WO2011162237A1 - 自己架橋型ポリヒドロキシポリウレタン樹脂、該樹脂を含む樹脂材料、該樹脂の製造方法、該樹脂を用いてなる擬革、表皮材及びウェザーストリップ用材料 - Google Patents
自己架橋型ポリヒドロキシポリウレタン樹脂、該樹脂を含む樹脂材料、該樹脂の製造方法、該樹脂を用いてなる擬革、表皮材及びウェザーストリップ用材料 Download PDFInfo
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- WO2011162237A1 WO2011162237A1 PCT/JP2011/064132 JP2011064132W WO2011162237A1 WO 2011162237 A1 WO2011162237 A1 WO 2011162237A1 JP 2011064132 W JP2011064132 W JP 2011064132W WO 2011162237 A1 WO2011162237 A1 WO 2011162237A1
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- resin
- self
- crosslinking
- polyhydroxypolyurethane
- compound
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- 0 CC(C)(C1CCC(*COC)CC1)C(CC1)CCC1*1OC1 Chemical compound CC(C)(C1CCC(*COC)CC1)C(CC1)CCC1*1OC1 0.000 description 3
- GTGQOOAAZHJUEU-UEJVZZJDSA-N CC[C@H](C)C1(CC1)C1NC1C Chemical compound CC[C@H](C)C1(CC1)C1NC1C GTGQOOAAZHJUEU-UEJVZZJDSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8029—Masked aromatic polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8074—Lactams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8077—Oximes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
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- 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]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
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- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
Definitions
- the present invention relates to a novel self-crosslinking polyhydroxypolyurethane resin, a resin material containing the resin, and a method for producing the same. More specifically, when used in forming materials such as films and molding materials, various coating materials, various paints, various binders, etc., it can be a product with excellent wear resistance, chemical resistance, and heat resistance, and it can be used as a manufacturing raw material. Since carbon dioxide is used and carbon dioxide can be fixed in the resin, the present invention relates to a technique for providing a self-crosslinking polyhydroxy polyurethane resin that is also useful from the viewpoint of preventing destruction of the global environment.
- the present invention relates to a pseudo-leather using a resin composition containing the above self-crosslinking polyhydroxypolyurethane resin as a main component, more specifically, excellent scratch resistance, abrasion resistance, chemical resistance, and heat resistance. Moreover, since the main component resin is carbon dioxide fixed in the structure, the present invention relates to artificial leather useful from the viewpoint of global environmental conservation.
- the present invention relates to a skin material made of a thermoplastic polyolefin resin used for automobile interior materials and home appliance parts. More specifically, by using the above-mentioned self-crosslinking polyhydroxy polyurethane resin for forming the top coat layer, the top coat layer is excellent in scratch resistance, abrasion resistance, chemical resistance, and heat resistance. It is related with the skin material made from thermoplastic polyolefin resin which can make a uniform matte film.
- the present invention provides a surface treatment layer for a band-shaped sealing part made of a polymer elastic material for preventing wind and rain from entering through a gap between a body and a part such as a door or window of an automobile or a building.
- the present invention relates to a material for weatherstrip useful for forming. More specifically, a surface treatment layer is formed using a material using the above-mentioned self-crosslinking type polyhydroxypolyurethane resin in a sliding contact portion that is in sliding contact with other parts of a weather strip made of a polymer elastic material.
- the surface treatment layer can be made particularly excellent in lubricity, wear resistance, heat resistance, and weather resistance, and is also useful from the viewpoint of environmental conservation.
- Polyhydroxy polyurethane resin using carbon dioxide as a raw material for production has been known for a long time (see, for example, Patent Documents 1 and 2), but its application development has not progressed. This is because the polyhydroxypolyurethane resin is clearly inferior in characteristics as compared with the polyurethane-based resin compared with the same type of polymer compound.
- (imitation leather) Conventionally, artificial leather is used for bags, bags, shoes, furniture, clothing, vehicle interior materials, electrical appliances, etc., and polyurethane-based resins are widely used as the resin for artificial leather.
- the “pseudo-leather” is a generic name for leather-like products manufactured to resemble natural leather, and is generally roughly classified into artificial leather, synthetic leather, and vinyl chloride leather.
- Artificial leather has a structure that most closely resembles natural leather among artificial leather, but uses non-woven fabric for the base fabric.
- a general method for producing artificial leather there are the following methods. First, a non-woven fabric is impregnated with a dimethylformamide (DMF) solution of a polyurethane-based resin, and then solidified and dried in a porous state by wet film formation (solidification in water). After that, there are a method in which a polyurethane resin is further coated or laminated on the surface to make it smooth, and a method in which the surface is ground and brushed to make it suede.
