WO2012176677A1 - 水性分散体、ならびにそれを用いてなる積層体、履物用接着剤および履物 - Google Patents
水性分散体、ならびにそれを用いてなる積層体、履物用接着剤および履物 Download PDFInfo
- Publication number
- WO2012176677A1 WO2012176677A1 PCT/JP2012/065189 JP2012065189W WO2012176677A1 WO 2012176677 A1 WO2012176677 A1 WO 2012176677A1 JP 2012065189 W JP2012065189 W JP 2012065189W WO 2012176677 A1 WO2012176677 A1 WO 2012176677A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aqueous dispersion
- acid
- mass
- polyolefin resin
- footwear
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J147/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/10—Footwear characterised by the material made of rubber
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0869—Acids or derivatives thereof
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B9/00—Footwear characterised by the assembling of the individual parts
- A43B9/12—Stuck or cemented footwear
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43D—MACHINES, TOOLS, EQUIPMENT OR METHODS FOR MANUFACTURING OR REPAIRING FOOTWEAR
- A43D25/00—Devices for gluing shoe parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
- C08J5/127—Aqueous adhesives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
- C09J111/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2311/00—Characterised by the use of homopolymers or copolymers of chloroprene
- C08J2311/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
- C08J2411/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2421/00—Characterised by the use of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/54—Aqueous solutions or dispersions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31826—Of natural rubber
- Y10T428/3183—Next to second layer of natural rubber
Definitions
- the present invention relates to an aqueous dispersion containing an acid-modified polyolefin resin, a rubber component and a tackifying component, and a laminate, an adhesive for footwear and footwear using the same.
- Rubber products such as conveyor belts, hoses and rubber linings are often used in harsh environments with strong vibrations and stresses.
- Polyolefin resins such as polyethylene resins and polypropylene resins have higher rigidity and higher weather resistance than rubber. Therefore, higher performance of rubber products can be expected if a composite material of polyolefin resin and rubber becomes possible.
- both polyolefin resin and rubber have poor adhesion, and it is difficult to bond them using adhesives and adhesive tapes, so that they can withstand use in harsh environments with strong vibration and stress, There is a need for powerful composite technology.
- an adhesive for footwear used for footwear manufacture and restoration requires excellent adhesiveness to materials such as polyolefin resin and rubber.
- Excellent adhesiveness is required for resins other than polyolefin resins, leather materials, and materials constituting woven fabrics and knitted fabrics.
- Patent Document 1 Patent Document 2, and the like propose an adhesive composition in which chloroprene rubber and a tackifier are combined as an adhesive having excellent adhesiveness to rubber.
- these adhesives have insufficient adhesiveness, in particular, poor adhesiveness with polyolefin resin, and cannot sufficiently adhere polyolefin resin and rubber.
- the adhesive proposed in Patent Document 1 is a solvent-based adhesive, and has a problem from the viewpoint of user health and environmental protection.
- the adhesive proposed in Patent Document 2 is a water-based adhesive, but this water-based adhesive may cause repellency depending on the type of base material during application, and improves wettability. When a small amount of an organic solvent such as alcohol was added to the polychloroprene latex, aggregation of the polychloroprene latex sometimes occurred.
- coating and drying this has stickiness and a tack
- a method for suppressing stickiness and tackiness on the surface of the coating film a method of adding a wax or inorganic fine particles to impart slipperiness to the surface is known.
- a laminate bonded with an adhesive composition in which a chloroprene rubber and a tackifier are combined has a tendency that the adhesive strength decreases when bending is repeated in an environment below freezing point.
- Patent Document 3 proposes an aqueous primer that can be applied to polyolefin resin by combining ethylene-vinyl acetate resin with chloroprene rubber and tackifier, but does not show performance as an adhesive.
- Patent Documents 4 and 5 Since most adhesives for footwear are solvent-based adhesives and there are problems from the viewpoint of environmental conservation as described above, water-based footwear adhesives are proposed in Patent Documents 4 and 5, etc. Has been. However, since the adhesive described in Patent Document 4 requires the surface of the adherend to be previously treated with a plasma treatment or a solvent-based primer, there is a problem that the manufacturing process becomes complicated and costly. In addition, since solvent-based primers are used, problems such as environmental conservation cannot be solved as a result. Moreover, in the adhesive agent of patent document 5, the material which can be bonded is limited to a specific thing, For example, the adhesiveness with respect to polyolefin resin is not examined.
- the aqueous composition in which the chloroprene rubber and the tackifier are combined causes aggregation when an organic solvent such as alcohol is added. Therefore, the wettability cannot be improved by adding an organic solvent such as alcohol.
- the adhesive composition in which chloroprene rubber and a tackifier are combined has a problem that the surface of the coating film is sticky or tacky at around room temperature.
- the laminate bonded with this adhesive composition has a problem in use in cold regions in winter because the adhesive strength tends to decrease when bending is repeated in an environment below freezing.
- none of the water-based footwear adhesives have sufficient adhesiveness, cost, and environmental protection.
- the object of the present invention is to solve the above-mentioned problems, sufficiently adhere the polyolefin resin and the rubber, and improve the wettability without the occurrence of agglomeration by adding an organic solvent such as alcohol. Furthermore, it is possible to have excellent adhesion without pretreatment of the surface of the adherend by plasma treatment or solvent-based primer, and to obtain a coating film with less stickiness and tackiness near the room temperature. It is possible to obtain a laminate in which the adhesive strength does not decrease even when bending is repeated under an environment below freezing point, and to provide an aqueous dispersion that can be used as an adhesive for footwear.
- the present inventors have found that an aqueous dispersion containing a specific acid-modified polyolefin resin, a rubber component, and a tackifier component solves the above problems, and The invention has been reached. That is, the gist of the present invention is as follows.
- the content of the rubber component (B) is 5 to 1900 parts by mass with respect to 100 parts by mass of the polyolefin resin (A), and the total of 100 parts by mass of the acid-modified polyolefin resin (A) and the rubber component (B).
- An adhesive for footwear comprising the aqueous dispersion according to (1) or (2) above, wherein a constituent member of the footwear is an adherend.
- the constituent member of the footwear includes at least one selected from the group consisting of leather material, woven fabric, knitted fabric, polyvinyl chloride resin, polyurethane resin, polyolefin resin, and rubber. Footwear adhesive. (13) Footwear obtained using the footwear adhesive described in (11) above.
- the aqueous dispersion of the present invention is excellent in adhesion to polyolefin resin and rubber, and can favorably adhere polyolefin resin and rubber.
- the aqueous dispersion of the present invention has excellent adhesion to various materials such as leather, metal, glass, plastic, paper, synthetic paper, and wood.
- the aqueous dispersion of the present invention can suppress the occurrence of aggregation due to the addition of an organic solvent such as alcohol, and therefore the wettability can be improved by the addition of the organic solvent.
- the aqueous dispersion of the present invention has excellent adhesiveness even if the surface of the adherend is not previously treated using a plasma treatment or a solvent-based primer.
- the dispersion of this invention is aqueous, there is little load given to a worker's health and environment. Furthermore, the coating film obtained from the aqueous dispersion of the present invention has little stickiness and tackiness on the surface, is excellent in surface slipperiness, can be wound on a roll and stored at room temperature. Moreover, the laminated body obtained by using the aqueous dispersion of the present invention as an adhesive can be used even in an environment below freezing point. The aqueous dispersion of the present invention can be used as an adhesive for footwear.
- the aqueous dispersion of the present invention contains an acid-modified polyolefin resin (A), a rubber component (B), a tackifier component (C), and an aqueous medium.
- the acid-modified polyolefin resin (A) contains an olefin component as a main component, and the olefin component includes carbon such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, and 1-hexene. Alkenes of several 2 to 6 are preferable, and a mixture thereof may be used.
- alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferable, ethylene and propylene are particularly preferable, and ethylene is further preferable.
- the content of the olefin component is preferably 45 to 99.9% by mass of the acid-modified polyolefin resin (A), more preferably 55 to 99.8% by mass, and 60 to 99.7% by mass. More preferred is 70 to 99.5% by mass, and most preferred is 80 to 99.0% by mass.
- the adhesiveness may be lowered.
- the acid-modified polyolefin resin (A) needs to contain an unsaturated carboxylic acid component from the viewpoint of improving adhesiveness and improving dispersibility in the case of an aqueous dispersion.
- unsaturated carboxylic acid component include acrylic acid, methacrylic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. Of these, acrylic acid, methacrylic acid and (anhydrous) maleic acid are preferable, and (anhydrous) maleic acid is particularly preferable.
- (anhydrous) to acid means “to acid or anhydrous to acid”.
- (anhydrous) maleic acid means maleic acid or maleic anhydride.
- the unsaturated carboxylic acid component only needs to be copolymerized with the olefin component, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization (graft modification). Is mentioned.
- the content of the unsaturated carboxylic acid component needs to be 0.1 to 10% by mass of the acid-modified polyolefin resin (A), preferably 0.2 to 8% by mass, The content is more preferably 5% by mass, further preferably 1 to 5% by mass, and particularly preferably 2 to 4% by mass.
- the content of the unsaturated carboxylic acid component is less than 0.1% by mass, it is difficult to reduce the adhesion or to form an aqueous dispersion.
- the content exceeds 10% by mass, There exists a tendency for adhesiveness and water-resistant adhesiveness (adhesion property when an adhesive layer touches moisture) to fall.
- the acid-modified polyolefin resin (A) may be able to impart more excellent adhesiveness by further copolymerization with components other than the olefin component and unsaturated carboxylic acid component.
- components other than the olefin component and unsaturated carboxylic acid component specifically, (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethyl maleate, diethyl maleate , Maleic diesters such as dibutyl maleate, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and vinyl versatate, and vinyl esters Examples thereof include vinyl alcohol obtained by saponification with a basic compound and the like, (meth) acrylic acid amides, and the like, and mixtures thereof.
- (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, etc.
- (Meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are more preferred.
- “(meth) acrylic acid” means “acrylic acid or methacrylic acid”.
- the content of these other components is preferably 1 to 45% by mass of the acid-modified polyolefin resin (A), more preferably 2 to 35% by mass, and further preferably 3 to 25% by mass. 4 to 18% by mass is particularly preferable.
- the content of other components is less than 1% by mass, the effect of improving the adhesiveness is small, and when the content exceeds 45% by mass, water-resistant adhesion and heat-resistant adhesion (hot bonding in a heated atmosphere) Tend to decrease.
- acid-modified polyolefin resin (A) examples include ethylene- (meth) acrylic acid ester- (anhydrous) maleic acid copolymer, ethylene-propylene- (meth) acrylic acid ester- (anhydrous) maleate.
- Acid copolymer ethylene-butene- (meth) acrylic acid ester- (anhydrous) maleic acid copolymer, propylene-butene- (meth) acrylic acid ester- (anhydrous) maleic acid copolymer, ethylene-propylene-butene -(Meth) acrylic acid ester- (anhydrous) maleic acid copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (anhydrous) maleic acid copolymer, ethylene-propylene- (anhydrous) maleic acid copolymer A copolymer, ethylene-butene- (anhydride) maleic acid copolymer, propylene-butene- (anhydride) maleic acid copolymer, Tylene-propylene-butene- (anhydrous) maleic acid copolymer, ethylene-vinyl acetate- (anhydrous) maleic copolymer, ethylene-vinyl acetate-acrylic- (
- the melting point of the acid-modified polyolefin resin (A) is preferably 50 ° C. or higher, more preferably 60 to 250 ° C., and particularly preferably 80 to 200 ° C.
- the melting point of the acid-modified polyolefin resin (A) is less than 50 ° C., the heat resistant adhesiveness tends to be lowered.
- the weight average molecular weight of the acid-modified polyolefin resin (A) is preferably 20,000 to 100,000, more preferably 25,000 to 70,000, further preferably 30,000 to 50,000, and 35,000 to 50,000. Is particularly preferred. If the weight average molecular weight of the acid-modified polyolefin resin (A) is less than 20000, the adhesiveness tends to decrease. On the other hand, when the weight average molecular weight exceeds 100,000, the aqueous dispersion tends to be difficult to obtain.
- melt flow rate value indicating the fluidity of the molten resin is preferably used as a measure of the molecular weight.
- the melt flow rate value of the acid-modified polyolefin resin (A) (190 ° C. according to ISO 1133, 21.2 N load) is preferably 1 to 300 g / 10 minutes, more preferably 2 to 200 g / 10 minutes. It is more preferably 3 to 100 g / 10 minutes, and particularly preferably 3 to 80 g / 10 minutes.
- the melt flow rate value exceeds 300 g / 10 min, the adhesiveness tends to decrease.
- the melt flow rate value is less than 1 g / 10 minutes, it tends to be difficult to obtain an aqueous dispersion.
- the acid-modified polyolefin resin (A) is not particularly required to be chlorinated for the purpose of improving adhesiveness or water dispersibility, and includes a chlorinated polyolefin resin from the viewpoint of environmental protection and manufacturing process simplification. Preferably not. However, if necessary for the purpose of use, the acid-modified polyolefin resin (A) may be chlorinated.
- the chlorination method may be carried out by dissolving the acid-modified polyolefin resin (A) in a chlorinated solvent and then irradiating it with ultraviolet rays or blowing gaseous chlorine in the presence of a radical generator. it can.
- the aqueous dispersion of the present invention contains an acid-modified polyolefin resin (A), a rubber component (B), a tackifier component (C) and an aqueous medium.
- the aqueous dispersion of the present invention is, for example, an acid-modified Manufacturing by mixing the aqueous dispersion (I) of the polyolefin resin (A), the aqueous dispersion (II) of the rubber component (B), and the aqueous dispersion (III) of the tackifier component (C). Can do.
- the acid-modified polyolefin resin (A) is dispersed in an aqueous medium by a known dispersion method such as a self-emulsification method or a forced emulsification method. Adopt it.
