JP2007505228A - Two-stage method for impregnating synthetic fibers - Google Patents

Two-stage method for impregnating synthetic fibers Download PDF

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JP2007505228A
JP2007505228A JP2006525726A JP2006525726A JP2007505228A JP 2007505228 A JP2007505228 A JP 2007505228A JP 2006525726 A JP2006525726 A JP 2006525726A JP 2006525726 A JP2006525726 A JP 2006525726A JP 2007505228 A JP2007505228 A JP 2007505228A
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博佐 渡辺
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Teijin Aramid BV
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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
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • 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
    • 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
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core

Abstract

本発明は、合成繊維にまず水性予備含浸組成物を含浸させ、続いてレゾルシノール−ホルムアルデヒドラテックス（RFL）組成物を含浸させる二段法に関する。この二段法において、予備含浸組成物は、少なくとも三官能性であるイソシアネート基を有する封止イソシアネートとラテックスとを含んでなり、そして封止イソシアネートとラテックスの重量比は９〜０．７、好ましくは４〜１である。さらに本発明は、封止された少なくとも三官能性であるイソシアネート化合物とラテックスとを含んでなり、水と、乳化剤と、２−ビニルピリジン共重合体とをさらに含んでなる合成繊維に含浸させるための予備含浸組成物、および、ゴムと、少なくとも表面部分に（１）封止三官能性イソシアネート化合物、好ましくはＨＤＩ三量体、（２）ＲＦＬ接着剤および（３）現場加硫ゴム化合物が分散されている繊維またはコードとの複合品に関する。
【選択図】なしThe present invention relates to a two-stage process in which a synthetic fiber is first impregnated with an aqueous pre-impregnated composition, followed by a resorcinol-formaldehyde latex (RFL) composition. In this two-stage method, the pre-impregnated composition comprises an encapsulated isocyanate having at least trifunctional isocyanate groups and a latex, and the weight ratio of encapsulated isocyanate to latex is preferably 9 to 0.7. Is 4-1. Further, the present invention is for impregnating a synthetic fiber comprising a sealed isocyanate compound which is at least trifunctional and a latex, and further comprising water, an emulsifier, and a 2-vinylpyridine copolymer. And (1) a sealing trifunctional isocyanate compound, preferably an HDI trimer, (2) an RFL adhesive, and (3) an in-situ vulcanized rubber compound dispersed at least on the surface portion The present invention relates to a composite product with a fiber or cord.
[Selection figure] None

Description

本発明は、合成繊維にまず予備含浸組成物を含浸させ、続いてレゾルシノール−ホルムアルデヒドラテックス（ＲＦＬ）組成物を含浸させる二段法に関する。   The present invention relates to a two-stage process in which a synthetic fiber is first impregnated with a pre-impregnated composition, followed by a resorcinol-formaldehyde latex (RFL) composition.

ゴム化合物に接着する目的で用いられるアラミド繊維のごとき繊維は、一般に、そのような合成繊維のゴムへの接着を強めるための含浸工程に附される。そのような組成物は、複合材料、例えば、補強繊維がタイヤゴム化合物に接合されているタイヤ、を製造するのに用いることができる。
繊維状補強材料、連続フィラメント糸、コードまたは短繊維といったゴム複合材料の製造において、複合材料のゴムマトリクスと強化繊維材料との間の接着性を強めることが重要である。
例えば、アラミド繊維は、タイヤの補強に用いられる繊維である。アラミド繊維の表面が結晶性であるため、アラミドとゴムの接着を実現することは非常に困難である。従って、繊維とゴムとの間に十分な接着性を得るためには、活性予備含浸工程が必要となる。そのような予備含浸工程を行う標準的な方法とは、エポキシ接着剤による予備含浸を行った後にレゾルシノールホルムアルデヒドラテックス（ＲＦＬ）による含浸を行う方法である。この方法によって、加硫ゴムとアラミド補強繊維との間に良好な接着性が生じる。 Fibers such as aramid fibers used for the purpose of adhering to rubber compounds are generally subjected to an impregnation step to enhance the adhesion of such synthetic fibers to rubber. Such compositions can be used to produce composite materials, such as tires in which reinforcing fibers are bonded to a tire rubber compound.
In the production of rubber composites such as fibrous reinforcing materials, continuous filament yarns, cords or short fibers, it is important to increase the adhesion between the rubber matrix of the composite material and the reinforcing fiber material.
For example, an aramid fiber is a fiber used for tire reinforcement. Since the surface of the aramid fiber is crystalline, it is very difficult to achieve adhesion between aramid and rubber. Therefore, an active pre-impregnation step is required to obtain sufficient adhesion between the fiber and the rubber. The standard method for performing such a pre-impregnation step is a method of performing pre-impregnation with an epoxy adhesive followed by impregnation with resorcinol formaldehyde latex (RFL). This method produces good adhesion between the vulcanized rubber and the aramid reinforcing fibers.

