WO2005085332A1 - 布帛と加硫ゴムの結合体及びその製造法 - Google Patents
布帛と加硫ゴムの結合体及びその製造法 Download PDFInfo
- Publication number
- WO2005085332A1 WO2005085332A1 PCT/JP2004/002788 JP2004002788W WO2005085332A1 WO 2005085332 A1 WO2005085332 A1 WO 2005085332A1 JP 2004002788 W JP2004002788 W JP 2004002788W WO 2005085332 A1 WO2005085332 A1 WO 2005085332A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fabric
- rubber
- fiber
- cloth
- weight
- Prior art date
Links
Classifications
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
- A43B13/16—Pieced soles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- 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
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
Definitions
- the present invention relates to a combination of a cloth and a vulcanized rubber and a method for producing the same, and more particularly, to a method for bonding rubber / rubber sponge / fiber.
- Patent Document 1 JP-A-54_4976
- Patent Document 2 Japanese Patent Application Laid-Open No. Hei 6-306201
- RFL mainly obtains a composite of rubber and fiber in the following three steps.
- the unvulcanized rubber is bonded to the fiber in the vulcanization step to obtain a composite.
- These vulcanization bonding conditions are generally press molding by heating and pressurizing.
- the vulcanization time to obtain rubber-fiber composites (molded products) such as rubber belts and hoses is as long as 20 to 30 minutes. This depends on the application and largely depends on the thickness of the product obtained (about 10 mm or more).
- the main purpose is to improve the reinforcing property and rigidity in order to make a composite (molded product) using the fiber itself as a rubber reinforcing material.
- the conventional technology found in general tires, belts, hoses, etc.
- An object of the present invention is to provide a combination of a fabric and a vulcanized rubber which does not require high-temperature treatment, does not cause a decrease in fiber strength, and has high energy efficiency, and a method for producing the same.
- An object of the present invention is to provide a combination of a cloth and a vulcanized rubber, which can complete vulcanization in a short time and has a high productivity and a required adhesive strength, and a method for producing the same.
- An object of the present invention is to provide a composite of a fabric and a vulcanized rubber, which does not discolor rubber / rubber sponge / fiber because it does not use formaldehyde, and which can be made strong, and a method for producing the same. Disclosure of the invention
- the present invention relates to the following inventions. 1. Impregnate the fabric with an isocyanate compound, dry it, then impregnate it with an adhesive containing a styrene-based polymer, dry it, place the unvulcanized rubber on the resulting fabric, and press it by hot pressing. A combined fabric and vulcanized rubber obtained by vulcanizing a vulcanized rubber and simultaneously adhering it to a fabric.
- Impregnating and drying the fabric with an isocyanate compound impregnating the obtained fabric with an adhesive containing a styrene-based polymer, and drying. Placing unvulcanized rubber on the obtained fabric and heating and pressing. And vulcanizing the unvulcanized rubber and simultaneously adhering the unvulcanized rubber to a fabric. 3. A method for producing a combined body of the above-mentioned cloth and vulcanized rubber, wherein the cloth is pre-treated with a solvent before the step of impregnating and drying the cloth with an isocyanate compound.
- the bonded body of fabric and vulcanized rubber and the fabric treatment method of the present invention are fundamentally different from the prior art, and are an invention relating to a completely new rubber / rubber sponge Z fiber bonding method.
- synthetic fibers such as polyester fiber, polyamide fiber, acrylic fiber, polypropylene fiber, acetate fiber, glass fiber, carbon fiber, aramide fiber, and polyimide fiber; natural fibers such as cotton, silk, and hemp;
- woven fabrics, nonwoven fabrics, knitted fabrics obtained from other fibers, and fabrics obtained by raising the surface thereof on the other hand can be exemplified.
- These fabrics are preferably pre-treated with a solvent before impregnation with the isocyanate compound.
- a solvent examples include toluene, ethyl acetate, methyl ethyl ketone, acetone and the like.
- the isocyanate compound is not particularly limited as long as it has an isocyanate group.
