JP5098155B2 - Phenolic resin molding material for damping material and damping material formed by molding the same - Google Patents
Phenolic resin molding material for damping material and damping material formed by molding the same Download PDFInfo
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- 238000013016 damping Methods 0.000 title claims description 59
- 239000012778 molding material Substances 0.000 title claims description 55
- 239000000463 material Substances 0.000 title claims description 39
- 239000005011 phenolic resin Substances 0.000 title claims description 37
- 238000000465 moulding Methods 0.000 title claims description 21
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims description 8
- 229920001568 phenolic resin Polymers 0.000 title claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 36
- 239000000806 elastomer Substances 0.000 claims description 33
- 239000003365 glass fiber Substances 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 10
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- SCUWTOMKAPTAND-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enenitrile Chemical compound C=CC=C.CC(=C)C#N SCUWTOMKAPTAND-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 19
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 10
- 239000004312 hexamethylene tetramine Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 9
- 229920000459 Nitrile rubber Polymers 0.000 description 7
- 239000004840 adhesive resin Substances 0.000 description 5
- 229920006223 adhesive resin Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920000800 acrylic rubber Polymers 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Vibration Prevention Devices (AREA)
- Springs (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、制振材用フェノール樹脂成形材料、およびこれを成形してなる制振材に関するものである。 The present invention relates to a phenol resin molding material for damping material and a damping material formed by molding the same.
従来、自動車や産業機械或いは家電製品などに使用されるモーター部品や、それらの周辺部品において振動や騒音を低減或いは防止するために、制振性や防音性を付与する方法として制振鋼板を用いたり、或いはゴムやエラストマを貼り付けたり、金属部品を樹脂製部品に置き換えたりする方法が一般的であった。制振鋼板を用いる場合、それ自身コストが高く、また加工性の面からも微細な構造を有する部分への適用は難しく、適用できる範囲が限定されてしまうという欠点があった。また、ゴムやエラストマを貼り付ける方法も、加工工数や部品点数が増えるため、コストアップの要因となる。 Conventionally, a damping steel plate has been used as a method of imparting damping properties and soundproofing to reduce or prevent vibration and noise in motor parts used in automobiles, industrial machinery, household appliances, etc. and their peripheral parts. Or by attaching rubber or elastomer, or replacing metal parts with resin parts. When using a damping steel plate, the cost is high per se, and it is difficult to apply to a portion having a fine structure from the viewpoint of workability, and the applicable range is limited. In addition, the method of attaching rubber or elastomer also increases costs because the number of processing steps and the number of parts increase.
一方、制振性が必要な部品を金属部品から樹脂製部品に置き換えると、金属部品に比べ大幅に制振効果が向上することが知られており、フェノール樹脂などの熱硬化性樹脂或いはＰＰＳなどの熱可塑性樹脂製のギヤケースやブラシホルダー、エンドブラケットが使用されている。一般的に、耐熱性、高寸法精度、寸法安定性が要求されるモーター部品やその周辺部品へ適用するためには弾性率が高くなる無機充填材を多く配合した成形材料を使用されている。
他方、制振性能は弾性率が低いほど優れることがよく知られており、成形材料の弾性率を下げるためにフェノール樹脂と相溶性の良いＮＢＲ粉末を配合する方法が開示されている（例えば、特許文献１参照）。しかしながら、より一層の制振性或いは防音性を付与するためには、樹脂製部品にゴムやエラストマを貼り付けた設計をせざるを得ないのが現状であり、優れた制振性或いは防音性を有する成形品を得ることができる樹脂成形材料が望まれている。
一方、分野は違うものの、接着樹脂組成物に制振性を付与することができるとされる技術が開示されている（例えば、特許文献２参照）。
On the other hand, it is well known that the vibration damping performance is better as the elastic modulus is lower, and a method of blending an NBR powder having good compatibility with a phenol resin in order to lower the elastic modulus of the molding material is disclosed (for example, Patent Document 1). However, in order to provide even more vibration damping or soundproofing, it is currently necessary to design with rubber or elastomer attached to resin parts, and excellent vibration damping or soundproofing. There is a demand for a resin molding material capable of obtaining a molded article having the following.
