JP2019148033A - Aromatic polyamide short fiber bundle for rubber reinforcement and rubber composition - Google Patents
Aromatic polyamide short fiber bundle for rubber reinforcement and rubber composition Download PDFInfo
- Publication number
- JP2019148033A JP2019148033A JP2018033351A JP2018033351A JP2019148033A JP 2019148033 A JP2019148033 A JP 2019148033A JP 2018033351 A JP2018033351 A JP 2018033351A JP 2018033351 A JP2018033351 A JP 2018033351A JP 2019148033 A JP2019148033 A JP 2019148033A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- aromatic polyamide
- fiber
- short fiber
- bundle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 179
- 229920001971 elastomer Polymers 0.000 title claims abstract description 91
- 239000005060 rubber Substances 0.000 title claims abstract description 91
- 239000004760 aramid Substances 0.000 title claims abstract description 62
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 62
- 230000002787 reinforcement Effects 0.000 title claims abstract description 7
- 239000000203 mixture Substances 0.000 title description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 53
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- 229920000126 latex Polymers 0.000 claims description 35
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 27
- 239000004816 latex Substances 0.000 claims description 24
- 229960001755 resorcinol Drugs 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 238000004513 sizing Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- -1 isocyanate compound Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000012948 isocyanate Substances 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 230000003014 reinforcing effect Effects 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 238000009864 tensile test Methods 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920002943 EPDM rubber Polymers 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920001494 Technora Polymers 0.000 description 3
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 3
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 239000004950 technora Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KATAXDCYPGGJNJ-UHFFFAOYSA-N 1,3-bis(oxiran-2-ylmethoxy)propan-2-ol Chemical compound C1OC1COCC(O)COCC1CO1 KATAXDCYPGGJNJ-UHFFFAOYSA-N 0.000 description 1
- 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
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- AOYQDLJWKKUFEG-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]hept-4-ene-4-carboxylate Chemical compound C=1C2OC2CCC=1C(=O)OCC1CC2OC2CC1 AOYQDLJWKKUFEG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 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 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920006017 homo-polyamide Polymers 0.000 description 1
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Abstract
Description
本発明は、ゴム補強用芳香族ポリアミド短繊維集束体に関するものである。また、本発明により得られる芳香族ポリアミド短繊維集束体は、ゴム資材の補強材料として、タイヤ、ベルト、ホース、その他の広範囲の分野に利用される。 The present invention relates to a bundle of aromatic polyamide short fibers for reinforcing rubber. In addition, the aromatic polyamide short fiber bundle obtained by the present invention is used in a wide range of fields such as tires, belts, hoses and the like as a reinforcing material for rubber materials.
従来、ゴムベルト等の力学特性を向上させるため、加硫可能なゴムにセルロース、ビニロン、ナイロン、ポリエステルなどの短繊維が配合されてきた。特に、これらの短繊維のうち芳香族ポリアミド（アラミド）短繊維は機械的特性、耐疲労性、耐熱性および化学的性質に優れているためゴム補強用短繊維として広く使用されている。しかしながら、芳香族ポリアミド短繊維は比較的表面が不活性であるためにゴムとの接着力が低い。また、ゴム配合時の分散性が悪いため、ゴムの混練時に繊維を均一に投入できないという問題があった。またマルチフィラメントの状態での集束性が乏しいために、短繊維にカットする際に短繊維が飛散しやすく、かつファイバーボールを形成しやすいという問題があった。そのため、芳香族ポリアミド繊維の優れた特性を十分に発揮することができなかった。 Conventionally, short fibers such as cellulose, vinylon, nylon and polyester have been blended with vulcanizable rubber in order to improve the mechanical properties of rubber belts and the like. In particular, among these short fibers, aromatic polyamide (aramid) short fibers are widely used as rubber reinforcing short fibers because of their excellent mechanical properties, fatigue resistance, heat resistance, and chemical properties. However, aromatic polyamide short fibers have a relatively low surface adhesion and thus have low adhesion to rubber. Further, since the dispersibility at the time of blending the rubber is poor, there has been a problem that the fibers cannot be uniformly fed when the rubber is kneaded. Further, since the converging property in the multifilament state is poor, there is a problem that the short fibers are likely to be scattered when being cut into short fibers and a fiber ball is easily formed. For this reason, the excellent characteristics of the aromatic polyamide fiber cannot be sufficiently exhibited.
このような問題を解決するために、特許文献１では短繊維の長さや切断方法を変更することによって分散性に優れた芳香族ポリアミド繊維の集束体を得る方法が開示されている。しかしながら、芳香族ポリアミド繊維の特性を十分に発揮し、ゴム製品としての性能を向上させるためには、さらなる改良の余地があった。 In order to solve such problems, Patent Document 1 discloses a method for obtaining a bundle of aromatic polyamide fibers having excellent dispersibility by changing the length of short fibers and the cutting method. However, there is room for further improvement in order to fully exhibit the characteristics of the aromatic polyamide fiber and improve the performance as a rubber product.
本発明者らは、上記の目的を達成すべく誠意検討を進めた結果、ゴム製品のモジュラスや耐摩耗性向上に有効なゴム補強用芳香族ポリアミド短繊維集束体を提供するに至った。すなわち、本発明は以下のようになる。 As a result of conducting sincerity studies to achieve the above object, the present inventors have come to provide an aromatic polyamide short fiber bundle for reinforcing rubber effective for improving the modulus and wear resistance of rubber products. That is, the present invention is as follows.
本発明のゴム補強用芳香族ポリアミド短繊維集束体は、単繊維繊度が０．１〜１．５ｄｔｅｘであり、その長さが０．３〜１２ｍｍである芳香族ポリアミド短繊維を１０本〜５万本集束した集束体であって、当該短繊維の幅［ｍｍ］/厚み［ｍｍ］が２．５以上であることを満たす扁平形状であることを特徴とする。 The aromatic polyamide short fiber bundle for rubber reinforcement of the present invention has 10 to 5 aromatic polyamide short fibers having a single fiber fineness of 0.1 to 1.5 dtex and a length of 0.3 to 12 mm. It is a bundling body in which all are bundled, and has a flat shape satisfying that the width [mm] / thickness [mm] of the short fiber is 2.5 or more.
さらには、芳香族ポリアミド短繊維の表面に、レゾルシン・ホルマリン・ラテックスとイソシアネート化合物とを含有する集束剤とを含有する集束剤が付着しており、集束剤の短繊維重量に対する固形分付着量が５〜１０重量％であり、イソシアネート化合物の添加量が、レゾルシン・ホルマリン・ゴムラテックス樹脂の全重量あたり、０．５〜４０重量％であることが好ましい。 Furthermore, a sizing agent containing a resorcinol / formalin / latex and a sizing agent containing an isocyanate compound adheres to the surface of the aromatic polyamide short fiber, and the solid content of the sizing agent with respect to the short fiber weight is reduced. The amount of the isocyanate compound added is preferably 0.5 to 40% by weight based on the total weight of the resorcin / formalin / rubber latex resin.
