JP6082645B2 - Friction material - Google Patents
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- JP6082645B2 JP6082645B2 JP2013084870A JP2013084870A JP6082645B2 JP 6082645 B2 JP6082645 B2 JP 6082645B2 JP 2013084870 A JP2013084870 A JP 2013084870A JP 2013084870 A JP2013084870 A JP 2013084870A JP 6082645 B2 JP6082645 B2 JP 6082645B2
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- 239000002783 friction material Substances 0.000 title claims description 67
- 239000000835 fiber Substances 0.000 claims description 92
- 150000001875 compounds Chemical class 0.000 claims description 40
- 239000004593 Epoxy Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 35
- 239000002131 composite material Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- -1 polyparaphenylene terephthalamide Polymers 0.000 claims description 15
- 239000002657 fibrous material Substances 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 12
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 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 claims description 9
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 9
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- 229920000223 polyglycerol Polymers 0.000 claims description 5
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 claims description 4
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 51
- 238000001723 curing Methods 0.000 description 16
- 239000004760 aramid Substances 0.000 description 14
- 229920003235 aromatic polyamide Polymers 0.000 description 14
- 229920006231 aramid fiber Polymers 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000003814 drug Substances 0.000 description 11
- 229940079593 drug Drugs 0.000 description 11
- 230000004580 weight loss Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001187 thermosetting polymer Polymers 0.000 description 10
- 239000002002 slurry Substances 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 230000013011 mating Effects 0.000 description 6
- 230000002093 peripheral effect Effects 0.000 description 6
- 229920000271 Kevlar® Polymers 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000004761 kevlar Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 102200082816 rs34868397 Human genes 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- OADIZUFHUPTFAG-UHFFFAOYSA-N 2-[2-(2-ethylhexoxy)ethoxy]ethanol Chemical compound CCCCC(CC)COCCOCCO OADIZUFHUPTFAG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- VVTGHWARMCSPKY-UHFFFAOYSA-N dodecan-1-amine;oxirane Chemical compound C1CO1.CCCCCCCCCCCCN VVTGHWARMCSPKY-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000002433 hydrophilic molecules Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009439 industrial construction Methods 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Gears, Cams (AREA)
- Braking Arrangements (AREA)
- Sliding-Contact Bearings (AREA)
Description
本発明は、自動車等のクラッチ板、ブレーキ板、産業機械や車両等のワッシャー、ギアー、軸及び軸受けに好適に使用される耐久性に優れた摩擦材料に関する。 The present invention relates to a friction material excellent in durability, which is suitably used for a clutch plate, a brake plate of an automobile or the like, a washer, a gear, a shaft and a bearing of an industrial machine or a vehicle.
摩擦材料は、大きな摩擦抵抗により駆動側の力を被駆動側に伝達したり、動いている物体を安全に停止させたりすることを目的として用いられ、具体的な用途としては、自動車等のクラッチ板やブレーキ板に使用される。一方、小さな摩擦抵抗により動いている物体を、より滑らかに滑らせたりすることを目的としても用いられ、具体的な用途としては、車両等のワッシャー、ギアー、軸及び軸受け等に使用される。 The friction material is used for the purpose of transmitting the driving force to the driven side with a large frictional resistance or for stopping the moving object safely. Used for plates and brake plates. On the other hand, it is also used for the purpose of sliding an object moving with a small frictional resistance more smoothly, and as a specific application, it is used for a washer, a gear, a shaft and a bearing of a vehicle or the like.
前者の摩擦材料は燒結金属等の金属摩擦材料と、有機繊維等から構成される有機質摩擦材料とがあり、自動車用自動変速機の湿式多板クラッチの摩擦材料として、殆どが有機質摩擦材料であり、ペーパー摩擦材料と呼ばれる摩擦材料が主に使用されている。一方、後者では、有機繊維等から構成される有機質摩擦材料であり、ペーパー摩擦材料と呼ばれる樹脂含浸の摩擦材料が主に使用されている。 The former friction materials include metal friction materials such as sintered metals and organic friction materials composed of organic fibers, etc., and most of them are organic friction materials as friction materials for wet multi-plate clutches in automatic transmissions for automobiles. A friction material called a paper friction material is mainly used. On the other hand, the latter is an organic friction material composed of organic fibers and the like, and a resin-impregnated friction material called a paper friction material is mainly used.
このような材料としては、アラミド繊維（東レ・デュポン社のケブラー（登録商標）、テイジン・アラミド社のトワロン（登録商標）等）を水中に分散させた後に抄紙し、乾燥後にフェノール樹脂等の熱硬化性樹脂を含浸させ、加熱・加圧成形することで製造されるものがあり、これは摩擦耐久性に優れた摩擦材料である。 As such materials, aramid fibers (Kevlar (registered trademark) of Toray DuPont, Twaron (registered trademark) of Teijin Aramid, etc.) are dispersed in water, paper is made, and after drying, heat such as phenol resin is used. Some are manufactured by impregnating a curable resin, followed by heating and pressure molding, and this is a friction material having excellent friction durability.
ペーパー摩擦材料では、耐熱性と強度に優れたアラミド繊維が表層一面に存在した樹脂成形体とすることにより、滑らかな摩擦特性を発揮することができる。ところが、近年の自動車業界においては、省エネルギー化、軽量化の追求により、各種使用部品の軽量化及び高効率化が進められている一方、エンジンは高回転、高出力化の傾向にあり、自動車用のワッシャー、ギアー、軸及び軸受けにおいても、自動車エンジンの高回転、高出力化に対応すべく、ペーパー摩擦材料に対して強度や耐熱性、摩擦低減の更なる改善が求められている。 In the paper friction material, smooth friction characteristics can be exhibited by using a resin molded body in which an aramid fiber excellent in heat resistance and strength exists on one surface. However, in recent years, in the automobile industry, various parts used have been made lighter and more efficient by pursuing energy saving and lighter weight. On the other hand, the engine tends to have higher speed and higher output. As for the washer, gear, shaft and bearing, further improvement in strength, heat resistance and friction reduction is required for the paper friction material in order to cope with high rotation and high output of the automobile engine.
そこで、バインダー的作用のある耐熱性非晶質含水アラミドフィブリッドを、高度にフィブリル化したアラミドパルプと共に水に分散させてスラリーとし、抄造することにより得た紙状物を乾燥・熱プレスすることにより、結合樹脂の含浸量を減らし、耐熱性の高い湿式摩擦材料とすることが開示されている（特許文献１参照）。しかしながら、この方法では、非晶質含水アラミドフィブリッドが微小であることから、抄造時にワイヤーメッシュの目詰まりが生じ、濾水時間が長くなる等の問題があり、また、高密度の紙状物となるために結合樹脂の含浸が不均一となり、強度及び耐久性面での課題がある。 Then, heat-resistant amorphous water-containing aramid fibrids that act as a binder are dispersed in water together with highly fibrillated aramid pulp to form a slurry, and paper-like materials obtained by papermaking are dried and hot pressed. Thus, it is disclosed that a wet friction material with high heat resistance is obtained by reducing the amount of impregnation of the binding resin (see Patent Document 1). However, in this method, since the amorphous hydrous aramid fibrids are minute, there are problems such as clogging of the wire mesh at the time of papermaking and a long drainage time, and a high density paper-like material. Therefore, the impregnation of the binder resin becomes non-uniform, and there are problems in terms of strength and durability.
一方で、紙状物の繊維状材料であるアラミド繊維と、フェノール樹脂等との接着性を向上させることで、アラミド繊維本来の耐熱性、耐摩耗性及び耐久性を生かす工夫もなされている（特許文献２〜４参照）。 On the other hand, by improving the adhesion between the aramid fiber, which is a fibrous material of paper-like material, and phenol resin, etc., a device that makes use of the heat resistance, wear resistance, and durability inherent in the aramid fiber has been made ( (See Patent Documents 2 to 4).
