JP4852932B2 - Phenol resin molding material and method for producing the same - Google Patents

Description

  The present invention relates to a phenol resin molding material and a method for producing the same.

Molded articles obtained from phenolic resin molding materials are heat-resistant and easy to process products, so they are used in many fields and the number of uses continues to increase. Among them, in the use of mechanical parts such as automobiles, the use of resin for ceramic or metal parts is being studied for the purpose of weight reduction and cost reduction. Among these, although there are many parts (for example, pulleys, pump parts, etc.) that originally require wear resistance, the reality is that they have not been put into practical use so far. For this reason, since mechanical characteristics and heat resistance, which are essential characteristics, have been emphasized, for example, glass fibers, spherical silica, crushed silica, and the like have been used as fillers. In this case, there is a problem that the mechanical strength is improved but the wear resistance is deteriorated. On the other hand, by adding a rubber component to a phenolic resin and further containing a specific fibrous base material and a friction modifier, a phenolic resin having high impact strength and flexural strength and low flexural modulus. A resin molding material is disclosed (for example, see Patent Document 1).
Japanese Unexamined Patent Publication No. Sho 63-24160

  The present invention provides a phenol resin molding material capable of obtaining a molded article having excellent wear resistance while maintaining mechanical strength at a practical level, and a method for producing the same.

Such a subject is achieved by the following present inventions (1) to ( 9 ).
(1) containing a polyamide resin molten phenol resin (a), an inorganic filler (b), a polyamide resin (c), and a fluororesin (d) ,
Content of the said polyamide resin molten phenol resin (a) is 20 to 40 weight% with respect to the whole molding material,
Content of the said inorganic filler (b) is 35 to 65 weight% with respect to the whole molding material,
Content of the said polyamide resin (c) is 0.1 to 8 weight% with respect to the whole molding material,
Content of the said fluororesin (d) is 0.1 to 6 weight% with respect to the whole molding material,
The phenol resin molding material, wherein a polyamide resin content in the polyamide resin molten phenol resin (a) is 5 to 25 parts by weight with respect to 100 parts by weight of the phenol resin.
( 2 ) The content ratio (d) :( a) between the fluororesin (d) and the polyamide resin-fused phenol resin (a) is from 3:97 to 15:85. The phenol according to (1) Resin molding material.
( 3 ) The phenol resin molding material according to (1) or (2) , wherein the thermal decomposition temperature of the fluororesin (d) is 370 ° C. or higher.
( 4 ) The content ratio (c) :( d) between the polyamide resin (c) and the fluororesin (d) is any one of (1) to ( 3 ) that is 50:50 to 75:25. 2. A phenolic resin molding material described in 1.
( 5 ) The total content of the polyamide resin (c) and the fluororesin (d) is 0.5 to 15% by weight with respect to the whole molding material, (1) to ( 4 ) The phenol resin molding material in any one.
( 6 ) The content ratio of the total content of the polyamide resin and the polyamide resin (c) in the polyamide resin molten phenol resin (a) and the fluororesin (d) is 10: 1 to 5: 3 ( The phenol resin molding material in any one of 1)-( 5 ).
( 7 ) The phenol resin according to any one of (1) to ( 6 ), wherein the polyamide resin (c) includes one or more selected from nylon 6, nylon 66, nylon 46, nylon 11, and nylon 12. Resin molding material.
( 8 ) The fluororesin (d) contains one or more selected from polytetrafluoroethylene, polychlorotrifluoroethylene, and polypyridene fluoride. (1) to ( 7 ) The phenol resin molding material as described.
( 9 ) A method for producing a phenol resin molding material according to any one of (1) to ( 8 ), comprising a step of previously melting the phenol resin and the polyamide resin (c). Manufacturing method of molding material.

