JPH1134182A - Pneumatic tire - Google Patents
Pneumatic tireInfo
- Publication number
- JPH1134182A JPH1134182A JP9190214A JP19021497A JPH1134182A JP H1134182 A JPH1134182 A JP H1134182A JP 9190214 A JP9190214 A JP 9190214A JP 19021497 A JP19021497 A JP 19021497A JP H1134182 A JPH1134182 A JP H1134182A
- Authority
- JP
- Japan
- Prior art keywords
- tire
- rubber
- compound
- styrene
- active hydrogen
- 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.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 claims abstract description 32
- 239000000835 fiber Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 229920000126 latex Polymers 0.000 claims abstract description 19
- 229920001971 elastomer Polymers 0.000 claims abstract description 18
- 239000005060 rubber Substances 0.000 claims abstract description 18
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 11
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000011324 bead Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- -1 polyol compound Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 25
- 229920005749 polyurethane resin Polymers 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000004816 latex Substances 0.000 description 9
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Tires In General (AREA)
- Tyre Moulding (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はポリエステルコード
をタイヤカバー層に用い、接着性に優れ、高速走行耐久
性に優れかつタイヤの軽量化を達成することのできる空
気入りタイヤに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pneumatic tire using a polyester cord for a tire cover layer and having excellent adhesion, high-speed running durability, and light weight.
【０００２】[0002]
【従来の技術】空気入りタイヤの高速耐久性に対するニ
ーズが高まっているなかで、現在はベルト層の外側に実
質的にタイヤ周方向に対し０°のナイロンカバー層を配
置して用いているが、そのカバー材は必要に応じてプラ
イ数やコード打ち込み本数をまして対処しているため、
高速性を重視したタイヤでは重量が重くなるという欠点
があった。それに対し、ナイロンよりもモジュラスの高
いポリエステルコードを用いることも提案されている
が、ナイロンよりも接着性が低いために実用上使えない
のが実情である（例えば特開昭５９−１２４４０７号公
報参照）。2. Description of the Related Art As the need for high-speed durability of a pneumatic tire has been increasing, a nylon cover layer substantially at 0 ° to the circumferential direction of the tire is currently used outside the belt layer. , Because the cover material is dealt with more than the number of plies and the number of cords as needed,
A tire that emphasizes high speed has a disadvantage that the weight increases. On the other hand, it has been proposed to use a polyester cord having a higher modulus than nylon. However, in practice, it is practically unusable because the adhesiveness is lower than that of nylon (see, for example, JP-A-59-124407). ).
【０００３】ポリエステル繊維は抗張力および弾性率が
高く、寸法安定性、耐熱性などに優れるが、ポリエステ
ル繊維はゴムとの接着性に劣るという問題があった。こ
のため例えばポリエステル繊維（例えばポリエチレンテ
レフタレート）とゴムとの接着方法としてポリエステル
繊維をエポキシ化合物で処理した後、従来からゴムとの
接着剤として汎用されているレゾルシン・ホルマリン・
ゴムラテックス（ＲＦＬ）で処理する方法や特開昭５４
−８２４９２号公報に提案されているように、ポリエポ
キシド化合物、ビニルピリジンラテックス、ブロックド
イソシアネート化合物の混合液で処理した後ＲＦＬで処
理する方法などが提案されているが、その接着力は未だ
十分とはいえなかった。特に今後、米国の燃費規制ＣＡ
ＦＥに対応する軽量化タイヤなどの開発でポリエステル
繊維をタイヤコードとして用いる場合には、接着性が益
々重要となることは確実で、ポリエステル繊維とゴムと
の接着の改善が一層必要である。[0003] Polyester fibers have high tensile strength and elastic modulus, and are excellent in dimensional stability, heat resistance, and the like. However, polyester fibers have a problem of poor adhesion to rubber. For this reason, for example, as a method of bonding polyester fiber (for example, polyethylene terephthalate) and rubber, polyester fiber is treated with an epoxy compound, and then resorcinol-formalin, which is conventionally widely used as an adhesive with rubber, is used.
Methods for treating with rubber latex (RFL)
As disclosed in JP-A-824492, a method of treating with a mixed solution of a polyepoxide compound, vinylpyridine latex, and a blocked isocyanate compound and then treating with a RFL has been proposed, but its adhesive strength is still insufficient. I couldn't say. Especially in the future, fuel efficiency regulations of the United States CA
When polyester fibers are used as tire cords in the development of lightweight tires and the like corresponding to FE, it is certain that the adhesiveness will become increasingly important, and it is necessary to further improve the adhesion between the polyester fibers and rubber.