- a known dispersion method such as a self-emulsification method or a forced emulsification method.
- Adopt it in order to obtain the aqueous dispersion (I) of the acid-modified polyolefin resin (A), an emulsifier and a dispersant that are optionally added for the purpose of promoting dispersion, such as a surfactant and a high acid value wax, are not used.
- the aqueous dispersion of the present invention is an anionic aqueous dispersion obtained by neutralizing the unsaturated carboxylic acid component of the acid-modified polyolefin resin (A) with a basic compound in an aqueous medium. From the viewpoint of The anionic aqueous dispersion of the acid-modified polyolefin resin (A) usually shows alkalinity.
- the aqueous medium used for aqueous dispersion of the acid-modified polyolefin resin (A) is a medium composed of water or a liquid containing water, and includes a neutralizing agent that contributes to dispersion stabilization, a water-soluble organic solvent, and the like. It may be.
- water-soluble organic solvents examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, Alcohols such as 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone; tetrahydrofuran, dioxane, etc.
- Ethers ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, mepionate , Esters such as ethyl propionate, diethyl carbonate, dimethyl carbonate; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol, diethylene glycol Glycol derivatives such as monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glyco
- the basic compound used to neutralize the unsaturated carboxylic acid component of the acid-modified polyolefin resin (A) includes ammonia; triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, And organic amine compounds such as morpholine, N-methylmorpholine, N-ethylmorpholine; alkali metals such as sodium hydroxide and potassium hydroxide. In addition, you may use these basic compounds in mixture of 2 or more types.
- the number average particle diameter of the acid-modified polyolefin resin (A) contained in the aqueous dispersion (I) of the acid-modified polyolefin resin (A) is preferably 0.5 ⁇ m or less, and 0.05 to 0.2 ⁇ m. It is more preferable that When the number average particle diameter of the acid-modified polyolefin resin (A) exceeds 0.5 ⁇ m, the storage stability of the obtained aqueous dispersion of the present invention tends to be lowered.
- the aqueous dispersion of the present invention needs to contain a rubber component (B).
- the content of the rubber component (B) needs to be 5 to 1900 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A), and 10 to 900 parts by mass. More preferably, the amount is 25 to 400 parts by mass.
- the adhesiveness with a base material containing rubber is lowered, and when the content exceeds 1900 parts by mass, the adhesiveness with a base material containing a polyolefin resin is reduced. Decreases.
- the rubber component (B) various known materials can be used. Examples include chloroprene rubber, isoprene rubber, urethane rubber, natural rubber, styrene butadiene rubber, styrene butadiene ethyl hexyl acrylate rubber, butyl rubber, nitrile rubber, ethylene propylene rubber, and the like alone or in combination of two or more. Can be used. Of these, chloroprene rubber is preferable because of its high effect of improving adhesiveness.
- the chloroprene rubber is polychloroprene which is a homopolymer of 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene) or a copolymer of a monomer capable of copolymerizing with chloroprene and chloroprene. It is.
- chloroprene rubber known chloroprene rubber can be used.
- Examples of monomers that can be copolymerized with chloroprene include 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, hydroxyethyl methacrylate, and hydroxypropyl.
- Examples include methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, glycerin monomethacrylate, acrylic acid or its esters, methacrylic acid or its esters, maleic acid, fumaric acid, etc., and two or more of these may be used in combination. .
- an unsaturated carboxylic acid component such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid because it has an effect of improving adhesiveness.
- methacrylic acid is preferable. More preferably, it is copolymerized.
- the content of the monomer copolymerizable with chloroprene is not particularly limited, but is preferably 40% by mass or less of the polychloroprene from the viewpoint of maintaining the polychloroprene characteristics.
- the unsaturated carboxylic acid is copolymerized, it is preferably 10% by mass or less of polychloroprene, more preferably 0.2 to 5% by mass, and 0.5 to 4% by mass. Is more preferable, and 0.7 to 3.5% by mass is particularly preferable.
- the copolymer includes a graft copolymer in which other monomers are graft-polymerized in the presence of polychloroprene.
- anionic emulsifiers include carboxylic acid type, sulfonic acid type, and sulfate ester type.
- 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), polyvinyl pyrrolidone or a copolymer thereof.
- examples thereof include polymers (for example, copolymers with vinyl acetate), those obtained by chemically modifying these (co) polymers, and cellulose derivatives (hydroxyethyl cellulose).
- the cation type include aliphatic amine salts, aliphatic quaternary ammonium salts, and the like, for example, octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, dilauryldimethylammonium chloride, and the like.
- an anionic emulsifier is used.
- the adhesiveness is inferior, and the mixing stability with the acid-modified polyolefin resin (A) and the tackifier component (C) tends to be lowered.
- the addition amount of the emulsifier and the dispersant is preferably 0.5 to 20% by mass of the total mass of the initially charged monomers. When the addition amount of the emulsifier and the dispersant is less than 0.5% by mass, the emulsifying power is not sufficient, and when the addition amount exceeds 20% by mass, the adhesiveness and the water-resistant adhesion tend to be lowered.
- the molecular weight, molecular weight distribution, gel content, molecular terminal structure, crystallization speed, etc. of the rubber component (B) may be adjusted in accordance with the properties of the target adhesive. It can be adjusted by controlling the polymerization temperature at the time of polymerizing, the polymerization initiator, the chain transfer agent and the polymerization terminator added at the time of polymerization, the final polymerization rate and the like.
- the aqueous dispersion of the present invention comprises an aqueous dispersion (I) of an acid-modified polyolefin resin (A), an aqueous dispersion (II) of a rubber component (B), and an aqueous dispersion (III) of a tackifier component (C). ),
- a latex obtained by emulsion polymerization of the rubber component (B) can be used as the aqueous dispersion (II) of the rubber component (B).
- the number average particle size of the rubber component (B) in the latex is preferably 0.5 ⁇ m or less, and more preferably 0.05 to 0.2 ⁇ m. When the number average particle diameter of the rubber component (B) exceeds 0.5 ⁇ m, the storage stability of the obtained aqueous dispersion of the present invention tends to be lowered.
- the latex of the rubber component (B) is preferably alkaline from the viewpoint of mixing stability with the acid-modified polyolefin resin (A) and the tackifier component (C).
- the latex is acidic, it is preferably used after being adjusted to be alkaline with a basic compound such as ammonia or amine.
- the aqueous dispersion of the present invention needs to contain a tackifier component (C).
- the content of the tackifier component (C) is 5 to 300 parts by mass with respect to 100 parts by mass of the total of the acid-modified polyolefin resin (A) and the rubber component (B). It is necessary, more preferably 10 to 150 parts by mass, still more preferably 25 to 100 parts by mass, and particularly preferably 40 to 100 parts by mass.
- the content of the tackifier component (C) is out of the range of 5 to 300 parts by mass, the adhesiveness is lowered.
- tackifier component (C) Various known materials can be used as the tackifier component (C).
- an aqueous dispersion (III) of the tackifier component (C) in which the tackifier component (C) is dispersed in an aqueous medium is used. It is preferable.
- the tackifier component (C) include rosins, rosin derivatives, petroleum resins, terpene resins, coumarone resins, indene resins, and the like. These may be used alone or in admixture of two or more. Can do.
- rosins or rosin derivatives include polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarated rosin, and glycerin esters, pentaerythritol esters, methyl esters, ethyl esters, butyl esters, ethylene glycol esters , Diethylene glycol ester, triethylene glycol ester and the like.
- Petroleum resins include petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and petroleum resins obtained by hydrogenation of these, maleic acid modified, phthalic acid modified Petroleum resin.
- terpene resin examples include low polymerization terpene, ⁇ -pinene polymer, ⁇ -pinene polymer, terpene phenol, aromatic modified terpene, hydrogenated terpene and the like.
- a terpene resin is preferable in terms of adhesiveness, and a terpene phenol resin is more preferable.
- the ring and ball softening point of the tackifier component (C) is preferably 80 to 180 ° C., more preferably 100 to 170 ° C., and 120 to 160 ° C. from the viewpoints of adhesion and heat-resistant adhesion. It is particularly preferred.
- the ring and ball method softening point is measured based on the method described in JIS K5903.
- aqueous medium constituting the aqueous dispersion (III) of the tackifier component (C) water or a medium comprising a liquid containing water is used, and a neutralizing agent or an emulsifier that contributes to dispersion stabilization, An organic solvent or the like may be contained.
- the number average particle diameter of the tackifier component (C) contained in the aqueous dispersion (III) of the tackifier component (C) is preferably 0.5 ⁇ m or less, and is 0.05 to 0.3 ⁇ m. It is more preferable. When the number average particle size of the tackifier component (C) exceeds 0.5 ⁇ m, the storage stability of the resulting aqueous dispersion of the present invention tends to be lowered.
- the aqueous dispersion (III) of the tackifier component (C) is preferably alkaline.
- the method for producing the aqueous dispersion of the present invention is not particularly limited, the aqueous dispersion (I) of the acid-modified polyolefin resin (A) as described above, the aqueous dispersion (II) of the rubber component (B) (latex) And an aqueous dispersion (III) of the tackifier component (C) is obtained individually, and a method of mixing these aqueous dispersions so as to have the aforementioned ratio is easy and preferable. When mixing aqueous dispersions, it is preferable to carry out stirring in order to maintain dispersion stability.
- the aqueous dispersion of the present invention containing the acid-modified polyolefin resin (A), the rubber component (B), the tackifier component (C) and the aqueous medium can be obtained.
- the aqueous medium is a medium composed of water or a liquid containing water.
- the number average particle size of the dispersed particles containing the acid-modified polyolefin resin (A), the rubber component (B), and the tackifier component (C) in the aqueous dispersion of the present invention is the composition when dispersed or coated. Is preferably 0.5 ⁇ m or less, more preferably 0.05 to 0.3 ⁇ m, and particularly preferably 0.06 to 0.2 ⁇ m.
- the solid content concentration of the non-volatile component including the acid-modified polyolefin resin (A), the rubber component (B), and the tackifier component (C) in the aqueous dispersion of the present invention is 5 to 70% by mass of the aqueous dispersion. It is preferably 20 to 60% by mass, more preferably 30 to 50% by mass.
- the viscosity of the aqueous dispersion of the present invention measured with a B-type viscometer at 20 ° C. is preferably 500 to 100,000 mPa ⁇ s, more preferably 1,000 to 50,000 mPa ⁇ s, and particularly preferably 3000 to 30,000 mPa ⁇ s.
- Additives include resins other than the acid-modified polyolefin resin (A), rubber component (B), and tackifier component (C) (hereinafter referred to as “other resins”), crosslinking agents, vulcanizing agents, and inorganic fine particles. Etc.
- resins include polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, acrylic resin, acrylic silicon resin, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic copolymer, and ethylene-aminoacrylamide copolymer.
- Ethylene-aminoacrylate copolymer polyvinylidene chloride, styrene-maleic acid resin, styrene-aminoalkylmaleimide copolymer, styrene-butadiene resin, styrene elastomer, butadiene resin, acrylonitrile-butadiene resin, poly (meth) acrylonitrile Resin, (meth) acrylamide resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyester resin, modified nylon resin, polyurethane resin, phenol resin, silicone resin, epoxy resin, fluorine-containing Resins, polyethyleneimine, and the like UV-curable resin.
- an acrylic resin and a polyurethane resin are preferable from the viewpoint of further improving the adhesiveness.
- these resins it is preferable to use those in which an aqueous dispersion or an aqueous solution is used.
- Suitable acrylic resins used for other resins include, for example, acrylic acid alkyl ester (a) having an alkyl group having 2 to 14 carbon atoms, polymerizable unsaturated carboxylic acid (b), and homopolymer glass transition temperature.
- Reactive surfactant 0 having an ethylenically unsaturated group copolymerizable with (a) to (c) in an amount of 100 parts by mass of a monomer mixture containing methacrylic acid alkyl ester (c) at 20 to 110 ° C.
- examples include acrylic resin emulsions obtained by emulsion polymerization in an aqueous medium in the presence of 1 to 10 parts by mass.
- the addition amount of the other resin is preferably 0.1 to 300 parts by mass with respect to 100 parts by mass of the total of the acid-modified polyolefin resin (A), the rubber component (B), and the tackifier component (C).
- the amount is more preferably 3 to 200 parts by mass, and particularly preferably 5 to 100 parts by mass.
- the aqueous dispersion of the present invention can be further improved in adhesion or heat resistant adhesion by adding a crosslinking agent or a vulcanizing agent.
- crosslinking agent a crosslinking agent having self-crosslinking property, a crosslinking agent having a plurality of functional groups that react with a carboxyl group in the molecule, a metal complex having a polyvalent coordination site, and the like can be used. Specific examples include hydrazide compounds, isocyanate compounds, blocked isocyanate compounds, melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents, organic peroxides, and the like. These crosslinking agents may be used in combination.
- the crosslinking agent may be a low molecular weight compound or a polymer type.
- crosslinking agent having a plurality of functional groups that react with carboxyl groups in the molecule is more preferable.
- crosslinking agents include oxazoline compounds, epoxy compounds, carbodiimide compounds, isocyanate compounds, hydrazide compounds, amine compounds, melamine compounds, and polyols, and oxazoline compounds, hydrazide compounds, amine compounds, carbodiimide compounds, and isocyanate compounds.
- Oxazoline compounds, hydrazide compounds, and amine compounds are particularly preferred because of excellent crosslinking effects.
- the addition amount of the crosslinking agent is 0.01 to 300 mass as the solid content of the crosslinking agent with respect to 100 mass parts of the total of (A), (B), and (C) from the viewpoint of sufficiently forming a crosslinked structure.
- Part is preferable, 0.1 to 100 parts by weight is more preferable, 0.2 to 50 parts by weight is further preferable, and 0.5 to 30 parts by weight is particularly preferable.