The present invention is a phenol resin molding material characterized by containing a polyamide resin molten phenol resin (a), an inorganic filler (b), a polyamide resin (c), and a fluororesin (d). The obtained molded product can have excellent wear resistance while maintaining the mechanical strength at a practical level.
Moreover, it can be materialized without particular problem in workability by setting the content of the polyamide resin molten phenol resin (a) to 20 to 40% by weight with respect to the entire molding material.
Furthermore, the workability at the time of melt kneading should be particularly improved by setting the polyamide resin molten phenol resin (a) to a melt amount of 10 to 30 parts by weight with respect to 100 parts by weight of the phenol resin. Can do.
Moreover, this invention is a manufacturing method of the said phenol resin molding material, A wear resistance characteristic can further be improved by melt | dissolving a polyamide resin and a phenol resin previously.

  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 polyamide resin molten phenol resin (a), an inorganic filler (b), a polyamide resin (c), and a fluororesin (d).
First, the polyamide resin molten phenol resin (a) used for the molding material of the present invention will be described.
The phenol resin used for the polyamide resin-fused phenol resin (a) is not particularly limited. Examples thereof include resol type phenol resins such as dimethylene ether type resole resin, oil-melted resol phenol resin melted with tung oil, linseed oil, walnut oil and the like.
Among these, novolac type phenol resins are preferable. Thereby, when synthesize | combining the said polyamide resin molten phenol resin (a), workability | operativity is good and it can melt-mix easily.

  In the phenol resin used in the present invention, when a novolak type phenol resin (hereinafter, sometimes simply referred to as “novolak resin”) is used, hexamethylenetetramine is usually used as a curing agent. Although hexamethylenetetramine is not particularly limited, it is preferably used in an amount of 10 to 25 parts by weight based on 100 parts by weight of the novolak resin. More preferably, it is 13-20 weight part with respect to 100 weight part of novolak resin. If the amount of hexamethylenetetramine used is too small, it will take time for curing during molding, and if it is too large, the molded product may be blistered.

The polyamide resin molten phenol resin (a) used in the molding material of the present invention is obtained by melting a polyamide resin in a phenol resin. Although it does not specifically limit as said polyamide resin, For example, nylon 6, nylon 66, nylon 46, nylon 11, and nylon 12 are mentioned. These can be used alone or in combination of two or more. Among these, nylon 6 is preferably used from the viewpoint of availability and low cost. The polyamide resin is preferably in the form of powder. By using a powdered polyamide resin, the degree of melt dispersion in the phenol resin can be increased.
Further, the particle diameter of the polyamide resin is such that 12 to 20 mesh is 95% by weight or more with respect to the entire polyamide resin (c), and 20 to 32 mesh is 90% by weight or more with respect to the entire polyamide resin (c). Preferably there is. By setting the particle diameter in the above range, the degree of melt dispersion in the phenol resin can be further increased.

  It is preferable that content of the said polyamide resin molten phenol resin (a) is 20 to 40 weight% with respect to the whole molding material. More preferably, it is 25 to 35% by weight. By making the content within the above range, workability at the time of melt kneading can be particularly improved.

  The polyamide resin content in the polyamide resin molten phenol resin (a) is preferably 5 to 25 parts by weight with respect to 100 parts by weight of the phenol resin (including hexamethylenetetramine in the case of a novolac resin). More preferably, it is 10-20 weight part. By setting it as the said content, workability | operativity at the time of especially melt kneading can be made favorable.

An inorganic filler (b) is used for the molding material of the present invention.
The inorganic filler (b) is not particularly limited. For example, talc, fired clay, unfired clay, mica and other silicates, oxides such as titanium oxide, alumina, silica and fused silica, calcium carbonate, Carbonates such as magnesium carbonate and hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, zinc borate and metaboric acid Examples thereof include borates such as barium, aluminum borate, calcium borate and sodium borate, nitrides such as aluminum nitride, boron nitride and silicon nitride, and glass fibers. Among these, glass fiber is preferable. When glass fiber is used, the mechanical strength of the obtained molded product can be maintained.
The content of the inorganic filler (b) is preferably 35 to 65% by weight, more preferably 40 to 60% by weight, based on the entire molding material. By making content of an inorganic filler (b) into the said range, especially workability | operativity of materialization can be ensured and the mechanical strength of the molded article obtained can be improved further.

