JPH0457833A - Method of treatment of glass fiber for reinforcing rubber - Google Patents
Method of treatment of glass fiber for reinforcing rubberInfo
- Publication number
- JPH0457833A JPH0457833A JP2168757A JP16875790A JPH0457833A JP H0457833 A JPH0457833 A JP H0457833A JP 2168757 A JP2168757 A JP 2168757A JP 16875790 A JP16875790 A JP 16875790A JP H0457833 A JPH0457833 A JP H0457833A
- Authority
- JP
- Japan
- Prior art keywords
- water
- rubber
- glass fiber
- fluorine
- liquid
- 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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 29
- 239000003365 glass fiber Substances 0.000 title claims abstract description 28
- 239000005060 rubber Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 8
- 230000003014 reinforcing effect Effects 0.000 title claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000126 latex Polymers 0.000 claims abstract description 23
- 239000005871 repellent Substances 0.000 claims abstract description 15
- 230000002940 repellent Effects 0.000 claims abstract description 14
- 239000000853 adhesive Substances 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 10
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000002787 reinforcement Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims 3
- 238000000576 coating method Methods 0.000 claims 3
- 239000004816 latex Substances 0.000 abstract description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 229920001897 terpolymer Polymers 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 abstract description 2
- 238000005452 bending Methods 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 239000012783 reinforcing fiber Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229920002681 hypalon Polymers 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Landscapes
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Reinforced Plastic Materials (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
いるゴム補強用ガラス繊維の処理方法に関するものであ
る。さらに詳しくは、歯付ベルトの如く、走行中に熱お
よび屈曲応力の両方を受ける製品の補強剤として使用さ
れるガラス繊維の処理方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for treating rubber reinforcing glass fibers used for reinforcing rubber products such as rubber belts and tires. More specifically, the present invention relates to a method for treating glass fibers used as reinforcing agents for products such as toothed belts that are subjected to both heat and bending stress during running.
〈従来の技術〉
ゴムベルト、タイヤ等のゴム製品の補強材として、ガラ
ス繊維コード等の補強繊維が広く用いられる。ゴムベル
ト等のゴム製品は繰り返し屈曲応力を受けるため屈曲疲
労を生じて性能が低下し、補強材とゴムマトリックスの
間に剥離が生したり、補強繊維が摩耗し、強度低下か生
じ易い。このような現象は熱及び水分によって特に加速
される傾向にある。このような屈曲疲労による剥離を防
止し、十分な補強効果を得るためには、補強繊維とゴム
との馴染み、接着力を大きくし、且つ耐熱、耐水性を持
たせる必要があり、このため補強繊維表面に種々の処理
剤か塗布される。<Prior Art> Reinforcing fibers such as glass fiber cords are widely used as reinforcing materials for rubber products such as rubber belts and tires. Rubber products such as rubber belts are subject to repeated bending stress, resulting in bending fatigue and performance deterioration. Peeling occurs between the reinforcing material and the rubber matrix, and reinforcing fibers wear out, resulting in a decrease in strength. Such phenomena tend to be particularly accelerated by heat and moisture. In order to prevent such peeling due to bending fatigue and obtain a sufficient reinforcing effect, it is necessary to increase the compatibility between reinforcing fibers and rubber, increase adhesive strength, and provide heat and water resistance. Various treatment agents are applied to the fiber surface.
処理剤としては各種のものが提案されている。Various types of processing agents have been proposed.
例えば特開昭平1−221433号公報には、レゾルシ
ン−ホルムアルデヒド水溶性縮合物、ビニルビリジンー
ブクジエンースチレンタポリマーラテックス、ジカルボ
キシル化ブタジェン−スチレン共重合体ラテックスおよ
びクロロスルホン化ポリエチレンラテックスを併用した
処理剤等各種処理剤が提案されている。For example, in JP-A-1-221433, a resorcinol-formaldehyde water-soluble condensate, a vinylpyridine-butadiene-styrene copolymer latex, a dicarboxylated butadiene-styrene copolymer latex, and a chlorosulfonated polyethylene latex are used in combination. Various processing agents such as processing agents have been proposed.
