JPH02157142A - Glass fiber collecting agent for reinforcing rubber - Google Patents
Glass fiber collecting agent for reinforcing rubberInfo
- Publication number
- JPH02157142A JPH02157142A JP63311714A JP31171488A JPH02157142A JP H02157142 A JPH02157142 A JP H02157142A JP 63311714 A JP63311714 A JP 63311714A JP 31171488 A JP31171488 A JP 31171488A JP H02157142 A JPH02157142 A JP H02157142A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- glass fiber
- rubber
- collecting agent
- aminosilane
- 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.)
- Granted
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 24
- 229920001971 elastomer Polymers 0.000 title claims abstract description 23
- 239000005060 rubber Substances 0.000 title claims abstract description 23
- 239000003365 glass fiber Substances 0.000 title claims abstract description 17
- 230000003014 reinforcing effect Effects 0.000 title claims abstract description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000126 latex Polymers 0.000 claims abstract description 7
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011115 styrene butadiene Substances 0.000 claims abstract description 3
- 239000004816 latex Substances 0.000 claims abstract 4
- 238000004513 sizing Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 239000000314 lubricant Substances 0.000 abstract description 8
- 239000004094 surface-active agent Substances 0.000 abstract description 7
- 230000002787 reinforcement Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000002480 mineral oil Substances 0.000 description 9
- 235000010446 mineral oil Nutrition 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000021523 carboxylation Effects 0.000 description 3
- 238000006473 carboxylation reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000015115 caffè latte Nutrition 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 102100030886 Complement receptor type 1 Human genes 0.000 description 1
- 101100007625 Homo sapiens CR1 gene Proteins 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000002752 cationic softener Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 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
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野］
本発明は、ゴムベルト、タイヤ等のゴム製品の補強用に
用いるガラス繊維の集束剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a sizing agent for glass fibers used for reinforcing rubber products such as rubber belts and tires.
［従来技術］
従来よりゴム補強用のガラス繊維の集束剤としては、そ
の基本組成として、シラン−接着剤−副資材（活性剤、
潤滑剤等）が−船釣であり、この接着剤としてゴム系、
樹脂系のものが種々知られている。例えば、■特開昭５
０−４２１９４号公報にはアクリロニクリルとアクリル
酸エステルの共重合物乳濁液を用いたもの、■特開昭５
７−２０９８５７号公報にはポリオキソアルキレンポリ
オールを用いたもの等が示されている。[Prior Art] Conventionally, the basic composition of glass fiber sizing agents for rubber reinforcement is silane, adhesive, and auxiliary materials (activators,
Lubricants, etc.) are used for boat fishing, and the adhesive used is rubber-based,
Various resin-based materials are known. For example, ■ Japanese Patent Publication No. 5
No. 0-42194 uses a copolymer emulsion of acryloniclyl and acrylic ester;
No. 7-209857 discloses a method using polyoxoalkylene polyol.
しかし、これらはいずれも接着性が十分とはいえないも
のである。However, none of these adhesives can be said to have sufficient adhesive properties.
［問題点を解決するための具体的手段］本発明者らは、
前記した従来法の問題点に鑑み、鋭意検討の結果本発明
に到達したものである。すなわち本発明は、アミノソラ
ンとカルボキンル化スヂレンーブタジエンラテノクスを
含有することを特徴とするゴム補強用ガラス繊維集束剤
である。[Specific means for solving the problem] The present inventors
In view of the problems of the conventional method described above, the present invention was arrived at as a result of intensive studies. That is, the present invention is a glass fiber sizing agent for rubber reinforcement characterized by containing aminosolane and carboxylated styrene-butadiene latenox.