従って、エポキシドおよびポリエチレンイミンがアラミド繊維のための接着促進剤として提案されている。イエンガー（Ｉｙｅｎｇａｒ）は、アラミド繊維をゴムに接着させるための二段接着系を提案している。第一段階すなわち予備含浸は、エポキシ化合物から成るべきである（Ｊ．Ａｐｐｌ．Ｐｏｌｙｍ．Ｓｃｉ．，２３１１，Ｖｏｌ．１１（１９６７））。米国特許第３，８７２，９３９号におけるＧ．Ｅ．ｖａｎ Ｇｉｌｌｓ（Ｔｈｅ ｇｅｎｅｒａｌ Ｔｉｒｅ ａｎｄ Ｒｕｂｂｅｒｓ Ｃｏ．）は、１，３−ブタジエン−スチレン−２−ビニルピリジン共重合体と熱反応性２，５−ビス（２，４−ジヒドロキシフェニルメチル）−４−クロロフェノールとから成るサブコートまたはトップコートとしてのグリセロールジグリシジルエーテルの２％溶液の使用を開示している。   Accordingly, epoxides and polyethyleneimines have been proposed as adhesion promoters for aramid fibers. Iyengar has proposed a two-step adhesive system for bonding aramid fibers to rubber. The first stage or pre-impregnation should consist of an epoxy compound (J. Appl. Polym. Sci., 2311, Vol. 11 (1967)). G. in U.S. Pat. No. 3,872,939. E. van Gills (The general Tire and Rubbers Co.) is a 1,3-butadiene-styrene-2-vinylpyridine copolymer and a thermally reactive 2,5-bis (2,4-dihydroxyphenylmethyl) -4-chloro. The use of a 2% solution of glycerol diglycidyl ether as a subcoat or topcoat consisting of phenol is disclosed.

ＥＰ３５３４７３では、慣用のエポキシ予備含浸組成物に加えて、フェニル封止４，４’−ジフェニルメタンジイソシアネートを含有する予備含浸組成物が用いられている。これらの溶液は、水およびイソシアネート以外の成分を全く含有していない。我々は、水性封止ジイソシアネート予備含浸組成物によって、ゴムに対する接着性が不十分である繊維およびコードがもたらされることを見い出した。   EP 353 473 uses pre-impregnated compositions containing phenyl-capped 4,4'-diphenylmethane diisocyanate in addition to conventional epoxy pre-impregnated compositions. These solutions contain no components other than water and isocyanate. We have found that the aqueous encapsulated diisocyanate pre-impregnated composition provides fibers and cords that have poor adhesion to rubber.

３官能以上のイソシアネート化合物を含有するポリエステル繊維のための予備含浸組成物がＪＰ５７１８７２３８に記載されている。多官能イソシアネートとジイソシアネートとの混合物を含有するそのような予備含浸組成物はＪＰ５１０３７１７４に記載されており、封止ポリイソシアネートと（ベントナイトのごとき）クレーとの混合物を含有するそのような予備含浸組成物はＪＰ５５０６２２６９に記載されている。しかしながら、これらの組成物はいずれも、ゴムへの接着に関してはあまり効果的ではなく、商業的に用いられていなかった。
その頃から開発されてきた接着技術は、事実上、常にエポキシドの使用に基づいてきたが、今日では、エポキシドの使用は、厳しさを増す一方である医療問題および政府規制により、好ましくないとされている。ＨＳＥ規制によれば、人体がエポキシドに曝されるのは好ましくない。そのような有毒な物質を使用せず、且つ、エポキシドをベースとした接着と実質的に等しい安全な含浸法のニーズが高まっている。 A pre-impregnation composition for polyester fibers containing trifunctional or higher functional isocyanate compounds is described in JP57187238. Such a pre-impregnated composition containing a mixture of a polyfunctional isocyanate and a diisocyanate is described in JP 51037174, and such a pre-impregnated composition containing a mixture of a sealing polyisocyanate and a clay (such as bentonite). Is described in JP55062269. However, none of these compositions are very effective for adhesion to rubber and have not been used commercially.
Adhesion techniques that have been developed since that time have always been based on the use of epoxides in practice, but today the use of epoxides has been considered unfavorable due to the increasing severity of medical problems and government regulations. Yes. According to HSE regulations, it is not preferred that the human body be exposed to epoxides. There is a growing need for safe impregnation methods that do not use such toxic materials and are substantially equivalent to epoxide-based adhesion.