On the other hand, although being in a different field, a technique is disclosed that can impart vibration damping properties to an adhesive resin composition (see, for example, Patent Document 2).
本発明の目的は、本来の要求特性である機械的強度を維持しつつ、制振性或いは防音性に優れた成形品が得られるフェノール樹脂成形材料、及びこれを成形してなる制振材を提供することである。 An object of the present invention is to provide a phenolic resin molding material capable of obtaining a molded product excellent in vibration damping properties or soundproofing properties while maintaining the mechanical strength which is an originally required characteristic, and a damping material formed by molding the same. Is to provide.
このような目的は、以下の（１）〜（４）に記載の本発明により達成される。
（１）フェノール樹脂（ａ）、ガラス転移点が−２０〜６０℃であるエラストマ（ｂ）、及びガラス繊維（ｃ）を含有し、
前記ガラス繊維（ｃ）の含有量は、制振材用フェノール樹脂成形材料全体に対して４０〜６０重量％であり、
前記エラストマ（ｂ）の含有量は、制振材用フェノール樹脂成形材料全体に対して３〜１３重量％であり、
前記エラストマ（ｂ）は、アクリロニトリルブタジエンゴムであることを特徴とする、制振材用フェノール樹脂成形材料（ただし、層状または板状無機充填材を含む制振材用フェノール樹脂成形材料を除く）。
（２）（１）に記載の制振材用フェノール樹脂成形材料を成形してなることを特徴とする制振材。
（３）前記制振材の曲げ弾性率は、１０〜１６ＧＰａである（２）に記載の制振材。
（４）前記制振材の損失係数は、０．０２以上である（２）又は（３）に記載の制振材。
Such an object is achieved by the present invention described in the following (1) to (4).
(1) containing a phenol resin (a), an elastomer (b) having a glass transition point of -20 to 60 ° C., and glass fiber (c),
Content of the said glass fiber (c) is 40 to 60 weight% with respect to the whole phenol resin molding material for damping materials,
The content of the elastomer (b) is 3 to 13% by weight with respect to the entire phenol resin molding material for damping material,
Said elastomeric (b) is characterized by an A methacrylonitrile-butadiene rubber, for vibration damping materials phenolic resin molding material (however, the damping material for phenolic resin molding material containing a layered or plate-like inorganic filler except).
(2) A vibration damping material obtained by molding the phenol resin molding material for a vibration damping material according to (1).
(3) The damping material according to (2), wherein the damping elastic modulus of the damping material is 10 to 16 GPa.
(4) The damping material according to (2) or (3), wherein a loss coefficient of the damping material is 0.02 or more.
本発明はフェノール樹脂（ａ）、ガラス転移点が−２０〜６０℃であるエラストマ（ｂ）、及びガラス繊維（ｃ）を含有する制振材用フェノール樹脂成形材料であり、本来の要求特性を維持しつつ、制振性或いは防音性に優れた成形品を得ることができる。
また、エラストマ（ｂ）の含有量を、成形材料全体に対して３〜１３重量％とすることで機械的強度や剛性を著しく低下させないことができる。
また、本発明によれば、制振性或いは防音性に優れた制振材を得ることができる。
The present invention is a phenol resin molding material for a vibration damping material containing a phenol resin (a), an elastomer (b) having a glass transition point of -20 to 60 ° C., and a glass fiber (c). While maintaining, it is possible to obtain a molded article excellent in vibration damping or soundproofing.
Moreover, mechanical strength and rigidity can not be reduced remarkably by making content of an elastomer (b) into 3 to 13 weight% with respect to the whole molding material.
Moreover, according to this invention, the damping material excellent in damping property or soundproofing can be obtained.
本発明は、フェノール樹脂（ａ）、ガラス転移点が−２０〜６０℃であるエラストマ（ｂ）、及びガラス繊維（ｃ）を含有することを特徴とする制振材用フェノール樹脂成形材料であり、これを成形してなる制振材である。 The present invention is a phenol resin molding material for a vibration damping material comprising a phenol resin (a), an elastomer (b) having a glass transition point of -20 to 60 ° C., and a glass fiber (c). This is a damping material formed by molding this.