Polyamide resin (c) is used for the molding material of the present invention.
Although it does not specifically limit as said polyamide resin (c), For example, nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, etc. are mentioned. These can be used alone or in combination of two or more. Among these, nylon 6 is preferably used from the viewpoint of availability and low cost.
The content of the polyamide resin (c) is preferably 0.1 to 8% by weight with respect to the entire molding material. More preferably, it is 0.5-7 weight%. By making content of a polyamide resin (c) into the said range, workability | operativity of materialization can be made especially favorable.
The polyamide resin (c) is preferably in the form of powder. By using the powdery polyamide resin (c), it is possible to further improve the effect of particularly improving the workability of materialization.
Further, the primary particle diameter of the polyamide resin (c) is 12 to 20 mesh with respect to the entire polyamide resin (c) and is 95% by weight or more, and 20 to 32 mesh with respect to the entire polyamide resin (c). Thus, it is preferably 90% by weight or more. By setting the particle diameter within the above range, the above characteristics can be further improved.

Fluorine resin (d) is used for the molding material of the present invention.
Although it does not specifically limit as said fluororesin (d), For example, a polytetrafluoroethylene, a polychloro trifluoroethylene, a poly bilidene fluoride etc. are mentioned. These can be used alone or in combination of two or more. Among these, it is preferable to use polytetrafluoroethylene from the viewpoint of availability and low cost.
The content of the fluororesin (d) is preferably 0.1 to 6% by weight with respect to the entire molding material. More preferably, it is 0.5 to 5% by weight. By making content of a fluororesin (d) into the said range, workability | operativity of materialization can be made especially favorable.

  The average particle diameter of the primary particles of the fluororesin (d) is preferably 5 to 25 μm, and more preferably 10 to 20 μm. By making the average particle diameter of the primary particles of the fluororesin (d) in the above range, it is possible to enhance the effect of improving the wear characteristics.

  The maximum particle diameter of the primary particles of the fluororesin (d) is preferably 100 μm or less. More preferably, it is 85 μm or less, and particularly preferably 75 μm or less. By making the maximum particle diameter of the primary particles of the fluororesin (d) as described above, it is possible to further increase the effect of improving the wear characteristics.

  The content ratio (d) :( a) between the fluororesin (d) and the polyamide resin-fused phenol resin (a) is preferably from 3:97 to 15:85. More preferably, it is 5: 95-12: 88. By making content ratio (d) :( a) into the said range, especially workability | operativity of materialization is securable.

  Furthermore, the thermal decomposition temperature of the fluororesin (d) is preferably 370 ° C. or higher. More preferably, it is 450 degreeC or more. By using the fluorine-based resin (d) having the thermal decomposition temperature, the effect as a solid lubricant can be maintained for a long time by using the fluorine-based resin (d) having a thermal decomposition temperature equal to or higher than the above temperature.

  The content ratio (c) :( d) of the polyamide resin (c) and the fluororesin (d) is preferably 50:50 to 75:25. More preferably, it is 55: 45-70: 30. By making content ratio (c) :( d) into the said range, especially workability | operativity of materialization can be made favorable.

The total content of the polyamide resin (c) and the fluororesin (d) is preferably 0.5 to 15% by weight with respect to the entire molding material. More preferably, it is 3 to 12% by weight.
By making the total content of the polyamide resin (c) and the fluororesin (d) in the above range, the material strength can be particularly maintained, and the wear resistance of the obtained molded product can be improved.

  Moreover, the total content of the polyamide resin and the polyamide resin (c) in the polyamide resin molten phenol (a) and the content ratio of the fluororesin (d) are preferably 10: 1 to 5: 3. More preferably, it is 5: 1 to 5: 2. By making a content ratio into the said range, workability | operativity of materialization can be made especially favorable.

