JP2015120848A - Phenol resin molding material and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenol resin molding material that is excellent in dimensional stability and low linear expansion without impairing heat resistance, mechanical strengh and sliding characteristics and to provide a method for producing the phenol resin molding material.SOLUTION: The phenol resin molding material comprises a phenol resin and an inorganic filler. The inorganic filler is at least one kind selected from the group consisting of a glass bead, a glass powder, a carbon fiber, a milled fiber and a lubricity-imparting agent and the content of the inorganic filler is not less than 400 pts.mass to not more than 900 pts.mass based on 100 pts.mass of the phenol resin. The lubricity-imparting agent may be at least one kind selected from the group consisting of graphite, a fluororesin powder and a molybdenum disulfide. The molding material may further contain a boron compound. The boron compound is preferably a boric acid, a boron oxide or a boron nitride. The inorganic filler may contain a glass bead, a carbon fiber, a glass powder or a milled fiber and a lubricity-imparting agent.

Description

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

  Molding materials containing phenolic resins are widely used in various fields as materials having an excellent balance of heat resistance, dimensional accuracy, wear resistance, mechanical strength, cost, and the like. In recent years, in the automotive field, for example, metal parts near the brakes and engine parts such as brake pistons and engine oil pump valves have been made resin. Such automobile parts are generally required to have heat resistance, dimensional accuracy, wear resistance, mechanical strength, and the like. In order to meet such demands, it is an effective means to add an inorganic filler and reduce the amount of resin.

  However, if the amount of resin in the molding material is reduced, moldability is lowered. In addition, the phenol resin has a property of shrinking after molding in order to cause a volume change in the molding process. On the other hand, the volume change of the inorganic filler is much smaller than that of the phenol resin. For this reason, residual strain occurs at the boundary surfaces due to the difference in volume change between the inorganic filler and the phenol resin. In particular, when a fibrous or plate-like anisotropic inorganic filler is used, the inorganic filler is oriented when the molding material flows, so the strain direction becomes non-uniform, and the shrinkage rate, moisture absorption, and dimensional changes after heat treatment Anisotropy occurs and warpage and distortion are likely to occur. Further, when the molding material contains an inorganic filler and a phenol resin, the degree of dimensional change varies depending on the shape and molding conditions of the molded product, and it is difficult to obtain a molded product with stable dimensional accuracy.

  In order to solve these disadvantages, various investigations have been made on the filler. As an example, it has been proposed to reduce the amount of phenol resin and to blend fused silica having different particle diameters (Japanese Patent Laid-Open No. 2009-102596). According to such a molding material, the dimensional accuracy is improved by reducing the amount of phenol resin, and by blending with fused silica having different particle sizes, the molding shrinkage rate, shrinkage anisotropy, The linear expansion coefficient can be reduced. However, since this phenol resin molding material uses fused silica, the Mohs hardness becomes high, the counterpart material wears and self-wears, and there is a risk that inconveniences such as load on production equipment may occur.

  As another proposal, it has been studied to add wollastonite or glass fiber in addition to borosilicate glass beads as a filler for the molding material (see JP 2009-102595 A). According to this molding material, shrinkage anisotropy can be reduced without impairing heat resistance and moldability. Therefore, after molding, moisture absorption treatment, suppress the occurrence of warpage and distortion due to dimensional changes after heat treatment, and reduce the thermal expansion coefficient to suppress the occurrence of cracks and the separation of the filler and phenolic resin interface. it can. However, since wollastonite and glass fibers are oriented when the molding material flows, the strain direction becomes non-uniform as described above, and there is anisotropy in the dimensional change after heat treatment after molding shrinkage and moisture absorption. It causes warping and distortion. Further, when the blending amount of the glass fiber is increased in order to reduce the molding shrinkage rate and the linear expansion coefficient, the kneading stability and moldability at the time of production are remarkably impaired. Therefore, from the viewpoint of manufacturability, there is a limit to the blending amount of the glass fiber, and as a result, the molding shrinkage rate and the linear expansion coefficient cannot be made sufficiently small.