まず、本発明の制振材用フェノール樹脂成形材料（以降、単に「成形材料」ということがある）について説明する。
本発明の成形材料は、フェノール樹脂（ａ）を用いる。
本発明の成形材料に用いるフェノール樹脂（ａ）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ノボラック樹脂等のノボラック型フェノール樹脂、レゾール型樹脂が挙げられるが、ノボラック型フェノール樹脂が成形性、コストの面で好ましい。
First, the phenol resin molding material for vibration damping material of the present invention (hereinafter sometimes simply referred to as “molding material”) will be described.
The molding material of the present invention uses a phenol resin (a).
The phenol resin (a) used for the molding material of 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, and resol type resin. Phenol resin is preferred in terms of moldability and cost.
また通常、ノボラック型フェノール樹脂を用いた場合は、硬化剤としてヘキサメチレンテトラミンを使用する。ヘキサメチレンテトラミンの含有量は、ノボラック樹脂１００重量部に対して１０〜２５重量部使用することが好ましい。更に好ましくは、ノボラック樹脂１００重量部に対して１３〜２０重量部である。ヘキサメチレンテトラミンの含有量が少なすぎると成形時の硬化に時間を必要とし、また多すぎると成形品にフクレを生じることがあるところ、上記範囲とすることで両者のバランスに優れる。 Usually, when a novolac type phenol resin is used, hexamethylenetetramine is used as a curing agent. The content of hexamethylenetetramine is preferably 10 to 25 parts by weight with respect to 100 parts by weight of the novolak resin. More preferably, it is 13-20 weight part with respect to 100 weight part of novolak resin. If the content of hexamethylenetetramine is too small, time is required for curing at the time of molding, and if it is too large, the molded product may be inflated.
本発明の成形材料に用いるフェノール樹脂（ａ）の含有量は、特に限定されないが、（ヘキサメチレンテトラミンを用いる場合はそれも含めて）成形材料全体に対して、２５〜４５重量％であることが好ましい。更に好ましくは３０〜４０重量％である。フェノール樹脂（ａ）の含有量が少なすぎると成形材料の生産が困難となるばかりか、材料の流動性が低下するために成形が困難になるといった問題が生じ、また多すぎると、成形収縮や後収縮による寸法変化が大きくなるため、所定の成形寸法を維持するのが難しいことがあるところ、上記範囲とすることで両者のバランスに優れる。 The content of the phenol resin (a) used in the molding material of the present invention is not particularly limited, but is 25 to 45% by weight with respect to the entire molding material (including hexamethylenetetramine when used). Is preferred. More preferably, it is 30 to 40% by weight. If the content of the phenol resin (a) is too small, not only the production of the molding material becomes difficult, but also the problem that the molding becomes difficult because the fluidity of the material is lowered, and if too much, the molding shrinkage or Since the dimensional change due to post-shrinkage becomes large, it may be difficult to maintain a predetermined molding dimension.
本発明の成形材料は、ガラス転移点が−２０〜６０℃であるエラストマ（ｂ）を含有することを特徴とする。更に好ましくは−２０〜４０℃である。これにより、得られる成形品に常温付近における優れた制振性或いは防音性を付与することできる。この理由は明確ではないが、エラストマのガラス転移温度においては分子鎖のミクロブラウン運動が活発化しているため、振動エネルギーが効率的に吸収されるからであると推測される。この機構を利用することにより、従来よりもエラストマの添加量を少なくすることができるため、得られる成形品の剛性や機械的強度の低下を抑制する効果を向上することができるものと考えられる。 The molding material of the present invention is characterized by containing an elastomer (b) having a glass transition point of -20 to 60 ° C. More preferably, it is -20-40 degreeC. Thereby, the vibration suppression property or the soundproofing property in the normal temperature vicinity can be provided to the molded article obtained. The reason for this is not clear, but it is presumed that vibrational energy is efficiently absorbed because the micro-Brownian motion of the molecular chain is active at the glass transition temperature of the elastomer. By using this mechanism, the amount of elastomer added can be reduced as compared with the conventional case, so that the effect of suppressing the decrease in rigidity and mechanical strength of the obtained molded product can be improved.