Now, the molding material of the present invention can obtain a molded product excellent in abrasion resistance while maintaining the mechanical strength at a practical level by adding a predetermined amount of each of the above compounding materials. Explains the mechanism by which excellent wear resistance is obtained.
The molding material of the present invention is characterized in that three components of a polyamide resin molten phenol resin (a), a polyamide resin (c) and a fluororesin (d) are used in combination. In particular, since the polyamide resin (c) functions to improve the compatibility between the polyamide resin-fused phenol resin (a) and the fluororesin (d), it is presumed that the wear resistance is improved.

  In the molding material of the present invention, additives such as a mold release agent, a curing aid, and a pigment can be added within the range not impairing the object of the present invention, in addition to the above-described compounding material.

  The molding material of the present invention can be obtained by, for example, premixing the above materials, performing melt kneading using a heating roll or a twin screw kneader, etc., and pulverizing or granulating after cooling. As conditions for the heating roll, high-speed roll surface temperature: 80 to 90 ° C., low-speed roll surface temperature: 20 to 30 ° C., roll pitch: 2.0 to 3.0 mm, high-speed rotation speed: 20 rpm, low-speed rotation Number: can be carried out at 14 rpm.

Next, a method for producing the molding material of the present invention (hereinafter sometimes simply referred to as “manufacturing method”) will be described.
The production method of the present invention is characterized by having a step of previously melting the phenol resin and the polyamide resin (c). By doing so, it is possible to synthesize a polyamide resin-fused phenol resin having a high melt dispersion degree of the polyamide resin to the phenol resin, and it is possible to further increase the range of improvement in the wear characteristics of the obtained molded product. The step of melting in advance is not particularly limited. For example, first, a phenol resin and a polyamide resin are charged into a four-necked flask and heated and mixed at 150 to 170 ° C. Next, when the phenol resin and the polyamide resin begin to dissolve, the stirring speed is increased to 170 to 200 rpm to obtain a uniform mixture. When the inside of the system becomes a uniform mixture, the system temperature is further increased to 180 to 200 ° C. to lower the viscosity of the mixture. At this time, water in the system is removed. After removing the water, the mixture is eluted out of the system. Cool and grind the mixture to finish.

In addition, the molding method of the molding material of the present invention is not particularly limited, and any method such as injection molding, transfer molding, and compression molding can be used. Of these, the injection molding method is particularly suitable. As an example of molding conditions for injection molding, various molded products can be molded at a temperature of 160 to 180 ° C., a pressure of 100 to 200 kg / cm ² , and a curing time of 30 seconds to 2 minutes.

  Next, this invention is demonstrated based on an Example and a comparative example.

1. Synthesis of Polyamide Resin Molten Phenol Resins A, B, and C (1) A predetermined amount of a novolac resin and a polyamide resin were put into a 5 l four-necked flask, and heated and mixed at 160 ° C. Next, after a mixture of 100 parts by weight of novolak resin and 20 parts by weight of polyamide resin began to dissolve, the stirring speed was increased to 170 to 180 rpm to make the mixture uniform, and then the system temperature was raised to 195 ° C. Next, water in the flask system was removed, and the mixture was eluted out of the flask system. Thereafter, the mixture was cooled and pulverized to obtain a polyamide resin-fused phenol resin A.
(2) Similarly, a polyamide resin molten phenol resin B was obtained using 100 parts by weight of novolac resin and 10 parts by weight of polyamide resin.
(3) Similarly, a polyamide resin-fused phenol resin C was obtained using 100 parts by weight of novolac resin and 30 parts by weight of polyamide resin.