  As another proposal, a material containing cashew dust and glass beads as a filler has been studied (see JP 2012-121932 A). However, cashew dust is inferior in heat resistance because it is an organic material, and in particular, it cannot satisfy the performance under heat. In addition, when a molded product containing cashew dust is used for an application that requires contact with oil and requires slidability, the oil may ooze out from the molded product and carbonize the oil. If the oil component is carbonized, a stable dynamic friction coefficient may not be obtained due to the presence of carbide on the sliding surface.

JP 2009-102596 A JP 2009-102595 A JP 2012-121932 A

  The present invention has been made based on the above circumstances, a phenol resin molding material excellent in dimensional stability and low linear expansion without impairing heat resistance, mechanical strength, and sliding characteristics, and a method for producing the same. The purpose is to provide.

  As a result of intensive studies to overcome the above-mentioned problems, the present inventors have found that the above-described problems can be solved by blending a specific inorganic filler into a phenol resin at a specific ratio, thereby completing the present invention. It came to.

  That is, the present invention is a phenol resin molding material containing a phenol resin and an inorganic filler, wherein the inorganic filler is selected from the group consisting of glass beads, glass powder, carbon fiber, milled fiber, and a lubricity imparting material. And a content of the inorganic filler is 400 parts by mass or more and 900 parts by mass or less with respect to 100 parts by mass of the phenol resin.

  According to the phenolic resin molding material of the present invention, by adding a specific inorganic filler to the phenolic resin at a specific ratio, the linear expansion coefficient, molding shrinkage ratio, and shrinkage anisotropy can be reduced, and dimensional stability and resistance to resistance can be reduced. It is possible to provide a molded article having excellent wear characteristics. Moreover, when a lubricity imparting material is contained as the inorganic filler, the friction coefficient can be stabilized and the wear resistance can be further improved.

  The phenol resin molding material may further contain a boron compound. The boron compound may be at least one selected from the group consisting of boric acid, boron oxide, and boron nitride. By containing a boron-based compound in this manner, a molded product with higher wear resistance can be obtained while ensuring mechanical strength.

  The lubricity imparting material is preferably at least one selected from the group consisting of graphite, fluororesin powder and molybdenum disulfide. By containing these lubricity imparting materials, the friction coefficient can be stabilized and the wear resistance can be further improved.

  The inorganic filler may contain at least one selected from the group consisting of the glass beads, the carbon fiber, the glass powder, and the milled fiber, and the lubricity-imparting material. By containing the lubricity-imparting material and other inorganic fillers in this way, the wear resistance of the molded product can be further improved while reducing linear expansion, molding shrinkage rate and shrinkage anisotropy. .

  The phenol resin molding material may be a granulated product obtained by stirring granulation. Thus, it is a granulated material obtained by stirring granulation, and can make uniform the particle size of a resin composition. Therefore, handling at the time of molding can be improved, and manufacturing efficiency can be improved. In addition, since the particle size of the resin composition is made uniform, the proportion of fine powder is reduced, so that generation of fine powder during handling can be suppressed, and adverse effects on the working environment can be suppressed.

  An organic solvent is preferable as the binding liquid for agitation granulation. Thus, since the binding liquid for granulation is an organic solvent, stirring of the resin composition at the time of granulation can be performed smoothly.

  The phenol resin is preferably dissolved in an organic solvent. In this case, the viscosity when 100 parts by mass of the phenol resin is dissolved in 35 parts by mass of the organic solvent is preferably 150 mPa · s or more and 300 mPa · s or less. Thus, by dissolving a phenol resin in an organic solvent, the affinity between the phenol resin and the inorganic filler is improved, and cracks and the like in the molded product can be suppressed, so that productivity is improved. Such an effect can be more suitably obtained by setting the viscosity of the phenol resin molding material in the above range. Further, by dissolving the phenol resin in the organic solvent, the handling property of the phenol resin molding material at the time of molding is improved, so that the productivity is improved.