【０００４】[0004]
【発明が解決しようとする課題】従って、本発明は従来
技術におけるポリエステル繊維とゴムとの接着性の問題
を解決してポリエステルコードをタイヤカバー層として
用いることによって高速走行耐久性に優れかつタイヤの
軽量化を達成することのできる空気入りタイヤを提供す
ることを目的とする。SUMMARY OF THE INVENTION Accordingly, the present invention solves the problem of the adhesion between polyester fiber and rubber in the prior art, and uses a polyester cord as a tire cover layer to provide a high-speed running durability and a high tire durability. An object of the present invention is to provide a pneumatic tire that can achieve weight reduction.
【０００５】[0005]
【課題を解決するための手段】本発明に従えば、左右一
対のビード部と、該ビード部に連らなる左右一対のサイ
ドウォール部と該サイドウォール部間に位置するトレッ
ド部、該左右一対のビード部間に設けられたカーカス層
及び該トレッド部におけるカーカス層上に設けられたベ
ルト層から成る空気入りタイヤにおいて、ポリエステル
繊維を（ａ）エポキシ化合物、（ｂ）スチレン／ブタジ
エン比が５／９５〜４５／５５（重量比）のスチレン−
ブタジエン共重合体ゴムラテックスおよび（ｃ）式
（１）が提供される。According to the present invention, a pair of left and right bead portions, a pair of left and right side wall portions connected to the bead portion, a tread portion located between the side wall portions, and a pair of left and right bead portions are provided. In the pneumatic tire comprising the carcass layer provided between the bead portions and the belt layer provided on the carcass layer in the tread portion, the polyester fiber is made of (a) an epoxy compound, and (b) a styrene / butadiene ratio of 5 / 95-45 / 55 (weight ratio) styrene
A butadiene copolymer rubber latex and (c) Formula (1) are provided.
【０００６】[0006]
【化２】 Embedded image
【０００７】〔式中、Ａは官能基数３〜５の有機ポリイ
ソシアネート化合物のイソシアネート残基を示し、Ｙは
熱処理によりイソシアネート基を遊離するブロック剤化
合物の活性水素残基を示し、Ｚは分子中、少なくとも１
個の活性水素原子および少なくとも１個のアニオン形成
性基を有する化合物の活性水素残基を示し、Ｘは２〜４
個の水酸基を有し平均分子量が５０００以下のポリオー
ル化合物の活性水素残基であり、ｎは２〜４の整数であ
り、ｐ＋ｍは２〜４の整数（ｍ≧０．２５）である〕で
示される熱反応型水溶性ポリウレタン樹脂を、成分
（ａ）、（ｂ）および（ｃ）を固形分重量比で、 （１）０．１≦（ａ）／〔（ｂ）＋（ｃ）〕≦２および （２）（ｃ）／（ｂ）≦２ の割合で配合してなる第１処理液で処理し、次にレゾル
シン・ホルマリン縮合物およびゴムラテックスからなる
第２処理液で処理して得られるポリエステルコードをゴ
ム被覆しタイヤトレッド部のベルト層の外側にカバー層
としてタイヤ周方向に対してほぼ０°の角度で配置した
ことを特徴とする空気入りタイヤが提供される。Wherein A represents an isocyanate residue of an organic polyisocyanate compound having 3 to 5 functional groups, Y represents an active hydrogen residue of a blocking agent compound which releases an isocyanate group by heat treatment, and Z represents , At least one
X represents an active hydrogen residue of a compound having at least one active hydrogen atom and at least one anion-forming group;
Is an active hydrogen residue of a polyol compound having three hydroxyl groups and an average molecular weight of 5,000 or less, n is an integer of 2 to 4, and p + m is an integer of 2 to 4 (m ≧ 0.25). The heat-reactive water-soluble polyurethane resin shown is prepared by mixing the components (a), (b) and (c) in a solid content ratio by weight: (1) 0.1 ≦ (a) / [(b) + (c)] ≦ 2 and (2) treatment with a first treatment liquid formulated in a ratio of (c) / (b) ≦ 2, followed by treatment with a second treatment liquid comprising a resorcinol-formalin condensate and rubber latex A pneumatic tire is provided, wherein the obtained polyester cord is covered with rubber and disposed as a cover layer at an angle of substantially 0 ° with respect to the tire circumferential direction outside the belt layer of the tire tread portion.
