JPH01126385A - Adhesive composition - Google Patents
Adhesive compositionInfo
- Publication number
- JPH01126385A JPH01126385A JP28338187A JP28338187A JPH01126385A JP H01126385 A JPH01126385 A JP H01126385A JP 28338187 A JP28338187 A JP 28338187A JP 28338187 A JP28338187 A JP 28338187A JP H01126385 A JPH01126385 A JP H01126385A
- Authority
- JP
- Japan
- Prior art keywords
- latex
- trithiol
- triazines
- adhesive composition
- adhesive
- 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
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 45
- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 229920000126 latex Polymers 0.000 claims abstract description 27
- 239000004816 latex Substances 0.000 claims abstract description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
- 101100294115 Caenorhabditis elegans nhr-4 gene Proteins 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 36
- 239000000806 elastomer Substances 0.000 abstract description 32
- 239000004753 textile Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000002657 fibrous material Substances 0.000 description 22
- 239000000835 fiber Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 9
- -1 polyethylene terephthalate Polymers 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920002681 hypalon Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229920006173 natural rubber latex Polymers 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 230000010062 adhesion mechanism Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical group C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- QZQIWEZRSIPYCU-UHFFFAOYSA-N trithiole Chemical compound S1SC=CS1 QZQIWEZRSIPYCU-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
■ 技術分野
本発明は繊維材料とエラストマーとを接着させるiam
処理用接着組成物に関し、より詳しくは、!a維材料を
、従来接着性が不十分であった極性基を有する非汎用エ
ラストマーとも高い接着性を示すようにする繊維処理用
接着組成物に関する。[Detailed Description of the Invention] ■ Technical Field The present invention is an iam bonding method for bonding fiber materials and elastomers.
For more information on adhesive compositions for treatment, please see! This invention relates to an adhesive composition for treating fibers that allows fiber materials to exhibit high adhesion to non-general-purpose elastomers having polar groups, which have conventionally had insufficient adhesion.
!I 従来技術
一般に、タイヤ、ベルトならびにホース等のエラストマ
ー製品の補強材として、繊維材料(ナイロン6およびナ
イロン66に代表されるポリアミド系繊維、ポリエチレ
ンテレフタレートに代表されるポリエステル系繊維、ポ
リビニルアルコールに代表されるビニロン繊維、レーヨ
ンに代表されるセルロース系繊維、ポリパラフェニレン
テレフタルアミドに代表される芳香系ポリアミド繊維等
)が使用されている。 そして、これら繊維材料をエラ
ストマーに接着させる場合には、通常、まず繊維材料を
レゾルシン−ホルマリン初期縮合物とラテックスとの混
合接着液(以下、RFLと称する)で処理し、次いでエ
ラストマー製品の原料であるエラストマー配合物と圧着
、加熱する。! I. Prior Art In general, fiber materials (polyamide fibers represented by nylon 6 and nylon 66, polyester fibers represented by polyethylene terephthalate, polyvinyl alcohol) are used as reinforcing materials for elastomer products such as tires, belts, and hoses. vinylon fibers, cellulose fibers typified by rayon, aromatic polyamide fibers typified by polyparaphenylene terephthalamide, etc.) are used. When bonding these fiber materials to an elastomer, the fiber materials are usually first treated with a mixed adhesive liquid (hereinafter referred to as RFL) of a resorcinol-formalin initial condensate and latex, and then treated with a raw material for the elastomer product. Press with some elastomer compound and heat.
このように繊維材料をRFLで処理すると、ia ui
材料を天然ゴム、ブタジェンゴム、スチレンブタジェン
ゴム、イソプレンゴム等の汎用エラストマーと接着させ
る場合には十分な接着力が得られる。When textile materials are treated with RFL in this way, ia ui
Sufficient adhesive strength can be obtained when the material is bonded to general-purpose elastomers such as natural rubber, butadiene rubber, styrene-butadiene rubber, and isoprene rubber.