本発明で使用するアミノシランとしては、特に限定され
ず、各種のアミノシランを用いることができ、具体的に
は、Ｔ−アミノプロピルトリメトキシシラン、δ−アミ
ノブチルトリエトキシソラン、ビス−（Ｔ−アミノプロ
ピル）ジメトキノンラン、δ−アミノブチルエチルジメ
］・キンソラン、Ｔ−アミノアリルトリメトキシシラン
、β−アミノビニルトリエトキシシラン、３−アミノソ
クロヘキシルエヂルトリエトキシシラン、ｐ−アミンフ
ェニルトリニドキシンラン、Ｎ−（β−アミノエチル）
−Ｔ−アミノプロビルトリメトキソシラン等が挙げられ
る。このうちガラス繊維とのなじみの点ではメトキンシ
ラン系よりもエトキシシラン系の方が好ましい。また、
カルボキシル化スチレンーブクジエンラテ／クス（以下
Ｃ−５Ｂ Ｒという）としてはカルボキシル化率が０１
〜３５％の範囲のものが市販されており、いずれも使用
することができるが、ガラス繊維とのなじみからカルボ
キシル化率は高い方が好ましく、２５〜３５％の範囲の
ものが推奨される。また、Ｃ−３ＢＲのスチレン含有率
は２０〜３０％の範囲が好ましい。The aminosilane used in the present invention is not particularly limited, and various aminosilanes can be used. Specifically, T-aminopropyltrimethoxysilane, δ-aminobutyltriethoxysolane, bis-(T-amino Propyl) dimethoquinonerane, δ-aminobutylethyldime]quinsolane, T-aminoallyltrimethoxysilane, β-aminovinyltriethoxysilane, 3-aminosochlorohexyledyltriethoxysilane, p-aminephenyltrinidoxinrane, N -(β-aminoethyl)
-T-aminopropyltrimethoxosilane and the like. Among these, the ethoxysilane type is preferable to the methquin silane type in terms of compatibility with glass fibers. Also,
Carboxylated styrene-bucdiene latte/cus (hereinafter referred to as C-5B R) has a carboxylation rate of 0.1
-35% is commercially available, and any of them can be used, but from the viewpoint of compatibility with glass fibers, a higher carboxylation rate is preferable, and a carboxylate in the range of 25-35% is recommended. Moreover, the styrene content of C-3BR is preferably in the range of 20 to 30%.
この範囲以下では処理後のガラス繊維が柔らか過ぎ、こ
れより多いと硬くなり過ぎるため、好ましくない。If it is less than this range, the glass fiber after treatment will be too soft, and if it is more than this, it will become too hard, which is not preferable.
本発明の集束剤においては、アミノシラン、Ｃ３ＢＲ以
外に通常集束剤に用いられる、界面活性剤、潤滑剤等の
各種副資材を用いることが好ましく、具体的には界面活
性剤としてノニオン系、カヂオン系の各種界面活性剤を
用いることができるが、液の安定性等の点からノニオン
系のものが好ましい。また、潤滑剤の使用により加工性
が向上し、動植物系、鉱物系等の各種潤滑剤が使用でき
る。このうち、液の安定性等から鉱物系のものが最も好
ましい。In the sizing agent of the present invention, in addition to aminosilane and C3BR, it is preferable to use various auxiliary materials such as surfactants and lubricants that are normally used in sizing agents. Specifically, nonionic and cationic surfactants are used as surfactants. Although various surfactants can be used, nonionic surfactants are preferred from the viewpoint of liquid stability. Furthermore, the use of a lubricant improves processability, and various lubricants such as animal/vegetable or mineral-based lubricants can be used. Among these, mineral-based ones are most preferred in terms of liquid stability and the like.
王剤であるアミツノラン、Ｃ−３ＢＲおよび界面活性剤
、潤滑剤等の副資材の使用量は特に制限はないが、これ
らの材料を多量の水に配合したものを用いるものであり
、一般には全体に対して、水が９０重量％以上となるよ
うに配合され、アミノシラン０１〜２０重量％、Ｃ−５
ＢＲ２，０〜１００重量％の範囲で用いられる。界面活
性剤の檄は通常００５〜０５重量％の範囲で、潤滑剤は
０４１〜２０重量％の範囲で使用される。There are no particular restrictions on the amount of the king agent Amitunoran, C-3BR, and auxiliary materials such as surfactants and lubricants used, but these materials are mixed with a large amount of water, and generally the total amount is , water is blended at 90% by weight or more, aminosilane 01-20% by weight, C-5
BR2, used in a range of 0 to 100% by weight. The amount of surfactant used is usually in the range of 0.05 to 0.5% by weight, and the amount of lubricant is used in the range of 0.41 to 20% by weight.