  The organic solvent is preferably at least one selected from the group consisting of methanol, ethanol and methyl ethyl ketone. Since these organic solvents have a low boiling point, the organic solvent can be easily removed during granulation or molding.

  The phenol resin molding material is preferably used as a molding material for automobile parts. The automobile parts are preferably compressors or engine oil circulation parts. By using the phenolic resin molding material as a molding material for automotive parts such as compressors, the weight of automotive parts can be reduced, and carbon and metal can be substituted, reducing the cost of materials and reducing the number of production steps. I can expect.

  Here, “glass beads” refers to spherical or substantially spherical ones. “Glass powder” refers to non-spherical and non-fibrous powder not contained in glass beads, glass fibers, and milled fibers. “Milled fiber” refers to a material obtained by pulverizing inorganic fibers such as glass fibers and carbon fibers. Therefore, milled fiber is distinguished from glass fiber and carbon fiber in that the fiber length is short (the aspect ratio is small).

  According to the phenolic resin molding material of the present invention, by adding a specific inorganic filler to the phenolic resin at a specific ratio, the linear expansion coefficient, molding shrinkage ratio, and shrinkage anisotropy can be reduced, and dimensional stability and resistance to resistance can be reduced. It is possible to provide a molded article having excellent wear characteristics. Moreover, when a lubricity imparting material is contained as the inorganic filler, the friction coefficient can be stabilized and the wear resistance can be further improved.

  Hereinafter, the phenol resin molding material of the present invention and the production method thereof will be described in detail.

[Phenolic resin molding materials]
The phenol resin molding material of the present invention contains a phenol resin (hereinafter also referred to as “(A) phenol resin”) and an inorganic filler (hereinafter also referred to as “(B) inorganic filler”). The said phenol resin molding material is also called a boron type compound (henceforth "(C) boron type compound") and an organic solvent (henceforth "(D) organic solvent") in the range which does not impair the effect of this invention. ) Or other additives (hereinafter also referred to as “(E) additives”).

<(A) Phenolic resin>
(A) A phenol resin is a main resin in the phenol resin molding material. The (A) phenolic resin is not particularly limited, and may be either a novolac type phenolic resin or a resol type phenolic resin, or a combination thereof.

  The novolac type phenol resin is preferable in that it has excellent dimensional stability and wear resistance. The novolac type phenol resin is obtained by condensing phenols and aldehydes in the presence of an acid catalyst.

  A resol-type phenol resin is preferable in that it has excellent dimensional stability at high temperatures and can prevent peripheral corrosion because it does not require hexamethylenetetramine as a curing agent. Examples of the resol type phenol resin include a methylol type and a dimethylene ether type. Among these, a dimethylene ether type phenol resin is preferable in that it has excellent wear resistance.

  When the novolac type phenol resin (NPh) and the resol type phenol resin (RPh) are used in combination, the mass ratio (NPh / RPh) of these phenol resins is preferably 0.1 or more and 15 or less. By setting the mass ratio (NPh / RPh) within such a range, the molding shrinkage rate and shrinkage anisotropy can be reduced, and the dimensional stability can be improved.

  When (D) the organic solvent is contained in the phenol resin molding material, the viscosity when (A) 100 parts by mass of the phenol resin is dissolved in 35 parts by mass of the (D) organic solvent is 150 mPa · s to 300 mPa · s. The following is preferred. (A) By setting it as the said range of the viscosity of a phenol resin, since the handleability of the said phenol resin molding material at the time of shaping | molding improves, productivity improves.

  The content of the (A) phenol resin in the phenol resin molding material is usually 1% by mass to 50% by mass, preferably 5% by mass to 20% by mass, more preferably 10% by mass to 15% by mass. . (A) If the content of the phenol resin is less than 1% by mass, the moldability deteriorates. On the other hand, if the content of the (A) phenol resin exceeds 50% by mass, the heat resistance, dimensional accuracy, wear resistance, mechanical strength and the like may be reduced.

