JP6185690B1 - Rubber reinforcing cord manufacturing method, rubber reinforcing cord and rubber product - Google Patents
Rubber reinforcing cord manufacturing method, rubber reinforcing cord and rubber product Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 173
- 230000003014 reinforcing effect Effects 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 55
- 229920000126 latex Polymers 0.000 claims abstract description 51
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 49
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 40
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000460 chlorine Substances 0.000 claims abstract description 29
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 29
- 229920002681 hypalon Polymers 0.000 claims abstract description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000004816 latex Substances 0.000 claims description 32
- 239000003365 glass fiber Substances 0.000 claims description 16
- 230000002787 reinforcement Effects 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003049 isoprene rubber Polymers 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 28
- 239000002253 acid Substances 0.000 description 11
- 239000003513 alkali Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003929 acidic solution Substances 0.000 description 7
- 239000012670 alkaline solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 241001589086 Bellapiscis medius Species 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000002585 base Substances 0.000 description 2
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- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- -1 phenylene benzoxazole Chemical compound 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
本発明のゴム補強用コードの製造方法は、ゴム製品を補強するためのゴム補強用コードを製造する方法であって、フェノール由来芳香族化合物−ホルムアルデヒド樹脂と、pH値が2.0以上2.5未満であるクロロスルフォン化ポリエチレンゴムラテックスとを混合して、前記フェノール由来芳香族化合物−ホルムアルデヒド樹脂と前記クロロスルフォン化ポリエチレンゴムラテックスとを含有する処理剤を調製する工程と、前記処理剤をゴム補強用繊維の少なくとも表面の一部に塗布して乾燥させて、前記ゴム補強用繊維の少なくとも表面の一部に被膜が形成されたゴム補強用コードを得る工程と、を含む。前記被膜における塩素含有率は、1〜30質量%である。The method for producing a rubber reinforcing cord of the present invention is a method for producing a rubber reinforcing cord for reinforcing a rubber product, wherein the phenol-derived aromatic compound-formaldehyde resin has a pH value of 2.0 or more. Mixing a chlorosulfonated polyethylene rubber latex that is less than 5 to prepare a treatment agent containing the phenol-derived aromatic compound-formaldehyde resin and the chlorosulfonated polyethylene rubber latex; and treating the treatment agent with rubber Applying to and drying at least a portion of the surface of the reinforcing fiber to obtain a rubber reinforcing cord having a coating formed on at least a portion of the surface of the rubber reinforcing fiber. The chlorine content in the coating is 1 to 30% by mass.
Description
本発明は、ゴム補強用コードの製造方法、ゴム補強用コード及びゴム製品に関する。 The present invention relates to a method for manufacturing a rubber reinforcing cord, a rubber reinforcing cord, and a rubber product.
歯付きゴムベルトなどのゴム製品について、その強度や耐久性を向上させるために、ガラス繊維や化学繊維などの補強用繊維を含む補強用コードをマトリックスゴム内に埋設することが広く行われている。補強用コードでは、一般に、マトリックスゴムと補強用繊維との接着性を高めるためや、ゴム製品が過酷な環境下(例えば、強酸性下や強アルカリ性下等)で使用される場合の補強用コードの耐性を高めるために、補強用繊維の表面に被膜が設けられる。このような被膜の材料として、クロロスルフォン化ポリエチレンゴムは、その高い耐熱性から幅広く使用されている(特許文献1〜6)。 In order to improve the strength and durability of a rubber product such as a toothed rubber belt, a reinforcing cord including a reinforcing fiber such as a glass fiber or a chemical fiber is embedded in a matrix rubber. Reinforcing cords are generally used to increase the adhesion between matrix rubber and reinforcing fibers, and when the rubber product is used in harsh environments (for example, under strong acidity or strong alkalinity). In order to increase the resistance, a coating is provided on the surface of the reinforcing fiber. As a material for such a film, chlorosulfonated polyethylene rubber is widely used because of its high heat resistance (Patent Documents 1 to 6).
クロロスルフォン化ポリエチレンゴムを含む被膜は、クロロスルフォン化ポリエチレンゴムラテックスを含む処理剤を補強用繊維の表面に塗布したのち乾燥させることによって形成される。 The film containing chlorosulfonated polyethylene rubber is formed by applying a treatment agent containing chlorosulfonated polyethylene rubber latex to the surface of the reinforcing fiber and then drying.
上述のとおり、被膜は、ゴム製品が強酸性下や強アルカリ性下等の過酷な環境で使用される場合であってもゴム補強用コードを保護して、当該ゴム補強用コードの強度を維持できるものであることが望ましい。 As described above, the coating can protect the rubber reinforcing cord and maintain the strength of the rubber reinforcing cord even when the rubber product is used in a severe environment such as under strong acidity or strong alkalinity. It is desirable to be a thing.
そこで、本発明の目的の一つは、クロロスルフォン化ポリエチレンゴムを含む被膜が設けられたゴム補強用コードであって、強酸性や強アルカリ性の過酷な環境下での使用に耐え得る被膜が実現されたゴム補強用コードを提供することである。さらに、本発明の別の目的の一つは、そのようなゴム補強用コードによって補強された、ゴム製品を提供することである。 Accordingly, one of the objects of the present invention is a rubber reinforcing cord provided with a coating containing chlorosulfonated polyethylene rubber, which realizes a coating that can withstand use in a harsh acidic or strong alkaline environment. It is to provide an improved rubber reinforcing cord. Furthermore, another object of the present invention is to provide a rubber product reinforced by such a rubber reinforcing cord.
本発明者らは、クロロスルフォン化ポリエチレンゴムを含む被膜の耐酸性及び耐アルカリ性の向上を目的とし、鋭意検討の末、被膜形成用の処理剤の調製に用いられるクロロスルフォン化ポリエチレンゴムラテックスのpH値及び遊離塩素濃度が、形成される被膜の耐酸性及び耐アルカリ性に大きな影響を及ぼすという事実を突き止め、以下の本発明のゴム補強用コードの製造方法及びゴム補強用コードに至った。 The inventors of the present invention aimed to improve the acid resistance and alkali resistance of a film containing chlorosulfonated polyethylene rubber, and after intensive studies, the pH of chlorosulfonated polyethylene rubber latex used for the preparation of a treatment agent for film formation Ascertaining the fact that the value and free chlorine concentration have a great influence on the acid resistance and alkali resistance of the formed film, the present inventors have reached the following method for producing a rubber reinforcing cord and rubber reinforcing cord of the present invention.