- the vulcanizing agent known ones can be used, and zinc oxide, sulfur, peroxide, etc. can be preferably used.
- the addition amount of the vulcanizing agent is preferably 0.01 to 10 parts by mass as the solid content of the vulcanizing agent with respect to 100 parts by mass of the rubber component (B).
- inorganic fine particles for example, metal fine particles and metal oxides such as magnesium oxide, tin oxide, titanium oxide, calcium carbonate, silica, barium sulfate, calcium silicate, zeolite, kaolinite, halloysite, magnesium carbonate, calcium sulfate
- inorganic particles such as mica, talc, pseudoboehmite, alumina, aluminum silicate, calcium silicate, magnesium silicate, zirconium oxide, zirconium hydroxide, cerium oxide, lanthanum oxide, and yttrium oxide. These may be used alone or in combination of two or more.
- the average particle diameter of the inorganic fine particles is preferably 0.0005 to 100 ⁇ m, more preferably 0.005 to 10 ⁇ m from the viewpoint of dispersion stability of the aqueous dispersion.
- the aqueous dispersion of the present invention may further include a leveling agent, an antifoaming agent, an anti-waxing agent, a pigment dispersant, an ultraviolet absorber, a catalyst, a photocatalyst, a UV curing agent, a wetting agent, and a penetrating agent.
- Various additives such as softeners, thickeners, dispersants, water repellents, antistatic agents, anti-aging agents, vulcanization accelerators, pigments or dyes, carbon black, carbon nanotubes, glass fibers, etc. Good. These may be used alone or in combination of two or more.
- the laminate of the present invention is obtained by laminating a coating film obtained from the aqueous dispersion of the present invention on at least a part of the substrate, and a coating film (adhesive layer) obtained from the aqueous dispersion of the present invention.
- the substrates adherered bodies
- the aqueous dispersion of the present invention is excellent in the slip property at room temperature of a coating film obtained by coating and drying. That is, in the laminate of the present invention in which the coating obtained from the aqueous dispersion of the present invention is laminated on the base material, the static friction coefficient (at ISO 8295) in an atmosphere of 23 ⁇ 2 ° C. when the coatings are overlapped with each other. Is preferably 1.5 or less, more preferably 1.3 or less, further preferably 1.2 or less, particularly preferably 1.0 or less, and 0.9 or less. Most preferably.
- the coefficient of static friction near room temperature is an indicator of stickiness and tackiness on the surface of the paint film near room temperature. If the coefficient of static friction exceeds 1.5, the paint film surface becomes sticky even at room temperature, which may cause adhesion of dust and make it difficult to handle. (Thus, the present invention employs the measurement of the coefficient of static friction at 23 ⁇ 2 ° C.).
- the adherend material to which the aqueous dispersion of the present invention can be adhered natural rubber, chloroprene rubber, isoprene rubber, urethane rubber, styrene butadiene rubber, butyl rubber, nitrile rubber , Rubber such as synthetic rubber such as ethylene propylene rubber, polypropylene, polypropylene copolymer, polyethylene, polyethylene copolymer, ethylene-vinyl acetate copolymer, polyolefin resin such as polyolefin thermoplastic elastomer, polyamide resin, Sheets and foams such as polyester resin, polyurethane resin, polyvinyl chloride resin, acrylic resin, molded articles; textile materials, woven fabrics, knitted fabrics, unemployed fabrics; leather materials such as natural leather, artificial leather, synthetic leather; metal, glass, Examples include paper, synthetic paper, wood, and concrete.
- the surface of the foam may have a skin layer.
- the aqueous dispersion penetrates from the surface of the woven fabric or the knitted fabric into the inside, so that it has excellent adhesive properties in general regardless of the types of fibers constituting the woven fabric or the knitted fabric. .
- a base material for example, a laminate comprising a base material containing a polyolefin resin and a base material containing rubber can be obtained through a coating film obtained from the aqueous dispersion of the present invention. .
- a method for producing a laminate by bonding an adherend through a coating film obtained from the aqueous dispersion of the present invention will be described.
- a bonding method using the aqueous dispersion of the present invention a known method can be used.
- a coating film (adhesive layer) is formed by applying the aqueous dispersion of the present invention to at least a part of the adherend surface, and then drying a part or all of volatile components such as an aqueous medium.
- a method in which adherends are pressure-bonded via a film (adhesive layer) can be employed.
- a known method can be employed, for example, ejection from a casting head, roll coating, knife coating, air knife coating, gravure roll coating, doctor roll coating, doctor knife coating, curtain flow. Examples include coats, spray coats, shower coats, wire bars, rod coats, dip coats, brush coats, and brush coats.
- the coating amount is preferably 0.2 g / m 2 or more, more preferably 1 to 1000 g / m 2 , more preferably 5 to 500 g / m 2 in terms of the solid content contained in the aqueous dispersion. It is particularly preferred. When the coating amount is less than 0.2 g / m 2 , the adhesiveness may be lowered.
- a known method can be adopted as a method for drying part or all of a volatile component such as an aqueous medium.
- a volatile component such as an aqueous medium.
- pulsed light using hot air, an infrared heater, a far infrared heater, a microwave, or a xenon flash lamp as a light source.
- Application and drying may be performed twice or more as necessary.
- a well-known method can also be adopted as a method of pressure-bonding adherends through an adhesive layer.
- the pressure at the time of pressure bonding is preferably as high as possible, and generally 0.01 MPa or more. However, if the pressure becomes too high, the shape of the adherend tends to collapse, so it is generally better to set the upper limit to 50 MPa.
- the pressure bonding time is preferably 0.5 to 300 seconds.
- the temperature of the adhesive layer at the start of pressure bonding is 40 ° C. or higher because adhesion can be improved. Therefore, it is preferable to perform the pressure bonding while the temperature of the adhesive layer is 40 ° C. or higher after the heat drying.
- an adhesive layer may be formed on the surface of the adherend that has not been surface-treated. After that, an adhesive layer may be formed.
- Surface treatment includes corona discharge treatment, flame plasma treatment, atmospheric pressure plasma treatment, low pressure plasma treatment, ozone treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, heat treatment, buffing, primer treatment, anchor coat treatment, acid treatment, alkali Treatment, chemical treatment, solvent treatment, degreasing treatment, etc. can be employed.
- the adherends are bonded with excellent adhesiveness.
- the strength (adhesion strength) required to peel off adherends bonded via the adhesive layer is somewhat strong or weak depending on the material and shape of the material, but usually a test piece cut to a width of 20 mm is used.
- a test piece cut to a width of 20 mm is used.
- it is 40 N / 20 mm or more, or material destruction of the adherend occurs during measurement.
- a laminate with an adherend bonded via an adhesive layer has little decrease in its adhesive strength even when it is repeatedly bent in a sub-freezing environment (hereinafter referred to as cold bending), and it can be used at extremely cold temperatures.
- the adhesive strength is preferably maintained.
- the ratio of the adhesive strength of the test piece subjected to the cold bending treatment to the adhesive strength of the test piece not subjected to the cold bending treatment, that is, the adhesive strength retention is preferably 50% or more, and 70% or more. More preferably, it is more preferably 80% or more, still more preferably 90% or more, and most preferably 95% or more.
- the aqueous dispersion of the present invention can sufficiently adhere polyolefin resin and rubber, adhesion between polypropylene resin and rubber, adhesion between ethylene-vinyl acetate copolymer and rubber, adhesion between polyethylene resin and rubber.
- it can be used for the production of various laminates by bonding a polyolefin-based thermoplastic elastomer and a metal, a polyolefin-based thermoplastic elastomer and a polypropylene resin, or the like.
- adhesion of rubber such as conveyor belts, hoses, rubber linings, adhesion of vulcanized rubber, manufacturing of door panels, adhesion of wallpaper, adhesion of resin moldings, adhesion of tiles, adhesion of flooring, etc.
- electrical equipment such as bonding of bases, automobiles, shoe making, automobile bumper primer, primer, anchor It can be used in a wide range of applications such as a coating agent.
- the aqueous dispersion of the present invention can be used for shoemaking applications, and in particular, can be suitably used as an adhesive for footwear, that is, an adhesive having a footwear component as an adherend.
- adherend materials to which the aqueous dispersion of the present invention can adhere can be suitably used.
- Polyurethane resin, polyolefin resin, rubber and the like can be preferably used. These may be used alone or in combination.
- the adhesive layer is formed by applying the footwear adhesive of the present invention to at least a part of the surface of the footwear component, and then drying part or all of the volatile components such as an aqueous medium in the adhesive. And the method of crimping
- the method shown as the method of applying the aqueous dispersion of the present invention described above can be adopted, and in particular, a knife coat A method such as brush coating or brush coating is preferred.
- a knife coat A method such as brush coating or brush coating is preferred.
- an adhesive for footwear may be applied after the primer treatment.
- an aqueous dispersion of an acid-modified polyolefin resin or the like can be preferably used.
- the application amount of the footwear adhesive is preferably 10 to 1000 g / m 2 , more preferably 50 to 500 g / m 2 in terms of the solid content contained in the footwear adhesive. Particularly preferred is 200 g / m 2 .
- the coating amount is less than 10 g / m 2, the adhesiveness required for footwear may not be obtained, and when it exceeds 1000 g / m 2 , it is disadvantageous in cost and the adhesiveness may be reduced. is there.
- drying method for forming an adhesive layer by drying part or all of a volatile component such as an aqueous medium in the applied adhesive
- hot air or infrared rays can be used. Drying by heating such as pulsed light using a heater, far infrared heater, microwave, xenon flash lamp as a light source is preferable.
- a method of heating by irradiating pulsed light using a xenon flash lamp as a light source after drying in advance with hot air, an infrared heater, a far-infrared heater, microwave, or the like may be employed.
- the application and drying steps as described above may be performed twice or more as necessary.
- a well-known method can also be adopted as a method of pressure-bonding the footwear components through the adhesive layer.
- the pressure at the time of pressure bonding is preferably as high as possible, and generally 0.01 MPa or more. However, if the pressure becomes too high, the shape of the constituent members of the footwear tends to collapse, so generally 20 MPa should be the upper limit.
- the pressure bonding time is preferably 0.5 to 300 seconds.
- the temperature of the adhesive layer at the start of pressure bonding is 40 ° C. or higher because adhesion can be improved. Therefore, it is preferable to perform the pressure bonding while the temperature of the adhesive layer is 40 ° C. or higher after the heat drying.
- the footwear of the present invention obtained by the above-described production method using an adhesive for footwear is excellent in adhesion between constituent members.
- the strength (adhesive strength) required to peel the constituent members bonded through the adhesive layer is somewhat strong or weak depending on the material or shape of the member, but usually a test piece cut to a width of 20 mm is used. When measured by using, it is preferably 20 N / 20 mm or more, more preferably 30 N / 20 mm or more, further preferably 40 N / 20 mm or more, particularly preferably 50 N / 20 mm, 60 N Most preferably, it is 20 mm or more, or material destruction of the adherend occurs during measurement. It is recognized that an adhesive capable of adhering a footwear component with the above strength is suitable as an adhesive for footwear.
- the adhesive for footwear of the present invention is excellent in adhesive strength retention in cold bending, the footwear of the present invention obtained therefrom has excellent shape stability even when used in cold regions.
- Aqueous Dispersion Number average particle diameter of dispersed particles Determined using a Microtrac particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., UPA150, MODEL No. 9340, dynamic light scattering method). The refractive index of the resin used for particle diameter calculation was 1.50.
- the obtained laminate was allowed to stand at room temperature for 24 hours, and then cut out with a width of 20 mm to obtain a test piece of 20 mm width ⁇ 100 mm length.
- two SBR sheets in the test piece were peeled off using a tensile tester (Intesco Corporation, Intesco Precision Universal Material Testing Machine 2020) under the conditions of a tensile speed of 50 mm / min, T-type peeling, and 25 ° C.
- the adhesive layers of the PP molded product and the SBR sheet were bonded together and pressure-bonded at a pressure of 2 MPa for 20 seconds using a press machine to obtain a laminate.
- the obtained laminate was allowed to stand at room temperature for 24 hours, and then cut out with a width of 20 mm to obtain a test piece of 20 mm width ⁇ 100 mm length.
- a tensile tester manufactured by Intesco, Intesco Precision Universal Material Tester 2020
- the PP molded product and the SBR sheet in the test piece were subjected to a tensile speed of 50 mm / min, 180 ° peeling, and 25 ° C.
- EVA ethylene-vinyl acetate resin (vinyl acetate content 30 mass%, hereinafter referred to as EVA) foam
- 100 mm x 50 mm x 2 mm SBR sheet black
- the SBR sheet was prepared by buffing one side of the Buff and removing the buffing wrinkles with air.
- 100 g of the aqueous dispersion (solid content mass) was prepared.
- / M 2 and applied with a brush. Next, it was introduced into a hot air dryer and dried at 90 ° C. for 20 minutes to form an adhesive layer.
- the adhesive layers of the EVA foam and the SBR sheet were bonded together and pressure-bonded at a pressure of 2 MPa for 20 seconds using a press machine to obtain a laminate.
- the obtained laminate was allowed to stand at room temperature for 24 hours, and then cut out with a width of 20 mm to obtain a test piece of 20 mm width ⁇ 100 mm length.
- a tensile tester manufactured by Intesco, Intesco Precision Universal Material Tester 2020
- the EVA foam and SBR sheet in the test piece were subjected to a tensile speed of 50 mm / min, T-type peeling, and 25 ° C.
- EVA / leather Adhesiveness 100mm x 50mm x 5mm EVA foam and 100mm x 50mm x 2mm cowhide (natural leather) are prepared, each of EVA foam and suede finish of cowhide
- the aqueous dispersion was applied to the surface with a brush so as to be 100 g (solid content mass) / m 2 .
- it was introduced into a hot air dryer and dried at 90 ° C. for 20 minutes to form an adhesive layer.