この目的を達成するために、合成繊維にまず水性予備含浸組成物を含浸させ、続いてレゾルシノール−ホルムアルデヒドラテックス（ＲＦＬ）組成物を含浸させる二段法が提供される。この二段法において、前記予備含浸組成物は、少なくとも三官能性であるイソシアネート基を有する封止イソシアネートとラテックスとを含んでなり、前記封止イソシアネートとラテックスの重量比は９〜０．７、好ましくは４〜１である。   To accomplish this goal, a two-stage process is provided in which synthetic fibers are first impregnated with an aqueous pre-impregnated composition followed by an impregnated resorcinol-formaldehyde latex (RFL) composition. In this two-stage method, the pre-impregnated composition comprises an encapsulated isocyanate having at least a trifunctional isocyanate group and a latex, and the weight ratio of the encapsulated isocyanate and the latex is 9 to 0.7. Preferably it is 4-1.

このように含浸された繊維は、慣用のエポキシド予備含浸によって得られるような接着性を維持するため、そのようなエポキシド処理は完全に使用放棄することができる。従って、エポキシド含有誘導体を実質的にあるいは全く含有していない予備含浸組成物を用いた含浸法を実施することが好ましい実施態様である。   Such impregnated fibers maintain their adhesion as obtained by conventional epoxide pre-impregnation, so that such epoxide treatment can be completely abandoned. Accordingly, it is a preferred embodiment to carry out an impregnation method using a pre-impregnation composition containing substantially or no epoxide-containing derivative.

他の実施態様において、予備含浸組成物は、封止された少なくとも三官能性であるイソシアネート化合物とラテックスとを含んでなっていてもよく、さらに水と、乳化剤と、２−ビニルピリジン共重合体とを含んでなっていてもよい。   In another embodiment, the pre-impregnated composition may comprise an encapsulated isocyanate compound that is at least trifunctional and a latex, and further comprises water, an emulsifier, and a 2-vinylpyridine copolymer. May be included.

前記予備含浸組成物のラテックス部分は、前記ＲＦＬ組成物のラテックス部分と同じまたは異なっていてもよく、共役オレフィンブロックと芳香族ブロックとのブロック共重合体である。そのようなブロック共重合体は、当該技術分野において周知である。前記予備含浸組成物のラテックス部分および前記ＲＦＬ組成物のラテックス部分がビニル−ピリジンブロック共重合体である場合にとりわけ良好な結果が得られることが分かった。好適な共重合体は、２−ビニルピリジン部分と、スチレン部分と、ブタジエン部分とを含んでなる。前記共重合体中のユニットの１０〜２０％が２−ビニルピリジン状構造体であることが好ましい。従って、好適な共重合体は、式［（Ｃ７Ｈ７Ｎ）ｌ（Ｃ８Ｈ８）ｍ（Ｃ４Ｈ６）ｎ］ｘを有する。前記式中、重量％比 ｌ：（ｍ＋ｎ）は１：９〜１：４であり、ｍ：ｎは２：３〜４：１である。ｌ：ｍ：ｎは、約１５：３５：５０であることが最も好ましい。 The latex portion of the pre-impregnated composition may be the same as or different from the latex portion of the RFL composition and is a block copolymer of a conjugated olefin block and an aromatic block. Such block copolymers are well known in the art. It has been found that particularly good results are obtained when the latex portion of the pre-impregnated composition and the latex portion of the RFL composition are vinyl-pyridine block copolymers. A suitable copolymer comprises a 2-vinylpyridine moiety, a styrene moiety, and a butadiene moiety. It is preferable that 10 to 20% of the units in the copolymer are 2-vinylpyridine-like structures. Accordingly, the preferred copolymer has the formula [(C 7 H 7 N) l (C 8 H 8) m (C 4 H 6) n] x. In the above formula, the weight% ratio l: (m + n) is 1: 9 to 1: 4, and m: n is 2: 3 to 4: 1. Most preferably, l: m: n is about 15:35:50.

