WO2010113697A1 - Molding phenolic resin material - Google Patents
Molding phenolic resin material Download PDFInfo
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- WO2010113697A1 WO2010113697A1 PCT/JP2010/054961 JP2010054961W WO2010113697A1 WO 2010113697 A1 WO2010113697 A1 WO 2010113697A1 JP 2010054961 W JP2010054961 W JP 2010054961W WO 2010113697 A1 WO2010113697 A1 WO 2010113697A1
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- WIPO (PCT)
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- molding material
- phenol resin
- resin molding
- phenolic resin
- cashew dust
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
Definitions
- the present invention relates to a phenol resin molding material.
- Patent Document 1 As automobiles become lighter, molded parts using phenolic resin molding materials are used as substitutes for metal parts in automotive mechanical parts. Since these mechanical parts are used as precision parts in a high temperature environment, both dimensional accuracy and thermal dimensional stability are required. Conventionally, by combining an inorganic base material such as glass fiber, glass bead, talc, and mica with a phenol resin molding material, both dimensional accuracy and hot dimensional stability have been achieved. (Patent Document 1)
- the present invention was made in order to solve the problem of high specific gravity of phenol resin molding materials by blending a conventional inorganic base material, and its purpose is to ensure mechanical strength while maintaining low specific gravity.
- An object of the present invention is to provide a phenol resin molding material having excellent dimensional stability during heating.
- a phenolic resin molding material comprising a novolac type phenolic resin, cashew dust and glass beads.
- the increase in specific gravity of the phenol resin molding material by the inorganic base material blending which has been a conventional problem, is improved, and the hot dimension is secured while ensuring the mechanical strength of the molded product using the molding material. Stability can be improved.
- the phenol resin molding material of the present invention contains a novolac type phenol resin.
- the novolak type phenol resin used in the present invention is not particularly limited, and examples thereof include novolak type phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, cashew modified novolak resin, and oil modified phenol resin. .
- the content of the novolak-type phenol resin in the phenol resin molding material is not particularly limited, but is preferably 15 to 50% by weight, particularly preferably 20 to 40% by weight, and more preferably 22 to 30% by weight. Preferably there is.
- the content of the novolac type phenol resin is not less than the above lower limit, the production of the phenol resin molding material is facilitated and the fluidity that facilitates the molding of the phenol resin molding material is obtained.
- the above upper limit value it is possible to suppress the dimensional change of the molded product due to the novolac type phenol resin and to secure the dimensional stability of the molded product obtained by curing the phenol resin molding material.
- novolak resins are usually cured using hexamethylenetetramine as a curing agent.
- the content of hexamethylenetetramine is not particularly limited, but is preferably 10 to 20 parts by weight with respect to 100 parts by weight of the novolak resin.
- the content of hexamethylenetetramine is less than the above lower limit, it takes time to cure the phenol resin molding material, and the molding material may be insufficiently cured.
- the upper limit is exceeded, the molded product obtained by curing the phenol resin molding material may swell.
- the phenolic resin molding material of the present invention contains cashew dust.
- the phenol resin molding material of the present invention uses an organic base cashew dust (specific gravity 1.1) having a low specific gravity instead of an inorganic base material having a high specific gravity which has been conventionally used for a phenol resin molding material.
- organic base materials such as wood flour (specific gravity 1.4) and cotton flock (specific gravity 1.4). Since heat resistance is inferior, there is a problem that dimensional stability during heating is lowered.
- cashew dust is an organic base material excellent in heat resistance, and by blending cashew dust, it is possible to achieve both dimensional stability during heating and lower specific gravity of the phenol resin molding material.
- the cashew dust used in the present invention is not particularly limited. Specifically, it is a pulverized product of a cured resin obtained by polycondensation of cashew nut shell liquid, and uses paraformaldehyde or furfural as a curing agent. Or what was manufactured without using a hardening
- the particle size of cashew dust used in the present invention is not particularly limited, but is preferably 1 to 400 ⁇ m, particularly preferably 1 to 150 ⁇ m, and more preferably 1 to 50 ⁇ m.
- the particle size of cashew dust can be measured using, for example, a particle size distribution measuring device. Specific examples include LA-920 manufactured by Horiba, Ltd.
- the content of cashew dust in the phenolic resin molding material is not particularly limited, but is preferably 1 to 20% by weight, particularly preferably 6 to 18% by weight, and more preferably 10 to 15% by weight. Is preferred.
- the content of cashew dust is preferably 1 to 20% by weight, particularly preferably 6 to 18% by weight, and more preferably 10 to 15% by weight. Is preferred.
- By setting the content of cashew dust to 1% by weight or more it is possible to improve the thermal dimensional stability of the phenolic resin molding material.
- the content of cashew dust is 20% by weight or less, the production of the phenol resin molding material is facilitated, and at the same time, the moldability can be secured without reducing the fluidity of the phenol resin molding material. .
- the phenol resin molding material of the present invention contains glass beads.
- glass beads By using glass beads together with cashew dust as a base material, it is possible to ensure the mechanical strength of a molded product obtained by curing a phenol resin molding material. Further, by using glass beads, the dimensional accuracy of the molding material can be improved as compared with the case of using glass fibers.
- the glass beads used in the present invention do not refer to small decorative balls with threading holes used for interior decorations and handicrafts, but mean that the overall shape is substantially spherical.
- the material has a higher heat softening temperature than a water-soluble molding material made of biodegradable resin such as starch.
- the content of the glass beads in the phenolic resin molding material is not particularly limited, but is preferably 30 to 50% by weight, particularly preferably 30 to 45% by weight, and further 32 to 40% by weight. Is preferred.
- the content of glass beads is 30% by weight or more, the mechanical strength of the phenol resin molding material can be improved.
- the content of the glass beads is 50% by weight or less, the production of the phenol resin molding material becomes easy, and the moldability can be ensured without deteriorating the fluidity of the phenol resin molding material.
- the phenol resin molding material of the present invention may contain other inorganic base material in addition to the glass beads.
- the inorganic base material that can be used in the present invention include calcined kaolinite, calcined clay, silica, glass powder, calcium carbonate, wollastonite, aluminum hydroxide, magnesium carbonate and other powdered inorganic base materials, or Examples include mica, talc, glass flake, glass fiber, synthetic hydrosite, graphite, molybdenum disulfide, boron nitride and other layered, needle-like or plate-like inorganic base materials. These may be used alone or in combination of two or more. Can be used.
- the content of inorganic base materials other than glass beads is preferably 25% by weight or less.
- a normal method is employ
- the phenol resin molding material of the present invention can be molded into a desired shape by a general molding method to produce a molded product. Molding conditions such as molding temperature and molding pressure can be set as appropriate.
- Cashew dust manufactured by Tohoku Kogyo Co., Ltd. was pulverized with a dynamic mill MYD10-X manufactured by Nippon Coke Kogyo Co., Ltd. Specifically, 8 kg of alumina ( ⁇ 5 mm) was charged into the pulverizer, the rotation speed was 600 rpm, and the cashew dust input speed was adjusted to obtain cashew dust having a predetermined particle size (see Table 1). The particle size of cashew dust was measured by LA-920 manufactured by Horiba Ltd.
- Test pieces were prepared using the molding materials obtained in Examples and Comparative Examples, and the following evaluations were performed. The results are shown in Tables 1 and 2. In Comparative Example 4, since a uniform molding material was not obtained, the following evaluation was not performed.
- Specific gravity In accordance with JIS K 6911.
- Bending strength According to JIS K 6911.