しかしながら、繊維材料を極性基を有するクロロブレン
ゴム、アクリロニトリル−ブタジェンゴム、エピクロル
ヒドリンゴム、塩素化ポリエチレン、クロロスルホニル
ポリエチレン等の非汎用エラストマーと接着させる場合
には十分な接着力が得られないという問題点がある。However, when bonding fiber materials to non-commercial elastomers such as chloroprene rubber, acrylonitrile-butadiene rubber, epichlorohydrin rubber, chlorinated polyethylene, and chlorosulfonyl polyethylene, which have polar groups, there is a problem in that sufficient adhesive strength cannot be obtained. be.
しかし、当該非汎用エラストマーは耐熱性、耐候性、耐
油性、耐炎性等、汎用エラストマーにない優れた特性を
有しているので、ホース、コンベヤベルトの他あらゆる
エラストマー製品に利用され、工業的に利用価値が大き
い。 この為、非汎用エラストマーと繊維材料との接着
改善に関し、従来より種々検討されてきたが、その接着
機構がかなり複雑であること、また、エラストマーへの
配合物の相違により、接着力がかなり左右されること等
により接着性の改善が困難で、満足できる水準に至って
いない。However, this non-general-purpose elastomer has excellent properties that general-purpose elastomers do not have, such as heat resistance, weather resistance, oil resistance, and flame resistance, so it is used in all kinds of elastomer products such as hoses and conveyor belts, and is used industrially. It has great utility value. For this reason, various studies have been made to improve the adhesion between non-general-purpose elastomers and fiber materials, but the adhesion mechanism is quite complex, and the adhesion strength varies considerably due to differences in the composition of the elastomer. It is difficult to improve the adhesion due to the fact that the adhesion is affected, and the adhesion has not yet reached a satisfactory level.
そこで、繊維材料に非汎用エラストマーに対しても高い
接着性を付与する繊維処理用接着組成物の開発が望まれ
ていた二
III 発明の目的
本発明は、かかる従来技術の問題点を解決しようとする
ものであって、1llia材料とあらゆるエラストマー
、特に非汎用エラストマーとの接着力を向上せしめる繊
維処理用接着組成物を提供することを目的とする。Therefore, it has been desired to develop an adhesive composition for treating fibers that imparts high adhesion to non-general-purpose elastomers to fiber materials. It is an object of the present invention to provide an adhesive composition for fiber treatment that improves the adhesive strength between 1llia material and any elastomer, especially non-common elastomer.
■ 発明の構成
本発明者は上記目的を達成すべく鋭意努力した結果、R
FLにトリチオール−5−)−リアジンまたはその誘導
体を添加したものを繊維処理用接着組成物として使用す
ることにより1a維材料とエラストマー配合物との接着
力が飛躍的に向上することを見い出し本発明を完成する
に至った。■ Structure of the Invention As a result of the inventor's earnest efforts to achieve the above object, R
It has been discovered that the adhesive strength between the 1a fiber material and the elastomer compound can be dramatically improved by using FL with trithiol-5-)-lyazine or its derivatives added as an adhesive composition for fiber treatment, and the present invention has been made. I was able to complete it.
即ち、本発明はレゾルシン−ホルマリン初期縮合物とラ
テックスか、らなる接着液(RFL)と、式(1) で
示されるトリチオール−S−トリアジン類
■
(式中、R,、R,およびR3の少なくとも2つは独立
的にSHまたはSM(但し、Mはアルカリ金属を表わす
)を表わし、R+ 、R2およびR5の残りはSH。That is, the present invention provides an adhesive liquid (RFL) consisting of a resorcin-formalin initial condensate and latex, and a trithiol-S-triazine represented by the formula (1) (where R, R, and R3 are At least two independently represent SH or SM (where M represents an alkali metal), and the remainder of R+, R2 and R5 is SH.
SM(但し、Mはアルカリ金属を表わす)、NHR4(
式中、R4はフェニル、シクロヘキシルまたはCnH2
n+I(但し、n = 1〜6 )を表わす)、
NRsRg(式中、RSおよびR6は独立的にフェニル
、シクロヘキシルまたはCIIH2n、。SM (where M represents an alkali metal), NHR4 (
In the formula, R4 is phenyl, cyclohexyl or CnH2
n+I (where n = 1 to 6)), NRsRg (wherein RS and R6 are independently phenyl, cyclohexyl or CIIH2n).
(但し、nl1111〜6)を表わす)、およびSR?