〈発明が解決しようとする課題〉
このような処理剤を用いることにより補強繊維とゴムマ
トリックス間の接着力及び処理剤自身の耐熱耐屈曲疲労
性は満足させることはできるが、処理剤自身の耐水性か
不充分なため、これらの処理剤で処理した補強繊維を用
いた場合、耐熱耐水耐屈曲疲労性に優れたゴム製品を得
難い欠点を有していた。この傾向はクロロスルホン化ポ
リエチレン及び水素添加ニトリルゴムのような接着性の
乏しい耐熱ゴムの補強用に用いる場合特に著しい。本発
明は従来技術の有していた前述の欠点を解消することに
ある。<Problems to be Solved by the Invention> By using such a treatment agent, it is possible to satisfy the adhesion between the reinforcing fibers and the rubber matrix and the heat resistance, bending fatigue resistance, and resistance of the treatment agent itself. Due to insufficient properties, when reinforcing fibers treated with these processing agents are used, it is difficult to obtain rubber products with excellent heat resistance, water resistance, bending fatigue resistance, and so on. This tendency is particularly remarkable when used for reinforcing heat-resistant rubbers with poor adhesion such as chlorosulfonated polyethylene and hydrogenated nitrile rubber. The present invention aims to overcome the aforementioned drawbacks of the prior art.
く課題を解決するための手段〉
本発明は前述の欠点を解決する目的のもとになされたも
のであり、ガラス繊維をゴムラテックス、レゾルシン−
ホルムアルデヒド水溶性縮合物及びフッソ系撥水撥油剤
を含む第1液で処理して熱処理した後、フッソ系撥水撥
油剤及びハロゲン含有ポリマー系接着剤を含む第2液で
処理して乾燥することを特徴とするゴム補強用ガラス繊
維の処理方法にある。Means for Solving the Problems> The present invention has been made with the aim of solving the above-mentioned drawbacks, and it combines glass fibers with rubber latex and resorcinol.
After treatment with a first liquid containing a formaldehyde water-soluble condensate and a fluorine-based water and oil repellent and heat treatment, treatment with a second liquid containing a fluorine-based water and oil repellent and a halogen-containing polymer adhesive and drying. A method for processing glass fiber for rubber reinforcement, characterized by:
次に、本発明を更に具体的に説明する。Next, the present invention will be explained in more detail.
まfil液について、ゴムラテックスとしてはブタジェ
ン−スチレン共重合体ラテックス、ジカルボキシル化ブ
タジェン−スチレン共重合体ラテックス、ビニルピリジ
ン−ブタジェン−スチレンターポリマーラテックス、ク
ロロスルホン化ポリエチレンラテックス等を好適に使用
できる。これらの中で、ジカルボキシル化ブタジェン−
スチレン共重合体ラテックス及びビニルピリジン−ブタ
ジェン−スチレンターポリマーラテックス及びクロロス
ルホン化ポリエチレンラテックスの混合物、例えば2種
または3種の混合物の場合はいずれかの1成分を20〜
80重量%含まれる混合物が特に好適な結果を得ること
ができる。ジカルボキシル化ブタジェン−スチレン共重
合体ラテックスとしては、ブタジェン20〜80wt%
、スチレン5〜70wt%およびエチレン性不飽和ジカ
ルボン酸1〜10 w t%を含有するものが特に適当
であり、N1pol 2570X5 (商品名、日本
ゼオン社製) 、JSR0668(商品名、日本合成ゴ
ム社製)等が好適に使用できる。ビニルピリジンーブタ
ジエンースチレンターボリマーラテックスとしては、当
業界の技術者に周知されている多数のその種のターポリ
マー類を使用できる。例えばビニルピリジン、ブタジェ
ン、スチレンの重合割合が10〜2060〜8010〜
2oのものが特に適当でありN1pol 2518F
S (商品名、日本ゼオン社製)、Pyratex(商
品名、住人ノーガタック社製)等か好適に使用できる。As for the rubber latex, butadiene-styrene copolymer latex, dicarboxylated butadiene-styrene copolymer latex, vinylpyridine-butadiene-styrene terpolymer latex, chlorosulfonated polyethylene latex, etc. can be suitably used as the rubber latex. Among these, dicarboxylated butadiene