本発明は、ゴム製品を補強するためのゴム補強用コードを製造する方法であって、
フェノール由来芳香族化合物−ホルムアルデヒド樹脂と、pH値が2.0以上2.5未満であるクロロスルフォン化ポリエチレンゴムラテックスとを混合して、前記フェノール由来芳香族化合物−ホルムアルデヒド樹脂と前記クロロスルフォン化ポリエチレンゴムラテックスとを含有する処理剤を調製する工程と、
前記処理剤をゴム補強用繊維の少なくとも表面の一部に塗布して乾燥させて、前記ゴム補強用繊維の少なくとも表面の一部に被膜が形成されたゴム補強用コードを得る工程と、
を含み、
前記被膜における塩素含有率が1〜30質量%である、
ゴム補強用コードの製造方法を提供する。The present invention is a method of manufacturing a rubber reinforcing cord for reinforcing a rubber product,
A phenol-derived aromatic compound-formaldehyde resin and a chlorosulfonated polyethylene rubber latex having a pH value of 2.0 or more and less than 2.5 are mixed, and the phenol-derived aromatic compound-formaldehyde resin and the chlorosulfonated polyethylene are mixed. Preparing a treatment agent containing rubber latex;
Applying the treatment agent to at least part of the surface of the rubber reinforcing fiber and drying to obtain a rubber reinforcing cord having a film formed on at least part of the surface of the rubber reinforcing fiber;
Including
The chlorine content in the coating is 1 to 30% by mass,
A method for manufacturing a rubber reinforcing cord is provided.
また、本発明は、ゴム製品を補強するためのゴム補強用コードであって、
ゴム補強用繊維と、前記ゴム補強用繊維の少なくとも表面の一部に形成された被膜とを含み、
前記被膜は、フェノール由来芳香族化合物−ホルムアルデヒド樹脂と、クロロスルフォン化ポリエチレンゴムラテックスとを含む処理剤を、前記ゴム補強用繊維に塗布して乾燥させることによって形成されており、
前記クロロスルフォン化ポリエチレンゴムラテックスのpH値が2.0以上2.5未満であり、
前記被膜における塩素含有率が1〜30質量%である、
ゴム補強用コードを提供する。Moreover, the present invention is a rubber reinforcing cord for reinforcing a rubber product,
A rubber reinforcing fiber, and a coating formed on at least a part of the surface of the rubber reinforcing fiber,
The coating is formed by applying a treatment agent containing a phenol-derived aromatic compound-formaldehyde resin and a chlorosulfonated polyethylene rubber latex to the rubber reinforcing fibers and drying the coating agent,
The pH value of the chlorosulfonated polyethylene rubber latex is 2.0 or more and less than 2.5,
The chlorine content in the coating is 1 to 30% by mass,
Provide a cord for rubber reinforcement.
また、本発明は、上記本発明のゴム補強用コードの製造方法で得られたゴム補強用コード、又は、上記本発明のゴム補強用コードで補強されたゴム製品を提供する。 The present invention also provides a rubber reinforcing cord obtained by the method for producing a rubber reinforcing cord of the present invention or a rubber product reinforced with the rubber reinforcing cord of the present invention.
本発明のゴム補強用コードの製造方法及び本発明のゴム補強用コードによれば、クロロスルフォン化ポリエチレンゴムを含む被膜が設けられたゴム補強用コードであって、被膜の耐酸性及び耐アルカリ性の向上が実現されたゴム補強用コードを提供することができる。 According to the method for producing a rubber reinforcing cord of the present invention and the rubber reinforcing cord of the present invention, the rubber reinforcing cord is provided with a coating containing a chlorosulfonated polyethylene rubber, which has acid resistance and alkali resistance of the coating. It is possible to provide a rubber reinforcing cord that has been improved.
以下、本発明の実施形態について具体的に説明する。なお、以下の記載は本発明を限定するものではない。 Hereinafter, embodiments of the present invention will be specifically described. The following description does not limit the present invention.
[ゴム補強用コード及びゴム補強用コードの製造方法]
本実施形態のゴム補強用コードは、ゴム製品を補強するためのコードである。このゴム補強用コードは、ゴム補強用繊維と、ゴム補強用繊維の少なくとも表面の一部に形成された被膜とを含む。被膜は、フェノール由来芳香族化合物−ホルムアルデヒド樹脂と、クロロスルフォン化ポリエチレンゴムラテックスとを含む処理剤を、ゴム補強用繊維に塗布して乾燥させることによって形成されている。処理剤に含まれるクロロスルフォン化ポリエチレンゴム(以下、CSMと記載する。)ラテックスのpH値は、2.0以上2.5未満である。また、被膜における塩素含有率は1〜30質量%である。[Rubber reinforcing cord and rubber reinforcing cord manufacturing method]
The rubber reinforcing cord of the present embodiment is a cord for reinforcing a rubber product. The rubber reinforcing cord includes a rubber reinforcing fiber and a coating formed on at least a part of the surface of the rubber reinforcing fiber. The coating is formed by applying a treatment agent containing a phenol-derived aromatic compound-formaldehyde resin and a chlorosulfonated polyethylene rubber latex to a rubber reinforcing fiber and drying it. The pH value of the chlorosulfonated polyethylene rubber (hereinafter referred to as CSM) latex contained in the treatment agent is 2.0 or more and less than 2.5. Moreover, the chlorine content rate in a film is 1-30 mass%.
