JPS6232127A - Antitack composition for unvulcanized rubber - Google Patents
Antitack composition for unvulcanized rubberInfo
- Publication number
- JPS6232127A JPS6232127A JP17207485A JP17207485A JPS6232127A JP S6232127 A JPS6232127 A JP S6232127A JP 17207485 A JP17207485 A JP 17207485A JP 17207485 A JP17207485 A JP 17207485A JP S6232127 A JPS6232127 A JP S6232127A
- Authority
- JP
- Japan
- Prior art keywords
- water
- soluble
- composition
- fatty acid
- resins
- 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
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- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は未加硫ゴムの防着用組成物に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a composition for protecting unvulcanized rubber.
さらに詳しくは粉体を使用せず、かつ、防着性に優れ九
加硫接着を阻害しない未′jJIl@ゴムの防着用組成
物に関する。More specifically, the present invention relates to an anti-wear composition for rubber that does not use powder, has excellent anti-adhesive properties, and does not inhibit vulcanization adhesion.
一般にゴム工場においてはゴムの混線工程中の貯蔵ある
いはチューブ等の製造時、未加硫ゴム同士が互いに接触
し、密着してしまう事が多く、密着防止方法が種々検討
されている。従久カオリン等の無機微粉末全未加硫ゴム
表面に直接付着させ又は水懸t1ilJ液にしてゴムに
塗布する方法がとられているが、この方法は密着防止効
果が優れているが、粉塵が飛散して、環境衛性上、作業
性上好ましくない。In general, in rubber factories, unvulcanized rubber often comes into contact with each other and sticks together during storage during the rubber cross-circuiting process or during the manufacture of tubes, etc., and various methods for preventing adhesion have been investigated. Inorganic fine powders such as Jukyu kaolin are applied directly to the surface of unvulcanized rubber, or made into a water-drenched t1ilJ solution and applied to the rubber. Although this method has an excellent adhesion prevention effect, is scattered, which is unfavorable in terms of environmental hygiene and workability.
近年に至っては、炭化水素系樹脂状物質、界面活性剤等
を組合わせて使用する方法(特開昭52−78945号
公報)、粉末状密着防止剤と水溶性造膜剤を塗布する方
法(特開昭55−61659号公報)等があるがいずれ
も粉の飛散は皆無とは言えない。又、未加硫ゴムへの濡
れが悪く均−表塗布が困難である。さらにシリコーン樹
脂系の高分子密着防止用組成物を塗布する方法も知られ
ているが、加硫ゴムの物理的性質全低下させるものが多
く、又、コストも高いので天川に供し得ない。又、界面
活性剤の水溶液を塗布する方法もあるが、満足する性能
が得られず、特に天然ゴムにおいては密着防止効果が殆
んど期待し得ない。In recent years, a method using a combination of a hydrocarbon resinous substance, a surfactant, etc. (Japanese Patent Application Laid-open No. 78945/1982), a method of applying a powdered adhesion preventive agent and a water-soluble film-forming agent ( JP-A No. 55-61659), but none of them can be said to be completely free of powder scattering. In addition, it has poor wetting to unvulcanized rubber, making it difficult to apply it evenly. Furthermore, a method of applying a silicone resin-based polymer adhesion prevention composition is also known, but it often deteriorates the physical properties of the vulcanized rubber, and is also expensive, so it cannot be used in Tenkawa. There is also a method of applying an aqueous solution of a surfactant, but satisfactory performance cannot be obtained, and especially with natural rubber, hardly any adhesion prevention effect can be expected.
本発明者らは密着防止剤の無粉化という点に留意し、鋭
意検討を進めた結果、水溶性高分子の薄膜を未加硫ゴム
上に均一に生成させる事により密着性防止能が著しく向
上し、かつ、加硫後物理的性質を低下させない事を見い
出し、本発明に到達したものである。The inventors of the present invention kept in mind the need to make the adhesion preventive agent powder-free, and as a result of intensive studies, the ability to prevent adhesion was significantly improved by uniformly forming a thin film of water-soluble polymer on unvulcanized rubber. The present invention was achieved by discovering that the physical properties are improved and the physical properties are not deteriorated after vulcanization.
即ち、本発明は造膜性ヲ有する水m性高分子30〜90
重量部と、アニオン性界面活性剤又は(及び)HLB3
S16の非イオン性界面活性剤70〜10!!量部八
とからなる未加硫ゴムの防着用組成物全提供するもので
ある。That is, the present invention uses water-based polymers with film-forming properties of 30 to 90%.
parts by weight, anionic surfactant or/and HLB3
S16 nonionic surfactant 70-10! ! The present invention provides a protective composition for unvulcanized rubber comprising 8 parts.