本発明による方法は、原則として、タイヤ用ゴム組成物、運搬伝道ベルトなどの補強繊維として一般に用いられるあらゆる合成繊維に適用することができる。そのような繊維は、アラミド、ポリエステルおよびポリエステルテレフタレートのうちの少なくとも１種を含有することが好ましい。本発明の文脈の中で特に有用な繊維とは、少なくともアラミドを含有する、好ましくはＰＰＴＡおよび／またはＰＰＯＤＰＴＡを含有する繊維である。
本発明による方法は、紡糸として用いられる繊維に含浸させるのに好適である。 The method according to the present invention can in principle be applied to any synthetic fiber generally used as a reinforcing fiber for tire rubber compositions, transport transmission belts and the like. Such fibers preferably contain at least one of aramid, polyester and polyester terephthalate. Particularly useful fibers in the context of the present invention are fibers containing at least aramid, preferably containing PPTA and / or PPODPTA.
The process according to the invention is suitable for impregnating fibers used as spinning.

封止イソシアネートは、少なくとも三官能性のイソシアネート基を有する。そのようなイソシアネートの例としては、１，６−ヘキサメチレンジイソシアネート（ＨＤＩ）三量体などが挙げられる。封止基は当該技術分野において周知であり、メチルエチルケトオキシムのごときケトオキシム基、３，５−ジメチルピラゾールのごときピラゾール誘導体、マロン酸エステルのごときエステル、カプロラクタム、およびアルキル化フェノールから選択される。最も好ましい封止イソシアネートは、メチルエチルケトオキシムまたは３，５−ジメチルピラゾール封止ヘキサメチレンジイソシアネート三量体のごとき封止ＨＤＩ三量体である。
前記ＲＦＬ含浸組成物は、乳化剤を含有していてもよい。好適な乳化剤は、ゴムラテックスを含んでなる乳化剤から選択される。 The encapsulating isocyanate has at least trifunctional isocyanate groups. Examples of such isocyanate include 1,6-hexamethylene diisocyanate (HDI) trimer. Sealing groups are well known in the art and are selected from ketoxime groups such as methyl ethyl ketoxime, pyrazole derivatives such as 3,5-dimethylpyrazole, esters such as malonic esters, caprolactams, and alkylated phenols. The most preferred encapsulated isocyanate is an encapsulated HDI trimer such as methyl ethyl ketoxime or 3,5-dimethylpyrazole encapsulated hexamethylene diisocyanate trimer.
The RFL impregnation composition may contain an emulsifier. Suitable emulsifiers are selected from emulsifiers comprising rubber latex.

本発明による非常に好適な予備含浸組成物とは、２．５〜４重量％の水分散３，５−ジメチルピラゾール封止イソシアネート化合物（ＨＤＩ三量体）と、１〜２．５重量％の２−ビニルピリジン共重合体（ラテックス）と、９０〜９６重量％の水とを含んでなる組成物である（前記重量％は固体に基づく）。
封止イソシアネートとラテックスの重量比は９〜０．７である。ラテックスの含有量が高過ぎるまたは低過ぎる組成物では、慣用のエポキシ予備含浸組成物の接着性に匹敵する接着性が得られない。 A highly suitable pre-impregnated composition according to the present invention comprises 2.5-4% by weight of water-dispersed 3,5-dimethylpyrazole-capped isocyanate compound (HDI trimer), It is a composition comprising 2-vinylpyridine copolymer (latex) and 90 to 96% by weight of water (the weight% is based on solids).
The weight ratio of sealing isocyanate to latex is 9 to 0.7. Compositions with too high or too low latex content do not provide adhesion comparable to that of conventional epoxy pre-impregnated compositions.