アミノシランの量がこの範囲より少ないと十分な接着強
度が得られず、この範囲より多いと液の安定性が損なわ
れるため好ましくない。If the amount of aminosilane is less than this range, sufficient adhesive strength cannot be obtained, and if it is more than this range, the stability of the liquid will be impaired, which is not preferable.
また、Ｃ−Ｓ Ｂ ＲＯ量がこの範囲より少ないと加工
性が十分ではなく、また、この範囲を越えるとゴム材料
との接着をより強固にするため用いられるレゾルシン・
ホルムアルデヒド樹脂ゴムラテックス（ＲＦ Ｌ ）分
散液の浸透が妨げられ、接着が不十分となる。Furthermore, if the amount of C-S B RO is less than this range, the processability will not be sufficient, and if it exceeds this range, resorcinol, which is used to strengthen the bond with the rubber material, will be used.
Penetration of the formaldehyde resin rubber latex (RF L ) dispersion is hindered, resulting in insufficient adhesion.
本発明の集束剤は通常の方法によりガラス繊維に適用さ
れる。すなわち、ガラスを溶融し、フィラメントの形態
となし、巻取る際、２００本程度を１束となし、集束剤
を塗布する。巻取ったストランドは常温で乾燥する。本
発明の集束剤の付着量は０１〜１５重量％の範囲が好ま
しく、望ましくは０２〜０５重量％である。この範囲よ
り少ないと加工性に劣り、この範囲より多いと接着性が
十分ではない。The sizing agent of the present invention is applied to glass fibers by conventional methods. That is, glass is melted and formed into a filament, and when wound up, about 200 filaments are made into a bundle and a sizing agent is applied. The wound strands are dried at room temperature. The adhesion amount of the sizing agent of the present invention is preferably in the range of 01 to 15% by weight, preferably 02 to 05% by weight. If it is less than this range, the processability will be poor, and if it is more than this range, the adhesiveness will not be sufficient.
このものは通常補強対象のゴム材料との接着のため３本
を引きそろえレゾルシン・ホルムアルデヒド樹脂ゴムラ
テックス分散液（ＲＦＬ）で処理し、通常２００〜３５
０°Ｃの範囲で乾燥をおこなう。This product is usually made of 3 pieces and treated with a resorcinol-formaldehyde resin rubber latex dispersion (RFL) for adhesion to the rubber material to be reinforced.
Dry at 0°C.
このＲＦＬ処理による固形分の付着量は１５〜２５重量
％の範囲が好ましい。The amount of solid content deposited by this RFL treatment is preferably in the range of 15 to 25% by weight.
このＲＦＬ処理ののちガラス繊維束に下撚りを加えたの
ち複数本を引きそろえてさらに上撚りをかけて補強用ガ
ラスコードとする。After this RFL treatment, a first twist is added to the glass fiber bundle, and then a plurality of fibers are pulled together and further twisted to obtain a reinforcing glass cord.
また、対象ゴム材料によっては、さらにゴム材料との接
着性を向上させるためゴム材料との接着性に優れた薬液
による処理を施すこともある。Furthermore, depending on the target rubber material, treatment with a chemical solution that has excellent adhesion to the rubber material may be performed in order to further improve the adhesion to the rubber material.
本発明の集束剤は安定性、加工性に優れ、ゴム材料との
接着強度が高く、高強度のゴム補強材料を提供すること
ができる。The sizing agent of the present invention has excellent stability and processability, has high adhesive strength with rubber materials, and can provide a high-strength rubber reinforcing material.