また、本実施形態のゴム補強用コードの製造方法の一実施形態は、
フェノール由来芳香族化合物−ホルムアルデヒド樹脂と、pH値が2.0以上2.5未満であるクロロスルフォン化ポリエチレンゴムラテックスとを混合して、前記フェノール由来芳香族化合物−ホルムアルデヒド樹脂と前記クロロスルフォン化ポリエチレンゴムラテックスとを含有する処理剤を調製する工程と、
前記処理剤をゴム補強用繊維の少なくとも表面の一部に塗布して乾燥させて、前記ゴム補強用繊維の少なくとも表面の一部に被膜が形成されたゴム補強用コードを得る工程と、
を含み、
前記被膜における塩素含有率が1〜30質量%である、
製造方法である。In addition, one embodiment of a method for producing a rubber reinforcing cord of the present embodiment is
A phenol-derived aromatic compound-formaldehyde resin and a chlorosulfonated polyethylene rubber latex having a pH value of 2.0 or more and less than 2.5 are mixed, and the phenol-derived aromatic compound-formaldehyde resin and the chlorosulfonated polyethylene are mixed. Preparing a treatment agent containing rubber latex;
Applying the treatment agent to at least part of the surface of the rubber reinforcing fiber and drying to obtain a rubber reinforcing cord having a film formed on at least part of the surface of the rubber reinforcing fiber;
Including
The chlorine content in the coating is 1 to 30% by mass,
It is a manufacturing method.
以下、本実施形態のゴム補強用コード及びゴム補強用コードの製造方法について、より具体的に説明する。 Hereinafter, the rubber reinforcing cord and the method for manufacturing the rubber reinforcing cord of the present embodiment will be described more specifically.
(補強用繊維)
本実施形態のゴム補強用コードに含まれるゴム補強用繊維及びゴム補強用コードの製造方法で用いられる補強用繊維は、ゴム製品の形状安定性や強度を高めることができる繊維であればよく、その材質や形状は特に限定されない。(Reinforcing fiber)
The rubber reinforcing fiber included in the rubber reinforcing cord of the present embodiment and the reinforcing fiber used in the method of manufacturing the rubber reinforcing cord may be fibers that can enhance the shape stability and strength of the rubber product, The material and shape are not particularly limited.
ゴム補強用繊維としては、例えば、ガラス繊維、ビニロン繊維に代表されるポリビニルアルコール繊維、ポリエステル繊維、ナイロン、アラミド(芳香族ポリアミド)などのポリアミド繊維、ポリアリレート繊維、ポリケトン繊維、炭素繊維又はポリパラフェニレンベンゾオキサゾール(PBO)繊維などを利用することができる。これらのなかでも、寸法安定性、耐熱性及び引張り強度などに優れる炭素繊維及びガラス繊維が好適に用いられる。例えば、高い耐久性が要求されるゴム製品を補強するためのゴム補強用コードを作製する場合には、十分な強度を有するガラス繊維(例えば高強度ガラス繊維)を用いることが好ましい。 Examples of the rubber reinforcing fiber include glass fiber, polyvinyl alcohol fiber typified by vinylon fiber, polyester fiber, nylon, polyamide fiber such as aramid (aromatic polyamide), polyarylate fiber, polyketone fiber, carbon fiber, or polyparaffin. A phenylene benzoxazole (PBO) fiber etc. can be utilized. Among these, carbon fibers and glass fibers that are excellent in dimensional stability, heat resistance, tensile strength, and the like are preferably used. For example, when producing a rubber reinforcing cord for reinforcing a rubber product that requires high durability, it is preferable to use glass fiber having sufficient strength (for example, high strength glass fiber).
ガラス繊維におけるガラスの種類は、特に限定されるものではないが、一般的な無アルカリガラスよりも、引張り強度に優れる高強度ガラスが好ましい。 Although the kind of glass in glass fiber is not specifically limited, High strength glass which is excellent in tensile strength is preferable to general alkali-free glass.
なお、繊維の構成は特に限定されるものではないが、例えばガラス繊維の場合は、繊維の最小構成単位であるフィラメントの平均径が5〜13μmのものが好ましい。例えば、このフィラメント50〜2000本を集束剤によって集束して、ゴム補強用繊維を作製する。複数本のゴム補強用繊維を集束して繊維ストランドとしてもよい。 In addition, although the structure of a fiber is not specifically limited, For example, in the case of glass fiber, the thing whose average diameter of the filament which is the minimum structural unit of a fiber is 5-13 micrometers is preferable. For example, 50 to 2000 filaments are bundled with a sizing agent to produce a rubber reinforcing fiber. A plurality of rubber reinforcing fibers may be bundled to form a fiber strand.
また、ゴム補強用繊維とゴム製品のマトリックスゴムとの接着性、及び、ゴム補強用繊維の耐ほつれ性をさらに向上させるために、ゴム補強用繊維(又は繊維ストランド)に撚りが施されてもよい。撚り数は、使用する繊維に応じて適切な撚り数を設定すればよい。例えば、ゴム補強用繊維としてガラス繊維を用いる場合には、撚り数は0〜4.0回/25mmの範囲であることが好ましい。また、必要なゴム補強用コードの太さや仕様に合わせて、複数回に分けて撚りを施してもよく、その撚り方向も限定されない。2段階に分けて撚りを施す場合には、例えば補強用繊維を数本束ねた繊維ストランドを下撚りして子縄を作り、さらにその子縄を数本束ねて上撚りしてコードを形成するとよい。このような繊維ストランド及びコードの作製に用いられる装置は、特に限定されないが、例えば、リング撚糸機、フライヤー撚糸機、撚り線機などを用いることができる。 Further, in order to further improve the adhesion between the rubber reinforcing fiber and the matrix rubber of the rubber product and the fray resistance of the rubber reinforcing fiber, the rubber reinforcing fiber (or fiber strand) may be twisted. Good. What is necessary is just to set the number of twists suitable for the number of twists according to the fiber to be used. For example, when glass fiber is used as the rubber reinforcing fiber, the number of twists is preferably in the range of 0 to 4.0 turns / 25 mm. Moreover, according to the thickness and specification of a required cord for rubber reinforcement, the twist may be applied in a plurality of times, and the twist direction is not limited. In the case of twisting in two stages, for example, a strand may be formed by twisting a fiber strand in which several reinforcing fibers are bundled, and then a cord may be formed by bundling several strands and twisting the strand. . Although the apparatus used for preparation of such a fiber strand and a cord is not specifically limited, For example, a ring twister, a fryer twister, a strand wire machine etc. can be used.