C0Ra (式中、RyはCnH,、(但し、nx
l〜3)、R6はCnH2n、1(1M1〜6)表わす
)、
から選ばれる1つを表わす〕
の1種以上とが含有されていることを特徴とする接着組
成物を提供する。(However, it represents nl1111-6)), and SR?
C0Ra (wherein, Ry is CnH, (however, nx
1-3), R6 represents one selected from CnH2n, 1 (1M1-6)), and R6 represents one selected from the following.
上記発明においては前記トリチオール−S −トリアジ
ン類が前記RFLのラテックスの固形分1001i量部
に対して1〜12!!量部含まれることが好ましい。In the above invention, the amount of the trithiol-S-triazine is 1 to 12 parts per 1001 i parts of the solid content of the latex of the RFL. ! It is preferable that a certain amount is included.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の接着組成物で使用するRFLとしては、従来繊
維処理用接着液として使用されてきたレゾルシン−ホル
マリンの初期締金物とラテックスとの混合液を使用する
ことができる。As the RFL used in the adhesive composition of the present invention, a mixed solution of resorcinol-formalin initial clamp and latex, which has been conventionally used as an adhesive for treating fibers, can be used.
即ち、RFLとしては、レゾルシンとホルマリンをそれ
らの仕込みモル比1.Olo、5〜1.015.0の範
囲で塩基性触媒下で反応させ、その反応物であるレゾル
シン・ホルマリン初期締金物とゴムラテックスの1i量
比が5/100〜50/100となるように両者を混合
したRFL、あるいは酸性触媒下で反応させたレゾルシ
ンホルマリン初期締金物を塩基で中和した後ホルマリン
とゴムラテックスを加え混合したRFL等をあげること
ができる。That is, for RFL, resorcin and formalin are charged at a molar ratio of 1. Olo, reacted under a basic catalyst in the range of 5 to 1.015.0, and the 1i ratio of the reactant resorcin/formalin initial clamping material to the rubber latex was 5/100 to 50/100. Examples include RFL in which both are mixed, or RFL in which formalin and rubber latex are added and mixed after neutralizing resorcinol-formalin initial clamping products with a base, which are reacted under an acidic catalyst.
また、RFLのラテックス成分としては、ラテックスが
極性基を有するか否かを問わず使用することができる。Moreover, as a latex component of RFL, it can be used regardless of whether the latex has a polar group or not.
具体的には天然ゴムラテックス、スチレン・ブタジェ
ン共重合体ラテックス、スチレン−ブタジェン−ビニル
ビリジン共重合体ラテックス、アクリロニトリル−ブタ
ジェン共重合体ラテックス、クロロブレンラテックス、
クロロスルホニルポリエチレンラテックス、アクリレー
トブタジェン共重合体ラテックス、ポリ塩化ビニルラテ
ックス、塩化ビニル−酢酸ビニル共重合体ラテックス等
を用いることが出来る。 但し、この場合、通常、被着
エラストマー配合物と同類のもの、例えば天然ゴム、ス
チレン・ブタジェン共重合体ゴムに対してはビニルピリ
ジン・スチレン・ブタジエン3元共重合体ゴムラテック
ス、スチレン・ブタジェン共重合体ゴムラテックス、天
然ゴムラテックスを、またクロロブレンゴムに対しては
クロロブレンゴムラテックスを、さらにまた、クロロス
ルホン化ポリエチレンゴムに対してはクロロスルホン化
ポリエチレンゴムラテックスを用いることが好ましい。Specifically, natural rubber latex, styrene-butadiene copolymer latex, styrene-butadiene-vinylpyridine copolymer latex, acrylonitrile-butadiene copolymer latex, chlorobrene latex,
Chlorosulfonyl polyethylene latex, acrylate butadiene copolymer latex, polyvinyl chloride latex, vinyl chloride-vinyl acetate copolymer latex, etc. can be used. However, in this case, the same type of elastomer compound as the adhered elastomer compound, such as natural rubber or styrene-butadiene copolymer rubber, is usually replaced with vinylpyridine-styrene-butadiene ternary copolymer rubber latex or styrene-butadiene copolymer rubber. It is preferable to use polymer rubber latex, natural rubber latex, chloroprene rubber latex for chloroprene rubber, and chlorosulfonated polyethylene rubber latex for chlorosulfonated polyethylene rubber.