本発明によれば、分散性や接着性に優れかつゴム製品のモジュラスや耐摩耗性向上に有効なゴム補強用芳香族ポリアミド短繊維集束体を得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, the aromatic polyamide short fiber bundle for rubber reinforcement which is excellent in the dispersibility and adhesiveness, and is effective in improving the modulus and abrasion resistance of rubber products can be obtained.
以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明の芳香族ポリアミド短繊維集束体とは、芳香族ポリアミド繊維からなる短繊維が集束した集束体である。集束体としては、芳香族ポリアミド短繊維を１０本〜５万本集束したものであることが好ましい。さらには、１００本〜１万本、より好ましくは１２００本〜５０００本の繊維束である。 The aromatic polyamide short fiber bundle of the present invention is a bundle of short fibers made of aromatic polyamide fibers. The bundle is preferably a bundle of 10 to 50,000 aromatic polyamide short fibers. Furthermore, it is a fiber bundle of 100 to 10,000, more preferably 1200 to 5000.
本発明の芳香族ポリアミド短繊維集束体は、芳香族ポリアミド繊維からなる短繊維が集束した集合体である。集束体は、幅［ｍｍ］／厚み［ｍｍ］の値が２．５より大きい扁平形状となることが好ましく、より好ましくは３より大きい範囲である。また、当該形状は処理剤を付着させる際に、各種ガイドで開繊しながら処理剤を含む溶液に浸漬し、浸漬後の連続繊維束を絞りロールで圧縮し円形状から扁平形状に成形した後、処理剤を乾燥・硬化させることで扁平形状が得られる。扁平形状とすることで、繊維束を構成する単繊維間内部まで処理剤が含浸しやすくなり、強固な集束性と、ゴム接着性を有する短繊維を得ることができる。 The aromatic polyamide short fiber bundle of the present invention is an aggregate of short fibers made of aromatic polyamide fibers. The converging body preferably has a flat shape with a value of width [mm] / thickness [mm] larger than 2.5, more preferably in a range larger than 3. In addition, when the treatment agent is attached, the shape is immersed in a solution containing the treatment agent while opening with various guides, and the continuous fiber bundle after the immersion is compressed with a squeeze roll and formed from a circular shape to a flat shape. A flat shape can be obtained by drying and curing the treatment agent. By adopting a flat shape, the treatment agent can easily be impregnated into the interior of the single fibers constituting the fiber bundle, and short fibers having strong focusing properties and rubber adhesiveness can be obtained.
また、扁平形状とすることで、繊維束の各繊維は外圧に対して離間しやすくなる。これは、扁平形状であるため、混練り時に発生する扁平形状の幅方向（長手方向）に加わる外力が、薄さ方向（厚さ方向）には分散しにくく、繊維が幅方向に圧縮されるように応力を受けて歪むことで繊維束から分散（剥離）しやすいためであると推測される。円形または楕円形の場合、外力が分散されるため分散が進まず、繊維塊として残存しやすくなると推測される。すなわち、本発明の集束体は、ゴム中に混練する際の外力（剪断力等）により均一に分散し、補強材として有効な働きを有するものである。 Moreover, it becomes easy to isolate | separate each fiber of a fiber bundle with respect to external pressure by setting it as a flat shape. Since this is a flat shape, the external force applied in the width direction (longitudinal direction) of the flat shape generated during kneading is not easily dispersed in the thin direction (thickness direction), and the fibers are compressed in the width direction. Thus, it is presumed that it is easy to disperse (peel) from the fiber bundle by being distorted under stress. In the case of a circle or ellipse, it is presumed that the external force is dispersed and the dispersion does not proceed and the fiber mass remains easily. That is, the bundling body of the present invention is uniformly dispersed by an external force (shearing force or the like) when kneaded in rubber and has an effective function as a reinforcing material.
本発明の芳香族ポリアミド短繊維集束体を構成する各繊維の単繊維繊度としては、０．１〜１．５ｄｔｅｘであることが好ましい。さらには０．２ｄｔｅｘ〜１．０ｄｔｅｘの範囲であることが好ましい。繊度が細すぎる場合には、断糸や毛羽が発生するために、良好な品質の繊維を安定して生産することが困難になるだけでなく、コストも高くなる傾向にある。一方、繊度が大きすぎる場合は、単位断面積あたりのゴムと短繊維との接触面積（表面積）が小さくなるため、ゴムの変形応力に対して拮抗するゴムと短繊維の接着力が不十分となり、ゴムの変形時に短繊維の一部、或いは大部分が破断せずに引き抜かれた状態になるため、繊維の特性を十分に生かし切ることができず、十分な補強物性が得られないと考えられている。 The single fiber fineness of each fiber constituting the aromatic polyamide short fiber bundle of the present invention is preferably 0.1 to 1.5 dtex. Further, it is preferably in the range of 0.2 dtex to 1.0 dtex. If the fineness is too thin, yarn breakage and fluff are generated, which makes it difficult not only to stably produce good quality fibers but also to increase the cost. On the other hand, when the fineness is too large, the contact area (surface area) between the rubber and the short fiber per unit cross-sectional area becomes small, and the adhesive force between the rubber and the short fiber that antagonizes the deformation stress of the rubber becomes insufficient. , Because part or most of the short fiber is pulled without breaking when the rubber is deformed, the fiber properties cannot be fully utilized, and sufficient reinforcing physical properties cannot be obtained. It has been.
また、本発明の芳香族ポリアミド短繊維集束体の各短繊維の繊維長としては、０．３〜１２ｍｍであることが好ましく、さらには０．３〜３．５ｍｍであることが好ましい。繊維長が短すぎる場合には、複数本の単繊維が集束した、良好な短繊維集束体を得る事が困難となり取扱性、作業性が困難となる傾向にある。また逆に繊維長が長すぎる場合には、補強対象のマトリックスと混合する際に単繊維同士が絡み合い、分散不良となりやすい傾向にある。 The fiber length of each short fiber of the aromatic polyamide short fiber bundle of the present invention is preferably 0.3 to 12 mm, more preferably 0.3 to 3.5 mm. When the fiber length is too short, it is difficult to obtain a good short fiber bundle in which a plurality of single fibers are bundled, and the handleability and workability tend to be difficult. On the other hand, when the fiber length is too long, the single fibers tend to be entangled with each other when mixed with the matrix to be reinforced, and the dispersion tends to be poor.