本発明に係る造膜性t−有する水溶性高分子としては、
水溶性アクリル系ポリマー(アクリロ にトリル・ア
クリル酸ブチルの共重合体、アクリル酸・マレイン酸共
重合体等)、カルボキシメチルセルロース、メチルセル
ロース、ポリビニルアルコール、水溶性アニオン樹ic
m水マレイン酸とビニル共重合体を加水分解して得た化
合物等)、水溶性メラずン樹脂(ヘキサメラミンと4−
フェノキシブタノール及び無水マレイン酸との反応物等
)、水溶性エポキシ樹脂(アミノポリアミド樹脂とエピ
ク四ルヒドリンとを反応させ友もの等)、水溶性ウレタ
ン樹脂(トルエンジイソシアナートとポリプロピレンジ
オールの反応物にトリエトキシシリルグロビルアミンを
反応させた物等)、水溶性ブタジェン樹脂(ポリブタジ
ェンと植物油と無水マレイン酸との反応物等)、水溶性
フェノール樹脂(フェノールとメラミンf NaOH水
溶液中でホルマリンと反応させ友反応物等)が挙げられ
、これらは単独又は併合してもよい。The water-soluble polymer having film-forming properties according to the present invention includes:
Water-soluble acrylic polymers (acrylic acid, tolyl/butyl acrylate copolymer, acrylic acid/maleic acid copolymer, etc.), carboxymethylcellulose, methylcellulose, polyvinyl alcohol, water-soluble anionic resin IC
Compounds obtained by hydrolyzing m-water maleic acid and vinyl copolymers, etc.), water-soluble melazine resins (compounds obtained by hydrolyzing hexamelamine and vinyl copolymers, etc.),
phenoxybutanol and maleic anhydride, etc.), water-soluble epoxy resins (aminopolyamide resin and epictetrahydrin reacted products, etc.), water-soluble urethane resins (toluene diisocyanate and polypropylene diol reactants, etc.) (reacted with triethoxysilylglobylamine, etc.), water-soluble butadiene resin (reacted with polybutadiene, vegetable oil, and maleic anhydride, etc.), water-soluble phenol resin (phenol and melamine reacted with formalin in an aqueous NaOH solution, etc.) (alternate reactants, etc.), and these may be used alone or in combination.
本発明に係る非イオン性界面活性剤としては。The nonionic surfactant according to the present invention includes:
ポリオキシエチレンアルキルエーテル、ポリオキシエチ
レンアルキルフェニルエーテル、ソルビタン脂肪酸エス
テル、ポリオキシエチレンンルヒタン脂肪酸エステル、
ポリエチレングリコ−h脂肪eエステル、オキシエチレ
ンプロピレンプロツクボリマー、脂肪酸グリセライド等
の中から選ばれるHLB3S16の範囲のものが挙げら
れ、又、アニオン性界面活性剤としては脂肪酸塩、アル
キル硫酸エステル塩、アルキルベンゼンスルホン酸塩、
ポリオキシエチレンアルキルエーテル硫酸塩等が挙げら
れる。これらは単独使用又は併合しても差しつかえない
。Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, polyoxyethylene luchitan fatty acid ester,
Examples of the anionic surfactant include those in the HLB3S16 range selected from polyethylene glyco-h fatty acid ester, oxyethylene propylene polymer, fatty acid glyceride, etc., and examples of the anionic surfactant include fatty acid salts, alkyl sulfate salts, alkylbenzene sulfonate,
Examples include polyoxyethylene alkyl ether sulfate. These may be used alone or combined.
本発明に係る水溶性高分子と非イオン又はアニオン性界
面活性剤の混合比は水溶性高分子30〜90部(重量基
準、以下同じ)、界面活性剤70〜10部であシ、好ま
しくは水溶性高分子50へ70部、界面活性剤50〜3
0sである。水溶性高分子がこの範囲より多くなると未
加硫ゴム表面への均一な付着が難かしく、密着防止、性
が低下し、これよシも少ないと加硫後の物理的性質の低
下が大きくなる。The mixing ratio of the water-soluble polymer and the nonionic or anionic surfactant according to the present invention is preferably 30 to 90 parts of the water-soluble polymer (based on weight, the same applies hereinafter) and 70 to 10 parts of the surfactant. 70 parts to water-soluble polymer 50, surfactant 50 to 3
It is 0s. If the amount of water-soluble polymer exceeds this range, it will be difficult to uniformly adhere to the unvulcanized rubber surface, resulting in poor adhesion prevention and properties, and if it is less than this, the physical properties after vulcanization will deteriorate significantly. .