上述したように、繊維ストランドは複数のゴム補強用繊維を集束させて形成されるが、表面に被膜が形成されているゴム補強用繊維を用いて繊維ストランドが形成されてもよいし、表面に被膜が設けられる前のゴム補強用繊維を用いて繊維ストランドが形成されて、その後に被膜が形成されてもよい。 As described above, the fiber strand is formed by converging a plurality of rubber reinforcing fibers. However, the fiber strand may be formed using a rubber reinforcing fiber having a coating formed on the surface, or on the surface. A fiber strand may be formed using the fiber for rubber reinforcement before a film is provided, and a film may be formed after that.
(被膜)
被膜は、処理剤をゴム補強用繊維の少なくとも表面の一部に塗布し、それを乾燥させる(処理剤中の溶媒を除去する)ことによって形成されている。(Coating)
The coating is formed by applying the treatment agent to at least a part of the surface of the rubber reinforcing fiber and drying it (removing the solvent in the treatment agent).
処理剤は水性であり、フェノール由来芳香族化合物−ホルムアルデヒド樹脂と、CSMラテックスとを混合することによって調製される。 The treating agent is aqueous and is prepared by mixing a phenol-derived aromatic compound-formaldehyde resin and CSM latex.
処理剤におけるフェノール由来芳香族化合物−ホルムアルデヒド樹脂の含有率は、固形分質量比で、1質量%以上が好ましく、3質量%以上がより好ましく、5質量%以上がさらに好ましい。また、処理剤におけるフェノール由来芳香族化合物−ホルムアルデヒド樹脂の含有率は、固形分質量比で、20質量%以下が好ましく、15質量%以下がより好ましく、10質量%以下がより好ましい。処理剤がフェノール由来芳香族化合物−ホルムアルデヒド樹脂を固形分質量比で1質量%以上含むことにより、繊維の保護層としての機能に優れた被膜を形成できる。一方、処理剤がフェノール由来芳香族化合物−ホルムアルデヒド樹脂を固形分質量比で20質量%以下含むことにより、形成される被膜の耐動的疲労性を向上させることができる。 The content ratio of the phenol-derived aromatic compound-formaldehyde resin in the treatment agent is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more in terms of solid content mass ratio. Moreover, the content rate of the phenol origin aromatic compound-formaldehyde resin in a processing agent is 20 mass% or less by solid content mass ratio, 15 mass% or less is more preferable, 10 mass% or less is more preferable. When the treatment agent contains 1% by mass or more of the phenol-derived aromatic compound-formaldehyde resin in a solid content mass ratio, it is possible to form a film having an excellent function as a fiber protective layer. On the other hand, when the treating agent contains a phenol-derived aromatic compound-formaldehyde resin in a solid content mass ratio of 20% by mass or less, the dynamic fatigue resistance of the formed film can be improved.
フェノール由来芳香族化合物−ホルムアルデヒド樹脂におけるフェノール由来芳香族化合物としては、例えば、モノ又は多価ヒドロキシフェノール、モノ又は多価クロロフェノールなどが挙げられる。フェノール由来芳香族化合物−ホルムアルデヒド樹脂の一例として、レゾルシノール−ホルムアルデヒド樹脂を挙げることができる。 Examples of the phenol-derived aromatic compound in the phenol-derived aromatic compound-formaldehyde resin include mono- or polyhydric hydroxyphenol, mono- or polyvalent chlorophenol, and the like. An example of a phenol-derived aromatic compound-formaldehyde resin is resorcinol-formaldehyde resin.
処理剤におけるCSMラテックスの含有率は、固形分質量比で、10質量%以上が好ましく、20質量%以上がより好ましく、30質量%以上がさらに好ましい。また、処理剤におけるCSMラテックスの含有率は、固形分質量比で、99質量%以下が好ましく、95質量%以下がより好ましく、90質量%以下がさらに好ましい。処理剤がCSMラテックスを固形分質量比で10質量%以上含むことにより、形成される被膜の耐熱特性を向上させることができる。 The content of the CSM latex in the treatment agent is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more in terms of solid content mass ratio. In addition, the content of the CSM latex in the treatment agent is preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less in terms of solid content. When the treatment agent contains CSM latex in a solid content mass ratio of 10% by mass or more, the heat resistance of the formed film can be improved.
CSMラテックスは、長期保存過程で加水分解反応してpH値の低下を引き起こす。このpH値の低下は、形成される被膜の耐酸性及び耐アルカリ性に大きな影響を及ぼす。そこで、本実施形態では、最終的に形成される被膜の耐酸性及び耐アルカリ性を向上させるために、処理剤の調製にpH値が2.0以上2.5未満の範囲内であるCSMラテックスが用いられる。pH値が2.0以上のCSMラテックスを用いることにより、形成される被膜の耐酸性が向上する。一方、pH値が2.5以上となると耐アルカリ性が低下し始める。CSMラテックスのpH値は、2.4以下が好ましい。CSMラテックスのpH値を上記範囲内に調整するために、アンモニアや水酸化ナトリウムなどの塩基をpH調整剤として添加してもよい。 CSM latex undergoes a hydrolysis reaction during a long-term storage process, causing a decrease in pH value. This decrease in pH value greatly affects the acid resistance and alkali resistance of the formed film. Therefore, in this embodiment, in order to improve the acid resistance and alkali resistance of the finally formed film, a CSM latex having a pH value in the range of 2.0 or more and less than 2.5 is used for preparing the treatment agent. Used. By using a CSM latex having a pH value of 2.0 or more, the acid resistance of the formed film is improved. On the other hand, when the pH value is 2.5 or more, the alkali resistance starts to decrease. The pH value of the CSM latex is preferably 2.4 or less. In order to adjust the pH value of the CSM latex within the above range, a base such as ammonia or sodium hydroxide may be added as a pH adjuster.