In the case of a mixture of styrene copolymer latex, vinylpyridine-butadiene-styrene terpolymer latex, and chlorosulfonated polyethylene latex, for example, a mixture of two or three, one component is
Particularly suitable results can be obtained with mixtures containing 80% by weight. As the dicarboxylated butadiene-styrene copolymer latex, butadiene 20 to 80 wt%
, 5 to 70 wt% of styrene and 1 to 10 wt% of ethylenically unsaturated dicarboxylic acid are particularly suitable, such as N1pol 2570X5 (trade name, manufactured by Nippon Zeon Co., Ltd.), JSR0668 (trade name, manufactured by Nippon Gosei Rubber Co., Ltd.). ) etc. can be suitably used. As the vinylpyridine-butadiene-styrene turbopolymer latex, a large number of such terpolymers known to those skilled in the art can be used. For example, the polymerization ratio of vinylpyridine, butadiene, and styrene is 10 to 2060 to 8010 to
2o is particularly suitable, N1pol 2518F
S (trade name, manufactured by Nippon Zeon Co., Ltd.), Pyratex (trade name, manufactured by Susumu Naugatuck Co., Ltd.), etc. can be suitably used.
クロロスルホン化ポリエチレンラテックスとしては、塩
素含1125〜43wt%及び硫黄含量1.0〜1.5
wt%のものが特に適当であり、Esprene (商
品名、住人化学社製)等が好適に使用できる。The chlorosulfonated polyethylene latex has a chlorine content of 1125 to 43 wt% and a sulfur content of 1.0 to 1.5.
wt% is particularly suitable, and Esprene (trade name, manufactured by Susumu Kagaku Co., Ltd.) and the like can be suitably used.
レゾルシン−ホルムアルデヒド水溶性縮合物(以下RF
という)としてはレゾルシンとホルムアルデヒドを水酸
化アルカリ、アミンなどのアルカリ性触媒の存在下で反
応させて得られるレゾール型の水溶性付加縮合物が好適
に使用できる。特に好ましくはレゾルシンとホルムアル
デヒドの反応モル比が1+0.5〜3の割合で反応させ
たものが望ましい。Resorcinol-formaldehyde water-soluble condensate (hereinafter referred to as RF)
A resol-type water-soluble addition condensate obtained by reacting resorcinol and formaldehyde in the presence of an alkaline catalyst such as an alkali hydroxide or an amine can be suitably used. Particularly preferred is one in which resorcinol and formaldehyde are reacted at a reaction molar ratio of 1+0.5 to 3.
フッソ系撥水撥油剤としては、3〜20個、好ましくは
6〜12個の炭素原子を有するパーフルオロアルキル基
を有し、水不溶性で融点、ガラス転移点あるいは軟化点
が20℃以上で分子量が約700〜約200000の化
合物の水分散体が好適に用いられる。The fluoro-based water and oil repellent has a perfluoroalkyl group having 3 to 20 carbon atoms, preferably 6 to 12 carbon atoms, is insoluble in water, has a melting point, glass transition point or softening point of 20°C or higher, and has a molecular weight of 20°C or higher. Aqueous dispersions of compounds having a molecular weight of about 700 to about 200,000 are preferably used.
このようなパーフルオロアルキル基含有有機フッソ化合
物としては、次のものが挙げられる。Examples of such perfluoroalkyl group-containing organic fluorine compounds include the following.