- examples thereof include phenylene diisocyanate, 1, reylene diisocyanate (TDI), xylylene diisocyanate (XDI), and triphenyl.
- Polyisocyanates such as methane triisocyanate (TTI), diphenyl methane diisocyanate (MDI), 1, squirrel (phenyl isocyanate), and hexamethylene diisocyanate Compounds can be exemplified.
- the solid content of the isocyanate solution is preferably 0.5 to 4.2% by weight, particularly preferably 1 to 3.5% by weight.
- the isocyanate compound After impregnating with the isocyanate compound, it is dried at about 40 to 100 ° (preferably at about 60 to 80 ° C), and then impregnated with an adhesive containing a styrene-based polymer and dried.
- styrene polymer examples include styrene butene rubber (SBR) and styrene butadiene thermoplastic elastomer (SBS).
- SBR styrene butene rubber
- SBS styrene butadiene thermoplastic elastomer
- the adhesive of the present invention can contain, for example, natural rubber, acrylonitrile butadiene rubber, and the like in addition to the styrene-based polymer.
- the adhesive of the present invention may further include a vulcanization accelerator, a plasticizer, an activator, a reinforcing material such as zinc white, sulfur, and white carbon.
- the styrene content in the solid content of the adhesive of the present invention is preferably 2 to 47% by weight, particularly preferably 5 to 40% by weight.
- the impregnating ratio of the adhesive to the fabric is preferably 30% by weight or more, and more preferably 40 to 100% by weight, based on the weight of the fabric.
- Examples of the method of impregnating the adhesive include, but are not limited to, a method of impregnating the cloth by immersing the cloth in a solution of the adhesive. After impregnating the adhesive, it is dried at about 40 to 100 ° C, preferably at about 60 to 80 ° C.
- the unvulcanized rubber is placed on the fabric obtained by impregnating the adhesive containing the isocyanate compound and the styrene-based polymer (closely adhered), and then heated and pressed to vulcanize the unvulcanized rubber. At the same time, it is bonded to the fabric to obtain a combined body of the fabric and the vulcanized rubber.
- the heating press is performed at about 140 to 180 ° (:, preferably, at about 150 to 16 O.
- the heating press time is usually preferably about 3 to 10 minutes.
- Unvulcanized rubber Examples of the rubber component include natural rubber, isoprene rubber, styrene rubber, acrylonitrile butadiene rubber, butadiene rubber, chloroprene rubber, and butyl rubber.
- the combination of the fabric and the vulcanized rubber obtained by the present invention is extremely excellent in lightness and flexibility. In addition, it is hard to be worn down and has excellent durability (wear resistance).
- the composite of the fabric and the vulcanized rubber of the present invention can be used, for example, for part or all of the sole of a shoe, and is preferably used as a sole having grip properties, more preferably as a sole having excellent grip properties. it can.
- gloves such as gloves, soccer gloves, one-point marks on clothes, one-off sapo, valet net CD support, fiber reinforced rubber (Fiber Reinforced Rub be: r), various equipment It can be used for tapes such as non-slip of the drip part, as well as floor materials.
- FIG. 1 is a schematic diagram of the measurement of the tear peel strength of a fabric and rubber, and a graph showing the load and displacement in a tear test.
- FIG. 2 is a graph showing the relationship between the amount of styrene in the adhesive and the tear peel strength.
- FIG. 3 is a graph showing a relationship between an impregnation ratio of an adhesive into a fabric and a tear peel strength.
- FIG. 4 is a graph showing the relationship between the solid content of the isocyanate solution and the tear strength.
- FIG. 5 is a graph showing tensile strength, elongation, and tear strength of the fabric after each of the treatment of the present invention and the RFL treatment in comparison with the strength of an untreated fabric.
- FIG. 6 is a schematic view showing a pattern in which a combined body of a fabric and vulcanized rubber is formed on a part of a shoe J using the method of the present invention.
