production of molding material (Example 1 )
19% by weight of novolak type phenolic resin, 8% by weight of dimethylene ether type resol type phenolic resin, 4% by weight of hexamethylenetetramine, 46% by weight of glass fiber as inorganic filler, 20% by weight of calcined clay, A composition was obtained by mixing 1% by weight of magnesium oxide as a curing aid, 1% by weight of aluminum stearate (monosubstituted salt), and 1% by weight of carbon black as a pigment.
The composition was melt-kneaded for about 10 minutes with a kneading roll at 80 to 90 ° C., cooled and pulverized to obtain a molding material.

(Example 2 )
A molding material was obtained in the same manner as in Example 1 except that aluminum stearate (monosubstituted salt) was replaced with aluminum stearate (disubstituted salt).

(Example 3 )
A molding material was obtained in the same manner as in Example 1 except that aluminum stearate (monosubstituted salt) was replaced with 12 hydroxyaluminum stearate (monosubstituted salt).

(Example 4 )
A molding material was obtained in the same manner as in Example 1 except that aluminum stearate (monosubstituted salt) was replaced with aluminum behenate (monosubstituted salt).

(Example 5 )
A molding material was obtained in the same manner as in Example 1 except that aluminum stearate (monosubstituted salt) was replaced with aluminum montanate (monosubstituted salt).

(Example 6 )
A molding material was prepared in the same manner as in Example 1 except that the amount of novolac type phenol resin was reduced to 16% by weight, hexamethylenetetramine was reduced to 3% by weight, and the amount of dimethylene ether type resol type phenol resin was increased to 12% by weight. Obtained.

(Example 7 )
A molding material was prepared in the same manner as in Example 1 except that the amount of novolak type phenolic resin was reduced to 13% by weight, hexamethylenetetramine was reduced to 2% by weight, and the amount of dimethylene ether type resol type phenolic resin was increased to 16% by weight. Obtained.

(Example 8 )
A molding material was obtained in the same manner as in Example 1 except that the novolak type phenol resin was reduced to 9% by weight, the dimethylene ether type resol type phenol resin was increased to 22% by weight, and hexamethylenetetramine was not added.

(Comparative Example 1)
26% by weight of novolak type phenolic resin, 5% by weight of hexamethylenetetramine, 46% by weight of glass fiber as inorganic filler, 20% by weight of calcined clay, 1% by weight of magnesium oxide as a curing aid, and mold release A composition was obtained by mixing 1% by weight of stearic acid as an agent and 1% by weight of carbon black as a pigment.
The composition was melt-kneaded for about 10 minutes with a kneading roll at 80 to 90 ° C., cooled and pulverized to obtain a molding material.

(Comparative Example 2)
A molding material was obtained in the same manner as in Comparative Example 1 except that the novolac type phenol resin was reduced to 19% by weight, the hexamethylenetetramine was reduced to 4% by weight, and 8% by weight of the dimethylene ether type resol type phenol resin was added. It was.

3. Sample Preparation and Evaluation Method (1) Charpy impact strength, bending strength, flexural modulus A sample was prepared by transfer molding (mold temperature: 175 ° C., curing time: 3 minutes), and performed according to JIS K 6911. .

(2) Copper plate peeling test Copper adhesion was measured by the evaluation method shown in Fig. 1 (copper plate peeling strength measurement method).
Using a sample that was sandwiched between two copper plates whose surfaces were uniformly polished with sandpaper having a roughness of 60, and molded and pressed under the following conditions, the copper and resin were separated by the peel strength of the two copper plates. The adhesion of was measured.
Evaluation sample Copper plate size: 4 cm × 10 cm × 0.3 cm thickness (effective bonding area 4 cm × 8 cm) 2 molding conditions Mold temperature: 150 ° C.
Mold clamping pressure (effective pressure): 15 MPa
Molding material preheating: None Curing time: 60 seconds Measurement conditions Horizontal peeling speed: 5 mm / min

As is apparent from the results in Table 1, Examples 1 to 8 are molding materials of the present invention containing a phenol resin containing a resol type phenol resin and a specific fatty acid aluminum, and molded articles obtained therefrom. Compared to the moldings obtained from the molding materials of Comparative Examples 1 and 2 that do not contain a specific fatty acid aluminum, the mechanical strength is substantially maintained and the adhesion between the copper and the resin is reduced. I was able to.

  The phenol resin molding material of the present invention can reduce the adhesion between the copper and the resin while maintaining the mechanical strength of the molded product, and facilitates removal of burrs attached to the copper surface after molding. For this reason, it is suitably applied as a molding material for parts such as insert molding of copper terminals.

Schematic which shows the measuring method of the copper plate peeling test in the Example of this invention.

Explanation of symbols

1: Copper plate 2: Molded and pressed phenolic resin molding material

Claims (2)

A phenol resin including a resol type phenol resin, a fatty acid aluminum selected from aluminum stearate, aluminum 12-hydroxystearate, aluminum behenate, and aluminum montanate , and glass fibers and powdered inorganic fillers as inorganic fillers A phenolic resin molding material characterized by that. 2. The phenol resin molding material according to claim 1, wherein the content of the fatty acid aluminum is 0.1 to 10 parts by weight with respect to 100 parts by weight of the phenol resin.

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