- DMF dimethylformamide
- Synthetic leather uses a fabric such as a woven fabric or a brushed fabric for the base fabric, but is generally divided into dry synthetic leather and wet synthetic leather. Furthermore, as a method for producing dry synthetic leather, a polyurethane resin is directly applied to the base fabric and dried, and after applying the polyurethane resin on the release paper, it is dried and filmed, and then adhered to the base fabric with an adhesive. There is a way to match. Further, the wet synthetic leather can be produced by impregnating or coating the base fabric with the DMF solution of the polyurethane resin described above, and then solidifying and drying in water to form a porous layer. Furthermore, by applying a polyurethane-based resin or laminating a layer on each surface obtained by the dry or wet methods as described above to make it smooth, or by raising the surface by grinding the surface There is a method of suede tone.
- thermoplastic polyolefin resins such as polypropylene resin (abbreviated as PP resin), ABS resin, AS resin, polyolefin-based thermoplastic elastomer (abbreviated as TPO resin), and the like are used as the material for forming the member. Yes.
- thermoplastic polyolefin resins have the problem that their surface adhesion, scratch resistance, abrasion resistance, and chemical resistance are inferior to those of vinyl chloride resins used in the past, and these problems have been improved. In order to do so, it is necessary to impart functionality to the surface. In addition, in order to realize a design that gives a high-class feeling, or in consideration of anti-glare to the driver for automobile interior materials, various coatings are applied to the thermoplastic polyolefin substrate. It has been broken.
- a method using a chlorinated polypropylene resin having good adhesion to a polyolefin-based resin substrate such as PP resin or TPO resin has been proposed as a paint used for these coatings.
- a paint in which a chlorinated polypropylene-modified acrylic resin is used as a binder resin and a matting agent such as an inorganic extender pigment (silica, talc) or acrylic resin particles is used, or chlorinated polypropylene is used.
- This is a method of imparting functionality to the surface of a polyolefin resin substrate by applying a polyester primer and applying a polyester resin or polyurethane resin thereon.
- Weather strip material Conventionally, materials for forming weather strips such as glass runs, door weather strips, body side weather strips, inside seals, and outside seals for automobiles and buildings include chloroprene rubber, styrene-butadiene rubber, nitrile rubber, EPDM rubber, etc. A polymer elastic material is used. And in order to give these surfaces performances such as lubricity, abrasion resistance, mold release, heat resistance, water resistance, and weather resistance, a surface treatment layer may be formed by a method such as coating or impregnation. Has been done.
- thermosetting polyurethane resin added with silicone oil see Patent Document 9
- thermosetting polyurethane resin containing an organopolysiloxane see Patent Document 10
- paints such as those composed of urethane prepolymer and silicone oil, hydrophobic silica, and polyisocyanate (see Patent Document 11) have been proposed.
- the polyhydroxy polyurethane resin has been reviewed again.
- carbon dioxide the raw material for this resin
- plastics that use carbon dioxide as a raw material are effective in solving problems such as global warming and resource depletion. It can be a means.
- JP 2009-144313 A JP 2007-270373 A JP 2005-154580 A
- the polyhydroxy polyurethane resin is clearly inferior in characteristics as compared with the polyurethane resin compared with the same kind of high molecular compound, and its application development is not progressing. .
- polyhydroxy polyurethane resin in order to make polyhydroxy polyurethane resin usable for industrial use, for example, it is possible to use it in the same manner as the same type of petrochemical plastics, as well as improving its performance and adding new added value.
- resins with improved performance essential for industrial materials such as further heat resistance, chemical resistance, and wear resistance.
- the first object of the present invention is to use a polyhydroxy polyurethane resin, which is a useful material considered to contribute to solving problems such as global warming and resource depletion, but whose application development has not progressed, for industrial use. It is to provide a technology that can be used as a material. More specifically, a self-crosslinked polyhydroxy polyurethane in which the product formed by the resin is an environmentally-friendly product and is sufficiently satisfactory in performance such as heat resistance, chemical resistance, and wear resistance. The object is to provide a resin.
- the second object of the present invention is to use a newly developed self-crosslinked polyhydroxypolyurethane resin in which carbon dioxide is incorporated and fixed in the resin, so that the surface is not inferior to the conventional artificial leather. It is intended to provide artificial leather useful as an environmentally friendly product that is excellent in scratch resistance, abrasion resistance, chemical resistance, and heat resistance, and also from the viewpoint of global environmental conservation.
- the third object of the present invention is to use a newly developed self-crosslinking polyhydroxypolyurethane resin, and its surface is excellent in scratch resistance, abrasion resistance, chemical resistance and heat resistance, More preferably, the surface is made of a thermoplastic polyolefin resin that is excellent in uniform matting effect and can be used for materials that incorporate carbon dioxide, and can contribute to the reduction of greenhouse gases, and can be an environmentally friendly product. Is to provide materials.
