JPS6328107B2 - - Google Patents
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- Publication number
- JPS6328107B2 JPS6328107B2 JP55098259A JP9825980A JPS6328107B2 JP S6328107 B2 JPS6328107 B2 JP S6328107B2 JP 55098259 A JP55098259 A JP 55098259A JP 9825980 A JP9825980 A JP 9825980A JP S6328107 B2 JPS6328107 B2 JP S6328107B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- rubber
- latex
- parts
- swellable
- 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.)
- Expired
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- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Sealing Material Composition (AREA)
Description
【発明の詳細な説明】
本発明は水膨潤性（親水性）物質の製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing water-swellable (hydrophilic) materials.
詳しくは本発明はすぐれた防水性、加工性を有
するコーキング材、止水材等として用いられる水
膨潤性（親水性）物質の製造法に関する。 Specifically, the present invention relates to a method for producing a water-swellable (hydrophilic) substance that has excellent waterproof properties and processability and is used as a caulking material, a water-stopping material, and the like.
止水材ないしコーキング材等として水膨潤性ポ
リウレタン樹脂又は水膨潤性ポリウレタン樹脂と
ゴムからなる組成物が用いられることについては
特公昭53−38750号、特開昭53−143653号、同54
−7461号、同54−7463号、同54−20066号等の各
公報に記載され公知である。 Regarding the use of water-swellable polyurethane resins or compositions consisting of water-swellable polyurethane resins and rubber as water-stopping materials or caulking materials, Japanese Patent Publications No. 53-38750, JP-A-53-143653, and 54 Nos.
It is described in various publications such as No. -7461, No. 54-7463, and No. 54-20066, and is well known.
しかしながら、従来かかる水膨潤性ポリウレタ
ン―ゴム組成物の製造に際しては、ウレタンとあ
る種のゴムの相溶性が著しく悪いために得られた
組成物が十分均一でなく、したがつて機械的強度
が不足し、表面粘着性がある（タツクがある）も
のとなり、実用上大きな困難が存在していた。 However, in the conventional production of such water-swellable polyurethane-rubber compositions, the compatibility between urethane and certain types of rubber is extremely poor, resulting in insufficient uniformity of the resulting compositions and, therefore, insufficient mechanical strength. However, the surface is sticky (tacky), which poses great practical difficulties.
本発明者らは上記相溶性を改良し、止水材等に
用いて高品質な水膨潤性ポリウレタン―ゴム組成
物を得ることを目的として検討を続けた結果、特
定の組成を有するポリウレタン樹脂組成物がゴム
類と相溶性の大きいことを見い出し本発明を完成
した。 The present inventors continued their studies with the aim of improving the above-mentioned compatibility and obtaining a high-quality water-swellable polyurethane-rubber composition for use in water-stopping materials, etc. As a result, a polyurethane resin composition having a specific composition was found. The present invention was completed by discovering that the compound has high compatibility with rubbers.
即ち、本発明は、末端にイソシアネート基を含
有する水膨潤性ポリウレタンプレポリマーａを水
中に天然ゴム、合成ゴム又は合成樹脂が乳化分散
しているラテツクスｂと硬化剤を用いて或いは用
いずに反応させて得られる天然ゴム、合成ゴム又
は合成樹脂分散性水膨潤性ポリウレタン樹脂組成
物ｃを、天然ゴム及び／又は合成ゴムと混練する
ことを特徴とする水膨潤性物質の製造法である。 That is, the present invention involves reacting a water-swellable polyurethane prepolymer (a) containing isocyanate groups at the terminal with a latex (b) in which natural rubber, synthetic rubber, or synthetic resin is emulsified and dispersed in water, with or without a curing agent. This is a method for producing a water-swellable substance, which is characterized in that the natural rubber, synthetic rubber, or synthetic resin-dispersible water-swellable polyurethane resin composition (c) obtained by the process is kneaded with natural rubber and/or synthetic rubber.
本発明に用いられるプレポリマーａとしては末
端にイソシアネート基を含有する水膨潤性のポリ
ウレタンプレポリマーが用いられる。例えば、水
酸基当量が400〜6000のエチレンオキサイド・プ
ロピレンオキサイドランダム／ブロツク重合ポリ
オキシアルキレングリコールを有機ジイソシアネ
ートと常法により反応せしめて得られるプロピレ
ンオキサイド／エチレンオキサイド比7/3〜0/10
のプレポリマーが挙げられる。 As the prepolymer a used in the present invention, a water-swellable polyurethane prepolymer containing isocyanate groups at the terminals is used. For example, a propylene oxide/ethylene oxide ratio of 7/3 to 0/10 obtained by reacting ethylene oxide/propylene oxide random/block polymerized polyoxyalkylene glycol having a hydroxyl equivalent of 400 to 6000 with an organic diisocyanate by a conventional method.