本発明の成形材料に用いる上記エラストマ（ｂ）としては、特に限定されないが、エラストマは、ポリ酢酸ビニル、アクリルゴムを用いることができる。
更に、アクリロニトリルの割合が４０重量％以上であるアクリロニトリルブタジエンゴム（以下、「ＮＢＲ」と略すことがある）を用いることもできる。アクリロニトリルの割合が上記数値以上であるとガラス転移点を通常のＮＢＲよりも高くすることができる。これらのエラストマ（ｂ）は、単独で用いても、２種以上を併用してもかまわない。この中でも、ポリ酢酸ビニルを用いることがフェノール樹脂との相溶性が良いこととガラス転移温度が最も室温に近いとの理由から好ましい。
Although it does not specifically limit as said elastomer (b) used for the molding material of this invention, Polyvinyl acetate and acrylic rubber can be used for an elastomer.
Furthermore, an acrylonitrile butadiene rubber (hereinafter sometimes abbreviated as “NBR”) having an acrylonitrile ratio of 40% by weight or more may be used. A glass transition point can be made higher than normal NBR as the ratio of an acrylonitrile is more than the said numerical value. These elastomers (b) may be used alone or in combination of two or more. Among these, it is preferable to use polyvinyl acetate because it has good compatibility with the phenol resin and the glass transition temperature is closest to room temperature.
上記エラストマ（ｂ）の含有量は、成形材料全体に対して３〜１３重量％であることが好ましく、３〜７重量％であることがさらに好ましい。上記範囲とすることで、特に制振性或いは防音性を高める効果を更に向上させることができる。 The content of the elastomer (b) is preferably 3 to 13% by weight, more preferably 3 to 7% by weight, based on the entire molding material. By setting it as the said range, especially the effect which improves damping property or soundproofing can be improved further.
本発明の成形材料は、ガラス繊維（ｃ）を含有することを特徴とする。このガラス繊維（ｃ）を用いることにより、得られる成形品に優れた機械的強度を付与することができる。ガラス繊維（ｃ）の含有量は、成形材料全体に対して４０〜６０重量％が好ましい。更に４５〜５５重量％が好ましい。上記範囲とすることで、特に機械的強度と制振性或いは防音性とのバランスを良好なものとすることができる。 The molding material of the present invention is characterized by containing glass fiber (c). By using this glass fiber (c), excellent mechanical strength can be imparted to the obtained molded product. As for content of glass fiber (c), 40 to 60 weight% is preferable with respect to the whole molding material. Furthermore, 45 to 55% by weight is preferable. By setting it as the said range, the balance of mechanical strength, damping property, or soundproofing property can be made especially favorable.
本発明の成形材料に用いるガラス繊維（ｃ）としては特に限定されないが、平均繊維径７〜１１μｍ、平均繊維長１〜３ｍｍ程度のものが好ましい。上記範囲のガラス繊維を用いることにより、特に機械的強度と成形性とバランスを優れたものととができる。 Although it does not specifically limit as glass fiber (c) used for the molding material of this invention, The thing of an average fiber diameter of 7-11 micrometers and an average fiber length of about 1-3 mm is preferable. By using the glass fiber in the above range, particularly excellent mechanical strength, moldability and balance can be achieved.
本発明の成形材料には、上記（ａ）〜（ｃ）成分のほか、充填材を配合することができる。これにより、目的とする成形品に要求される機械的特性、電気的特性などを付与することができる。
本発明の成形材料に用いられる充填材としては特に限定されないが、例えば、木粉、パルプ粉、各種繊維粉砕物、フェノール樹脂積層板、成形品の粉砕物などの有機充填材や、シリカ、アルミナ、水酸化アルミニウム、ガラス、タルク、クレー、マイカ、炭酸カルシウム、カーボンなどの無機粉末を１種類以上用いることができる。また、本発明のフェノール樹脂成形材料には、本発明の目的を損なわない範囲で、更に滑剤、着色剤、効果促進剤、難燃剤などの各種添加剤を適宜配合することができる。
In addition to the above components (a) to (c), a filler can be blended in the molding material of the present invention. Thereby, mechanical characteristics, electrical characteristics, and the like required for the target molded article can be imparted.