本発明の防着用組成物の使用方法としては、当既防着用
組放物金1〜10%(M量基準、以下同じ)、好ましく
は3〜5%の水浴液にし、これを未加硫ゴムの表面へ付
着させ、その後乾燥して密着防止効果を生じさせる方法
等がある。The method for using the protective composition of the present invention is to make a water bath solution containing 1 to 10% (based on the amount of M, the same applies hereinafter), preferably 3 to 5%, of the pre-protective assembled parabolic metal, and add it to the unvulcanized There is a method of adhering it to the rubber surface and then drying it to produce an adhesion prevention effect.
又、対象ゴムは天然、合成ゴムのいずれも効果がみられ
る。未加硫ゴムへの付着方法は吹き付け、ハケ塗シ等の
いずれの方法でもよく、乾燥は自然乾燥、熱風乾燥等い
ずれでもよい。Furthermore, the effect can be seen on both natural and synthetic rubbers. The method of adhering to the unvulcanized rubber may be any method such as spraying or brushing, and the drying may be natural drying, hot air drying, or the like.
次に本発明の効果全実施例により説明するが、本発明は
これら実施例に限定されるものではない。Next, the effects of the present invention will be explained with reference to all examples, but the present invention is not limited to these examples.
実施例1
ポリアクリル酸40%水溶液1009にポリオキシエチ
レンフェニルエーテル(KO=10モル)t−10Ji
l混合した(水溶性高分子/界面活性剤=80/20
)。Example 1 Polyoxyethylene phenyl ether (KO = 10 mol) t-10Ji in 40% polyacrylic acid aqueous solution 1009
l mixed (water-soluble polymer/surfactant = 80/20
).
実施例2
カルボキンメチルセルロース20%水溶液100gにポ
リオキシエチレンンルビタンステアリルエステル(KO
=20モル>2sl#j合した(水溶性高分子/界面活
性剤=87/15)。Example 2 Polyoxyethylene rubitan stearyl ester (KO
=20mol>2sl#j was combined (water-soluble polymer/surfactant=87/15).
実施例3
ポリアクリル酸ソーダ40%水溶液10.0Iiにポリ
オキシエチレンラウリルエーテル硫酸ナトリウム51を
混合した(水溶性高分子/界面活性剤=89/11)。Example 3 51 parts of sodium polyoxyethylene lauryl ether sulfate was mixed with 10.0Ii of a 40% aqueous solution of sodium polyacrylate (water-soluble polymer/surfactant = 89/11).
実施例4
ポリビニルアルコール50%水1g100#にポリオキ
シエチレンツルとタンステアリルエフ、fk(E O=
20モル)59、ラウリル硫酸ナトリウムIJ9?混合
した(水溶性高分子/界面活性剤=83/17 )。Example 4 Polyoxyethylene vine and tanstearylef, fk (E O=
20 mol) 59, Sodium lauryl sulfate IJ9? They were mixed (water-soluble polymer/surfactant = 83/17).
実施例5
アクリル酸とマレイン酸共重合物のNa塩40%水溶1
100,9にポリオキシエチレンフエニ#!−チル(1
! O= 10モル) 25.l9t−混合し九(水溶
性高分子/界面活性剤==*62/38 )。Example 5 40% aqueous solution of Na salt of acrylic acid and maleic acid copolymer 1
Polyoxyethylene phenylene #100.9! -chill (1
! O = 10 moles) 25. 19t-Mixed nine (water-soluble polymer/surfactant ==*62/38).
試験方法
天然ゴム未加硫組成物kvf4整し、厚さ3IImのシ
ートを作成し、これt試片とし次。この試片に防着剤と
して前記実施例1〜5の組成物全塗布し、その塗布時の
状態、及び乾燥後の飛散性を調べ友。又、下記方法によ
シ、未加硫ゴムの防着性及び加硫後の接着強度及び剥離
状態を評価し九。結果を表−1に示す。 カ
オy>尚、標準例として従来より使用されているPみの
系、比較例として、カオリンとポリビニルアルコール(
水溶性造膜剤)の50:50混金物、ポリアクリル酸N
aのみ、界面活性剤(ポリオキシエチレンンルビタンス
テアリルエステル(IK020モル付加))のみの系を
用い、同様に評価した。Test method: A natural rubber unvulcanized composition was adjusted to KVF4, and a sheet with a thickness of 3 IIm was prepared, and this was used as a test specimen. All of the compositions of Examples 1 to 5 were applied as an anti-adhesive agent to this test piece, and the condition at the time of application and the scattering properties after drying were examined. In addition, the anti-adhesive properties of unvulcanized rubber, adhesive strength and peeling state after vulcanization were evaluated using the following methods. The results are shown in Table-1. Kao y>In addition, as a standard example, the P-only system that has been used conventionally, and as a comparative example, kaolin and polyvinyl alcohol (
50:50 mixture of water-soluble film forming agent), polyacrylic acid N
A similar evaluation was made using a system containing only a and a surfactant (polyoxyethylene rubitan stearyl ester (addition of 20 moles of IK0)).