【０００８】[0008]
【発明の実施の形態】本発明に係る空気入りタイヤの構
造には特に限定はなく、従来から知られている任意の構
造の空気入りタイヤ、更には現在開発中の各種構造の空
気入りタイヤ構造とすることができ、要はトレッド部を
前記構成のものとすればよい。DESCRIPTION OF THE PREFERRED EMBODIMENTS The structure of the pneumatic tire according to the present invention is not particularly limited, and any conventionally known pneumatic tires, as well as various types of pneumatic tire structures currently under development. What is essential is that the tread portion has the above-described configuration.
【０００９】以下、その一例を添付図１を参照して説明
する。図１は本発明の空気入りタイヤの好ましい一例の
子午線方向半断面説明図である。図１において、本発明
の空気入りタイヤＡは、左右一対のビード部１１，１１
とこれらビード部１１，１１に連結する左右一対のサイ
ドウォール部１２，１２とこれらサイドウォール部１
２，１２間に配されるトレッド部１３からなり、更に左
右一対のビード部１１，１１間にはカーカス層１４が装
架されており、トレッド部１３においては、この外周を
取り囲むようにベルト層１５が配置され、その外側にカ
バー層１６が配置されている。１０はトレッド表面であ
る。An example will be described below with reference to FIG. FIG. 1 is a half sectional view in the meridian direction of a preferred example of the pneumatic tire of the present invention. In FIG. 1, a pneumatic tire A of the present invention has a pair of right and left bead portions 11, 11.
And a pair of left and right side wall portions 12 and 12 connected to the bead portions 11 and 11 and the side wall portion 1
A carcass layer 14 is mounted between a pair of left and right bead portions 11 and 11, and a belt layer is provided around the outer periphery of the tread portion 13 in the tread portion 13. 15 and a cover layer 16 is disposed outside thereof. 10 is a tread surface.
【００１０】ところで、本発明に従えば、前記カバー層
を構成する、ポリエステル繊維は先ずエポキシ化合物、
特定のスチレン・ブタジエンゴム（ＳＢＲ）ラテックス
および前記式（１）の熱反応型水溶性ポリウレタン樹脂
からなる第１処理液で処理され、次にレゾルシン・ホル
マリン縮合物およびゴムラテックスからなる第２処理液
（ＲＦＬ処理液）で処理される。According to the present invention, the polyester fiber constituting the cover layer is firstly an epoxy compound,
Treated with a first processing liquid comprising a specific styrene-butadiene rubber (SBR) latex and a heat-reactive water-soluble polyurethane resin of the above formula (1), and then a second processing liquid comprising a resorcinol-formalin condensate and rubber latex (RFL treatment solution).
【００１１】本発明において使用されるポリエステル繊
維の代表例はポリエチレンテレフタレートなどである
が、従来からゴム補強用として使用されているまたはそ
の使用が検討されている任意のポリエステル繊維とする
ことができ、市販品として、東レ（株）製テトロンなど
が知られている。A typical example of the polyester fiber used in the present invention is polyethylene terephthalate and the like, but any polyester fiber which has been conventionally used for rubber reinforcement or whose use is considered, Tetoron manufactured by Toray Industries, Inc. is known as a commercially available product.
【００１２】本発明において用いられる第１処理液は、
（ａ）エポキシ化合物、（ｂ）ＳＢＲラテックスおよび
（ｃ）熱反応型水溶性ポリウレタン樹脂から成り、こら
れは以下の組成（固形分重量比）を満足するものでなけ
ればならない。 （１）０．１≦（ａ）／〔（ｂ）＋（ｃ）〕≦２および （２）（ｃ）／（ｂ）≦２ 特に好ましい配合は、各固形分がＳＢＲラテックス１０
０重量部に対し、エポキシ化合物２０〜７０重量部およ
び熱反応型水溶性ポリウレタン樹脂１０〜１００重量部
である。The first treatment liquid used in the present invention is:
It consists of (a) an epoxy compound, (b) an SBR latex, and (c) a heat-reactive water-soluble polyurethane resin, which must satisfy the following composition (solid content weight ratio). (1) 0.1 ≦ (a) / [(b) + (c)] ≦ 2 and (2) (c) / (b) ≦ 2 Particularly preferred composition is that each solid content is SBR latex 10
20 to 70 parts by weight of the epoxy compound and 10 to 100 parts by weight of the heat-reactive water-soluble polyurethane resin with respect to 0 parts by weight.
