JP2010222510A - Phenol resin molding material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phenol resin molding material which gives a molded product having flame resistance at V-0 standard and excellent mechanical strengths without lowering tracking resistance and friction resistance. <P>SOLUTION: The phenol resin molding material contains: (a) a phenol resin; (b) glass fibers; (c) organic natural fibers; (d) aluminum hydroxide and/or magnesium hydroxide; and (e) zinc borate. Based on the whole of the molding material, the total amount of filler materials containing the components (b)-(e) is 40-65 wt.%. Also, for the total amount of the filler materials containing (b)-(e) components, amounts of components (b)-(e) are 40-80 wt.% (b), 5-30 wt.% (c), 5-30 wt.% (d) and 1-10 wt.% (e) respectively. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a phenol resin molding material.

Phenolic resin molding materials are widely used in the heavy electrical field and electrical parts due to their excellent heat resistance and electrical insulation. Magnet switch molded products have high demands for high reliability, and there is a tendency to reduce the size and thickness of parts. In recent years, flame resistance (94UL, V-0), mechanical strength, wear resistance, tracking resistance However, the conventional phenol resin molding materials cannot satisfy all of these requirements.
For this reason, as a means for improving this, a study based on a combination of a phenol resin, an inorganic base material, an organic base material, boric acid and zinc borate (for example, see Patent Document 1) is included in the inorganic base material. There was a problem that the tracking resistance was inferior due to a small amount of crystal water. Moreover, although examination by the combination of a phenol resin, an inorganic base material, glass fiber, and polyvinyl butyral is also made | formed (for example, refer patent document 2), there existed a problem that abrasion resistance is inferior.

Japanese Patent Laid-Open No. 08-176401 Japanese Patent Laid-Open No. 10-238781

  The present invention provides a phenolic resin molding material that does not have a decrease in tracking resistance and abrasion resistance, has a flame resistance of V-0 level, and can obtain a molded article excellent in mechanical strength.

Such an object is achieved by the following present inventions [1] to [2].
[1]
(A) phenolic resin,
(B) glass fiber,
(C) organic natural fiber,
(D) aluminum hydroxide and / or magnesium hydroxide,
(E) zinc borate,
The total content of the filler containing the components (b) to (e) is 40 to 65% by weight with respect to the entire molding material.
Content of each said (b)-(e) component with respect to the total content of the filler containing said (b)-(e) component is (b) 40-80 weight%, (c) 5-30 weight% (D) 5 to 30% by weight and (e) 1 to 10% by weight.
[2] The phenol resin molding material according to the above [1], which contains a resol type phenol resin as the (a) phenol resin.

  According to the present invention, it is possible to obtain a phenol resin molding material that does not have a decrease in tracking resistance and wear resistance, has a flame resistance of V-0 level, and can obtain a molded product excellent in mechanical strength.

The phenol resin molding material of the present invention (hereinafter sometimes simply referred to as “molding material”) will be described in detail below.
The molding material of the present invention is
(A) phenolic resin,
(B) glass fiber,
(C) organic natural fiber,
(D) aluminum hydroxide and / or magnesium hydroxide,
(E) zinc borate,
The total content of the filler containing the components (b) to (e) is 40 to 65% by weight with respect to the entire molding material.
Content of each said (b)-(e) component with respect to the total content of the filler containing said (b)-(e) component is (b) 40-80 weight%, (c) 5-30 weight% (D) 5 to 30% by weight and (e) 1 to 10% by weight.

The molding material of the present invention contains (a) a phenol resin.
As the phenol resin used in the present invention, a novolac type phenol resin (hereinafter sometimes referred to as “novolac resin”) and a resol type phenol resin (hereinafter sometimes referred to as “resole resin”) may be used alone or in combination. it can.
For example, a method using a resole resin alone, a method using a resole resin and a novolac resin in combination, a method using a novolac resin alone, and the like can be mentioned.
In the molding material of the present invention, it is preferable to use a resol resin. Specifically, a method using a resole resin alone or a method using a resole resin and a novolac resin in combination is preferable.
When the resole resin is used alone, it can be cured without using a curing agent. Moreover, when using a resole resin and a novolak resin together, since a resole resin can be used in order to harden a novolak resin, it can be hardened also in this case, without using a hardening | curing agent.
This eliminates the need to use hexamethylenetetramine as a curing agent, as in the case of using a novolac resin alone, thereby preventing the generation of corrosive gas such as ammonia gas during curing. Reliability can be enhanced when used for applications.

The molding material of this invention contains (b) glass fiber. Thereby, the mechanical strength and heat resistance which were excellent in the molded article using the molding material of this invention can be provided.
Although it does not specifically limit as glass fiber used here, For example, the chopped strand currently used for the normal phenol resin molding material can be used suitably.

The molding material of this invention contains (c) organic natural fiber. Thereby, the abrasion resistance excellent in the molded article can be provided.
Although it does not specifically limit as an organic natural fiber used here, For example, an anti-cotton pulp, a powder pulp, a raw cotton pulp, a crushed cloth etc. can be used.
As the organic natural fiber, a fiber having a fine fiber length of 1 mm or less is preferable in view of the degree of defibration, the degree of dispersion, the bulk of the molding material, and the like.

The molding material of the present invention contains (d) aluminum hydroxide and / or magnesium hydroxide. Since these contain crystal water, a flame retardance can be provided to a molded article.
As aluminum hydroxide and magnesium hydroxide, those having a particle size of 300 μm or less can be suitably used.

The molding material of the present invention contains (e) zinc borate. Thereby, a flame retardance can be provided to a molded article.
As the zinc borate, those having a particle size of 300 μm or less can be suitably used.

  In addition to the above components (b) to (e), the molding material of the present invention can contain inorganic fillers and organic fillers other than the components (b) to (e) as necessary. .

The content of the components (b) to (e) used in the molding material of the present invention includes the inorganic fillers other than the components (b) to (e) and the organic fillers, including those when molding. It is 40 to 65% by weight based on the whole material.
By setting the content of the filler to the above lower limit value or more, various properties such as heat resistance, mechanical strength, flame resistance, and tracking resistance of the molded product can be improved. Moreover, workability at the time of manufacturing a molding material can be made favorable by setting it as the said upper limit or less.

The content of the glass fiber (b) used in the molding material of the present invention is 40 to 80% by weight with respect to the total content of the filler containing the components (b) to (e).
By setting the glass fiber content to the above lower limit value or more, the mechanical strength and heat resistance of the molded product can be improved. Moreover, the abrasion resistance of a molded article can be made favorable by setting it as the said upper limit or less.

The content of the organic natural fiber (c) used in the molding material of the present invention is 5 to 30% by weight with respect to the total content of the filler containing the components (b) to (e).
By setting the content of the organic natural fiber to the above lower limit or more, the wear resistance of the molded product can be improved. Moreover, by setting it as the said upper limit or less, flame resistance, tracking resistance, and the pouring property of the material in the hopper at the time of shaping | molding can be made favorable.

The content of (d) aluminum hydroxide and / or magnesium hydroxide used in the molding material of the present invention is 5 to 30% by weight with respect to the total content of the filler containing the components (b) to (e). is there.
By making content of aluminum hydroxide and / or magnesium hydroxide more than the said lower limit, the flame resistance of a molded article and tracking resistance can be made favorable. Moreover, by setting it as the said upper limit or less, mechanical strength and abrasion resistance can be made favorable.

The content of (e) zinc borate used in the molding material of the present invention is 1 to 10% by weight based on the total content of the filler containing the components (b) to (e).
By setting the content of zinc borate to the above lower limit value or more, the flame resistance and tracking resistance of the molded product can be improved. Moreover, by setting it as the said upper limit or less, sclerosis | hardenability, mechanical strength, and abrasion resistance can be made favorable.

In the molding material of the present invention, as described above, various kinds of fillers are used in combination.
First, the following effects can be obtained by using glass fibers and organic natural fibers in combination. In other words, it is effective in improving mechanical strength and heat resistance, but when used in excess, it uses glass fibers that affect wear resistance and organic natural fibers that are effective in improving wear resistance in combination. Thus, both desired mechanical strength and wear resistance can be expressed at a high level.
Furthermore, the following effects can be obtained by using a predetermined amount of zinc borate and aluminum hydroxide and / or magnesium hydroxide. In other words, protection of internal combustibles by promoting the formation of a zinc borate carbonized layer and glass layer during combustion, formation of an oxygen barrier layer, and endothermic during dehydration of crystal water contained in aluminum hydroxide and / or magnesium hydroxide Due to the synergistic effect of the action, both desired flame resistance and tracking resistance can be expressed at a high level.
Thus, in the molding material of the present invention, by blending a predetermined amount of these fillers in combination, the mechanical strength, abrasion resistance, flame resistance, and excellent molded article formed by molding this molding material, and Tracking resistance can be imparted.

  If desired, the molding material of the present invention can be added to various additives used in ordinary phenol resin molding materials, such as curing agents, curing catalysts, mold release agents such as zinc stearate and calcium stearate, fillers and phenol resins. An adhesion improver for improving the adhesiveness, a coupling agent, a coloring pigment for coloring, a coloring dye, a solvent and the like can be blended.

As a method for producing the molding material of the present invention, for example, a blend of resin, filler, additive and the like is heated, melted and kneaded using a roll, a kneader, an extruder, etc., and then pelletized or cooled and pulverized. After the resin is impregnated into the filler by adding a varnish in which the resin is dissolved in a solvent and stirring using a Henschel mixer, a super mixer, etc. And a method of removing the solvent to form a molding material.
In any manufacturing method, the above-described composition of the present invention can provide a molding material excellent in flame resistance, mechanical strength, wear resistance, and tracking resistance. A method of producing with a roll, a kneader, or an extruder from which a molding material with few components is obtained is desirable.
The molding material obtained as described above is heated, pressed and cured by a molding method such as normal injection molding, transfer molding and compression molding, so that it has excellent mechanical strength, wear resistance, flame resistance and tracking resistance. A molded product having the following is obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by this Example. Table 1 shows the molding material compositions of Examples and Comparative Examples.

1. Manufacture of a molding material Each compound used for the present Example and the comparative example is as follows.
1) Phenolic resin (resole type): Dimethylene ether resol type phenolic resin (
Sumitomo Bakelite PR-53529)
2) Phenolic resin (Novolak type): Novolac type phenolic resin (A-1084 manufactured by Sumitomo Bakelite Co., Ltd.)
3) Glass fiber: Chopped strand manufactured by Owens Corning Japan Ltd. Fiber length 3 mm Fiber diameter 11 μm
4) Organic natural fiber: 80 mesh pass pulverized cloth manufactured by Kawajin Shoten Co., Ltd. 5) Aluminum hydroxide: 80 mesh size Hydrite, manufactured by Sumitomo Chemical Co., Ltd. 6) Magnesium hydroxide: 80 mesh pass, Kisuma 7 manufactured by Kyowa Chemical Industry Co., Ltd. ) Talc: Particle size 80 mesh pass SP manufactured by Fuji Talc Industrial Co., Ltd.
8) Zinc borate: particle size 80 mesh pass Firebrake made by Borax Japan
9) Polyvinyl butyral: polymerization degree 1500 butyralization degree 70 mol%
10) Colorant: Carbon black 11) Release agent: Stearic acid 12) Curing accelerator: Slaked lime

  These were blended in the proportions shown in Table 1, kneaded between heated mixing rolls at 80 to 100 ° C. for 5 to 10 minutes, and then cooled in a sheet form to obtain a granular molding material.

2. Evaluation of Molded Article Using the molding material obtained above, a test piece for measuring the following characteristics (1) to (5) was prepared by transfer molding. The molding conditions were a mold temperature of 175 ° C. and a curing time of 3 minutes. Table 2 shows the evaluation results of the molded products.

(1) Bending strength (mechanical strength)
Measured according to JIS K 6911 “General Thermosetting Plastics Test Method”.
(2) Charpy impact strength (mechanical strength)
Measured according to JIS K 6911 “General Thermosetting Plastics Test Method”.
(3) Flame resistance According to UL94 V-0 standard "UL combustion test method", the test piece of 3.2 mm in thickness was measured.
(4) Amount of wear (wear resistance)
It was measured by the Suzuki type abrasion test method. The data shows the amount of wear on the molded product. The conditions are as follows.
・ Load: 20kg
・ Peripheral speed: 50mm / sec
-Time: 4 hours-Counterpart material: Aluminum (5) Tracking resistance Measured according to JIS C 2134 "Test Method for Determining Comparative Tracking Index and Guaranteed Tracking Index of Solid Electrical Insulating Material in Wet State".

  In the molding materials of the present invention obtained in Examples 1 to 4, molded articles having excellent tracking resistance and abrasion resistance were obtained while maintaining high flame resistance and mechanical strength.

In Comparative Example 1, aluminum hydroxide and / or magnesium hydroxide was not added, but talc was added instead, but the flame resistance and tracking resistance were lowered.
In Comparative Example 2, polyvinyl butyral was added without adding organic natural fibers, but the wear resistance was lowered.
In Comparative Example 3, the glass fiber content was less than the predetermined amount, and the mechanical strength was reduced.
In Comparative Example 4, no zinc borate was added, and the flame resistance and tracking resistance were lowered.
In Comparative Example 5, the molding material could not be manufactured because the total amount of the filler was larger than the predetermined amount.
In Comparative Example 6, since the total amount of the filler was less than the predetermined amount, the mechanical strength was lowered.

  The phenolic resin molding material of the present invention is a molding material that is excellent in flame resistance and mechanical strength, and that can obtain a molded product having good tracking resistance and wear resistance. For this reason, it is suitably used for electric and electronic parts, automobile parts, general-purpose machine parts, and the like.

Claims (2)

(A) phenolic resin,
(B) glass fiber,
(C) organic natural fiber,
(D) aluminum hydroxide and / or magnesium hydroxide,
(E) zinc borate,
The total content of the filler containing the components (b) to (e) is 40 to 65% by weight with respect to the entire molding material.
The content of each component (b) to (e) with respect to the total content of the filler containing the components (b) to (e) is (b) 40 to 80% by weight, and (c) 5 to 30% by weight. (D) 5 to 30% by weight and (e) 1 to 10% by weight. The phenol resin molding material according to claim 1, wherein the phenol resin contains (a) a resol type phenol resin.