特許文献２、３には、水系エポキシ樹脂エマルジョン中にアラミドパルプを分散させ、次いで濾別、脱水することにより、エポキシ樹脂により表面処理されたアラミドパルプを製造し、これを用いて湿式摩擦材料を製造することにより、フェノール樹脂との接着性、無機粒子の保持性に優れる製品が得られることが開示されている。しかしながら、湿式抄紙時に、表面処理したエポキシ樹脂が水中に溶出し、抄紙排水のＣＯＤ値が高くなるため環境面で課題がある。 In Patent Documents 2 and 3, aramid pulp is dispersed in an aqueous epoxy resin emulsion, then filtered and dehydrated to produce an aramid pulp surface-treated with an epoxy resin, and a wet friction material is produced using the aramid pulp. It is disclosed that a product excellent in adhesiveness with a phenol resin and retention of inorganic particles can be obtained by manufacturing. However, when wet papermaking, the surface-treated epoxy resin elutes in water, and the COD value of papermaking wastewater becomes high, so that there is an environmental problem.
特許文献４には、水分率１５重量％以上のアラミド繊維を、エポキシ又はウレタン系バインダーで、あるいはそれらとシランカップリング剤との併用で、アラミド繊維の表面及び内部を処理した処理繊維と、メタ系アラミド繊維パルプとを用いて作製した紙に、フェノール樹脂を含浸した後、加熱硬化させることにより、未処理繊維を用いた場合よりも引張強度が向上することが開示されている。この方法によれば、抄紙排水のＣＯＤ値の問題は解消される。しかしながら、この処理繊維は水分散性が悪いため、処理繊維とメタ系アラミド繊維パルプとが不均一な状態で存在する紙状物となり、結合樹脂の含浸が不均一になることで、強度及び耐久性面で課題がある。 Patent Document 4 discloses that an aramid fiber having a moisture content of 15% by weight or more is treated with an epoxy or urethane-based binder, or a combination of these and a silane coupling agent, and a treated fiber obtained by treating the surface and the inside of an aramid fiber. It is disclosed that the tensile strength is improved as compared with the case of using untreated fibers by impregnating a phenol resin with a paper produced using a system aramid fiber pulp, followed by heat curing. According to this method, the problem of the COD value of papermaking waste water is solved. However, since this treated fiber has poor water dispersibility, the treated fiber and meta-aramid fiber pulp become a paper-like material that exists in a non-uniform state, and the impregnation of the binder resin becomes non-uniform, resulting in strength and durability. There is a problem in terms of sex.
本発明の目的は、環境にやさしく、フェノール樹脂等の熱硬化性樹脂の浸透性及び接着性が良好で、強度、耐熱性、低摩擦特性に優れる摩擦材料を提供することにある。 An object of the present invention is to provide a friction material that is environmentally friendly, has good permeability and adhesion of thermosetting resins such as phenolic resins, and is excellent in strength, heat resistance, and low friction characteristics.
本発明は上記課題を解決するため、次の手段をとるものである。 In order to solve the above problems, the present invention takes the following means.
（１）水分率１５〜２００重量％に調整されたポリパラフェニレンテレフタルアミド繊維骨格内に、硬化性エポキシ化合物および必要に応じて硬化剤を浸透・含浸させると共に、下記一般式（Ｉ）で表される相溶化剤を、前記硬化性エポキシ化合物との合計量として０．１重量％以上１０．０重量％以下、浸透・含浸させてなるポリパラフェニレンテレフタルアミド繊維複合体を、繊維状材料として含むことを特徴とする摩擦材料。
(1) the moisture content from 15 to 200 wt% to adjust the polyparaphenylene terephthalamide fibers in the backbone, the curable epoxy compound and a curing agent optionally infiltrated-impregnated Rutotomoni, the following general formula (I) A polyparaphenylene terephthalamide fiber composite obtained by impregnating and impregnating the compatibilizing agent represented in a total amount of 0.1% by weight to 10.0% by weight with the curable epoxy compound as a fibrous material A friction material characterized by including as
（式中、Ｒ(Wherein R
１ 1
は炭素原子数１〜１０のアルキル基、または炭素原子数１〜１０のアルケニル基であり、ＲIs an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 1 to 10 carbon atoms, and R
２2
は水素原子、または炭素原子数１〜５のアルキル基または炭素原子数１〜５のアルケニル基を示す。また、Ａは炭素原子数２〜４のアルキレン基を、ｎはオキシアルキレン基（ＡＯ）の平均付加モル数を表す１〜１０の整数である。なお、−（ＡＯ）−においては、同一のオキシアルキレン基が付加していても、２種類以上のオキシアルキレン基が付加していてもよい。）Represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 1 to 5 carbon atoms. A is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 10 representing the average added mole number of an oxyalkylene group (AO). In-(AO)-, the same oxyalkylene group may be added, or two or more oxyalkylene groups may be added. )
（２）硬化性エポキシ化合物が、グリセロールジグリシジルエーテル、グリセロールトリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテルから選ばれる１種類または、２種類以上の混合物である、前記（１）に記載の摩擦材料。
(2) a curable epoxy compound, glycerol diglycidyl ether, glycerol triglycidyl ether, sorbitol polyglycidyl ether, one selected from polyglycerol polyglycidyl ether or a mixture of two or more, according to the above (1) Friction material.
（３）記載の硬化性エポキシ化合物が、ビスフェノール型エポキシ樹脂である、前記（１）に摩擦材料。
( 3 ) The friction material according to (1) , wherein the curable epoxy compound according to ( 3 ) is a bisphenol type epoxy resin.
（４）前記（１）〜（３）のいずれかに記載のポリパラフェニレンテレフタルアミド繊維複合体を切断してなる短繊維を繊維状材料として含み、該繊維状材料を用い湿式抄造により得られる紙状物に、熱硬化性樹脂としてフェノール樹脂を重量比で３０％以上７０％以下含浸させたことを特徴とする摩擦材料。
( 4 ) A short fiber obtained by cutting the polyparaphenylene terephthalamide fiber composite according to any one of (1) to ( 3 ) is included as a fibrous material, and obtained by wet papermaking using the fibrous material. A friction material, wherein a paper-like material is impregnated with a phenol resin as a thermosetting resin in a weight ratio of 30% to 70%.
（５）ＪＩＳ法Ｋ７２１８に記載の限界ＰＶ値（ｋＰａ・ｍ／ｓ）が４５０以上１，０００以下である前記（１）〜（４）のいずれかに記載の摩擦材料。
( 5 ) The friction material according to any one of (1) to ( 4 ), wherein a limit PV value (kPa · m / s) described in JIS method K7218 is 450 or more and 1,000 or less.
（６）前記（１）〜（５）いずれかに記載の摩擦材料を用いたワッシャー。
( 6 ) A washer using the friction material according to any one of (1) to ( 5 ).
（７）前記（１）〜（５）のいずれかに記載の摩擦材料を用いたギアー。
( 7 ) A gear using the friction material according to any one of (1) to ( 5 ).
（８）前記（１）〜（５）のいずれかに記載の摩擦材料を用いた軸及び軸受け。
( 8 ) A shaft and a bearing using the friction material according to any one of (1) to ( 5 ).
（９）前記（１）〜（５）のいずれかに記載の摩擦材料を用いたクラッチ板。
( 9 ) A clutch plate using the friction material according to any one of (1) to ( 5 ).
（１０）前記（１）〜（５）のいずれかに記載の摩擦材料を用いたブレーキ板。
( 10 ) A brake plate using the friction material according to any one of (1) to ( 5 ).