<(B) Inorganic filler>
(B) The inorganic filler reduces the linear expansion coefficient, molding shrinkage ratio, and shrinkage anisotropy of the phenol resin molding material, and improves mechanical strength such as bending strength and dimensional stability of the molded product. . This (B) inorganic filler is at least one selected from the group consisting of glass beads, glass powder, carbon fibers, milled fibers, and a lubricity-imparting material.

(Glass beads)
Glass beads are spherical or substantially spherical. The glass beads may be spherical or substantially spherical in appearance, and include a hollow glass balloon. Examples of the material of the glass beads include A glass, E glass, S glass, D glass, and high elastic modulus glass. Among these, E glass that is excellent in strength improvement and cost is preferable. The average particle diameter of the glass beads is preferably 1 μm or more and 500 μm or less. Here, the “average particle diameter” refers to the median diameter (d50) measured using laser scattering diffraction type particle size distribution measurement. Hereinafter, the term “average particle diameter” is defined in the same manner.

(Glass powder)
Glass powder refers to non-spherical and non-fibrous powder not contained in glass beads, glass fibers, and milled fibers. The material and average particle diameter of the glass powder are the same as those of the glass beads.

(Carbon fiber)
The carbon fiber is not particularly limited as the carbon fiber, and examples thereof include PAN-based carbon fiber, pitch-based carbon fiber, phenol-based carbon fiber, and the like. Among these, PAN-based carbon fiber is preferable. The average fiber diameter of the carbon fibers is preferably 3 μm or more and 15 μm or less, and more preferably 5 μm or more and 13 μm or less. The average fiber length of the carbon fibers is preferably 1 mm or more and 3 mm or less. By using carbon fibers having an average fiber diameter and fiber length in such a range, workability when producing a phenol resin molding material can be improved, and the mechanical strength of the molded body can be improved. .

(Milled fiber)
The milled fiber is obtained by pulverizing inorganic fiber into a powder form, a cotton form or the like, and has a fiber length and an aspect ratio smaller than those of the carbon fiber. As this milled fiber, glass milled fiber obtained by pulverizing glass fiber, carbon milled fiber obtained by pulverizing carbon fiber are preferable, and carbon milled fiber is more preferable. The average fiber length of the milled fiber is preferably 10 μm or more and 200 μm or less, and more preferably 30 μm or more and 150 μm or less. The average fiber diameter of the milled fiber is preferably 3 μm to 15 μm, and more preferably 5 μm to 13 μm. The aspect ratio of the milled fiber is preferably 2 or more and 10 or less, and more preferably 3 or more and 8 or less.

(Lubricity imparting material)
The lubricity-imparting material imparts lubricity to the molded product in addition to the role of the inorganic filler described above. Examples of the lubricity-imparting material include a carbon material, a fluororesin, and a metal sulfide. Among these, a carbon material and a fluororesin are preferable. These lubricity-imparting materials may be used alone or in combination of two or more. The said phenol resin molding material can provide the molded article which is excellent in abrasion resistance by containing a lubricity imparting material.

  The carbon material has a layered structure, for example, and is distinguished from carbon fibers that are fibrous. Examples of the carbon material include graphite and graphite fluoride, and graphite is preferable. The graphite may be natural graphite or artificial graphite. Natural graphite is classified into flake graphite closest to the crystallinity of true graphite, then flake graphite with high crystallinity, and soil-like graphite due to the difference in crystallinity. It can also be used with other graphite. The average particle diameter of this graphite is preferably 1 μm or more and 150 μm, and more preferably 5 μm or more and 50 μm or less.

  Note that fluorinated graphite cannot be clearly classified as an inorganic substance, but is treated as an inorganic substance in this specification.

  The fluororesin is not particularly limited, but polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexapropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoro An ethylene / perfluorodioxole copolymer (TFE / PDD) is exemplified, and among these, polytetrafluoroethylene (PTFE) is preferable. The average particle size of the fluororesin powder is preferably 1 μm or more and 50 μm or less, and more preferably 1 μm or more and 20 μm. The maximum particle size of the fluororesin powder is preferably 100 μm or less, and more preferably 50 μm or less.

