JPH0778207B2 - Adhesive composition with rubber fibers - Google Patents
Adhesive composition with rubber fibersInfo
- Publication number
- JPH0778207B2 JPH0778207B2 JP63258069A JP25806988A JPH0778207B2 JP H0778207 B2 JPH0778207 B2 JP H0778207B2 JP 63258069 A JP63258069 A JP 63258069A JP 25806988 A JP25806988 A JP 25806988A JP H0778207 B2 JPH0778207 B2 JP H0778207B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- rubber
- monomer
- adhesive composition
- 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.)
- Expired - Fee Related
Links
- 239000000853 adhesive Substances 0.000 title claims description 32
- 230000001070 adhesive effect Effects 0.000 title claims description 32
- 229920001971 elastomer Polymers 0.000 title claims description 13
- 239000000203 mixture Substances 0.000 title claims description 13
- 239000000835 fiber Substances 0.000 title description 15
- 239000000178 monomer Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 description 20
- 239000004816 latex Substances 0.000 description 19
- 229920000126 latex Polymers 0.000 description 19
- 229920000728 polyester Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- -1 isocyanate compound Chemical class 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- KYPOHTVBFVELTG-UPHRSURJSA-N (z)-but-2-enedinitrile Chemical compound N#C\C=C/C#N KYPOHTVBFVELTG-UPHRSURJSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical compound C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 description 1
- IFSCTBJNLAYMCD-UHFFFAOYSA-N 4-[[3-chloro-5-[(2,4-dihydroxyphenyl)methylidene]-6-hydroxycyclohex-3-en-1-ylidene]methyl]benzene-1,3-diol Chemical compound OC1C(=CC=2C(=CC(O)=CC=2)O)CC(Cl)=CC1=CC1=CC=C(O)C=C1O IFSCTBJNLAYMCD-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011297 pine tar Substances 0.000 description 1
- 229940068124 pine tar Drugs 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
- Tyre Moulding (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、ゴムと繊維との接着剤組成物に関するもので
ある。さらに詳しくは、タイヤ、ベルト、ホース等のゴ
ム製品に含まれる補強用ポリエステル繊維とゴムとの接
着に適した改良された接着剤組成物に関するものであ
る。TECHNICAL FIELD The present invention relates to an adhesive composition of rubber and fiber. More specifically, it relates to an improved adhesive composition suitable for adhering rubber and reinforcing polyester fibers contained in rubber products such as tires, belts and hoses.
（従来の技術及び発明が解決しようとする問題点） ポリエステル繊維は、ナイロン繊維と比較して伸びが少
なく寸法安定性に優れているため、ラジアルタイヤのカ
ーカス用コード等の用途を中心にゴム補強用繊維として
広く用いられているが、耐熱性が劣るため、高温加硫後
や高温覆歴後の繊維／ゴム間の接着力（耐熱接着力）の
低下が激しく、また通常加硫後の繊維／ゴム間の接着力
（初期接着力）も低く、これらの改良が強く望まれてい
る。(Problems to be solved by conventional techniques and inventions) Polyester fiber has less elongation and excellent dimensional stability compared to nylon fiber, so rubber reinforcement is mainly used for carcass cords of radial tires. It is widely used as a fiber for applications, but because of its poor heat resistance, the adhesive strength (heat resistant adhesive strength) between the fiber and rubber after high-temperature vulcanization or after high-temperature vulcanization is severely reduced, and the fiber after normal vulcanization The adhesive strength between rubber / rubber (initial adhesive strength) is also low, and improvement of these is strongly desired.
従来から用いられているゴム補強用のナイロン繊維やレ
ーヨン繊維は、ポリエステル繊維に比べゴムとの接着に
活性であるため、ブタジエン−スチレン−ビニルピリジ
ン共重合体ラテックス単独またはそれとブタジエン−ス
チレン−共重合体ラテックスとの混合物、及びレゾルシ
ン−ホルマリン樹脂（RFレジン）からなる接着剤組成物
（RFL）を用いて接着処理するだけで、十分な初期接着
力、耐熱接着力が得られていた。Conventionally used rubber-reinforcing nylon fibers and rayon fibers are more active in adhering to rubber than polyester fibers.Therefore, butadiene-styrene-vinylpyridine copolymer latex alone or butadiene-styrene-copolymer latex is used. Sufficient initial adhesive strength and heat resistant adhesive strength were obtained only by performing an adhesive treatment using a mixture with the combined latex and an adhesive composition (RFL) composed of a resorcin-formalin resin (RF resin).