さらに具体的に言うと、本発明は、硫黄加硫可能なゴムにアラミド繊維を接着させるための方法、すなわち、（１）（ａ）２．５〜４重量％の水分散３，５−ジメチルピラゾール封止イソシアネート化合物（ＨＤＩ三量体）と、（ｂ）１〜２．５重量％の２−ビニルピリジン共重合体と、（ｃ）９０〜９６重量％の水とで構成される水性分散液に繊維を浸漬させることによって、コーティングされた繊維を作る工程と、（２）前記コーティングされた繊維を乾燥および硬化させることによって、予備含浸された繊維を作る工程と、（３）前記予備含浸された繊維にＲＦＬ接着剤を含浸させることによって、含浸された繊維を作る工程と、（４）前記含浸された繊維を乾燥および硬化させることによって、含浸された繊維を作る工程と、（５）硬化させた含浸繊維を硫黄加硫可能なゴムに接触させる工程と、（６）前記加硫可能なゴムを硬化させる工程と、を含んでなる方法を提供する（前記重量％は固体に基づく）。   More specifically, the present invention relates to a method for adhering aramid fibers to a sulfur vulcanizable rubber, i.e. (1) (a) 2.5 to 4 wt% water-dispersed 3,5-dimethyl. An aqueous dispersion composed of a pyrazole-capped isocyanate compound (HDI trimer), (b) 1 to 2.5% by weight of 2-vinylpyridine copolymer, and (c) 90 to 96% by weight of water. Making a coated fiber by immersing the fiber in a liquid; (2) making a pre-impregnated fiber by drying and curing the coated fiber; and (3) the pre-impregnation Impregnating the impregnated fiber with an RFL adhesive to make an impregnated fiber; (4) making the impregnated fiber by drying and curing the impregnated fiber; and (5) And (6) a step of curing the vulcanizable rubber, wherein the weight percent is based on solids. .

他の実施態様において、本発明は、繊維およびコードに関する。前記繊維またはコードは、少なくともその表面部分に、（１）水分散３，５−ジメチルピラゾール封止イソシアネート化合物（ＨＤＩ三量体）のごとき封止三官能性イソシアネート、（２）ＲＦＬ接着剤および（３）現場（ｉｎ ｓｉｔｕ）加硫ゴム化合物が分散されている。   In other embodiments, the invention relates to fibers and cords. The fibers or cords are at least on the surface thereof (1) an encapsulated trifunctional isocyanate such as a water-dispersed 3,5-dimethylpyrazole encapsulated isocyanate compound (HDI trimer), (2) an RFL adhesive and ( 3) In situ vulcanized rubber compound is dispersed.

さらに、ゴムと繊維との複合品が提供される。前記繊維は、少なくともその表面部分に、（１）水分散３，５−ジメチルピラゾール封止イソシアネート化合物（ＨＤＩ三量体）のごとき封止三官能性イソシアネート、（２）ＲＦＬ接着剤および（３）現場加硫ゴム化合物が分散されている。   Further, a composite product of rubber and fiber is provided. The fiber has at least a surface portion thereof, (1) a water-dispersed 3,5-dimethylpyrazole-capped isocyanate compound (HDI trimer), a sealed trifunctional isocyanate, (2) an RFL adhesive, and (3) In-situ vulcanized rubber compound is dispersed.

下記実施例によって本発明をさらに説明するが、下記実施例は本発明を限定するものではない。
実施例１
本実施例では、アラミド繊維に対する三官能性封止イソシアネートと２−ビニルピリジン共重合体の併用の効果を示すためのアラミド試験サンプルを用いた試験を行った。
接着剤
実験対照としてのアラミド繊維用接着剤は、エポキシとＲＦＬの二重塗布であった。アラミド繊維に多官能エポキシ樹脂予備含浸剤と比較用のＲＦＬトップコートとを含浸させた。
実験用接着剤（サブコート）は、予備含浸剤である３．５重量％のＴｒｉｘｅｎｅ（登録商標）ＢＩ７９８６（イギリス、Ｂａｘｅｎｄｅｎ Ｃｈｅｍｉｃａｌｓ社製の３，５−ジメチルピラゾール封止ＨＤＩ三量体）および１．５重量％（固体に基づく）のＰｌｉｏｃｏｒｄ（登録商標）ＶＰ１０６Ｓ（アメリカ、Ｇｏｏｄｙｅａｒ Ｃｈｅｍｉｃａｌｓ社製の２−ビニルピリジン共重合体ラテックス）と、トップコートであるＲＦＬとで構成される。 The following examples further illustrate the invention, but the examples are not intended to limit the invention.
Example 1
In the present Example, the test using the aramid test sample for showing the effect of combined use of the trifunctional sealing isocyanate and 2-vinylpyridine copolymer with respect to the aramid fiber was conducted.
The adhesive for aramid fibers as an adhesive experimental control was a double application of epoxy and RFL. Aramid fibers were impregnated with a polyfunctional epoxy resin pre-impregnating agent and a comparative RFL topcoat.
The experimental adhesive (subcoat) was pre-impregnated with 3.5% by weight of Trixene® BI7986 (3,5-dimethylpyrazole-encapsulated HDI trimer from Baxenden Chemicals, UK) and 5% by weight (based on solids) Pliocord® VP106S (2-vinylpyridine copolymer latex manufactured by Goodyear Chemicals, USA) and RFL as the top coat.