- the surface material made of thermoplastic polyolefin resin means that a top coat layer is formed directly or via a primer layer for the purpose of imparting surface functionality to the surface of a sheet substrate made of thermoplastic polyolefin resin. Means something.
- the fourth object of the present invention is to use a newly developed self-crosslinking polyhydroxypolyurethane resin to form a sliding contact portion of a polymeric elastic material constituting a weather strip in sliding contact with other parts.
- the material for forming the surface treatment layer is a material that also contributes to environmental conservation
- the formed surface treatment layer is a useful weather material that has excellent lubricity, wear resistance, heat resistance, and weather resistance. It is to provide strip material.
- the present invention provides a self-crosslinking polyhydroxypolyurethane resin having an isocyanate group masked in its structure, which is derived from a reaction between a 5-membered cyclic carbonate compound and an amine compound.
- the more preferable form of the resin includes the following.
- the masked isocyanate group is a reaction product of an organic polyisocyanate group and a masking agent, and the masked portion is dissociated by heat treatment to form an isocyanate group, which reacts with a hydroxyl group in the structure.
- Self-crosslinking polyhydroxypolyurethane resin as described above, which is self-crosslinking.
- the present invention provides a method for producing the self-crosslinking polyhydroxypolyurethane resin as another embodiment, using a modifier having at least one free isocyanate group and a masked isocyanate group, A polyisocyanate having a masked isocyanate group in its structure by reacting a free isocyanate group of the modifier with a hydroxyl group in a polyhydroxypolyurethane resin derived from a reaction between a 5-membered cyclic carbonate compound and an amine compound.
- a method for producing a self-crosslinking polyhydroxypolyurethane resin characterized by obtaining a hydroxypolyurethane resin.
- the 5-membered cyclic carbonate compound is a reaction product of an epoxy compound and carbon dioxide, and 1 to 25% by mass of carbon dioxide in a polyhydroxy polyurethane resin derived from the reaction of the compound and an amine compound.
- the present invention provides a resin material obtained by mixing the self-crosslinking polyhydroxypolyurethane resin with another binder resin.
- the present invention is mainly composed of a self-crosslinking polyhydroxy polyurethane resin having an isocyanate group masked in its structure, which is derived from a reaction between a 5-membered cyclic carbonate compound and an amine compound.
- the artificial leather characterized by filling or laminating a resin composition with a base fabric.
- the artificial leather includes the following.
- the 5-membered cyclic carbonate compound is a reaction product of an epoxy compound and carbon dioxide, and carbon dioxide is contained in the range of 1 to 25% by mass in the structure of the self-crosslinking polyhydroxy polyurethane resin.
- the masked isocyanate group is a reaction product of an organic polyisocyanate group and a masking agent, and the masked portion is dissociated by heat treatment to form an isocyanate group.
- the artificial leather as described above which reacts with a hydroxyl group in the structure to self-crosslink.
- the artificial leather as described above, wherein the resin composition further contains another resin.
- the present invention includes, as another embodiment, a thermoplastic polyolefin resin sheet and a topcoat layer formed on the sheet directly or via a primer layer, and the topcoat layer Provided with a thermoplastic polyolefin resin skin material characterized in that it is formed of a resin composition comprising as a main component a self-crosslinking polyhydroxy polyurethane resin containing an isocyanate group masked in the molecule To do.
- the masked isocyanate group is a reaction product of an organic polyisocyanate group and a masking agent.
- the masked portion is dissociated by heat treatment to form an isocyanate group, and a hydroxyl group in the structure of the polyhydroxy polyurethane resin.
- a skin material that reacts with and self-crosslinks. A skin material, wherein the self-crosslinking polyhydroxypolyurethane resin is obtained by modifying a polyhydroxypolyurethane resin derived from a reaction between a 5-membered cyclic carbonate compound and an amine compound with a modifier.
- a skin material obtained by reacting an epoxy compound and carbon dioxide with the 5-membered cyclic carbonate compound.
- the resin composition forming the top coat layer is one or a combination of two or more selected from organic fine powders and inorganic fine powders as a matting agent with respect to 100 parts by mass of the self-crosslinking polyhydroxy polyurethane resin.
- a skin material comprising 1 to 150 parts by mass of a material comprising A skin material, wherein the resin composition forming the top coat layer further comprises a binder resin other than the self-crosslinking polyhydroxy polyurethane resin.
- the present invention provides, as another embodiment, a weather strip material for coating and / or impregnating a polymer elastic body material to form a surface treatment layer in a sliding contact portion in sliding contact with another component.
- a weatherstrip material characterized by being a resin composition comprising
- the weather strip material include the following.
- the masked isocyanate group is a reaction product of an organic polyisocyanate group and a masking agent.
- the masked portion is dissociated by heat treatment to form an isocyanate group, which reacts with a hydroxyl group in the structure.