  Examples of the metal sulfide include tin monosulfide, tin disulfide, tin trisulfide, tungsten disulfide, and molybdenum disulfide. Among these, molybdenum disulfide is preferable. The average particle size of the metal sulfide is preferably 0.1 μm or more and 10 μm or less, and more preferably 1 μm or more and 3 μm or less.

  As the lubricity-imparting material, graphite, polytetrafluoroethylene (PTFE), and molybdenum disulfide are more preferable in terms of reducing the wear coefficient and having less influence on the counterpart material, and graphite is more preferable in terms of excellent wear resistance. .

  (B) Content of an inorganic filler is 400 to 900 mass parts with respect to 100 mass parts of phenol resins. (B) When the content of the inorganic filler is within the above range, it is possible to reduce the linear expansion coefficient, the molding shrinkage ratio, and the shrinkage anisotropy, and to provide a molded article having excellent dimensional stability and wear resistance. it can. In order to obtain such effects more appropriately, the content of the (B) inorganic filler is preferably 450 parts by mass or more and 700 parts by mass or less, and more preferably 500 parts by mass or more and 650 parts by mass or less.

<(C) Boron-based compound>
(C) The boron-based compound suppresses a decrease in wear resistance and mechanical strength of the molded product, and is an optional component of the phenol resin molding material. Examples of this (C) boron-based compound include boric acid, boron oxide, boron nitride, borate, borax, borate ester and the like. Examples of borates include metal salts such as metaboric acid and tetraboric acid, and specific examples include zinc borate. Among these, boric acid, boron oxide, boron nitride, zinc borate, and borax are preferable, and boric acid, boron oxide, and boron nitride are more preferable. These boron compounds may be used alone or in combination of two or more.

  (C) As content of a boron-type compound, 0.5 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of (A) phenol resin, and 1.0 mass part or more and 7.0 mass parts or less are preferable. More preferred. (C) The fall of abrasion resistance can be suppressed because content of a boron-type compound shall be 0.5 mass part or more. On the other hand, the fall of mechanical strength can be suppressed by making content of (C) boron type compound into 10 mass parts or less.

<(D) Organic solvent>
(D) The organic solvent dissolves the (A) phenol resin and is an optional component of the phenol resin molding material. (D) As an organic solvent, methanol, ethanol, methyl ethyl ketone, isopropyl alcohol, acetone, ethylene glycol etc. are mentioned, for example. Among these, methanol, ethanol, and methyl ethyl ketone are preferable because of their low boiling point and easy removal.

  Content of (D) organic solvent in the said phenol resin molding material is 15 to 50 mass% with respect to 100 mass parts of (A) phenol resin, for example. (D) When content of an organic solvent is less than 15 mass%, there exists a possibility that (A) phenol resin cannot fully be melt | dissolved. On the other hand, when the content of (D) the organic solvent exceeds 50% by mass, it is difficult to remove (D) the organic solvent, and the generation rate of defective products may be increased.

<(E) Additive>
(E) As an additive, a hardening | curing agent, a mold release agent, a hardening accelerator, a coupling agent, a pigment etc. are mentioned, for example. These (E) additives may be used individually by 1 type, and may use 2 or more types together.

  Examples of the curing agent include hexamethylenetetramine. Examples of the mold release agent include calcium stearate and zinc stearate. Examples of the curing accelerator include slaked lime and magnesium oxide.

  The coupling agent prevents the (B) inorganic filler from falling off during sliding of the molded product. This coupling agent is contained in (A) the phenol resin during the adjustment of the phenol resin molding material, and (B) an inorganic filler whose surface is subjected to coupling treatment is added during the adjustment of the phenol resin molding material. It is different from doing. Thus, by making the said phenol resin molding material ((A) phenol resin) contain a coupling agent, the adhesiveness of (A) phenol resin and (B) inorganic filler improves, and wear resistance and machine It is possible to improve the mechanical strength. Although it does not specifically limit as a coupling agent, For example, a silane coupling agent, a titanate coupling agent, etc. are mentioned, A silane coupling agent with a higher adhesive improvement effect is more preferable.