本発明の芳香族ポリアミド短繊維集束体とは、芳香族ポリアミド繊維からなる短繊維が集束した集束体である。ここで芳香族ポリアミド繊維とは、ポリアミドを構成する繰返し単位の８０モル％以上好ましくは９０モル％以上が、芳香族ホモポリアミド、または、芳香族コポリアミドからなる繊維である。ここで繊維となる芳香族基は同一、または相異なる芳香族基からなるものでも構わない。また、芳香族基の水素原子は、ハロゲン原子、低級アルキル基、フェニル基で置換されていても良い。具体的には、パラ型芳香族ポリアミド繊維であるポリパラフェニレンテレフタルアミド繊維（例えば、テイジンアラミドＢ．Ｖ．製、「トワロン」）や、共重合型の芳香族ポリアミド繊維であるコポリパラフェニレン・３，４’−オキシジフェニレン・テレフタルアミド繊維（例えば、帝人株式会社製、「テクノーラ」）、メタ型芳香族ポリアミド繊維であるポリメタフェニレンイソフタルアミド繊維（例えば、帝人株式会社製、「コーネックス」）等が例示される。 The aromatic polyamide short fiber bundle of the present invention is a bundle of short fibers made of aromatic polyamide fibers. Here, the aromatic polyamide fiber is a fiber in which 80 mol% or more, preferably 90 mol% or more of the repeating unit constituting the polyamide is composed of an aromatic homopolyamide or an aromatic copolyamide. Here, the aromatic groups to be fibers may be the same or different aromatic groups. The hydrogen atom of the aromatic group may be substituted with a halogen atom, a lower alkyl group, or a phenyl group. Specifically, polyparaphenylene terephthalamide fiber (for example, “Twaron” manufactured by Teijin Aramid BV), which is a para-type aromatic polyamide fiber, and copolyparaphenylene- 3,4′-oxydiphenylene terephthalamide fiber (for example, “Technola” manufactured by Teijin Limited), polymetaphenylene isophthalamide fiber (for example, manufactured by Teijin Limited, “Conex” ]) And the like.
また、本発明の集束体としては、このような芳香族ポリアミド繊維の中でも特にパラ型芳香族ポリアミド繊維であることが、耐熱性および強度に優れており好ましい。ここでパラ型芳香族ポリアミド繊維とは、芳香族ポリアミドの延鎖結合が共軸または平行で、かつ、反対方向に向いているポリアミドからなる繊維である。 Further, among the aromatic polyamide fibers, para-aromatic polyamide fibers are particularly preferable as the bundle of the present invention because of excellent heat resistance and strength. Here, the para-type aromatic polyamide fiber is a fiber made of polyamide in which the chain bond of the aromatic polyamide is coaxial or parallel and faces in the opposite direction.
具体的には、共重合型のパラ型芳香族ポリアミド繊維であるコポリパラフェニレン・３，４’−オキシジフェニレン・テレフタルアミド繊維（例えば、帝人株式会社製、「テクノーラ」）は、耐屈曲疲労性に優れることから、ゴムとの混練時に強いせん断応力下で混練されても損傷することがないため、ゴムのモジュラスや耐摩耗性向上に非常に有効であることから好ましい。 Specifically, copolyparaphenylene • 3,4′-oxydiphenylene • terephthalamide fiber (for example, “Technola” manufactured by Teijin Limited), which is a copolymer type para-aromatic polyamide fiber, is resistant to bending fatigue. Since it is excellent in property, it is not damaged even when kneaded with a rubber under a strong shearing stress, and therefore it is preferable because it is very effective in improving the modulus and wear resistance of the rubber.
本発明の芳香族ポリアミド短繊維集束体は、ゴムラテックスを含有する樹脂被膜によって集束されていることが好ましい。その際の樹脂被膜の固形分付着量は５〜１０重量％であることが好ましい。これら樹脂被膜は、単繊維表面を活性化させゴムとの接着力を向上させることが可能であり、さらに、靱性のある皮膜で集束することで、ゴムとの混練工程まで集束体形状を維持することを可能とし、混練工程前に単繊維がばらけることでファイバーボールが形成されることを抑制できる。 It is preferable that the aromatic polyamide short fiber bundle of the present invention is bundled with a resin coating containing rubber latex. In this case, the solid content of the resin coating is preferably 5 to 10% by weight. These resin coatings can activate the surface of single fibers and improve the adhesive strength with rubber. Furthermore, by focusing with a tough coating, the shape of the focusing body is maintained until the kneading step with rubber. This makes it possible to suppress the formation of fiber balls by separating the single fibers before the kneading step.
さらに、芳香族ポリアミド短繊維集束体は、レゾルシン・ホルマリン・ラテックスを含有する樹脂被膜によって集束されていることが好ましい。レゾルシン・ホルマリン・ラテックス樹脂としては、レゾルシンとホルムアルデヒドのモル比が１：０．６〜１：８の範囲にあるものが好ましく、１：０．８〜１：６の範囲にあるものがさらに好ましい。ホルムアルデヒドの量が少なすぎる場合、レゾルシン・ホルマリンの縮合物の架橋密度が低下すると共に分子量の低下を招くため、樹脂層の凝集力が低下し、接着性の低下や耐屈曲疲労性の低下する傾向があり好ましくない。他方、ホルムアルデヒドの量が多すぎる場合、レゾルシン・ホルマリン縮合物の架橋密度が上昇し、硬化するため、被着体のゴムとの共加硫時にレゾルシン・ホルマリン・ラテックス樹脂とゴムとの相溶化が阻害され接着性が低下する傾向があり好ましくない。 Furthermore, the aromatic polyamide short fiber bundle is preferably bundled with a resin film containing resorcin / formalin / latex. The resorcin / formalin / latex resin preferably has a resorcin / formaldehyde molar ratio in the range of 1: 0.6 to 1: 8, more preferably in the range of 1: 0.8 to 1: 6. . If the amount of formaldehyde is too small, the crosslink density of the condensate of resorcin / formalin will decrease and the molecular weight will decrease, so the cohesive strength of the resin layer will decrease and the adhesiveness and bending fatigue resistance will tend to decrease Is not preferable. On the other hand, if the amount of formaldehyde is too large, the cross-linking density of the resorcin / formalin condensate increases and cures, so that compatibilization of the resorcin / formalin / latex resin with the rubber occurs during co-vulcanization with the rubber of the adherend. It is not preferred because it tends to be hindered and adhesiveness tends to decrease.
レゾルシン・ホルマリン・ラテックス樹脂におけるレゾルシン・ホルマリンとゴムラテックスとの配合比率は、固形分重量比として、レゾルシン・ホルマリン：ゴムラテックスが、好ましくは１：３〜１：１６の範囲、さらに好ましくは１：４〜１：１０である。ゴムラテックスの比率が少なすぎる場合、ゴムとの共加硫成分が少なくなりすぎるため接着力が低下する傾向があり好ましくない。他方、ゴムラテックスの比率が多すぎる場合、接着剤皮膜として充分な強度を得ることができないため、集束性が低下する傾向があり好ましくない。 The blending ratio of resorcin / formalin and rubber latex in the resorcin / formalin / latex resin is preferably in the range of 1: 3 to 1:16, more preferably 1: 4 to 1:10. When the ratio of the rubber latex is too small, the co-vulcanized component with the rubber becomes too small, and the adhesive force tends to decrease, which is not preferable. On the other hand, when the ratio of rubber latex is too large, sufficient strength as an adhesive film cannot be obtained.
本発明のレゾルシンは、予めオリゴマー化したレゾルシン−ホルマリン初期縮合物やクロロフェノールとレゾルシンをホルマリンとオリゴマー化した多核クロロフェノール系レゾルシン−ホルマリン初期縮合物を、単独または組み合わせて用いてもよい。 As the resorcin of the present invention, a resorcin-formalin initial condensate previously oligomerized or a polynuclear chlorophenol-based resorcin-formalin condensate obtained by oligomerizing chlorophenol and resorcin with formalin may be used alone or in combination.
