WO2003037980A1 - Composition de latex de polychloroprene, primaire a base d'eau et procede de fixation par adhesif - Google Patents
Composition de latex de polychloroprene, primaire a base d'eau et procede de fixation par adhesif Download PDFInfo
- Publication number
- WO2003037980A1 WO2003037980A1 PCT/JP2002/011463 JP0211463W WO03037980A1 WO 2003037980 A1 WO2003037980 A1 WO 2003037980A1 JP 0211463 W JP0211463 W JP 0211463W WO 03037980 A1 WO03037980 A1 WO 03037980A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polychloroprene
- parts
- latex composition
- water
- weight
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
- C08L11/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
Definitions
- the present invention exhibits good adhesive strength to adherends such as rubber, elastomers, synthetic resins, etc., and is useful as a main component of aqueous adhesives and primers used for bonding these adherends. To provide a latex composition. Background art
- solvent-based primers and adhesives have been mainly used as a method for bonding hardly adherent adherends such as rubber, elastomers, and synthetic resins.
- organic solvents such as toluene, ethyl acetate, and methyl ethyl ketone are used in large amounts, which is unfavorable in terms of worker health and safety and the environment.
- the present invention provides a water-based primer or a polychloroprene-based latex composition suitable as a main component of a water-based primer or a water-based adhesive that provides an adhesive strength comparable to that of a conventionally used solvent-based primer or adhesive.
- the purpose is to provide. Disclosure of the invention
- a polychloroprene latex composition containing polychloroprene and sodium orthosilicate as essential components and dispersing or dissolving them in water is a rubber
- the inventors have found that excellent adhesion strength is provided to adherends such as elastomers and synthetic resins, and have completed the present invention.
- the present invention has the following gist. 1
- a polychloroprene-based latex composition comprising, as essential components, polychloroprene and sodium orthosilicate, which are dispersed or dissolved in water.
- the polychloroprene as referred to in the present invention is a homopolymer of 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene) or a copolymer of chloroprene and a monomer copolymerizable with chloroprene. It is a copolymer.
- copolymer as used herein also includes a graft copolymer obtained by subjecting another monomer to the polymerization in the presence of polychloroprene.
- Preferred monomers copolymerizable with the above-mentioned black-mouthed platen are, for example, 2,3-dichloro-1,3-butadiene, 1,3-butadiene, 1,3-butadiene, Styrene, isoprene, styrene, acrylonitrile, acrylic acid or its esters, methacrylic acid or its esters, and the like. If necessary, two or more kinds may be used.
- the method of polymerizing black-mouthed polyprene to obtain polycloth-prene is not particularly limited, but a method based on emulsion polymerization is general and simple.
- a method based on emulsion polymerization is general and simple.
- the polychloroprene latex of the present invention it is necessary to disperse the polyclone prene in water, but when the polychloroprene is obtained by an emulsion polymerization method, the obtained polychloroprene latex is used as it is. be able to.
- the emulsifier and the dispersant or emulsifier used in the emulsion polymerization method of the polychloroprene latex are not particularly limited, and various anion types, nonionic types, and cationic types commonly used for black color prene latex can be used.
- anion type emulsifier examples include a carboxylic acid type, a sulfonic acid type, a sulfate ester type, and the like.
- examples thereof include alkali metal salts of rosin acid, alkyl sulfonates having 8 to 20 carbon atoms, alkyl aryl sulfates, and naphthenates.
- Examples include condensates of sodium phosphorus sulfonate and formaldehyde.
- nonionic type examples include polyvinyl alcohol or a copolymer thereof (for example, a copolymer with acrylamide), polyvinyl ether or a copolymer thereof (for example, a copolymer with maleic acid), polypinylpyrrolidone or The copolymer (for example, a copolymer with vinyl acetate), or those obtained by chemically modifying these (co) polymers, or a cellulose-based derivative (hydroxyethyl cellulose) can be used.
- Specific examples of the cationic type include an aliphatic amine salt and an aliphatic quaternary ammonium salt, and examples include o-chloride, dilauryl dimethyl ammonium chloride and the like.
- the emulsifier and / or Z or dispersant in the polybutene-based latex are used at the time of polymerization of the soda. And preferably 0.5 to 20 parts by mass. If the amount is less than 0.5 part by mass, the emulsifying power is not sufficient, and if it exceeds 20 parts by mass, there is a disadvantage that the water-resistant adhesive strength is reduced.
- the combination temperature is not particularly limited, but the polymerization temperature is preferably 0 to 50 ° C in order to smoothly carry out the polymerization reaction.
- a persulfate such as potassium persulfate, an organic peroxide such as tert-butyl hydroperoxide, and the like are preferably used, but are not limited thereto.