1)未加硫ゴムの防活性の評価
試片’Ismxsasの大きさに切断したもの2枚を1
組とし、これに標準例、比較例、実施例の防着剤全それ
ぞれ5%、5%の水溶液又は懸濁液にし、これを刷毛で
ゴム表面に塗布し、熱風乾燥金した後、塗布面同士を接
触させ、1(n2当り100gの圧力をかけ16時間室
温にて放置した後、それのはがれ易さt−gぺ九。1) Evaluation of anti-activation test pieces for unvulcanized rubber Two pieces cut to the size of 'Ismxsas'
Prepare a 5% and 5% aqueous solution or suspension of the anti-adhesion agents of the standard example, comparative example, and example, respectively, apply this to the rubber surface with a brush, dry it with hot air, and then apply it to the coated surface. After bringing them into contact with each other, applying a pressure of 100 g per n2 and leaving them at room temperature for 16 hours, the ease of peeling is t-g p9.
2)7JII硫後の接着強度 1)と同様に試片の1組に標準例、比較例。2) Adhesive strength after 7JII sulfurization As in 1), one set of specimens includes a standard example and a comparative example.
実施例の物質t3%、5%の水溶液又は懸濁液にし、こ
れ全ゴム表面に塗布し、熱風乾燥をした後、塗布面同士
t−150℃で15分加硫接yIIt−行なった。その
後、引張試験上行〜・接着面の強度を調べた。A 3% or 5% aqueous solution or suspension of the substance of the example was applied to all rubber surfaces, dried with hot air, and then vulcanization bonded to the coated surfaces at t-150° C. for 15 minutes. Thereafter, a tensile test was performed to examine the strength of the adhesive surface.
表−1かられかる様に実施fI]はいずれも塗布時に均
一に塗布比°米、かつ防着効果も良好であり、加硫後の
物理的性質も全く低下しない。又、粉体を使用していな
いので乾燥後も粉の飛散はなく良好である。As can be seen from Table 1, all of the samples obtained in Example 1 had a uniform coating ratio during coating, had a good anti-adhesion effect, and had no deterioration in physical properties after vulcanization. In addition, since no powder is used, there is no scattering of powder even after drying, which is good.
以上の様に本発明の防着用組成物はゴム工場における粉
塵の飛散等を防止し、作業環境の改良に寄与するもので
ある。As described above, the protective composition of the present invention prevents the scattering of dust in rubber factories and contributes to improving the working environment.
Claims (1)
アニオン性界面活性剤又は(及び)HLB3〜16の非
イオン性界面活性剤70〜10重量部とからなる未加硫
ゴムの防着用組成物。 2、水溶性高分子が、水溶性アクリル系ポリマー、カル
ボキシメチルセルロース、メチルセルロース、ポリビニ
ルアルコール、水溶性アニオン樹脂、水溶性メラミン樹
脂、水溶性エポキシ樹脂、水溶性ウレタン樹脂、水溶性
ブタジエン樹脂、水溶性フェノール樹脂の中から選ばれ
る1種又は2種以上である特許請求の範囲第1項記載の
未加硫ゴムの防着用組成物。 3、非イオン性界面活性剤がポリオキシエチレンアルキ
ルエーテル、ポリオキシエチレンアルキルフェニルエー
テル、ソルビタン脂肪酸エステル、ポリオキシエチレン
ソルビタン脂肪酸エステル、ポリエチレングリコール脂
肪酸エステル、オキシエチレンプロピレンブロックポリ
マー、脂肪酸グリセライドの中から選ばれるHLB3〜
16の範囲のものの1種又は2種以上であり、アニオン
性界面活性剤が脂肪酸塩、アルキル硫酸エステル塩、ア
ルキルベンゼンスルホン酸塩、ポリオキシエチレンアル
キルエーテル硫酸塩の中から選ばれる1種又は2種以上
である特許請求の範囲第1項又は2項記載の未加硫ゴム
の防着用組成物。[Scope of Claims] 1. 30 to 90 parts by weight of a water-soluble polymer having film-forming properties;
A composition for protecting unvulcanized rubber, comprising 70 to 10 parts by weight of an anionic surfactant or/and a nonionic surfactant with an HLB of 3 to 16. 2. Water-soluble polymers include water-soluble acrylic polymers, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, water-soluble anion resins, water-soluble melamine resins, water-soluble epoxy resins, water-soluble urethane resins, water-soluble butadiene resins, and water-soluble phenols. The composition for protecting unvulcanized rubber according to claim 1, which is one or more selected from resins. 3. The nonionic surfactant is selected from polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, oxyethylene propylene block polymer, and fatty acid glyceride. HLB3~