処理剤における塩素含有率が高すぎる場合、処理剤のpH調整が困難となり、その結果、形成される被膜の耐酸性及び耐アルカリ性を向上させることが困難になる。このような問題を生じさせないために、処理剤における塩素含有率は、形成される被膜における塩素含有率が1〜30質量%の範囲内となるように調整される必要がある。処理剤における塩素含有率を決定する要因には、CSMのポリマー上の塩素量と、CSMラテックスの長期保存過程で起こる加水分解反応に起因する遊離塩素とが含まれる。そこで、遊離塩素の増加も考慮した上で、用いるCSMのポリマー上の塩素量を決定し、形成される被膜における塩素含有率が1〜30質量%の範囲内となるようにする。なお、CSMではポリマー上の塩素量の変更が可能であるので、処理剤によって形成される被膜における塩素含有率が1〜30質量%の範囲内となるように、CSMのポリマー上の塩素量を変更するとよい。具体的には、被膜における塩素含有率が30質量%以下となるように、使用されるCSMラテックスのCSMポリマーのグレードを適宜選択して処理剤における塩素含有率を調整するとよい。被膜における塩素含有率は、2〜25質量%とすることが好ましい。なお、被膜における塩素含有率は、形成された被膜の塩素含有率をエネルギー分散型蛍光X線分析装置(EDX)を用いて測定することによって得られる。 When the chlorine content in the treating agent is too high, it becomes difficult to adjust the pH of the treating agent, and as a result, it becomes difficult to improve the acid resistance and alkali resistance of the formed film. In order not to cause such a problem, the chlorine content in the treatment agent needs to be adjusted so that the chlorine content in the formed film is in the range of 1 to 30% by mass. Factors that determine the chlorine content in the treating agent include the amount of chlorine on the polymer of the CSM and the free chlorine resulting from the hydrolysis reaction that occurs during the long term storage of the CSM latex. Therefore, in consideration of an increase in free chlorine, the amount of chlorine on the polymer of the CSM to be used is determined so that the chlorine content in the formed film is in the range of 1 to 30% by mass. In addition, since the amount of chlorine on the polymer can be changed in the CSM, the amount of chlorine on the polymer of the CSM is adjusted so that the chlorine content in the film formed by the treatment agent is in the range of 1 to 30% by mass. It is good to change. Specifically, the chlorine content in the treatment agent may be adjusted by appropriately selecting the CSM polymer grade of the CSM latex used so that the chlorine content in the coating is 30% by mass or less. The chlorine content in the coating is preferably 2 to 25% by mass. In addition, the chlorine content rate in a film is obtained by measuring the chlorine content rate of the formed film using an energy dispersive X-ray fluorescence analyzer (EDX).
処理剤は、被膜の接着力を高めたり安定性を改善したりするために、CSMラテックス以外のゴムラテックスなどをさらに含んでいてもよい。例えば、処理剤は、ブタジエンラテックス、ブタジエン−スチレン共重合体ラテックス、ジカルボキシル化ブタジエン−スチレン共重合体ラテックス、ビニルピリジン・ブタジエン・スチレン・ターポリマーラテックス、イソプレンゴムラテックス、アクリロニトリル−ブタジエン共重合体ラテックス、水素添加アクリロニトリル−ブタジエン共重合体ラテックス及びポリオレフィンエマルジョンからなる群より選ばれる少なくともいずれか1種を含んでいてもよい。処理剤に含まれるこれらのラテックス及び/又はエマルジョンの合計は、例えば5〜85質量%であり、好ましくは15〜80質量%である。 The treatment agent may further contain a rubber latex other than the CSM latex in order to increase the adhesion of the coating or improve the stability. For example, the treatment agent is butadiene latex, butadiene-styrene copolymer latex, dicarboxylated butadiene-styrene copolymer latex, vinylpyridine / butadiene / styrene / terpolymer latex, isoprene rubber latex, acrylonitrile-butadiene copolymer latex. In addition, at least one selected from the group consisting of a hydrogenated acrylonitrile-butadiene copolymer latex and a polyolefin emulsion may be included. The total of these latexes and / or emulsions contained in the treatment agent is, for example, 5 to 85% by mass, and preferably 15 to 80% by mass.
処理剤には、被膜の接着力を高めたり安定性を改善したりするために、充填材、可塑剤、老化防止剤、金属酸化物及び架橋助剤などが適宜加えられてもよい。例えば、処理剤は、イソシアネート及び熱硬化系樹脂などの添加材をさらに含んでいてもよい。 A filler, a plasticizer, an anti-aging agent, a metal oxide, a crosslinking aid, and the like may be appropriately added to the treatment agent in order to increase the adhesion of the film or improve the stability. For example, the treating agent may further contain additives such as isocyanate and thermosetting resin.
なお、処理剤の調製に用いられるCSMラテックスのpH値を2.0以上2.5未満の範囲内とすることは上述のとおりであるが、さらに調製された処理剤のpH値を調整してもよい。したがって、処理剤には、アンモニアや水酸化ナトリウムなどの塩基がpH調整剤としてさらに添加されてもよい。なお、処理剤のpH値は、例えば5.0〜12.0の範囲内に調整される。 In addition, although it is as above-mentioned that the pH value of CSM latex used for preparation of a processing agent shall be in the range of 2.0 or more and less than 2.5, adjusting the pH value of the prepared processing agent further Also good. Therefore, a base such as ammonia or sodium hydroxide may be further added to the treatment agent as a pH adjuster. In addition, the pH value of a processing agent is adjusted in the range of 5.0-12.0, for example.
被膜の厚さや、ゴム補強用コード全体に占める被膜の割合には特に限定はなく、ゴム補強用コードに要求される特性やゴム補強用繊維の種類などに応じて適宜決定することが可能である。例えば、ゴム補強用繊維とゴム製品のマトリックスゴムとの接着性及びゴム補強用繊維の耐ほつれ性をさらに向上させるためには、ゴム補強用コード全体に占める被膜の割合を5〜30質量%とすることが好ましく、7〜27質量%とすることがより好ましく、10〜25質量%とすることがさらに好ましい。 The thickness of the coating and the ratio of the coating to the entire rubber reinforcing cord are not particularly limited and can be appropriately determined according to the characteristics required for the rubber reinforcing cord, the type of rubber reinforcing fiber, and the like. . For example, in order to further improve the adhesion between the rubber reinforcing fiber and the matrix rubber of the rubber product and the fray resistance of the rubber reinforcing fiber, the ratio of the coating to the entire rubber reinforcing cord is 5 to 30% by mass. It is preferable to set it to 7 to 27% by mass, and more preferably 10 to 25% by mass.