ゴムラテックスとしては、例えば、水素添加アクリロニトリルーブタジエンゴムラテックス、アクリロニトリル−ブタジエンラテックス、イソプレンゴムラテックス、ウレタンゴムラテックス、スチレン−ブタジエンゴムラテックス、ビニルピリジン−スチレン−ブタジエンゴムラテックス、クロロプレンゴムラテックス、ブタジエンゴムラテックス、クロロスルホン化ポリエチレンラテックスを例示することができ、これらを単独または併用して使用することができる。特に各種樹脂との親和性が高く、また樹脂層の強度を高めることができることから、ゴムラテックスとして、ビニルピリジン−スチレン−ブタジエンゴムラテックス共重合体を用いることが好ましい。 Examples of the rubber latex include hydrogenated acrylonitrile-butadiene rubber latex, acrylonitrile-butadiene latex, isoprene rubber latex, urethane rubber latex, styrene-butadiene rubber latex, vinylpyridine-styrene-butadiene rubber latex, chloroprene rubber latex, butadiene rubber latex. Chlorosulfonated polyethylene latex can be exemplified, and these can be used alone or in combination. In particular, a vinylpyridine-styrene-butadiene rubber latex copolymer is preferably used as the rubber latex because it has high affinity with various resins and can increase the strength of the resin layer.
更にレゾルシン・ホルマリン・ラテックス樹脂に、架橋剤として、イソシアネート化合物を併用することが好ましい。なかでも、処理剤の経時安定性がよく、レゾルシン・ホルマリン・ラテックスとの相互作用が良好なことから、ブロックドイソシアネート化合物が好ましい。このブロックドイソシアネート化合物として、ジメチルピラゾールブロック、メチルエチルケトンオキシムブロック、カプロラクタムブロックのブロックドイソシアネートを例示することができる。これらは単独または組み合わせて用いてもよい。 Furthermore, it is preferable to use an isocyanate compound as a crosslinking agent in the resorcin / formalin / latex resin. Of these, a blocked isocyanate compound is preferred because the treatment agent has good stability over time and good interaction with resorcin / formalin / latex. Examples of the blocked isocyanate compound include blocked isocyanates of dimethylpyrazole block, methyl ethyl ketone oxime block, and caprolactam block. These may be used alone or in combination.
イソシアネート化合物の添加量は、レゾルシン・ホルマリン・ゴムラテックス樹脂の全重量あたり、０．５〜４０重量％が好ましく、さらには１０〜３０重量％であることが好ましい。添加量を増やすと通常は接着力が向上するが、添加量が多すぎると接着剤のゴムに対する相容性が低下し、ゴムとの接着力が低下する傾向があり好ましくない。 The addition amount of the isocyanate compound is preferably 0.5 to 40% by weight, more preferably 10 to 30% by weight, based on the total weight of the resorcin / formalin / rubber latex resin. Increasing the amount added usually improves the adhesive strength. However, if the amount added is too large, the compatibility of the adhesive with the rubber tends to decrease, and the adhesive strength with the rubber tends to decrease.
また、本発明の目的を阻害しない範囲で、集束剤に平滑剤、乳化剤、制電剤、難燃剤、耐光剤、紫外線吸収剤、酸化防止剤、防錆剤、抗菌剤、顔料、シランカップリング剤、無機系微粒子などの機能剤を包含してもよく、また、繊維製造工程で付与する工程処理剤（油剤など）を除去することは必須とされない。 In addition, a smoothing agent, an emulsifier, an antistatic agent, a flame retardant, a light-resistant agent, an ultraviolet absorber, an antioxidant, a rust-proofing agent, an antibacterial agent, a pigment, and a silane coupling are used as a sizing agent as long as the object of the present invention is not impaired Functional agents such as agents and inorganic fine particles may be included, and it is not essential to remove process treatment agents (oil agents, etc.) applied in the fiber production process.
芳香族ポリアミド短繊維に、上記のような集束剤を付与する方法としては、混合水溶液処理剤として該処理剤溶液を満たした液浴に浸漬する方法、走行する糸に集束剤水溶液を付与した駆動ローラーを接触させる方法等が挙げられる。また、処理剤の固形分付着量を調整するために、圧接ローラーによる絞り、スクレバーによるかき落とし、空気吹きつけによる吹き飛ばし、吸引、ビーターなどの手段を適時用いることができる。 As a method for applying a sizing agent as described above to an aromatic polyamide short fiber, a method of immersing in a liquid bath filled with the treating agent solution as a mixed aqueous solution treating agent, a drive in which a sizing agent aqueous solution is applied to a traveling yarn Examples include a method of bringing a roller into contact. Moreover, in order to adjust the solid content adhesion amount of the treatment agent, means such as squeezing by a pressure roller, scraping by a scrubber, blowing by air blowing, suction, beater, etc. can be used as appropriate.
上記の集束剤は繊維への付着後に、１００℃〜２５０℃の温度で６０〜３００秒間の乾燥、熱処理を行うことで接着層を形成することができる。芳香族ポリアミド繊維に接着層を形成させるためには、１００〜１８０℃の温度で６０〜２４０秒間の乾燥させ、次いで２００〜２４５℃の温度で６０〜２４０秒間の熱処理を行うことが好ましいが、集束剤水溶液の固形分付着量に応じて適宜調整した上で条件は設定することができる。 The above sizing agent can form an adhesive layer by performing drying and heat treatment at a temperature of 100 ° C. to 250 ° C. for 60 to 300 seconds after adhering to the fiber. In order to form an adhesive layer on the aromatic polyamide fiber, it is preferable to dry at a temperature of 100 to 180 ° C. for 60 to 240 seconds, and then to perform a heat treatment at a temperature of 200 to 245 ° C. for 60 to 240 seconds, Conditions can be set after adjusting appropriately according to the solid content adhesion amount of the sizing agent aqueous solution.
また、本発明の芳香族ポリアミド短繊維集束体は、繊維の強度を向上させるためにも、一旦長繊維として製造した後に短繊維にカットすることが好ましい。カットの方法としては、芳香族ポリアミド繊維集束体の切断が可能ないずれのカッターを用いてカットしてもよく、具体的にはロータリーカッター、ギロチンカッター等を用いてカットすればよい。カットの時期としては、繊維に集束剤を付与、乾燥した後であることが作業性や品質の均一化のためには好ましい。 Moreover, in order to improve the strength of the fiber, the aromatic polyamide short fiber bundle of the present invention is preferably produced once as a long fiber and then cut into short fibers. As a cutting method, it may be cut using any cutter capable of cutting the aromatic polyamide fiber bundle, and specifically, it may be cut using a rotary cutter, a guillotine cutter or the like. The cutting time is preferably after the sizing agent is applied to the fiber and dried, in order to make workability and quality uniform.
また、短繊維混練ゴム（ゴムシート）は、集束体の分散性の確保およびゴム組成物としての性能を向上するためにも、短繊維集束体を未加硫ゴム中へ配合する際に、短繊維集束体をゴムポリマー当たり５〜２５重量％となるように配合することが好ましい。 In addition, the short fiber kneaded rubber (rubber sheet) is short when blending the short fiber bundle into the unvulcanized rubber in order to secure the dispersibility of the bundle and improve the performance as a rubber composition. It is preferable to blend the fiber bundle so as to be 5 to 25% by weight per rubber polymer.