【００１３】本発明において用いられるエポキシ化合物
は、グリシジル基を分子中に１個またはそれ以上有する
公知のエポキシ化合物、好ましくはグリセロールポリグ
リシジルエーテル、ジグリセロールポリグリシジルエー
テル、ソルビトールポリグリシジルエーテルなどのポリ
オール系エポキシ化合物である。第１処理液中のエポキ
シ化合物の配合量が少な過ぎると十分な接着性が得られ
ないおそれがあり、逆に多過ぎると処理液の安定性を低
下させるおそれがあるので好ましくない。The epoxy compound used in the present invention is a known epoxy compound having one or more glycidyl groups in a molecule, preferably a polyol based compound such as glycerol polyglycidyl ether, diglycerol polyglycidyl ether and sorbitol polyglycidyl ether. It is an epoxy compound. If the amount of the epoxy compound in the first treatment liquid is too small, sufficient adhesiveness may not be obtained, while if too large, the stability of the treatment liquid may be reduced, which is not preferable.
【００１４】本発明の第１処理液に用いられるＳＢＲラ
テックスは、スチレン／ブタジエンのモノマー比（重量
比）が５／９５〜４５／５５、好ましくは１０／９０〜
３０／７０の範囲の共重合体ゴムラテックスである。ス
チレン／ブタジエン重量比においてスチレン含量が少な
過ぎるとディップ処理時のロールへのガムアップなどの
加工性低下のおそれがあり、逆に多過ぎると接着力が低
下するおそれがある。ＳＢＲラテックスは従来公知の任
意の乳化重合法で製造することができ、好ましい固形分
含量は３０〜６０重量％である。なお、第１処理液中に
配合されるＳＢＲラテックスの量が少な過ぎると十分な
接着が得られないおそれがあり、逆に多過ぎるとディッ
プ処理時の加工性が低下するおそれがあるので好ましく
ない。The SBR latex used in the first treatment liquid of the present invention has a styrene / butadiene monomer ratio (weight ratio) of 5/95 to 45/55, preferably 10/90 to 45/55.
It is a copolymer rubber latex in the range of 30/70. If the styrene content in the styrene / butadiene weight ratio is too small, processability such as gum up to a roll during dipping may be reduced, and if it is too large, the adhesive strength may be reduced. The SBR latex can be produced by any conventionally known emulsion polymerization method, and preferably has a solid content of 30 to 60% by weight. In addition, if the amount of the SBR latex blended in the first processing liquid is too small, sufficient adhesion may not be obtained. Conversely, if the amount is too large, workability during dip processing may decrease, which is not preferable. .
【００１５】本発明の第１処理液に第三の成分として配
合される熱反応型水溶性ポリウレタン樹脂の例として
は、例えば式（１）のＸが２〜４個の水酸基を有するポ
リエーテルポリオール化合物（例えばビスフェノールＡ
のエチレンオキサイド付加物）の活性水素残基、または
式（１）のＸが２〜４個の水酸基を有するポリエステル
ポリオール化合物（例えばカプロラクトンの開環重合で
得られるポリエステルポリオール化合物）の活性水素残
基であるポリウレタン樹脂などを挙げることができる。Examples of the heat-reactive water-soluble polyurethane resin to be added as the third component to the first treatment liquid of the present invention include, for example, polyether polyol having the formula (1) wherein X has 2 to 4 hydroxyl groups. Compounds (eg, bisphenol A
Or an active hydrogen residue of a polyester polyol compound of the formula (1) wherein X has 2 to 4 hydroxyl groups (for example, a polyester polyol compound obtained by ring-opening polymerization of caprolactone). And the like.
【００１６】本発明の第１処理液中に配合される熱反応
型水溶性ポリウレタン樹脂の配合量が少な過ぎると接着
力が低下するおそれがあり、逆に多過ぎるとコードが硬
くなり、耐疲労性低下のおそれがあるので好ましくな
い。If the amount of the heat-reactive water-soluble polyurethane resin mixed in the first treatment liquid of the present invention is too small, the adhesive strength may decrease. On the other hand, if the amount is too large, the cord becomes hard and the fatigue resistance becomes poor. It is not preferable because the property may be lowered.