なお、被膜は、ゴム補強用繊維の表面の少なくとも一部に設けられていればよいが、ゴム補強用繊維とマトリックスゴムとの接着性及びゴム補強用繊維の耐ほつれ性をさらに向上させるためには、ゴム補強用繊維の全体を覆うように設けられていることが好ましい。 The coating only needs to be provided on at least a part of the surface of the rubber reinforcing fiber, in order to further improve the adhesion between the rubber reinforcing fiber and the matrix rubber and the fray resistance of the rubber reinforcing fiber. Is preferably provided so as to cover the entire rubber reinforcing fiber.
必要に応じて、上記の被膜上にさらに別の被膜が設けられていてもよい。別の被膜は、マトリックスゴムの種類に応じて公知の被膜から適宜選択すればよいため、特には限定されない。例えば、CSM及び架橋剤を含む被膜などを用いることができる。 If necessary, another film may be provided on the above film. Another coating is not particularly limited because it may be appropriately selected from known coatings according to the type of matrix rubber. For example, a film containing CSM and a crosslinking agent can be used.
処理剤の塗布方法及び乾燥方法については特に限定はない。通常は、処理剤の入った浴槽中にゴム補強用繊維又はゴム補強用繊維を集束した繊維ストランドを浸漬した後、乾燥炉内で乾燥して溶媒を除去して被膜を形成する。 There is no particular limitation on the coating method and the drying method of the treatment agent. Usually, after a fiber reinforcing fiber or a fiber strand in which the rubber reinforcing fiber is bundled is immersed in a bath containing a treatment agent, the film is formed by drying in a drying furnace to remove the solvent.
被膜が形成された補強用繊維又は繊維ストランドを複数作製して、それらを撚り合わせてもよい。これにより、被膜を介して複数の補強用繊維を互いに密着させることができる。 A plurality of reinforcing fibers or fiber strands with a coating formed thereon may be produced and twisted together. Thereby, a plurality of reinforcing fibers can be adhered to each other through the coating.
上記被膜の上にさらに別の被膜を設ける場合は、次に、その被膜を形成するための工程を実施するとよい。 When another film is provided on the above film, a process for forming the film may be performed next.
[ゴム製品]
本実施形態のゴム製品について説明する。本実施形態のゴム製品は、マトリックスゴムと、マトリックスゴムに埋め込まれたゴム補強用コードとを含む。ゴム補強用コードには、上記の本実施形態のゴム補強用コードが用いられる。ゴム製品のマトリックスゴムにゴム補強用コードを埋設する手段は、特に限定されるものではなく、公知の手段を適用できる。本実施形態のゴム製品は、マトリックスゴムの特性に由来する高い耐熱性と、ゴム補強用コードを埋設することによる高い強度及び高い耐屈曲疲労性とを併せ備える。したがって、このゴム製品は、様々な用途に適用でき、車輌用エンジンのタイミングベルトなどの用途に特に適している。[Rubber product]
The rubber product of this embodiment will be described. The rubber product of this embodiment includes a matrix rubber and a rubber reinforcing cord embedded in the matrix rubber. As the rubber reinforcing cord, the rubber reinforcing cord of the present embodiment is used. The means for embedding the rubber reinforcing cord in the matrix rubber of the rubber product is not particularly limited, and known means can be applied. The rubber product of this embodiment has both high heat resistance derived from the characteristics of matrix rubber and high strength and high bending fatigue resistance by embedding a rubber reinforcing cord. Therefore, this rubber product can be applied to various uses, and is particularly suitable for uses such as a timing belt of a vehicle engine.
本実施形態のゴム製品は、例えば、まず本実施形態のゴム補強用コードを準備し、次にこのゴム補強用コードをゴムと架橋剤とを含むマトリックスゴムに埋め込み、そして、架橋剤の反応が充分に進行する条件で熱処理を行い、ゴム補強用コードの被膜のゴムとゴム製品のマトリックスゴムとを同時に架橋する。 The rubber product of this embodiment is prepared, for example, by first preparing the rubber reinforcing cord of this embodiment, and then embedding the rubber reinforcing cord in a matrix rubber containing rubber and a crosslinking agent, and the reaction of the crosslinking agent is performed. Heat treatment is performed under sufficiently proceeding conditions to simultaneously crosslink the rubber of the rubber reinforcing cord film and the matrix rubber of the rubber product.
以下、実施例及び比較例を挙げて、本発明の実施形態をさらに具体的に説明する。 Hereinafter, embodiments of the present invention will be described more specifically with reference to examples and comparative examples.
[実施例1〜10及び比較例1〜6]
<ゴム補強用コードの製造>
ガラスフィラメント(Eガラス組成、平均直径9μm)を200本集束したガラス繊維(ゴム補強用繊維)を用意した。このガラス繊維を3本引き揃えて、以下の表1及び2に示す処理剤を含浸させたのち、250℃で2分間熱処理を施して処理剤を乾燥させて、繊維ストランドを作製した。繊維ストランドでは、3本のガラス繊維の表面を覆うように被膜が形成されていた。3本のガラス繊維は、この被膜によって互いに接着されていた。なお、実施例6〜8、比較例3及び比較例4では、pH調整目的でCSMラテックスにアンモニアが添加された。表1及び2には、pH調整前後のCSMラテックスのpH値が示されている。また、実施例及び比較例においては、調製された処理剤にもpH調整剤が添加されて、処理剤のpH値が10.5に調整された。[Examples 1 to 10 and Comparative Examples 1 to 6]
<Manufacture of rubber reinforcing cord>
Glass fibers (rubber reinforcing fibers) in which 200 glass filaments (E glass composition, average diameter 9 μm) were bundled were prepared. Three glass fibers were drawn and impregnated with the treating agent shown in Tables 1 and 2 below, and then heat treated at 250 ° C. for 2 minutes to dry the treating agent, thereby producing fiber strands. In the fiber strand, a film was formed so as to cover the surfaces of the three glass fibers. The three glass fibers were bonded together by this coating. In Examples 6 to 8, Comparative Example 3 and Comparative Example 4, ammonia was added to the CSM latex for the purpose of pH adjustment. Tables 1 and 2 show the pH values of the CSM latex before and after pH adjustment. In Examples and Comparative Examples, a pH adjuster was also added to the prepared treatment agent, and the pH value of the treatment agent was adjusted to 10.5.