(1)炭素数3〜20個のパーフルオロアルキル基を有
するビニル単量体の単独重合体またはフルオロアルキル
基を含まないビニル単量体との共重合体。(1) A homopolymer of a vinyl monomer having a perfluoroalkyl group having 3 to 20 carbon atoms or a copolymer with a vinyl monomer containing no fluoroalkyl group.
パーフルオロアルキル基を有するビニル単量体の例とし
て、次のものか挙げられる。Examples of vinyl monomers having perfluoroalkyl groups include the following.
CF (CF2)7(CH2)1.0COCH−CH2
CF (CF )CH0COC(CH3) −CH2
(CF3)20F(CF2)6(CH2)30COCH
=CH2
CF (CF ) (CH2) 20COC(CH
3)=CH2
CF (CF)SON(C3H7)(CH2)20CO
CH−CH2
CF (CF )So N (CH2CH20COC
H=CH2)2
またパーフルオロアルキル基を含まないビニル単量体の
例として、
塩化ビニル、エチレン、酢酸ビニル、フッ化ビニリデン
、アクリルニトリル、スチレン、アクリル酸とそのアル
キルエステル、アクリルアミド、ブタジェン、クロロブ
レンなとか挙げられ、これらは2種以上併用してもよい
。CF (CF2)7(CH2)1.0COCH-CH2
CF (CF)CH0COC(CH3) -CH2
(CF3)20F(CF2)6(CH2)30COCH
=CH2 CF (CF) (CH2) 20COC(CH
3)=CH2 CF (CF)SON(C3H7)(CH2)20CO
CH-CH2 CF (CF) So N (CH2CH20COC
H=CH2)2 Examples of vinyl monomers that do not contain perfluoroalkyl groups include vinyl chloride, ethylene, vinyl acetate, vinylidene fluoride, acrylonitrile, styrene, acrylic acid and its alkyl esters, acrylamide, butadiene, and chlorobrene. Two or more of these may be used in combination.
(2)炭素数3〜20個のパーフルオロアルキル基含有
の1価もしくは多価アルコールとフッソ化されていても
よい1価もしくは多価カルボン酸とのエステル。(2) Ester of a monohydric or polyhydric alcohol containing a perfluoroalkyl group having 3 to 20 carbon atoms and a monohydric or polyhydric carboxylic acid which may be fluorinated.
フッソ化されていてもよい1価もしくは多価アルコール
と炭素数3〜20個のパーフルオロアルキル基含有の1
価もしくは多価カルボン酸とのエステル。A monohydric or polyhydric alcohol which may be fluorinated and a perfluoroalkyl group containing 3 to 20 carbon atoms
Esters with monovalent or polyvalent carboxylic acids.
これらのエステルを形成する成分の例としては次のよう
な化合物がある。Examples of components that form these esters include the following compounds.
CF (CF) 5ON(C3H7)CH2CH20C
F (CF)SON(C2H5)CH2CH(0H)C
H20H
CF (CF2)7S02N(C3H7)CH2COO
H1安息香酸、アジピン酸、フタル酸、マレイン酸、エ
チレングリコール、プロピレングリコール、グリセリン
、エチレングリコールモノエチルエーテル。CF (CF) 5ON(C3H7)CH2CH20C
F (CF)SON(C2H5)CH2CH(0H)C
H20H CF (CF2)7S02N(C3H7)CH2COO
H1 Benzoic acid, adipic acid, phthalic acid, maleic acid, ethylene glycol, propylene glycol, glycerin, ethylene glycol monoethyl ether.
(3)炭素数3〜20個のパーフルオロアルキル基を有
する1価または多価アルコールと1価または多価イソシ
アネートとのウレタン。(3) Urethane made of a monohydric or polyhydric alcohol having a perfluoroalkyl group having 3 to 20 carbon atoms and a monohydric or polyhydric isocyanate.