【００１７】本発明に係る第１処理液は前記各成分を一
般的な方法で混合して調製することができ、必要に応じ
コードへの浸透性を良くするために界面活性剤（例えば
スルホコハク酸ナトリウム）などを配合することができ
る。第１処理液によるポリエステル繊維などの処理方法
は一般的な繊維の処理方法と同じく、液中への侵漬ロー
ル塗布、スプレー噴霧などによることができる。ポリエ
ステル繊維などへの第１処理液の付着量は好ましくは３
〜８重量％である。処理されたポリエステル繊維などは
例えば８０〜１５０℃の温度で乾燥された後、更に例え
ば２００〜２５０℃の温度で熱処理される。The first treatment liquid according to the present invention can be prepared by mixing the above-mentioned components by a general method. If necessary, a surfactant (for example, sulfosuccinic acid) may be added to improve the permeability of the cord. Sodium) and the like. The processing method of the polyester fiber or the like with the first processing liquid can be performed by applying a dipping roll into the liquid, spraying spraying, or the like in the same manner as the general fiber processing method. The amount of the first treatment liquid adhering to polyester fibers or the like is preferably 3
８8% by weight. The treated polyester fiber or the like is dried at a temperature of, for example, 80 to 150 ° C., and is further heat-treated at a temperature of, for example, 200 to 250 ° C.
【００１８】本発明に従って第１処理液で処理されたポ
リエステル繊維は、次に従来から繊維とゴムとの接着剤
として汎用されている第２処理液（ＲＦＬ処理液）で処
理される。この第２処理液は従来から汎用されているも
のとすることができ、典型的にはレゾルシン・ホルマリ
ン／ゴムラテックス（例えばスチレン・ブタジエンラテ
ックス／ビニルピリジン・スチレン・ブタジエンタ−ポ
リマーラテックスなどの３０〜６０％エマルジョン）＝
１／２〜１／１０（重量比）であり、これらの成分に加
えて、必要に応じブロックドイソシアネート水分散体な
どを配合することができる。The polyester fiber treated with the first treatment liquid according to the present invention is then treated with a second treatment liquid (RFL treatment liquid) which has been widely used as an adhesive between fiber and rubber. The second processing solution may be one commonly used in the past, and typically has a resorcinol-formalin / rubber latex (e.g., a styrene-butadiene latex / vinylpyridine-styrene-butadiene-polymer latex, etc.). 60% emulsion) =
It is 1/2 to 1/10 (weight ratio), and in addition to these components, a blocked aqueous isocyanate dispersion or the like can be blended if necessary.
【００１９】本発明に従った第２処理液の処理方法は従
来の方法と同じとすることができる。ポリエステル繊維
への付着量は好ましくは２〜６重量％である。処理され
たポリエステル繊維などは例えば温度８０〜１５０℃で
乾燥され、更に例えば温度２００〜２５０℃で熱処理さ
れる。The processing method of the second processing liquid according to the present invention can be the same as the conventional method. The amount of adhesion to the polyester fiber is preferably 2 to 6% by weight. The treated polyester fiber or the like is dried at, for example, a temperature of 80 to 150 ° C., and further heat-treated at a temperature of, for example, 200 to 250 ° C.
【００２０】本発明に従って第１処理液および第２処理
液で処理されたポリエステル繊維は、汎用の未加硫ゴム
（例えば天然ゴム、ＳＢＲゴム、ポリイソプレンゴム、
ポリブタジエンゴム）に汎用の加硫配合剤（例えば加硫
剤、加硫促進剤、カーボンブラック、老化防止剤、充填
剤など）が配合されたゴム配合物と常法に従って一体化
加硫され、ゴム／コード複合体としてカバー層に使用す
ることができる。The polyester fiber treated with the first treatment liquid and the second treatment liquid according to the present invention is a general-purpose unvulcanized rubber (for example, natural rubber, SBR rubber, polyisoprene rubber,
Polybutadiene rubber) is compounded with a general-purpose vulcanizing compounding agent (for example, vulcanizing agent, vulcanization accelerator, carbon black, anti-aging agent, filler, etc.) and vulcanized integrally according to a conventional method. / Can be used in the cover layer as a code composite.