Although it does not specifically limit as a filler used for the molding material of this invention, For example, organic fillers, such as a wood powder, a pulp powder, various fiber pulverized products, a phenol resin laminated board, a pulverized product, silica, an alumina One or more inorganic powders such as aluminum hydroxide, glass, talc, clay, mica, calcium carbonate, and carbon can be used. In addition, various additives such as a lubricant, a colorant, an effect accelerator and a flame retardant can be appropriately blended with the phenol resin molding material of the present invention as long as the object of the present invention is not impaired.
本発明の成形材料は通常の方法により製造される。即ち、上記の各成分を所定の配合割合で混合し、加熱ロール、コニーダ、二軸押し出し機などを使用して溶融混練した後に冷却、粉砕することにより得られる。 The molding material of this invention is manufactured by a normal method. That is, it is obtained by mixing each of the above components at a predetermined blending ratio, melt kneading using a heating roll, a kneader, a twin screw extruder, etc., and then cooling and pulverizing.
次に、本発明の成形材料を成形してなる制振材について説明する。本発明の制振材はこれまで説明した本発明のフェノール樹脂成形材料を、圧縮成形、トランスファ成形、射出成形などの通常の成形方法により成形して得ることができる。 Next, a vibration damping material formed by molding the molding material of the present invention will be described. The damping material of the present invention can be obtained by molding the phenol resin molding material of the present invention described so far by a usual molding method such as compression molding, transfer molding, injection molding or the like.
この制振材の曲げ弾性率は１０〜１６ＧＰａが好ましく、更に好ましくは１４〜１６ＧＰａである。
また、上記制振材の損失係数は、０．０２以上が好ましい。
The flexural modulus of this damping material is preferably 10 to 16 GPa, more preferably 14 to 16 GPa.
The loss factor of the damping material is preferably 0.02 or more.
上記のように、曲げ弾性率を１０〜１６ＧＰａとし、且つ損失係数を０．０２以上とすることで本来の要求特性である機械的強度を維持しつつ、制振性或いは防音性を向上させる効果をバランスよく高めることができる。
以上のことから本発明の制振材は、自動車用、汎用機械用、家庭電化製品用及び周辺機器用の部品として好適である。
As described above, the effect of improving the vibration damping property or the soundproofing property while maintaining the mechanical strength which is the originally required property by setting the bending elastic modulus to 10 to 16 GPa and the loss factor to 0.02 or more. Can be improved in a well-balanced manner.
From the above, the damping material of the present invention is suitable as a part for automobiles, general-purpose machines, home appliances, and peripheral devices.
ここで、特許文献１に開示されている接着樹脂硬化物との差を明確にしておく。この接着樹脂硬化物においては、実施例からも明らかのようにエラストマ（表１、３にはラテックス系アクリル樹脂が樹脂全体に対して８３．５重量％、表５にはアクリルゴムを６５重量％含有していることが記載されている）を大量に含有量させることによって接着剤に制振性を与えているものと推測される。一方、本発明の成形材料に用いるエラストマの含有量は、上記のとおり、成形材料全体に対して３〜１３重量％と少ない量であるが、得られる成形品に優れた制振性を発現するものである。
また、上記接着樹脂硬化物の弾性率と、本発明の成形材料から得られる成形品の弾性率は前者が数百ｐｓｉに比べ、数十万ｐｓｉであり、その差は歴然としている。また、当然ながら、前者は使用時には液状であるのに対し、本発明の成形材料は固形であることも違いを明確にするものである。従って、特許文献１で開示されている接着樹脂硬化物と本発明の成形材料とは同一のものではないことは明白である。
Here, the difference from the cured adhesive resin disclosed in Patent Document 1 is clarified. In this cured adhesive resin, as is clear from the examples, elastomers (Tables 1 and 3 show that latex acrylic resin is 83.5% by weight based on the total resin, and Table 5 shows 65% by weight of acrylic rubber. It is presumed that the vibration-damping property is imparted to the adhesive by containing a large amount of (which is described as being contained). On the other hand, the content of the elastomer used in the molding material of the present invention is as small as 3 to 13% by weight based on the whole molding material as described above, but exhibits excellent vibration damping properties in the obtained molded product. Is.