- Weather strip material that self-crosslinks A weatherstrip material wherein the self-crosslinking polyhydroxypolyurethane resin is obtained by modifying a polyhydroxypolyurethane resin derived from a reaction between a 5-membered cyclic carbonate compound and an amine compound with a modifier.
- the five-membered cyclic carbonate compound is obtained by reacting an epoxy compound with carbon dioxide; the self-crosslinking polyhydroxy polyurethane resin contains carbon dioxide as a raw material, and 1 carbon dioxide is contained in the resin.
- Weather strip material containing -25% by mass. 1 to 100 parts by mass of diorganopolysiloxane having an average polymerization degree of 5,000 to 10,000 and / or silicone oil having a kinematic viscosity of 100 to 10,000 CS with respect to 100 parts by mass of the self-crosslinking polyhydroxypolyurethane resin.
- a material for weatherstrip which is a resin composition formulated by blending at a ratio of An additive composed of one or a combination of two or more selected from organic fine powder and inorganic fine powder is blended at a ratio of 1 to 150 parts by weight with respect to 100 parts by weight of the self-crosslinking polyhydroxypolyurethane resin.
- a weatherstrip material which is a resin composition.
- a resin composition comprising a binder resin other than the self-crosslinking type polyhydroxy polyurethane resin.
- a polyhydroxypolyurethane resin which is a useful material that is considered to contribute to solving global warming, resource depletion, and the like, but whose application development has not progressed, is made a material that can be effectively used for industrial use.
- a self-crosslinking polyhydroxypolyurethane resin is provided. More specifically, while the product formed from the resin is an environmentally friendly product that incorporates carbon dioxide and can contribute to the reduction of greenhouse gases, it also has performances such as heat resistance, chemical resistance, and wear resistance. A self-crosslinking polyhydroxy polyurethane resin is provided that is sufficiently satisfactory.
- the resin provided above it is comparable to the conventional artificial leather, has excellent surface scratch resistance, wear resistance, chemical resistance, heat resistance, From the viewpoint of global environmental conservation, which can contribute to the reduction of carbon dioxide, which is a global problem as a global warming gas, by using a material in which carbon is incorporated and fixed in resin as a material for forming artificial leather.
- An artificial leather that is an excellent environmentally friendly product is provided.
- the surface thereof has scratch resistance, abrasion resistance, chemical resistance. Environment and heat resistance, more preferably excellent uniform matting effect, and at the same time, by enabling the use of materials incorporating carbon dioxide, it can contribute to the reduction of greenhouse gases
- a skin material made of thermoplastic polyolefin resin, which is a corresponding product, is provided.
- a material for forming a surface treatment layer in a sliding contact portion that is in sliding contact with other parts of a polymer elastic material that is a base material for a weather strip of an automobile or a building is provided above.
- the formed surface treatment layer is excellent in lubricity, wear resistance, heat resistance and weather resistance, and a useful material contributing to environmental conservation is provided.
- the material includes a self-crosslinking polyhydroxypolyurethane resin provided above, a diorganopolysiloxane having an average degree of polymerization of 5,000 to 10,000, and / or a kinematic viscosity of 100 to 10,000 CS. Because of the composition containing the above silicone oil, the surface treatment layer formed has excellent basic characteristics, and since carbon dioxide can be used as a raw material, it is also a useful material from the viewpoint of global environmental conservation. And an environmentally friendly product using the material.
- the self-crosslinking type polyhydroxy polyurethane resin of the present invention is characterized by having a masked isocyanate group in the structure derived from the reaction of a 5-membered cyclic carbonate compound and an amine compound.
- the self-crosslinking type polyhydroxy polyurethane resin uses a modifier having at least one free isocyanate group and a masked isocyanate group, and the free isocyanate group of the modifier is converted into a 5-membered cyclic carbonate compound and an amine. It can be obtained by reacting with a hydroxyl group in a polyhydroxy polyurethane resin derived from a reaction with a compound. And since this 5-membered cyclic carbonate compound is obtained by reacting an epoxy compound and carbon dioxide, it becomes a material which contributes to environmental conservation. Below, each component is demonstrated.
- the modifier used in the present invention is a reaction product of the organic polyisocyanate compound and the masking agent described above, and the following can be used as the masking agent.
- Alcohol-based, phenol-based, active methylene-based, acid amide-based, imidazole-based, urea-based, oxime-based, and pyridine-based compounds may be used alone or in combination.
- Specific examples of the masking agent include the following.
- Examples of alcohols include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, and cyclohexanol.
- Examples of the phenol type include phenol, cresol, ethylphenol, and nonylphenol.
- Examples of the active methylene group include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone and the like.
- Examples of acid amides include acetanilide, acetic acid amide, ⁇ -caprolactam, ⁇ -butyrolactam, and the like.
- Examples of the imidazole series include imidazole and 2-methylimidazole.
- Examples of the urea system include urea, thiourea, and ethylene urea.