- Dimensional change rate at 150 ° C . The change rate (500 hours) in the orthogonal direction of the ⁇ 50 ⁇ 3 mmt disk was measured.
- test pieces used for measurement of specific gravity, bending strength, and 150 ° C. dimensional change rate were as follows. Molding was performed. (1) Transfer molding (2) Temperature: 175 ° C (3) Curing time: 3 minutes
- Examples 1 to 9 are phenol resin molding materials containing glass beads and cashew dust in combination.
- Example 1, Example 2, and Example 8 were compared, the specific gravity of the molded product was reduced and the dimensional change rate at 150 ° C. was improved as the amount of cashew dust was increased. The dimensional accuracy was almost unchanged.
- the bending strength of the molded product was improved by increasing the amount of glass beads.
- the particle size of cashew dust becomes smaller in the range of 1 to 360 ⁇ m, the bending strength of the molded product is improved, and particularly contains cashew dust having a particle size of 1 to 50 ⁇ m.
- good bending strength was obtained. Specific gravity, 150 ° C. dimensional change rate, and dimensional accuracy were unchanged.
- Example 9 is a molding material having a glass bead content of less than 30% by weight.
- the dimensional accuracy decreased with the decrease in the amount of glass beads.
- the specific gravity, 150 ° C. dimensional change rate, and bending strength were almost unchanged.
- Comparative Example 1 was a molding material containing no cashew dust, and the obtained molded product had a high specific gravity.
- Comparative Example 2 is a molding material obtained by replacing a part of glass beads with a novolac resin in the formulation of the molding material of Comparative Example 1. The obtained molded product had a lower specific gravity than Comparative Example 1, but the 150 ° C. dimensional change rate and dimensional accuracy were reduced.
- Comparative Example 3 is a molding material in which wood powder, which is another organic material, is blended in place of cashew dust in the molding material of Example 8. Although the obtained molded article had a low specific gravity, the dimensional change at 150 ° C. and the dimensional accuracy were very low. As described above, Comparative Example 4 could not be evaluated because a uniform material could not be obtained.
- the phenolic resin molding material of the present invention has a low specific gravity and can provide a molded product having excellent thermal dimensional stability while ensuring mechanical strength. Therefore, it is suitable as a molding material used for molded products that require such characteristics, such as automotive parts (motor-related parts such as various motor gear cases, motor brush holders, various bushes), various gear parts, hydraulic valve parts, etc. It is.
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Abstract
Disclosed is a molding phenolic resin material which is a molding material that can be used for automotive components (motor-related components, such as various motor gear cases, motor blush holders and various bushes), various gear components and hydraulic valve components, and which has mechanical strength, a low specific gravity and excellent dimensional stability at high temperatures.
The molding phenolic resin material is characterized by comprising a novolac-type phenolic resin, cashew dust, and glass beads. It is preferred that the cashew dust have a particle diameter of 1 to 50 μm and be contained in an amount of 1 to 20% by weight and the glass beads be contained in an amount of 30 to 50% by weight in the molding phenolic resin material.
Description
本発明は、フェノール樹脂成形材料に関するものである。
The present invention relates to a phenol resin molding material.
自動車の軽量化に伴い、自動車用機構部品において、金属部品の代替としてフェノール樹脂成形材料を用いた成形品が使用されている。これらの機構部品は高温環境下において、精密部品として使用されることから、寸法精度と熱時寸法安定性の両立が要求されている。従来は、フェノール樹脂成形材料にガラス繊維、ガラスビーズ、タルク、マイカなどの無機基材を配合することで、寸法精度と熱時寸法安定性を両立させていた。（特許文献１）
As automobiles become lighter, molded parts using phenolic resin molding materials are used as substitutes for metal parts in automotive mechanical parts. Since these mechanical parts are used as precision parts in a high temperature environment, both dimensional accuracy and thermal dimensional stability are required. Conventionally, by combining an inorganic base material such as glass fiber, glass bead, talc, and mica with a phenol resin molding material, both dimensional accuracy and hot dimensional stability have been achieved. (Patent Document 1)
しかしながら、無機基材であるガラス繊維（比重２．５）、ガラスビーズ（比重２．５）、タルク（比重２．６）、マイカ（比重２．８）の比重はフェノール樹脂（比重１．２）よりも大きいため、無機基材を配合したフェノール樹脂成形材料の比重も大きくなってしまう。結果として成形品重量が増加し、フェノール樹脂成形材料の使用量も増えることになり、成形品のコストアップにつながるという問題があった。
However, the specific gravity of glass fibers (specific gravity 2.5), glass beads (specific gravity 2.5), talc (specific gravity 2.6) and mica (specific gravity 2.8), which are inorganic base materials, is phenol resin (specific gravity 1.2). Therefore, the specific gravity of the phenol resin molding material containing the inorganic base material is also increased. As a result, there is a problem that the weight of the molded product increases and the amount of the phenol resin molding material used increases, leading to an increase in cost of the molded product.
本発明は従来の無機基材配合による、フェノール樹脂成形材料の高比重化の問題点を解決するためになされたもので、その目的とすることは、低比重でありながら機械強度を確保しつつ、熱時寸法安定性に優れたフェノール樹脂成形材料を提供することにある。
The present invention was made in order to solve the problem of high specific gravity of phenol resin molding materials by blending a conventional inorganic base material, and its purpose is to ensure mechanical strength while maintaining low specific gravity. An object of the present invention is to provide a phenol resin molding material having excellent dimensional stability during heating.
このような目的は、下記の本発明［１］～［４］により達成される。
［１］ ノボラック型フェノール樹脂、カシューダスト及びガラスビーズを含有することを特徴とするフェノール樹脂成形材料。
［２］ フェノール樹脂成形材料中の前記カシューダストの含有量が１～２０重量％である［１］記載のフェノール樹脂成形材料。
［３］ フェノール樹脂成形材料中の前記ガラスビーズの含有量が３０～５０重量％である［１］又は［２］記載のフェノール樹脂成形材料。
［４］ フェノール樹脂成形材料中の前記カシューダストの粒径が１～５０μｍである［１］乃至［３］のいずれかに記載のフェノール樹脂成形材料。 Such an object is achieved by the following present inventions [1] to [4].
[1] A phenolic resin molding material comprising a novolac type phenolic resin, cashew dust and glass beads.
[2] The phenol resin molding material according to [1], wherein the content of the cashew dust in the phenol resin molding material is 1 to 20% by weight.
[3] The phenol resin molding material according to [1] or [2], wherein the content of the glass beads in the phenol resin molding material is 30 to 50% by weight.
[4] The phenol resin molding material according to any one of [1] to [3], wherein the cashew dust in the phenol resin molding material has a particle size of 1 to 50 μm.
［１］ ノボラック型フェノール樹脂、カシューダスト及びガラスビーズを含有することを特徴とするフェノール樹脂成形材料。
［２］ フェノール樹脂成形材料中の前記カシューダストの含有量が１～２０重量％である［１］記載のフェノール樹脂成形材料。
［３］ フェノール樹脂成形材料中の前記ガラスビーズの含有量が３０～５０重量％である［１］又は［２］記載のフェノール樹脂成形材料。
［４］ フェノール樹脂成形材料中の前記カシューダストの粒径が１～５０μｍである［１］乃至［３］のいずれかに記載のフェノール樹脂成形材料。 Such an object is achieved by the following present inventions [1] to [4].
[1] A phenolic resin molding material comprising a novolac type phenolic resin, cashew dust and glass beads.
[2] The phenol resin molding material according to [1], wherein the content of the cashew dust in the phenol resin molding material is 1 to 20% by weight.