コードの加工
双糸構造を用いてアラミドコードを作製した。１６８０ｄｔｅｘのＰＰＴＡヤーン（帝人製のＴｗａｒｏｎ（登録商標））または１６７０ｄｔｅｘのＰＰＯＤＰＴＡヤーン（帝人製のＴｅｃｈｎｏｒａ（登録商標））をＺ方向として３３０ｔｐｍで撚った。撚り合わせによって、２本の撚糸を組み合わせ、Ｓ方向として３３０ｔｐｍで撚った。この未含浸コードを予備含浸接着剤に浸漬させ、１５０℃で１２０秒間乾燥させ、２４０℃で９０秒間硬化させ、ＲＦＬに浸漬させ、そして２３５℃で９０秒間硬化させた。
試験用化合物
含浸させたアラミドコードを乗用車用タイヤプライゴム用化合物で試験した。主成分は天然ゴムであった。
結果および考察
Ｔｒｉｘｅｎｅ（登録商標）ＢＩ７９８６とＰｌｉｏｃｏｒｄ（登録商標）ＶＰ１０６Ｓの評価を、アラミド接着剤について行った。浸漬させたアラミドコードをＲＦＬにさらに浸漬させ、静的接着および接着の耐熱性について試験した。その結果を表１にまとめた。 The aramid cord using the processing ply yarns structure of the code was produced. A 1680 dtex PPTA yarn (Teijin Twaron®) or 1670 dtex PPODPTA yarn (Teijin Technora®) was twisted at 330 tpm in the Z direction. Two twisted yarns were combined by twisting and twisted at 330 tpm in the S direction. The unimpregnated cord was dipped in a pre-impregnated adhesive, dried at 150 ° C. for 120 seconds, cured at 240 ° C. for 90 seconds, dipped in RFL, and cured at 235 ° C. for 90 seconds.
The aramid cord impregnated with the test compound was tested with a compound for tire ply rubber for passenger cars. The main component was natural rubber.
Results and Discussion Trixene® BI7986 and Pliocord® VP106S were evaluated for aramid adhesives. The soaked aramid cord was further soaked in RFL and tested for static adhesion and heat resistance of the adhesion. The results are summarized in Table 1.

本実施例および下記実施例において、静的剥離接着および接着の耐熱性の試験は、コードをゴムの中に埋め込んだ後、前記ゴムを金型内で硬化させる試験（ＡＳＴＭ Ｄ ４３９３に基づく。ＳＰＡＦ＝Ｓｔｒａｐ Ｐｅｅｌ Ａｄｈｅｓｉｏｎ Ｆｏｒｃｅ）を指す。次に、前記複合サンプルに、前記ゴムが前記コード層と分離するまで、室温雰囲気（静的接着）または１２０℃雰囲気（耐熱性）内において負荷をかけた。前記負荷はニュートン（Ｎ）で測定した。   In this example and the following examples, static peel adhesion and heat resistance test for adhesion are tests (based on ASTM D 4393, where the rubber is cured in a mold after the cord is embedded in the rubber. SPAF. = Strap Peel Adhesion Force). Next, the composite sample was loaded in a room temperature atmosphere (static adhesion) or a 120 ° C. atmosphere (heat resistance) until the rubber separated from the cord layer. The load was measured in Newton (N).