- Examples of oximes include formamide oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime.
- Examples of the pyridine series include 2-hydroxypyridine and 2-hydroxyquinoline.
- a modifier having at least one free isocyanate group and the other having a masked isocyanate group used in the present invention by reacting the organic polyisocyanate compound listed above with the masking agent listed above.
- the synthesis method is not particularly limited, but the masking agent and the organic polyisocyanate compound are functional groups in which one or more isocyanate groups are excessive in one molecule, in the presence or absence of an organic solvent and a catalyst. It can be easily obtained by reacting at a temperature of 0 to 150 ° C., preferably 20 to 80 ° C., for 30 minutes to 3 hours.
- the self-crosslinking polyhydroxypolyurethane resin of the present invention is obtained by modifying a polyhydroxypolyurethane resin with a specific modifier as described above.
- the polyhydroxypolyurethane resin used at that time is obtained by a reaction between a 5-membered cyclic carbonate compound and an amine compound. Each component used in the reaction will be described below.
- the 5-membered cyclic carbonate compound used in the present invention can be produced by reacting an epoxy compound and carbon dioxide as shown by the following [Formula-A]. More particularly, the epoxy compound is oxidized in the presence or absence of an organic solvent and in the presence of a catalyst at a temperature of 40 ° C. to 150 ° C. under atmospheric pressure or slightly elevated pressure for 10 to 20 hours. Obtained by reacting with carbon.
- Examples of the epoxy compound that can be used above include the following compounds.
- the epoxy compounds listed above are preferable compounds that can be used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also other compounds that are currently commercially available and can be easily obtained from the market can be used.
- Examples of the catalyst used in the reaction between the epoxy compound as described above and carbon dioxide include a base catalyst and a Lewis acid catalyst.
- Base catalysts include tertiary amines such as triethylamine and tributylamine, cyclic amines such as diazabicycloundecene, diazabicyclooctane and pyridine, alkalis such as lithium chloride, lithium bromide, lithium fluoride and sodium chloride.
- Metal salts alkaline earth metal salts such as calcium chloride, quaternary ammonium salts such as tetrabutylammonium chloride, tetraethylammonium bromide, benzyltrimethylammonium chloride, carbonates such as potassium carbonate and sodium carbonate, zinc acetate, lead acetate, acetic acid Examples thereof include metal acetates such as copper and iron acetate, metal oxides such as calcium oxide, magnesium oxide and zinc oxide, and phosphonium salts such as tetrabutylphosphonium chloride.
- Lewis acid catalyst examples include tin compounds such as tetrabutyltin, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin octoate.
- the amount of the catalyst may be about 0.1 to 100 parts by weight, preferably 0.3 to 20 parts by weight, per 50 parts by weight of the epoxy compound. If the amount used is less than 0.1 parts by mass, the effect as a catalyst is small, and if it exceeds 100 parts by mass, various performances of the final resin may be deteriorated. However, in the case where the residual catalyst causes a serious performance deterioration, it may be configured to be removed by washing with pure water.
- organic solvent examples include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, and tetrahydrofuran.
- organic solvents and other poor solvents such as methyl ethyl ketone, xylene, toluene, tetrahydrofuran, diethyl ether, and cyclohexanone may be used in a mixed system.
- the polyhydroxypolyurethane resin used in the present invention comprises a 5-membered cyclic carbonate compound obtained as described above and an amine compound at 20 ° C. in the presence of an organic solvent. It can be obtained by reacting at a temperature of ⁇ 150 ° C.
- a diamine is preferable and what was conventionally used for manufacture of a polyurethane resin can be used, and it is not specifically limited.
- aliphatic diamines such as methylenediamine, ethylenediamine, trimethylenediamine, 1,3-diaminopropane, hexamethylenediamine, octamethylenediamine; phenylenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4 , 4'-methylenebis (phenylamine), 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, metaxylylenediamine, paraxylylenediamine, and other aromatic diamines; 1,4-cyclohexanediamine, 4 , 4'-diaminocyclohexylmethane, 1,4
- the amine compounds listed above are preferred compounds in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.
- the polyhydroxy polyurethane resin used in the present invention preferably has a number average molecular weight (standard polystyrene conversion value measured by GPC) of about 2,000 to 100,000, more preferably 5,000 to 70. About 1,000.
- the polyhydroxy polyurethane resin used in the present invention preferably has a hydroxyl value of 20 to 300 mgKOH / g.
- the hydroxyl group content is less than the above range, the effect of reducing carbon dioxide is insufficient.
- the hydroxyl group content exceeds the above range, various physical properties as a polymer compound are insufficient.
- the self-crosslinking type polyhydroxypolyurethane resin of the present invention can be obtained by reacting a modifier and a polyhydroxypolyurethane resin, each obtained as described above. Specifically, it can be synthesized by reacting a hydroxyl group in the polyhydroxy polyurethane resin with at least one free isocyanate group in the modifier.