[3] The phenol resin molding material according to [1] or [2], wherein the content of the glass beads in the phenol resin molding material is 30 to 50% by weight.
[4] The phenol resin molding material according to any one of [1] to [3], wherein the cashew dust in the phenol resin molding material has a particle size of 1 to 50 μm.
本発明によれば、従来課題となっていた無機基材配合によるフェノール樹脂成形材料の高比重化が改善されるうえに、該成形材料を用いた成形品の機械強度を確保しつつ熱時寸法安定性の向上が可能である。
According to the present invention, the increase in specific gravity of the phenol resin molding material by the inorganic base material blending, which has been a conventional problem, is improved, and the hot dimension is secured while ensuring the mechanical strength of the molded product using the molding material. Stability can be improved.
本発明のフェノール樹脂成形材料は、ノボラック型フェノール樹脂を含有する。
本発明に用いるノボラック型フェノール樹脂としては、特に限定されないが、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡノボラック樹脂、カシュー変性ノボラック樹脂、及び油変性フェノール樹脂等のノボラック型フェノール樹脂が挙げられる。
フェノール樹脂成形材料におけるノボラック型フェノール樹脂の含有量は、特に限定されないが、１５～５０重量％であることが好ましく、特に２０～４０重量％であることが好ましく、さらに、２２～３０重量％であることが好ましい。ノボラック型フェノール樹脂の含有量が、上記下限値以上であることにより、フェノール樹脂成形材料の生産が容易になると共に、フェノール樹脂成形材料の成形を行いやすい流動性が得られる。一方、上記上限値以下であることにより、ノボラック型フェノール樹脂による成形品の寸法変化を抑制し、フェノール樹脂成形材料を硬化して得られる成形品の寸法安定性を確保することができる。 The phenol resin molding material of the present invention contains a novolac type phenol resin.
The novolak type phenol resin used in the present invention is not particularly limited, and examples thereof include novolak type phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, cashew modified novolak resin, and oil modified phenol resin. .
The content of the novolak-type phenol resin in the phenol resin molding material is not particularly limited, but is preferably 15 to 50% by weight, particularly preferably 20 to 40% by weight, and more preferably 22 to 30% by weight. Preferably there is. When the content of the novolac type phenol resin is not less than the above lower limit, the production of the phenol resin molding material is facilitated and the fluidity that facilitates the molding of the phenol resin molding material is obtained. On the other hand, by being below the above upper limit value, it is possible to suppress the dimensional change of the molded product due to the novolac type phenol resin and to secure the dimensional stability of the molded product obtained by curing the phenol resin molding material.
本発明に用いるノボラック型フェノール樹脂としては、特に限定されないが、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡノボラック樹脂、カシュー変性ノボラック樹脂、及び油変性フェノール樹脂等のノボラック型フェノール樹脂が挙げられる。
フェノール樹脂成形材料におけるノボラック型フェノール樹脂の含有量は、特に限定されないが、１５～５０重量％であることが好ましく、特に２０～４０重量％であることが好ましく、さらに、２２～３０重量％であることが好ましい。ノボラック型フェノール樹脂の含有量が、上記下限値以上であることにより、フェノール樹脂成形材料の生産が容易になると共に、フェノール樹脂成形材料の成形を行いやすい流動性が得られる。一方、上記上限値以下であることにより、ノボラック型フェノール樹脂による成形品の寸法変化を抑制し、フェノール樹脂成形材料を硬化して得られる成形品の寸法安定性を確保することができる。 The phenol resin molding material of the present invention contains a novolac type phenol resin.
The novolak type phenol resin used in the present invention is not particularly limited, and examples thereof include novolak type phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, cashew modified novolak resin, and oil modified phenol resin. .
The content of the novolak-type phenol resin in the phenol resin molding material is not particularly limited, but is preferably 15 to 50% by weight, particularly preferably 20 to 40% by weight, and more preferably 22 to 30% by weight. Preferably there is. When the content of the novolac type phenol resin is not less than the above lower limit, the production of the phenol resin molding material is facilitated and the fluidity that facilitates the molding of the phenol resin molding material is obtained. On the other hand, by being below the above upper limit value, it is possible to suppress the dimensional change of the molded product due to the novolac type phenol resin and to secure the dimensional stability of the molded product obtained by curing the phenol resin molding material.
これらのノボラック型フェノール樹脂（以下、ノボラック樹脂という）は、通常、硬化剤としてヘキサメチレンテトラミンを使用して硬化させる。ヘキサメチレンテトラミンの含有量は、特に限定されないが、ノボラック樹脂１００重量部に対して１０～２０重量部であることが好ましい。ヘキサメチレンテトラミンの含有量が、上記下限値未満ではフェノール樹脂成形材料の硬化に時間を要し、かつ該成形材料の硬化が不十分となることがある。また、上記上限値を越えるとフェノール樹脂成形材料を硬化して得られる成形品に膨れが生じることがある。
These novolak-type phenolic resins (hereinafter referred to as novolak resins) are usually cured using hexamethylenetetramine as a curing agent. The content of hexamethylenetetramine is not particularly limited, but is preferably 10 to 20 parts by weight with respect to 100 parts by weight of the novolak resin. When the content of hexamethylenetetramine is less than the above lower limit, it takes time to cure the phenol resin molding material, and the molding material may be insufficiently cured. On the other hand, if the upper limit is exceeded, the molded product obtained by curing the phenol resin molding material may swell.
本発明のフェノール樹脂成形材料はカシューダストを含有する。
本発明のフェノール樹脂成形材料は、従来フェノール樹脂成形材料に使用されていた高比重の無機基材の代わりに、低比重である有機基材のカシューダスト（比重１．１）を使用する。フェノール樹脂成形材料の比重を低減するためには木粉（比重１．４）やコットンフロック（比重１．４）などの有機基材を使用することが有効ではあるが、これらの有機基材は耐熱性が劣るため、熱時寸法安定性が低下するという問題がある。これに対して、カシューダストは耐熱性に優れる有機基材であり、カシューダストを配合することにより、フェノール樹脂成形材料の熱時寸法安定性と低比重化の両立が可能となる。
本発明に用いるカシューダストとしては、特に限定されないが、具体的には、カシューナッツ殻液を重縮合して得た樹脂硬化物の粉砕物であり、硬化剤として、パラホルムアルデヒド、フルフラールを使用したもの、或いは、硬化剤を使用しないで製造されたものが挙げられる。 The phenolic resin molding material of the present invention contains cashew dust.
The phenol resin molding material of the present invention uses an organic base cashew dust (specific gravity 1.1) having a low specific gravity instead of an inorganic base material having a high specific gravity which has been conventionally used for a phenol resin molding material. In order to reduce the specific gravity of phenol resin molding materials, it is effective to use organic base materials such as wood flour (specific gravity 1.4) and cotton flock (specific gravity 1.4). Since heat resistance is inferior, there is a problem that dimensional stability during heating is lowered. On the other hand, cashew dust is an organic base material excellent in heat resistance, and by blending cashew dust, it is possible to achieve both dimensional stability during heating and lower specific gravity of the phenol resin molding material.
The cashew dust used in the present invention is not particularly limited. Specifically, it is a pulverized product of a cured resin obtained by polycondensation of cashew nut shell liquid, and uses paraformaldehyde or furfural as a curing agent. Or what was manufactured without using a hardening | curing agent is mentioned.