本発明の摩擦材料を構成する繊維状材料は、硬化性エポキシ化合物と必要に応じて相溶化剤をポリパラフェニレンテレフタルアミド繊維骨格内に浸透・含浸させた繊維複合体を含むため、抄紙排水のＣＯＤ値が低く、また、湿式抄造した紙状物に熱硬化性樹脂を含浸させたプリプレグは、耐熱性、強度及び低摩耗特性に優れている。そのため、車両及び産業用機械のワッシャー、ギアー、軸及び軸受け、クラッチ板、ブレーキ板に好適な、自動車エンジンの高回転や高出力化にも対応できる高強度、高耐熱性、低摩擦特性を有する耐久性に優れた摩擦材料を提供できる。 The fibrous material constituting the friction material of the present invention includes a fiber composite in which a curable epoxy compound and a compatibilizer as necessary are impregnated and impregnated into the polyparaphenylene terephthalamide fiber skeleton. A prepreg obtained by impregnating a thermosetting resin with a paper-like product made by wet papermaking has a low COD value and is excellent in heat resistance, strength, and low wear characteristics. Therefore, it is suitable for washers, gears, shafts and bearings, clutch plates and brake plates for vehicles and industrial machines, and has high strength, high heat resistance, and low friction characteristics that can cope with high rotation and high output of automobile engines. A friction material with excellent durability can be provided.
以下、本発明の摩擦材料について詳細に説明する。
本発明の摩擦材料は、水分率１５〜２００重量％に調整されたポリパラフェニレンテレフタルアミド繊維骨格内に、硬化性エポキシ化合物および必要に応じて硬化剤を更には下記一般式（Ｉ）で表される相溶化剤を合計０．１重量％以上１０．０重量％以下を、浸透・含浸させてなるポリパラフェニレンテレフタルアミド繊維複合体を、繊維状材料として含むものである。
Hereinafter, the friction material of the present invention will be described in detail.
In the friction material of the present invention, a curable epoxy compound and, if necessary, a curing agent are further represented by the following general formula (I) in a polyparaphenylene terephthalamide fiber skeleton adjusted to a moisture content of 15 to 200% by weight. A polyparaphenylene terephthalamide fiber composite obtained by impregnating and impregnating a total of 0.1% by weight or more and 10.0% by weight or less of the compatibilizer is included as a fibrous material.
本発明におけるポリパラフェニレンテレフタルアミド（以下、「ＰＰＴＡ」称する。）とは、テレフタル酸とパラフェニレンジアミンを重縮合して得られる重合体であるが、少量のジカルボン酸及びジアミンを共重合したものも使用することができ、得られる重合体又は共重合体の数平均分子量は通常２０，０００〜２５，０００の範囲内が好ましい。 In the present invention, polyparaphenylene terephthalamide (hereinafter referred to as “PPTA”) is a polymer obtained by polycondensation of terephthalic acid and paraphenylene diamine, which is obtained by copolymerizing a small amount of dicarboxylic acid and diamine. The number average molecular weight of the resulting polymer or copolymer is usually preferably in the range of 20,000 to 25,000.
ＰＰＴＡ繊維の製造方法の代表例としては、ＰＰＴＡを濃硫酸に溶解して、１８〜２０重量％の粘調な溶液とし、これを紡糸口金から吐出して、わずかの間空気中に紡出後、水中へ紡糸する。この時、口金吐出時のせん断速度を２５，０００〜５０，０００ｓｅｃ−１にするのが好ましい。その後、紡糸浴中で凝固した繊維を水酸化ナトリウム水溶液で中和処理した後、１００〜１５０℃で、好ましくは２０秒間以下熱処理することにより、水分率が１５〜２００重量％の範囲内にあるＰＰＴＡ繊維を調製することができる。 As a typical example of the production method of PPTA fiber, PPTA is dissolved in concentrated sulfuric acid to obtain a viscous solution of 18 to 20% by weight, and this is discharged from a spinneret and after being spun in air for a short time. Spin into water. At this time, it is preferable to set the shear rate during discharge of the die to 25,000 to 50,000 sec −1 . Thereafter, the fiber solidified in the spinning bath is neutralized with an aqueous sodium hydroxide solution and then heat-treated at 100 to 150 ° C., preferably 20 seconds or less, so that the moisture content is in the range of 15 to 200% by weight. PPTA fibers can be prepared.
硬化性エポキシ化合物は、脂肪族エポキシ化合物、芳香環を有するエポキシ化合物のいずれも使用でき、これらを併用することもできる。 As the curable epoxy compound, either an aliphatic epoxy compound or an epoxy compound having an aromatic ring can be used, and these can be used in combination.
脂肪族エポキシ化合物としては、グリセロール、ソルビトール、ポリグリセロールなどの多価アルコールのグリシジルエーテル化合物から選ばれる１種または、２種以上の混合物であることが好ましい。例えば、グリセロールジグリシジルエーテル、グリセロールトリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテルなどが挙げられる。これらの中でも、グリセロールジグリシジルエーテル、グリセロールトリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテルが特に好ましく用いられる。 The aliphatic epoxy compound is preferably one or a mixture of two or more selected from glycidyl ether compounds of polyhydric alcohols such as glycerol, sorbitol, and polyglycerol. Examples thereof include glycerol diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, and the like. Among these, glycerol diglycidyl ether, glycerol triglycidyl ether, sorbitol polyglycidyl ether, and polyglycerol polyglycidyl ether are particularly preferably used.
芳香環を有するエポキシ化合物としては、ビスフェノール型エポキシ樹脂から選ばれる１種または、２種以上の混合物であることが好ましい。例えば、ビス（４−ヒドロキシフェニル）メタン［ビスフェノールＦ］、２，２−ビス（４−ヒドロキシフェニル）プロパン［ビスフェノールＡ］、２，２−ビス（３−メチル−４−ヒドロキシフェニル）プロパン［ビスフェノールＣ］などのグリシジルエーテル化物が挙げられる。これらの中でも、常温で液状の、ビスフェノールＡ、ビスフェノールＦのグリシジルエーテル化物が特に好ましく用いられる。 The epoxy compound having an aromatic ring is preferably one or a mixture of two or more selected from bisphenol type epoxy resins. For example, bis (4-hydroxyphenyl) methane [bisphenol F], 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 2,2-bis (3-methyl-4-hydroxyphenyl) propane [bisphenol C] and the like. Among these, glycidyl etherified products of bisphenol A and bisphenol F that are liquid at room temperature are particularly preferably used.
硬化剤としては、アミン化合物が好ましく、三級アミン化合物が特に好ましい。例えば、ジメチルオクチルアミン、ジメチルデシルアミン、ジメチルラウリルアミンや、脂肪族一級アミンにエチレンオキサイドを付加した長鎖アルキルポリオキシエチレン型三級アミンなどが挙げられる。 As the curing agent, an amine compound is preferable, and a tertiary amine compound is particularly preferable. Examples thereof include dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, and long-chain alkylpolyoxyethylene type tertiary amine obtained by adding ethylene oxide to an aliphatic primary amine.
相溶化剤は、下記一般式（Ｉ）で表されるグリコールエーテル系化合物が好ましく用いられる。Ｒ１ の炭素原子数が大きくなると、水溶性が低下するため水分率の高いＰＰＴＡ繊維に浸透・含浸し難くなる。ｎが大きくなると、高分子量化することによりＰＰＴＡ繊維に浸透・含浸し難くなる。相溶化剤は、硬化性エポキシ化合物よりも親水性の化合物であることが望ましい。 As the compatibilizer, a glycol ether compound represented by the following general formula (I) is preferably used. When the number of carbon atoms in R 1 is increased, water solubility is lowered, so that it is difficult to penetrate and impregnate PPTA fibers having a high moisture content. When n becomes large, it becomes difficult to penetrate and impregnate PPTA fibers by increasing the molecular weight. The compatibilizer is preferably a hydrophilic compound rather than a curable epoxy compound.