- the adhesive layer of EVA foam and cowhide was bonded together and pressed using a press machine at a pressure of 2 MPa for 20 seconds to obtain a laminate.
- the obtained laminate was allowed to stand at room temperature for 24 hours, and then cut out with a width of 20 mm to obtain a test piece of 20 mm width ⁇ 100 mm length.
- a tensile tester manufactured by Intesco, Intesco Precision Universal Material Tester 2020
- the EVA foam and cowhide in the test piece were pulled under the conditions of a tensile speed of 50 mm / min, T-type peeling, and 25 ° C.
- the adhesive layers of the PU sheet and the canvas were bonded to each other and pressure-bonded at a pressure of 2 MPa for 20 seconds using a press machine to obtain a laminate.
- the obtained laminate was allowed to stand at room temperature for 24 hours, and then cut out with a width of 20 mm to obtain a test piece of 20 mm width ⁇ 100 mm length.
- a tensile tester manufactured by Intesco, Intesco Precision Universal Material Tester 2020
- the PU sheet and the canvas in the test piece are peeled off at a tensile speed of 50 mm / min, T-type peeling, and 25 ° C.
- Adhesive strength retention ratio in cold bending A test piece having a structure of SBR sheet / SBR sheet was prepared by the method described in the above "(2) Adhesiveness of rubber / rubber". The obtained test piece was subjected to the following cold bending treatment three times. Thereafter, the test piece was allowed to stand at room temperature for 24 hours, and using a tensile tester (manufactured by Intesco, Intesco Precision Universal Material Testing Machine 2020) under conditions of a tensile speed of 50 mm / min, T-type peeling, and 25 ° C. The strength (adhesive strength) required to peel off the SBR sheets in the test piece was measured.
- Adhesive strength retention rate (%) adhesive strength of test piece subjected to cold bending treatment / adhesive strength of test piece not subjected to cold bending treatment ⁇ 100 (1)
- the aqueous dispersion (I) of acid-modified polyolefin resin was produced by the following method.
- the ethylene-ethyl acrylate-maleic anhydride copolymer PO1, PO2 based on the methods described in British Patent No. 2091745, US Pat. No. 4,617,366 and US Pat. No. 4,644,044 And PO3 were produced.
- Table 1 shows the characteristics of PO1, PO2 and PO3.
- the system was gradually depressurized to remove isopropanol and water. After removing 180 g or more of isopropanol and water, when the system temperature reached 35 ° C., water was added to adjust the solids concentration of the aqueous dispersion to 30% by mass, and a 180 mesh stainless steel filter Under pressure to obtain a milky white uniform aqueous dispersion of PO1, PO2 or PO3.
- the number average particle size of the aqueous dispersions of PO1, PO2 and PO3 was in the range of 0.07 to 0.08 ⁇ m.
- the mixture was cooled to about 80 ° C. while stirring at a rotational speed of 300 rpm.
- the system was gradually depressurized to remove n-propanol and water.
- water was added to adjust the solid content concentration of the aqueous dispersion to 20% by mass, and 180 mesh stainless steel
- the mixture was filtered under pressure using a filter manufactured by the method to obtain a milky white uniform aqueous dispersion of N0903HC or AN42115C.
- the number average particle size of the aqueous dispersions of N0903HC and AN42115C was in the range of 0.18 to 0.20 ⁇ m.
- the system was gradually depressurized to remove isopropanol and water. After removing 125 g or more of isopropanol and water, when the temperature inside the system reached 35 ° C., water was added to adjust the solid content concentration of the aqueous dispersion to 20% by mass, and a 180 mesh stainless steel filter Filtration under pressure gave a milky white uniform N1560 or 5990 aqueous dispersion.
- the number average particle size of the aqueous dispersions of N1560 and 5990 was in the range of 0.04 to 0.05 ⁇ m.
- Table 1 shows the characteristics of the acid-modified polyolefin resin used.
- the additive added to the aqueous dispersion of the present invention was produced by the following method.
- ⁇ Production of aqueous dispersion of acrylic resin> A reaction vessel equipped with a stirrer, a thermometer, a nitrogen seal tube, and a cooler was charged with 250 g of ion-exchanged water and purged with nitrogen for 1 hour while stirring. To this, 1.5 g of ammonium persulfate (polymerization initiator) was added and the temperature was adjusted to 60 ° C., and then 500 g of n-butyl acrylate, 50 g of isobutyl methacrylate, 10 g of acrylic acid, n-dodecyl mercaptan (chain transfer agent).
- Example 1 As the aqueous dispersion (I) of the acid-modified polyolefin resin (A), an aqueous dispersion of ethylene-ethyl acrylate-maleic anhydride copolymer PO1 was used. As an aqueous dispersion (II) of the rubber component (B), chloroprene-methacrylic acid copolymer latex (manufactured by Tosoh Corporation, Skyprene GFL-280, solid content concentration 55 mass%, number average particle size 0.1 ⁇ m) is used.
- chloroprene-methacrylic acid copolymer latex manufactured by Tosoh Corporation, Skyprene GFL-280, solid content concentration 55 mass%, number average particle size 0.1 ⁇ m
- the zinc oxide aqueous dispersion (manufactured by Yamazaki Kogyo Co., Ltd., AZ-SW) was added to 3 parts by mass of zinc oxide with respect to 100 parts by mass of Skyprene GFL-280 solid content.
- a polychloroprene latex (hereinafter referred to as GFL280) obtained by adding as described above was used.
- an aqueous dispersion (III) of the tackifier component (C) an aqueous dispersion of a terpene phenol tackifier component (manufactured by Arakawa Chemical Co., Ltd., Tamanol E-200NT, solid content concentration 53 mass%, number average particle size 0. 25 ⁇ m, softening point 150 ° C., hereinafter referred to as E200NT). Both are mixed so that the solid content of GFL-280 is 5 parts by mass with respect to 100 parts by mass of the solid content of the aqueous dispersion of PO1, and then the solid content of the mixed solution of (A) and (B) is 100 masses.
- Example 14 As the aqueous dispersion (I) of the acid-modified polyolefin resin (A), except that an aqueous dispersion of ethylene-methacrylic acid copolymer N0903HC was used, (A), (B), An aqueous dispersion containing (C) was obtained.
- Example 15 As the aqueous dispersion (I) of the acid-modified polyolefin resin (A), except that an aqueous dispersion of ethylene-methacrylic acid copolymer AN42115C was used, (A), (B), An aqueous dispersion containing (C) was obtained.
- Example 16 (A) The same operation as in Example 3 was performed except that an aqueous dispersion of ethylene-ethyl acrylate-maleic anhydride copolymer PO2 was used as the aqueous dispersion (I) of the acid-modified polyolefin resin (A). , (B) and (C) were obtained.
- Example 17 (A) The same operation as in Example 3 was performed except that an aqueous dispersion of ethylene-ethyl acrylate-maleic anhydride copolymer PO3 was used as the aqueous dispersion (I) of the acid-modified polyolefin resin (A). , (B) and (C) were obtained.
- Example 18 (A) The same procedure as in Example 3 was followed, except that an aqueous dispersion of ethylene-propylene-butene-maleic anhydride copolymer PO4 was used as the aqueous dispersion (I) of the acid-modified polyolefin resin (A). , (B) and (C) were obtained.
- Example 19 As an aqueous dispersion (II) of the rubber component (B), styrene-butadiene-ethylhexyl acrylate copolymer latex (manufactured by Asahi Kasei Chemicals Corporation, L7430, solid content concentration 50 mass%, number average particle size 0.15 ⁇ m, below The aqueous dispersion containing (A), (B), (C) and was obtained in the same manner as in Example 3, except that L7430 was used.
- Example 20 As an aqueous dispersion (III) of the tackifier component (C), an aqueous dispersion of a rosin ester tackifier component (manufactured by Arakawa Chemical Co., Ltd., Tamanol E-650, solid content concentration 50 mass%, number average particle diameter 0.2 ⁇ m) An aqueous dispersion containing (A), (B), and (C) was obtained in the same manner as in Example 3, except that a softening point of 160 ° C., hereinafter referred to as E650) was used.
- E650 softening point of 160 ° C.
- Example 21 An aqueous dispersion of an acrylic resin obtained by the production of an aqueous dispersion of an acrylic resin as an additive to the aqueous dispersion containing (A), (B), and (C) obtained by the same operation as in Example 3.
- the solid content is 10 parts by mass with respect to 100 parts by mass of the total solids of (A), (B), and (C) in the dispersion containing (A), (B), and (C).
- the aqueous dispersion containing (A), (B), (C) and an acrylic resin was obtained by adding and stirring as described above.
- Example 22 (A), (B), (C) and the polyurethane resin were used in the same manner as in Example 21 except that the polyurethane resin aqueous dispersion obtained in the production of the polyurethane resin aqueous dispersion was used as an additive. An aqueous dispersion containing was obtained.
- Example 23 As an additive, a water-dispersed polyisocyanate compound (manufactured by Takeda Pharmaceutical Company Limited, Takenate WD-730, isocyanate group content 18.6% by mass, hereinafter referred to as WD730) was used, and WD730 was converted into (A), (B ), (C) (A), (B), (C) in the same manner as in Example 21 except that the solid content was 3 parts by mass with respect to 100 parts by mass of the total solid content. And an aqueous dispersion containing WD730.
- a water-dispersed polyisocyanate compound manufactured by Takeda Pharmaceutical Company Limited, Takenate WD-730, isocyanate group content 18.6% by mass, hereinafter referred to as WD730
- WD730 was converted into (A), (B ), (C) (A), (B), (C) in the same manner as in Example 21 except that the solid content was 3 parts by mass with respect to 100 parts by mass of the total solid content.
- Example 24 An aqueous dispersion containing (A), (B), (C) and ADH in the same manner as in Example 23, except that adipic acid dihydrazide (Otsuka Chemical Co., Ltd., hereinafter referred to as ADH) was used as an additive. Got the body.
- ADH adipic acid dihydrazide
- aqueous dispersion of PO1 is used as the aqueous dispersion (I) of the acid-modified polyolefin resin (A)
- E200NT is used as the aqueous dispersion (III) of the tackifier component (C)
- the solid content of the aqueous dispersion of PO1 is 100. Both were mixed so that the solid content of E200NT was 50 parts by mass with respect to parts by mass. Water was added so that the solid content concentration of the obtained liquid mixture of (A) and (C) was 30% by mass to obtain an aqueous dispersion containing (A) and (C). Each mixing was performed while stirring.
- GFL280 is used as the aqueous dispersion (II) of the rubber component (B), E200NT is used as the aqueous dispersion (III) of the tackifier component (C), and the solid content of E200NT is 100 parts by mass of the solid content of GFL280. Both were mixed so that it might be 50 mass parts. Water was added so that the solid content concentration of the obtained liquid mixture of (B) and (C) was 30% by mass to obtain an aqueous dispersion containing (B) and (C). Each mixing was performed while stirring.
- aqueous dispersion of PO1 is used as the aqueous dispersion (I) of the acid-modified polyolefin resin (A)
- GFL280 is used as the aqueous dispersion (II) of the rubber component (B)
- the solid content of the aqueous dispersion of PO1 is 100 mass. Both were mixed so that the solid content of GFL-280 was 100 parts by mass relative to the part. Water was added so that the solid content concentration of the obtained liquid mixture of (A) and (B) was 30% by mass to obtain an aqueous dispersion containing (A) and (B). Each mixing was performed while stirring.
- Comparative Examples 4-5 (A), (B), and (A) in the same manner as in Example 1 except that the mixed amount of the acid-modified polyolefin resin (A), the rubber component (B), and the tackifier component (C) was changed to the amount shown in Table 2. An aqueous dispersion containing (C) was obtained.
- Comparative Example 7 As the aqueous dispersion (I) of the acid-modified polyolefin resin (A), except that an aqueous dispersion of ethylene-acrylic acid copolymer 5990 was used, (A), (B), An aqueous dispersion containing (C) was obtained.
- the aqueous dispersions of the present invention obtained in Examples 1 to 24 have good adhesion to rubber sheets, polyolefin resin molded products and foams, polyurethane resin sheets, leather and linen fabrics. It was excellent. Moreover, the adhesiveness had the outstanding adhesive strength retention with respect to cold bending. Furthermore, the aqueous dispersion was excellent in mixing stability with an organic solvent, and the coating film surface obtained from the aqueous dispersion was free from stickiness and tack and excellent in slipperiness. From a comparison between Examples 3, 16, and 17 and Examples 14 and 15, it is more preferable to use an ethylene-acrylic acid ester-maleic anhydride copolymer as the acid-modified polyolefin resin (A).
- the adhesiveness was inferior. This is considered to be caused by poor adhesion to the interface of the rubber substrate.
- the aqueous dispersion of Comparative Example 2 did not contain the acid-modified polyolefin resin (A), it was inferior in adhesiveness. This is considered to be caused by poor adhesion to the interface of the polyolefin resin substrate.
- the obtained coating film was sticky even at room temperature and was inferior in slipperiness. Further, when the aqueous dispersion was diluted with alcohol, aggregation occurred.