以下、本発明を実施例により具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例１
γ−アミノプロピルトリエトキンシラン（Ａ−１，１０
０、日本ユニカー社製）０５重重量、（、−３ＢＲ（Ｌ
−１４３２、カルボキシル化率３０％、旭化成工業社製
）４．２重量％、アルキルフェノールエーテル（へ°ネ
ト用Ｎ−１００８Ｃ、松本油脂社製） ０．１２重量％
、鉱物性オイル（）゛リアンＣ−４４４、松本油脂社製
）０．５重量％、純水９４６８重量％となるように調合
して集束剤を調製した。Example 1 γ-aminopropyltriethquin silane (A-1,10
0, manufactured by Nippon Unicar Co., Ltd.) 05 weight, (, -3BR (L
-1432, carboxylation rate 30%, manufactured by Asahi Kasei Industries, Ltd.) 4.2% by weight, alkylphenol ether (N-1008C for Heneto, manufactured by Matsumoto Yushi Co., Ltd.) 0.12% by weight
A sizing agent was prepared by mixing 0.5% by weight of mineral oil (Lian C-444, manufactured by Matsumoto Yushi Co., Ltd.) and 9468% by weight of pure water.
常法によりガラスを溶融し、フィラメント（９μｍ）の
形態となし、２００本を束として前記集束剤を塗布して
巻取り、常温で乾燥し、集束剤固形分村着量０４重量％
のストランドを得た。Glass was melted by a conventional method to form a filament (9 μm), 200 pieces were made into a bundle, coated with the above-mentioned sizing agent, rolled up, dried at room temperature, and the solid content of the sizing agent was 04% by weight.
I got a strand of.
このストランド３本を引きそろえ次のように調製したレ
ゾルシン ホルムアルデヒド樹脂ゴムラテックス分散液
（ＲＦ Ｌ ）により処理した。These three strands were drawn together and treated with a resorcin formaldehyde resin rubber latex dispersion (RF L ) prepared as follows.
ＲＦ Ｌの則ＪＬ
ビニルピリジン、スヂレンおよびブタジェンを１５・１
５ニア０の割合で含有する■Ｐ（住友ノーガソタ社製、
商品名ピラテ・／クス、固形分４１重量％）を４４７重
量部、ＳＢＲ（日本合成ゴム社製２１０８、固形分４０
ｆｔ ｉｔ ％ ）を１９５重量部、レゾルシンとホル
ムアルデヒドの付加縮合物を６７重量％含む水Ｍ’Ｓを
３２０重量部、その他アンモニア水（２５％）２２重量
部からなるＲＦＬを調製した。RF L's Law JL Vinylpyridine, styrene and butadiene at 15.1
■P (manufactured by Sumitomo Naugasota Co., Ltd.) containing at a ratio of 5 to 0
Product name: Pirate/Cus, solid content: 41% by weight), 447 parts by weight, SBR (manufactured by Japan Synthetic Rubber Co., Ltd. 2108, solid content: 40%)
ft it %), 320 parts by weight of water M'S containing 67% by weight of an addition condensate of resorcinol and formaldehyde, and 22 parts by weight of aqueous ammonia (25%) was prepared.
このものの固形分４−１着量は１９重量％であった。The solid content of this product was 19% by weight.
２８０°Ｃで２２秒間乾燥後、このガラス繊維束を１０
ｃｍ当り１６回の下撚りを与え、１３本引きそろえて１
０ＣＩ１１当り８回の上撚りを施したものを補強用ガラ
スコードとし、クロロプレンゴムとの接着性（剥離強度
）を評価したところ３１Ｋｇ／２５ｍｍであった。After drying at 280°C for 22 seconds, the glass fiber bundle was
Give 16 twists per cm, pull out 13 strands, and make 1
A reinforcing glass cord that had been twisted 8 times per 0CI11 was evaluated for adhesion (peel strength) to chloroprene rubber and found to be 31 kg/25 mm.