また、短繊維混練ゴム（ゴムシート）は、ゴム組成物の性能の指標である、ＪＩＳ Ｋ６２５１のダンベル状３号形を用いた方法にて引張試験を実施した５％伸長時の応力が７ＭＰａ以上、１０％伸長時の応力が１３ＭＰａ以上であることが好ましい。 Moreover, the short fiber kneaded rubber (rubber sheet) has a stress at 5% elongation of 7 MPa or more when a tensile test is carried out by a method using dumbbell shape No. 3 of JIS K6251 which is an index of the performance of the rubber composition. The stress at 10% elongation is preferably 13 MPa or more.
また、本発明に使用する芳香族ポリアミド繊維は、ゴムラテックスを含有する集束剤の内層で、各単繊維の一部、或いは全体がエポキシ化合物によって予め処理されていても構わない。これにより、各単繊維とゴムラテックスを含有する集束剤の親和性が向上し、より集束性が向上する。 Moreover, the aromatic polyamide fiber used in the present invention may be an inner layer of a sizing agent containing a rubber latex, and a part or the whole of each single fiber may be pretreated with an epoxy compound. Thereby, the affinity of the sizing agent containing each single fiber and rubber latex is improved, and the sizing property is further improved.
各単繊維に対するエポキシ化合物やイソシアネート化合物の固形分付着量は、単繊維の重量を基準として、好ましくは０．０５〜５．０重量％、さらに好ましくは０．２〜２．０重量％である。表面処理に用いるエポキシ化合物としては、具体的には、エチレングリコール、グリセロール、ソルビトール、ペンタエリスリトール、ポリエチレングリコール等の多価アルコールとエピクロルヒドリンの如きハロゲン含有エポキシドとの反応生成物、レゾルシン、ピス（４−ヒドロキシフェニル）ジメチルメタン、フェノール・ホルムアルデヒド樹脂、レゾルシン・ホルムアルデヒド樹脂等の多価フェノールと前記ハロゲン含有エポキシドとの反応生成物、過酢酸または過酸化水素等で不飽和化合物を酸化して得られるポリエポキシド化合物、すなわち３，４−エポキシシクロヘキセンエポキシド、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキセンカルボキシレート、ビス（３、４−エポキシ−６−メチル−シクロヘキシルメチル）アジベートを挙げることができる。これらのうち、多価アルコールとエピクロルヒドリンとの反応生成物が好ましく、多価アルコールのポリグリシジルエーテル化合物のようなポリエポキシド化合物と硬化剤により生成される化合物も好ましい。 The solid content adhesion amount of the epoxy compound or isocyanate compound to each single fiber is preferably 0.05 to 5.0% by weight, more preferably 0.2 to 2.0% by weight, based on the weight of the single fiber. . Specific examples of the epoxy compound used for the surface treatment include a reaction product of a polyhydric alcohol such as ethylene glycol, glycerol, sorbitol, pentaerythritol, and polyethylene glycol with a halogen-containing epoxide such as epichlorohydrin, resorcin, pis (4- Hydroxyphenyl) Reaction product of polyhydric phenol such as dimethylmethane, phenol-formaldehyde resin, resorcinol-formaldehyde resin and the above halogen-containing epoxide, polyepoxide compound obtained by oxidizing unsaturated compound with peracetic acid or hydrogen peroxide 3,4-epoxycyclohexene epoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, bis (3,4-epoxy-6-methyl-cycl A hexyl methyl) Ajibeto. Of these, a reaction product of a polyhydric alcohol and epichlorohydrin is preferred, and a compound produced by a polyepoxide compound such as a polyglycidyl ether compound of a polyhydric alcohol and a curing agent is also preferred.
ポリエポキシド化合物を用いる場合には、乳化剤、例えばアルキルベンゼンスルフォン酸ソーダ、ジオクチルスルフォサクシネートナトリウム塩を用いて、乳化液としてもよい。また、ポリエポキシド化合物には、アミン系やイミダゾール系の硬化剤、ポリイソシアネートとオキシム、フェノール、カプロラクタムなどのブロック化剤との付加化合物であるブロックドポリイソシアネート、エチレンイミンとの反応化合物であるエチレン尿素を併用してもよい。 When a polyepoxide compound is used, an emulsifier such as sodium alkylbenzene sulfonate or dioctyl sulfosuccinate sodium salt may be used as an emulsion. Polyepoxide compounds include amine and imidazole curing agents, blocked polyisocyanates that are addition compounds of polyisocyanates and blocking agents such as oxime, phenol, caprolactam, and ethylene urea, a reaction compound with ethyleneimine. May be used in combination.
ポリエポキシ化合物を用いる場合、ポリエポキシド化合物の重量をＡ重量部とし、硬化剤、ブロックドポリイソシアネートおよびエチレン尿素の重量をＢ重量部としたときの両者の関係が、０．０５≦（Ａ）／〔（Ａ）＋（Ｂ）〕≦０．９の条件を満たすことが好ましい。この範囲であると、特に良好な接着性を得ることができる。 When using a polyepoxy compound, the weight of the polyepoxide compound is A part by weight, and the relationship between the weight of the curing agent, blocked polyisocyanate and ethylene urea is B part by weight is 0.05 ≦ (A) / It is preferable that the condition [(A) + (B)] ≦ 0.9 is satisfied. In this range, particularly good adhesiveness can be obtained.
芳香族ポリアミド繊維にエポキシ化合物で表面処理する場合、例えば、エポキシ化合物を含む溶液をパラ型芳香族ポリアミド繊維の製糸工程で油剤と混合して繊維の単糸に付着させる、或いは芳香族ポリアミド繊維の製糸後、製糸工程とは別の工程で処理剤を繊維の単繊維に付着させ、付着後１００〜２５０℃の温度で１０〜１２０秒間熱処理することで、表面処理することができる。 When surface treatment with an epoxy compound is performed on an aromatic polyamide fiber, for example, a solution containing the epoxy compound is mixed with an oil agent in the process of making a para-type aromatic polyamide fiber and adhered to a single yarn of the fiber, or the aromatic polyamide fiber The surface treatment can be performed by attaching the treatment agent to the single fibers of the fiber in a step different from the yarn production step after the yarn production, and performing heat treatment at a temperature of 100 to 250 ° C. for 10 to 120 seconds after the attachment.
このような本発明の芳香族ポリアミド短繊維集束体は、扁平形状であるため処理剤が含浸しやすく、かつ混練り工程前まで繊維束状態を保つため、製造時の取扱性が良好で、ゴム等との混練り工程等にて複合する事により、組成物中で繊維が均一に分散・配置されることによって、機械的強度および耐摩耗性に優れた芳香族ポリアミド繊維強化ゴム組成物を提供する事ができる。 Such an aromatic polyamide short fiber bundle of the present invention has a flat shape, so that the treatment agent is easily impregnated, and the fiber bundle state is maintained until before the kneading step. By mixing in the kneading process etc., etc., an aromatic polyamide fiber reinforced rubber composition having excellent mechanical strength and abrasion resistance is provided by uniformly dispersing and arranging the fibers in the composition. I can do it.