Figure 2007505228
Figure 2007505228

実施例２
本発明によるエポキシ非含有予備含浸組成物の接着性および従来技術によるエポキシ予備含浸組成物の接着性を、標準コード（すなわち、Ｔｗａｒｏｎ（登録商標）１０００、１６８０ｄｔｅｘ／２、１Z ３３０ × ２Ｓ ３３０）および標準ゴム（Ｄｕｎｌｏｐ（登録商標）５３２０、ＮＲゴム）およびタイヤカーカスゴム（ＮＲ／ＳＢＲ＝７０／３０重量比）を用いて求めた。
ヤーンおよびコード
Ｔｗａｒｏｎ（登録商標）１０００、１６８０ｄｔｅｘ／２、１Z ４４０ × ２S ４４０ （オートバイ用タイヤ用途）
二種類の撚糸機、すなわち、二段撚糸機であるＲｅｚｚｅｎｉ ｒｉｎｇ撚糸機および直接撚糸機であるＳａｕｒｅｒ Ａｌｌｍａ、を用いた。
含浸液
標準的な従来技術の含浸液（エポキシ予備含浸液）（２％の三官能グリシジルグリセリンエーテル（エポキシド）／ＲＦＬ）
本発明による含浸液（エポキシ非含有予備含浸液）（非エポキシド／ＲＦＬ）
ＨＤＩ三量体／Ｖｐラテックス＝７５／２５（重量比）、濃度＝５％
手順
予備含浸液： １２０ ｓ × １５０ Ｃ （９Ｎ） − ９０ ｓ × ２４０ Ｃ （９Ｎ）
ＲＦＬ含浸液： ９０ ｓ × ２３５ Ｃ （９Ｎ）
評価（ＳＰＡＦ）
標準ゴム（Ｄｕｎｌｏｐ（登録商標）５３２０、ＮＲ） １５０ Ｃ × ２０ ｍｉｎ
ＢＳ／ＦＳ ゴム （ｃｒａ） （ＮＲ／ＳＢＲ） １６０ Ｃ × ２０ ｍｉｎ
未含浸コードおよび含浸コードの破壊強度を表ＩＩに示す。 Example 2
The adhesion of the epoxy-free pre-impregnated composition according to the present invention and the adhesion of the epoxy pre-impregnated composition according to the prior art are determined according to standard codes (ie Twaron® 1000, 1680 dtex / 2, 1Z 330 × 2S 330) and It was determined using standard rubber (Dunlop® 5320, NR rubber) and tire carcass rubber (NR / SBR = 70/30 weight ratio).
Yarn and Cord Twaron® 1000, 1680 dtex / 2, 1Z 440 × 2S 440 (for motorcycle tires)
Two types of twisting machines were used: a rezzeni ring twisting machine which is a two-stage twisting machine and a Sauer Allma which is a direct twisting machine.
Impregnation liquid Standard prior art impregnation liquid (epoxy pre-impregnation liquid) (2% trifunctional glycidyl glycerin ether (epoxide) / RFL)
Impregnating liquid according to the present invention (epoxy-free pre-impregnating liquid) (non-epoxide / RFL)
HDI trimer / Vp latex = 75/25 (weight ratio), concentration = 5%
Procedure Pre-impregnation liquid: 120 s x 150 C (9N)-90 s x 240 C (9N)
RFL impregnation liquid: 90 s × 235 C (9N)
Evaluation (SPAF)
Standard rubber (Dunlop® 5320, NR) 150 C × 20 min
BS / FS rubber (cra) (NR / SBR) 160 C x 20 min
Table II shows the breaking strength of the unimpregnated cord and the impregnated cord.

Figure 2007505228
Figure 2007505228

接着性
ＳＰＡＦ特性を、エポキシド／ＲＦＬ（従来技術）および非エポキシド／ＲＦＬ（本発明）について、ＮＲゴムおよびＮＲ／ＳＢＲゴムを用いて、二段撚糸機と直接撚糸機の両方で測定したところ、すべての条件下においてほぼ同じであることが示された。すべての値は、２８０〜３２０N／２ｃｍの範囲内であった。
ゴム被覆率
ゴム被覆率は以下のようにして求めた。剥離接着力を測定した後、剥離表面を観察し、残ったゴムの割合を求めた。結果を表ＩＩＩに示す。 Adhesive SPAF properties were measured for both epoxide / RFL (prior art) and non-epoxide / RFL (invention) using NR rubber and NR / SBR rubber on both a two-stage twister and a direct twister. It was shown to be approximately the same under all conditions. All values were in the range of 280-320 N / 2 cm.
Rubber coverage The rubber coverage was determined as follows. After measuring the peel adhesive strength, the peeled surface was observed to determine the ratio of the remaining rubber. The results are shown in Table III.