上記一般式（Ｉ）において、Ｒ１ は炭素原子数１〜１０、好ましくは炭素原子数４〜８のアルキル基またはアルケニル基であり、Ｒ２ は水素原子、または炭素原子数１〜５のアルキル基または炭素原子数１〜５のアルケニル基を示す。好ましくは、Ｒ２ は水素原子である。また、Ａは炭素原子数２〜４のアルキレン基、好ましくは炭素原子数２〜３のアルキレン基であり、ｎはオキシアルキレン基（ＡＯ）の平均付加モル数を表す１〜１０の整数、好ましくは２〜８である。なお、−（ＡＯ）−においては、同一のオキシアルキレン基が付加していても、２種類以上のオキシアルキレン基が付加していてもよい。 In the general formula (I), R 1 is an alkyl group or alkenyl group having 1 to 10 carbon atoms, preferably 4 to 8 carbon atoms, and R 2 is a hydrogen atom or alkyl having 1 to 5 carbon atoms. A group or an alkenyl group having 1 to 5 carbon atoms; Preferably, R 2 is a hydrogen atom. A is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, and n is an integer of 1 to 10 representing the average number of moles added of the oxyalkylene group (AO), preferably Is 2-8. In-(AO)-, the same oxyalkylene group may be added, or two or more oxyalkylene groups may be added.
一般式（Ｉ）で示される化合物の具体例としては、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノ２−エチルヘキシルエーテル、ジプロピレングリコールモノブチルエーテル、ポリプロピレングリコール（ｎ＝３）グリセリルエーテルなどが挙げられる。グリコールエーテル系化合物は、それぞれ単独で使用してもよいし、２種類以上を適宜組み合わせて使用してもよい。 Specific examples of the compound represented by the general formula (I) include diethylene glycol monobutyl ether, diethylene glycol mono 2-ethylhexyl ether, dipropylene glycol monobutyl ether, polypropylene glycol (n = 3) glyceryl ether and the like. The glycol ether compounds may be used alone or in combination of two or more.
本発明のＰＰＴＡ繊維複合体では、硬化性エポキシ化合物及び相溶化剤の繊維への含浸量は、これらの合計量として、好ましくは０．１重量％以上１０．０重量％以下である。ここで、「含浸量」は、ＰＰＴＡ繊維の水分率を０％に換算したときの繊維重量に対する値である。望ましい含浸量は、それぞれ、０．１〜２．０重量％であり、特に好ましくは０．２〜１．０重量％である。 In the PPTA fiber composite of the present invention, the amount of impregnation into the fiber of the curable epoxy compound and the compatibilizer is preferably 0.1 wt% or more and 10.0 wt% or less as the total amount thereof. Here, the “impregnation amount” is a value relative to the fiber weight when the moisture content of the PPTA fiber is converted to 0%. Desirable amounts of impregnation are each 0.1 to 2.0% by weight, particularly preferably 0.2 to 1.0% by weight.
硬化剤を併用する場合、硬化剤の含浸量は０．０２〜１．０重量％が好ましく、特に好ましくは０．０４〜０．５重量％である。硬化性エポキシ化合物と硬化剤を浸透・含浸させたＰＰＴＡ繊維複合体では、硬化剤の触媒効果により硬化性エポキシ化合物が反応しやすくなることで、より短時間で、後述する硬化性エポキシ化合物のエージングを終了することができる。 When a curing agent is used in combination, the impregnation amount of the curing agent is preferably 0.02 to 1.0% by weight, particularly preferably 0.04 to 0.5% by weight. In PPTA fiber composites that have been impregnated and impregnated with a curable epoxy compound and a curing agent, the curable epoxy compound is likely to react due to the catalytic effect of the curing agent, so that the aging of the curable epoxy compound described later can be performed in a shorter time. Can be terminated.
次に、ＰＰＴＡ繊維複合体の製造方法を詳細に説明する。
先ず、水分率が１５〜２００重量％の範囲内にあるＰＰＴＡ繊維に、硬化性エポキシ化合物、硬化性エポキシ化合物と硬化剤、硬化性エポキシ化合物と相溶化剤、又は、硬化性エポキシ化合物と相溶化剤と硬化剤を付与し、ＰＰＴＡ繊維骨格内にこれらの薬剤を浸透・含浸させる。
Next, the manufacturing method of a PPTA fiber composite is demonstrated in detail.
First, PPTA fibers having a moisture content in the range of 15 to 200% by weight are compatibilized with a curable epoxy compound, a curable epoxy compound and a curing agent, a curable epoxy compound and a compatibilizing agent, or a curable epoxy compound. An agent and a curing agent are applied, and these agents are permeated and impregnated into the PPTA fiber skeleton.
薬剤を浸透・含浸させるＰＰＴＡ繊維の水分率が１５重量％以上の場合、平衡水分率よりも高い水分を含有する乾燥前の状態であるため、結晶サイズが比較的小さく、ＰＰＴＡ繊維結晶間の間隙が広いので、硬化性エポキシ化合物や相溶化剤を繊維骨格内に浸透・含浸させることが容易である。また、水分率が２００重量％以下であれば、繊維の巻き出しや巻き取り操作も容易である。水分率が２０〜５０重量％の範囲内にあることが、より好ましい。 When the moisture content of the PPTA fiber to be infiltrated and impregnated with the drug is 15% by weight or more, the crystal size is relatively small because the moisture content is higher than the equilibrium moisture content, and the gap between the PPTA fiber crystals is relatively small. Therefore, it is easy to permeate and impregnate the fiber skeleton with a curable epoxy compound or a compatibilizing agent. Further, when the moisture content is 200% by weight or less, the fiber unwinding and winding operations are easy. It is more preferable that the moisture content is in the range of 20 to 50% by weight.
浸透・含浸させた後、乾燥して、ＰＰＴＡ繊維の水分率を１５重量％未満、より好ましくは１０重量％未満、更に好ましくは３〜１０重量％の範囲内とし、繊維表面及び繊維内部に、硬化性エポキシ化合物のコーティング層、硬化性エポキシ化合物と相溶化剤のコーティング層、あるいは、硬化性エポキシ化合物と相溶化剤と硬化剤のコーティング層を形成する。 After impregnating and impregnating, the moisture content of the PPTA fiber is less than 15% by weight, more preferably less than 10% by weight, and still more preferably in the range of 3 to 10% by weight. A coating layer of a curable epoxy compound, a coating layer of a curable epoxy compound and a compatibilizing agent, or a coating layer of a curable epoxy compound, a compatibilizing agent and a curing agent is formed.
薬剤を浸透・含浸させたＰＰＴＡ繊維複合体は、乾燥により繊維骨格内の水分を除去することで、繊維表面及び繊維内部に、エポキシ化合物や相溶化剤を強固に含浸させることができる。また、当該乾燥は、エポキシ化合物を硬化させるためのエージングの役割も果たす。その結果、ＰＰＴＡ繊維複合体を水中に分散させた場合（すなわち湿式抄造時）でも、含浸させた薬剤が水中に溶出するのを抑制できるので、抄紙排水のＣＯＤ値が高くなる恐れが無い。 The PPTA fiber composite impregnated and impregnated with a chemical agent can be impregnated with an epoxy compound or a compatibilizing agent firmly on the fiber surface and inside the fiber by removing moisture in the fiber skeleton by drying. The drying also serves as an aging for curing the epoxy compound. As a result, even when the PPTA fiber composite is dispersed in water (that is, during wet papermaking), it is possible to suppress the impregnated drug from eluting into the water, so that there is no possibility that the COD value of papermaking wastewater increases.