- the aqueous dispersions of Comparative Examples 3, 4, and 5 were inferior in adhesiveness because the rubber component (B) or tackifier component (C) was not contained in an appropriate amount. It was confirmed that the aqueous dispersions of Comparative Examples 6 and 7 were inferior in various performances because the polyolefin resin (A) in which the content of the unsaturated carboxylic acid component deviated from the amount specified in the present invention was used. Moreover, when the melt flow rate value of polyolefin resin (A) deviated from the preferable range of this invention, it was confirmed that adhesiveness is inferior.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
Description
しかしながら、ポリオレフィン樹脂やゴムは、共に接着性に乏しく、接着剤や粘着テープを用いてこれらを接着することは困難であり、強い振動や応力のかかる過酷な環境での使用に耐えうるような、強力な複合化技術が必要とされている。
しかしこれらの接着剤は、接着性が不十分であり、特にポリオレフィン樹脂との接着性は乏しく、ポリオレフィン樹脂とゴムとを十分に接着させることができないものであった。
また、特許文献1で提案された接着剤は溶剤系の接着剤であり、使用者の健康や環境保全の観点からも問題があった。一方、特許文献2で提案された接着剤は、水系接着剤であるが、この水系接着剤は、塗布の際に基材の種類によってはハジキが発生する場合があり、濡れ性を改善するためにアルコールなどの有機溶媒を少量添加すると、ポリクロロプレンラテックスの凝集が発生することがあった。
また、クロロプレンゴムと粘着付与剤とを組み合わせた接着剤組成物を用いて接着した積層体は、氷点下の環境で、屈曲を繰り返した場合に、接着強度が低下する傾向があった。
しかしながら、特許文献4記載の接着剤では、予めプラズマ処理や溶剤系のプライマーにより、被着体の表面を処理することが必要であるため、製造工程が複雑となりコストがかかる問題がある。加えて、溶剤系のプライマーを用いるため、結果として環境保全などの課題は解決できていない。
また特許文献5記載の接着剤では、接着可能な材料が特定のものに限定されており、例えば、ポリオレフィン樹脂に対する接着性については検討されていない。
また、クロロプレンゴムと粘着付与剤とを組み合わせた水性組成物は、アルコールなどの有機溶媒添加により凝集が発生するため、アルコールなどの有機溶媒を添加して濡れ性を改善することができなかった。
さらに、クロロプレンゴムと粘着付与剤とを組み合わせた接着剤組成物は、室温付近での塗膜表面のベタつきやタックが強すぎるといった問題があった。またこの接着剤組成物を用いて接着した積層体は、氷点下の環境下で屈曲を繰り返した場合に、接着強度が低下する傾向にあるため、冬季の寒冷地での使用に問題があった。
また水系の履物用接着剤においても、十分な接着性とコスト、環境保全を両立したものはなかった。
すなわち、本発明の要旨は、以下のとおりである。
(1)不飽和カルボン酸成分の含有量が0.1~10質量%である酸変性ポリオレフィン樹脂(A)、ゴム成分(B)、粘着付与成分(C)および水性媒体を含有し、酸変性ポリオレフィン樹脂(A)100質量部に対して、ゴム成分(B)の含有量が5~1900質量部であり、酸変性ポリオレフィン樹脂(A)とゴム成分(B)の総和100質量部に対して、粘着付与成分(C)の含有量が5~300質量部であることを特徴とする水性分散体。
(2)酸変性ポリオレフィン樹脂(A)がエチレン-(メタ)アクリル酸エステル-(無水)マレイン酸共重合体であることを特徴とする(1)に記載の水性分散体。
(3)酸変性ポリオレフィン樹脂(A)のメルトフローレート値(ISO1133に準ずる190℃、21.2N荷重)が1~300g/10分であることを特徴とする(1)または(2)に記載の水性分散体。
(4)ゴム成分(B)がクロロプレンゴムであることを特徴とする(1)または(2)に記載の水性分散体。
(5)粘着付与成分(C)がテルペン系樹脂であることを特徴とする(1)または(2)に記載の水性分散体。
(6)水性分散体中の分散粒子の数平均粒子径が0.5μm以下であることを特徴とする(1)または(2)に記載の水性分散体。
(7)得られる塗膜の23±2℃雰囲気下での表面の静摩擦係数(ISO8295に準ずる)が1.5以下であることを特徴とする(1)または(2)に記載の水性分散体。
(8)少なくとも基材の一部に、(1)または(2)に記載の水性分散体より得られる塗膜が積層されてなる積層体。
(9)塗膜の23±2℃雰囲気下での表面の静摩擦係数(ISO8295に準ずる)が1.5以下であることを特徴とする(8)に記載の積層体。
(10)ポリオレフィン樹脂を含む基材とゴムを含む基材とが、(1)または(2)に記載の水性分散体より得られる塗膜を介して接着されてなる積層体。
(11)上記(1)または(2)に記載の水性分散体からなる接着剤であって、履物の構成部材を被着体とすることを特徴とする履物用接着剤。
(12)履物の構成部材が、皮革材料、織物、編物、ポリ塩化ビニル樹脂、ポリウレタン樹脂、ポリオレフィン樹脂及びゴムからなる群より選ばれる1種以上を含むことを特徴とする(11)に記載の履物用接着剤。
(13)上記(11)に記載の履物用接着剤を用いて得られた履物。
また、本発明の水性分散体は、アルコールなどの有機溶媒添加による凝集の発生が抑えられ、このため有機溶媒添加によって濡れ性の向上が図れる。
本発明の水性分散体は、プラズマ処理や溶剤系のプライマーを用いて予め被着体の表面を処理しなくても優れた接着性を有する。
そして本発明の分散体は水性であるため、作業者の健康や環境に与える負荷が少ない。
さらに、本発明の水性分散体より得られる塗膜は、表面にベタつきやタックが少なく、表面の滑り性に優れ、ロールに巻き取り室温保存することができる。
また、本発明の水性分散体を接着剤として得られた積層体は、氷点下の環境下でも使用可能である。
本発明の水性分散体は、履物用接着剤として利用することが可能である。
本発明の水性分散体は、酸変性ポリオレフィン樹脂(A)、ゴム成分(B)、粘着付与成分(C)および水性媒体を含有する。
酸変性ポリオレフィン樹脂(A)は、主成分としてオレフィン成分を含有するものであり、オレフィン成分としては、エチレン、プロピレン、イソブチレン、2-ブテン、1-ブテン、1-ペンテン、1-ヘキセンなどの炭素数2~6のアルケンが好ましく、これらの混合物を用いてもよい。中でも、接着性を向上させる観点から、エチレン、プロピレン、イソブチレン、1-ブテンなどの炭素数2~4のアルケンがより好ましく、エチレン、プロピレンが特に好ましく、エチレンがさらに好ましい。
不飽和カルボン酸成分としては、アクリル酸、メタクリル酸、(無水)マレイン酸、(無水)イタコン酸、フマル酸、クロトン酸などのほか、不飽和ジカルボン酸のハーフエステル、ハーフアミドなどが挙げられる。中でもアクリル酸、メタクリル酸、(無水)マレイン酸が好ましく、特に(無水)マレイン酸が好ましい。なお、「(無水)~酸」とは、「~酸または無水~酸」を意味する。すなわち、(無水)マレイン酸とは、マレイン酸または無水マレイン酸を意味する。
不飽和カルボン酸成分は、オレフィン成分と共重合されていればよく、その形態は限定されず、共重合の状態としては、例えば、ランダム共重合、ブロック共重合、グラフト共重合(グラフト変性)などが挙げられる。
そのような他の成分として、具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチルなどの(メタ)アクリル酸エステル類、マレイン酸ジメチル、マレイン酸ジエチル、マレイン酸ジブチルなどのマレイン酸ジエステル類、メチルビニルエーテル、エチルビニルエーテルなどのアルキルビニルエーテル類、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、バーサチック酸ビニルなどのビニルエステル類、並びにビニルエステル類を塩基性化合物などでケン化して得られるビニルアルコール、(メタ)アクリル酸アミド類などやこれらの混和物が挙げられる。中でも、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチルなどの(メタ)アクリル酸エステル類、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、バーサチック酸ビニルなどのビニルエステル類成分が好ましく、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチルなどの(メタ)アクリル酸エステル類がより好ましい。なお、「(メタ)アクリル酸~」とは、「アクリル酸~またはメタクリル酸~」を意味する。
これらの他の成分は、酸変性ポリオレフィン樹脂(A)中に共重合されていればよく、その形態は限定されず、共重合の状態としては、例えば、ランダム共重合、ブロック共重合、グラフト共重合(グラフト変性)などが挙げられる。
酸変性ポリオレフィン樹脂(A)の水性分散体(I)を得るために、酸変性ポリオレフィン樹脂(A)を水性媒体中に分散させる方法としては、自己乳化法や強制乳化法など公知の分散方法を採用すればよい。なお、酸変性ポリオレフィン樹脂(A)の水性分散体(I)の製造には、界面活性剤や高酸価ワックスなど、分散化を促進する目的で任意で添加される乳化剤や分散剤を使用しない分散方法を採用することが、接着性や耐水接着性を高める観点から好ましい。
本発明の水性分散体は、水性媒体中で酸変性ポリオレフィン樹脂(A)の不飽和カルボン酸成分を塩基性化合物によって中和することで得られるアニオン性の水性分散体であることが、接着性の観点から好ましい。なお、酸変性ポリオレフィン樹脂(A)のアニオン性水性分散体は、通常アルカリ性を示す。
本発明の水性分散体は、ゴム成分(B)を含有することが必要である。
本発明の水性分散体において、ゴム成分(B)の含有量は、酸変性ポリオレフィン樹脂(A)100質量部に対して、5~1900質量部であることが必要であり、10~900質量部であることがより好ましく、25~400質量部であることが特に好ましい。ゴム成分(B)の含有量が5質量部未満であると、ゴムを含む基材との接着性が低下し、含有量が1900質量部を超えると、ポリオレフィン樹脂を含む基材との接着性が低下する。
クロロプレンと共重合可能な単量体の含有量は、特に限定するものではないが、ポリクロロプレン特性保持の観点から、ポリクロロプレンの40質量%以下であることが好ましい。なお、不飽和カルボン酸を共重合させる場合は、ポリクロロプレンの10質量%以下であることが好ましく、0.2~5質量%であることがより好ましく、0.5~4質量%であることがさらに好ましく、0.7~3.5質量%であることが特に好ましい。不飽和カルボン酸が少な過ぎると接着性の向上効果が充分ではない場合があり、10質量%を超えると乳化状態が不安定になる場合がある。なお共重合体には、ポリクロロプレン存在下にその他の単量体をグラフト重合させた様なグラフト共重合体も含まれる。
アニオン型の乳化剤としては、カルボン酸型、スルホン酸型、硫酸エステル型等があり、例えば、ロジン酸のアルカリ金属塩、炭素数が8~20個のアルキルスルホネート、アルキルアリールサルフェート、ナフタリンスルホン酸ナトリウムとホルムアルデヒドとの縮合物等が挙げられる。
ノニオン型の具体例としては、ポリビニルアルコールまたはその共重合体(例えば、アクリルアミドとの共重合体)、ポリビニルエーテルまたはその共重合体(例えば、マレイン酸との共重合体)、ポリビニルピロリドンまたはその共重合体(例えば、酢酸ビニルとの共重合体)、あるいは、これら(共)重合体を化学修飾したもの、あるいは、セルロース系誘導体(ヒドロキシエチルセルロース)等が挙げられる。
カチオン型の具体例としては、脂肪族アミン塩、脂肪族4級アンモニウム塩等が挙げられ、例えば、オクタデシルトリメチルアンモニウムクロリド、ドデシルトリメチルアンモニウムクロリド、ジラウリルジメチルアンモニウムクロリド等が挙げられる。
これらの中でも、アニオン型の乳化剤を用いることが好ましい。アニオン型以外のものでは接着性が劣ったり、酸変性ポリオレフィン樹脂(A)や粘着付与成分(C)との混合安定性が低下する傾向にある。乳化剤や分散剤の添加量は、初期仕込み単量体の合計質量の0.5~20質量%が好ましい。乳化剤や分散剤の添加量が0.5質量%未満の場合には、乳化力が十分でなく、添加量が20質量%を超えると接着性や耐水接着性を低下させる傾向がある。
本発明の水性分散体は、粘着付与成分(C)を含有することが必要である。
本発明の水性分散体において、粘着付与成分(C)の含有量は、酸変性ポリオレフィン樹脂(A)とゴム成分(B)の総和100質量部に対して、5~300質量部であることが必要であり、10~150質量部であることがより好ましく、25~100質量部であることがさらに好ましく、40~100質量部であることが特に好ましい。粘着付与成分(C)の含有量が5~300質量部の範囲を外れる場合は、接着性が低下する。
粘着付与成分(C)としては、例えば、ロジン類、ロジン誘導体、石油系樹脂、テルペン系樹脂、クマロン樹脂、インデン樹脂などが挙げられ、これらの単独で又は2種以上を混合して使用することができる。
ロジン類またはロジン誘導体としては、重合ロジン、不均化ロジン、水素添加ロジン、マレイン化ロジン、フマル化ロジン、及びこれらのグリセリンエステル、ペンタエリスリトールエステル、メチルエステル、エチルエステル、ブチルエステル、エチレングリコールエステル、ジエチレングリコールエステル、トリエチレングリコールエステルなどが挙げられる。
石油系樹脂としては、炭素数5個の石油留分を重合した石油樹脂、炭素数9個の石油留分を重合した石油樹脂、及びこれらを水素添加した石油樹脂、マレイン酸変性、フタル酸変性した石油樹脂などが挙げられる。
テルペン系樹脂としては、低重合テルペン系、α-ピネン重合体、β-ピネン重合体、テルペンフェノール系、芳香族変性テルペン系、水素添加テルペンなどが挙げられる。
これらの中でも、接着性の点でテルペン系樹脂が好ましく、テルペンフェノール系樹脂がより好ましい。
また、粘着付与成分(C)の水性分散体(III)はアルカリ性であることが好ましい。
また、本発明の水性分散体中の酸変性ポリオレフィン樹脂(A)、ゴム成分(B)、粘着付与成分(C)を含んだ不揮発成分の固形分濃度は、水性分散体の5~70質量%であることが好ましく、20~60質量%であることがより好ましく、30~50質量%であることが特に好ましい。