この例としては、フェニルイソシアネート、トリレンジ
イソシアネート、ヘキサメチレンジイソシアネートとの
ウレタンがある。Examples of this are urethanes with phenyl isocyanate, tolylene diisocyanate, hexamethylene diisocyanate.
これ等の水分散体が例示でき、DicguardF−7
0およびF−60(商品名、大日本インキ化学社製)等
が好適に使用できる。Examples of these water dispersions include Dicguard F-7
0 and F-60 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), etc. can be suitably used.
上述した本発明第2液の濃度は5〜15wt%好ましく
は7〜10wt%とするのが適当である。濃度があまり
薄いとガラス繊維への付着か不充分となり、叉濃度があ
まり濃い過ぎると付着むらか生じ易い。第2液の付着量
は固形分としてガラス繊維重量の1.5〜7.0wt%
、好ましくは2.5〜5.0wt%とするのが適当であ
り、この量があまり少ないと本発明の効果か充分でなく
、叉この量があまり多いと繊維の柔軟性が低下する。The concentration of the second liquid of the present invention mentioned above is suitably 5 to 15 wt%, preferably 7 to 10 wt%. If the concentration is too low, adhesion to glass fibers will be insufficient, and if the concentration is too high, uneven adhesion will likely occur. The amount of the second liquid attached is 1.5 to 7.0 wt% of the weight of the glass fiber as a solid content.
, preferably 2.5 to 5.0 wt %; if this amount is too small, the effect of the present invention will not be sufficient, and if this amount is too large, the flexibility of the fiber will decrease.
第2液を付与したガラス繊維を80〜150℃、好まし
くは100〜120℃で乾燥する。乾燥時間は溶剤残量
を0.5wt%以下となるように設定するのが適当であ
る。The glass fiber to which the second liquid has been applied is dried at 80 to 150°C, preferably 100 to 120°C. It is appropriate to set the drying time so that the remaining amount of solvent is 0.5 wt% or less.
本発明のガラス繊維で補強すべきゴムの種類に特に限定
はないが、クロロスルホン化ポリエチレンゴム、水素添
加ニトリルゴム等が例示でき、極めて好適な結果を得る
ことができ、耐熱耐水耐屈曲性に優れたタイミングベル
ト等の補強ゴム製品が得られる。There is no particular limitation on the type of rubber to be reinforced with the glass fibers of the present invention, but chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber, etc. can be used as examples, and very suitable results can be obtained, with excellent heat resistance, water resistance, and bending resistance. Excellent reinforced rubber products such as timing belts can be obtained.
〈作用〉
本発明処理剤の第1液および第2液はともにフッソ系撥
水撥油剤を含有しているので、耐水性及び耐油性が向上
し、本発明処理剤で処理したガラス繊維を補強材として
用いた場合、自動車エンジンルームのような高温度、高
湿度、で油分の多い環境下で屈曲応力を受けても、ガラ
ス繊維とゴムマトリックス間の接着力の低下が起こらな
いため疲労が生じ難くなるものと思われる。<Function> Since both the first and second liquids of the treatment agent of the present invention contain a fluorine-based water and oil repellent, water resistance and oil resistance are improved and the glass fibers treated with the treatment agent of the present invention are reinforced. When used as a material, even if subjected to bending stress in a high temperature, high humidity, and oily environment such as an automobile engine compartment, the adhesive strength between the glass fiber and the rubber matrix does not decrease, causing fatigue. I think it will become difficult.
以下実施例により本発明を更に詳細に説明する。The present invention will be explained in more detail with reference to Examples below.