<Method for producing phenolic resin molding material>
The phenol resin molding material is, for example, (A) a phenol resin and (B) an inorganic filler, and if necessary, (C) a boron-based compound, (D) an organic solvent, and (E) an additive granulation. It is manufactured as a granulated product. Examples of the stirring granulation method include a method using a Henschel mixer, a super mixer, or the like.

  In the stirring granulation step, a binding liquid for granulation can be used. As the binding liquid for granulation, for example, the same one as exemplified as the organic solvent (D) can be used. When (D) an organic solvent is used as the binding liquid for granulation, methanol, ethanol and methyl ethyl ketone are preferred from the viewpoint of being easy to remove among those exemplified as (D) organic solvent.

  Moreover, the granulated product of the phenol resin molding material can also be produced by making a kneaded product obtained by heating and kneading with a pressure kneader, a twin screw extruder or the like into a sheet and pulverizing it. The sheet can be pulverized using, for example, a pelletizer or a power mill.

  The average particle size (d50) of the granulated product is preferably 1,000 μm or more and 10,000 μm or less, and more preferably 1,000 μm or more and 5,000 μm or less. By making the average particle diameter (d50) of the granulated product within the above range, the handling property at the time of molding can be improved, and the material melting in the cylinder at the time of injection molding becomes uniform, so that the filling Defects can be suppressed and productivity can be improved.

  If the said phenol resin molding material is prepared with such a manufacturing method, each component is mix | blended uniformly and the granulated material excellent in the handleability by which the uniform particle diameter was achieved can be obtained efficiently. In particular, when producing the phenol resin molding material as a granulated product by stirring granulation, it is possible to suppress the generation of fine powder, and can provide a dust-free molding material that is less likely to adversely affect the work environment, Hygiene can be improved.

  The phenol resin molding material is obtained by kneading (A) a phenol resin, (B) an inorganic filler and (D) an organic solvent, and (C) a boron compound and (E) an additive as necessary. You can also. The phenol resin molding material obtained by such a production method uses (A) a phenol resin dissolved in (D) an organic solvent.

<Uses of phenolic resin molding materials>
The phenol resin molding material can be applied to injection molding, transfer molding, compression molding and the like. Further, the phenol resin molding material has excellent dimensional stability, wear resistance and impact resistance. Accordingly, the phenol resin molding material is suitable as a molding material for automobile parts, for example, compressors and engine oil circulation parts. The automotive molded article thus obtained exhibits excellent dimensional stability even when used for a long time at high temperatures.

  The molding conditions in the case of using the phenol resin molding material are not particularly limited. For example, in the case of injection molding, the cylinder temperature is usually 70 ° C. or higher and 100 ° C. or lower at the front, and 30 ° C. or higher and 50 ° C. or lower at the rear. The mold temperature (curing temperature) is usually 160 ° C. or higher and 180 ° C. or lower.

  When the molded product thus obtained is used as a sliding member for use, it is preferable to perform a baking treatment after molding. Sliding characteristics can be improved by subjecting the molded product to firing treatment. As the firing treatment, various known methods can be used, and examples thereof include a method of firing a molded product in a firing furnace in a vacuum atmosphere or an inert gas atmosphere such as nitrogen gas. Note that the inside of the firing furnace is preferably in an oxygen-free state.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by a following example. In the examples, “parts” and “%” indicate “parts by mass” and “% by mass” unless otherwise specified. Moreover, when describing a compounding quantity using a mass part in this specification, a phenol resin is described as a mass part with respect to 100 mass parts.