- Sumitomo Bayer Urethane composed of 27% by weight of tris (phenylisocyanate) thiophene phosphate, 71% by weight of ethyl acetate, and 2% by weight of benzene with monochromatic mouth
- Desmodule RFE manufactured by Co., Ltd. is diluted 1:10 with toluene and isocyanate -An isocyanate solution having a content of 2.45% by weight of the compound was prepared.
- An adhesive consisting of natural rubber and styrene butadiene rubber (SBR) with a styrene content of 23.5% by weight and having the composition shown in Table 1 was diluted with toluene at a ratio of 5:95 to prepare an adhesive solution (1). did.
- the content of styrene based on the total solid content of the adhesive was 4.7% by weight.
- Unvulcanized rubber having the composition shown in Table 2 was prepared by rolling, and a 4.5 mm thick unvulcanized rubber sheet was prepared.
- a woven cloth (surface raised 50 cm x 25 cm) obtained from polyester fiber is immersed in a toluene solution for 1 minute, taken out, left at 70 ° C for 25 minutes, dried, and then added to the isocyanate solution of Reference Example 1 for 3 minutes. After immersion for 3 minutes, the product was dried at 70 ° C. for 30 minutes, then immersed in the adhesive solution of Reference Example 3 for 3 minutes, taken out, and dried at 70 ° C. for 30 minutes. The impregnation ratio of the adhesive to the fabric was 45% by weight based on the weight of the fabric.
- the unvulcanized rubber sheet of Reference Example 3 was placed on the obtained fabric, and heated and pressed at 155 ° C for 5 minutes to vulcanize the unvulcanized rubber and simultaneously adhere to the fabric to vulcanize the fabric. A rubber conjugate was obtained.
- the tear peel strength between the rubber and the fabric of the obtained composite was measured by the following method. As a result, a tearing-off strength of 5.4 kgf ⁇ cm was obtained. Table 3 shows the results. Measuring method
- Tensile testing machine STROGRAPH VI-B manufactured by Toyo Seiki Seisaku-sho, Ltd.
- SBR Styrene butadiene rubber
- Table 3 and FIG. 2 show the results of measuring the tear-peeling strength between the rubber and the fabric of the obtained composite in the same manner as in Example 1. [Table 3]
- Example 2 When preparing the adhesive solution of Reference Example 2, the ratio of toluene was changed so that the impregnation ratio of the adhesive into the fabric was 20% by weight (Comparative Example 2), 35% by weight, 80% by weight, and 130% by weight. A combined body of the cloth and the vulcanized rubber was obtained in the same manner as in Example 1 except that (Examples 6 to 8) were used.
- FIG. 3 shows the result of measuring the tear-peeling strength between the rubber and the fabric of the obtained combined body in the same manner as in Example 1.
- Example 1 When preparing the isocyanate solution of Reference Example 1, the concentration of the solids in the isocyanate solution was changed to 1.2%, 2.0%, 2.5%, and 3.7% by weight by changing the ratio of toluene. Examples 9 to 12), 0% by weight, and 4.5% by weight (Comparative Examples 3 to 4) were performed in the same manner as in Example 1 to obtain a conjugate of a cloth and a vulcanized rubber.
- FIG. 4 shows the results of measuring the tear-peeling strength between the rubber and the fabric of the obtained combined body in the same manner as in Example 1.
- a bonded body of a vulcanized rubber and a fabric was obtained in the same manner as in Example 1 except that the fabric was immersed in an isocyanate solution and dried without using an adhesive in Example 1.
- the tear strength between the rubber and the fabric of the obtained conjugate was 1.6 kgf ⁇ cm.
- the cloth was impregnated with the adhesive at a ratio of 30% by weight based on the weight of the cloth, and the uncured rubber and the cloth were heated and pressed at 160 ° C for 6 minutes, except that the cloth was heated in the same manner as in Example 1. And a composite of vulcanized rubber.
- the tear strength between the rubber and the fabric of the obtained composite was 6.5 kgf ⁇ cm.
- the color of the fabric was improved to a light gray color rather than the original dark gray color.