Examples include prepolymers.
本発明に用いられるラテツクスｂとは天然ゴ
ム、合成ゴム又は合成樹脂が水中に乳化分散して
いるラテツクスであり、天然ゴムラテツクス、
SBRラテツクス、CRラテツクス、IIRラテツク
ス、エチレン―酢酸ビニルラテツクス、酢酸ビニ
ルラテツクス、塩化ビニルラテツクス、アクリル
ラテツクス等が挙げられる。水分含量は特に限定
されない。 The latex b used in the present invention is a latex in which natural rubber, synthetic rubber, or synthetic resin is emulsified and dispersed in water, and includes natural rubber latex,
Examples include SBR latex, CR latex, IIR latex, ethylene-vinyl acetate latex, vinyl acetate latex, vinyl chloride latex, and acrylic latex. The moisture content is not particularly limited.
プレポリマーａはラテツクスｂ中の水分と反応
して硬化するがこのとき、アミン又はポリオール
系の硬化剤を併用し、一部のプレポリマーを硬化
剤で硬化させてもよい。プレポリマーａとラテツ
クスｂは、プレポリマーa100部（重量部以下同
じ）に対して50％固形分のラテツクスb3〜2000
部（好ましくは３〜500部）程度の割合で反応さ
せるのが好ましい。ラテツクスｂ中の水分量によ
り割合は変動する。 Prepolymer a is cured by reacting with moisture in latex b. At this time, an amine or polyol type curing agent may be used in combination, and a part of the prepolymer may be cured with the curing agent. Prepolymer a and latex B have a solid content of 50% solids per 100 parts of prepolymer a (same parts by weight) as latex b3 to 2000.
(preferably 3 to 500 parts). The ratio varies depending on the amount of water in latex b.
このようにしてプレポリマーａとラテツクスｂ
を硬化剤を用いて或いは用いずに反応させ、天然
ゴム又は合成ゴム又は合成樹脂がその中に分散し
ている水膨潤性ポリウレタン樹脂組成物ｃが得ら
れる。 In this way, prepolymer a and latex b
are reacted with or without a curing agent to obtain a water-swellable polyurethane resin composition c in which natural rubber or synthetic rubber or synthetic resin is dispersed.
本発明の組成物ｃはプレポリマーａの硬化が部
分的であればペースト状態となり、硬化がほとん
ど完了すれば弾性体状となるが、本発明の実施に
はいずれの状態であつてもさしつかえない。ペー
スト状態の組成物ｃをゴム類と混練した場合は、
後に硬化を完了させることが望ましい。この硬化
の完了は大気中の水分による養生、加熱等通常の
方法で行なえばよい。 The composition c of the present invention becomes a paste state if the prepolymer a is partially cured, and becomes an elastic body state if the curing is almost completed, but any state is acceptable for carrying out the present invention. . When composition c in a paste state is kneaded with rubber,
It is desirable to complete the curing afterwards. This curing can be completed by conventional methods such as curing with atmospheric moisture or heating.
上記ポリウレタン樹脂組成物ｃと天然ゴム及
び／又は合成ゴムとをゴムロール等で混練して本
発明の水膨潤性物質を得る。ポリウレタン樹脂組
成物c100部に対し、天然ゴム及び／又は合成ゴム
30〜2000部、好ましくは50〜1000部を混練するの
がよい。また、上記合成ゴムとしてはSBR，
BR，IR，NBR，CR，EPM，EPDM，IIR，
ACN，CSN等のゴムが挙げられる。 The water-swellable material of the present invention is obtained by kneading the polyurethane resin composition c and natural rubber and/or synthetic rubber using a rubber roll or the like. Natural rubber and/or synthetic rubber per 100 parts of polyurethane resin composition
It is recommended to knead 30 to 2000 parts, preferably 50 to 1000 parts. In addition, the above synthetic rubbers include SBR,
BR, IR, NBR, CR, EPM, EPDM, IIR,
Examples include rubbers such as ACN and CSN.