本発明のフェノール樹脂成形材料は、従来フェノール樹脂成形材料に使用されていた高比重の無機基材の代わりに、低比重である有機基材のカシューダスト（比重１．１）を使用する。フェノール樹脂成形材料の比重を低減するためには木粉（比重１．４）やコットンフロック（比重１．４）などの有機基材を使用することが有効ではあるが、これらの有機基材は耐熱性が劣るため、熱時寸法安定性が低下するという問題がある。これに対して、カシューダストは耐熱性に優れる有機基材であり、カシューダストを配合することにより、フェノール樹脂成形材料の熱時寸法安定性と低比重化の両立が可能となる。
本発明に用いるカシューダストとしては、特に限定されないが、具体的には、カシューナッツ殻液を重縮合して得た樹脂硬化物の粉砕物であり、硬化剤として、パラホルムアルデヒド、フルフラールを使用したもの、或いは、硬化剤を使用しないで製造されたものが挙げられる。 The phenolic resin molding material of the present invention contains cashew dust.
The phenol resin molding material of the present invention uses an organic base cashew dust (specific gravity 1.1) having a low specific gravity instead of an inorganic base material having a high specific gravity which has been conventionally used for a phenol resin molding material. In order to reduce the specific gravity of phenol resin molding materials, it is effective to use organic base materials such as wood flour (specific gravity 1.4) and cotton flock (specific gravity 1.4). Since heat resistance is inferior, there is a problem that dimensional stability during heating is lowered. On the other hand, cashew dust is an organic base material excellent in heat resistance, and by blending cashew dust, it is possible to achieve both dimensional stability during heating and lower specific gravity of the phenol resin molding material.
The cashew dust used in the present invention is not particularly limited. Specifically, it is a pulverized product of a cured resin obtained by polycondensation of cashew nut shell liquid, and uses paraformaldehyde or furfural as a curing agent. Or what was manufactured without using a hardening | curing agent is mentioned.
本発明において用いるカシューダストの粒径は特に限定されないが、１～４００μｍであることが好ましく、特に１～１５０μｍであることが好ましく、さらに、１～５０μｍであることが好ましい。カシューダストの粒径を上記上限値以下とすることで、フェノール樹脂成形材料を硬化して得られる成形品の機械強度を向上させることができる。一方、カシューダストの粒径を上記下限値以上とすることで、フェノール樹脂成形材料の生産が容易になると共に、フェノール樹脂成形材料の流動性を低下させずに成形性を確保することができる。
カシューダストの粒径は、例えば、粒度分布測定装置を用いて測定することができる。具体的には、例えば、（株）堀場製作所社製のＬＡ－９２０等が挙げられる。 The particle size of cashew dust used in the present invention is not particularly limited, but is preferably 1 to 400 μm, particularly preferably 1 to 150 μm, and more preferably 1 to 50 μm. By setting the particle size of cashew dust to the upper limit or less, the mechanical strength of a molded product obtained by curing the phenol resin molding material can be improved. On the other hand, by setting the cashew dust particle size to be equal to or larger than the above lower limit, the production of the phenol resin molding material is facilitated, and the moldability can be ensured without reducing the fluidity of the phenol resin molding material.
The particle size of cashew dust can be measured using, for example, a particle size distribution measuring device. Specific examples include LA-920 manufactured by Horiba, Ltd.
カシューダストの粒径は、例えば、粒度分布測定装置を用いて測定することができる。具体的には、例えば、（株）堀場製作所社製のＬＡ－９２０等が挙げられる。 The particle size of cashew dust used in the present invention is not particularly limited, but is preferably 1 to 400 μm, particularly preferably 1 to 150 μm, and more preferably 1 to 50 μm. By setting the particle size of cashew dust to the upper limit or less, the mechanical strength of a molded product obtained by curing the phenol resin molding material can be improved. On the other hand, by setting the cashew dust particle size to be equal to or larger than the above lower limit, the production of the phenol resin molding material is facilitated, and the moldability can be ensured without reducing the fluidity of the phenol resin molding material.
The particle size of cashew dust can be measured using, for example, a particle size distribution measuring device. Specific examples include LA-920 manufactured by Horiba, Ltd.
フェノール樹脂成形材料におけるカシューダストの含有量は、特に限定されないが、１～２０重量％であることが好ましく、特に６～１８重量％であることが好ましく、さらに、１０～１５重量％であることが好ましい。カシューダストの含有量を１重量％以上とすることで、フェノール樹脂成形材料の熱時寸法安定性を向上させることができる。一方、カシューダストの含有量を２０重量％以下とすることで、フェノール樹脂成形材料の生産が容易になるとともに共に、フェノール樹脂成形材料の流動性を低下させずに成形性を確保することができる。
The content of cashew dust in the phenolic resin molding material is not particularly limited, but is preferably 1 to 20% by weight, particularly preferably 6 to 18% by weight, and more preferably 10 to 15% by weight. Is preferred. By setting the content of cashew dust to 1% by weight or more, it is possible to improve the thermal dimensional stability of the phenolic resin molding material. On the other hand, when the content of cashew dust is 20% by weight or less, the production of the phenol resin molding material is facilitated, and at the same time, the moldability can be secured without reducing the fluidity of the phenol resin molding material. .
本発明のフェノール樹脂成形材料は、ガラスビーズを配合する。基材としてカシューダストと共にガラスビーズを用いることで、フェノール樹脂成形材料を硬化して得られる成形品の機械強度を確保することができる。また、ガラスビーズを用いることによって、ガラス繊維を用いる場合と比べて、成形材料の寸法精度を向上させることができる。
本発明に用いるガラスビーズは、室内装飾や手芸品などに使用する糸通し孔のついた小さな飾り玉を指すものではなく、全体形状が略球状のものを意味するものであって、ガラスを主材とし、でんぷん等の生分解性樹脂からなる水溶性成形材料よりも高い熱軟化温度を有しているものである。
具体的に言えば、例えば、株式会社ユニオン製のＵＮＩＢＥＡＤＳユニビーズのＵＢ－１３ＬＡ、ＵＢ－３４ＬＡ、ＵＢ－５８ＬＡ等を含むものである。
フェノール樹脂成形材料におけるガラスビーズの含有量は、特に限定されないが、３０～５０重量％であることが好ましく、特に３０～４５重量％であることが好ましく、さらに、３２～４０重量％であることが好ましい。ガラスビーズの含有量を３０重量％以上とすることで、フェノール樹脂成形材料の機械強度を向上させることができる。一方、ガラスビーズの含有量を５０重量％以下とすることで、フェノール樹脂成形材料の生産が容易になると共に、フェノール樹脂成形材料の流動性を低下させずに成形性を確保することができる。 The phenol resin molding material of the present invention contains glass beads. By using glass beads together with cashew dust as a base material, it is possible to ensure the mechanical strength of a molded product obtained by curing a phenol resin molding material. Further, by using glass beads, the dimensional accuracy of the molding material can be improved as compared with the case of using glass fibers.
The glass beads used in the present invention do not refer to small decorative balls with threading holes used for interior decorations and handicrafts, but mean that the overall shape is substantially spherical. The material has a higher heat softening temperature than a water-soluble molding material made of biodegradable resin such as starch.
Specifically, for example, UNIBEADS unibeads UB-13LA, UB-34LA, and UB-58LA manufactured by Union Co., Ltd. are included.
The content of the glass beads in the phenolic resin molding material is not particularly limited, but is preferably 30 to 50% by weight, particularly preferably 30 to 45% by weight, and further 32 to 40% by weight. Is preferred. By setting the content of glass beads to 30% by weight or more, the mechanical strength of the phenol resin molding material can be improved. On the other hand, when the content of the glass beads is 50% by weight or less, the production of the phenol resin molding material becomes easy, and the moldability can be ensured without deteriorating the fluidity of the phenol resin molding material.