〈実施例〉
レゾルシン−ホルムアルデヒド水溶性縮合物(固形分含
量8wt%、レゾルシンとホルムアルデヒドの反応モル
比 1:1.5)3重量部、ビニルピリジン−ブタジェ
ン−スチレンターポリマーラテックス(N1pol 2
518FS商品名、 日本ゼオン製、固形分含量40w
t%)30重量部、ジカルボキシル化ブタジェン−スチ
レン共重合体ラテックス(Nipol 2570X5商
品名、日本ゼオン製、固形分含量40wt%)15重量
部、クロロスルホン化ポリエチレンラテックス(Esp
rene 200商品名、住人化学製、固形分含14
0wt%)20重量部、25%アンモニア水1重量部、
フッソ系撥水撥油剤(Dicguard F−70商品
名、大日本インキ化学製、固形分含!20wt%) 1
重量部、水4重量部からなる第1液を、9μmのガラス
繊維を200本集束してなるガラス繊維束を3本引き揃
えて常法に従って付与し、250°Cの温度で2分間熱
処理して第1液の付着量がガラス繊維に対して20wt
%のガラス繊維束を得た。<Example> 3 parts by weight of resorcinol-formaldehyde water-soluble condensate (solid content 8 wt%, reaction molar ratio of resorcinol and formaldehyde 1:1.5), vinylpyridine-butadiene-styrene terpolymer latex (N1pol 2
518FS product name, manufactured by Nippon Zeon, solid content 40w
t%) 30 parts by weight, dicarboxylated butadiene-styrene copolymer latex (Nipol 2570
rene 200 product name, made by Juju Chemical, solid content: 14
0wt%) 20 parts by weight, 1 part by weight of 25% ammonia water,
Fluorine-based water and oil repellent (Dicguard F-70 trade name, manufactured by Dainippon Ink Chemical, solid content included! 20wt%) 1
A first liquid consisting of 4 parts by weight and 4 parts by weight of water was applied in accordance with a conventional method to three glass fiber bundles made of 200 9 μm glass fibers, and heat treated at a temperature of 250°C for 2 minutes. The amount of the first liquid attached to the glass fiber is 20wt.
% glass fiber bundles were obtained.
次にこのガラス繊維束を1インチ当り2,1回のZ方向
(S方向)の下撚りを与え、更にこの下撚りを与えた繊
維束を13本合糸して1インチ当り2.1回のS方向(
Z方向)の上撚りを施し、ECG150 3/13 2
.l5(Z)のガラス繊維コードを得た。Next, this glass fiber bundle is first twisted in the Z direction (S direction) 2.1 times per inch, and then 13 fiber bundles that have been given this first twist are twisted together 2.1 times per inch. S direction (
Z-direction) with upper twist, ECG150 3/13 2
.. A glass fiber cord of 15 (Z) was obtained.
次にこのガラス繊維コートに、クロロスルホン化ポリエ
チレン、イソシアネート及び有機溶剤より成るハロゲン
含有ポリマー系接着剤液(ケムロック402 商品名、
ロードコーポレーンヨン製、固形分含量15wt%)
50重量部、パーフルオロアルキル基含有アクリル共重
合体(Dieguard F−327商品名、大日本
インキ化学製、固形分含量7.5wt%)0.8重量部
、トリクロロエチレン50重量部よりなる第2液を常法
によって付与し、110’Cの温度で1分間乾燥して第
2液の付着量かガラス繊維コードに対して3.5wt%
のガラス繊維コードを得た。Next, a halogen-containing polymer adhesive solution (Chemlock 402 trade name,
Manufactured by Lord Corporation Rayon, solid content 15wt%)
50 parts by weight, 0.8 parts by weight of perfluoroalkyl group-containing acrylic copolymer (Dieguard F-327 trade name, manufactured by Dainippon Ink Chemical, solid content 7.5 wt%), and 50 parts by weight of trichlorethylene. was applied by a conventional method and dried at a temperature of 110'C for 1 minute to reduce the amount of the second liquid deposited to 3.5 wt% based on the glass fiber cord.
obtained glass fiber cord.