使用ゴム：クロロプレンゴム
クロロプレンゴム（昭和型ニーデュポン社製、ネオン０
レン ＧＲＴ６０． ネオブレンＷＲＴ４０ ）
１００ 重量部に対して、カーボンブラックＨＡＦ
４５重量部、亜鉛華５重量部、老化防止剤５重量部、
プロセスオイル４重量部、酸化マグネシウム４重量部、
ステアリン酸１重量部、イオウ０．５重量部、パラフィ
ンワックス０３重量部、加硫促進剤１重量部を配合した
もの。Rubber used: Chloroprene rubber Chloroprene rubber (manufactured by Showa type Ni Dupont Co., Ltd., neon 0
Ren GRT60. Neoblen WRT40)
Carbon black HAF per 100 parts by weight
45 parts by weight, 5 parts by weight of zinc white, 5 parts by weight of anti-aging agent,
4 parts by weight of process oil, 4 parts by weight of magnesium oxide,
Contains 1 part by weight of stearic acid, 0.5 part by weight of sulfur, 03 parts by weight of paraffin wax, and 1 part by weight of a vulcanization accelerator.
なお、測定方法は次のとおりである。The measurement method is as follows.
紅１先支
試験片はゴムシー）（３ｍｍ厚）上に処理済の補強ガラ
スコードを１９〜２０本／２５ｎ＋ｍならべ、さらにそ
の上に布をかぶせ、１４５°Ｃ３２５分間、２０Ｋｇ／
Ｃａ１の圧力で加硫成形して調製した。このものを剥
離速度５０ｍｍ／分で測定した。19 to 20 treated reinforced glass cords/25n+m were lined up on a rubber sheet (3mm thick), a cloth was placed over it, and the cord was heated at 145°C for 325 minutes at 20Kg/25n+m.
It was prepared by vulcanization molding at a pressure of Ca1. This product was measured at a peeling speed of 50 mm/min.
実施例２〜５
集束剤としてアミノシランの種類、量、Ｃ−３ＢＲの種
類、量を変えて次の組成のものとする以外は実施例１と
同様にして処理をおこない、剥離強度を測定した。Examples 2 to 5 The treatment was carried out in the same manner as in Example 1, except that the type and amount of aminosilane and the type and amount of C-3BR were changed to have the following composition as a sizing agent, and the peel strength was measured.
実施例２
Ｔ −アミノ７０ロヒ０ルトリエトキシシラン（前記と
同一品）
−５ＢＲ
（前記と同一品）
アルキルフェノールエーテル
（前記と同一品）
鉱物性オイル
純水
剥離強度： ２５Ｋｇ／２５ｍｍ
実施例３
Ｔ −アミラフ０ロビルトリエトキシシラン（前記と同
一品）
−５ＢＲ
（前記と同一品）
アルキルフェノールエーテル
（前記と同一品）
鉱物性オイル
純水
剥離強度： ３０Ｋｇ／２５ｍｌｌ１０２重量％
４２重量％
０１２重量％
０．５重量％
９４９８重量％
０８重量％
４．２重量％
０．１２重量％
０．５重量％
９４．３８重量％
実施例４
Ｔ −アミノブロヒ０ルトすｌ１ジシラン ０
５ 重量％（Ａ−１１１０、日本ユニカー社製）
Ｃ−５ＢＲ４，２重量％
（前記と同一品）
アルキルフェノールエーテル
０．１２重量％（前記と同一品）
鉱物性オイル ０５重量％純水
９４６８重量％剥離強度： ２４Ｋｇ／
２５ｍｍ
実施例５
Ｔ −アミノプロピルトリエトキシシラン（前記と同一
品）
Ｃ−ＳＢＲ ４ 、 ０重量％（
Ｌ−２６３１、旭化成工業社製）
アルキルフェノールエーテル
０．１２ｆｔ ｉ ％（前記と同一品）
鉱物性オイル ０．５重量％純水
９４８８重量％剥離強度： ２５Ｋｇ
／２５ｍｍ
比較例１〜６
集束剤として次の組成とする以外は実施例１と同様にし
て補強用ガラスコードを得、同様にして剥離強度を測定