ポリエステル繊維用のRFLにも、ブタジエン−スチレン
−ビニルピリジン共重合体ラテックス単独またはそれと
ブタジエン−スチレン共重合体ラテックスとの混合物が
使用されているが、ナイロン、レーヨン繊維用のRFLだ
けによる処理では実用的な接着力が得られず、あらかじ
めポリエステル繊維をエポキシ樹脂やイソシアネート化
合物で前処理した後RFLで処理したり、RFLにバルカボン
ドＥ（ICI Vulnax 社製）等の接着剤を添加した接着処
理液を用いる等して実用に供されている。For RFL for polyester fiber, butadiene-styrene-vinylpyridine copolymer latex alone or a mixture of it and butadiene-styrene copolymer latex is used, but it is practically used only with RFL for nylon and rayon fibers. Adhesive strength is not obtained, and polyester fiber is pre-treated with epoxy resin or isocyanate compound in advance and then treated with RFL, or an adhesive treatment liquid in which an adhesive such as VALCABOND E (manufactured by ICI Vulnax) is added to RFL is used. It has been put to practical use by using it.
一方、RFLに使用するラテックスの面でも改良がなされ
ており、例えば、特開昭61−26629号及び特開昭61−266
30号公報にみられる様にカルボン酸もしくはエステルに
て変性されたビニルピリジン系共重合体ラテックスを用
いることが提案されている。しかしながら、ポリエステ
ル繊維の場合、RFL浸漬後のコード強力の低下が著るし
く、また耐熱接着力にも劣り、高い耐熱性が要求される
用途での使用においては問題があるのが実情である。On the other hand, improvements have also been made in the latex used for RFL, for example, JP-A-61-26629 and JP-A-61-266.
It has been proposed to use a vinylpyridine-based copolymer latex modified with a carboxylic acid or an ester as seen in JP-A-30. However, in the case of polyester fiber, the strength of the cord after dipping in RFL is remarkably lowered, and the heat resistant adhesive strength is also poor, so that there is a problem in use in applications requiring high heat resistance.
（問題点を解決するための手段） 本発明者等は、ポリエステル繊維が有する上記の問題を
解決するために鋭意検討を重ねた結果、本発明を完成す
るに至った。(Means for Solving the Problems) The present inventors have completed the present invention as a result of intensive studies for solving the above-mentioned problems of the polyester fiber.
すなわち、本発明は、 共役ジエン系単量体40〜80重量％、シアン化ビニル系単
量体２〜30重量％、ビニルピリジン５〜35重量％、不飽
和酸単量体0.5〜10重量％および芳香族ビニル系単量体
０〜52.5重量％からなる共重合体ラテックスとレソルジ
ン−ホルマリン樹脂を含むことを特徴とするゴムと繊維
との接着剤組成物を提供するものである。That is, the present invention is a conjugated diene monomer 40 to 80% by weight, vinyl cyanide monomer 2 to 30% by weight, vinylpyridine 5 to 35% by weight, unsaturated acid monomer 0.5 to 10% by weight. And a rubber-fiber adhesive composition comprising a copolymer latex comprising 0 to 52.5% by weight of an aromatic vinyl monomer and a resordin-formalin resin.
以下に本発明について詳しく説明する。The present invention will be described in detail below.
本発明の共重合体ラテックスに使用される共役ジエン系
単量体としては例えば、1,3−ブタジエン、２−メチル
−1,3−ブタジエン、2,3−ジメチル−1,3−ブタジエン
等があげられ、これらを１種もしくは２種以上使用する
ことができる。Examples of the conjugated diene-based monomer used in the copolymer latex of the present invention include 1,3-butadiene, 2-methyl-1,3-butadiene, and 2,3-dimethyl-1,3-butadiene. These may be used alone or in combination of two or more.
共役ジエン系単量体が、40重量％未満では初期接着力が
低下し、80重量％を越えると耐熱接着力が低下する。望
ましくは45〜75重量％である。If the content of the conjugated diene-based monomer is less than 40% by weight, the initial adhesive force will decrease, and if it exceeds 80% by weight, the heat resistant adhesive force will decrease. It is preferably 45 to 75% by weight.
本発明の共重合体ラテックスに使用されるシアン化ビニ
ル系単量体としてはアクリロニトリル、メタクリロニト
リル、フマロニトリル、マレオニトリル等があげられ、
これらを１種もしくは２種以上使用することができる。
シアン化ビニル系単量体が２重量％未満では耐熱接着力
が低下し、30重量％を越えると初期接着力が低下する。
望ましくは３〜15重量％である。Examples of the vinyl cyanide-based monomer used in the copolymer latex of the present invention include acrylonitrile, methacrylonitrile, fumaronitrile, and maleonitrile.