以下、実施例により本発明をさらに詳細に説明する。なお、実施例で用いた評価方法は下記の通りである。 Hereinafter, the present invention will be described in more detail with reference to examples. The evaluation methods used in the examples are as follows.
（１）繊維長
得られた芳香族ポリアミド短繊維集束体から無作為に５０本の集束体を選び、目盛付きの顕微鏡にて各集束体の繊維長を測定し、その平均値を繊維長とした。
(1) Fiber length From the obtained aromatic polyamide short fiber bundles, 50 bundles were selected at random, the fiber length of each bundle was measured with a microscope with a scale, and the average value was determined as the fiber length. did.
（２）短繊維集束体の幅
得られた芳香族ポリアミド短繊維集束体から無作為に５０本の集束体を選び、目盛付きの顕微鏡にて各集束体の幅を測定し、その平均値を幅とした。
(2) Width of short fiber bundles Select 50 bundles randomly from the obtained aromatic polyamide short fiber bundles, measure the width of each bundle with a graduated microscope, and calculate the average value. The width.
（３）短繊維集束体の厚み
得られた芳香族ポリアミド短繊維集束体から無作為に５０本の集束体を選び、(株)テクロック製の定圧厚さ測定器(ＪＩＳ Ｋ６３２８準拠)にて各集束体の厚さを測定し、その平均値を厚みとした。
(3) Thickness of short fiber bundles 50 bundles were randomly selected from the obtained aromatic polyamide short fiber bundles, and each was measured with a constant pressure thickness measuring instrument (according to JIS K6328) manufactured by Teclock Corporation. The thickness of the focusing body was measured, and the average value was taken as the thickness.
（４）短繊維集束体の嵩密度
短繊維束を１０００ｍｌメスシリンダーに１００ｇ採取し、このメスシリンダーを３０ｍｍの高さから落下させることを１０回繰り返して、そのメスシリンダーの短繊維束の体積Ｖとその重量Ｗ（ｇ）から下記式を用いて算出した。嵩密度（ｇ／ｌ）＝Ｗ／Ｖ
(4) Bulk density of short fiber bundles Collecting 100 g of short fiber bundles into a 1000 ml graduated cylinder and dropping this graduated cylinder from a height of 30 mm 10 times, the volume V of the short fiber bundle of the graduated cylinder And its weight W (g) was calculated using the following formula. Bulk density (g / l) = W / V
（５）短繊維混練ゴムの５％応力、１０％応力
短繊維集束体を表１に示すエチレンプロピレンジエンゴムを主成分とする未加硫ゴム中に、短繊維集束体をエチレンプロピレンジエンゴムポリマー当たり１０重量％となるように配合し、ＭＳ加圧型ニーダー（ＤＳ３−１０ＭＨＨＳ守山製作所株式会社製）にて８０℃以下の温度で８分間混練した。その後、オープンロール（関西ロール(株)製 ９インチテストロール）にて０．６〜０．７ｍｍ厚さにシート出しを行った。その後、シートを積層し、１５０℃で３０分間、１ＭＰaの条件でプレス加硫により２ｍｍ厚の短繊維混練ゴム（ゴムシート）を作成した。
得られた短繊維混練ゴム（ゴムシート）について、短繊維の配向方向にサンプルを切り出し、ＪＩＳ Ｋ６２５１のダンベル状３号形を用いた方法にて引張試験を実施し、５％伸長時と１０％伸長時の応力を測定した。
(5) 5% stress and 10% stress of short fiber kneaded rubber The short fiber bundle is made of ethylene propylene diene rubber polymer in the unvulcanized rubber whose main component is ethylene propylene diene rubber shown in Table 1. The mixture was blended so as to be 10% by weight, and kneaded for 8 minutes at a temperature of 80 ° C. or less using an MS pressure type kneader (DS3-10MHHS manufactured by Moriyama Seisakusho Co., Ltd.). Thereafter, the sheet was put out to a thickness of 0.6 to 0.7 mm using an open roll (9-inch test roll manufactured by Kansai Roll Co., Ltd.). Thereafter, the sheets were laminated, and a short fiber kneaded rubber (rubber sheet) having a thickness of 2 mm was formed by press vulcanization under conditions of 1 MPa at 150 ° C. for 30 minutes.
About the obtained short fiber kneaded rubber (rubber sheet), a sample was cut out in the orientation direction of the short fiber, and a tensile test was carried out by a method using a dumbbell shape No. 3 of JIS K6251. The stress during elongation was measured.
（６）短繊維混練ゴムの摩耗量
短繊維混練ゴム（ゴムシート）の表面を３２０番のサンドペーパーで摩擦し、耐摩耗性の指標とした。具体的には、オリエンテック株式会社の摩擦摩耗試験機を用い、サンドペーパーを取り付けた金属板に、（５）の短繊維混練ゴムの短繊維配向方向の断面がサンドペーパーに当たるように、０．１９ＭＰaの荷重を負荷した状態で１００ｒｐｍの速度で回転摩耗させ、１０分間経過後の摩耗量を重量変化から求め比較する方法を用いた。摩耗量が少ないほど、耐摩耗性に優れることを示す。
(6) Abrasion amount of short fiber kneaded rubber The surface of short fiber kneaded rubber (rubber sheet) was rubbed with No. 320 sandpaper, and used as an index of wear resistance. Specifically, using a friction and wear tester manufactured by Orientec Co., Ltd., a metal plate to which sandpaper is attached is adjusted so that the cross section in the short fiber orientation direction of the short fiber kneaded rubber of (5) hits the sandpaper. A method was used in which rotational wear was performed at a speed of 100 rpm under a load of 19 MPa, and the amount of wear after 10 minutes was determined from the change in weight and compared. The smaller the amount of wear, the better the wear resistance.
（７）短繊維混練ゴムの繊維塊の数
２ｍｍ厚みの短繊維混練ゴム（ゴムシート）を短繊維配向の垂直方向に裁断機でカットし、５０ｃｍ長の断面をデジタルマイクロスコープで観察し、単繊維同士が絡まり合って０．５ｍｍ以上の塊として観察される繊維塊の数を測定した。繊維塊が少ないほど、分散性に優れることを示す。
(7) Number of fiber masses of short fiber kneaded rubber A 2 mm thick short fiber kneaded rubber (rubber sheet) was cut with a cutting machine in the vertical direction of short fiber orientation, and a 50 cm long cross section was observed with a digital microscope. The number of fiber lumps observed as lumps of 0.5 mm or more due to entanglement of fibers was measured. The smaller the fiber mass, the better the dispersibility.
［実施例１］
デナコールＥＸ−３１３（グリセロールポリグリシジルエーテル、ナガセケムテックス（株）製）１７．５ｇと、界面活性剤としてのネオコールＳＷ−３０（ジオクチルスルフォサクシネートナトリウム塩、第一工業製薬（株）製）１４．５ｇと、ピペラジン４ｇと、水６５６．２ｇとを混合し、固形分濃度３．７重量％のエポキシ溶液を調製した。
[Example 1]
Denacol EX-313 (glycerol polyglycidyl ether, manufactured by Nagase ChemteX Corporation) 17.5 g and Neocor SW-30 (dioctylsulfosuccinate sodium salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a surfactant 14.5 g, piperazine 4 g, and water 656.2 g were mixed to prepare an epoxy solution having a solid content concentration of 3.7% by weight.