なお、本発明においては、このようなRFLを水系で使
用するのが好ましい。In addition, in the present invention, it is preferable to use such RFL in an aqueous system.
本発明においてはRFLに下記式(1)で表わされるト
リチオール−s−トリアジンおよびその読導体の1 f
ffi以上が添加されている。In the present invention, RFL includes trithiol-s-triazine represented by the following formula (1) and 1 f of its conductor.
ffi or more is added.
R。R.
(式中、R,%R2およびRsの少なくとも2つは独立
的にSHまたはSM(但し、Mはアルカリ金属を表わす
)を表わし、R,、R,およびRSの残りはSH。(wherein, at least two of R, %R2 and Rs independently represent SH or SM (where M represents an alkali metal), and the remainder of R, %R and RS is SH.
SM(但し、Mはアルカリ金属を表わす)、NHR4(
式中、R4はフェニル、シクロヘキシルまたはCnH2
−t(但し、n = 1〜8 )を表わす)、
NR,R,(式中、R8およびR6は独立的にフェニル
、シクロヘキシルまたはCnH2n+1(但し、nw1
〜6)を表わす)、およびSR? C0Ra (式中
、R2はCnH2n(但し、n=+1〜3)、R,はC
nH2n*+(n−1〜6)表わす)、
から選ばれる1つを表わす〕
式(1)で表わされるトリチオール−S−トリアジン類
のうち、本発明において特に好適に用いられる化合物と
しては、トリチオール−s −トリアジン、2−アニリ
ノ−4,6−シチオールー5−)−リアジン、2−ジブ
チルアミノー4.6−シチオールーs−トリアジン、2
−ジフェニルアミノ−4,6−ジチオール−S−トリア
ジン、2−アニリノ−4,6−シチオールーs−トリア
ジンモノナトリウム等があげられる。SM (where M represents an alkali metal), NHR4 (
In the formula, R4 is phenyl, cyclohexyl or CnH2
-t (however, n = 1 to 8)), NR,R, (wherein R8 and R6 are independently phenyl, cyclohexyl or CnH2n+1 (however, nw1
~6)), and SR? C0Ra (wherein, R2 is CnH2n (however, n=+1 to 3), R, is C
nH2n*+ (n-1 to 6)), represents one selected from] Among trithiol-S-triazines represented by formula (1), trithiol is particularly preferably used in the present invention. -s-triazine, 2-anilino-4,6-sithio-5-)-lyazine, 2-dibutylamino-4,6-sithio-s-triazine, 2
-diphenylamino-4,6-dithiol-S-triazine, 2-anilino-4,6-sithio-s-triazine monosodium, and the like.
これら、トリチオール−8−トリアジン類は前記RFL
の水系あるいは溶剤系組成物に添加される。 この際、
トリチオール−8−トリアジン類を添加した組成物の液
の安定性は接着性や作業性に大きな影響を与えるので十
分に留意する必要がある。 例えば、トリチオール−S
−トリアジン類のナトリウム置換体のような易水溶性の
ものをRFLの水系組成物に添加する場合はそのまま添
加しても容易に均一分散するので好ましいが、一方、ト
リチオール−5−トリアジンのような難水溶性のものは
、エーテル類やセロソルブ類に溶解させた後添加し、組
成物の分散性を向上させるのが好ましい。These trithiol-8-triazines are the RFL
It is added to water-based or solvent-based compositions. On this occasion,
The stability of the liquid composition to which trithiol-8-triazines are added has a great effect on adhesiveness and workability, so it is necessary to pay sufficient attention to this. For example, trithiol-S
- When adding easily water-soluble triazines such as sodium-substituted triazines to the aqueous RFL composition, it is preferable because they can be easily and uniformly dispersed even if added as is. On the other hand, triazines such as trithiol-5-triazine It is preferable that poorly water-soluble substances are added after being dissolved in ethers or cellosolves to improve the dispersibility of the composition.