- a chain transfer agent is used as needed for the polymerization of black-mouthed plain, but the type thereof is not particularly limited, and those usually used for emulsion polymerization of black-mouthed plain can be used.
- known chain transfer agents such as long-chain alkyl mercaptans such as n-dodecyl mercaptan and tert-dodecyl mercaptan, diisopropylxanthogen disulfide, and jordform can be used.
- Polymerization terminator (polymerization inhibitor) for polychloroprene mp is not particularly limited, and for example, 2,6-tert-butyl-4-methylphenol, phenothiazine, hydroxyamine and the like can be used.
- the final polymerization rate of polyclonal polyprene is not particularly limited and can be arbitrarily adjusted. Unreacted monomers are removed by a demonomer operation, but the method is not particularly limited.
- the polychloroprene-based latex of the present invention can control the solid content concentration to a necessary concentration by concentrating or diluting the polychloroprene latex obtained by polymerization by adding water or the like.
- Examples of the method for concentration include concentration under reduced pressure, but are not particularly limited.
- the properties of the polychloroprene-based latex in the present invention are not particularly limited, but the polymerization temperature, polymerization initiator, chain transfer agent, polymerization terminator, final polymerization rate, demonomerization, concentration conditions, etc. are appropriately selected. By controlling the concentration, it is possible to adjust the solid concentration, the molecular weight of the toluene-soluble portion, the toluene-insoluble content (gel content), and the like. From the viewpoint of the balance between the initial adhesive strength and the normal adhesive strength, it is preferable to adjust the gel content of the chloroprene (co) polymer in the polychloroprene latex to preferably 3 to 60% by weight. .
- the gel content is determined as follows.
- the polychloroprene-based latex sample is freeze-dried and weighed accurately to obtain A. Dissolve in toluene (adjusted to 0.6%), use a centrifuge, and add 200 mesh wire mesh Separate the gel using. After air-drying the gel, dry it at 100 ° C for 1 hour, and weigh it accurately. Using the above A and B, calculate the gel content by the following formula.
- Sodium Kei acid is represented by the general formula Na 2 ⁇ ⁇ n S i 0 2 ⁇ mH 2 0, the mole ratio of Na 2 O and S I_ ⁇ 2, i.e. sodium Orusokei acid by a factor n, sodium meta Kei acid, Kei Sodium silicate No. 1, sodium silicate No. 2, sodium silicate No. 3, sodium silicate No. 4, etc., and in the present invention, sodium orthosilicate is particularly used.
- the use of sodium orthosilicate has an excellent effect in terms of adhesive strength as compared with other sodium silicates, as will be shown in Examples described later.
- the content of sodium orthosilicate in the polycloth-prene latex is not particularly limited.
- 0.1 to 30 parts by weight per 100 parts by weight (solid content) of polychloroprene is preferable, and more preferably:! ⁇ 15 parts by weight.
- the polychloroprene-based latex composition of the present invention exhibits sufficient adhesive strength as it is, but the effect can be further enhanced by including polyethyleneimine.
- the content of polyethyleneimine is preferably 0.1 to 5 parts by weight (solid content), and particularly preferably 0.5 to 3 parts by weight, based on 100 parts by weight (solid content) of the polyclonal prene-based latex. Is preferred.
- Polyethyleneimine used in the present invention is a polymer having the following general formula, and the synthesis method is not particularly limited. In general, it can be synthesized by ring-opening polymerization of ethyleneimine.
- X and y are selected so that the average molecular weight of the polymer is preferably at least 1,000, particularly preferably at least 10,000.
- the type of tackifier resin to be added to the water-based adhesive is not particularly limited.
- a resin having a softening point temperature of 50 to 160 ° C is preferable.
- rosin resins are preferred.
- the amount of the tackifying resin is preferably 1 to 80 parts by weight (solid content), particularly preferably 5 to 50 parts by weight, based on 100 parts by weight (solid content) of the polychloroprene latex. It is suitable.
- the method of compounding the tackifier resin is not particularly limited, but it is preferable to add it as an aqueous emulsion in order to uniformly disperse the resin in the latex.
- the aqueous emulsion of the tackifying resin is produced by emulsifying a solution dissolved in an organic solvent such as toluene in water using an emulsifier, dispersing the mixture in water, heating the organic solvent under reduced pressure, and removing the fine particles.
- There is a method of pulverizing the emulsion into milk and dispersing the emulsion but the former which can produce a finer emulsion is preferable.