- the fibers were washed and treated with the isocyanate compound in the same manner as in Example 1, heat-treated at 250 ° C for 1 minute, and then treated with a mixed solution (RFL) of the initial compound of resorcinol-formaldehyde and rubber latex (250 ° C).
- CX was heat-treated for 1 minute, and the unvulcanized rubber and the fabric were hot-pressed at 160 ° C. for 6 minutes to obtain a combined fabric and vulcanized rubber.
- the tear strength between the rubber and the fabric of the obtained bonded article was 2.7 kgf ⁇ cm. Further, the color of the fabric was changed from the original dark gray color to brown.
- Fig. 5 shows the tensile strength, elongation, and tear strength of the fiber after the treatments (1) and (2), together with the strength of the untreated fiber.
- Tensile strength, elongation, and tear strength were measured according to JIS L1018, respectively.
- Test example 2 A vulcanized rubber was placed in a pattern on the polyester cloth impregnated with the adhesive of Example 3 as shown in FIG. 6 (c), and a combined body of the cloth and the vulcanized rubber was obtained in the same manner as in Example 1. .
- the perimeter is cut into the desired shape using a punching die as shown in Fig. 6 (d), and glued to the forefoot of the shoe tool shown in Fig. 6 (b) with a urethane adhesive. (a) was obtained.
- the method of the present invention does not require high-temperature treatment, does not cause a decrease in fiber strength, and can provide a combination of a vulcanized rubber and a fabric with high energy efficiency. Further, in the present invention, vulcanization is completed in a short time, the productivity is high, and a bonded body of a cloth and a vulcanized rubber having a necessary adhesive strength can be obtained.
- a rubber / rubber sponge sponge / fiber has no discoloration, and it is possible to obtain a composite of a fabric and a vulcanized rubber which can be made strong.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006510581A JP4351700B2 (ja) | 2004-03-05 | 2004-03-05 | 布帛と加硫ゴムの結合体及びその製造法 |
PCT/JP2004/002788 WO2005085332A1 (ja) | 2004-03-05 | 2004-03-05 | 布帛と加硫ゴムの結合体及びその製造法 |
CN2004800422351A CN101001903B (zh) | 2004-03-05 | 2004-03-05 | 布帛和硫化橡胶的复合物及其制造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2004/002788 WO2005085332A1 (ja) | 2004-03-05 | 2004-03-05 | 布帛と加硫ゴムの結合体及びその製造法 |
Publications (1)
Publication Number | Publication Date |
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WO2005085332A1 true WO2005085332A1 (ja) | 2005-09-15 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2004/002788 WO2005085332A1 (ja) | 2004-03-05 | 2004-03-05 | 布帛と加硫ゴムの結合体及びその製造法 |
Country Status (3)
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JP (1) | JP4351700B2 (ja) |
CN (1) | CN101001903B (ja) |
WO (1) | WO2005085332A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008514467A (ja) * | 2004-09-30 | 2008-05-08 | アンセル・ヘルスケア・プロダクツ・エルエルシー | ライナーにより接着支持されたポリマーシェルおよび製造方法 |
JP2015504802A (ja) * | 2011-12-16 | 2015-02-16 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | 含浸フェルトを含むトレッドを有するタイヤ |
WO2015025398A1 (ja) * | 2013-08-22 | 2015-02-26 | 株式会社アシックス | 物品の製造システム、物品の製造方法およびパレット |