トリチオール−8−トリアジン類をRFLに添加した接
着組成物の分散性を向上させ、安定性を維持させる添加
剤としては、該接着組成物の接着性を損なわない限り、
pH調整剤、界面活性剤等の安定剤等種々のものを適宜
用いることができる。 例えば、トリチオール−s−ト
リアジン類はアルカリ金属置換体を除いて酸性であるこ
とにより、RFLに添加した際液の安定性を損い凝固を
招く恐れがあるので、接着組成物にカセイソーダやアン
モニア水等を添加してpH調整を行と共にノニオン系界
面活性剤で安定化させることが好ましい。As additives that improve the dispersibility and maintain stability of the adhesive composition in which trithiol-8-triazines are added to RFL, as long as they do not impair the adhesive properties of the adhesive composition, the following additives may be used:
Various stabilizers such as pH adjusters and surfactants can be used as appropriate. For example, trithiol-s-triazines are acidic except for alkali metal substitutes, so when added to RFL, they may impair the stability of the liquid and cause coagulation, so caustic soda or ammonia water may be added to the adhesive composition. It is preferable to adjust the pH by adding a nonionic surfactant and stabilize the pH with a nonionic surfactant.
次にトリチオール−S−トリアジン類の、RF Lへの
添加量について述べる。 ト リ チオール−s−ト
リアジン類をRFLに添加した本発明の゛繊維処理用接
着組成物は、その添加量を問わず従来のRFLからなる
繊維処理用接着組成物に比べて著しく繊維材料とエラス
トマー配合物との接着力を向上させるが、その添加量を
適切に制御することにより、接着力を飛躍的に向上させ
ることができる。Next, the amount of trithiol-S-triazines added to RF L will be described. The adhesive composition for treating fibers of the present invention in which trithiol-s-triazines are added to RFL has a remarkable effect on fiber materials and elastomer than the conventional adhesive composition for treating fibers consisting of RFL, regardless of the amount added. It improves the adhesive force with the compound, but by appropriately controlling the amount added, the adhesive force can be dramatically improved.
即ち、特に高い接着力が必要とされる場合にはトリチオ
ール−S−トリアジン類の添加量は、RFLのラテック
スの固形分100!量部に対して1〜12重量部、より
好ましくは3〜9重量部とするのが良い、 この範囲で
高い接着力が安定的に得られるからである。 また、ト
リチオール−9S−トリアジン類は比較的高価な化合物
であるため、接着組成物の経済性の面からも3〜6重量
部とするのが好ましい。That is, when particularly high adhesive strength is required, the amount of trithiol-S-triazines added should be 100% of the solid content of RFL latex! The amount is preferably 1 to 12 parts by weight, more preferably 3 to 9 parts by weight, because high adhesive strength can be stably obtained within this range. In addition, since trithiol-9S-triazines are relatively expensive compounds, it is preferable to use 3 to 6 parts by weight from the economic standpoint of the adhesive composition.
本発明の接着組成物は従来の接着組成物と同様に繊維材
料に施される。 例えば、繊維材料を本発明の接着組成
物に浸漬した後100〜180℃、3〜5分間の条件で
乾燥し、さらに150℃〜260℃、30秒〜3分間の
条件で熱処理し、しかる後詰処理済繊維材料とエラスト
マー配合物とを一体加硫する。 このように繊維材料を
処理することによりエラストマーが極性基を有さない汎
用エラストマーである場合だけでなく、極性基を有する
非汎用エラストマーであってもia維材料とエラストマ
ー配合物との接着力を飛躍的に向上させることができる
。The adhesive composition of the present invention is applied to fibrous materials in the same manner as conventional adhesive compositions. For example, a fiber material is immersed in the adhesive composition of the present invention, dried at 100 to 180°C for 3 to 5 minutes, further heat-treated at 150 to 260°C for 30 seconds to 3 minutes, and then packed. The treated fiber material and elastomer compound are vulcanized together. By treating the fiber material in this way, the adhesive strength between the IA fiber material and the elastomer compound can be improved not only when the elastomer is a general-purpose elastomer that does not have polar groups, but also when it is a non-general-purpose elastomer that has polar groups. It can be improved dramatically.
■ 実施例 以下、実施例により本発明を具体的に説明する。■ Example Hereinafter, the present invention will be specifically explained with reference to Examples.