薬剤を浸透・含浸させたＰＰＴＡ繊維複合体の乾燥は、任意の製造段階で実施することができ、例えば、水分率の高いＰＰＴＡ繊維複合体を乾燥した後にボビンに巻き取る方法、水分率の高いＰＰＴＡ繊維複合体を一旦ボビンに巻き取った後ボビンから巻き出して乾燥する方法、水分率の高いＰＰＴＡ繊維複合体を巻き取ったボビンを乾燥条件下に曝す方法のいずれを採用してもよい。 The PPTA fiber composite impregnated with and impregnated with the drug can be dried at any production stage. For example, the PPTA fiber composite having a high water content is dried and wound on a bobbin, or the water content is high. Either a method in which the PPTA fiber composite is once wound around a bobbin and then unwound from the bobbin and dried, or a method in which the bobbin wound with the PPTA fiber composite having a high moisture content is exposed to dry conditions may be employed.
乾燥方法も、ＰＰＴＡ繊維の水分率を１５重量％未満、より好ましくは１０重量％未満にできる方法であれば、加熱乾燥（５０〜３００℃、好ましくは７０〜２５０℃）、熱風乾燥、減圧乾燥、マイクロ波乾燥、高周波乾燥などを採用することができ、これらの方法を併用することもできる。 If the moisture content of the PPTA fiber is less than 15% by weight, more preferably less than 10% by weight, drying by heating (50 to 300 ° C., preferably 70 to 250 ° C.), hot air drying, reduced pressure drying is possible. Further, microwave drying, high-frequency drying, and the like can be employed, and these methods can be used in combination.
硬化性エポキシ化合物及び相溶化剤を、ＰＰＴＡ繊維に付与する場合は、予め、硬化性エポキシ化合物と相溶化剤を、硬化性エポキシ化合物／相溶化剤＝２／８〜８／２（重量比）の割合で含有する薬剤原液を調製しておき、この薬剤原液を上記のＰＰＴＡ繊維に付与し、薬剤を含浸・浸透させるのがよい。薬剤原液を水などの溶媒で希釈した薬剤希釈液を用いてもよい。硬化剤は、なくても反応は進行するが、用いる硬化性エポキシ化合物の特性、所望の反応速度などによっては、使用してもよい。 When the curable epoxy compound and the compatibilizer are applied to the PPTA fiber, the curable epoxy compound and the compatibilizer are preliminarily set to be curable epoxy compound / compatibilizer = 2/8 to 8/2 (weight ratio). It is preferable to prepare a stock solution containing this ratio, apply this stock solution to the PPTA fiber, and impregnate and permeate the drug. A drug diluent obtained by diluting a drug stock solution with a solvent such as water may be used. The reaction proceeds without a curing agent, but may be used depending on the characteristics of the curable epoxy compound used, the desired reaction rate, and the like.
薬剤原液には、その他の成分として、油剤、非イオン界面活性剤などの浸透剤、シリコーン系化合物、フッ素系化合物、有機界面活性剤などの平滑剤、オキサゾリンや酸無水物などの樹脂改良剤、シラン系やイソシアネート系などのカップリング剤などが、それぞれ２０重量％以下の量、含有されていてもよい。 In the drug stock solution, as other components, oil agents, penetrants such as nonionic surfactants, smootheners such as silicone compounds, fluorine compounds, organic surfactants, resin modifiers such as oxazolines and acid anhydrides, A coupling agent such as silane or isocyanate may be contained in an amount of 20% by weight or less.
上記の薬剤原液あるいは薬剤希釈液を、ＰＰＴＡ繊維に付与する方法は、特に限定されるものではなく、従来公知の任意の方法が採用されてよく、例えば、浸漬給油法、スプレー給油法、ローラー給油法、計量ポンプを用いたガイド給油法などの方法で付与される。 The method for applying the drug stock solution or the drug diluent to the PPTA fiber is not particularly limited, and any conventionally known method may be employed. For example, immersion oil supply method, spray oil supply method, roller oil supply And a guide oiling method using a metering pump.
ＰＰＴＡ繊維複合体では、繊維骨格内に浸透・含浸させた硬化性エポキシ化合物によって、結合樹脂との濡れ性、接着性が向上し、紙状物又はこれを積層してシート状の繊維基材を形成した際に、ＰＰＴＡ繊維の一部が結合樹脂の層から抜ける現象や、シート状の繊維基材が相互に剥離する現象を防止する効果がある。また、繊維骨格内に浸透・含浸させた相溶化剤によって、結合樹脂との濡れ性が向上することで、結合樹脂中へのＰＰＴＡ繊維の分散性が高められると共に、水との親和性が向上することで、湿式抄造時におけるＰＰＴＡ繊維の水分散性が良好となり、均一性に優れる紙状物を製造できる。 In PPTA fiber composites, the curable epoxy compound that has penetrated and impregnated into the fiber skeleton improves the wettability and adhesiveness with the binding resin, and a paper-like material or a laminate of this is used to form a sheet-like fiber substrate. When formed, there is an effect of preventing a phenomenon in which part of the PPTA fiber comes off from the binder resin layer and a phenomenon in which the sheet-like fiber base material peels from each other. In addition, the compatibilizing agent impregnated and impregnated into the fiber skeleton improves the wettability with the binding resin, thereby improving the dispersibility of PPTA fibers in the binding resin and improving the affinity with water. By doing so, the water dispersibility of the PPTA fiber at the time of wet papermaking becomes good, and a paper-like material having excellent uniformity can be produced.
上記の方法で製造されたＰＰＴＡ繊維複合体を１〜１００ｍｍ、好ましくは１〜５０ｍｍに切断した短繊維（カットファイバー）を、繊維状材料の少なくとも一部として用い、従来法に準じて、繊維状物を湿式抄造し紙状物を製造する。湿式抄造した紙状物は、適宜な温度（例えば８０〜１５０℃）で乾燥する。 A short fiber (cut fiber) obtained by cutting the PPTA fiber composite produced by the above method into 1 to 100 mm, preferably 1 to 50 mm, is used as at least a part of the fibrous material, Paper is made by wet papermaking. The wet papermaking material is dried at an appropriate temperature (for example, 80 to 150 ° C.).
ＰＰＴＡ繊維複合体の配合量は、繊維状材料全量に対して、５０〜１００重量％が好ましく、より好ましくは７０〜９７重量％、更に好ましくは８０〜９５重量％である。配合量が少なすぎるとＰＰＴＡ繊維複合体による効果が得られ難くなる。 The blending amount of the PPTA fiber composite is preferably 50 to 100% by weight, more preferably 70 to 97% by weight, and still more preferably 80 to 95% by weight with respect to the total amount of the fibrous material. When there are too few compounding quantities, the effect by a PPTA fiber composite will become difficult to be acquired.
ＰＰＴＡ繊維複合体以外の繊維状材料としては、フィブリル化できる繊維が好ましく、例えば、アクリル繊維、アラミド繊維、ポリパラフェニレンベンゾビスオキサゾール繊維、セルロース繊維、液晶ポリエステル系繊維、羊毛繊維などを用いることができる。これらの繊維の中で、耐熱性と高強度の観点から、アラミド繊維、アクリル繊維、セルロース繊維が好ましく、摩耗特性の観点から、更に好ましいのはアラミド繊維である。アラミド繊維の中でも、特にパラ系アラミドが好ましい。最も好ましいのは、パラ系アラミド繊維を高度にフィブリル化したアラミドパルプである。 As the fibrous material other than the PPTA fiber composite, fibers that can be fibrillated are preferable. For example, acrylic fibers, aramid fibers, polyparaphenylenebenzobisoxazole fibers, cellulose fibers, liquid crystal polyester fibers, wool fibers, and the like are used. it can. Among these fibers, aramid fibers, acrylic fibers, and cellulose fibers are preferable from the viewpoint of heat resistance and high strength, and aramid fibers are more preferable from the viewpoint of wear characteristics. Of the aramid fibers, para-aramid is particularly preferable. Most preferred is highly fibrillated aramid pulp from para-aramid fibers.
そして、前記のようにして形成された紙状物に、結合樹脂としてフェノール樹脂等の熱硬化性樹脂をメタノールやアセトンなどの有機溶剤にて溶解させ含浸させる。適宜、摩擦調整材や無機材料を添加できる。含浸方法は、スプレーなどによる吹き付け法、熱硬化性樹脂が入った浴にディップする方法などがあるが、特に限定されない。含浸率は形成された紙状物に対して等量の熱硬化性樹脂が好ましく、樹脂比率が３０％よりも少なくなると、耐熱性は向上するが樹脂との接着性が低下し、強度低下するので好ましくなく、樹脂比率が７０％を超えると耐熱性の低下、摩擦特性の向上につながり好ましくないので、適宜設定できる。 Then, the paper-like material formed as described above is impregnated by dissolving a thermosetting resin such as a phenol resin as a binding resin in an organic solvent such as methanol or acetone. A friction modifier or an inorganic material can be added as appropriate. Examples of the impregnation method include a spraying method using a spray and the like, and a method of dipping in a bath containing a thermosetting resin, but are not particularly limited. As for the impregnation rate, an equal amount of thermosetting resin is preferable with respect to the formed paper-like material, and when the resin ratio is less than 30%, the heat resistance is improved, but the adhesiveness with the resin is lowered and the strength is lowered. Therefore, it is not preferable, and if the resin ratio exceeds 70%, it is not preferable because it leads to a decrease in heat resistance and an improvement in frictional characteristics, and can be set as appropriate.
その後、熱硬化性樹脂等を含浸した紙状物から６０℃以下の温度で揮発成分を除去しプリプレグを作製する。 Thereafter, volatile components are removed from the paper-like material impregnated with a thermosetting resin or the like at a temperature of 60 ° C. or lower to prepare a prepreg.
その後、プリプレグをプレス機等を用いて１３０℃以上１９０℃以下で１分以上１５分以下、圧力５０ｋｇｆ／ｃｍ２以上５００ｋｇｆ／ｃｍ２以下で加熱プレスし、得られた熱硬化性樹脂成形体に１３０〜１９０℃の高温処理を施し硬化させることにより摩擦材料とする。摩擦材料は、必要に応じて任意の大きさや形状に裁断したり、成形加工したりして、自動車や産業用建機・機械の低摩擦材として、ワッシャー、ギアー、軸及び軸受け、クラッチ板、ブレーキ板などの摩擦材料として利用できる。 Thereafter, the prepreg is heated and pressed at 130 ° C. or more and 190 ° C. or less for 1 minute or more and 15 minutes or less at a pressure of 50 kgf / cm 2 or more and 500 kgf / cm 2 or less, and the resulting thermosetting resin molding is obtained. A high temperature treatment at 130 to 190 ° C. is applied and cured to obtain a friction material. Friction materials are cut into any size and shape as necessary, and processed as low-friction materials for automobiles and industrial construction machines / machines. Washers, gears, shafts and bearings, clutch plates, It can be used as a friction material for brake plates.
以下に実施例をあげて本発明を更に具体的に説明するが、本発明は、実施例に限定されるものではない。なお、実施例中の「％」及び「部」は特に断りのない限り、それぞれ「重量％」及び「重量部」を示す。 EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the examples. In the examples, “%” and “parts” represent “% by weight” and “parts by weight”, respectively, unless otherwise specified.
［実施例１］
ＰＰＴＡ（分子量約２０，０００）１ｋｇを４ｋｇの濃硫酸に溶解し、直径０．１ｍｍのホールを１，０００個有する口金からせん断速度３０，０００ｓｅｃ−１となるよう吐出し、４℃の水中に紡糸した後、１０％の水酸化ナトリウム水溶液で、１０℃×１５秒の条件で中和処理し、その後、１１０℃×１５秒間熱処理をして、水分率３５％の乾燥前のＰＰＴＡ繊維（水分率０％換算のとき総繊度１，６７０ｄｔｅｘ）を調製した。
[Example 1]
1 kg of PPTA (molecular weight of about 20,000) is dissolved in 4 kg of concentrated sulfuric acid, and discharged from a die having 1,000 holes with a diameter of 0.1 mm so as to have a shear rate of 30,000 sec −1 and into 4 ° C. water. After spinning, it was neutralized with 10% aqueous sodium hydroxide under conditions of 10 ° C. × 15 seconds, and then heat treated at 110 ° C. × 15 seconds to give PPTA fibers (moisture content) with a moisture content of 35% before drying. A total fineness of 1,670 dtex) was prepared when the rate was converted to 0%.
このＰＰＴＡ繊維に、硬化性エポキシ化合物としてソルビトールポリグリシジルエーテルを４０部、相溶化剤としてジエチレングリコールモノ２−エチルヘキシルエーテル６０部、硬化剤としてラウリルアミンエチレンオキサイド１０モル付加体５部を含有する薬剤原液を付与し、硬化性エポキシ化合物と相溶化剤と硬化剤をＰＰＴＡ繊維に浸透・含浸させた後、ボビンに巻き取り、水分率３５％のＰＰＴＡ繊維複合体を製造した。含浸量（対絶乾繊維重量換算）は、硬化性エポキシ化合物が０．５％、相溶化剤が０．５％、硬化剤が０．０６％であった。 A drug stock solution containing 40 parts of sorbitol polyglycidyl ether as a curable epoxy compound, 60 parts of diethylene glycol mono-2-ethylhexyl ether as a compatibilizer, and 5 parts of laurylamine ethylene oxide 10 mol adduct as a curing agent is added to this PPTA fiber. After applying and impregnating the PPTA fiber with a curable epoxy compound, a compatibilizer and a curing agent, the PPTA fiber was wound around a bobbin to produce a PPTA fiber composite having a moisture content of 35%. The amount of impregnation (in terms of dry fiber weight) was 0.5% for the curable epoxy compound, 0.5% for the compatibilizing agent, and 0.06% for the curing agent.
この後、このＰＰＴＡ繊維複合体をボビンから巻き出し、コンピュートリータ処理機（リッツラー社製）を用いて、３．９Ｎの張力での緊張下１３０℃２０秒間、加熱乾燥・エージングして巻き取り、水分率が６．９％のＰＰＴＡ繊維複合体を得た。得られたＰＰＴＡ繊維複合体を３ｍｍに切断し、ＰＰＴＡ繊維複合体の短繊維を得た。 Thereafter, the PPTA fiber composite is unwound from the bobbin, and is wound by heating, drying and aging at 130 ° C. for 20 seconds under a tension of 3.9 N using a compute treater (manufactured by Ritzler), A PPTA fiber composite having a moisture content of 6.9% was obtained. The obtained PPTA fiber composite was cut into 3 mm to obtain PPTA fiber composite short fibers.
パラ系アラミドパルプ（デュポン社製、商品名：ケブラー、ＣＳＦ２６０ｍｌ）、上記で得たＰＰＴＡ繊維複合体の短繊維（１．６７ｄｔｅｘ×３ｍｍ）をそれぞれ１０／９０とする配合で水中に順次添加混合し、１％濃度の水性スラリーを調製した。この水性スラリーを用いて抄造し、乾燥後、紙状物を得た。この抄紙排水のＣＯＤは、所定の排出基準値をクリアーしていた。 Para-aramid pulp (manufactured by DuPont, trade name: Kevlar, CSF 260 ml) and the PPTA fiber composite short fiber (1.67 dtex × 3 mm) obtained above were added and mixed sequentially in water with a composition of 10/90 respectively. A 1% strength aqueous slurry was prepared. Papermaking was performed using this aqueous slurry, and a paper-like product was obtained after drying. The COD of this papermaking wastewater cleared a predetermined discharge standard value.
次に、得られた目付が１９７．１ｇ／ｍ２の紙状物をレゾール型フェノール樹脂を等量のメタノールで希釈した樹脂液に浸漬させて、含浸させた後、６０℃で２０分間乾燥して樹脂重量比が５１％（紙状物重量比が４９％）のプリプレグを得た。 Next, the obtained paper material having a basis weight of 197.1 g / m 2 is immersed in a resin solution obtained by diluting a resol-type phenol resin with an equal amount of methanol, impregnated, and then dried at 60 ° C. for 20 minutes. Thus, a prepreg having a resin weight ratio of 51% (paper weight ratio of 49%) was obtained.
このプリプレグを７枚重ねとし、金型に入れ加熱プレス機を用いて１６０℃で５分間、圧力２００ｋｇｆ／ｃｍ２で加熱プレスを行った。この際、金型及び上蓋鉄板を予め１６０℃程度まで加熱しておき、始めの３０秒間で上蓋鉄板の自重で脱気作業を行い、その後、圧力３０ｋｇｆ／ｃｍ２でのプレスと圧力開放を２、３回繰り返した後、圧力２００ｋｇｆ／ｃｍ２で５分間保持した。更にプレス後、１７０℃で３時間の熱硬化処理を行い、摩擦材料を得た。 Seven prepregs were stacked, placed in a mold, and heated and pressed at 160 ° C. for 5 minutes at a pressure of 200 kgf / cm 2 using a heating press. At this time, the mold and the upper lid iron plate are heated to about 160 ° C. in advance, and the degassing work is performed by the weight of the upper lid iron plate for the first 30 seconds, and then the press and pressure release at a pressure of 30 kgf / cm 2 are performed. After repeating three times, the pressure was maintained at 200 kgf / cm 2 for 5 minutes. Further, after the pressing, a thermosetting treatment was performed at 170 ° C. for 3 hours to obtain a friction material.
［比較例１］
パラ系アラミドパルプ（デュポン社製、商品名：ケブラー、ＣＳＦ２６０ｍｌ）、パラ系アラミド短繊維（東レ・デュポン社製、商品名：ケブラー、１．６７ｄｔｅｘ×３ｍｍ）をそれぞれ１０／９０とする配合で水中に順次添加混合し、１％濃度の水性スラリーを調製した。この水性スラリーを用いて抄造し、乾燥後、目付２０１．６ｇ／ｍ２の紙状物を得た。そして、この紙状物を実施例１と同じ方法でプリプレグならびに７枚重ねの摩擦材料を得た。
[Comparative Example 1]
Para-aramid pulp (manufactured by DuPont, trade name: Kevlar, CSF 260 ml), para-aramid short fibers (manufactured by Toray DuPont, trade name: Kevlar, 1.67 dtex × 3 mm) are each formulated to be 10/90 in water. 1% aqueous slurry was prepared. Papermaking was performed using this aqueous slurry, and after drying, a paper-like material having a basis weight of 201.6 g / m 2 was obtained. A prepreg and a seven-layered friction material were obtained from this paper-like material in the same manner as in Example 1.
［比較例２］
実施例１において、紡糸及び中和処理した後、２００℃×１５秒間熱処理して、水分率７％のＰＰＴＡ繊維（水分率０％換算のとき総繊度１，６７０ｄｔｅｘ）を調製した。得られたＰＰＴＡ繊維に実施例１と同様の薬剤原液を付与し、水分率７％のＰＰＴＡ繊維複合体を得た。得られたＰＰＴＡ繊維複合体を３ｍｍに切断し、ＰＰＴＡ繊維複合体の短繊維を得た。
[Comparative Example 2]
In Example 1, after spinning and neutralizing treatment, heat treatment was performed at 200 ° C. for 15 seconds to prepare a PPTA fiber having a moisture content of 7% (total fineness of 1,670 dtex when converted to a moisture content of 0%). The obtained PPTA fiber was applied with the same drug stock solution as in Example 1 to obtain a PPTA fiber composite having a moisture content of 7%. The obtained PPTA fiber composite was cut into 3 mm to obtain PPTA fiber composite short fibers.
パラ系アラミドパルプ（デュポン社製、商品名：ケブラー、ＣＳＦ２６０ｍｌ）、上記で得たＰＰＴＡ繊維複合体の短繊維（１．６７ｄｔｅｘ×３ｍｍ）をそれぞれ１０／９０とする配合で水中に順次添加混合し、１％濃度の水性スラリーを調製した後、この水性スラリーを用いて抄造、乾燥することにより紙状物を得た。このときの抄紙排水のＣＯＤは、所定の排出基準値を超えていたため、紙状物を用いた摩擦材料の評価は実施しなかった。 Para-aramid pulp (manufactured by DuPont, trade name: Kevlar, CSF 260 ml) and the PPTA fiber composite short fiber (1.67 dtex × 3 mm) obtained above were added and mixed sequentially in water with a composition of 10/90 respectively. After preparing a 1% concentration aqueous slurry, paper was obtained by making paper and drying using this aqueous slurry. Since the COD of the papermaking waste water at this time exceeded a predetermined discharge standard value, evaluation of the friction material using a paper-like material was not performed.
＜評価試験＞
（１）引張強度、引張弾性率、曲げ強度、曲げ弾性率；
作製した摩擦材料について、ＡＳＴＭ Ｄ６３８号の方法により引張強度、引張弾性率を、ＡＳＴＭ Ｄ７９０号の方法により曲げ強度、曲げ弾性率を測定した。
<Evaluation test>
(1) Tensile strength, tensile modulus, flexural strength, flexural modulus;
About the produced friction material, the tensile strength and the tensile elastic modulus were measured by the method of ASTM D638, and the bending strength and the bending elastic modulus were measured by the method of ASTM D790.
（２）摩擦特性；
鈴木式摩耗試験機を使用し、試験条件は、サンプルは３０ｍｍ×３０ｍｍ×２ｍｍ、相手（リング）材料は「Ｓ４５Ｃ」、リング面積は２００ｍｍ２、相手材料（Ｓ４５Ｃ）、試験開始時の重量に対する摩耗量の割合（減耗率）、試験速度０．１５ｍ／ｓｅｃ、荷重１６５Ｎ、５００Ｎ、６６７Ｎ、１，０００Ｎ、１，３４０Ｎ、滑り距離１３ｋｍ、Ｎ＝３にて測定した。
(2) Friction characteristics;
Using Suzuki type abrasion tester, test conditions, the sample is 30 mm × 30 mm × 2 mm, partner (ring) material "S45C", the ring area 200 mm 2, the counter material (S45C), wear on the weight at the start of the test The ratio (amount of wear) of the quantity, the test speed was 0.15 m / sec, the load was 165 N, 500 N, 667 N, 1,000 N, 1,340 N, the sliding distance was 13 km, and N = 3.
ＰＶ値：ＪＩＳ法のＫ７２１８（Ａ法）に準拠した。荷重と周速度条件は以下の通り。
125（kPa・m/sec）：加圧力 167(N）×周速度0.15(m/sec)
375（kPa・m/sec）：加圧力 500(N）×周速度0.15(m/sec)
500（kPa・m/sec）：加圧力 667(N）×周速度0.15(m/sec)
750（kPa・m/sec）：加圧力1,000(N）×周速度0.15(m/sec)
1,000（kPa・m/sec）：加圧力1,340(N）×周速度0.15(m/sec)
走行距離：１３ｋｍ
限界ＰＶ値の判断：熱硬化性樹脂（レゾール型フェノール）の硬化温度(175℃)とした。175℃以上では摩擦材料が炭化を開始するので好ましくない。
PV value: compliant with JIS method K7218 (A method). The load and peripheral speed conditions are as follows.