Further, the elastic modulus of the cured adhesive resin and the elastic modulus of the molded product obtained from the molding material of the present invention are several hundred thousand psi compared to several hundred psi for the former, and the difference is obvious. Of course, the former is in a liquid state at the time of use, whereas the molding material of the present invention is in a solid state to clarify the difference. Therefore, it is clear that the cured adhesive resin disclosed in Patent Document 1 is not the same as the molding material of the present invention.
本発明の制振材を成形する場合には、通常の成形条件を適用することができる。
例えば射出成形により成形する場合は、金型温度１７５℃、シリンダ先端温度９０℃、硬化時間２分間の条件で実施することができる。
When molding the vibration damping material of the present invention, normal molding conditions can be applied.
For example, when molding by injection molding, it can be carried out under conditions of a mold temperature of 175 ° C., a cylinder tip temperature of 90 ° C., and a curing time of 2 minutes.
以下、本発明を実施例によりさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
１．成形材料の製造
（参考例１）
成形材料全体に対して、ノボラック型フェノール樹脂３６重量％、ヘキサメチレンテトラミン６重量％、ガラス繊維５０重量％、エラストマ（Ａ）を５重量％、硬化助剤として酸化マグネシウムを１重量％、着色剤としてカーボンブラック１重量％、離型剤としてステアリン酸カルシウム１重量％配合した原料混合物を、９０℃の加熱ロールにより３分間溶融混練した後取り出し、冷却後顆粒状に粉砕して成形材料を得た。
1. Manufacturing of molding materials ( Reference Example 1)
36% by weight of novolak-type phenolic resin, 6% by weight of hexamethylenetetramine, 50% by weight of glass fiber, 5% by weight of elastomer (A), 1% by weight of magnesium oxide as a curing aid, and coloring agent, based on the whole molding material A raw material mixture containing 1% by weight of carbon black and 1% by weight of calcium stearate as a release agent was melt-kneaded for 3 minutes with a heating roll at 90 ° C., taken out, cooled, and pulverized into granules to obtain a molding material.
（参考例２）
エラストマ（Ａ）の配合量を１０重量％とし、ノボラック型フェノール樹脂を３２重量％とし、ヘキサメチレンテトラミンを５重量％とした以外は、参考例１と同様にして成形材料を得た。
( Reference Example 2)
A molding material was obtained in the same manner as in Reference Example 1 except that the blending amount of the elastomer (A) was 10% by weight, the novolac type phenol resin was 32% by weight, and hexamethylenetetramine was 5% by weight.
（参考例３）
エラストマ（Ａ）の代わりにエラストマ（Ｂ）とした以外は、参考例１と同様にして成形材料を得た。
( Reference Example 3)
A molding material was obtained in the same manner as in Reference Example 1 except that the elastomer (B) was used instead of the elastomer (A).
（実施例１）
エラストマ（Ａ）の代わりにエラストマ（Ｃ）とした以外は、参考例１と同様にして成形材料を得た。
(Example 1 )
A molding material was obtained in the same manner as in Reference Example 1 except that the elastomer (C) was used instead of the elastomer (A).
（比較例１）
成形材料全体に対して、ノボラック型フェノール樹脂３６重量％、ヘキサメチレンテトラミン６重量％、ガラス繊維５０重量％、エラストマ（Ｄ）を５重量％、硬化助剤として酸化マグネシウムを１重量％、着色剤としてカーボンブラック１重量％、離型剤としてステアリン酸カルシウム１重量％配合した原料混合物を、９０℃の加熱ロールにより３分間溶融混練した後取り出し、冷却後顆粒状に粉砕して成形材料を得た。
(Comparative Example 1)
36% by weight of novolak-type phenolic resin, 6% by weight of hexamethylenetetramine, 50% by weight of glass fiber, 5% by weight of elastomer (D), 1% by weight of magnesium oxide as a curing aid, and coloring agent, based on the whole molding material A raw material mixture containing 1% by weight of carbon black and 1% by weight of calcium stearate as a release agent was melt-kneaded for 3 minutes with a heating roll at 90 ° C., taken out, cooled, and pulverized into granules to obtain a molding material.