(実施例1〜5、比較例1)
表1に示した組成で、トリチオール−5−トリアジンを
RFLに添加した本発明の接着組成物(実施例1〜5)
とトリチオール−S−トリアジンを含まない比較例の接
着組成物を製造した。(Examples 1 to 5, Comparative Example 1) Adhesive composition of the present invention having the composition shown in Table 1 and adding trithiol-5-triazine to RFL (Examples 1 to 5)
A comparative adhesive composition containing no trithiol-S-triazine was prepared.
繊維材料としてはナイロン66ヤーン(旭化成工業社製
、1980,1−309TiILT−3)とし、これを
上記接着組成物に浸漬し、乾燥しく140℃、60秒間
、200 g/c)、熱処理しく200℃、100秒間
、zoog/c)して繊維材料に接着処理を施した。Nylon 66 yarn (manufactured by Asahi Kasei Kogyo Co., Ltd., 1980, 1-309TiILT-3) was used as the fiber material, which was dipped in the above adhesive composition, dried at 140°C for 60 seconds (200 g/c), and heat-treated at 200 g/c). °C for 100 seconds (zoog/c) to apply an adhesive treatment to the fiber material.
次に、接着処理を施した繊維材料をすき間なく並べて繊
維層とし、この繊維層上に表2に示すゴム配合物の厚さ
3.0mmのシートを圧着し、しかる後148℃、45
分で加硫を行った・ 加硫後1幅25mmに切り出し、
90°剥離法で接着力を測定した。 測定結果を表1に
あわせて示す。Next, the adhesive-treated fiber materials were arranged without gaps to form a fiber layer, and a sheet of the rubber compound shown in Table 2 with a thickness of 3.0 mm was pressed onto this fiber layer.
Vulcanized in minutes. After vulcanization, cut into 25mm wide pieces.
Adhesive strength was measured using a 90° peel method. The measurement results are also shown in Table 1.
表 2
日 SRF 旭#50、旭カーボン製◆5 アンテー
ジOD、用ロ化学製
◆6 フッコール 115ON、富士興産製、
◆T TU サンセラー22、三新化学工業製
表1に示した通り、トリチオール−S−トリアジンをR
FLに添加した本発明の接着組成物で接着処理したナイ
ロン66は無添加の比較例の接着組成物で処理したもの
と比らべて接着力が高かった。 特にビニルピリジン共
重合体ラテックス固型分に対しa/1ooの比率のもの
は、フ、 OKgf725 amと最大値を示し、比較
例のものに対して55%接着力の向上が図れた。Table 2 SRF Asahi #50, manufactured by Asahi Carbon ◆5 Antige OD, manufactured by Yoro Kagaku ◆6 Fukol 115ON, manufactured by Fuji Kosan, ◆T TU Suncellar 22, manufactured by Sanshin Kagaku Kogyo As shown in Table 1, Trithiol-S - R triazine
Nylon 66 treated with the adhesive composition of the present invention added to FL had higher adhesive strength than that treated with the adhesive composition of the comparative example without additives. In particular, those with a ratio of a/1oo to the vinyl pyridine copolymer latex solid content showed the maximum value of OKgf725 am, and the adhesive strength was improved by 55% compared to that of the comparative example.
■ 発明の効果
本発明によれば、繊維材料を本発明の接着組成物で処理
することにより、繊維材料を、極性基を有さない汎用エ
ラストマーの他、極性基を有する非汎用エラストマーを
含むあらゆるエラストマー配合物に強力に接着すること
ができる。■ Effects of the Invention According to the present invention, by treating a fiber material with the adhesive composition of the present invention, the fiber material can be treated with any type of elastomer, including a general-purpose elastomer without a polar group, as well as a non-general-purpose elastomer with a polar group. Capable of strongly adhering to elastomer formulations.
従って、本発明によれば、従来繊維材料で十分に補強で
きなかったエラストマー、即ち耐熱性、耐候性、耐油性
、耐炎性等に優れた極性基を有するエラストマーを繊維
材料で強力に補強することができる。Therefore, according to the present invention, elastomers that could not be sufficiently reinforced with fiber materials in the past, that is, elastomers having polar groups with excellent heat resistance, weather resistance, oil resistance, flame resistance, etc., can be strongly reinforced with fiber materials. Can be done.