- the modification rate of the self-crosslinking polyhydroxypolyurethane resin of the present invention with a modifier is preferably 2 to 60%. If the modification rate is less than 2%, sufficient crosslinking does not occur, so that the heat resistance and chemical resistance of the product may be insufficient. On the other hand, if the modification rate exceeds 60%, the possibility that the dissociated isocyanate group remains without reacting is not preferable.
- the reaction between the modifier and the polyhydroxypolyurethane resin is facilitated by reacting at a temperature of 0 to 150 ° C., preferably 20 to 80 ° C. for 30 minutes to 3 hours in the presence or absence of an organic solvent and a catalyst. Can be done. However, attention should be paid to the fact that the reaction is performed at a temperature lower than the dissociation temperature of the masking agent during the reaction, and it is necessary that the synthesized polyhydroxy polyurethane resin has a masked isocyanate group in its structure.
- the self-crosslinking polyhydroxy polyurethane resin of the present invention that can be obtained as described above can be used as it is as a film / molding material, various coating materials, various paints, various binders, etc. A product excellent in chemical resistance and heat resistance can be obtained.
- various conventionally known resins can be mixed as a binder resin with a self-crosslinking polyhydroxypolyurethane resin and used as a resin material.
- a resin that can chemically react with an isocyanate group generated by dissociation of a masking portion in the structure of the self-crosslinking polyhydroxypolyurethane resin is preferable.
- a resin having no reactivity as described above can be used as a resin material in combination with the self-crosslinking polyhydroxy polyurethane resin of the present invention as appropriate according to the purpose.
- binder resin that can be used in combination with the self-crosslinking type polyhydroxy polyurethane resin of the present invention
- various conventionally used resins can be used and are not particularly limited.
- acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl butyral resin, epoxy resin, polyamide resin Etc. can be used.
- resins obtained by modifying various resins with silicone or fluorine can be used.
- the amount used varies depending on the product to be produced and the purpose of use, but is preferably 5 to 90 parts by weight, more preferably 100 parts by weight of the self-crosslinking polyhydroxy polyurethane resin of the present invention. 60 parts by mass or less may be added.
- the more the proportion of use of the self-crosslinking polyhydroxypolyurethane resin of the present invention the more preferable the environmentally friendly product.
- the masked portion is dissociated by heat treatment to generate an isocyanate group. And since the generated isocyanate group reacts with the hydroxyl group in the polyhydroxypolyurethane resin to form a crosslinked resin by self-crosslinking, it has excellent heat resistance, chemical resistance, Abrasion can be obtained.
- the polyhydroxypolyurethane resin used when synthesizing the self-crosslinking polyhydroxypolyurethane resin of the present invention is synthesized using a 5-membered cyclic carbonate compound. Since the compound is obtained by reacting an epoxy compound with carbon dioxide, it can be fixed by incorporating carbon dioxide into the resin. This means that according to the present invention, it is possible to provide an environmental protection material that is useful from the viewpoint of reducing greenhouse gases and that cannot be achieved by conventional products.
- the self-crosslinking polyhydroxypolyurethane resin of the present invention is very useful as various molding materials, synthetic leather and artificial leather materials, fiber coating materials, surface treatment materials, heat-sensitive recording materials, releasable materials, paints, binders for printing inks, etc. It is.
- artificial leather synthetic leather and artificial leather material
- a skin material made of thermoplastic polyolefin resin and a material for weather strip will be described.
- the artificial leather of the present invention mainly comprises the self-crosslinking polyhydroxy polyurethane resin of the present invention having an isocyanate group masked in its structure, which is derived from the reaction of the above-mentioned 5-membered cyclic carbonate compound and an amine compound.
- a resin composition as a component (hereinafter referred to as a resin composition for artificial leather) is filled or laminated on a base fabric.
- the masked isocyanate group of the resin is a reaction product of an organic polyisocyanate group and a masking agent, and the masked portion is dissociated by heat treatment to generate an isocyanate group, and a self-crosslinking polyhydroxy polyurethane resin It reacts with a hydroxyl group in the structure and self-crosslinks. For this reason, by using the resin, it is possible to obtain artificial leather having excellent surface scratch resistance, abrasion resistance, chemical resistance, and heat resistance.
- the self-crosslinking polyhydroxypolyurethane resin particularly preferred from the viewpoint of global environmental protection used in the present invention is a 5-membered cyclic carbonate compound, which is a reaction product of an epoxy compound and carbon dioxide, and has a structure containing carbon dioxide. It contains carbon in the range of 1 to 25% by mass.
- the resin composition for artificial leather may further contain other resins.
- the modification rate of the resin with a modifier is preferably 2 to 60%.
- performances such as wear resistance, chemical resistance and heat resistance after heat treatment can be controlled to some extent.