16, and the anionic surfactant is one or two selected from fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, and polyoxyethylene alkyl ether sulfates. The protective composition for unvulcanized rubber according to claim 1 or 2, which is as follows.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17207485A JPS6232127A (en) | 1985-08-05 | 1985-08-05 | Antitack composition for unvulcanized rubber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17207485A JPS6232127A (en) | 1985-08-05 | 1985-08-05 | Antitack composition for unvulcanized rubber |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6232127A true JPS6232127A (en) | 1987-02-12 |
Family
ID=15935057
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17207485A Pending JPS6232127A (en) | 1985-08-05 | 1985-08-05 | Antitack composition for unvulcanized rubber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6232127A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04339839A (en) * | 1991-05-17 | 1992-11-26 | Okamoto Ind Inc | Surface treatment of rubber product |
JP2010247864A (en) * | 2009-04-16 | 2010-11-04 | Matsumoto Yushi Seiyaku Co Ltd | Adhesion-proof agent pack for unvulcanized rubber |
WO2018030395A1 (en) * | 2016-08-09 | 2018-02-15 | ライオン・スペシャリティ・ケミカルズ株式会社 | Abhesive composition for unvulcanized rubber |
WO2019098171A1 (en) * | 2017-11-16 | 2019-05-23 | ライオン・スペシャリティ・ケミカルズ株式会社 | Antistatic agent for unvulcanized rubber and aqueous dispersion of antistatic agent for unvulcanized rubber |
US11267985B2 (en) | 2019-04-08 | 2022-03-08 | Polymer Solutions Group | Anti-tack formulation of high solids content, diluted anti-tack formulation and method of use of diluted anti-tack formulation |
US11692092B2 (en) | 2020-05-22 | 2023-07-04 | Lion Specialty Chemicals Co., Ltd. | Anti-sticking agent composition for unvulcanized rubber, aqueous dispersion liquid of anti-sticking agent composition for unvulcanized rubber, and unvulcanized rubber |
-
1985
- 1985-08-05 JP JP17207485A patent/JPS6232127A/en active Pending
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04339839A (en) * | 1991-05-17 | 1992-11-26 | Okamoto Ind Inc | Surface treatment of rubber product |
JPH0753808B2 (en) * | 1991-05-17 | 1995-06-07 | オカモト株式会社 | Surface treatment method for rubber products |
JP2010247864A (en) * | 2009-04-16 | 2010-11-04 | Matsumoto Yushi Seiyaku Co Ltd | Adhesion-proof agent pack for unvulcanized rubber |
WO2018030395A1 (en) * | 2016-08-09 | 2018-02-15 | ライオン・スペシャリティ・ケミカルズ株式会社 | Abhesive composition for unvulcanized rubber |
US10759945B2 (en) | 2016-08-09 | 2020-09-01 | Lion Specialty Chemicals Co., Ltd. | Anti-adhesive composition for unvulcanized rubber |
WO2019098171A1 (en) * | 2017-11-16 | 2019-05-23 | ライオン・スペシャリティ・ケミカルズ株式会社 | Antistatic agent for unvulcanized rubber and aqueous dispersion of antistatic agent for unvulcanized rubber |
JP2019089970A (en) * | 2017-11-16 | 2019-06-13 | ライオン・スペシャリティ・ケミカルズ株式会社 | Adhesion preventive for unvulcanized rubber, and water dispersion of adhesion preventive for unvulcanized rubber |
US11267985B2 (en) | 2019-04-08 | 2022-03-08 | Polymer Solutions Group | Anti-tack formulation of high solids content, diluted anti-tack formulation and method of use of diluted anti-tack formulation |
US11692092B2 (en) | 2020-05-22 | 2023-07-04 | Lion Specialty Chemicals Co., Ltd. | Anti-sticking agent composition for unvulcanized rubber, aqueous dispersion liquid of anti-sticking agent composition for unvulcanized rubber, and unvulcanized rubber |
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