ポリウレタン樹脂組成物ｃと天然ゴムあるいは
合成ゴムは混練性、相溶性に優れ、得られた水膨
潤性物質は均質で機械強度、止水特性に優れ、シ
ール材、パツキング材、コーキング材、止水材等
として広範な用途に用いられる。 Polyurethane resin composition c and natural rubber or synthetic rubber have excellent kneadability and compatibility, and the resulting water-swellable substance is homogeneous and has excellent mechanical strength and water-stopping properties, and can be used as a sealing material, packing material, caulking material, and water-stopping material. It is used for a wide range of purposes such as materials.
本発明のゴムには、充填剤（例えばカーボンブ
ラツク、無水ケイ酸カルシウム、炭酸カルシウ
ム、硫酸バリウム、酸化亜鉛、クレーなど）、増
粘剤（例えば、ロジン、石油樹脂、クマロン樹
脂、フエノール樹脂など）、溶剤（例えば、トル
エン、ベンゼン、キシレンなど）、加硫剤（例え
ば、硫黄、酸化鉛、酸化マグネシウムなど）、促
進剤（例えば、グアニジン、アミン、チユウラ
ム、チアゾールなど）、安定剤、老化防止剤など
の公知の物質を添加してもよい。 The rubber of the present invention contains fillers (e.g., carbon black, anhydrous calcium silicate, calcium carbonate, barium sulfate, zinc oxide, clay, etc.), thickeners (e.g., rosin, petroleum resin, coumaron resin, phenolic resin, etc.). , solvents (e.g. toluene, benzene, xylene, etc.), vulcanizing agents (e.g. sulfur, lead oxide, magnesium oxide, etc.), accelerators (e.g. guanidine, amines, thiuram, thiazole, etc.), stabilizers, anti-aging agents. You may add known substances such as.
さらに本発明は、必須の構成成分である上記物
質とともに、必要に応じて一般に使用されている
添加剤、例えばタール、アスフアルト、動植物油
脂類、DOP，DBP等の可塑剤、炭酸カルシウム、
クレイ、タルク、二酸化チタン等の充填剤等や着
色剤、抗酸化剤の適当量を含有せしめてもよい。 Furthermore, in addition to the above-mentioned substances as essential constituents, the present invention also includes commonly used additives, such as tar, asphalt, animal and vegetable oils, plasticizers such as DOP and DBP, calcium carbonate,
Appropriate amounts of fillers such as clay, talc, and titanium dioxide, colorants, and antioxidants may be included.
又、本発明の方法により得られた水膨潤性物質
を使用する場合、その使用態様は、定形状、不定
形状を問わない。即ち、充填箇所（目地）の断面
寸法がほぼ一定である場合には本発明の水膨潤性
物質を硬化成形し定形物となし、これを充填箇所
に押込んで漏水を防止してもよく、又充填箇所の
断面寸法が一定でない場合には、本発明の水膨潤
性物質を充填箇所に充填しそこで硬化膨潤させる
ことにより漏水を防止してもよい。 Further, when using the water-swellable substance obtained by the method of the present invention, the usage mode does not matter whether it is a fixed shape or an irregular shape. That is, when the cross-sectional dimensions of the filling location (joint) are approximately constant, the water-swellable material of the present invention may be cured and molded into a regular shape, and this may be pushed into the filling location to prevent water leakage. If the cross-sectional dimensions of the filling area are not constant, water leakage may be prevented by filling the water-swellable substance of the present invention into the filling area and allowing it to harden and swell.
以下、実施例により本発明を更に詳しく説明す
る。尚、例中の部は重量基準である。 Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts in the examples are based on weight.
実施例 １
親水性ウレタンプレポリマー（グリセリンにプ
ロピレンオキサイドとエチレンオキサイドを付加
させて得られた平均分子量3000のトリオール１モ
ルとTDI―80 ３モルを反応させたもの）100部と
SBRラテツクス（70％SBR含量）100部をニーダ
で混練しながら反応させ、ゴム状の弾性体を得
る。これを素練したNR RSS―３号400部とロー
ルで80℃で混練しカーボンブラツク、白艶華、促
進剤、老化防止剤を加えて、プレス加硫したもの
は引張強さ70Kg／cm2，伸び750％，吸水率100％で
あつた。Example 1 100 parts of a hydrophilic urethane prepolymer (one mole of a triol with an average molecular weight of 3000 obtained by adding propylene oxide and ethylene oxide to glycerin and three moles of TDI-80 were reacted) and
A rubber-like elastic body is obtained by reacting 100 parts of SBR latex (70% SBR content) while kneading it in a kneader. This was kneaded with 400 parts of masticated NR RSS-No. 3 at 80℃ using a roll, and carbon black, white gloss, accelerator, and anti-aging agent were added, and press vulcanization was performed to give a tensile strength of 70Kg/cm 2 and elongation. 750%, and the water absorption rate was 100%.