- the modification rate is less than 2%, sufficient crosslinking does not occur, which makes it possible to produce artificial leather. If used, heat resistance and chemical resistance may be insufficient, which is not preferable.
- the modification rate exceeds 60%, the texture of the artificial leather is impaired by overcrosslinking, and the possibility that the dissociated isocyanate group remains without reacting is not preferable.
- the resin composition for artificial leather is used in the form of an organic solvent solution or an aqueous dispersion in the production of artificial leather.
- the following organic solvent is preferably used. Examples thereof include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone and the like.
- the resin concentration in 100% by mass of the organic solvent solution is preferably 10 to 60% by mass. If the resin concentration is less than 10% by mass, the film formability in wet film formation is inferior, and the thickness of the film is insufficient. On the other hand, if the resin concentration exceeds 60% by mass, the formation of the porous layer in the wet film formation may be incomplete and the organic solvent may remain in the film. Is also not preferable.
- the resin composition for artificial leather is used in the form of an aqueous dispersion, it is preferably used as follows. That is, a carboxyl group is introduced into the resin by semi-esterifying or semi-amidating a hydroxyl group or NH group in the self-crosslinking polyhydroxy polyurethane resin with an acid anhydride. Thereafter, the carboxyl group is preferably neutralized with ammonia, an organic amine compound, an inorganic base or the like to form a carboxylate and used as a self-emulsifying aqueous dispersion.
- the acid anhydride used here include phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, and the like.
- the organic amine compound examples include monoethanolamine, diethanolamine, triethanolamine, diethylethanolamine, aminoethylethanolamine and the like.
- the resin composition for artificial leather may be an aqueous dispersion emulsified in water with a surfactant according to a conventional method.
- various other resins known in the art are used for the above-mentioned resin composition for artificial leather in order to adjust workability such as impregnation, coating and coating, and the texture and performance of the obtained artificial leather. Can be used in combination.
- Other resins used for mixing are preferably those in which the masked isocyanate groups in the self-crosslinking polyhydroxypolyurethane resin can chemically react with the isocyanate groups generated by dissociation by heating or the like.
- the present invention is not limited to this, and resins having no reactivity can also be used in the present invention.
- polyurethane conventionally used as a material for forming artificial leather is used.
- System resins are preferred, but not particularly limited.
- acrylic resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, phenoxy resin, vinyl chloride resin, vinyl chloride-vinyl acetate resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl Butyral resins, epoxy resins, polyamide resins and the like can also be used.
- the amount used is 5 to 90 parts by mass with respect to 100 parts by mass of the polyhydroxy polyurethane resin of the present invention.
- the more the proportion of the self-crosslinking polyhydroxypolyurethane resin of the present invention is used the more the obtained artificial leather becomes a more environmentally friendly product.
- additives such as antioxidants, ultraviolet absorbers, hydrolysis inhibitors, pigments, dyes, flame retardants and fillers may be blended in the resin composition for artificial leather. .
- the artificial leather of the present invention is characterized in that the base fabric is filled or laminated with the resin composition for artificial leather, the main component of which is the self-crosslinking polyhydroxy polyurethane resin of the present invention described above.
- the method for producing the artificial leather of the present invention is not limited at all within the scope of the present invention, and known artificial leather and synthetic leather production methods can be used.
- the artificial leather of the present invention is provided with a vinyl chloride resin layer containing a plasticizer on a base fabric, and this is used as a base sheet, and the self-crosslinking type polymer characterizing the present invention is formed on the base sheet. What formed the layer which consists of a resin composition for pseudo leathers which has a hydroxy polyurethane resin as a main component is also contained.
- any base fabric (base material sheet) conventionally used for manufacturing artificial leather can be used and is not particularly limited.
- the masking portion of the isocyanate group masked by heat treatment is dissociated to generate an isocyanate group.
- generated isocyanate group and the hydroxyl group in polyhydroxy polyurethane resin react and self-crosslink and produce
- excellent adhesion and flexibility of the resin to the base sheet, and excellent performance of imparting an antistatic effect to the formed resin layer can be obtained, and the performance of the artificial leather can be improved.
- the formed artificial leather has excellent scratch resistance, abrasion resistance, chemical resistance, and heat resistance.
- the self-crosslinking polyhydroxypolyurethane resin of the present invention used for the production of the artificial leather uses a polyhydroxypolyurethane resin synthesized using a 5-membered cyclic carbonate compound. Since the 5-membered cyclic carbonate compound is obtained by reacting an epoxy compound with carbon dioxide, it can be fixed by incorporating carbon dioxide into the resin. This means that the present invention makes it possible to provide artificial leather that is useful from the viewpoint of greenhouse gas reduction and that can be provided as an environmental protection product that cannot be achieved with conventional products.