中でも、カルボキシル基と反応する官能基を分子内に複数個有する架橋剤がより好ましい。このような架橋剤としては、オキサゾリン化合物、エポキシ化合物、カルボジイミド化合物、イソシアネート化合物、ヒドラジド化合物、アミン化合物、メラミン化合物、及びポリオールが挙げられ、オキサゾリン化合物、ヒドラジド化合物、アミン化合物、カルボジイミド化合物、イソシアネート化合物が架橋の効果に優れるため好ましく、オキサゾリン化合物、ヒドラジド化合物、アミン化合物が特に好ましい。
架橋剤の添加量は、架橋構造を十分に形成させる観点から、(A)、(B)、(C)の総和100質量部に対して、架橋剤の固形分として、0.01~300質量部であることが好ましく、0.1~100質量部であることがより好ましく、0.2~50質量部であることがさらに好ましく、0.5~30質量部であることが特に好ましい。
無機微粒子の平均粒子径としては、水性分散体の分散安定性の面から0.0005~100μmが好ましく、0.005~10μmがより好ましい。
本発明の積層体は、少なくとも基材の一部に、本発明の水性分散体より得られる塗膜が積層されてなるものであり、本発明の水性分散体より得られる塗膜(接着層)を介して基材(被着体)同士が積層されてなるものを含む。
このような基材を用い、本発明の水性分散体より得られる塗膜を介して、例えば、ポリオレフィン樹脂を含む基材とゴムを含む基材とが接着されてなる積層体を得ることができる。
本発明の水性分散体を用いた接着方法は公知の方法を用いることができる。例えば、被着体表面の少なくとも一部に本発明の水性分散体を塗布してから、水性媒体などの揮発成分の一部または全てを乾燥させることで塗膜(接着層)を形成し、塗膜(接着層)を介して被着体同士を圧着させる方法を採用することができる。
塗布量としては、水性分散体の含有する固形分量に換算して0.2g/m2以上であることが好ましく、1~1000g/m2であることがより好ましく、5~500g/m2であることが特に好ましい。塗布量が0.2g/m2未満の場合は、接着性が低下することがある。
圧着時の圧力としては、可能な限り高い圧力が好ましく、一般に0.01MPa以上が好ましい。ただ、圧力が高くなりすぎると、被着体の形状が崩れやすくなるので、一般に50MPaを上限とするのがよい。
他方、圧着時間としては、0.5~300秒が好ましい。
また圧着開始時の接着層の温度は40℃以上であることが接着性を良好にできることから好ましい。よって、圧着は加熱乾燥の後に接着層の温度が40℃以上である間に実施することが好ましい。
表面処理としては、コロナ放電処理、フレームプラズマ処理、大気圧プラズマ処理、低圧プラズマ処理、オゾン処理、電子線照射処理、紫外線照射処理、熱処理、バフ掛け、プライマー処理、アンカーコート処理、酸処理、アルカリ処理、薬品処理、溶剤処理、脱脂処理などが採用できる。
本発明の履物用接着剤を用いた履物の製造方法は、公知の方法を用いることができる。例えば、履物の構成部材表面の少なくとも一部に、本発明の履物用接着剤を塗布してから、接着剤中の水性媒体などの揮発成分の一部または全てを乾燥させることで接着層を形成し、接着層を介して履物の構成部材同士を圧着させる方法を採用することができる。
履物の構成部材を以上のような強度で接着することが可能な接着剤は、履物用接着剤として適していると認められる。
各種の特性について、以下の方法で測定または評価した。
(1)構成
1H-NMR分析(日本電子社製、ECA500、500MHz)より求めた。テトラクロロエタン(d2)を溶媒とし、120℃で測定した。
(2)融点
酸変性ポリオレフィン樹脂10mgをサンプルとし、DSC(示差走査熱量測定)装置(パーキンエルマー社製、DSC7)を用いて昇温速度10℃/分の条件で測定を行って融点を求めた。
(3)メルトフローレート値(MFR)
ISO1133記載(190℃、21.2N荷重)の方法で測定した。
(1)分散粒子の数平均粒子径
マイクロトラック粒度分布計(日機装社製、UPA150、MODEL No.9340、動的光散乱法)を用いて求めた。粒子径算出に用いる樹脂の屈折率は1.50とした。
(2)アルコール希釈安定性
水性分散体20gに、イソプロパノール濃度が70質量%のイソプロパノール水溶液20gを、撹拌状態で徐々に滴下し、水性分散体の状態を下記の指標で目視で評価した。
○:凝集が全くない。
△:若干の凝集物が確認できる。
×:固形分のほとんどが凝集した。
(1)滑り性(静摩擦係数)
厚さ100μmのポリエチレンテレフタレート(以下、PETと称す)フィルムのコロナ面に、乾燥後の塗膜厚みが3~10μmの範囲となるように水性分散体を塗布し、100℃で2分間乾燥した。得られたコートフィルム(積層体)を用いて、ISO8295に準じて(雰囲気温度23±2℃、荷重19.6N、引張速度100mm/分)、静摩擦係数を測定した。なお、コートフィルムの塗工面同士を重ね合わせて評価した(塗膜同士の摩擦係数を求めた)。
100mm×50mm×2mmのスチレンブタジエンゴム(以下、SBRと称す)シート(黒)の片面をバフ掛けし、バフ掛けの粕をエアーで取り除いたSBRシートを2枚用意し、それぞれのバフ掛け面に、水性分散体を100g(固形分質量)/m2になるように刷毛で塗布した。次に、熱風乾燥機へ導入し90℃で20分間乾燥して接着層を形成させた。乾燥後、直ちに2枚のSBRシートの接着層同士を貼り合わせ、プレス機を用いて2MPaの圧力で20秒間圧着し、積層体を得た。
得られた積層体を室温下で24時間静置した後、20mm巾で切り出し、20mm巾×100mm長の試験片を得た。次に引張試験機(インテスコ社製、インテスコ精密万能材料試験機2020型)を用いて、引張速度50mm/分、T型剥離、25℃の条件で、試験片中の2枚のSBRシートを剥離するのに必要な強度(接着強度)を測定した。測定はn=5で行い、平均値を接着性とした。
100mm×50mm×3mmのポリプロピレン樹脂(以下、PPと称す)成形品の片面をバフ掛けし、バフ掛けの粕をエアーで取り除いた後、バフ掛け面にコロナ処理を施したPP成形品と、100mm×50mm×2mmのSBRシート(黒)の片面をバフ掛けし、バフ掛けの粕をエアーで取り除いたSBRシートとを用意し、それぞれのバフ掛け面に、水性分散体を100g(固形分質量)/m2になるように刷毛で塗布した。次に、熱風乾燥機へ導入し90℃で20分間乾燥して接着層を形成させた。乾燥後、直ちにPP成形品とSBRシートの接着層同士を貼り合わせ、プレス機を用いて2MPaの圧力で20秒間圧着し、積層体を得た。
得られた積層体を室温下で24時間静置した後、20mm巾で切り出し、20mm巾×100mm長の試験片を得た。次に引張試験機(インテスコ社製、インテスコ精密万能材料試験機2020型)を用いて、引張速度50mm/分、180°剥離、25℃の条件で、試験片中のPP成形品とSBRシートとを剥離するのに必要な強度(接着強度)を測定した。測定はn=5で行い、平均値を接着性とした。
100mm×50mm×5mmのエチレン-酢酸ビニル樹脂(酢酸ビニル含有量30質量%、以下、EVAと称す)発泡体と、100mm×50mm×2mmのSBRシート(黒)の片面をバフ掛けし、バフ掛けの粕をエアーで取り除いたSBRシートとを用意し、EVA発泡体の片面とSBRシートのバフ掛け面のそれぞれの面に、水性分散体を100g(固形分質量)/m2になるように刷毛で塗布した。次に、熱風乾燥機へ導入し90℃で20分間乾燥して接着層を形成させた。乾燥後、直ちにEVA発泡体とSBRシートの接着層同士を貼り合わせ、プレス機を用いて2MPaの圧力で20秒間圧着し、積層体を得た。
得られた積層体を室温下で24時間静置した後、20mm巾で切り出し、20mm巾×100mm長の試験片を得た。次に引張試験機(インテスコ社製、インテスコ精密万能材料試験機2020型)を用いて、引張速度50mm/分、T型剥離、25℃の条件で、試験片中のEVA発泡体とSBRシートとを剥離するのに必要な強度(接着強度)を測定した。測定はn=5で行い、平均値を接着性とした。
100mm×50mm×5mmのEVA発泡体と、100mm×50mm×2mmの牛皮(天然皮革)とを用意し、EVA発泡体の片面と牛皮のスエード仕上げ面のそれぞれの面に、水性分散体を100g(固形分質量)/m2になるように刷毛で塗布した。次に、熱風乾燥機へ導入し90℃で20分間乾燥して接着層を形成させた。乾燥後、直ちにEVA発泡体と牛皮の接着層同士を貼り合わせ、プレス機を用いて2MPaの圧力で20秒間圧着し、積層体を得た。
得られた積層体を室温下で24時間静置した後、20mm巾で切り出し、20mm巾×100mm長の試験片を得た。次に引張試験機(インテスコ社製、インテスコ精密万能材料試験機2020型)を用いて、引張速度50mm/分、T型剥離、25℃の条件で、試験片中のEVA発泡体と牛皮とを剥離するのに必要な強度(接着強度)を測定した。測定はn=5で行い、平均値を接着性とした。
100mm×50mm×2mmのポリウレタン樹脂(以下、PUと称す)シートの片面をバフ掛けし、バフ掛けの粕をエアーで取り除いたPUシートと、100mm×50mm×1mmのキャンバス(麻織物)とを用意し、PUシートのバフ掛け面とキャンバスの麻織面のそれぞれの面に、水性分散体を100g(固形分質量)/m2になるように刷毛で塗布した。次に、熱風乾燥機へ導入し90℃で20分間乾燥して接着層を形成させた。乾燥後、直ちにPUシートとキャンバスの接着層同士を貼り合わせ、プレス機を用いて2MPaの圧力で20秒間圧着し、積層体を得た。
得られた積層体を室温下で24時間静置した後、20mm巾で切り出し、20mm巾×100mm長の試験片を得た。次に引張試験機(インテスコ社製、インテスコ精密万能材料試験機2020型)を用いて、引張速度50mm/分、T型剥離、25℃の条件で、試験片中のPUシートとキャンバスとを剥離するのに必要な強度(接着強度)を測定した。測定はn=5で行い、平均値を接着性とした。
上記「(2)ゴム/ゴムの接着性」に記載された方法で、SBRシート/SBRシートの構成の試験片を作製した。
得られた試験片を、下記の冷間屈曲処理を3回行った。
その後、試験片を室温下で24時間静置し、引張試験機(インテスコ社製、インテスコ精密万能材料試験機2020型)を用いて、引張速度50mm/分、T型剥離、25℃の条件で、試験片中のSBRシート同士を剥離するのに必要な強度(接着強度)を測定した。測定はn=5で行い、測定値の平均値を求め、この値を「冷間屈曲処理を施した試験片の接着強度」とした。また、上記「(2)ゴム/ゴムの接着性」において測定された接着強度の平均値を「冷間屈曲処理を施していない試験片の接着強度」として、これらの値から接着強度保持率を下記式(1)より求めた。
冷間屈曲処理:試験片を-40℃の冷蔵室に2時間静置した後に、-40℃の環境下で、半径5mm円柱に、試験片の20mmの辺が円柱の軸方向と平行になるようにして、試験片の全体を巻きつけて直ぐに巻き出した。この巻きつけと巻き出し作業を5回繰り返した。
接着強度保持率(%)=冷間屈曲処理を施した試験片の接着強度/冷間屈曲処理を施していない試験片の接着強度×100 (1)
<エチレン-アクリル酸エチル-無水マレイン酸共重合体の水性分散体製造>
英国特許第2091745号明細書、米国特許第4617366号明細書および米国特許第4644044号明細書に記載された方法をもとに、エチレン-アクリル酸エチル-無水マレイン酸共重合体であるPO1、PO2およびPO3を製造した。PO1、PO2およびPO3の特性を表1に示す。
次いで、撹拌機とヒーターを備えた1リットル容ガラス容器に、上記で得られたPO1、PO2またはPO3を100g、イソプロパノールを100g、2-ジメチルアミノエタノールを5g、蒸留水を295g仕込んだ。撹拌翼の回転速度を300rpmとして撹拌したところ、容器底部には樹脂粒状物の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、10分後にヒーターの電源を入れ加熱した。そして系内温度を120℃に保ってさらに120分間撹拌し分散化させた。その後、回転速度300rpmのまま攪拌しつつ約80℃まで冷却したところで、系内を徐々に減圧して、イソプロパノールと水を除去した。イソプロパノールと水を180g以上除去した後、系内温度が35℃になったところで、水を添加して水性分散体の固形分濃度を30質量%となるように調整し、180メッシュのステンレス製フィルターで加圧濾過して、乳白色の均一なPO1、PO2またはPO3の水性分散体を得た。PO1、PO2およびPO3の水性分散体の数平均粒子径は0.07~0.08μmの範囲内であった。
国際公開第2004/104090号に記載された方法をもとに、エチレン-プロピレン-ブテン-無水マレイン酸共重合体であるPO4を製造した。PO4の特性を表1に示す。
次いで、撹拌機とヒーターを備えた1リットル容ガラス容器に、上記で得られたPO4を75g、テトラヒドロフランを150g、2-ジメチルアミノエタノールを8g、蒸留水を267g仕込んだ。撹拌翼の回転速度を300rpmとして撹拌したところ、容器底部には樹脂粒状物の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、10分後にヒーターの電源を入れ加熱した。そして系内温度を130℃に保ってさらに120分間撹拌し分散化させた。その後、回転速度300rpmのまま攪拌しつつ約80℃まで冷却したところで、系内を徐々に減圧して、テトラヒドロフランと水を除去した。テトラヒドロフランと水を250g以上除去した後、系内温度が35℃になったところで、水を添加して水性分散体の固形分濃度を30質量%となるように調整し、180メッシュのステンレス製フィルターで加圧濾過して、乳白色の均一なPO4の水性分散体を得た。PO4の水性分散体の数平均粒子径は0.12μmであった。
エチレン-メタクリル酸共重合体(三井・デュポンポリケミカル社製、ニュクレルN0903HC、以下、N0903HCと称す)、エチレン-メタクリル酸共重合体(三井・デュポンポリケミカル社製、ニュクレルAN42115C、以下、AN42115Cと称す)、エチレン-メタクリル酸共重合体(三井・デュポンポリケミカル社製、ニュクレルN1560、以下、N1560と称す)、エチレン-アクリル酸共重合体(ダウ・ケミカル社製、プリマコール5990、以下、5990と示す)を用いて、下記の方法によりそれらの水性分散体を製造した。N0903HC、AN42115C、N1560、5990の特性を表1に示す。
撹拌機とヒーターを備えた1リットル容ガラス容器に、N0903HCまたはAN42115Cを75g、n-プロパノールを175g、2-ジメチルアミノエタノールを20g、蒸留水を230g仕込んだ。撹拌翼の回転速度を300rpmとして撹拌したところ、容器底部には樹脂粒状物の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、10分後にヒーターの電源を入れ加熱した。そして系内温度を150℃に保ってさらに120分間撹拌し分散化させた。その後、回転速度300rpmのまま攪拌しつつ約80℃まで冷却したところで、水を200g追加した後、系内を徐々に減圧して、n-プロパノールと水を除去した。n-プロパノールと水を350g以上除去した後、系内温度が35℃になったところで、水を添加して水性分散体の固形分濃度を20質量%となるように調整し、180メッシュのステンレス製フィルターで加圧濾過して、乳白色の均一なN0903HCまたはAN42115Cの水性分散体を得た。N0903HCおよびAN42115Cの水性分散体の数平均粒子径は0.18~0.20μmの範囲内であった。