本発明に用いるガラスビーズは、室内装飾や手芸品などに使用する糸通し孔のついた小さな飾り玉を指すものではなく、全体形状が略球状のものを意味するものであって、ガラスを主材とし、でんぷん等の生分解性樹脂からなる水溶性成形材料よりも高い熱軟化温度を有しているものである。
具体的に言えば、例えば、株式会社ユニオン製のＵＮＩＢＥＡＤＳユニビーズのＵＢ－１３ＬＡ、ＵＢ－３４ＬＡ、ＵＢ－５８ＬＡ等を含むものである。
フェノール樹脂成形材料におけるガラスビーズの含有量は、特に限定されないが、３０～５０重量％であることが好ましく、特に３０～４５重量％であることが好ましく、さらに、３２～４０重量％であることが好ましい。ガラスビーズの含有量を３０重量％以上とすることで、フェノール樹脂成形材料の機械強度を向上させることができる。一方、ガラスビーズの含有量を５０重量％以下とすることで、フェノール樹脂成形材料の生産が容易になると共に、フェノール樹脂成形材料の流動性を低下させずに成形性を確保することができる。 The phenol resin molding material of the present invention contains glass beads. By using glass beads together with cashew dust as a base material, it is possible to ensure the mechanical strength of a molded product obtained by curing a phenol resin molding material. Further, by using glass beads, the dimensional accuracy of the molding material can be improved as compared with the case of using glass fibers.
The glass beads used in the present invention do not refer to small decorative balls with threading holes used for interior decorations and handicrafts, but mean that the overall shape is substantially spherical. The material has a higher heat softening temperature than a water-soluble molding material made of biodegradable resin such as starch.
Specifically, for example, UNIBEADS unibeads UB-13LA, UB-34LA, and UB-58LA manufactured by Union Co., Ltd. are included.
The content of the glass beads in the phenolic resin molding material is not particularly limited, but is preferably 30 to 50% by weight, particularly preferably 30 to 45% by weight, and further 32 to 40% by weight. Is preferred. By setting the content of glass beads to 30% by weight or more, the mechanical strength of the phenol resin molding material can be improved. On the other hand, when the content of the glass beads is 50% by weight or less, the production of the phenol resin molding material becomes easy, and the moldability can be ensured without deteriorating the fluidity of the phenol resin molding material.
本発明のフェノール樹脂成形材料は、ガラスビーズに加えてその他の無機基材を含有してもよい。
本発明に用いることの出来る無機基材としては、焼成されたカオリナイト、焼成クレー、シリカ、ガラス粉末、炭酸カルシウム、ウォラストナイト、水酸化アルミニウム、炭酸マグネシウム等の粉末状の無機基材、あるいはマイカ、タルク、ガラスフレーク、ガラス繊維、合成ハイドロサイト、黒鉛、二硫化モリブテン、窒化ホウ素などの層状、針状又は板状等の無機基材が挙げられ、これらを単独或いは２種類以上配合して用いることが出来る。フェノール樹脂成形材料において、ガラスビーズ以外の無機基材の含有量は、２５重量％以下であることが好ましい。 The phenol resin molding material of the present invention may contain other inorganic base material in addition to the glass beads.
Examples of the inorganic base material that can be used in the present invention include calcined kaolinite, calcined clay, silica, glass powder, calcium carbonate, wollastonite, aluminum hydroxide, magnesium carbonate and other powdered inorganic base materials, or Examples include mica, talc, glass flake, glass fiber, synthetic hydrosite, graphite, molybdenum disulfide, boron nitride and other layered, needle-like or plate-like inorganic base materials. These may be used alone or in combination of two or more. Can be used. In the phenol resin molding material, the content of inorganic base materials other than glass beads is preferably 25% by weight or less.
本発明に用いることの出来る無機基材としては、焼成されたカオリナイト、焼成クレー、シリカ、ガラス粉末、炭酸カルシウム、ウォラストナイト、水酸化アルミニウム、炭酸マグネシウム等の粉末状の無機基材、あるいはマイカ、タルク、ガラスフレーク、ガラス繊維、合成ハイドロサイト、黒鉛、二硫化モリブテン、窒化ホウ素などの層状、針状又は板状等の無機基材が挙げられ、これらを単独或いは２種類以上配合して用いることが出来る。フェノール樹脂成形材料において、ガラスビーズ以外の無機基材の含有量は、２５重量％以下であることが好ましい。 The phenol resin molding material of the present invention may contain other inorganic base material in addition to the glass beads.
Examples of the inorganic base material that can be used in the present invention include calcined kaolinite, calcined clay, silica, glass powder, calcium carbonate, wollastonite, aluminum hydroxide, magnesium carbonate and other powdered inorganic base materials, or Examples include mica, talc, glass flake, glass fiber, synthetic hydrosite, graphite, molybdenum disulfide, boron nitride and other layered, needle-like or plate-like inorganic base materials. These may be used alone or in combination of two or more. Can be used. In the phenol resin molding material, the content of inorganic base materials other than glass beads is preferably 25% by weight or less.
本発明のフェノール樹脂成形材料を製造する方法は、通常の方法が採用される。即ち、まず、上記の配合物を所定の配合割合で混合し、更に必要に応じて着色剤、硬化触媒等を加えて原料混合物を調製する。続いて、得られた原料混合物を、加熱ロールにより混練した後、シート状に成形し、冷却する。次に得られたシート状成形物を顆粒状に粉砕することで本発明のフェノール樹脂成形材料が得られる。
本発明のフェノール樹脂成形材料は、一般的な成形方法により所望の形状に成形することで、成形品を作製することができる。成形温度、成形圧力等の成形条件は適宜設定することができる。 A normal method is employ | adopted as the method of manufacturing the phenol resin molding material of this invention. That is, first, the above blend is mixed at a predetermined blending ratio, and a colorant, a curing catalyst and the like are further added as necessary to prepare a raw material mixture. Subsequently, the obtained raw material mixture is kneaded with a heating roll, then formed into a sheet and cooled. Next, the phenol resin molding material of this invention is obtained by grind | pulverizing the obtained sheet-like molding into a granular form.
The phenol resin molding material of the present invention can be molded into a desired shape by a general molding method to produce a molded product. Molding conditions such as molding temperature and molding pressure can be set as appropriate.
本発明のフェノール樹脂成形材料は、一般的な成形方法により所望の形状に成形することで、成形品を作製することができる。成形温度、成形圧力等の成形条件は適宜設定することができる。 A normal method is employ | adopted as the method of manufacturing the phenol resin molding material of this invention. That is, first, the above blend is mixed at a predetermined blending ratio, and a colorant, a curing catalyst and the like are further added as necessary to prepare a raw material mixture. Subsequently, the obtained raw material mixture is kneaded with a heating roll, then formed into a sheet and cooled. Next, the phenol resin molding material of this invention is obtained by grind | pulverizing the obtained sheet-like molding into a granular form.
The phenol resin molding material of the present invention can be molded into a desired shape by a general molding method to produce a molded product. Molding conditions such as molding temperature and molding pressure can be set as appropriate.
実施例および比較例により本発明を説明する。なお、本発明はこれらの実施例になんら限定されるものではない。
The present invention will be described with reference to examples and comparative examples. The present invention is not limited to these examples.