した。Example 2 T-amino 70-chlorotriethoxysilane (same product as above) -5BR (same product as above) Alkylphenol ether (same product as above) Mineral oil Pure water peel strength: 25Kg/25mm Example 3 T- Amiraf Olovyltriethoxysilane (same as above) -5BR (same as above) Alkylphenol ether (same as above) Mineral oil pure water peel strength: 30Kg/25ml 102% by weight 42% by weight 012% by weight 0. 5% by weight 9498% by weight 08% by weight 4.2% by weight 0.12% by weight 0.5% by weight 94.38% by weight Example 4 T-aminobrophyllodisilane 0
5% by weight (A-1110, manufactured by Nippon Unicar Co., Ltd.) C-5BR4.2% by weight (same product as above) Alkylphenol ether
0.12% by weight (same product as above) Mineral oil 05% by weight Pure water
9468wt% peel strength: 24Kg/
25 mm Example 5 T-aminopropyltriethoxysilane (same product as above) C-SBR 4, 0% by weight (
L-2631, manufactured by Asahi Kasei Industries, Ltd.) Alkylphenol ether
0.12ft i% (same product as above) Mineral oil 0.5% by weight Pure water
9488wt% peel strength: 25Kg
/25mm Comparative Examples 1 to 6 Reinforcing glass cords were obtained in the same manner as in Example 1, except that the sizing agent had the following composition, and the peel strength was measured in the same manner.
比較例Ｉ
Ｔ −アミノ７０口ビルトリエトキシシラン
０．５ 重ｉｔ％（前記と同一品）
アミロース゛化澱粉 ２．
０ 重量％（Ｓ−１３０、シキシマ社製）
動植物油脂 ０５重量％（マコノールＴ
Ｓ−２７、松本油脂社製）力付ン系界面活性剤
０３重量％（カチオニックソフナー、 オニックスケ
ミカル 社製）純水 ９６７重量
％剥離強度： ６ Ｋｇ／２５ｍｍ
比較例２
Ｔ −アミノプロピルトリエトキシシラン（前記と同一
品）
ホ０リヒ゛ニルアルコール
１．ｏｆｆｉ！％（コ゛ーセノールＧＬー０５日本合
成化学工業社製）り゛リセリン
０ ５ 重量％（日本油脂社製）
アルキルフェノールエーテル
０．１２重ｔ ％（前記と同一品）
純水 ９７８８量％剥離強度：
８ Ｋｇ／２５ｍｍ
比較例３
γ −アミノプロピルトリエトキシシラン ０
．５ ｆｔｆｔ％（前記と同一品）
ＳＢＲラテ・敷ス
１ ８ 重量％（０５６１、日本合成ゴム社製）
アクリル系接着剤 ０．８重量％（
Ｓ−８０、松本油脂社製）
アルキルフェノールエーテル
Ｏ．１２ｍｉ％（前記と同一品）
鉱物性オイル ０５重量％純水
９６．２８重１％剥離強度： １９Ｋｇ
／２５ｍｍ
比較例４
γ −アミノ７０ロヒ０ルトリエトキシシラン
０ ５ ｉ１％（前記と同一品）
アク１几エマルシ゛ヨン
３．７ 重ｔ％（ＡＰ−６１．９、昭和高分子社製
）
アルキルフェルルエーテル
０．１２ｆｔ １ ％（前記と同一品）
鉱物性オイル ０５重量％純水
９５１８重量％剥離強度’ ７ Ｋｇ／
２５ｍｍ
比較例５
γ −アミノ７０ロヒ０ルトリエトキシシラン
０．５ 重１％（前記と同一品）
エポキシ系接着剤 ２．０重量％（工ボルシ
゛ヨンＥＡ−１、 カネネ゛−ＮＳＣ社製）アクリル系
接着剤 ０８重量％（前記と同一品）
アルキルフェノ刊しエーテル
ｏ １２ｆｔ １ ％（前記と同一品）
鉱物性オイル ０．５重量％純水
９６０８重量％剥離強度： １９Ｋｇ
／２５ｍｍ
比較例６
Ｔ −アミノ７０口ビル１リエ］・キシシラン
０．５ ｆｆｉ１％（前記と同一品）
アクリルアミド系接着剤 ８ ０
重量％（ＫＰ４０２ 、共栄社油脂社製）
アルキルフェルルエーテル
０． １２ｆｆｉ ｉｔ ％（前記と同一品）
鉱物性オイル ０５重量％純水
９０８８重量％剥離強度： １６Ｋｇ／２
５ｍｍ
［発明の効果］
本発明のガラス繊維集束剤は安定性、加工性に優れ、こ
れを用いたガラス繊維は各種ゴム材料との接着性が高く
、高強度のゴム補強体を得ることができるものである。Comparative Example I T-amino 70-neck pyrutriethoxysilane
0.5 weight% (same product as above) Amylodinated starch 2.