撹拌機とヒーターを備えた1リットル容ガラス容器に、N1560または5990を75g、イソプロパノールを50g、2-ジメチルアミノエタノールを7g、蒸留水を368g仕込んだ。撹拌翼の回転速度を300rpmとして撹拌したところ、容器底部には樹脂粒状物の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、10分後にヒーターの電源を入れ加熱した。そして系内温度を130℃に保ってさらに120分間撹拌し分散化させた。その後、回転速度300rpmのまま攪拌しつつ約80℃まで冷却したところで、系内を徐々に減圧して、イソプロパノールと水を除去した。イソプロパノールと水を125g以上除去した後、系内温度が35℃になったところで、水を添加して水性分散体の固形分濃度を20質量%となるように調整し、180メッシュのステンレス製フィルターで加圧濾過して、乳白色の均一なN1560または5990の水性分散体を得た。N1560および5990の水性分散体の数平均粒子径は0.04~0.05μmの範囲内であった。
<アクリル樹脂の水性分散体製造>
攪拌機、温度計、窒素シール管、冷却器のついた反応容器にイオン交換水250gを入れ、攪拌しながら1時間窒素置換させた。これに過硫酸アンモニウム(重合開始剤)を1.5g加え、温度を60℃にし、その後、アクリル酸n-ブチル500g、メタクリル酸イソブチル50g、アクリル酸10g、n-ドデシルメルカプタン(連鎖移動剤)0.5g、及びスルホコハク酸ジエステルアンモニウム塩20gを水120gで乳化したものを、3時間かけて滴下し、乳化重合させてアクリル樹脂の水性分散体を得た。
攪拌機、温度計、窒素シール管、冷却器のついた反応器に、数平均分子量1970のポリテトラメチレングリコールを345g、イソホロンジイソシアネートを77.8g、ジブチルチンジラウレートを0.03g仕込み、80℃で2時間反応させた。次いでこの反応液を50℃まで冷却した後、3-ジメチルアミノプロパノールを11.7g、トリエチルアミンを8.85g、アセトンを177g質量部添加し、3時間反応させた。さらに、この反応液にアセトンを175g加えて30℃まで冷却し、イソホロンジイソシアネート13.4g、モノエタノ-ルアミン1.07g、イソプロパノール87.9g、水1039gからなる混合液を加えて高速攪拌し、この液からアセトン、水及びイソプロパノールを留去して、ポリエーテル型のポリウレタン樹脂の水性分散体(固形分濃度50質量%)を得た。
酸変性ポリオレフィン樹脂(A)の水性分散体(I)として、エチレン-アクリル酸エチル-無水マレイン酸共重合体PO1の水性分散体を用いた。
またゴム成分(B)の水性分散体(II)として、クロロプレン-メタクリル酸共重合体ラテックス(東ソー社製、スカイプレンGFL-280、固形分濃度55質量%、数平均粒子径0.1μm)を2-ジメチルアミノエタノールでpH8に調整した後に、酸化亜鉛水性分散体(山崎工業社製、AZ-SW)を、スカイプレンGFL-280の固形分100質量部に対して酸化亜鉛が3質量部になるように添加して得たポリクロロプレンラテックス(以下、GFL280と称す)を用いた。
また粘着付与成分(C)の水性分散体(III)として、テルペンフェノール系粘着付与成分の水性分散体(荒川化学社製、タマノルE-200NT、固形分濃度53質量%、数平均粒子径0.25μm、軟化点150℃、以下、E200NTと称す)を用いた。
PO1の水性分散体の固形分100質量部に対して、GFL-280の固形分が5質量部になるように両者を混合し、次いで(A)、(B)の混合液の固形分100質量部に対して、E200NTの固形分が50質量部になるように両者を混合した。得られた(A)、(B)、(C)の混合液の固形分濃度が30質量%になるように水を添加して、(A)、(B)、(C)を含む水性分散体を得た。なおそれぞれの混合は攪拌しながら行った。
酸変性ポリオレフィン樹脂(A)、ゴム成分(B)、粘着付与成分(C)の混合量を表2に示す量とした以外は、実施例1と同様の操作で(A)、(B)、(C)を含む水性分散体を得た。
酸変性ポリオレフィン樹脂(A)の水性分散体(I)として、エチレン-メタクリル酸共重合体N0903HCの水性分散体を用いた以外は、実施例3と同様の操作で(A)、(B)、(C)を含む水性分散体を得た。
酸変性ポリオレフィン樹脂(A)の水性分散体(I)として、エチレン-メタクリル酸共重合体AN42115Cの水性分散体を用いた以外は、実施例3と同様の操作で(A)、(B)、(C)を含む水性分散体を得た。
酸変性ポリオレフィン樹脂(A)の水性分散体(I)として、エチレン-アクリル酸エチル-無水マレイン酸共重合体PO2の水性分散体を用いた以外は、実施例3と同様の操作で(A)、(B)、(C)を含む水性分散体を得た。
酸変性ポリオレフィン樹脂(A)の水性分散体(I)として、エチレン-アクリル酸エチル-無水マレイン酸共重合体PO3の水性分散体を用いた以外は、実施例3と同様の操作で(A)、(B)、(C)を含む水性分散体を得た。
酸変性ポリオレフィン樹脂(A)の水性分散体(I)として、エチレン-プロピレン-ブテン-無水マレイン酸共重合体PO4の水性分散体を用いた以外は、実施例3と同様の操作で(A)、(B)、(C)を含む水性分散体を得た。
ゴム成分(B)の水性分散体(II)として、スチレン-ブタジエン-エチルへキシルアクリレート共重合体ラテックス(旭化成ケミカルズ社製、L7430、固形分濃度50質量%、数平均粒子径0.15μm、以下、L7430と称す)を用いた以外は、実施例3と同様の操作で(A)、(B)、(C)およびを含む水性分散体を得た。
粘着付与成分(C)の水性分散体(III)として、ロジンエステル系粘着付与成分の水性分散体(荒川化学社製、タマノルE-650、固形分濃度50質量%、数平均粒子径0.2μm、軟化点160℃、以下、E650と称す)を用いた以外は、実施例3と同様の操作で(A)、(B)、(C)を含む水性分散体を得た。
実施例3と同様の操作によって得られた(A)、(B)、(C)を含む水性分散体に、添加剤として、前記アクリル樹脂の水性分散体製造で得たアクリル樹脂の水性分散体を、(A)、(B)、(C)を含む分散体中の(A)、(B)、(C)の固形分の総和100質量部に対して、固形分が10質量部になるように添加、攪拌して(A)、(B)、(C)およびアクリル樹脂を含む水性分散体を得た。
添加剤として、前記ポリウレタン樹脂の水性分散体製造で得たポリウレタン樹脂の水性分散体を用いた以外は、実施例21と同様の操作で(A)、(B)、(C)およびポリウレタン樹脂を含む水性分散体を得た。
添加剤として、水分散型ポリイソシアネート化合物(武田薬品工業社製、タケネートWD-730、イソシアネート基含有率18.6質量%、以下、WD730と称す)を用い、WD730を、(A)、(B)、(C)の固形分の総和100質量部に対して、固形分が3質量部になるようにした以外は、実施例21と同様の操作で(A)、(B)、(C)およびWD730を含む水性分散体を得た。
添加剤として、アジピン酸ジヒドラジド(大塚化学社製、以下、ADHと称す)を用いた以外は、実施例23と同様の操作で(A)、(B)、(C)およびADHを含む水性分散体を得た。
酸変性ポリオレフィン樹脂(A)の水性分散体(I)としてPO1の水性分散体を用い、粘着付与成分(C)の水性分散体(III)としてE200NTを用い、PO1の水性分散体の固形分100質量部に対してE200NTの固形分が50質量部になるように両者を混合した。得られた(A)、(C)の混合液の固形分濃度が30質量%になるように水を添加して(A)、(C)を含む水性分散体を得た。なおそれぞれの混合は攪拌しながら行った。
ゴム成分(B)の水性分散体(II)としてGFL280を用い、粘着付与成分(C)の水性分散体(III)としてE200NTを用い、GFL280の固形分100質量部に対してE200NTの固形分が50質量部になるように両者を混合した。得られた(B)、(C)の混合液の固形分濃度が30質量%になるように水を添加して(B)、(C)を含む水性分散体を得た。なおそれぞれの混合は攪拌しながら行った。
酸変性ポリオレフィン樹脂(A)の水性分散体(I)としてPO1の水性分散体を用い、ゴム成分(B)の水性分散体(II)としてGFL280を用い、PO1の水性分散体の固形分100質量部に対してGFL-280の固形分が100質量部になるように両者を混合した。得られた(A)、(B)の混合液の固形分濃度が30質量%になるように水を添加して(A)、(B)を含む水性分散体を得た。なおそれぞれの混合は攪拌しながら行った。
酸変性ポリオレフィン樹脂(A)、ゴム成分(B)、粘着付与成分(C)の混合量を表2に示す量とした以外は、実施例1と同様の操作で(A)、(B)、(C)を含む水性分散体を得た。
酸変性ポリオレフィン樹脂(A)の水性分散体(I)として、エチレン-メタクリル酸共重合体N1560の水性分散体を用いた以外は、実施例3と同様の操作で(A)、(B)、(C)を含む水性分散体を得た。
酸変性ポリオレフィン樹脂(A)の水性分散体(I)として、エチレン-アクリル酸共重合体5990の水性分散体を用いた以外は、実施例3と同様の操作で(A)、(B)、(C)を含む水性分散体を得た。
実施例3、16、17と、実施例14、15との比較から、酸変性ポリオレフィン樹脂(A)として、エチレン-アクリル酸エステル-無水マレイン酸共重合体を用いる方が、エチレン-メタクリル酸共重合体を用いるよりも、接着性の点で好ましいものであった。
実施例21~24において、添加剤として他の樹脂や架橋剤を添加すると、性能が向上することが確認された。
上記のように、実施例において、冷間屈曲に対して優れた強度保持性が確認された。この現象の詳細なメカニズムは不明であるが、接着層を構成するポリオレフィン樹脂(A)、ゴム成分(B)、粘着付与成分(C)のそれぞれが有する固有の粘弾性特性が、低温時において互いに干渉しあい、これらの混合物から得られる接着層において、屈曲に対してこの様な特性が発現されると考えられる。
また比較例2の水性分散体は、酸変性ポリオレフィン樹脂(A)を含有していないため接着性に劣るものであった。これはポリオレフィン樹脂基材の界面との接着性に劣ることが原因とみられる。また、得られる塗膜は室温でもベタつきがあり、滑り性に劣るものであった。さらには水性分散体をアルコールで希釈すると凝集が発生した。
比較例3、4、5の水性分散体は、ゴム成分(B)または粘着付与成分(C)が適正量含有されていないため、接着性に劣るものであった。
比較例6、7の水性分散体は、不飽和カルボン酸成分の含有量が本発明で規定する量を外れるポリオレフィン樹脂(A)を使用したため、各種性能に劣ることが確認された。また、ポリオレフィン樹脂(A)のメルトフローレート値が本発明の好ましい範囲を外れると、接着性がより劣ることが確認された。
Claims (13)
- 不飽和カルボン酸成分の含有量が0.1~10質量%である酸変性ポリオレフィン樹脂(A)、ゴム成分(B)、粘着付与成分(C)および水性媒体を含有し、酸変性ポリオレフィン樹脂(A)100質量部に対して、ゴム成分(B)の含有量が5~1900質量部であり、酸変性ポリオレフィン樹脂(A)とゴム成分(B)の総和100質量部に対して、粘着付与成分(C)の含有量が5~300質量部であることを特徴とする水性分散体。
- 酸変性ポリオレフィン樹脂(A)がエチレン-(メタ)アクリル酸エステル-(無水)マレイン酸共重合体であることを特徴とする請求項1に記載の水性分散体。
- 酸変性ポリオレフィン樹脂(A)のメルトフローレート値(ISO1133に準ずる190℃、21.2N荷重)が1~300g/10分であることを特徴とする請求項1または2に記載の水性分散体。
- ゴム成分(B)がクロロプレンゴムであることを特徴とする請求項1または2に記載の水性分散体。
- 粘着付与成分(C)がテルペン系樹脂であることを特徴とする請求項1または2に記載の水性分散体。
- 水性分散体中の分散粒子の数平均粒子径が0.5μm以下であることを特徴とする請求項1または2に記載の水性分散体。
- 得られる塗膜の23±2℃雰囲気下での表面の静摩擦係数(ISO8295に準ずる)が1.5以下であることを特徴とする請求項1または2に記載の水性分散体。
- 少なくとも基材の一部に、請求項1または2に記載の水性分散体より得られる塗膜が積層されてなる積層体。
- 塗膜の23±2℃雰囲気下での表面の静摩擦係数(ISO8295に準ずる)が1.5以下であることを特徴とする請求項8に記載の積層体。
- ポリオレフィン樹脂を含む基材とゴムを含む基材とが、請求項1または2に記載の水性分散体より得られる塗膜を介して接着されてなる積層体。
- 請求項1または2に記載の水性分散体からなる接着剤であって、履物の構成部材を被着体とすることを特徴とする履物用接着剤。
- 履物の構成部材が、皮革材料、織物、編物、ポリ塩化ビニル樹脂、ポリウレタン樹脂、ポリオレフィン樹脂及びゴムからなる群より選ばれる1種以上を含むことを特徴とする請求項11に記載の履物用接着剤。
- 請求項11に記載の履物用接着剤を用いて得られた履物。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/126,962 US9193892B2 (en) | 2011-06-23 | 2012-06-14 | Aqueous dispersion, and laminate, adhesive for footwear, and footwear made using same |
JP2013521540A JP5933543B2 (ja) | 2011-06-23 | 2012-06-14 | 水性分散体、ならびにそれを用いてなる積層体、履物用接着剤および履物 |
CN201280030168.6A CN103619944B (zh) | 2011-06-23 | 2012-06-14 | 水性分散体及使用其形成的层叠体、鞋用粘接剂及鞋 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-139966 | 2011-06-23 | ||
JP2011139966 | 2011-06-23 | ||
JP2011264340 | 2011-12-02 | ||
JP2011-264340 | 2011-12-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012176677A1 true WO2012176677A1 (ja) | 2012-12-27 |
Family
ID=47422517
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/065189 WO2012176677A1 (ja) | 2011-06-23 | 2012-06-14 | 水性分散体、ならびにそれを用いてなる積層体、履物用接着剤および履物 |
Country Status (5)
Country | Link |
---|---|
US (1) | US9193892B2 (ja) |
JP (1) | JP5933543B2 (ja) |
CN (1) | CN103619944B (ja) |
TW (1) | TWI527862B (ja) |
WO (1) | WO2012176677A1 (ja) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015086230A (ja) * | 2013-10-28 | 2015-05-07 | ユニチカ株式会社 | 金属板用接着剤 |