Figure 2007505228
Figure 2007505228

これらの結果は、エポキシを含有しない予備含浸液は従来技術のエポキシド含浸液に匹敵するものであり、それ故に、新しい接着方法として適用することができることを示している。   These results indicate that the pre-impregnation liquid without epoxy is comparable to the prior art epoxide impregnation liquid and can therefore be applied as a new bonding method.

Claims (11)

合成繊維にまず水性予備含浸組成物を含浸させ、続いてレゾルシノール−ホルムアルデヒドラテックス（RFL）組成物を含浸させる二段法において、
前記予備含浸組成物は、少なくとも三官能性であるイソシアネート基を有する封止イソシアネートとラテックスとを含んでなり、前記封止イソシアネートとラテックスの重量比は９〜０．７、好ましくは４〜１である、
ことを特徴とする前記方法。 In a two-stage process where a synthetic fiber is first impregnated with an aqueous pre-impregnated composition followed by a resorcinol-formaldehyde latex (RFL) composition.
The pre-impregnated composition comprises a sealing isocyanate having at least a trifunctional isocyanate group and a latex, and the weight ratio of the sealing isocyanate to the latex is 9 to 0.7, preferably 4 to 1. is there,
Said method. 前記予備含浸組成物にはエポキシド含有誘導体が実質的に含有されていない、請求項１に記載の方法。 The method of claim 1, wherein the pre-impregnated composition is substantially free of epoxide-containing derivatives. 前記予備含浸組成物と前記ＲＦＬ組成物のラテックス部分は、共役オレフィンブロックと芳香族ブロックとのブロック共重合体である、請求項１または２に記載の方法。 The method of claim 1 or 2, wherein the latex portion of the pre-impregnated composition and the RFL composition is a block copolymer of a conjugated olefin block and an aromatic block. 前記ラテックス部分は、ビニル−ピリジンブロック共重合体である、請求項３に記載の方法。 4. The method of claim 3, wherein the latex portion is a vinyl-pyridine block copolymer. 前記合成繊維は、アラミド、ポリエステルおよびポリエステルテレフタレートのうちの少なくとも１種を含有する繊維である、請求項１〜４のいずれか１つに記載の方法。 The method according to claim 1, wherein the synthetic fiber is a fiber containing at least one of aramid, polyester, and polyester terephthalate. 前記合成繊維は、少なくともアラミドを含有する、好ましくはＰＰＴＡおよび／またはＰＰＯＤＰＴＡを含有する繊維である、請求項５に記載の方法。 6. The method according to claim 5, wherein the synthetic fiber is a fiber containing at least aramid, preferably PPTA and / or PPODPTA. 紡糸が用いられる、請求項１〜６のいずれか１つに記載の方法。 7. A method according to any one of claims 1 to 6, wherein spinning is used. 前記封止イソシアネートは封止ＨＤＩ三量体である、請求項１〜７のいずれか１つに記載の方法。 The method according to any one of claims 1 to 7, wherein the encapsulated isocyanate is an encapsulated HDI trimer. 合成繊維に含浸させるための予備含浸組成物であって、
封止された少なくとも三官能性であるイソシアネート化合物とラテックスとを含んでなり、水と、乳化剤と、２−ビニルピリジン共重合体とをさらに含んでなる前記組成物。 A pre-impregnation composition for impregnating synthetic fibers,
The said composition which comprises the isocyanate compound and latex which are at least trifunctional sealed, and further contains water, an emulsifier, and a 2-vinylpyridine copolymer. （１）封止三官能性イソシアネート化合物、好ましくはＨＤＩ三量体、（２）ＲＦＬ接着剤および（３）現場加硫ゴム化合物が、少なくともその表面部分に分散されている繊維またはコード。 A fiber or cord in which (1) a sealing trifunctional isocyanate compound, preferably an HDI trimer, (2) an RFL adhesive, and (3) an in-situ vulcanized rubber compound is dispersed at least on the surface portion thereof. ゴムと請求項１０に記載の繊維またはコードとの複合品。 A composite product of rubber and the fiber or cord according to claim 10.
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