- the solids concentration of the polychloroprene latex composition of the present invention is not particularly limited, but is preferably 70% by weight or less in order not to impair the stability of the emulsified system. Further, when the polyprene latex composition of the present invention is used as an aqueous adhesive, it is preferably 40 to 70% by weight, and when it is used as an aqueous primer, it is preferably It is preferable that the solid content is adjusted to 10 to 40% by weight for use. Such adjustment of the solid content can be arbitrarily performed by dilution with pure water or concentration by removing water.
- the solid concentration of the polychloroprene-based latex in the present invention is determined as follows. Weigh only the aluminum pan and call it A. Weigh the aluminum dish containing 2 ml of the latex sample and call it B. Aluminum dish with latex sample 1 After drying in an atmosphere of 10 ° C for 2 hours, weigh and set to C. The solid content (% by weight) is calculated by the following equation.
- the polychloroprene latex composition according to the present invention may further comprise a thickener, a metal oxide, a filler, a film-forming aid, an ultraviolet absorber, an antioxidant, and a plasticizer according to the required performance.
- a vulcanizing agent, a vulcanization accelerator, an antifoaming agent and the like can be arbitrarily added.
- the polychloroprene-based latex composition of the present invention can be adjusted to any viscosity by adding a thickener.
- thickeners include polyvinyl alcohol (PVA), sodium polyacrylate, water-soluble polyurethane, associative polyurethane-based emulsion, alkali-swellable acrylic-based emulsion, potassium oxymethyl cellulose (CMC), methyl cellulose (MC), Examples include hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), polyvinyl alcohol, and synthetic smectite.
- the amount of the thickener to be added is preferably 0.01 to 10 parts by mass (in terms of solids) with respect to 100 parts by mass (in terms of solids) of polychlorinated propylene latex. By blending in this range, it is possible to control the viscosity of the polychloroprene latex composition without adversely affecting the adhesive properties.
- the material such as rubber, elastomer, and synthetic resin to which the polychloroprene-based latex composition of the present invention is applied is not particularly limited. Specifically, butadiene rubber (BR), chloroprene rubber (CR), natural rubber (NR), isoprene rubber (IR), styrene butadiene rubber (SBR), butyl rubber (IIR), norpolene rubber (NOR), nitrile rubber (NBR), hydrogenated nitrile rubber (H NBR), brominated butyl rubber (BIIR), chlorinated butyl rubber (CIIR), acrylonitrile-isoprene copolymer (NIR), vulcanization of ethylene-propylene-gen rubber (EPDM), etc.
- BR butadiene rubber
- CR chloroprene rubber
- NR natural rubber
- IR isoprene rubber
- SBR butyl rubber
- IIR butyl rubber
- NOR norpolene rubber
- NBR hydrogenated
- PVC pinyl chloride resin
- EVA ethylene-vinyl acetate copolymer
- RB 1, 2 Polybutadiene
- ABS tri-butadiene-styrene copolymer
- compositions, cross-link density, shape, etc., of these materials are not particularly limited, and foams can be applied. It can be used in any field, such as grips for sports equipment, shoe soles, and building materials.
- vulcanized SBR size of glue margin is 2 Omm wide x 7 Omm long
- puffing surface polishing
- a gauze impregnated with the aqueous primer obtained in Example 1 was lightly wiped with a gauze impregnated with the aqueous primer obtained in Example 1, and dried at 60 ° C. for 10 minutes.
- a water-based adhesive was applied thereon with a brush of 200 g (wet) / m 2 , dried in an atmosphere of 60 ° C. for 6 minutes, laminated, and pressed with a hand roller.
- the test pieces obtained by this method were evaluated as follows.
- T-peel strength was measured at a tensile speed of 20 O mmZmin using a tensile tester.
- T-peel strength was measured at a tensile speed of 20 OmmZmin using a tensile tester.
- Example 2 With the primer prepared in Example 1, before adding pure water, 3.3 parts of polyethyleneimine (epomin ⁇ —100 (solid content: 30%) ⁇ manufactured by Nippon Shokubai Co., Ltd.) was further added. Thereafter, a test was conducted in the same manner as in Example 1 except that the solid content was adjusted to 20% with pure water, and the test was performed as Example 2.
- polyethyleneimine epomin ⁇ —100 (solid content: 30%) ⁇ manufactured by Nippon Shokubai Co., Ltd.
- Example 1 A test was performed in the same manner as in Example 1 except that the aqueous primer was not used, and the result was set as Comparative Example 1.
- Example 1 A test was conducted in the same manner as in Example 1 except that a solvent-based primer was used instead of the water-based primer, and Comparative Example 6 was performed.
- the solvent-based primer was prepared as follows.