［カシューダストの調整］
東北加工（株）製のカシューダストを、日本コークス工業（株）社製のダイナミックミルＭＹＤ１０－Ｘで粉砕した。具体的には、該粉砕機に、アルミナ（φ５ｍｍ）を８ｋｇ充填し、回転数６００ｒｐｍとし、カシューダスト投入速度を調整することで所定の粒度（表１参照）のカシューダストを得た。カシューダストの粒径は（株）堀場製作所社製のＬＡ－９２０によって測定した。 [Adjustment of cashew dust]
Cashew dust manufactured by Tohoku Kogyo Co., Ltd. was pulverized with a dynamic mill MYD10-X manufactured by Nippon Coke Kogyo Co., Ltd. Specifically, 8 kg of alumina (φ5 mm) was charged into the pulverizer, the rotation speed was 600 rpm, and the cashew dust input speed was adjusted to obtain cashew dust having a predetermined particle size (see Table 1). The particle size of cashew dust was measured by LA-920 manufactured by Horiba Ltd.
東北加工（株）製のカシューダストを、日本コークス工業（株）社製のダイナミックミルＭＹＤ１０－Ｘで粉砕した。具体的には、該粉砕機に、アルミナ（φ５ｍｍ）を８ｋｇ充填し、回転数６００ｒｐｍとし、カシューダスト投入速度を調整することで所定の粒度（表１参照）のカシューダストを得た。カシューダストの粒径は（株）堀場製作所社製のＬＡ－９２０によって測定した。 [Adjustment of cashew dust]
Cashew dust manufactured by Tohoku Kogyo Co., Ltd. was pulverized with a dynamic mill MYD10-X manufactured by Nippon Coke Kogyo Co., Ltd. Specifically, 8 kg of alumina (φ5 mm) was charged into the pulverizer, the rotation speed was 600 rpm, and the cashew dust input speed was adjusted to obtain cashew dust having a predetermined particle size (see Table 1). The particle size of cashew dust was measured by LA-920 manufactured by Horiba Ltd.
［実施例１～９、比較例１～３］
表１および表２に示す材料および配合にて、材料を予備混合した後、加熱ロールにより混練し、冷却後に粉砕することでフェノール樹脂成形材料を得た。 [Examples 1 to 9, Comparative Examples 1 to 3]
In the materials and blends shown in Tables 1 and 2, the materials were premixed, then kneaded with a heating roll, and pulverized after cooling to obtain a phenol resin molding material.
表１および表２に示す材料および配合にて、材料を予備混合した後、加熱ロールにより混練し、冷却後に粉砕することでフェノール樹脂成形材料を得た。 [Examples 1 to 9, Comparative Examples 1 to 3]
In the materials and blends shown in Tables 1 and 2, the materials were premixed, then kneaded with a heating roll, and pulverized after cooling to obtain a phenol resin molding material.
［比較例４］
表２に示す材料および配合にて、材料を予備混合した後、加熱ロールにより混練したが均一に混練できず、冷却後に粉砕したが均一なフェノール樹脂成形材料は得られなかった。 [Comparative Example 4]
In the materials and blends shown in Table 2, the materials were premixed and then kneaded with a heating roll, but could not be uniformly kneaded, and pulverized after cooling, but a uniform phenol resin molding material was not obtained.
表２に示す材料および配合にて、材料を予備混合した後、加熱ロールにより混練したが均一に混練できず、冷却後に粉砕したが均一なフェノール樹脂成形材料は得られなかった。 [Comparative Example 4]
In the materials and blends shown in Table 2, the materials were premixed and then kneaded with a heating roll, but could not be uniformly kneaded, and pulverized after cooling, but a uniform phenol resin molding material was not obtained.
表の注：
（１）ノボラック樹脂：住友ベークライト社製 Ａ－１０８２（数平均分子量８５０）
（２）ヘキサメチレンテトラミン：長春石油化学社製 ヘキサミン
（３）ガラス繊維：日東紡社製：ＣＳ３Ｅ４７９Ｓ（繊維長３ｍｍ、繊維径１１μｍ）
（４）ガラスビーズ：ユニオン社製 ＵＢ－１３ＬＡ
（５）カシューダスト：東北加工社製 ＦＦ－１０８１
（６）木粉：カネキ燃料社製 木粉１００メッシュ
（７）硬化助剤：協和化学工業社製 キョーワマグ３０
（８）滑剤：日東化成工業社製 ステアリン酸カルシウム
（９）着色剤：三菱化学社製 カーボン７５０Ｂ Table note:
(1) Novolac resin: A-1082 (number average molecular weight 850) manufactured by Sumitomo Bakelite Co., Ltd.
(2) Hexamethylenetetramine: manufactured by Changchun Petrochemical Co., Ltd. Hexamine (3) Glass fiber: manufactured by Nittobo Co., Ltd .: CS3E479S (fiber length: 3 mm, fiber diameter: 11 μm)
(4) Glass beads: Union UB-13LA
(5) Cashew dust: FF-1081 manufactured by Tohoku Processing Co., Ltd.
(6) Wood flour: Kaneki Fuel Co., Ltd. Wood powder 100 mesh (7) Curing aid: Kyowa Chemical Industry Co., Ltd. Kyowa Mug 30
(8) Lubricant: Calcium stearate manufactured by Nitto Kasei Kogyo Co., Ltd. (9) Colorant: Carbon 750B manufactured by Mitsubishi Chemical Corporation
（１）ノボラック樹脂：住友ベークライト社製 Ａ－１０８２（数平均分子量８５０）
（２）ヘキサメチレンテトラミン：長春石油化学社製 ヘキサミン
（３）ガラス繊維：日東紡社製：ＣＳ３Ｅ４７９Ｓ（繊維長３ｍｍ、繊維径１１μｍ）
（４）ガラスビーズ：ユニオン社製 ＵＢ－１３ＬＡ
（５）カシューダスト：東北加工社製 ＦＦ－１０８１
（６）木粉：カネキ燃料社製 木粉１００メッシュ
（７）硬化助剤：協和化学工業社製 キョーワマグ３０
（８）滑剤：日東化成工業社製 ステアリン酸カルシウム
（９）着色剤：三菱化学社製 カーボン７５０Ｂ Table note:
(1) Novolac resin: A-1082 (number average molecular weight 850) manufactured by Sumitomo Bakelite Co., Ltd.
(2) Hexamethylenetetramine: manufactured by Changchun Petrochemical Co., Ltd. Hexamine (3) Glass fiber: manufactured by Nittobo Co., Ltd .: CS3E479S (fiber length: 3 mm, fiber diameter: 11 μm)
(4) Glass beads: Union UB-13LA
(5) Cashew dust: FF-1081 manufactured by Tohoku Processing Co., Ltd.
(6) Wood flour: Kaneki Fuel Co., Ltd. Wood powder 100 mesh (7) Curing aid: Kyowa Chemical Industry Co., Ltd. Kyowa Mug 30
(8) Lubricant: Calcium stearate manufactured by Nitto Kasei Kogyo Co., Ltd. (9) Colorant: Carbon 750B manufactured by Mitsubishi Chemical Corporation
実施例および比較例で得られた成形材料を用いて試験片を作製し、以下に示す評価を行った。結果を表１及び表２に示す。尚、比較例４では、均一な成形材料が得られなかったため、以下の評価は行わなかった。
（１）比重：ＪＩＳ Ｋ ６９１１に準ずる。
（２）曲げ強さ：ＪＩＳ Ｋ ６９１１に準ずる。
（３）１５０℃寸法変化率：φ５０×３ｍｍｔ円盤の直行方向の変化率（５００時間）を測定した。
（４）寸法精度：外径４０ｍｍ、内径３４ｍｍ、厚み３ｍｍの円筒形を有する寸法評価用成形品の内径を測定し（ｎ＝１８）、ばらつきの標準偏差σから８σを求めた。 Test pieces were prepared using the molding materials obtained in Examples and Comparative Examples, and the following evaluations were performed. The results are shown in Tables 1 and 2. In Comparative Example 4, since a uniform molding material was not obtained, the following evaluation was not performed.