【００２１】以上の通り本発明に従えば、ポリエステル
繊維は、特定のエポキシ化合物、特定のスチレン・ブタ
ジエンゴムおよび特定の熱反応型水溶性ポリウレタン樹
脂からなる第１処理液で先ず処理され、次いでＲＦＬ処
理液で処理されることでゴムとの接着性に優れたものと
なり、例えばこのように処理したポリエステルコードを
すだれ状にゴム被覆し、ポリエステル繊維とゴム（例え
ば汎用の未加硫ゴムに、加硫剤、加硫促進剤、カーボン
ブラック、老化防止剤、充填剤等を適宜配合した配合
物）との複合体として前記カバー層に使用することによ
ってタイヤの耐久性が著しく高められる。なお、本発明
ではこの複合体を補強層としてタイヤ周方向に対し、ほ
ぼ０°で配置して用いる。As described above, according to the present invention, the polyester fiber is first treated with a first treatment liquid comprising a specific epoxy compound, a specific styrene-butadiene rubber and a specific heat-reactive water-soluble polyurethane resin, and then the RFL is used. By being treated with the treatment liquid, the adhesiveness to rubber becomes excellent. For example, the polyester cord treated in this way is covered with a rubber cord, and the polyester fiber and rubber (for example, a general-purpose unvulcanized rubber is vulcanized). When the cover layer is used as a composite with a sulfuric acid, a vulcanization accelerator, a carbon black, an antioxidant, a filler, and the like as appropriate, the durability of the tire is significantly increased. In the present invention, the composite is used as a reinforcing layer at a substantially 0 ° angle with respect to the tire circumferential direction.
【００２２】[0022]
【実施例】以下、実施例及び比較例に基づいて本発明を
更に詳細に説明するが、本発明は以下の実施例に限定さ
れるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
【００２３】以下の例において用いた接着性及び高速耐
久性は以下の方法で評価した。接着性評価法 タイヤからサンプルを切りだしベルト／カバー材間の１
００℃雰囲気下での剥離試験を行い、そのカバー層のゴ
ム付度合いをナイロン材を１００として評価。指数が高
い方が接着性が高い。The adhesiveness and high-speed durability used in the following examples were evaluated by the following methods. Adhesion evaluation method Cut out a sample from the tire and remove 1 between the belt and cover material.
A peeling test was performed in a 00 ° C. atmosphere, and the degree of rubberization of the cover layer was evaluated with a nylon material being 100. The higher the index, the higher the adhesion.
【００２４】タイヤ試験法 下表に示すような２種類のタイヤについて試験した。 ───────────────────────────────── タイヤ種類 第１タイヤ(185／65R14) 第２タイヤ(225／60R16) ───────────────────────────────── 空気圧 ２２０kPa ２２０kPa ───────────────────────────────── 荷 重 ４．４５kN ６．３１kN ───────────────────────────────── リ ム １４×５Ｊ １６×６１／２JJ ───────────────────────────────── 試験方法は、サンプルタイヤを、ステップ１として８１
km／ｈで２時間、次にステップ２として１２１km／ｈで
３０分間、そして更にステップ３として１２９km／ｈで
３０分間、以後３０分毎に８km／ｈづつ増速し、故障に
至るまで走行させる。このようにして故障に至るまでの
走行距離をナイロン材を１００として、その指数で表
す。 Tire Test Method Two types of tires were tested as shown in the table below.種類 Tire type 1st tire (185 / 65R14) 2nd tire (225 / 60R16 ) ───────────────────────────────── Air pressure 220kPa 220kPa ───────────── ────────────────────Load 4.45kN 6.31kN ────────────────────── ─────────── Lim 14 × 5J 16 × 61 / 2JJ ───────────────────────────── ──── The test method was as follows:
2 hours at km / h, then 30 minutes at 121 km / h as step 2 and 30 minutes at 129 km / h as step 3; after that, increase the speed by 8 km / h every 30 minutes, and run until failure. . In this way, the running distance up to the failure is represented by an index with the nylon material as 100.
【００２５】実施例１及び比較例１〜３ 表Ｉに示すようにカバー材の有機繊維を種々変えた以外
は同一の構成の第一の空気入りタイヤ（１８５／６５Ｒ
１４）を製造して接着性及び高速耐久性を評価し、部材
重量を測定した。結果を表Ｉに示す。 Example 1 and Comparative Examples 1 to 3 As shown in Table I, a first pneumatic tire (185 / 65R) having the same structure except that the organic fibers of the cover material were variously changed.