<Example 1>
(Preparation of phenol resin composition)
Under the following conditions, 100 parts by weight of novolak type phenolic resin, 400 parts by weight of glass beads as inorganic filler, 5 parts of boric acid as boron compound, 15 parts by weight of hexamethylenetetramine as additives, 10 parts by weight of calcium stearate, Recoble 1 Part by mass, 3 parts by mass of spirit black and 3 parts by mass of silane coupling agent were blended and mixed uniformly to obtain a phenol resin composition.

Machine: “FM1050J / I” by Mitsui Miike Chemical Industries, Ltd.
Temperature: Temperature rise from 40 ° C. to 80 ° C. in 10 minutes, then temperature drop from 80 ° C. to 40 ° C. in 5 minutes Rotational speed: 1,000 rpm for 10 minutes from start, then 500 rpm for 5 minutes

(Preparation of test piece)
Using the obtained phenol resin composition, injection molding was performed under the following conditions to obtain a test piece of Example 1.

Cylinder temperature: front 85 ° C, rear 40 ° C
Mold temperature: 170 ° C
Curing time: 60 seconds

<Examples 2-27 and Comparative Examples 1-11>
Example 2 to 27 and Comparative Examples 1 to 11 were prepared in the same manner as in Example 1 except that the blending ratio of each component was as shown in Table 1. In Table 1, “-” means that the corresponding component is not added. Moreover, the detail of each component used in Examples 1-27 and Comparative Examples 1-11 is as follows.

<Phenolic resin>
Resol type phenolic resin: “CP701K” from Asahi Organic Materials Co., Ltd.
Novolac type phenolic resin: “CP1006” from Asahi Organic Materials Co., Ltd.

<Inorganic filler>
Carbon fiber: “Torayca chopped fiber T008A” manufactured by Toray Industries, Inc.
Glass beads: Unitika's “Unibeads UB-06L”
Glass powder: “Unibeads UP-05L” from Unitika
Carbon milled fiber: "Toray milled fiber MLD300" manufactured by Toray Industries, Inc.
Graphite: “Blue PA” from Nippon Graphite Industries Co., Ltd.
Fluororesin: Daikin's "Lublon"
Molybdenum disulfide: “Molyheite” by Nippon Graphite Industries
Glass fiber: Nittobo's “CS3E479S”

<Organic solvent>
Methanol: Sumitomo Chemical Co., Ltd. Ethanol: Sumitomo Chemical Co., Ltd. Methyl ethyl ketone: Sumitomo Chemical Co., Ltd. Acetone: Sumitomo Chemical Co., Ltd.

<Boron compound>
Boric acid: Nitto Denko Corporation Boron oxide: Nitto Denko Corporation Boron nitride: Showa N

<Additives>
Hexamethylenetetramine: Changchun's “Sperfine”
Slaked lime: Irigo lime industry Calcium stearate: Tannan Chemical Industry Co., Ltd. Recoble: Partially saponified ester of Montanic acid from Clariant Japan Spirit Black: Orient Chemical Co., Ltd. Silane coupling agent: "KBE903" from Shin-Etsu Chemical Co., Ltd.

(Evaluation of specimen)
About the test pieces of Examples 1 to 27 and Comparative Examples 1 to 11, based on the following methods, dissolution viscosity, molding shrinkage rate, shrinkage anisotropy, dimensional change rate, bending strength, linear expansion coefficient, molding appearance, and friction wear The test was evaluated. The results are shown in Tables 1-3.

(1) Dissolution viscosity About the said test piece, dissolution viscosity was measured according to JIS-K7117-1 standard (1999).

(2) Molding Shrinkage The molding shrinkage of the above test piece was measured according to JIS-K6911 standard (2006).
(3) Shrinkage anisotropy About the said test piece, the difference of the molding shrinkage rate of the vertical direction and the molding shrinkage rate of a parallel direction of the test piece according to JIS-K6911 standard (2006) was measured.
(4) Dimensional change rate Using a test piece according to JIS-K6911 standard (2006), the difference in dimensions before heat treatment and after 20 ° C. × 1000 hours was measured.
(5) Bending strength Bending strength was measured according to JIS-K6911 standard (2006).
(6) Linear expansion coefficient Using a test specimen of φ5 × L20mm, the rate of temperature increase during measurement was 5 ° C / min, the displacement amount of the length was plotted, and the linear expansion coefficient was determined from the relationship between the measured temperature and the displacement amount. Was calculated.
(7) Molding appearance About the test piece, the presence or absence of abnormality in the smoothness of the outer surface was visually evaluated as follows.
○: No abnormality is observed ×: Abnormality is observed (8) Friction and wear test The friction and wear test was performed by measuring the resin wear amount, the counterpart wear amount, and the friction coefficient under the following sliding conditions.