実施例 ２
親水性ウレタンプレポリマー（グリセリンにプ
ロピレンオキサイド、及びグリセリンにエチレン
オキサイドを付加させて得られた平均分子量2000
及び平均分子量3000のトリオール各0.5モルを
TDI―80 ３モルと反応させたもの）100部と40％
MOCA硬化剤10部とカチオン化ネオプレンラテ
ツクスとをニーダーで室温で混練させながら反応
させ、白色塊状のゴム状物質を得る（電化ネオプ
レン100部）。Example 2 Hydrophilic urethane prepolymer (average molecular weight 2000 obtained by adding propylene oxide to glycerin and ethylene oxide to glycerin)
and 0.5 mol each of a triol with an average molecular weight of 3000.
Reacted with 3 moles of TDI-80) 100 parts and 40%
10 parts of MOCA curing agent and cationized neoprene latex are reacted while kneading in a kneader at room temperature to obtain a white lumpy rubbery material (100 parts of electrified neoprene).
これをネオプレンゴムに加圧ニーダー中で60℃
で混練後、カーボンブラツク、炭酸カルシウム各
50部を加え、更に加硫剤、促進剤、老化防止剤を
加えて、ロールで混練し、プレス加硫を行なつた
ところ、引張強さ65Kg／cm2，伸び600％，硬度
60゜，吸水率60％の吸水性ゴムを得た。 This is made into neoprene rubber in a pressure kneader at 60℃.
After kneading with carbon black and calcium carbonate
After adding 50 parts and further adding a vulcanizing agent, accelerator, and anti-aging agent, kneading with a roll and performing press vulcanization, the result was a tensile strength of 65 Kg/cm 2 , an elongation of 600%, and a hardness.
A water-absorbing rubber with an angle of 60° and a water absorption rate of 60% was obtained.
実施例 ３
グリセリンにエチレンオキサイドを付加させて
得られた平均分子量3000のトリオール１モルと
TDI―80 ３モルを従来法により反応せしめる事
より得られたプレポリマー95部とSBRラテツク
ス（70％固型分）90部とを混合し重合させ、ウレ
タン弾性体を得た。Example 3 1 mol of triol with an average molecular weight of 3000 obtained by adding ethylene oxide to glycerin
95 parts of a prepolymer obtained by reacting 3 moles of TDI-80 using a conventional method and 90 parts of SBR latex (70% solids) were mixed and polymerized to obtain a urethane elastomer.
ロールでNR250部に上記ウレタン弾性体を185
部加え更にフイラー、加硫剤、加硫助剤などを添
加した後、プレス加硫成型した。ロール混練り性
良好であり、加硫品は表面均質でタツクなく、強
度は引張強さ85Kgｆ／cm2，伸び920％、硬さ
（HS）45であり、吸水率（水７日間浸漬時wt％
増）94％だつた。 Roll 185% of the above urethane elastic material to NR250 part.
After adding a filler, a vulcanizing agent, a vulcanizing aid, etc., press vulcanization molding was carried out. It has good roll kneading properties, and the surface of the vulcanized product is homogeneous and smooth.The tensile strength is 85 kgf/cm 2 , the elongation is 920%, the hardness (HS) is 45, and the water absorption rate (wt when immersed in water for 7 days) is 45. %
increase) was 94%.
実施例 ４
グリセリンにエチレンオキサイド／プロピレン
オキサイド重量比8/2を付加させて得られた平均
分子量2000及び平均分子量3000のトリオール各
0.5モルとTDI―80 ３モルを従来法により反応せ
しめる事により得られたプレポリマー105部と液
状MOCA硬化剤（MOCA濃度40％）10部とネオ
プレンゴムラテツクス（50％固型分）65部とを混
合し重合させウレタン弾性体を得た。Example 4 Triols with an average molecular weight of 2000 and an average molecular weight of 3000 obtained by adding ethylene oxide/propylene oxide at a weight ratio of 8/2 to glycerin.
105 parts of prepolymer obtained by reacting 0.5 mol and 3 mol of TDI-80 by a conventional method, 10 parts of liquid MOCA curing agent (MOCA concentration 40%), and 65 parts of neoprene rubber latex (50% solids). were mixed and polymerized to obtain a urethane elastomer.