14) was manufactured, and the adhesion and high-speed durability were evaluated, and the weight of the member was measured. The results are shown in Table I.
【００２６】[0026]
【表１】 [Table 1]
【００２７】なお、使用したタイヤの製造に用いたタイ
ヤの他の部材の材料は以下の通りである。The materials of other members of the tire used for manufacturing the used tire are as follows.
【００２８】実施例３〜４及び比較例４〜６ 表IIに示すようにカバー材の有機繊維を種々変えた以外
は同一の構成の第二の空気入りタイヤ（２２５／６０Ｒ
１６）を製造して接着性及び高速耐久性を前述のように
して評価し、部材重量を測定した。結果を表IIに示す。 Examples 3-4 and Comparative Examples 4-6 A second pneumatic tire (225 / 60R) having the same construction as shown in Table II except that the organic fibers of the cover material were variously changed.
16) was manufactured, and the adhesion and high-speed durability were evaluated as described above, and the weight of the member was measured. The results are shown in Table II.
【００２９】[0029]
【表２】 [Table 2]
【００３０】なお、使用したタイヤの製造に用いたタイ
ヤの他の部材は以下の通りである。The other members of the tire used for manufacturing the used tire are as follows.
【００３１】[0031]
【発明の効果】以上説明した通り、本発明に従えば高い
接着力が得られる特定の２段処理を用いることでポリエ
ステルコードをカバー層に利用可能となり、高速耐久性
を維持しつつタイヤの軽量化が達成出来る。As described above, according to the present invention, the polyester cord can be used for the cover layer by using a specific two-step treatment which can provide a high adhesive strength, and the tire can be lightweight while maintaining high-speed durability. Can be achieved.
【図１】本発明の空気入りタイヤの一例の子午線方向半
断説明図である。FIG. 1 is a partially cutaway view in the meridian direction of an example of a pneumatic tire of the present invention.
１０…トレッド表面 １１…ビード部 １２…サイドウォール １３…トレッド部 １４…カーカス層 １５…ベルト層 １６…カバー層 DESCRIPTION OF SYMBOLS 10 ... Tread surface 11 ... Bead part 12 ... Side wall 13 ... Tread part 14 ... Carcass layer 15 ... Belt layer 16 ... Cover layer
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 75/04 Ｃ０８Ｌ 75/04 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 75/04 C08L 75/04
Claims (1)
らなる左右一対のサイドウォール部と該サイドウォール
部間に位置するトレッド部、該左右一対のビード部間に
設けられたカーカス層及び該トレッド部におけるカーカ
ス層上に設けられたベルト層から成る空気入りタイヤに
おいて、ポリエステル繊維を（ａ）エポキシ化合物、
（ｂ）スチレン／ブタジエン比が５／９５〜４５／５５
（重量比）のスチレン−ブタジエン共重合体ゴムラテッ
クスおよび（ｃ）式（１）： 【化１】 〔式中、Ａは官能基数３〜５の有機ポリイソシアネート
化合物のイソシアネート残基を示し、Ｙは熱処理により
イソシアネート基を遊離するブロック剤化合物の活性水
素残基を示し、Ｚは分子中、少なくとも１個の活性水素
原子および少なくとも１個のアニオン形成性基を有する
化合物の活性水素残基を示し、Ｘは２〜４個の水酸基を
有し平均分子量が５０００以下のポリオール化合物の活
性水素残基であり、ｎは２〜４の整数であり、ｐ＋ｍは
２〜４の整数（ｍ≧０．２５）である〕で示される熱反
応型水溶性ポリウレタン樹脂を、成分（ａ）、（ｂ）お
よび（ｃ）を固形分重量比で、 （１）０．１≦（ａ）／〔（ｂ）＋（ｃ）〕≦２および （２）（ｃ）／（ｂ）≦２ の割合で配合してなる第１処理液で処理し、次にレゾル
シン・ホルマリン縮合物およびゴムラテックスからなる
第２処理液で処理して得られるポリエステルコードをゴ
ム被覆しタイヤトレッド部のベルト層の外側にカバー層
としてタイヤ周方向に対してほぼ０°の角度で配置した
ことを特徴とする空気入りタイヤ。1. A pair of left and right beads, a pair of left and right sidewalls connected to the beads, a tread located between the sidewalls, and a carcass layer provided between the pair of left and right beads. And a pneumatic tire comprising a belt layer provided on a carcass layer in the tread portion, wherein the polyester fiber comprises: (a) an epoxy compound;
(B) styrene / butadiene ratio of 5/95 to 45/55