These may be used alone or in combination of two or more.
If the amount of the vinyl cyanide-based monomer is less than 2% by weight, the heat-resistant adhesive strength will decrease, and if it exceeds 30% by weight, the initial adhesive strength will decrease.
It is preferably 3 to 15% by weight.
本発明の共重合体ラテックスに使用されるビニルピリジ
ンとしては、２−ビニルピリジン、３−ビニルピリジ
ン、４−ビニルピリジン、２−メチル−５−ビニルピリ
ジン等があげられ、これらを１種もしくは２種以上使用
することができる。これらの中で２−ビニルピリジンを
使用することが望ましい。ビニルピリジンが５重量％未
満では初期および耐熱接着力共に低下し、35重量％を越
えると初期接着力が低下する。望ましくは、10〜30重量
％である。Examples of the vinyl pyridine used in the copolymer latex of the present invention include 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, 2-methyl-5-vinyl pyridine, etc., and one or two of them may be used. More than one species can be used. Of these, it is desirable to use 2-vinylpyridine. If the amount of vinyl pyridine is less than 5% by weight, both the initial and heat-resistant adhesive strength will decrease, and if it exceeds 35% by weight, the initial adhesive strength will decrease. Desirably, it is 10 to 30% by weight.
本発明の共重合体ラテックスに使用することのできる不
飽和酸単量体としては、フマル酸、アクリル酸、イタコ
ン酸、メタクリル酸等があげられ、１種もしくは２種以
上使用することができる。不飽和酸単量体が0.5重量％
未満では耐熱接着力が低下し、10重量％を越えると初期
接着力が低下する。望ましくは１〜７重量％である。Examples of the unsaturated acid monomer that can be used in the copolymer latex of the present invention include fumaric acid, acrylic acid, itaconic acid, methacrylic acid and the like, and one or more kinds can be used. 0.5% by weight of unsaturated acid monomer
If it is less than 10% by weight, the heat-resistant adhesive strength is lowered, and if it exceeds 10% by weight, the initial adhesive strength is lowered. It is preferably 1 to 7% by weight.
本発明の共重合体ラテックスに使用することのできる芳
香族ビニル系単量体としては、スチレン、α−メチルス
チレン、モノクロロスチレン等が挙げられ、１種もしく
は２種以上使用することができる。芳香族ビニル系単量
体は０〜52.5重量％にて使用されるが、望ましくは０〜
41重量％である。Examples of the aromatic vinyl-based monomer that can be used in the copolymer latex of the present invention include styrene, α-methylstyrene, monochlorostyrene and the like, and one or more kinds can be used. The aromatic vinyl monomer is used in an amount of 0 to 52.5% by weight, preferably 0 to 52.5% by weight.
41% by weight.
また、本発明の共重合体ラテックスにおける重量平均粒
子径は、耐熱接着力の面で70〜140nmであることが好ま
しい。The weight average particle size of the copolymer latex of the present invention is preferably 70 to 140 nm in terms of heat resistant adhesive strength.
本発明の共重合体ラテックスは、公知の方法により製造
される。すなわち、一括添加方法、分割添加方法、連続
添加方法、二段重合方法、パワーフィード方法などが適
用できる。The copolymer latex of the present invention is produced by a known method. That is, a batch addition method, a divided addition method, a continuous addition method, a two-step polymerization method, a power feed method, etc. can be applied.
本発明におけるレゾルシン−ホルマリン樹脂は、従来公
知のものが使用できる。As the resorcin-formalin resin in the present invention, conventionally known resins can be used.
また、該レゾルシン−ホルマリン樹脂（固形分）の使用
量は、通常、共重合体ラテックス（固形分）100重量部
当り、８〜30重量部である。The amount of the resorcin-formalin resin (solid content) used is usually 8 to 30 parts by weight per 100 parts by weight of the copolymer latex (solid content).
本発明の接着剤組成物には、イソシアネート、ブロック
ドイソシアネート、エチレン尿素、ポリエポキシド、変
性ポリ塩化ビニルなどを適宜配合することができる。Isocyanate, blocked isocyanate, ethylene urea, polyepoxide, modified polyvinyl chloride and the like can be appropriately blended in the adhesive composition of the present invention.
以下に、実施例をあげて本発明を具体的に説明するが、
本発明はこれら実施例によって何ら制限されるものでは
ない。なお、実施例中の部および％は断りのない限り全
て重量部および重量％を意味する。Hereinafter, the present invention will be specifically described with reference to examples.