ロールでNR230部に上記ウレタン弾性体を180
部加え更にフイラー、加硫剤、加硫助剤などを添
加した後、プレス加硫成型した。ロール混練り性
良好であり、加硫品は表面均質でタツクなく強度
は引張強さ87Kgｆ／cm2，伸び870％，硬さ（HS）
46であり吸水率は87％だつた。 Roll 180% of the above urethane elastic material onto NR230 part.
After adding a filler, a vulcanizing agent, a vulcanizing aid, etc., press vulcanization molding was carried out. It has good roll kneading properties, and the vulcanized product has a homogeneous surface and is smooth, with a tensile strength of 87 kgf/cm 2 , elongation of 870%, and hardness (HS).
46, and the water absorption rate was 87%.
比較例 １
ロールでNR250部に実施例１で得られたプレ
ポリマー95部、更にフイラー、加硫剤、加硫助剤
を加え混練りしたが、混合性悪く容易に均一にな
らなかつた。外観上不均一だつたが、これをプレ
ス加硫成型した。Comparative Example 1 95 parts of the prepolymer obtained in Example 1 was added to 250 parts of NR, and a filler, a vulcanizing agent, and a vulcanization aid were added and kneaded using a roll, but the mixture was not easily homogeneous due to poor mixing properties. Although the appearance was non-uniform, this was press vulcanized and molded.
加硫品は表面が均質でなく、タツクが残つた。
強度は引張強さ、51Kgｆ／cm2，伸び650％，硬さ
（HS）37と小さく、吸水率は80％だつた。 The surface of the vulcanized product was not homogeneous and tacks remained.
The tensile strength was 51 Kgf/cm 2 , the elongation was 650%, and the hardness (HS) was 37, and the water absorption was 80%.
Claims (1)
ポリウレタンプレポリマーａを水中に天然ゴム、
合成ゴム又は合成樹脂が乳化分散しているラテツ
クスｂと、硬化剤を用いてあるいは用いずに反応
させて得られる天然ゴム、合成ゴム又は合成樹脂
の分散している水膨潤性ポリウレタン樹脂組成物
ｃを、天然ゴム及び／又は合成ゴムと混練するこ
とを特徴とする水膨潤性物質の製造法。1 Water-swellable polyurethane prepolymer a containing isocyanate groups at the end is added to natural rubber,
Water-swellable polyurethane resin composition c in which natural rubber, synthetic rubber or synthetic resin is dispersed, obtained by reacting latex b in which synthetic rubber or synthetic resin is emulsified and dispersed, with or without a curing agent. A method for producing a water-swellable substance, which comprises kneading with natural rubber and/or synthetic rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9825980A JPS5723618A (en) | 1980-07-18 | 1980-07-18 | Preparation of water-swelling substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9825980A JPS5723618A (en) | 1980-07-18 | 1980-07-18 | Preparation of water-swelling substance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5723618A JPS5723618A (en) | 1982-02-06 |
| JPS6328107B2 true JPS6328107B2 (en) | 1988-06-07 |
Family
ID=14214948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9825980A Granted JPS5723618A (en) | 1980-07-18 | 1980-07-18 | Preparation of water-swelling substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5723618A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4609690A (en) * | 1983-09-29 | 1986-09-02 | Ashland Oil, Inc. | Aqueous hydroxyl-acrylic latex and water dispersible multi-isocyanate adhesive composition |
| JPH0676514B2 (en) * | 1984-12-28 | 1994-09-28 | 東武化学株式会社 | Water-swellable composition |
| JPH07773B2 (en) * | 1986-04-01 | 1995-01-11 | 三井東圧化学株式会社 | One-component polyurethane sealing material composition |
| JPH07102853B2 (en) * | 1991-04-11 | 1995-11-08 | 株式会社エクス | Holder for bag support |
| GB0008338D0 (en) * | 2000-04-06 | 2000-05-24 | Specialised Latex Services Lim | Latex rubber products |
| JP4541951B2 (en) | 2005-03-31 | 2010-09-08 | キヤノン株式会社 | Image processing apparatus, image processing method, and program |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51131546A (en) * | 1975-05-12 | 1976-11-16 | Ipposha Oil Ind Co Ltd | Adhesive materials with bulkiness and improved elasticity |
-
1980
- 1980-07-18 JP JP9825980A patent/JPS5723618A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5723618A (en) | 1982-02-06 |
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