(Weight ratio) styrene-butadiene copolymer rubber latex and (c) formula (1): [Wherein, A represents an isocyanate residue of an organic polyisocyanate compound having 3 to 5 functional groups, Y represents an active hydrogen residue of a blocking agent compound that releases an isocyanate group by heat treatment, and Z represents at least 1 X represents an active hydrogen residue of a compound having two active hydrogen atoms and at least one anion-forming group, and X represents an active hydrogen residue of a polyol compound having 2 to 4 hydroxyl groups and having an average molecular weight of 5,000 or less. And n is an integer of 2 to 4, and p + m is an integer of 2 to 4 (m ≧ 0.25)], the components (a), (b) and (C) is blended at a solid content weight ratio of (1) 0.1 ≦ (a) / [(b) + (c)] ≦ 2 and (2) (c) / (b) ≦ 2. First resorcinol solution, and then resorcinol-forma A polyester cord obtained by treating with a second treating solution comprising a rubber condensate and a rubber latex was covered with rubber and disposed as a cover layer outside the belt layer of the tire tread at an angle of approximately 0 ° with respect to the tire circumferential direction. A pneumatic tire, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9190214A JPH1134182A (en) | 1997-07-15 | 1997-07-15 | Pneumatic tire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9190214A JPH1134182A (en) | 1997-07-15 | 1997-07-15 | Pneumatic tire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1134182A true JPH1134182A (en) | 1999-02-09 |
Family
ID=16254376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9190214A Pending JPH1134182A (en) | 1997-07-15 | 1997-07-15 | Pneumatic tire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1134182A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6896930B2 (en) * | 2002-04-18 | 2005-05-24 | Toyo Boseki Kabushiki Kaisha | Method for manufacturing a polyester fiber cord for reinforcing rubber materials |
| WO2006093182A1 (en) * | 2005-03-03 | 2006-09-08 | Toyo Boseki Kabushiki Kaisha | Reinforcing polyester cord for rubbers and process for production thereof |
| WO2007072703A1 (en) * | 2005-12-22 | 2007-06-28 | Toyo Boseki Kabushiki Kaisha | Ply cord for polyester tire cap and process for producing the same |
| JP2012523341A (en) * | 2009-04-09 | 2012-10-04 | ソシエテ ド テクノロジー ミシュラン | Pneumatic tire with belt reinforced with thermoplastic polymer film |
| WO2019124502A1 (en) * | 2017-12-22 | 2019-06-27 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition and pneumatic tire |
| CN110049881A (en) * | 2016-12-09 | 2019-07-23 | 株式会社普利司通 | Heavy duty tire |
-
1997
- 1997-07-15 JP JP9190214A patent/JPH1134182A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6896930B2 (en) * | 2002-04-18 | 2005-05-24 | Toyo Boseki Kabushiki Kaisha | Method for manufacturing a polyester fiber cord for reinforcing rubber materials |
| WO2006093182A1 (en) * | 2005-03-03 | 2006-09-08 | Toyo Boseki Kabushiki Kaisha | Reinforcing polyester cord for rubbers and process for production thereof |
| WO2007072703A1 (en) * | 2005-12-22 | 2007-06-28 | Toyo Boseki Kabushiki Kaisha | Ply cord for polyester tire cap and process for producing the same |
| JP2012523341A (en) * | 2009-04-09 | 2012-10-04 | ソシエテ ド テクノロジー ミシュラン | Pneumatic tire with belt reinforced with thermoplastic polymer film |
| US9186871B2 (en) | 2009-04-09 | 2015-11-17 | Michelin Recherche Et Technique S.A. | Pneumatic tire, the belt of which is reinforced by a thermoplastic polymer film |
| CN110049881A (en) * | 2016-12-09 | 2019-07-23 | 株式会社普利司通 | Heavy duty tire |
| CN110049881B (en) * | 2016-12-09 | 2021-06-08 | 株式会社普利司通 | Heavy load tire |
| WO2019124502A1 (en) * | 2017-12-22 | 2019-06-27 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition and pneumatic tire |
| JPWO2019124502A1 (en) * | 2017-12-22 | 2020-11-19 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition and pneumatic tires |
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