- the polychloroprene latex composition of the present invention exhibits good adhesive strength and can be suitably used as a main component of an aqueous primer.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020047005359A KR100880136B1 (ko) | 2001-11-02 | 2002-11-01 | 폴리클로로프렌계 라텍스 조성물, 수계 프라이머 및접착방법 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001337538A JP4024033B2 (ja) | 2001-11-02 | 2001-11-02 | ポリクロロプレン系ラテックス組成物、水系プライマー、及び接着方法 |
JP2001-337539 | 2001-11-02 | ||
JP2001337539A JP3830374B2 (ja) | 2001-11-02 | 2001-11-02 | ポリクロロプレン系ラテックス組成物 |
JP2001-337538 | 2001-11-02 |
Publications (1)
Publication Number | Publication Date |
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WO2003037980A1 true WO2003037980A1 (fr) | 2003-05-08 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2002/011463 WO2003037980A1 (fr) | 2001-11-02 | 2002-11-01 | Composition de latex de polychloroprene, primaire a base d'eau et procede de fixation par adhesif |
Country Status (4)
Country | Link |
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KR (1) | KR100880136B1 (fr) |
CN (1) | CN100339426C (fr) |
TW (1) | TWI275610B (fr) |
WO (1) | WO2003037980A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10717838B2 (en) | 2013-03-14 | 2020-07-21 | Bridgestone Americas Tire Operations, Llc | Refresh agent |
US11407926B2 (en) | 2011-12-07 | 2022-08-09 | Bridgestone Corporation | Water-based adhesives |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101108539B1 (ko) * | 2009-03-10 | 2012-02-29 | 한국신발피혁연구소 | 포화 신발용 수성 접착제 조성물 |
KR101108549B1 (ko) * | 2009-03-10 | 2012-01-31 | 한국신발피혁연구소 | 포화 신발용 수성형 프라이머 조성물 |
KR20110018061A (ko) * | 2009-08-17 | 2011-02-23 | 헨켈테크놀러지스 (유) | 접착용 다기능 처리제를 이용한 신발의 제조방법 |
JP2011127038A (ja) * | 2009-12-18 | 2011-06-30 | Nitto Denko Corp | 水分散型粘着剤組成物および粘着シート |
WO2018030210A1 (fr) * | 2016-08-10 | 2018-02-15 | 昭和電工株式会社 | Latex d'un copolymère greffé de chloroprène, son procédé de production, agent collant et adhésif |
CN110669160B (zh) * | 2019-10-31 | 2022-05-20 | 重庆化医长寿化工集团有限公司 | 一种工程防水用氯丁胶乳的制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2000319453A (ja) * | 1999-05-06 | 2000-11-21 | Denki Kagaku Kogyo Kk | クロロプレンラテックス組成物およびその製造方法 |
JP2001049043A (ja) * | 1999-08-10 | 2001-02-20 | Denki Kagaku Kogyo Kk | クロロプレンラテックス組成物およびその製造方法 |
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CN1034941A (zh) * | 1988-02-12 | 1989-08-23 | 成都科技大学 | 氨基聚乙烯醇乳化沥青防水涂料 |
JP2003319453A (ja) | 2002-04-18 | 2003-11-07 | Ntt Docomo Hokkaido Inc | 携帯通信端末制御方法、携帯通信端末、サーバ装置、プログラムおよび記録媒体 |
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2002
- 2002-11-01 TW TW091132525A patent/TWI275610B/zh not_active IP Right Cessation
- 2002-11-01 WO PCT/JP2002/011463 patent/WO2003037980A1/fr active Application Filing
- 2002-11-01 KR KR1020047005359A patent/KR100880136B1/ko not_active IP Right Cessation
- 2002-11-01 CN CNB028221826A patent/CN100339426C/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000319453A (ja) * | 1999-05-06 | 2000-11-21 | Denki Kagaku Kogyo Kk | クロロプレンラテックス組成物およびその製造方法 |
JP2001049043A (ja) * | 1999-08-10 | 2001-02-20 | Denki Kagaku Kogyo Kk | クロロプレンラテックス組成物およびその製造方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11407926B2 (en) | 2011-12-07 | 2022-08-09 | Bridgestone Corporation | Water-based adhesives |
US10717838B2 (en) | 2013-03-14 | 2020-07-21 | Bridgestone Americas Tire Operations, Llc | Refresh agent |
US11773230B2 (en) | 2013-03-14 | 2023-10-03 | Bridgestone Americas Tire Operations, Llc | Refresh agent |
Also Published As
Publication number | Publication date |
---|---|
CN100339426C (zh) | 2007-09-26 |
KR100880136B1 (ko) | 2009-01-23 |
CN1582315A (zh) | 2005-02-16 |
TW200300155A (en) | 2003-05-16 |
TWI275610B (en) | 2007-03-11 |
KR20040062562A (ko) | 2004-07-07 |
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