0% by weight (S-130, manufactured by Shikishima) Animal and vegetable oils 05% by weight (Maconol T
S-27, manufactured by Matsumoto Yushi Co., Ltd.) Strengthening surfactant
03% by weight (cationic softener, manufactured by Onyx Chemical Co., Ltd.) Pure water 967% by weight Peel strength: 6 Kg/25mm Comparative example 2 T-aminopropyltriethoxysilane (same product as above) Polyvinyl alcohol
1. Offi! % (Cosenol GL-05 manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.) Lycerin
0 5% by weight (manufactured by NOF Corporation) Alkylphenol ether
0.12% by weight (same product as above) Pure water 9788% by weight Peel strength:
8 Kg/25mm Comparative example 3 γ-aminopropyltriethoxysilane 0
．． 5 ftft% (same product as above) SBR latte/sheet
1 8% by weight (0561, manufactured by Japan Synthetic Rubber Co., Ltd.) Acrylic adhesive 0.8% by weight (
S-80, manufactured by Matsumoto Yushi Co., Ltd.) Alkylphenol ether
O. 12mi% (same product as above) Mineral oil 05% by weight Pure water
96.28 weight 1% peel strength: 19Kg
/25mm Comparative Example 4 γ-Amino 70% triethoxysilane
0 5 i1% (same product as above) 1 liter emulsion
3.7 wt% (AP-61.9, manufactured by Showa Kobunshi Co., Ltd.) Alkyl ferrule ether
0.12ft 1% (same product as above) Mineral oil 05% by weight Pure water
9518wt% peel strength' 7 Kg/
25mm Comparative Example 5 γ-amino70rotriethoxysilane
0.5 1% by weight (same product as above) Epoxy adhesive 2.0% by weight (Engineered Volsion EA-1, manufactured by Kanene-NSC) Acrylic adhesive 08% by weight (same product as above) Alkylphenol Published by Ether
o 12ft 1% (same product as above) Mineral oil 0.5% by weight Pure water
9608wt% peel strength: 19Kg
/25mm Comparative Example 6 T-amino 70-neck building 1 layer] xysilane
0.5 ffi1% (same product as above) Acrylamide adhesive 8 0
Weight% (KP402, manufactured by Kyoeisha Yushi Co., Ltd.) Alkyl ferrule ether
0. 12ffi it% (same product as above) Mineral oil 05% by weight Pure water
9088wt% peel strength: 16Kg/2
5 mm [Effects of the Invention] The glass fiber sizing agent of the present invention has excellent stability and processability, and the glass fibers using this agent have high adhesiveness with various rubber materials, and a high-strength rubber reinforcement body can be obtained. It is something.