US9962996B2 (en) | 2011-12-16 | 2018-05-08 | Compagnie Generale Des Etablissements Michelin | Tread comprising tread pattern elements covered with an impregnated fibre assembly |
CN109762215A (zh) * | 2019-01-17 | 2019-05-17 | 北京化工大学 | 高性能聚酰亚胺长纤维增强橡胶复合材料及其制备方法 |
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CN102133806A (zh) * | 2010-01-27 | 2011-07-27 | 翰林国际工艺有限公司 | 鞋底回收加工方法及该方法制成的复合材料 |
DE102012207300B4 (de) * | 2012-05-02 | 2019-10-24 | Adidas Ag | Verfahren zur Herstellung eines Schafts für einen Schuh und danach hergestellter Schaft und Schuh |
CN102742983B (zh) * | 2012-07-19 | 2016-01-06 | 力其国际有限公司 | 橡胶层面模压制品的制作方法 |
CN105747365B (zh) * | 2016-04-22 | 2018-07-20 | 福建登泰科技有限公司 | 一种无需修边打粗可一体成型的鞋底及其制作工艺 |
CN106585053A (zh) * | 2016-12-01 | 2017-04-26 | 天津鼎兴橡塑有限公司 | 一种橡胶跑道卷材的生产工艺 |
KR101913554B1 (ko) | 2017-09-14 | 2018-10-31 | 손미숙 | 고무 조성물, 이를 이용한 필름 및 이 필름의 제조방법 |
CN109503960B (zh) * | 2018-12-07 | 2021-07-06 | 江苏先诺新材料科技有限公司 | 一种聚酰亚胺纤维增强橡胶复合材料及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5413590A (en) * | 1977-07-01 | 1979-02-01 | Asahi Chem Ind Co Ltd | Improvement in adhesiveness of synthetic fiber material for reinforcing elastomers |
JPH08113657A (ja) * | 1994-10-17 | 1996-05-07 | Bando Chem Ind Ltd | 繊維材料とゴム組成物との接着方法 |
WO1999003907A1 (en) * | 1997-07-18 | 1999-01-28 | Minnesota Mining And Manufacturing Company | Primer composition and bonding of organic polymeric substrates |
WO2001014461A1 (en) * | 1999-08-23 | 2001-03-01 | Teijin Limited | Process for producing an adhesive-treated polyester fiber cord |
-
2004
- 2004-03-05 JP JP2006510581A patent/JP4351700B2/ja not_active Expired - Lifetime
- 2004-03-05 CN CN2004800422351A patent/CN101001903B/zh not_active Expired - Fee Related
- 2004-03-05 WO PCT/JP2004/002788 patent/WO2005085332A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5413590A (en) * | 1977-07-01 | 1979-02-01 | Asahi Chem Ind Co Ltd | Improvement in adhesiveness of synthetic fiber material for reinforcing elastomers |
JPH08113657A (ja) * | 1994-10-17 | 1996-05-07 | Bando Chem Ind Ltd | 繊維材料とゴム組成物との接着方法 |
WO1999003907A1 (en) * | 1997-07-18 | 1999-01-28 | Minnesota Mining And Manufacturing Company | Primer composition and bonding of organic polymeric substrates |
WO2001014461A1 (en) * | 1999-08-23 | 2001-03-01 | Teijin Limited | Process for producing an adhesive-treated polyester fiber cord |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008514467A (ja) * | 2004-09-30 | 2008-05-08 | アンセル・ヘルスケア・プロダクツ・エルエルシー | ライナーにより接着支持されたポリマーシェルおよび製造方法 |
JP2015504802A (ja) * | 2011-12-16 | 2015-02-16 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | 含浸フェルトを含むトレッドを有するタイヤ |
US9962996B2 (en) | 2011-12-16 | 2018-05-08 | Compagnie Generale Des Etablissements Michelin | Tread comprising tread pattern elements covered with an impregnated fibre assembly |
WO2015025398A1 (ja) * | 2013-08-22 | 2015-02-26 | 株式会社アシックス | 物品の製造システム、物品の製造方法およびパレット |
JPWO2015025398A1 (ja) * | 2013-08-22 | 2017-03-02 | 株式会社アシックス | 物品の製造システム、物品の製造方法およびパレット |
CN109762215A (zh) * | 2019-01-17 | 2019-05-17 | 北京化工大学 | 高性能聚酰亚胺长纤维增强橡胶复合材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP4351700B2 (ja) | 2009-10-28 |
CN101001903B (zh) | 2010-07-21 |
JPWO2005085332A1 (ja) | 2008-01-17 |
CN101001903A (zh) | 2007-07-18 |
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