（比較例２）
エラストマ（Ｄ）の配合量を１０％とし、ノボラック型フェノール樹脂を３２重量％とし、ヘキサメチレンテトラミンを５重量％とした以外は、比較例１と同様にして成形材料を得た。
用いた配合剤の配合量を表１上段に示す。数値は全て成形材料全体に対する重量％を表している。
また、下段には後述の評価方法による結果を示す。
(Comparative Example 2)
A molding material was obtained in the same manner as in Comparative Example 1, except that the amount of the elastomer (D) was 10%, the novolac type phenol resin was 32% by weight, and the hexamethylenetetramine was 5% by weight.
The amount of the compounding agent used is shown in the upper part of Table 1. All the numerical values represent weight% with respect to the whole molding material.
Moreover, the result by the below-mentioned evaluation method is shown in the lower stage.
（使用した原料）
（１）ノボラック型フェノール樹脂：住友ベークライト社製ＰＲ−５０７１６
（２）ヘキサメチレンテトラミン：住友精化社製ウロトロピン
（３）エラストマ（Ａ）：日本合成化学工業社製ポリ酢酸ビニル ゴーセニール（Ｔｇ ３０℃）
（４）エラストマ（Ｂ）：アクリルゴム（Ｔｇ −１５℃）
（５）エラストマ（Ｃ）：日本ゼオン社製アクリロニトリルブタジエンゴム（Ｔｇ −２０℃、 アクリロニトリル比４１％） ＨＦ０１
（６）エラストマ（Ｄ）：ＪＳＲ社製アクリロニトリルブタジエンゴム ＰＮＣ３８（Ｔｇ −３０℃、アクリロニトリルの割合 ３３重量％）ＨＦ２１
（７） ガラス繊維：日本板硝子社製チョップドストランド（平均繊維系１１μｍ、平均繊維長３ｍｍ）
（８）離型剤：ステアリン酸カルシウム
（９）着色剤：カーボンブラック
（１０）硬化助剤：酸化マグネシウム
(Raw materials used)
(1) Novolac type phenolic resin: PR-50716 manufactured by Sumitomo Bakelite Co., Ltd.
(2) Hexamethylenetetramine: Urotropin manufactured by Sumitomo Seika Co., Ltd. (3) Elastomer (A): Polyvinyl acetate gosenyl (Tg 30 ° C.) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
(4) Elastomer (B): Acrylic rubber (Tg-15 ° C)
(5) Elastomer (C): Acrylonitrile butadiene rubber manufactured by Nippon Zeon Co., Ltd. (Tg-20 ° C, acrylonitrile ratio 41%) HF01
(6) Elastomer (D): Acrylonitrile butadiene rubber PNC38 (Tg-30 ° C., ratio of acrylonitrile 33 wt%) manufactured by JSR HF21
(7) Glass fiber: Chopped strand manufactured by Nippon Sheet Glass Co., Ltd. (average fiber type 11 μm, average fiber length 3 mm)
(8) Mold release agent: calcium stearate (9) Colorant: Carbon black (10) Curing aid: Magnesium oxide
２．試験片の成形
実施例及び比較例で得られた成形材料を用いて、下記の成形方法、成形条件により、１０×１７０×４ｍｍの試験片を成形した。
（１）成形方法：射出成形
（２）射出成形の条件
金型温度：１７５℃
硬化時間：１分間
シリンダ温度設定：先端９０℃／末端５０℃
2. Molding of Test Pieces Using the molding materials obtained in Examples and Comparative Examples, 10 × 170 × 4 mm test pieces were molded by the following molding method and molding conditions.
(1) Molding method: injection molding (2) Conditions for injection molding Mold temperature: 175 ° C
Curing time: 1 minute Cylinder temperature setting: Tip 90 ° C / Terminal 50 ° C
３．評価方法
（１）曲げ強さ、曲げ弾性率
上記制振材の成形と同様の成形条件で評価用試料を作成し、ＪＩＳ Ｋ６９１１「熱硬化性プラスチック一般試験法」に準拠して測定した。
3. Evaluation Method (1) Bending Strength and Flexural Modulus An evaluation sample was prepared under the same molding conditions as those for the above damping material, and measured according to JIS K6911 “General Thermosetting Plastic Testing Method”.