Claims (1)
テックスを含有することを特徴とするゴム補強用ガラス
繊維集束剤。A glass fiber sizing agent for reinforcing rubber, characterized by containing aminosilane and carboxylated styrene-butadiene latex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63311714A JPH02157142A (en) | 1988-12-09 | 1988-12-09 | Glass fiber collecting agent for reinforcing rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63311714A JPH02157142A (en) | 1988-12-09 | 1988-12-09 | Glass fiber collecting agent for reinforcing rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02157142A true JPH02157142A (en) | 1990-06-15 |
| JPH0565454B2 JPH0565454B2 (en) | 1993-09-17 |
Family
ID=18020587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63311714A Granted JPH02157142A (en) | 1988-12-09 | 1988-12-09 | Glass fiber collecting agent for reinforcing rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02157142A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007197553A (en) * | 2006-01-26 | 2007-08-09 | Central Glass Co Ltd | Coating liquid for glass fiber and rubber-reinforcing glass fiber using the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5595646A (en) * | 1978-12-29 | 1980-07-21 | Ppg Industries Inc | Elastic coating composition for glass fiber and coated glass fiber |
| JPS57166340A (en) * | 1979-11-23 | 1982-10-13 | Ppg Industries Inc | Coating composition |
| JPS5888148A (en) * | 1981-11-18 | 1983-05-26 | Unitika Ltd | Sizing agent for glass fiber |
-
1988
- 1988-12-09 JP JP63311714A patent/JPH02157142A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5595646A (en) * | 1978-12-29 | 1980-07-21 | Ppg Industries Inc | Elastic coating composition for glass fiber and coated glass fiber |
| JPS57166340A (en) * | 1979-11-23 | 1982-10-13 | Ppg Industries Inc | Coating composition |
| JPS5888148A (en) * | 1981-11-18 | 1983-05-26 | Unitika Ltd | Sizing agent for glass fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007197553A (en) * | 2006-01-26 | 2007-08-09 | Central Glass Co Ltd | Coating liquid for glass fiber and rubber-reinforcing glass fiber using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0565454B2 (en) | 1993-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI262904B (en) | A substantially non-discoloring sizing composition, fiber and composite manufactured from such composition and method of manufacturing such fiber and composite | |
| JPH02133446A (en) | Composite material of rubber composition with fiber and hose | |
| JP3379561B2 (en) | Latex composition and method for producing the same | |
| US6106943A (en) | Cord for reinforcing a rubber and treating material thereof | |
| DE3202207A1 (en) | RUBBER-LIKE Graft COPOLYMER AND METHOD FOR GLUING RUBBER ON GLASS FIBERS | |
| FI61180C (en) | GLASFIBER VARS YTA AOTMINSTONE DELVIS AER OEVERDRAGEN MED ETT APPRETURMEDEL | |
| KR0127672B1 (en) | Adhesive composition | |
| WO1998001614A1 (en) | Treatment for rubber-reinforcing fibers, reinforcing fibers, and reinforced rubbers | |
| US3228903A (en) | Process for controlling the hydrolysis of an organo-silane to form a stable dispersion | |
| JPH02157142A (en) | Glass fiber collecting agent for reinforcing rubber | |
| JP3528652B2 (en) | Fiber treatment agent, reinforcing fiber treated therewith, and rubber product reinforced with the fiber | |
| DE3001838A1 (en) | METHOD FOR GLUING GLASS FIBERS WITH RUBBER OR RUBBER | |
| JPH10140123A (en) | Adhesive composition for tire-reinforcing organic fiber | |
| JPH0450144A (en) | Rubber-reinforcing fiber | |
| JP3876019B2 (en) | Manufacturing method of cord / rubber composite | |
| JPH046664B2 (en) | ||
| JPS639079B2 (en) | ||
| JPH0818854B2 (en) | Glass fiber for rubber reinforcement | |
| JPS6253004B2 (en) | ||
| JPH08120573A (en) | Glass fiber for reinforcement of hydrogenated nitrile rubber | |
| JPH02204347A (en) | Glass fiber bundling agent for reinforcing rubber | |
| JPH0443094B2 (en) | ||
| JPH06306344A (en) | Adhesive composition for rubber-reinforcing fiber | |
| KR100508225B1 (en) | Rubber reinforcing fiber treatment agent, reinforcing fiber and rubber reinforcing product | |
| JP3360605B2 (en) | Rubber reinforcing cord and its treating agent |