(Sliding conditions)
Resin: Square plate test piece of 30 mm x 30 mm x 3 mm Mating material: Hollow cylinder with outer diameter 25.6 mm, inner diameter 20 mm, length 15 mm Mating material: S45C
Test surface pressure: 4.9 MPa
Test speed: 0.67 m / sec Test time: 1 hour Environment: No lubrication at normal temperature

  As is apparent from Tables 1 to 3, the test pieces of Examples 1 to 27 have a small molding shrinkage rate, shrinkage anisotropy and dimensional change rate, and are suitable for bending strength, linear expansion coefficient, molding appearance and frictional wear test. It was excellent.

According to the phenolic resin molding material of the present invention, by adding a specific inorganic filler to the phenolic resin at a specific ratio, the linear expansion coefficient, molding shrinkage ratio, and shrinkage anisotropy can be reduced, and dimensional stability and resistance to resistance can be reduced. It is possible to provide a molded article having excellent wear characteristics. Moreover, when a lubricity imparting material is contained as the inorganic filler, the friction coefficient can be stabilized and the wear resistance can be further improved.

Claims (13)

A phenolic resin molding material containing a phenolic resin and an inorganic filler,
The inorganic filler is at least one selected from the group consisting of glass beads, glass powder, carbon fiber, milled fiber, and a lubricity imparting material,
Content of the said inorganic filler is 400 to 900 mass parts with respect to 100 mass parts of said phenol resins, The phenol resin molding material characterized by the above-mentioned.   The phenol resin molding material according to claim 1, further comprising a boron compound.   The phenol resin molding material according to claim 2, wherein the boron-based compound is at least one selected from the group consisting of boric acid, boron oxide, and boron nitride.   The phenol resin molding material according to claim 1, 2 or 3, wherein the lubricity imparting material is at least one selected from the group consisting of graphite, fluororesin powder and molybdenum disulfide.   5. The method according to claim 1, wherein the inorganic filler contains at least one selected from the group consisting of the glass beads, the carbon fiber, the glass powder, and the milled fiber, and the lubricity imparting material. The phenol resin molding material of Claim 1.   The phenol resin molding material according to any one of claims 1 to 5, which is a granulated product obtained by stirring granulation.   The phenol resin molding material according to claim 6, wherein the binding liquid for granulation in the stirring granulation is an organic solvent.   The phenol resin molding material according to any one of claims 1 to 5, wherein the phenol resin is dissolved in an organic solvent.   The phenol resin molding material according to claim 8, wherein a viscosity when 100 parts by mass of the phenol resin is dissolved in 30 parts by mass or more and 40 parts by mass or less of the organic solvent is 150 mPa · s or more and 300 mPa · s or less.   The phenol resin molding material according to any one of claims 7 to 9, wherein the organic solvent is at least one selected from the group consisting of methanol, ethanol, and methyl ethyl ketone.   The phenol resin molding material according to any one of claims 1 to 10, which is used as a molding material for automobile parts.   The phenol resin molding material according to claim 11, wherein the automobile part is a circulating part of a compressor or engine oil. It is a manufacturing method of the phenol resin molding material according to any one of claims 1 to 12,
Having a step of producing a granulated product by stirring granulation of a phenol resin and an inorganic filler;
The method for producing a phenol resin molding material, wherein the inorganic filler is at least one selected from the group consisting of glass beads, glass powder, carbon fiber, milled fiber, and a lubricity-imparting material.