(1) Specific gravity: In accordance with JIS K 6911.
(2) Bending strength: According to JIS K 6911.
(3) Dimensional change rate at 150 ° C .: The change rate (500 hours) in the orthogonal direction of the φ50 × 3 mmt disk was measured.
(4) Dimensional accuracy: The inner diameter of a molded product for dimensional evaluation having a cylindrical shape with an outer diameter of 40 mm, an inner diameter of 34 mm, and a thickness of 3 mm was measured (n = 18), and 8σ was determined from the standard deviation σ of variation.
（１）比重：ＪＩＳ Ｋ ６９１１に準ずる。
（２）曲げ強さ：ＪＩＳ Ｋ ６９１１に準ずる。
（３）１５０℃寸法変化率：φ５０×３ｍｍｔ円盤の直行方向の変化率（５００時間）を測定した。
（４）寸法精度：外径４０ｍｍ、内径３４ｍｍ、厚み３ｍｍの円筒形を有する寸法評価用成形品の内径を測定し（ｎ＝１８）、ばらつきの標準偏差σから８σを求めた。 Test pieces were prepared using the molding materials obtained in Examples and Comparative Examples, and the following evaluations were performed. The results are shown in Tables 1 and 2. In Comparative Example 4, since a uniform molding material was not obtained, the following evaluation was not performed.
(1) Specific gravity: In accordance with JIS K 6911.
(2) Bending strength: According to JIS K 6911.
(3) Dimensional change rate at 150 ° C .: The change rate (500 hours) in the orthogonal direction of the φ50 × 3 mmt disk was measured.
(4) Dimensional accuracy: The inner diameter of a molded product for dimensional evaluation having a cylindrical shape with an outer diameter of 40 mm, an inner diameter of 34 mm, and a thickness of 3 mm was measured (n = 18), and 8σ was determined from the standard deviation σ of variation.
尚、実施例１～９および比較例１～３で得られた成形材料について、上記評価のうち、比重、曲げ強さ、及び１５０℃寸法変化率測定に使用した試験片は以下に示す条件で成形を行った。
（１）トランスファー成形
（２）温度：１７５℃
（３）硬化時間：３分間 Regarding the molding materials obtained in Examples 1 to 9 and Comparative Examples 1 to 3, among the above evaluations, the test pieces used for measurement of specific gravity, bending strength, and 150 ° C. dimensional change rate were as follows. Molding was performed.
(1) Transfer molding (2) Temperature: 175 ° C
(3) Curing time: 3 minutes
（１）トランスファー成形
（２）温度：１７５℃
（３）硬化時間：３分間 Regarding the molding materials obtained in Examples 1 to 9 and Comparative Examples 1 to 3, among the above evaluations, the test pieces used for measurement of specific gravity, bending strength, and 150 ° C. dimensional change rate were as follows. Molding was performed.
(1) Transfer molding (2) Temperature: 175 ° C
(3) Curing time: 3 minutes
また、実施例１～９および比較例１～３で得られた成形材料について、上記寸法精度測定に使用した試験片は以下に示す条件で成形を行った。
（１）インジェクション成形
（２）温度：１７５℃
（３）射出圧力：１００ＭＰａ
（４）硬化時間：２５秒 For the molding materials obtained in Examples 1 to 9 and Comparative Examples 1 to 3, the test pieces used for the dimensional accuracy measurement were molded under the following conditions.
(1) Injection molding (2) Temperature: 175 ° C
(3) Injection pressure: 100 MPa
(4) Curing time: 25 seconds
（１）インジェクション成形
（２）温度：１７５℃
（３）射出圧力：１００ＭＰａ
（４）硬化時間：２５秒 For the molding materials obtained in Examples 1 to 9 and Comparative Examples 1 to 3, the test pieces used for the dimensional accuracy measurement were molded under the following conditions.
(1) Injection molding (2) Temperature: 175 ° C
(3) Injection pressure: 100 MPa
(4) Curing time: 25 seconds
実施例１～９はガラスビーズ及びカシューダストを組み合わせて配合したフェノール樹脂成形材料である。
実施例１、実施例２、および実施例８を対比すると、カシューダスト配合量の増加に伴い、成形品の比重が低下すると共に１５０℃寸法変化率が向上した。寸法精度はほぼ変わらなかった。また、ガラスビーズ配合量の増加により、成形品の曲げ強さが向上した。
実施例２～７を対比すると、カシューダストの粒径が１～３６０μｍの範囲において小さくなるに伴い、成形品の曲げ強さが向上し、特に、１～５０μｍの粒径を有するカシューダストを含有する実施例４～７において良好な曲げ強さが得られた。比重、１５０℃寸法変化率、および寸法精度は変わらなかった。
実施例９はガラスビーズの含有量が３０重量％より少ない成形材料である。実施例２と対比するとガラスビーズ配合量の減少に伴い寸法精度が低下した。比重、１５０℃寸法変化率、曲げ強さはほぼ変わらなかった。 Examples 1 to 9 are phenol resin molding materials containing glass beads and cashew dust in combination.
When Example 1, Example 2, and Example 8 were compared, the specific gravity of the molded product was reduced and the dimensional change rate at 150 ° C. was improved as the amount of cashew dust was increased. The dimensional accuracy was almost unchanged. Moreover, the bending strength of the molded product was improved by increasing the amount of glass beads.
In contrast to Examples 2 to 7, as the particle size of cashew dust becomes smaller in the range of 1 to 360 μm, the bending strength of the molded product is improved, and particularly contains cashew dust having a particle size of 1 to 50 μm. In Examples 4 to 7, good bending strength was obtained. Specific gravity, 150 ° C. dimensional change rate, and dimensional accuracy were unchanged.
Example 9 is a molding material having a glass bead content of less than 30% by weight. When compared with Example 2, the dimensional accuracy decreased with the decrease in the amount of glass beads. The specific gravity, 150 ° C. dimensional change rate, and bending strength were almost unchanged.
実施例１、実施例２、および実施例８を対比すると、カシューダスト配合量の増加に伴い、成形品の比重が低下すると共に１５０℃寸法変化率が向上した。寸法精度はほぼ変わらなかった。また、ガラスビーズ配合量の増加により、成形品の曲げ強さが向上した。
実施例２～７を対比すると、カシューダストの粒径が１～３６０μｍの範囲において小さくなるに伴い、成形品の曲げ強さが向上し、特に、１～５０μｍの粒径を有するカシューダストを含有する実施例４～７において良好な曲げ強さが得られた。比重、１５０℃寸法変化率、および寸法精度は変わらなかった。
実施例９はガラスビーズの含有量が３０重量％より少ない成形材料である。実施例２と対比するとガラスビーズ配合量の減少に伴い寸法精度が低下した。比重、１５０℃寸法変化率、曲げ強さはほぼ変わらなかった。 Examples 1 to 9 are phenol resin molding materials containing glass beads and cashew dust in combination.
When Example 1, Example 2, and Example 8 were compared, the specific gravity of the molded product was reduced and the dimensional change rate at 150 ° C. was improved as the amount of cashew dust was increased. The dimensional accuracy was almost unchanged. Moreover, the bending strength of the molded product was improved by increasing the amount of glass beads.