The present invention is in no way limited by these examples. All parts and% in the examples mean parts by weight and% by weight, unless otherwise specified.
〈共重合体ラテックスＡ〜ＤおよびＦ〜Ｌの製造〉 攪拌機付きオートクレーブに、水150部、ポリオキシエ
チレンラウリルエーテル５部、エチレンジアミン四酢酸
ナトリウム0.05部、tert−ドデシルメルカプタン0.5部
および過硫酸カリウム0.3部、ならびに表−１に示した
単量体混合物100部を仕込み、全体を50℃に保ち重合を
行う。重合転化率が50％に達した時点で、tert−ドデシ
ルメルカプタン0.5部を添加する。更に、重合転化率が9
5％に達したならば、ハロドロキノン0.05部を添加し、
重合を停止させる。次いで、減圧蒸留にて未反応単量体
を除去し、共重合体ラテックスＡ〜ＤおよびＦ〜Ｌを得
た。<Production of Copolymer Latex A to D and FL to L> In an autoclave equipped with a stirrer, 150 parts of water, 5 parts of polyoxyethylene lauryl ether, 0.05 part of sodium ethylenediaminetetraacetate, 0.5 part of tert-dodecylmercaptan and 0.3 parts of potassium persulfate. And 100 parts of the monomer mixture shown in Table 1 are charged and the whole is kept at 50 ° C. to carry out polymerization. When the polymerization conversion rate reaches 50%, 0.5 part of tert-dodecyl mercaptan is added. Furthermore, the polymerization conversion rate is 9
If it reaches 5%, add 0.05 parts of halodroquinone,
Stop the polymerization. Next, unreacted monomers were removed by vacuum distillation to obtain copolymer latexes A to D and FL.
〈共重体ラテックスＥ及びＭの製造〉 攪拌機付きオートクレーブに、水130部、ロジン酸カリ
ウム４部、ナフタレンスルホン酸ナトリウム・ホルマリ
ン縮合物１部、水酸化ナトリウム0.5部を加え溶解させ
る。これに、表−１に示した単量体混合物100部を添加
し、更に、tert−ドデシルメルカプタン0.5部を加えて
乳化させる。次いで、過硫酸カリウム0.5部を加え、全
体を50℃に保ち重合を行う。重合転化率が92％に達した
ならば、ハイドロキノン0.1部を加え、重合を停止させ
る。得られた共重合体ラテックスは減圧蒸留により未反
応単量体を除去し、共重合体ラテックスＥ及びＭを得
た。<Production of Copolymer Latex E and M> To an autoclave equipped with a stirrer, 130 parts of water, 4 parts of potassium rosinate, 1 part of sodium naphthalenesulfonate / formalin condensate, and 0.5 part of sodium hydroxide are added and dissolved. To this, 100 parts of the monomer mixture shown in Table 1 is added, and 0.5 part of tert-dodecyl mercaptan is further added to emulsify. Then, 0.5 part of potassium persulfate is added and the whole is kept at 50 ° C. to carry out polymerization. When the polymerization conversion rate reaches 92%, 0.1 part of hydroquinone is added to terminate the polymerization. Unreacted monomers were removed from the obtained copolymer latex by distillation under reduced pressure to obtain copolymer latexes E and M.
〈RFL液の調製〉 水333.5部に水酸化ナトリウム1.3部、レゾルシン16.6部
および37％ホルマリン14.6部を加え、25℃にて２時間熟
成することにより、RFレジンを作成する。<Preparation of RFL solution> To 333.5 parts of water, 1.3 parts of sodium hydroxide, 16.6 parts of resorcin and 14.6 parts of 37% formalin are added, and aged at 25 ° C for 2 hours to prepare an RF resin.