JP2015110727A (ja) * | 2013-11-01 | 2015-06-18 | 日本エイアンドエル株式会社 | 接着剤組成物 |
JP2016087877A (ja) * | 2014-10-31 | 2016-05-23 | 国立大学法人大阪大学 | シートの製造方法 |
JP2016216564A (ja) * | 2015-05-18 | 2016-12-22 | ミドリ安全株式会社 | エラストマー及びその製造方法 |
KR20170056621A (ko) * | 2014-09-17 | 2017-05-23 | 도요보 가부시키가이샤 | 변성 폴리프로필렌 수지를 함유하는 자기 유화형 에멀션 |
JP2019006955A (ja) * | 2017-06-28 | 2019-01-17 | 東ソー株式会社 | ポリクロロプレンゴムラテックス接着剤 |
WO2021161735A1 (ja) * | 2020-02-14 | 2021-08-19 | 東洋紡株式会社 | ポリオレフィン系接着剤組成物 |
US11685823B2 (en) | 2014-05-13 | 2023-06-27 | Dow Global Technologies Llc | Crosslinkable polymeric compositions with amine-functionalized interpolymers, methods for making the same, and articles made therefrom |
JP7439750B2 (ja) | 2018-04-23 | 2024-02-28 | 株式会社レゾナック | 接着剤組成物用ラテックス及び接着剤組成物 |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101340696B1 (ko) * | 2012-09-05 | 2013-12-12 | 삼성토탈 주식회사 | 폴리유산 수지 함유 폴리프로필렌계 수지 조성물 |
TW201514234A (zh) * | 2013-07-16 | 2015-04-16 | Skinprotect Corp Sdn Bhd | 彈性體薄膜形成組成物及製自彈性體薄膜之物件(三) |
TWI547243B (zh) * | 2014-03-20 | 2016-09-01 | 誠泰工業科技股份有限公司 | 鞋底構造接著製程方法 |
CN106573445A (zh) * | 2014-07-29 | 2017-04-19 | 惠普发展公司,有限责任合伙企业 | 在表面上的弹性体涂层 |
GB201504291D0 (en) * | 2015-03-13 | 2015-04-29 | Dupont Teijin Films Us Ltd | PV cells |
JP6563728B2 (ja) * | 2015-07-29 | 2019-08-21 | 株式会社ディスコ | レーザー加工方法 |
CN105505310A (zh) * | 2015-12-14 | 2016-04-20 | 桐乡市亿源鞋业有限公司 | 快速固化鞋胶 |
KR20200142224A (ko) * | 2019-06-12 | 2020-12-22 | 현대자동차주식회사 | 충격흡수용 범퍼 및 이의 제조방법 |
CN114072479B (zh) * | 2019-07-12 | 2024-01-05 | 陶氏环球技术有限责任公司 | 水性聚合物制剂 |
CN110484165B (zh) * | 2019-07-18 | 2021-09-24 | 南京利德东方橡塑科技有限公司 | 一种耐高、低温环保型氯丁橡胶胶粘剂及制备方法 |
EP3825375A1 (de) * | 2019-11-20 | 2021-05-26 | Covestro Deutschland AG | Nassverklebung von lagerstabilen 1k-sprühklebstoffen auf basis polychloropren |
CN113930001B (zh) * | 2021-10-26 | 2023-03-21 | 湖北祥源新材科技股份有限公司 | 具有热粘接性能的低气味聚乙烯发泡材料及其制备方法 |
CN115595107B (zh) * | 2022-10-14 | 2023-06-16 | 广东裕田霸力科技股份有限公司 | 免打磨eva处理剂及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001342446A (ja) * | 2000-05-30 | 2001-12-14 | Aron Ever-Grip Ltd | 接着剤組成物 |
JP2007217564A (ja) * | 2006-02-17 | 2007-08-30 | Arakawa Chem Ind Co Ltd | 粘着付与樹脂エマルジョンおよびその製造方法ならびに水系粘・接着剤組成物 |
JP2009235289A (ja) * | 2008-03-28 | 2009-10-15 | Unitika Ltd | 水性分散体および積層体 |
JP2011012196A (ja) * | 2009-07-03 | 2011-01-20 | Tosoh Corp | エマルション及びその製造法 |
JP2011052062A (ja) * | 2009-08-31 | 2011-03-17 | Tosoh Corp | 変性ポリオレフィンエマルション及びその製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5967048A (ja) * | 1982-10-12 | 1984-04-16 | 出光興産株式会社 | 積層体 |
JP3531749B2 (ja) | 1993-05-28 | 2004-05-31 | 電気化学工業株式会社 | ポリクロロプレンラテックス及びその組成物 |
JPH10212465A (ja) | 1997-01-29 | 1998-08-11 | Tosoh Corp | クロロプレンゴム接着剤組成物 |
JP2002051808A (ja) | 2000-08-10 | 2002-02-19 | Nooteepu Kogyo Kk | 履物及び履物の製造法 |
JP2003277715A (ja) | 2002-03-26 | 2003-10-02 | Dainippon Ink & Chem Inc | 靴用水性ポリウレタン接着剤 |
JP2004189964A (ja) | 2002-12-13 | 2004-07-08 | Denki Kagaku Kogyo Kk | 水系プライマー及び接着方法 |
US7964662B2 (en) * | 2006-04-27 | 2011-06-21 | Bostik, Inc. | Adhesive formulation for vacuum forming applications |
JP5183048B2 (ja) * | 2006-09-14 | 2013-04-17 | ユニチカ株式会社 | 水性接着剤およびそれを用いた積層体 |
-
2012
- 2012-06-14 JP JP2013521540A patent/JP5933543B2/ja active Active
- 2012-06-14 CN CN201280030168.6A patent/CN103619944B/zh active Active
- 2012-06-14 US US14/126,962 patent/US9193892B2/en not_active Expired - Fee Related
- 2012-06-14 WO PCT/JP2012/065189 patent/WO2012176677A1/ja active Application Filing
- 2012-06-21 TW TW101122170A patent/TWI527862B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001342446A (ja) * | 2000-05-30 | 2001-12-14 | Aron Ever-Grip Ltd | 接着剤組成物 |
JP2007217564A (ja) * | 2006-02-17 | 2007-08-30 | Arakawa Chem Ind Co Ltd | 粘着付与樹脂エマルジョンおよびその製造方法ならびに水系粘・接着剤組成物 |
JP2009235289A (ja) * | 2008-03-28 | 2009-10-15 | Unitika Ltd | 水性分散体および積層体 |
JP2011012196A (ja) * | 2009-07-03 | 2011-01-20 | Tosoh Corp | エマルション及びその製造法 |
JP2011052062A (ja) * | 2009-08-31 | 2011-03-17 | Tosoh Corp | 変性ポリオレフィンエマルション及びその製造方法 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015086230A (ja) * | 2013-10-28 | 2015-05-07 | ユニチカ株式会社 | 金属板用接着剤 |
JP2015110727A (ja) * | 2013-11-01 | 2015-06-18 | 日本エイアンドエル株式会社 | 接着剤組成物 |
US11685823B2 (en) | 2014-05-13 | 2023-06-27 | Dow Global Technologies Llc | Crosslinkable polymeric compositions with amine-functionalized interpolymers, methods for making the same, and articles made therefrom |
KR20170056621A (ko) * | 2014-09-17 | 2017-05-23 | 도요보 가부시키가이샤 | 변성 폴리프로필렌 수지를 함유하는 자기 유화형 에멀션 |
KR102270524B1 (ko) | 2014-09-17 | 2021-06-29 | 도요보 가부시키가이샤 | 변성 폴리프로필렌 수지를 함유하는 자기 유화형 에멀션 |
JP2016087877A (ja) * | 2014-10-31 | 2016-05-23 | 国立大学法人大阪大学 | シートの製造方法 |
JP2016216564A (ja) * | 2015-05-18 | 2016-12-22 | ミドリ安全株式会社 | エラストマー及びその製造方法 |
JP2019006955A (ja) * | 2017-06-28 | 2019-01-17 | 東ソー株式会社 | ポリクロロプレンゴムラテックス接着剤 |
JP7439750B2 (ja) | 2018-04-23 | 2024-02-28 | 株式会社レゾナック | 接着剤組成物用ラテックス及び接着剤組成物 |
WO2021161735A1 (ja) * | 2020-02-14 | 2021-08-19 | 東洋紡株式会社 | ポリオレフィン系接着剤組成物 |
JPWO2021161735A1 (ja) * | 2020-02-14 | 2021-08-19 |
Also Published As
Publication number | Publication date |
---|---|
US20140137435A1 (en) | 2014-05-22 |
CN103619944B (zh) | 2016-06-15 |
TW201305296A (zh) | 2013-02-01 |
JPWO2012176677A1 (ja) | 2015-02-23 |
TWI527862B (zh) | 2016-04-01 |
JP5933543B2 (ja) | 2016-06-08 |
CN103619944A (zh) | 2014-03-05 |
US9193892B2 (en) | 2015-11-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5933543B2 (ja) | 水性分散体、ならびにそれを用いてなる積層体、履物用接着剤および履物 | |
JP4717463B2 (ja) | 水性分散体および積層体 | |
JP2006199961A (ja) | 熱可塑性基体のための水性フロック接着剤 | |
CN108473820B (zh) | 单组分层压胶粘剂用于复合膜层压的用途 | |
WO2007074674A1 (ja) | 接着性組成物 | |
JPWO2018043586A1 (ja) | クロロプレンゴムラテックス接着剤組成物 | |
JP2007204671A (ja) | 水性分散体および積層体 | |
JP2019506467A (ja) | 複合フィルムの製造のための乳化剤含分が低い水性ポリマー分散液 | |
JP5017916B2 (ja) | 樹脂水性分散体および積層体 | |
JP2017222804A (ja) | ポリクロロプレンラテックス接着剤組成物 | |
JP5184216B2 (ja) | 水性分散体および積層体 | |
JP5183048B2 (ja) | 水性接着剤およびそれを用いた積層体 | |
JP2011057804A (ja) | 植毛用水性接着剤 | |
JP2020100772A (ja) | 水系コート剤、塗膜、および積層体 | |
JP5808936B2 (ja) | 積層体及びその製造方法 | |
TW201335301A (zh) | 水性接著劑 | |
WO2015093517A1 (ja) | 水性エマルション | |
JP2012176555A (ja) | 積層体の製造方法 | |
JP2002003797A (ja) | エラストマー材の接着方法及び接着構造体 | |
JP2014125586A (ja) | 水性接着剤 | |
JP7439750B2 (ja) | 接着剤組成物用ラテックス及び接着剤組成物 | |
JP2021187084A (ja) | 積層体、およびその製造方法 | |
WO2022138131A1 (ja) | 粘着剤組成物、共重合体分散液、セット、粘着テープ、及び接着方法 | |
WO2022138132A1 (ja) | 粘着剤組成物、共重合体分散液、セット、粘着テープ、及び接着方法 | |
TW202300616A (zh) | 聚烯烴系黏接劑組成物及疊層體 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12803270 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013521540 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14126962 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12803270 Country of ref document: EP Kind code of ref document: A1 |