このコードを補強繊維として表−1の配合のゴムを用い
巾19mm、長さ980mmの歯付きベルトを作成した
。A toothed belt having a width of 19 mm and a length of 980 mm was prepared using this cord as a reinforcing fiber and rubber having the composition shown in Table 1.
この歯付きベルトを6000rpmの駆動モーターを備
えた注水走行試験機に装着し、ベルト歯面とプーリー歯
面が噛み合い始める部分に水をIL / Hrの速度で
滴下しながら24Hrs走行させた後のベルトの引っ張
り強度保持率を求めた。This toothed belt was attached to a water injection running test machine equipped with a 6000 rpm drive motor, and the belt was run for 24 hours while water was dripped at the part where the belt tooth surface and the pulley tooth surface begin to mesh at a speed of IL/Hr. The tensile strength retention rate was determined.
結果を表−2に示す。The results are shown in Table-2.
く比較例〉
実施例でフッソ系撥水撥油剤を用いない他は実施例と全
く同様な試験を行った。結果を表−2に示す。Comparative Example> A test was carried out in exactly the same manner as in the example except that the fluorine-based water and oil repellent was not used. The results are shown in Table-2.
〈発明の効果〉
本発明処理方法で処理したガラス繊維で補強したゴム製
品は、補強繊維とマトリックスゴム間の結合力が大きく
、繰り返し屈曲応力を受けても強度が低下せす、かつ耐
水性が大きく、高湿環境下で繰り返し屈曲応力を与えて
も強度低下か少ない。<Effects of the Invention> Rubber products reinforced with glass fibers treated by the treatment method of the present invention have a large bonding force between the reinforcing fibers and the matrix rubber, and their strength does not decrease even when subjected to repeated bending stress, and they have low water resistance. It is large, so even if repeated bending stress is applied in a high humidity environment, the strength will only decrease.
(以下空白) 表−1 ゴム配合 配 ム 薬 重量部 水素化ニトリルゴム (ゼットポ ル2020) カ ボンブラック 酸 化 亜 鉛 ステアリン酸 チ オコル 硫 黄 0。(blank below) Table-1 rubber compound Distribution Mu medicine Weight part hydrogenated nitrile rubber (Zetpo Le 2020) mosquito bomb black acid transformation sub lead stearic acid blood Ocol sulfur yellow 0.
テトラメチルチウラム ジスルフィ ド 1。Tetramethylthiuram Disulfy de 1.
シクロへキシルベンゾ チアジルスルフェンアミ ド 1、 表−X 実施例 比較例 ベルト強度 保持率(%)cyclohexylbenzo Thiadylsulfenamide de 1, Table-X Example Comparative example belt strength Retention rate (%)
Claims (4)
水溶性縮合物及びフッソ系撥水撥油剤を含む第1液で処
理して熱処理した後、フッソ系撥水撥油剤及びハロゲン
含有ポリマー系接着剤を含む第2液で処理して乾燥する
ことを特徴とするゴム補強用ガラス繊維の処理方法。(1) After being treated with a first liquid containing rubber latex, a resorcinol-formaldehyde water-soluble condensate, and a fluorine-based water and oil repellent and heat-treated, a second liquid containing a fluorine-based water and oil repellent and a halogen-containing polymer adhesive is applied. A method for processing glass fiber for rubber reinforcement, which is characterized by processing with a liquid and drying.
溶性縮合物及びフッソ系撥水撥油剤は、ゴムラテックス
に対して各々5〜15wt%、0.1〜1.5wt%含
まれている特許請求の範囲第1項記載のゴム補強用ガラ
ス繊維の処理方法。(2) A patent claim in which the resorcinol-formaldehyde water-soluble condensate and the fluorine-based water/oil repellent in the first liquid are contained in amounts of 5 to 15 wt% and 0.1 to 1.5 wt%, respectively, based on the rubber latex. A method for treating glass fibers for rubber reinforcement according to item 1.