Claims (2)
からなる接着液(以下、RFLと称する)と、式(1)
で示されるトリチオール−s−トリアジン類 ▲数式、化学式、表等があります▼(1) 〔式中、R_1、R_2およびR_3の少なくとも2つ
は独立的にSHまたはSM(但し、Mはアルカリ金属を
表わす)を表わし、R_1、R_2およびR_3の残り
はSH、 SM(但し、Mはアルカリ金属を表わす)、NHR_4
{式中、R_4はフェニル、シクロヘキシルまたはC_
nH_2_n_+_1(但し、n=1〜6)を表わす}
、 NR_5R_6{式中、R_5およびR_6は独立的に
フェニル、シクロヘキシルまたはC_nH_2_n_+
_1(但し、n=1〜6)を表わす}、および SR_7COR_8{式中、R_7はC_nH_2_n
(但し、n=1〜3)、R_8はC_nH_2_n_+
_1(n=1〜6)表わす}、 から選ばれる1つを表わす〕 の1種以上とが含有されていることを特徴とする接着組
成物。(1) An adhesive liquid (hereinafter referred to as RFL) consisting of a resorcinol-formalin initial condensate and latex, and a formula (1)
Trithiol-s-triazines represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, at least two of R_1, R_2 and R_3 are independently SH or SM (However, M is an alkali metal The rest of R_1, R_2 and R_3 are SH, SM (where M represents an alkali metal), NHR_4
{In the formula, R_4 is phenyl, cyclohexyl or C_
nH_2_n_+_1 (however, n = 1 to 6)}
, NR_5R_6 {wherein R_5 and R_6 are independently phenyl, cyclohexyl or C_nH_2_n_+
_1 (where n=1 to 6)}, and SR_7COR_8 {wherein, R_7 is C_nH_2_n
(However, n = 1 to 3), R_8 is C_nH_2_n_+
_1 (n=1 to 6)}, and one or more of the following:
Lのラテックスの固形分100重量部に対して1〜12
重量部含まれる特許請求の範囲第1項に記載の接着組成
物。(2) The trithiol-s-triazines are the RF
1 to 12 parts per 100 parts by weight of solid latex L
The adhesive composition according to claim 1, comprising parts by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28338187A JPH01126385A (en) | 1987-11-10 | 1987-11-10 | Adhesive composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28338187A JPH01126385A (en) | 1987-11-10 | 1987-11-10 | Adhesive composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01126385A true JPH01126385A (en) | 1989-05-18 |
Family
ID=17664773
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28338187A Pending JPH01126385A (en) | 1987-11-10 | 1987-11-10 | Adhesive composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01126385A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100569343B1 (en) * | 2004-06-03 | 2006-04-07 | 엘에스전선 주식회사 | Adhesive composition containing photoreactive polycyanurate polymer and an adhesive sheet using the same |
WO2007005452A1 (en) * | 2005-06-29 | 2007-01-11 | Saint-Gobain Abrasives, Inc. | High performance resin for abrasive products |
-
1987
- 1987-11-10 JP JP28338187A patent/JPH01126385A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100569343B1 (en) * | 2004-06-03 | 2006-04-07 | 엘에스전선 주식회사 | Adhesive composition containing photoreactive polycyanurate polymer and an adhesive sheet using the same |
WO2007005452A1 (en) * | 2005-06-29 | 2007-01-11 | Saint-Gobain Abrasives, Inc. | High performance resin for abrasive products |
KR100904628B1 (en) * | 2005-06-29 | 2009-06-25 | 생-고뱅 어브레이시브즈, 인코포레이티드 | High-performance resin for abrasive products |
KR100954510B1 (en) * | 2005-06-29 | 2010-04-27 | 생-고뱅 어브레이시브즈, 인코포레이티드 | High-performance resin for abrasive products |
US8062394B2 (en) | 2005-06-29 | 2011-11-22 | Saint-Gobain Abrasives, Inc. | High-performance resin for abrasive products |
US8802791B2 (en) | 2005-06-29 | 2014-08-12 | Saint-Gobain Abrasives, Inc. | High-performance resin for abrasive products |
US9023955B2 (en) | 2005-06-29 | 2015-05-05 | Saint-Gobain Abrasives, Inc. | High-performance resin for abrasive products |
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