2. Creation of phenolic resin molding materials
<Example 1>
Polyamide resin melted novolak phenol resin A 30% by weight, hexamethylenetetramine 9% by weight, glass fiber 50% by weight, polyamide resin 5% by weight, fluororesin A 3% by weight, magnesium oxide 1 as a curing catalyst % By weight, calcium stearate 1% by weight as a release agent, carbon black 1% by weight as a colorant, kneaded for 5 minutes with a heating roll at 85 to 90 ° C., and then pulverized by a pulverizer. A molding material was obtained.

<Example 2>
A molding material was obtained in the same manner as in Example 1 except that the polyamide resin-fused novolac phenol resin A was reduced to 25% by weight and the glass fiber was increased to 55% by weight.

<Example 3>
A molding material was obtained in the same manner as in Example 1 except that the polyamide resin-fused novolac type phenol resin A was increased to 35% by weight and the glass fiber was decreased to 45% by weight.

<Example 4>
A molding material was obtained in the same manner as in Example 1 except that the fluororesin B was used in place of the fluororesin A.

<Example 5>
A molding material was obtained in the same manner as in Example 1 except that the fluororesin C was used in place of the fluororesin A.

<Example 6>
A molding material was obtained in the same manner as in Example 1, except that the glass fiber was increased to 52% by weight and the fluororesin A was decreased to 1% by weight.

< Comparative Example 4 >
A molding material was obtained in the same manner as in Example 1 except that the glass fiber was reduced to 46% by weight and the fluororesin A was increased to 7% by weight.

< Comparative Example 5 >
A molding material was obtained in the same manner as in Example 1 except that the polyamide resin molten phenol resin C was used instead of the polyamide resin molten phenol resin A.

<Comparative Example 1>
30% by weight of polyamide resin unmelted novolak type phenol resin, 9% by weight of hexamethylenetetramine, 50% by weight of glass fiber, 5% by weight of polyamide resin, 3% by weight of fluororesin A, and oxidized as a curing catalyst based on the entire molding material 1% by weight of magnesium, 1% by weight of calcium stearate as a release material, 1% by weight of carbon black as a colorant, kneaded for 5 minutes with a heating roll at 85 to 90 ° C., and then pulverized by a pulverizer Thus, a molding material was obtained.

<Comparative Example 2>
A molding material was obtained in the same manner as in Comparative Example 1 except that the polyamide resin molten phenol resin A was used in place of the novolak type phenol resin, the glass fiber was increased to 53 wt%, and the fluororesin A was not used.

<Comparative Example 3>
A molding material was obtained in the same manner as in Comparative Example 2 except that the glass fiber was increased to 55% by weight, the polyamide resin was not used, and 3% by weight of the fluororesin A was blended.
It shows in Table 1 about the mixing | blending of an Example and a comparative example.

In the table, the materials used are as shown below.
(1) Novolac type phenolic resin: A-1077P manufactured by Sumitomo Bakelite Co., Ltd.
(2) Hexamethylenetetramine: manufactured by Mitsubishi Gas Chemical Co., Ltd. Hexamine (3) Glass fiber: manufactured by Nippon Sheet Glass Co., Ltd. Chopped strand (average fiber diameter 11 μm, average fiber length 3 mm)
(4) Polyamide resin: nylon 6 manufactured by Ube Industries, Ltd.
(5) Fluorine resin:
Fluorine-based resin A manufactured by Kitamura Co., Ltd. Polytetrafluoroethylene KT-600M (maximum particle size 74 μm, thermal decomposition temperature 450 ° C.);
Fluorine-based resin B manufactured by Kitamura Polytetrafluoroethylene KT-300M (maximum particle diameter 148 μm, thermal decomposition temperature 450 ° C.);
Fluorine-based resin C manufactured by Kitamura Polytetrafluoroethylene KTL-20N (maximum particle size 88 μm, thermal decomposition temperature 250 ° C.)
(6) Curing catalyst: Magnesium oxide (7) Release agent: Calcium stearate (8) Colorant: Carbon black The following evaluations were performed on the molding materials and molded articles obtained in the examples and comparative examples. The results are shown in Table 2.