このようにして得られた繊維ストランドを、2.0回/25mmの割合でZ方向に下撚りした。そして、下撚りした繊維ストランドを11本引き揃え、2.0回/25mmの割合でS方向に上撚りした。このようにして得たゴム補強用コードにおける被膜の割合は、20質量%であった。 The fiber strand thus obtained was twisted in the Z direction at a rate of 2.0 times / 25 mm. Then, 11 strands of fiber strands that were twisted were aligned and twisted in the S direction at a rate of 2.0 times / 25 mm. The ratio of the coating film in the rubber reinforcing cord thus obtained was 20% by mass.
各実施例及び各比較例のゴム補強用コードについての評価項目及びその方法は、以下のとおりである。 The evaluation items and methods for the rubber reinforcing cords of the examples and comparative examples are as follows.
<被膜における塩素含有率>
ゴム補強用コードの表面から被膜の一部をカッターナイフで摘出し、EDX(日本電子株式会社製「JSM−IT100」)でその被膜の塩素含有率を分析した。<Chlorine content in coating>
A part of the film was extracted from the surface of the rubber reinforcing cord with a cutter knife, and the chlorine content of the film was analyzed by EDX (“JSM-IT100” manufactured by JEOL Ltd.).
<コードの耐酸性及び耐アルカリ性>
作製したゴム補強用コードを、酸性溶液又はアルカリ性溶液に2時間室温にて浸漬し、その後、引張強度を測定した。また、酸性溶液又はアルカリ性溶液に浸漬していないゴム補強用コードの引張強度も測定した。引張強度は、一定荷重速度式試験機(「オートグラフ」、島津製作所製)を用い、つかみ間隔250mm、荷重速度300mm/minにてゴム補強用コードを引っ張った際の破断強度(最大の引張荷重値)を測定することによって求めた。酸性溶液又はアルカリ性溶液に浸漬していないゴム補強用コードの引張強度に対する、酸性溶液又はアルカリ性溶液に浸漬したゴム補強用コードの引張強度の割合(強度維持率)を以下の式より求めて、耐酸性及び耐アルカリ性を評価した。酸性溶液にはHClの1N水溶液を用いた。アルカリ性溶液にはNaOHの1N水溶液を用いた。
強度維持率(%)={(酸性(又はアルカリ性)溶液に浸漬したコードの引張強度)/(酸性(又はアルカリ性)溶液に浸漬していないコードの引張強度)}×100<Acid resistance and alkali resistance of cord>
The produced rubber reinforcing cord was immersed in an acidic solution or an alkaline solution at room temperature for 2 hours, and then the tensile strength was measured. Moreover, the tensile strength of the rubber reinforcing cord not immersed in the acidic solution or alkaline solution was also measured. Tensile strength is the breaking strength (maximum tensile load) when a rubber reinforcing cord is pulled with a constant load rate type tester ("Autograph", manufactured by Shimadzu Corporation) at a gripping interval of 250 mm and a load rate of 300 mm / min. Value). The ratio (strength maintenance rate) of the tensile strength of the rubber reinforcing cord immersed in the acidic solution or alkaline solution to the tensile strength of the rubber reinforcing cord not immersed in the acidic solution or alkaline solution is obtained from the following formula, and the acid resistance And alkali resistance were evaluated. A 1N aqueous solution of HCl was used as the acidic solution. A 1N aqueous solution of NaOH was used as the alkaline solution.
Strength maintenance ratio (%) = {(Tensile strength of cord immersed in acidic (or alkaline) solution) / (Tensile strength of cord not immersed in acidic (or alkaline) solution)} × 100
表1に示されているように、処理剤の調製に用いられるCSMラテックスのpH値が2.0以上2.5未満の範囲内であり、かつ被膜における塩素含有率が1〜30質量%の範囲内である実施例のゴム補強用コードは、酸性溶液浸漬後の引張強度及びアルカリ性溶液浸漬後の引張強度の低下率が10%未満、すなわち強度維持率が90%以上であり、優れた耐酸性及び耐アルカリ性を有していた。一方、表2に示されているように、処理剤の調製に用いられるCSMラテックスのpH値が2.0以上2.5未満の範囲外である比較例のゴム補強用コードは、酸性溶液浸漬後の引張強度及びアルカリ性溶液浸漬後の引張強度の少なくともいずれか一方の強度維持率が90%未満であり、引張強度の低下が大きかった。 As shown in Table 1, the pH value of the CSM latex used for the preparation of the treatment agent is in the range of 2.0 or more and less than 2.5, and the chlorine content in the coating is 1 to 30% by mass. The rubber reinforcing cords of the examples within the range have a reduction rate of tensile strength after immersion in an acidic solution and a tensile strength after immersion in an alkaline solution of less than 10%, that is, a strength maintenance rate of 90% or more, and excellent acid resistance. And alkali resistance. On the other hand, as shown in Table 2, the rubber reinforcing cord of the comparative example in which the pH value of the CSM latex used for the preparation of the treatment agent is outside the range of 2.0 or more and less than 2.5 is immersed in an acidic solution. The strength maintenance rate of at least one of the subsequent tensile strength and the tensile strength after immersion in the alkaline solution was less than 90%, and the decrease in tensile strength was large.
本発明のゴム補強用コードは、耐酸性及び耐アルカリ性を有するので、強酸性下や強アルカリ性下等の過酷な環境で使用されるゴム製品を含む様々なゴム製品のゴム補強用コードとして適用できる。 Since the rubber reinforcing cord of the present invention has acid resistance and alkali resistance, it can be applied as a rubber reinforcing cord for various rubber products including rubber products used in harsh environments such as strongly acidic and strongly alkaline. .