125 (kPa · m / sec): Applied pressure 167 (N) x Peripheral speed 0.15 (m / sec)
375 (kPa · m / sec): Applied pressure 500 (N) x Peripheral speed 0.15 (m / sec)
500 (kPa · m / sec): Applied pressure 667 (N) x Peripheral speed 0.15 (m / sec)
750 (kPa · m / sec): Applied pressure 1,000 (N) x Peripheral speed 0.15 (m / sec)
1,000 (kPa · m / sec): Pressure 1,340 (N) x Peripheral speed 0.15 (m / sec)
Mileage: 13km
Judgment of limit PV value: It was set as the curing temperature (175 degreeC) of a thermosetting resin (resole type phenol). Above 175 ° C., the friction material starts to carbonize, which is not preferable.
摩擦材減量体積：下記式より求めた。
摩擦前重さ(ｇ)−摩擦後重さ(ｇ)＝減量重さ(Δｇ)
摩擦材の比重(ρ)
摩擦減量体積(ｖ)＝減量重さ(Δｇ)／ 比重(ρ)
Friction material weight loss: determined from the following formula.
Weight before friction (g)-Weight after friction (g) = Weight loss (Δg)
Specific gravity of friction material (ρ)
Friction weight loss volume (v) = weight loss weight (Δg) / specific gravity (ρ)
摩擦係数：下記式より求めた。
摩擦係数(μ)＝摩擦トルク(Ｔ)／荷重(Ｎ)
Friction coefficient: determined from the following formula.
Friction coefficient (μ) = Friction torque (T) / Load (N)
相手材温度：摩擦金属リングの実測値。 Counterpart material temperature: Measured value of friction metal ring.
相手材減量体積：下記式より求めた。
摩擦前相手材重さ(ｇ)−摩擦後相手材重さ(ｇ)＝相手材減量重さ(Δｇ)
相手材摩擦材の比重(ρ)
相手材摩擦減量体積(ｖ)＝相手材減量重さ(Δｇ)／ 比重(ρ)
Counterpart material weight loss volume: determined from the following formula.
Pre-friction mating material weight (g)-Post-friction mating material weight (g) = mating material weight loss (Δg)
Specific gravity of mating material (ρ)
Mating material friction weight loss (v) = Mating material weight loss (Δg) / Specific gravity (ρ)
（３）摩擦材料の組成分析；
赤外分光分析（FT-IR）により赤外線吸収スペクトル波長（ｃｍ−１）を測定した。
測定機：フーリエ変換赤外分光光度計（島津製）IR Prestig-21。
(3) Composition analysis of friction material;
The infrared absorption spectrum wavelength (cm −1 ) was measured by infrared spectroscopic analysis (FT-IR).
Measuring instrument: Fourier transform infrared spectrophotometer (manufactured by Shimadzu) IR Prestig-21.
上記の実施例１及び比較例１で得られた摩擦材料について、上述した評価試験により評価した。その結果を表１、表２、図１、図２に示す。 The friction materials obtained in Example 1 and Comparative Example 1 were evaluated by the evaluation test described above. The results are shown in Table 1, Table 2, FIG. 1 and FIG.
表１より、繊維状材料として、本発明のＰＰＴＡ繊維複合体を用いた実施例１の摩擦材料は、比較例１の摩擦材料に比べて、ボイドが無く、高密度で繊維体積比率（Ｖｆ）が高く、引張強度、引張弾性率、破断強度、曲げ強度及び曲げ弾性率の点で優れ、耐熱性、機械的強度及び耐久性に優れる摩擦材料となり得ることがわかる。これは、繊維材料とフェノール樹脂との接着性が向上したことに起因するものである。 From Table 1, the friction material of Example 1 using the PPTA fiber composite of the present invention as the fibrous material has no voids and has a high density and a fiber volume ratio (Vf) compared to the friction material of Comparative Example 1. It can be seen that the friction material is excellent in terms of tensile strength, tensile elastic modulus, breaking strength, bending strength and bending elastic modulus, and excellent in heat resistance, mechanical strength and durability. This is due to the improved adhesion between the fiber material and the phenol resin.
表２より、ＰＶ値が大きくなると摩擦材の減量体積は多くなる傾向にあるが、実施例１は比較例１より少なく、摩擦耐久性に優れている。また、摩擦係数は逆に小さくなる傾向にあるが、実施例１は比較例１より若干小さく、低摩擦特性に優れた摩擦材料である。 From Table 2, although the weight loss volume of the friction material tends to increase as the PV value increases, Example 1 is less than Comparative Example 1 and is excellent in friction durability. Although the friction coefficient tends to be smaller, Example 1 is a friction material that is slightly smaller than Comparative Example 1 and excellent in low friction characteristics.
赤外線吸収スペクトル波長において、ソルビトールポリグリシジルエーテルエポキシ樹
脂の特定波長は１，１８０ｃｍ−１と８３０ｃｍ−１である（材料実践工学）ことから、実施例１の１，１９５ｃｍ−１の８３０ｃｍ−１が該当する。しかし、比較例１は１，２６８ｃｍ−１と８０５ｃｍ−１であり該当しないので、赤外線吸収スペクトル波長を特定することにより、摩擦材料内のソルビトールポリグリシジルエーテルエポキシ樹脂の有無を検証することができた。なお、レゾール型フェノール樹脂の赤外線吸収スペクトル波長３，３００ｃｍ−１は容易に検証できた。
In the infrared absorption spectrum wavelength, the specific wavelengths of sorbitol polyglycidyl ether epoxy resin are 1,180 cm −1 and 830 cm −1 (material practical engineering), and therefore, 195 cm −1 of 1,195 cm −1 in Example 1 is applicable. To do. However, since Comparative Example 1 is 1,268 cm −1 and 805 cm −1 and is not applicable, the presence or absence of sorbitol polyglycidyl ether epoxy resin in the friction material could be verified by specifying the infrared absorption spectrum wavelength. . The infrared absorption spectrum wavelength of 3,300 cm −1 of the resol type phenolic resin could be easily verified.
図１より、ＰＶ値が大きくなると、相手材（鋼材：Ｓ４５Ｃ）減量体積は多くなるが、実施例１は比較例１に比べて少なく、相手材の耐久性は優れている。 As shown in FIG. 1, when the PV value increases, the weight loss volume of the counterpart material (steel material: S45C) increases, but Example 1 is smaller than Comparative Example 1 and the durability of the counterpart material is excellent.
図２より、ＰＶ値が大きくなると、相手材温度は高くなるが、実施例１は比較例１に比べて低く、ＰＶ値が４５０ｋＰａ・ｍ／ｓ以上１，０００ｋＰａ・ｍ／ｓ以下では実施例１の温度は限界の１７５℃以上にはなりにくく、摩擦耐久性に優れている。なお、比較例１ではＰＶ値が５００ｋＰａ・ｍ／ｓ以上ではすでに摩擦材料は炭化を開始した。 As shown in FIG. 2, when the PV value is increased, the counterpart material temperature is increased. However, Example 1 is lower than Comparative Example 1, and the PV value is 450 kPa · m / s or more and 1,000 kPa · m / s or less. The temperature of No. 1 is unlikely to exceed the limit of 175 ° C. and is excellent in friction durability. In Comparative Example 1, the friction material already started to be carbonized when the PV value was 500 kPa · m / s or more.
本発明の摩擦材料は、耐熱性、機械的特性及び摩擦耐久性に優れていることから、車両用及び産業機械用の低摩擦材料などに好適に用いられる。 Since the friction material of the present invention is excellent in heat resistance, mechanical properties, and friction durability, it is suitably used for low friction materials for vehicles and industrial machines.
Claims (10)
A brake plate using the friction material according to claim 1.
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