(1) Mechanical properties Using the molding materials obtained in the examples and comparative examples, test pieces for measuring properties by transfer molding were prepared. The molding conditions were a mold temperature of 175 ° C. and a curing time of 3 minutes. Each characteristic was evaluated after molding. The bending strength was measured according to JIS K 6911.

(2) Abrasion characteristics The molding materials obtained in the examples and comparative examples were transfer molded (mold temperature: 175 ° C., curing time: 3 minutes) to mold test materials for evaluating sliding characteristics. For the sliding characteristics, the amount of wear of the test material and the amount of wear of the mating material were measured by “S-45C” as the mating material by a sliding wear test (Suzuki abrasion tester).

(3) Roll workability Roll workability was evaluated according to the following criteria.
○: Some unevenness in the thickness of the sheet is observed, but there is no practical problem. ◎: The thickness of the sheet is uniform.

Examples 1 to 9 are polyamide resin molten phenol resin (a), inorganic filler (b), polyamide resin (c), and molding resin of the present invention containing fluorine resin (d). Compared to Comparative Examples 1 to 3 which did not include all, the obtained molded articles had the same mechanical characteristics, but exhibited excellent wear characteristics.
In particular, Examples 1 to 3 were more excellent than other examples in wear characteristics because the content of each compound was in the optimum range. Moreover, since Examples 1-6 had the optimal particle content of a fluorine resin with a small particle diameter and high thermal decomposition temperature, and the polyamide content of a polyamide resin molten phenol resin, it was excellent in roll workability.

Claims (9)

Containing a polyamide resin molten phenol resin (a), an inorganic filler (b), a polyamide resin (c), and a fluorine-based resin (d) ;
Content of the said polyamide resin molten phenol resin (a) is 20 to 40 weight% with respect to the whole molding material,
Content of the said inorganic filler (b) is 35 to 65 weight% with respect to the whole molding material,
Content of the said polyamide resin (c) is 0.1 to 8 weight% with respect to the whole molding material,
Content of the said fluororesin (d) is 0.1 to 6 weight% with respect to the whole molding material,
The phenol resin molding material, wherein a polyamide resin content in the polyamide resin molten phenol resin (a) is 5 to 25 parts by weight with respect to 100 parts by weight of the phenol resin.   2. The phenol resin molding material according to claim 1, wherein the content ratio (d) :( a) of the fluororesin (d) and the polyamide resin-fused phenol resin (a) is from 3:97 to 15:85. .   The phenol resin molding material according to claim 1 or 2, wherein a thermal decomposition temperature of the fluororesin (d) is 370 ° C or higher.   The phenol resin according to any one of claims 1 to 3, wherein a content ratio (c) :( d) of the polyamide resin (c) and the fluororesin (d) is 50:50 to 75:25. Molding material.   The phenol resin according to any one of claims 1 to 4, wherein a total content of the polyamide resin (c) and the fluororesin (d) is 0.5 to 15% by weight with respect to the entire molding material. Molding material.   The total content of the polyamide resin and the polyamide resin (c) in the polyamide resin molten phenol resin (a) and the content ratio of the fluororesin (d) is 10: 1 to 5: 3. The phenolic resin molding material according to any one of 5.   The phenol resin molding material according to any one of claims 1 to 6, wherein the polyamide resin (c) contains at least one selected from nylon 6, nylon 66, nylon 46, nylon 11, and nylon 12.   The phenol resin molding according to any one of claims 1 to 7, wherein the fluororesin (d) contains at least one selected from polytetrafluoroethylene, polychlorotrifluoroethylene, and polybilidene fluoride. material.   It is a manufacturing method of the phenol resin molding material in any one of Claims 1-8, Comprising: It has the process of melt | dissolving a phenol resin and a polyamide resin (c) previously, The manufacturing method of the phenol resin molding material characterized by the above-mentioned. .