In contrast to Examples 2 to 7, as the particle size of cashew dust becomes smaller in the range of 1 to 360 μm, the bending strength of the molded product is improved, and particularly contains cashew dust having a particle size of 1 to 50 μm. In Examples 4 to 7, good bending strength was obtained. Specific gravity, 150 ° C. dimensional change rate, and dimensional accuracy were unchanged.
Example 9 is a molding material having a glass bead content of less than 30% by weight. When compared with Example 2, the dimensional accuracy decreased with the decrease in the amount of glass beads. The specific gravity, 150 ° C. dimensional change rate, and bending strength were almost unchanged.
比較例１は、カシューダストを含有しない成形材料であり、得られた成形品は高比重であった。
比較例２は、比較例１の成形材料の配合においてガラスビーズの一部をノボラック樹脂に置換した成形材料である。得られた成形品は比較例１よりも低比重となったが、１５０℃寸法変化率及び寸法精度は低下した。
比較例３は、実施例８の成形材料においてカシューダストに替えて他の有機材料である木粉を配合した成形材料である。得られた成形品は、比重は低いものの、１５０℃寸法変化及び寸法精度は非常に低下した
上記したように比較例４は均一な材料が得られず評価できなかった。 Comparative Example 1 was a molding material containing no cashew dust, and the obtained molded product had a high specific gravity.
Comparative Example 2 is a molding material obtained by replacing a part of glass beads with a novolac resin in the formulation of the molding material of Comparative Example 1. The obtained molded product had a lower specific gravity than Comparative Example 1, but the 150 ° C. dimensional change rate and dimensional accuracy were reduced.
Comparative Example 3 is a molding material in which wood powder, which is another organic material, is blended in place of cashew dust in the molding material of Example 8. Although the obtained molded article had a low specific gravity, the dimensional change at 150 ° C. and the dimensional accuracy were very low. As described above, Comparative Example 4 could not be evaluated because a uniform material could not be obtained.
比較例２は、比較例１の成形材料の配合においてガラスビーズの一部をノボラック樹脂に置換した成形材料である。得られた成形品は比較例１よりも低比重となったが、１５０℃寸法変化率及び寸法精度は低下した。
比較例３は、実施例８の成形材料においてカシューダストに替えて他の有機材料である木粉を配合した成形材料である。得られた成形品は、比重は低いものの、１５０℃寸法変化及び寸法精度は非常に低下した
上記したように比較例４は均一な材料が得られず評価できなかった。 Comparative Example 1 was a molding material containing no cashew dust, and the obtained molded product had a high specific gravity.
Comparative Example 2 is a molding material obtained by replacing a part of glass beads with a novolac resin in the formulation of the molding material of Comparative Example 1. The obtained molded product had a lower specific gravity than Comparative Example 1, but the 150 ° C. dimensional change rate and dimensional accuracy were reduced.
Comparative Example 3 is a molding material in which wood powder, which is another organic material, is blended in place of cashew dust in the molding material of Example 8. Although the obtained molded article had a low specific gravity, the dimensional change at 150 ° C. and the dimensional accuracy were very low. As described above, Comparative Example 4 could not be evaluated because a uniform material could not be obtained.
本発明のフェノール樹脂成形材料は、低比重である上に、機械強度を確保しつつ優れた熱時寸法安定性を有する成形品を得ることができる。従って、このような特性を要求される成形品、例えば自動車用部品（各種モーターギアケース、モーターブラシホルダー、各種ブッシュ等モーター関連部品）、各種ギア部品、油圧バルブ部品等に用いられる成形材料として好適である。
The phenolic resin molding material of the present invention has a low specific gravity and can provide a molded product having excellent thermal dimensional stability while ensuring mechanical strength. Therefore, it is suitable as a molding material used for molded products that require such characteristics, such as automotive parts (motor-related parts such as various motor gear cases, motor brush holders, various bushes), various gear parts, hydraulic valve parts, etc. It is.
Claims (4)
- ノボラック型フェノール樹脂、カシューダスト及びガラスビーズを含有することを特徴とするフェノール樹脂成形材料。 A phenolic resin molding material comprising a novolac-type phenolic resin, cashew dust and glass beads.
- フェノール樹脂成形材料中の前記カシューダストの含有量が１～２０重量％である請求の範囲第１項に記載のフェノール樹脂成形材料。 The phenol resin molding material according to claim 1, wherein the content of the cashew dust in the phenol resin molding material is 1 to 20% by weight.
- フェノール樹脂成形材料中の前記ガラスビーズの含有量が３０～５０重量％である請求の範囲第１項又は第２項に記載のフェノール樹脂成形材料。 The phenol resin molding material according to claim 1 or 2, wherein the content of the glass beads in the phenol resin molding material is 30 to 50% by weight.
- フェノール樹脂成形材料中の前記カシューダストの粒径が１～５０μｍである請求の範囲第１項乃至第３項のいずれかに記載のフェノール樹脂成形材料。 The phenol resin molding material according to any one of claims 1 to 3, wherein a particle size of the cashew dust in the phenol resin molding material is 1 to 50 µm.
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| CN102875959A (en) * | 2012-09-20 | 2013-01-16 | 常熟市永祥机电有限公司 | Preparation method for macromolecular composite phenolic aldehyde material filled with glass beads |
| CN102875960A (en) * | 2012-09-20 | 2013-01-16 | 常熟市永祥机电有限公司 | Macromolecular composite phenolic aldehyde material filled with glass beads |
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| CN107109030A (en) * | 2014-12-25 | 2017-08-29 | 住友电木株式会社 | Slide unit phenolic resin moulding material and slide unit |
| JP6657740B2 (en) * | 2015-10-06 | 2020-03-04 | 日立化成株式会社 | Sliding material, molded product thereof, and sliding member |
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| JP2002265751A (en) * | 2001-03-13 | 2002-09-18 | Sumitomo Bakelite Co Ltd | Phenolic resin molding material |
| JP2003105322A (en) * | 2001-09-27 | 2003-04-09 | Nisshinbo Ind Inc | Nonasbestos friction material |
| JP2003292727A (en) * | 2002-03-29 | 2003-10-15 | Dainippon Ink & Chem Inc | Thermoset resin composition, cured product thereof and friction material |
| JP2006249206A (en) * | 2005-03-10 | 2006-09-21 | Sumitomo Bakelite Co Ltd | Phenol resin composition for friction material |
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| JP2002265751A (en) * | 2001-03-13 | 2002-09-18 | Sumitomo Bakelite Co Ltd | Phenolic resin molding material |
| JP2003105322A (en) * | 2001-09-27 | 2003-04-09 | Nisshinbo Ind Inc | Nonasbestos friction material |
| JP2003292727A (en) * | 2002-03-29 | 2003-10-15 | Dainippon Ink & Chem Inc | Thermoset resin composition, cured product thereof and friction material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102875959A (en) * | 2012-09-20 | 2013-01-16 | 常熟市永祥机电有限公司 | Preparation method for macromolecular composite phenolic aldehyde material filled with glass beads |
| CN102875960A (en) * | 2012-09-20 | 2013-01-16 | 常熟市永祥机电有限公司 | Macromolecular composite phenolic aldehyde material filled with glass beads |
| CN102875960B (en) * | 2012-09-20 | 2013-10-30 | 常熟市永祥机电有限公司 | Macromolecular composite phenolic aldehyde material filled with glass beads |
| CN102875959B (en) * | 2012-09-20 | 2013-11-20 | 常熟市永祥机电有限公司 | Preparation method for macromolecular composite phenolic aldehyde material filled with glass beads |
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