次いで、前述の共重合体ラテックスＡ〜Ｌそれぞれ100
部の中に、得られたRFレジンを23.3部添加し、25℃にて
20時間熟成させる。その後、バルカボンドＥ（ICI Vuln
ax 社製2,6−ビス（２′,4′−ジヒドロキシフェニルメ
チレン）−４−クロロフェノール）を35部添加し、水に
て固形分を15％に調製して、表−３に示すRFL液１〜13
を得た。Then, each of the above-mentioned copolymer latexes A to L is 100
23.3 parts of the obtained RF resin in 25 parts, and at 25 ° C
Aged for 20 hours. After that, Barca Bond E (ICI Vuln
35 parts of ax company 2,6-bis (2 ', 4'-dihydroxyphenylmethylene) -4-chlorophenol) was added, and the solid content was adjusted to 15% with water. Liquid 1-13
Got
〈タイヤコード浸漬処理ならびにコード強力および接着
力測定〉 試験用シングルコードディッピングマシンを用いて、得
られたRFL液１〜13にて各々ポリエステル・タイヤコー
ド（1500D/2）の浸漬処理を行った。この処理されたタ
イヤコードを表−２の配合処方に基づくゴム配合物では
さみ、140℃で45分、および170℃で100分の各々の条件
にて加硫プレスした。ASTMD2138−67（H Pull Test）に
従い接着力を測定し、高温覆歴による接着力の低下を測
定した。<Tire Cord Immersion Treatment and Cord Strength and Adhesion Measurement> Using a test single cord dipping machine, each of the obtained RFL liquids 1 to 13 was subjected to immersion treatment of polyester tire cord (1500D / 2). The treated tire cord was sandwiched with a rubber compound based on the compounding recipe shown in Table 2 and vulcanized and pressed under the conditions of 140 ° C. for 45 minutes and 170 ° C. for 100 minutes. The adhesive strength was measured according to ASTM D2138-67 (H Pull Test), and the decrease in adhesive strength due to high temperature covering history was measured.
また、浸漬処理された各々のタイヤコードをJIS−L1017
に従いコード強力を測定した。In addition, each tire cord that has been subjected to immersion treatment is JIS-L1017
The cord strength was measured in accordance with.
結果を表−３に示す。The results are shown in Table-3.
表−２ 配合ゴム処方 天然ゴム 40部 SBR＃1502 60部 SRFカーボン 20部 REFカーボン 20部 パインタール ５部 スチレン化フェノール ２部 ステアリン酸 2.5部 亜 鉛 華 ５部 加硫促進剤CZ※ 1.2部 硫 黄 2.4部 ※:N−シクロヘキシル−２−ベンゾチアジル−スルフェ
ンアミド （発明の効果） 本発明の接着剤組成物は、従来のものに比べて浸漬後の
コードの強力の低下が少なく、かつゴムとの接着力に優
れる。 Table-2 Compounded rubber prescription Natural rubber 40 parts SBR # 1502 60 parts SRF carbon 20 parts REF carbon 20 parts Pine tar 5 parts Styrenated phenol 2 parts Stearic acid 2.5 parts Lead sinter 5 parts Vulcanization accelerator CZ * 1.2 parts Sulfur Yellow 2.4 parts *: N-cyclohexyl-2-benzothiazyl-sulfenamide (Advantages of the Invention) The adhesive composition of the present invention has less decrease in the strength of the cord after immersion as compared with the conventional adhesive composition, and is excellent in adhesive strength with rubber.
Claims (1)
化ビニル系単量体２〜30重量％、ビニルピリジン５〜35
重量％、不飽和酸単量体0.5〜10重量％および芳香族ビ
ニル系単量体０〜52.5重量％からなる共重合体ラテック
スとレゾルシン−ホルマリン樹脂を含むことを特徴とす
るゴムと繊維との接着剤組成物。1. A conjugated diene monomer 40 to 80% by weight, a vinyl cyanide monomer 2 to 30% by weight, and vinylpyridine 5 to 35.
% Rubber, 0.5 to 10% by weight of an unsaturated acid monomer and 0 to 52.5% by weight of an aromatic vinyl monomer, and a resorcin-formalin resin. Adhesive composition.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63258069A JPH0778207B2 (en) | 1988-10-13 | 1988-10-13 | Adhesive composition with rubber fibers |
| EP89112255A EP0350773B1 (en) | 1988-07-07 | 1989-07-05 | Adhesive composition |
| DE89112255T DE68907142T2 (en) | 1988-07-07 | 1989-07-05 | Adhesive mixture. |
| KR1019890009637A KR0127672B1 (en) | 1988-07-07 | 1989-07-06 | Adhesive composition |
| US07/376,548 US4963613A (en) | 1988-07-07 | 1989-07-07 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63258069A JPH0778207B2 (en) | 1988-10-13 | 1988-10-13 | Adhesive composition with rubber fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02105829A JPH02105829A (en) | 1990-04-18 |
| JPH0778207B2 true JPH0778207B2 (en) | 1995-08-23 |
Family
ID=17315098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63258069A Expired - Fee Related JPH0778207B2 (en) | 1988-07-07 | 1988-10-13 | Adhesive composition with rubber fibers |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0778207B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7250583B2 (en) * | 2019-03-27 | 2023-04-03 | 東レ・デュポン株式会社 | Aramid staple fiber bundle for rubber reinforcement and method for producing the same |
-
1988
- 1988-10-13 JP JP63258069A patent/JPH0778207B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02105829A (en) | 1990-04-18 |
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