Claims (15)
フェノール由来芳香族化合物−ホルムアルデヒド樹脂と、pH値が2.0以上2.5未満であるクロロスルフォン化ポリエチレンゴムラテックスとを混合して、前記フェノール由来芳香族化合物−ホルムアルデヒド樹脂と前記クロロスルフォン化ポリエチレンゴムラテックスとを含有する処理剤を調製する工程と、
前記処理剤をゴム補強用繊維の少なくとも表面の一部に塗布して乾燥させて、前記ゴム補強用繊維の少なくとも表面の一部に被膜が形成されたゴム補強用コードを得る工程と、
を含み、
前記被膜における塩素含有率が1〜30質量%である、
ゴム補強用コードの製造方法。 A method of manufacturing a rubber reinforcing cord for reinforcing a rubber product,
A phenol-derived aromatic compound-formaldehyde resin and a chlorosulfonated polyethylene rubber latex having a pH value of 2.0 or more and less than 2.5 are mixed, and the phenol-derived aromatic compound-formaldehyde resin and the chlorosulfonated polyethylene are mixed. Preparing a treatment agent containing rubber latex;
Applying the treatment agent to at least part of the surface of the rubber reinforcing fiber and drying to obtain a rubber reinforcing cord having a film formed on at least part of the surface of the rubber reinforcing fiber;
Including
The chlorine content in the coating is 1 to 30% by mass,
A method of manufacturing a rubber reinforcing cord.
請求項1に記載のゴム補強用コードの製造方法。 The pH value of the chlorosulfonated polyethylene rubber latex used for the preparation of the treatment agent is 2.0 to 2.4.
The manufacturing method of the cord for rubber reinforcement of Claim 1.
請求項1又は2に記載のゴム補強用コードの製造方法。 The chlorine content in the coating is 2 to 25% by mass,
The manufacturing method of the cord for rubber reinforcement of Claim 1 or 2.
請求項1〜3のいずれか1項に記載のゴム補強用コードの製造方法。 The content rate of the phenol-derived aromatic compound-formaldehyde resin in the treatment agent is 1 to 20% by mass in terms of solid content mass ratio,
The manufacturing method of the cord for rubber reinforcement of any one of Claims 1-3.
請求項1〜4のいずれか1項に記載のゴム補強用コードの製造方法。 The content of the chlorosulfonated polyethylene rubber latex in the treatment agent is 10 to 90% by mass in terms of solid content,
The manufacturing method of the cord for rubber reinforcement according to any one of claims 1 to 4.
請求項1〜5のいずれか1項に記載のゴム補強用コードの製造方法。 The treating agent is butadiene latex, butadiene-styrene copolymer latex, dicarboxylated butadiene-styrene copolymer latex, vinylpyridine / butadiene / styrene / terpolymer latex, isoprene rubber latex, acrylonitrile-butadiene copolymer latex, Further containing at least one selected from the group consisting of hydrogenated acrylonitrile-butadiene copolymer latex and polyolefin emulsion,
The manufacturing method of the cord for rubber reinforcement of any one of Claims 1-5.
請求項1〜6のいずれか1項に記載のゴム補強用コードの製造方法。 The phenol-derived aromatic compound is mono- or polyhydric hydroxyphenol,
The manufacturing method of the rubber | gum reinforcement cord of any one of Claims 1-6.
請求項1〜7のいずれか1項に記載のゴム補強用コードの製造方法。 The mass of the coating is 5 to 30% of the mass of the rubber reinforcing cord.
The manufacturing method of the cord for rubber reinforcement of any one of Claims 1-7.
請求項1〜8のいずれか1項に記載のゴム補強用コードの製造方法。 The rubber reinforcing fiber is at least one selected from the group consisting of glass fiber and carbon fiber,
The manufacturing method of the rubber | gum reinforcement cord of any one of Claims 1-8.
請求項9に記載のゴム補強用コードの製造方法。 The rubber reinforcing fiber is a glass fiber,
The manufacturing method of the cord for rubber reinforcement of Claim 9.
請求項9又は10に記載のゴム補強用コードの製造方法。 The glass fiber is a high-strength glass fiber,
The manufacturing method of the cord for rubber reinforcement of Claim 9 or 10.
ゴム補強用繊維と、前記ゴム補強用繊維の少なくとも表面の一部に形成された被膜とを含み、
前記被膜は、フェノール由来芳香族化合物−ホルムアルデヒド樹脂と、クロロスルフォン化ポリエチレンゴムラテックスとを含む処理剤を、前記ゴム補強用繊維に塗布して乾燥させることによって形成されており、
前記クロロスルフォン化ポリエチレンゴムラテックスのpH値が2.0以上2.5未満であり、
前記被膜における塩素含有率が1〜30質量%である、
ゴム補強用コード。 A rubber reinforcing cord for reinforcing a rubber product,
A rubber reinforcing fiber, and a coating formed on at least a part of the surface of the rubber reinforcing fiber,
The coating is formed by applying a treatment agent containing a phenol-derived aromatic compound-formaldehyde resin and a chlorosulfonated polyethylene rubber latex to the rubber reinforcing fibers and drying the coating agent,
The pH value of the chlorosulfonated polyethylene rubber latex is 2.0 or more and less than 2.5,
The chlorine content in the coating is 1 to 30% by mass,
Cord for rubber reinforcement.
請求項12に記載のゴム補強用コード。 The pH value of the chlorosulfonated polyethylene rubber latex of the treatment agent is 2.0 to 2.4.
The rubber reinforcing cord according to claim 12.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4632500B1 (en) * | 1967-08-10 | 1971-09-22 | ||
JPH0147511B2 (en) * | 1980-12-19 | 1989-10-13 | Seitetsu Kagaku Kogyo Kk | |
JPH06508652A (en) * | 1991-06-27 | 1994-09-29 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | Stabilized chlorinated resin latex |
JPH11158744A (en) * | 1997-11-26 | 1999-06-15 | Nippon Glass Fiber Co Ltd | Glass fiber cord for rubber-reinforcement and rubber belt |
WO2012141020A1 (en) * | 2011-04-11 | 2012-10-18 | 住友精化株式会社 | Chlorosulfonated polyethylene latex |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS4632500B1 (en) * | 1967-08-10 | 1971-09-22 | ||
JPH0147511B2 (en) * | 1980-12-19 | 1989-10-13 | Seitetsu Kagaku Kogyo Kk | |
JPH06508652A (en) * | 1991-06-27 | 1994-09-29 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | Stabilized chlorinated resin latex |
JPH11158744A (en) * | 1997-11-26 | 1999-06-15 | Nippon Glass Fiber Co Ltd | Glass fiber cord for rubber-reinforcement and rubber belt |
WO2012141020A1 (en) * | 2011-04-11 | 2012-10-18 | 住友精化株式会社 | Chlorosulfonated polyethylene latex |
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