また、レゾルシン／ホルマリン（Ｒ／Ｆ）のモル比が１／０．６であるレゾルシン−ホルマリン初期縮合物（スミカノール７００Ｓ、住友化学（株）製、濃度６５重量％）１９．８ｇを、水１５４．５ｇに１０％苛性ソーダ水５．０ｇと２０％アンモニア水１９．９ｇを加えたアルカリ水溶液に溶解し、これにビニルピリジン−スチレン−ブタジエンゴムラテックス（ニポール２５１８ＦＳ，日本ゼオン（株）製、濃度４０重量％）４１５ｇと水３６８．９ｇを添加した。この液に、３７％ホルマリン水１６．８ｇ、およびメチルエチルケトンオキシムブロックジフェニルメタンジイソシアネート（ＤＭ６４００，明成化学工業（株）製、濃度４２％）を添加し、２０℃で４８時間熟成して、固形分濃度２０重量％のレゾルシン・ホルマリン・ラテックス樹脂を含む水分散体（レゾルシン・ホルマリン・ラテックス樹脂処理剤）を調製した。 In addition, 19.8 g of a resorcin-formalin initial condensate (Sumikanol 700S, manufactured by Sumitomo Chemical Co., Ltd., concentration 65% by weight) having a resorcin / formalin (R / F) molar ratio of 1 / 0.6 was added to water 154 Dissolved in an alkaline aqueous solution in which 5.0 g of 10% caustic soda water and 19.9 g of 20% ammonia water were added to 5 g, vinyl pyridine-styrene-butadiene rubber latex (Nipol 2518FS, manufactured by Nippon Zeon Co., Ltd., concentration 40) % By weight) 415 g and water 368.9 g were added. To this solution, 16.8 g of 37% formalin water and methyl ethyl ketone oxime block diphenylmethane diisocyanate (DM6400, manufactured by Meisei Chemical Industry Co., Ltd., concentration 42%) were added and aged at 20 ° C. for 48 hours to obtain a solid content of 20 An aqueous dispersion (resorcin / formalin / latex resin treating agent) containing wt% of resorcin / formalin / latex resin was prepared.
総繊度１６７０ｄｔｅｘ（単繊維繊度０．８ｄｔeｘ、短繊維の集束本数２０００本）のフィラメントを有するコポリパラフェニレン・３、４’−オキシジフェニレンテレフタルアミド繊維（帝人(株)テクノーラ）を開繊した状態で、上記のエポキシ溶液を表面処理し、絞りロールで圧縮乾燥後、上記のレゾルシン・ホルマリン・ラテックス樹脂処理剤中に浸漬処理した後、１３０℃で２分間乾燥し、引き続き２３５℃で１分間熱処理をした。得られたコポリパラフェニレン・３、４’−オキシジフェニレンテレフタルアミド繊維（帝人(株)テクノーラ）繊維束の集束剤の固形分付着量を表２に示す。その後、この繊維束をギロチンカッターで３ｍｍの繊維長にカットしゴム補強用芳香族ポリアミド短繊維集束体を得た。 Copolyparaphenylene 3,4'-oxydiphenylene terephthalamide fiber (Teijin Corp. Technora) having filaments with a total fineness of 1670 dtex (single fiber fineness 0.8 dtex, 2,000 short fibers bundled) is opened Then, the epoxy solution is surface-treated, compressed and dried with a squeeze roll, dipped in the above-mentioned resorcin / formalin / latex resin treatment agent, dried at 130 ° C. for 2 minutes, and subsequently heat treated at 235 ° C. for 1 minute. Did. Table 2 shows the solid content of the sizing agent of the obtained copolyparaphenylene-3,4'-oxydiphenylene terephthalamide fiber (Teijin Corp. Technora) fiber bundle. Then, this fiber bundle was cut into a fiber length of 3 mm with a guillotine cutter to obtain an aromatic polyamide short fiber bundle for reinforcing rubber.
得られた短繊維集束体を表１に示すエチレンプロピレンジエンゴムを主成分とする未加硫ゴム中に、短繊維集束体をエチレンプロピレンジエンゴムポリマー当たり１０重量％となるように配合し、ＭＳ加圧型ニーダー（ＤＳ３−１０ＭＨＨＳ守山製作所株式会社製）にて８０℃以下の温度で８分間混練した。その後、オープンロール（関西ロール(株)製 ９インチテストロール）にて０．６〜０．７ｍｍ厚さにシート出しを行った。その後、シートを積層し、１５０℃で３０分間、１ＭＰaの条件でプレス加硫により２ｍｍ厚の短繊維混練ゴム（ゴムシート）を作成し、その評価結果を表２に示す。 The obtained short fiber bundles were blended in an unvulcanized rubber mainly composed of ethylene propylene diene rubber shown in Table 1 so that the short fiber bundles were 10% by weight per ethylene propylene diene rubber polymer, and MS It knead | mixed for 8 minutes at the temperature of 80 degrees C or less with the pressurization type | mold kneader (DS3-10MHHS Moriyama Seisakusho make). Thereafter, the sheet was put out to a thickness of 0.6 to 0.7 mm using an open roll (9-inch test roll manufactured by Kansai Roll Co., Ltd.). Thereafter, the sheets were laminated, and a short fiber kneaded rubber (rubber sheet) having a thickness of 2 mm was prepared by press vulcanization under conditions of 1 MPa at 150 ° C. for 30 minutes. The evaluation results are shown in Table 2.
［実施例２］
レゾルシン・ホルマリン・ラテックス樹脂処理剤を固形分濃度１０重量％となるように調整し、処理した以外は実施例１と同様にゴム補強用芳香族ポリアミド短繊維集束体および短繊維混練ゴム（ゴムシート）を得た。得られた短繊維混練ゴム（ゴムシート）の評価結果を表２に示す。
[Example 2]
Except that the resorcin / formalin / latex resin treatment agent was adjusted to a solid content concentration of 10% by weight and treated, the aromatic polyamide short fiber bundle for reinforcing rubber and rubber kneaded rubber (rubber sheet) were the same as in Example 1. ) Table 2 shows the evaluation results of the obtained short fiber kneaded rubber (rubber sheet).
［実施例３］
エポキシ溶液の表面処理後の絞りロールでの圧縮力を調整し、扁平度合いを変更した以外は実施例２と同様にゴム補強用芳香族ポリアミド短繊維集束体および短繊維混練ゴム（ゴムシート）を得た。得られた短繊維混練ゴム（ゴムシート）の評価結果を表２に示す。
[Example 3]
Except for adjusting the compressive force of the squeeze roll after the surface treatment of the epoxy solution and changing the flatness, the aromatic polyamide short fiber bundle for rubber reinforcement and the short fiber kneaded rubber (rubber sheet) were used in the same manner as in Example 2. Obtained. Table 2 shows the evaluation results of the obtained short fiber kneaded rubber (rubber sheet).