剤はともにパーフルオロアルキル基を有する、水不溶性
化合物の水分散体である特許請求の範囲第1項または第
2項記載のゴム補強用ガラス繊維のの処理方法。(3) The fluorine-based water and oil repellent in the first liquid and the second liquid are both a water dispersion of a water-insoluble compound having a perfluoroalkyl group, according to claim 1 or 2. A method of processing glass fiber for rubber reinforcement.
ン−ホルムアルデヒド水溶性縮合物及びフッソ系撥水撥
油剤を含む第1の被覆と、その上に、フッソ系撥水撥油
剤及びハロゲン含有ポリマー系接着剤を含む第2の被覆
とを有するゴム補強用ガラス繊維。(4) A first coating containing rubber latex, a water-soluble condensate of resorcinol-formaldehyde, and a fluorine-based water and oil repellent on the surface of the glass fiber, and a fluorine-based water and oil repellent and a halogen-containing polymer adhesive on top of the first coating. and a second coating containing a rubber reinforcing glass fiber.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2168757A JP2894799B2 (en) | 1990-06-27 | 1990-06-27 | Glass fiber for rubber reinforcement |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2168757A JP2894799B2 (en) | 1990-06-27 | 1990-06-27 | Glass fiber for rubber reinforcement |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0457833A true JPH0457833A (en) | 1992-02-25 |
JP2894799B2 JP2894799B2 (en) | 1999-05-24 |
Family
ID=15873872
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2168757A Expired - Fee Related JP2894799B2 (en) | 1990-06-27 | 1990-06-27 | Glass fiber for rubber reinforcement |
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Country | Link |
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JP (1) | JP2894799B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7019071B2 (en) | 2001-11-06 | 2006-03-28 | Asahi Fiber Glass Company, Limited | Binder for inorganic fiber and heat insulating acoustic inorganic fiber material |
WO2017183660A1 (en) * | 2016-04-21 | 2017-10-26 | 日本板硝子株式会社 | Rubber-reinforcing cord and rubber product using same |
WO2023106282A1 (en) * | 2021-12-07 | 2023-06-15 | 竹本油脂株式会社 | Sizing agent for inorganic fibers, inorganic fibers, production method therefor, and composite material |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63126975A (en) * | 1986-11-14 | 1988-05-30 | 旭フアイバ−グラス株式会社 | Treatment of rubber reinforcing fiber |
JPS63126974A (en) * | 1986-11-14 | 1988-05-30 | 旭フアイバ−グラス株式会社 | Treatment agent for rubber reinforcing fiber |
-
1990
- 1990-06-27 JP JP2168757A patent/JP2894799B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63126975A (en) * | 1986-11-14 | 1988-05-30 | 旭フアイバ−グラス株式会社 | Treatment of rubber reinforcing fiber |
JPS63126974A (en) * | 1986-11-14 | 1988-05-30 | 旭フアイバ−グラス株式会社 | Treatment agent for rubber reinforcing fiber |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7019071B2 (en) | 2001-11-06 | 2006-03-28 | Asahi Fiber Glass Company, Limited | Binder for inorganic fiber and heat insulating acoustic inorganic fiber material |
WO2017183660A1 (en) * | 2016-04-21 | 2017-10-26 | 日本板硝子株式会社 | Rubber-reinforcing cord and rubber product using same |
JPWO2017183660A1 (en) * | 2016-04-21 | 2019-02-21 | 日本板硝子株式会社 | Rubber reinforcing cord and rubber product using the same |
WO2023106282A1 (en) * | 2021-12-07 | 2023-06-15 | 竹本油脂株式会社 | Sizing agent for inorganic fibers, inorganic fibers, production method therefor, and composite material |
JP2023084543A (en) * | 2021-12-07 | 2023-06-19 | 竹本油脂株式会社 | Sizing agent for inorganic fibers, inorganic fibers and production method thereof, and composite material |
Also Published As
Publication number | Publication date |
---|---|
JP2894799B2 (en) | 1999-05-24 |
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