（２）振動減衰特性
制振性能は上記で得られた試験片を用い、以下に示す中央加振法により評価した。
加振器に接続されたインピーダンスヘッドに重心位置で接着された試験片を０〜２０ｋHの周波数で振動させ、インピーダンスヘッドにより加速度と力を同時に検出し、機械インピーダンスを算出する。得られた機械インピーダンスの反共振点における半値幅から式（Ｉ）を用いて損失係数ηを導出した。
η＝Δｆｎ／ｆｎ （Ｉ）
ここで、ｎは共振の次数、ｆｎは反共振周波数、Δｆｎは半値幅である。
(2) Vibration damping characteristics Damping performance was evaluated by the following central excitation method using the test piece obtained above.
A test piece bonded to the impedance head connected to the vibrator at the center of gravity is vibrated at a frequency of 0 to 20 kHz, and acceleration and force are simultaneously detected by the impedance head to calculate mechanical impedance. The loss coefficient η was derived from the half width at the antiresonance point of the obtained mechanical impedance using the formula (I).
η = Δf n / f n (I)
Here, n is the order of resonance, f n is the antiresonance frequency, and Δf n is the half width.
表１の結果から明らかのように、ガラス転移点が−２０〜６０℃であるエラストマを含む本発明の成形材料から得られた実施例１の制振材は、ガラス転移点が上記範囲のエラストマを含まない比較例１、２に比較して、本来の要求特性である機械的強度を維持しつつ、制振性或いは防音性に優れたものとすることができた。
As is clear from the results in Table 1, the vibration damping material of Example 1 obtained from the molding material of the present invention containing an elastomer having a glass transition point of -20 to 60 ° C. has an elastomer having a glass transition point in the above range. Compared to Comparative Examples 1 and 2 that do not contain, the mechanical strength, which is the original required characteristic, was maintained, and the vibration damping property or the soundproofing property was excellent.
Claims (4)
前記ガラス繊維（ｃ）の含有量は、制振材用フェノール樹脂成形材料全体に対して４０〜６０重量％であり、
前記エラストマ（ｂ）の含有量は、制振材用フェノール樹脂成形材料全体に対して３〜１３重量％であり、
前記エラストマ（ｂ）は、アクリロニトリルブタジエンゴムであることを特徴とする、制振材用フェノール樹脂成形材料（ただし、層状または板状無機充填材を含む制振材用フェノール樹脂成形材料を除く）。 Containing a phenol resin (a), an elastomer (b) having a glass transition point of -20 to 60 ° C., and glass fiber (c),
Content of the said glass fiber (c) is 40 to 60 weight% with respect to the whole phenol resin molding material for damping materials,
The content of the elastomer (b) is 3 to 13% by weight with respect to the entire phenol resin molding material for damping material,
Said elastomeric (b) is characterized by an A methacrylonitrile-butadiene rubber, for vibration damping materials phenolic resin molding material (however, the damping material for phenolic resin molding material containing a layered or plate-like inorganic filler except).
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| CN110117389A (en) * | 2019-04-25 | 2019-08-13 | 赵晓莉 | A kind of sound absorbing rubber and preparation method thereof |
| CN115386152A (en) * | 2022-10-08 | 2022-11-25 | 昆山浩恩高分子材料有限公司 | TPE composite material for earphone cable and preparation method thereof |
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| JPS6123648A (en) * | 1984-07-11 | 1986-02-01 | Central Glass Co Ltd | Heat-resistant damping material |
| JP3661180B2 (en) * | 1998-09-08 | 2005-06-15 | 東海ゴム工業株式会社 | High damping material composition |
| GB2400105B (en) * | 2001-12-20 | 2005-08-31 | World Properties Inc | Adhesive resin with high damping properties and method of manufacture thereof |
| JP2004256741A (en) * | 2003-02-27 | 2004-09-16 | Sumitomo Bakelite Co Ltd | Phenolic resin molding material and vibration damping material |
| JP2005179525A (en) * | 2003-12-19 | 2005-07-07 | Yamauchi Corp | Rubber composition for vibration isolation |
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