［比較例１］
総繊度１６７０ｄｔｅｘ（単繊維繊度１．７ｄｔeｘ、短繊維の集束本数１０００本）のフィラメントを有するコポリパラフェニレン・３、４’−オキシジフェニレンテレフタルアミド繊維（帝人(株)テクノーラ）を用いた以外は実施例１と同様にゴム補強用芳香族ポリアミド短繊維集束体および短繊維混練ゴム（ゴムシート）を得た。得られた短繊維混練ゴム（ゴムシート）の評価結果を表２に示す。
[Comparative Example 1]
Other than using copolyparaphenylene 3,4'-oxydiphenylene terephthalamide fiber (Teijin Corp. Technora) having filaments with a total fineness of 1670 dtex (single fiber fineness of 1.7 dtex, bundled number of short fibers of 1000) In the same manner as in Example 1, an aromatic polyamide short fiber bundle for reinforcing rubber and a short fiber kneaded rubber (rubber sheet) were obtained. Table 2 shows the evaluation results of the obtained short fiber kneaded rubber (rubber sheet).
［比較例２］
エポキシ溶液の表面処理後に絞りロールでの※圧縮力を調整し、略楕円形状に変更した以外は実施例２と同様にゴム補強用芳香族ポリアミド短繊維集束体および短繊維混練ゴム（ゴムシート）を得た。得られた短繊維混練ゴム（ゴムシート）の評価結果を表２に示す。
[Comparative Example 2]
Except for adjusting the compression force with the squeeze roll after the surface treatment of the epoxy solution and changing it to a substantially elliptical shape, the aromatic polyamide short fiber bundle for reinforcing rubber and the short fiber kneaded rubber (rubber sheet) are the same as in Example 2. Got. Table 2 shows the evaluation results of the obtained short fiber kneaded rubber (rubber sheet).
本発明の芳香族ポリアミド短繊維集束体は、ゴムに添加することにより芳香族ポリアミド繊維強化ゴム組成物を得ることができ、モジュラスを始めとする機械的強度、耐摩耗性に優れ、伝動ベルトや、ゴムホース、タイヤやゴムロール等の用途に好適に使用できる。 The aromatic polyamide short fiber bundle of the present invention can be added to rubber to obtain an aromatic polyamide fiber reinforced rubber composition, which has excellent mechanical strength including modulus and abrasion resistance, transmission belt, , Rubber hoses, tires, rubber rolls and the like.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018033351A JP7160541B2 (en) | 2018-02-27 | 2018-02-27 | Aromatic polyamide short fiber bundle for rubber reinforcement and rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018033351A JP7160541B2 (en) | 2018-02-27 | 2018-02-27 | Aromatic polyamide short fiber bundle for rubber reinforcement and rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019148033A true JP2019148033A (en) | 2019-09-05 |
| JP7160541B2 JP7160541B2 (en) | 2022-10-25 |
Family
ID=67849188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018033351A Active JP7160541B2 (en) | 2018-02-27 | 2018-02-27 | Aromatic polyamide short fiber bundle for rubber reinforcement and rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7160541B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005194668A (en) * | 2004-01-08 | 2005-07-21 | Toyobo Co Ltd | Rubber-reinforcing polybenzazole dipped cord and method for producing the same |
| JP2012207326A (en) * | 2011-03-29 | 2012-10-25 | Du Pont-Toray Co Ltd | Poly-para-phenylene terephthalamide fiber composite and method for producing the same |
| JP2013167040A (en) * | 2012-02-17 | 2013-08-29 | Du Pont-Toray Co Ltd | Aramid fiber |
| WO2015159795A1 (en) * | 2014-04-17 | 2015-10-22 | 旭化成せんい株式会社 | Short rubber reinforcement fiber, rubber composition containing said short fiber, and power transmission belt |
| JP2015183315A (en) * | 2014-03-25 | 2015-10-22 | 東レ・デュポン株式会社 | Aromatic polyamide short fiber for rubber reinforcement |
-
2018
- 2018-02-27 JP JP2018033351A patent/JP7160541B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005194668A (en) * | 2004-01-08 | 2005-07-21 | Toyobo Co Ltd | Rubber-reinforcing polybenzazole dipped cord and method for producing the same |
| JP2012207326A (en) * | 2011-03-29 | 2012-10-25 | Du Pont-Toray Co Ltd | Poly-para-phenylene terephthalamide fiber composite and method for producing the same |
| JP2013167040A (en) * | 2012-02-17 | 2013-08-29 | Du Pont-Toray Co Ltd | Aramid fiber |
| JP2015183315A (en) * | 2014-03-25 | 2015-10-22 | 東レ・デュポン株式会社 | Aromatic polyamide short fiber for rubber reinforcement |
| WO2015159795A1 (en) * | 2014-04-17 | 2015-10-22 | 旭化成せんい株式会社 | Short rubber reinforcement fiber, rubber composition containing said short fiber, and power transmission belt |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7160541B2 (en) | 2022-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20060135917A (en) | Composition for cord coating, cord for rubber reinforcement made with the same, and rubber product made with the same | |
| JP2007162161A (en) | Glass fiber for reinforcement of rubber product and method for producing the same | |
| JP2016176168A (en) | Cord for rubber reinforcement | |
| JP7067972B2 (en) | Composite fiber cord for rubber reinforcement | |
| JP2011241504A (en) | Aromatic polyamide short fiber bundle | |
| JP2009275303A (en) | Rubber-reinforcing fiber and method for producing the same | |
| JP2019148033A (en) | Aromatic polyamide short fiber bundle for rubber reinforcement and rubber composition | |
| JP2005009010A (en) | Reinforcing fiber for rubber product | |
| WO2019049590A1 (en) | Fiber cord for reinforcing rubber | |
| JP2005042229A (en) | Carbon fiber cord for driving belt reinforcement and driving belt using the same | |
| JP4172234B2 (en) | Manufacturing method of carbon fiber cord for rubber reinforcement | |
| JP2006214043A (en) | Rubber-reinforcing carbon yarn | |
| WO2007072703A1 (en) | Ply cord for polyester tire cap and process for producing the same | |
| JP2022177782A (en) | Synthetic fiber cord for automobile hose reinforcement and method for producing the same | |
| JP6877193B2 (en) | Fiber cord for rubber reinforcement and its manufacturing method | |
| JP2007186818A (en) | Fiber treating agent, cord for reinforcement of rubber produced by utilizing the agent and rubber product utilizing the cord for reinforcement | |
| JPH08100370A (en) | Aramide fiber cord for power transmission belt | |
| JP4944742B2 (en) | Rubber reinforcing fiber and method for producing the same | |
| JP6877155B2 (en) | Carbon fiber cord for rubber reinforcement | |
| JPH07268771A (en) | Treatment of aramid short fiber for rubber reinforcement | |
| JP2019163560A (en) | Composite fiber cord for reinforcing rubber, and method for producing the same | |
| JP7303018B2 (en) | Aramid fiber cord for rubber hose reinforcement | |
| JP6890370B2 (en) | Aramid short fiber bundle for rubber reinforcement | |
| JPH0860555A (en) | Method for treating polyester fiber | |
| JP2005023481A (en) | Carbon fiber cord for rubber reinforcement and fiber-reinforced rubber material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20201117 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20210922 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20211005 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20211102 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220405 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220526 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220927 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20221013 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7160541 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |