JPS60248767A - Phenolic resin molding material for compression molding - Google Patents

Abstract

PURPOSE:To obtain the titled material giving a molded article having smooth and glossy surface, excellent appearance and remarkably improved Charpy impact strength, by compounding a base resin with a specific organic fiber having high tensile strength. CONSTITUTION:The objective material can be produced by compounding 100 pts.wt. of a phenolic resin and/or a modified phenolic resin with 20-150pts.wt. of an organic fiber having a tensile strength of >=6g/denier and diameter of 10-20mum. The (modified) phenolic resin is preferably a benzylic ether phenolic resin, ammonia resol-type phenolic resin, bisphenol-A-modified phenolic resin, aniline-modified phenolic resin, or amine-modified phenolic resin, and the organic fiber is preferably polyvinyl alcohol fiber, polyamide fiber or polyester fiber.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a phenolic resin molding material for compression molding that allows molded products with excellent surface smoothness and high impact strength to be obtained.
More specifically, the present invention relates to a phenolic resin molding material for compression molding that uses organic fibers having a specific tensile strength and diameter to provide a molded product with a smooth surface, excellent appearance, and high impact strength.

The phenolic resin molding material of the present invention provides molded products that have excellent impact strength and good appearance in addition to the heat resistance, heat creep resistance, and electrical properties that are the characteristics of phenolic resin. Gray car, micro switch? Electrical and electronic parts such as pins, mechanical parts such as gears, cams, bearing washers, seal rings, etc.
It can be used for automotive parts such as connectors and nollies.

[Conventional technology and its problems]

Traditionally, phenolic resin molding materials have good heat resistance, arc resistance,
Although it has excellent electrical properties, it has the problem of relatively low impact strength, for example, Charpy impact strength is 2 to 3K.
It is about gf-1-. Therefore, in order to improve the impact strength, glass fiber is widely used as a fibrous reinforcing material, but molded products obtained by compression molding a molding material using glass fiber have improved impact strength, but do not easily slide. It has 4 points: poor durability and abrasion resistance, and low impact from falling balls.

In addition, cotton cloth chips and the like are used as fibrous reinforcing materials, but in this case, although the impact strength is improved to some extent, it is not possible to obtain a molded product with a smooth surface, and the gloss of the molded product is deteriorated. Is the surface deco? There is a problem that it becomes difficult to use. In addition, organic fibers are rarely used as fibrous reinforcing materials due to their price limitations, and phenolic resin molding materials that contain organic fibers and can produce molded products with extremely high impact strength have not been found. The current situation is that there is no such thing.

In view of the problems of the prior art described above, the present inventors first developed a phenolic resin molding material for injection molding (Japanese Patent Application No. 58-1604).
07) was filed. This is based on polyvinyl alcohol fiber (hereinafter abbreviated as vinylon fiber) in phenolic resin with selected solubility and matrix parameters (according to "Adhesion Encyclopedia (Part 1)" written by Shibasaki, published by Kobunshi Publishing Co., Ltd., 1951, p. 33). This relates to a high-impact phenolic resin molding material for injection molding, which is made by blending the fibers with a unique relationship between the tensile strength of the fiber and the impact strength of the molded product, and the solubility parameter of the phenolic resin and the solubility of the vinylon fiber. This was done based on the discovery that they are related.

As a result of further intensive research, the present inventors discovered a new factor that improves the surface smoothness of phenolic resin molded products, and also discovered that phenolic resin can be used regardless of its solubility parameter for compression molding. It was discovered that, in addition to fibers, synthetic fibers having a tensile strength of 61-denier or higher, such as polyamide fibers (hereinafter abbreviated as nylon fibers) and ester fibers, can be suitably used, leading to the present invention. .

[Object of the Invention] The object of the present invention is to provide a phenolic resin molding material for compression molding that can yield excellent molded products that have a smooth, glossy, and smooth surface, and have high Charpy impact strength. It is possible to provide the following.

[Structure of the invention and its operation]

The phenolic resin molding material of the present invention has been made to achieve the above object, and has a tensile strength of 61-/denier or more based on 100 parts by weight of phenolic resin and/l- or modified phenolic resin. and the diameter is 1
It contains 20 to 150 parts by weight of organic fibers having a diameter of 0 to 20 μm.

To explain its effect, it is thought that the surface smoothness of a molded product is primarily affected by the thickness of the organic fibers, and thin fibers have good dispersibility and are dotted on the surface of the molded product, resulting in a smooth surface. . Furthermore, the organic fibers on the surface shrink once during heating and compression molding, but after molding, due to the elasticity of the fibers, a phenomenon is observed in which many fibers return to their original diameter and rise to the surface. Thick fibers have a high protrusion rate, making it difficult to obtain a smooth surface. Therefore, if fibers with a small diameter are used, the surface smoothness will be good. On the other hand, if the diameter is too small, the tensile strength of the fiber itself will be low and it will be difficult to obtain a molded product with high impact strength.

This is considered to be because the tensile strength of the organic fiber primarily affects the impact strength of the molded article.

[Detailed description of the invention]

The phenolic resin and modified phenolic resin used in the present invention may be of the Nogarakya or resol type,
Examples of phenolic resins include unmodified straight 7-derac type phenol resin, resol type phenol W resin,
Penzylic ether type phenol resin, ammonia aresol type phenol resin, etc. are preferable, and as the modified phenol resin, bisphenol A modified phenol resin,
Aniline-modified phenolic resins, amine-modified phenolic resins, and the like are preferred. Incidentally, these resins can be used alone or in combination.

The organic fiber used in the present invention is vinylon f;! ! I,
Synthetic fibers such as nylon 6.6 fiber and polyester fiber are preferred, with vinylon fiber being particularly preferred. These organic fibers are 61/denier or more,
Preferably has a tensile strength of 7.5 f/denier or more,
and its diameter is 10 to 20 μm, preferably 12 to 17
It is μm. Those having a tensile strength of less than 6y-/denier and a diameter of less than 10 .mu.m are not preferred because although they have good surface smoothness, molded articles with high impact strength cannot be obtained even when used in large quantities. The tensile strength of organic fiber is 6? /denier or more, but if the diameter is larger than 20 μm, a molded product with high impact strength can be obtained, but the surface will be uneven and lack luster, making it undesirable. There is no particular limitation on the fiber length, but the commonly used fiber length is 1 to 61.
1III can be preferably used.

The organic fiber is preferably used in an amount of 20 to 150 parts by weight, more preferably 30 to 70 parts by weight, per 100 parts by weight of the phenolic fiber and/or modified phenol resin. If the amount used is less than 20 parts by weight, the desired improvement in Charpy impact strength will be substantially small; if it exceeds 150 parts by weight, the Charpy impact strength will be much higher, but the material will be difficult to mold. This is not desirable because it becomes In addition, in the present invention, in addition to organic fibers, other organic and inorganic fillers such as cellulose and plastic fibers, which are usually used in phenolic resin molding materials, are used in combination in consideration of heat resistance, bending strength, tensile strength, etc. It is also effective to do so.

The phenolic resin molding material of the present invention is preferably used for compression molding. In compression molding, the organic fibers in the phenolic resin molding material of the present invention are not susceptible to thermal history, so they are less likely to be dissolved in the phenolic resin used when heated, and the tensile strength of the organic fibers can be maintained. The phenolic resin molding material exhibits high impact strength. The phenol resin molding material of the present invention can be produced by conventional methods, and one method will be described below.

Phenolic resin and or modified phenolic resin 100
Weight part, tensile strength is 61/denier or more and diameter is 1
20 to 150 parts by weight of organic fibers having a diameter of 0 to 20 μm, and appropriate amounts of organic substances such as cellulose and glass fiber, inorganic fillers, curing agents, curing catalysts, mold release agents,
By blending additives such as colorants, uniformly dispersing and mixing them together with an appropriate amount of solvent in a Henschel mixer, and then kneading and granulating them under heating and high-speed stirring, a granular phenolic resin molding material for compression molding with a diameter of 2 to 20+ mm is obtained. can be obtained.

〔Example〕

Hereinafter, the present invention will be explained in more detail according to Examples, but it goes without saying that the technical scope of the present invention is not limited to these Examples.

[Example 1] Part by weight? Rack-type phenolic resin 100 Vinylon fiber (tensile strength 7.81-/Denyl 70-L,
(Diameter: 14.8μsXl) Wood flour: 30 Hexamethylenetetramine: 20 Magnesium oxide: 10 Stearic acid: 10 Spirit black: 5 Methanol: 80 The above mixture was uniformly dispersed and mixed in a Henschel mixer.
The mixture was further kneaded while heating and stirring at high speed to obtain a granular phenol resin molding material. Using this molding material, 160℃, 20
Compression molding was performed under conditions of 0.0 for 2.5 minutes to obtain JIS test pieces for measuring Charpy impact strength. Test results,
The Charby impact strength of this test piece was 9.2 f-crr.
v'rx? Met. Also, using this molding material, 160
Compression molding was performed under the conditions of ℃, 150ψi, and 3 minutes,
A JIS water absorption test piece was obtained, and the surface of the test piece was measured at several random locations using a roughness tester (small plate 5E-3A),
A large number of cross-sectional curves were obtained. Surface smoothness is JIS-B-
According to 601 (Surface Roughness), it is expressed as the average value of the maximum height of the extracted portion from a large number of obtained cross sections, and the smoother the surface, the smaller the maximum height. The maximum height in this example was 8 μm.

The obtained molded product had excellent surface smoothness and high impact strength. It also had a good appearance, such as being shiny. Other physical properties were as shown in Table 1.

[Example 2] A molding material was obtained in the same manner as in Example 1, except that the blending amount of vinylon fiber was changed to 20 parts by weight, and the blending amount of wood flour was changed to 80 parts by weight. Each test piece was obtained from this molding material in the same manner as in Example 1. Charpy impact strength is 4
．． 5 k19f-cm/am2 and 6C1, and the maximum height was 6 μm. Other physical properties were as shown in Table 1 @ [Example 3] Example 1 except that the blended amount of vinylon fiber was changed to 110 parts by weight and the blended amount of wood flour was changed to 10 parts by weight. A molding material was obtained in the same manner as above. Each test piece was obtained from this molding material in the same manner as in Example 1. Charpy impact strength is 15.1 kgf-cm/cry? Furthermore, the maximum height was 13 μm. Other physical properties were as shown in Table 1.

[Example 4] Parts by weight Resol type phenolic resin (72% methanol 140-ol solution) Vinyl oydm (tensile strength 7.s?/r Neal, 5° diameter 14.8 μm, 1 ■ hardened product) Wood flour 50 Calcium hydroxide 10 Stearic acid 10 Spiritsila, Ri 5 The above formulation was uniformly dispersed and mixed in a Henschel mixer,
Further, the mixture was mixed under heating and high-speed stirring to obtain a granular phenolic resin molding material. Each test piece was cut from this molding material in the same manner as in Example 1.

Charpy impact strength is 7.5 kgf-
Further, the maximum height was 9μ full. Other physical properties were as shown in Table 1.

[Example 5] Weight part benzolic ether type phenol all & 100 vinylon fiber (tensile strength 7.8 f/denier, 70 diameter 1
4.8 μm, 1 strength product) Wood flour 30 Calcium hydroxide 10 Stearin I [10 Spirit black 5 Methanol 80 The above mixture was uniformly dispersed and mixed in a Henschel mixer,
The mixture was further kneaded while heating and stirring at high speed to obtain a granular phenol resin molding material. Each test piece was obtained from this molding material by piecing it in the same manner as in Example 1.

The Charpy impact strength was 9.0 yf, and the maximum height was 8 μm. Other physical properties were as shown in Table 1).

[Example 6] Same as Example 1, except that in Example 5, meta-xylene diamine-modified phenol resin was used for the benzylic ether type phenol resin, and 15 parts by weight of sameethylenetetramine was added. A molding material was obtained. Each test piece was obtained from this molding material in the same manner as in Example 1.

The Charpy impact strength was 8.7 yt-crJcrrr'', and the maximum height was 8 μm.Other physical properties were as shown in Table 1. [Example 7] In Example 1 , the tensile strength of vinylon fiber is 7.
．． A molding material was obtained in the same manner as in Example 1, except that nylon 6.6 fibers having a diameter of 81/denier, a diameter of 14.8 μm, and a 1 m cut product were used. Each test piece was obtained from this molding material in the same manner as in Example 1. The Charpy impact strength is 9.1kgf-~, and the maximum height is 8μ.
It was m. Other physical properties were as shown in Table 1.

[Example 8] In Example 1, the vinylon fiber glue had a tensile strength of 7.01-/denier, a diameter of 14.8 firn,
A molding material was obtained in the same manner as in Example 1 except that 1 tan cut polyester fiber was used. Each test piece was obtained from this molding material in the same manner as in Example 1. Charpy impact strength is 8.8 kgf-cm/ar? The maximum height was 9 μm. Other physical properties were as shown in Table 1.

[Comparative Example 1] Tensile strength 7.8/-/denier, diameter 25.7 μm, 1
A molding material was obtained in the same manner as in Example 1 except that vinyllongue fibers made by inertia were used. Example 1 from this molding material
Each test piece was obtained in the same manner as above. Charpy 4E
The impact strength was 9.5K11lf--excellent, and the maximum height was 38 μm. Other physical properties were as shown in Table 1.

The obtained molded product had high zero impact strength, but had poor surface smoothness, similar to the cloth chip compounded molded product obtained in Example 3, and had a poor appearance.

[Comparative Example 2] A molding material was obtained in the same manner as in Example 1, except that vinylon fibers having a tensile strength of 3.5 f/denier, a diameter of 1015 μm, and a one-tone cut product were used. Each test piece was obtained from this molding material in the same manner as in Example 1. Charpy impact strength is 5.5 kgf-cm/cyr? Also, the maximum height was 6 prn. Other physical properties were as shown in Table 1.

The molded product obtained had good surface smoothness but low zero impact strength.

[Comparative Example 3] Parts by weight Resol type phenol fat (61 meth 170 Nor solution) Cloth chips (4 questions) 100 Calcium hydroxide 10 Stearic acid 10 Spiri, Doppler, Ri 5 The above mixture was uniformly dispersed with a Henschel mixer mix,
Even faster heating! The mixture was kneaded with stirring to obtain a granular phenolic resin molding material. Each test piece was obtained from this molding material in the same manner as in Example 1.

The Charpy impact strength was 4.0 kgf-cm2, and the maximum height was 30 μm. Other physical properties were as shown in Table 1.

Margins below [Effects of the Invention] The molded product obtained by heating and compression molding the organic 11 sphere fiber-containing phenolic resin molding material according to the present invention has a good appearance with a smooth and glossy surface. It also has high Charpy impact strength. This effect is particularly remarkable when vinylon fiber is used as the organic fiber. Other features that could not be obtained using conventional lath fiber reinforcement materials. It has the advantage that it has good sliding properties and abrasion resistance, and the specific gravity of the material itself is low, making it possible to obtain lightweight molded products.

patent applicant Asahi Organic Materials Industry Co., Ltd. patent application agent Patent attorney Akira Aoki Patent attorney Kazuyuki Nishidate Patent Attorney Ishi 1) Takashi Patent attorney Rin Yamaguchi

Claims (1)

[Claims] 1.7 6? for 100 parts by weight of enol resin and/or modified phenol resin / 20 to 20 organic fibers having a tensile strength of 1 denier or more and a diameter of 10 to 20 μm
A phenolic resin molding material for compression molding, characterized in that it contains 150 parts by weight. 2. The phenolic resin molding material according to claim 1, wherein the organic fiber is polyvinyl alcohol fiber. 3. The 7-enol resin molding material according to claim 1, wherein the organic fiber is polyamide fiber or polyester fiber. 4.7 The phenolic resin molding material according to claim 1, 2 or 3, wherein the enol resin and the modified phenol resin are a noblack type phenolic resin or a resol type phenolic resin. 5. The phenolic resin molding material according to claim 1, 2, 3, or 4, wherein the phenolic resin is a benzylic ether type phenol resin or an ammonia resol type 7-primary phenolic resin. 6. Enol resin molding according to claim 1, 2, 3, or 4, wherein the modified phenol resin is bisphenol A-modified phenol 41H]W, aniline-modified phenol resin, or amine-modified phenol resin. material.