- the skin material made of the thermoplastic polyolefin resin of the present invention has a thermoplastic polyolefin resin sheet and a topcoat layer formed on the sheet directly or via a primer layer, and the topcoat layer is It is formed by the above-mentioned resin composition (hereinafter referred to as a resin composition for skin material) containing as a main component a self-crosslinking polyhydroxy polyurethane resin containing an isocyanate group masked in the molecule.
- a resin composition for skin material containing as a main component a self-crosslinking polyhydroxy polyurethane resin containing an isocyanate group masked in the molecule.
- the topcoat layer is formed by directly applying the resin composition for skin material having the above specific structure on the thermoplastic polyolefin resin sheet, or the primer layer is formed on the resin sheet.
- the top coat layer is formed by applying the resin composition for skin material having the above specific structure on the primer layer.
- this topcoat layer is formed by the resin composition for skin materials which has as a main component the self-crosslinking type polyhydroxy polyurethane resin containing the isocyanate group masked in the molecule
- the resin composition for skin materials may mix
- another resin may be included.
- the modification rate of the resin with a modifier is preferably 2 to 60%, more preferably 5 to 40%.
- Performances such as wear resistance, chemical resistance and heat resistance after heat treatment can be controlled to some extent by the ratio of the modification rate. If the modification rate is less than 2%, the heat resistance and chemical resistance required for the skin material obtained by sufficient crosslinking may not be sufficiently obtained.
- the modification rate exceeds 60%, the bending whitening property suitable as the skin material of the present invention is impaired due to overcrosslinking, and the possibility that the dissociated isocyanate group remains without reacting in the resin increases. It is not preferable.
- the skin material made of the thermoplastic polyolefin resin of the present invention comprises a resin composition for a skin material mainly composed of the self-crosslinking type polyhydroxypolyurethane resin of the present invention, directly or on a primer layer on a thermoplastic polyolefin resin sheet described later. It is obtained by applying as a top coat layer.
- a resin composition for skin material mainly composed of the self-crosslinking type polyhydroxypolyurethane resin of the present invention, directly or on a primer layer on a thermoplastic polyolefin resin sheet described later. It is obtained by applying as a top coat layer.
- other components used in the resin composition for skin material will be described.
- ⁇ Delustering agent> it is also preferable to form a topcoat layer using the resin composition for skin materials which adds a matting agent to the self-crosslinking type polyhydroxy polyurethane resin of this invention as needed.
- the matting agent organic fine powder and / or inorganic fine powder can be used singly or in combination of two or more kinds.
- the organic fine powder used in this case is not particularly limited, and examples thereof include acrylic resin particles, styrene resin particles, styrene-acrylic resin particles, phenol resin particles, melamine resin particles, acrylic-polyurethane resin particles, Examples include polyurethane resin particles, polyester resin particles, nylon resin particles, silicone resin particles, and polyethylene resin particles.
- the average particle size of these powders is preferably in the range of 0.1 to 10 ⁇ m, and the shape is preferably spherical or substantially spherical because the matteness of the formed coating film is particularly excellent.
- inorganic fine powder examples include talc, mica, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, carbon fiber, glass fiber, metal fiber, carbon black, titanium oxide, molybdenum, and magnesium hydroxide. , Bentonite, graphite and the like.
- the average particle size of these powders is 10 ⁇ m or less in accordance with the object of the present invention, but is preferably as small as possible.
- the addition amount of the matting agent as mentioned above is 1 to 150 parts by mass, preferably 3 to 60 parts by mass with respect to 100 parts by mass of the self-crosslinking polyhydroxy polyurethane resin. If the amount is less than 1 part by mass, the effect of addition cannot be sufficiently obtained.
- the skin material resin composition used in the present invention is basically an organic solvent solution or an aqueous dispersion (solution) comprising the self-crosslinking polyhydroxypolyurethane resin of the present invention.
- organic solvent used in the case of an organic solvent solution include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone and the like.
- the concentration of the resin in the organic solvent is preferably 3 to 60% by mass. When the resin concentration is less than 3% by mass, the film formability is inferior, and the thickness of the film is insufficient. On the other hand, if the resin concentration exceeds 60% by mass, the formation of the film after drying may be incomplete, and problems such as residual organic solvent in the film may occur, which is not preferable.
- the resin composition for skin material used in the present invention is used as an aqueous dispersion (solution), it is preferably prepared as follows. First, the hydroxyl group or NH group in the self-crosslinking type polyhydroxy polyurethane resin of the present invention is half-esterified or half-amidated with an acid anhydride to introduce a carboxyl group into the resin. Thereafter, the carboxyl group is preferably neutralized with ammonia, an organic amine compound, an inorganic base or the like to form a carboxylate and used as a self-emulsifying aqueous dispersion.
- the acid anhydride used in the above examples include phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, and the like.
- the organic amine compound examples include monoethanolamine, diethanolamine, triethanolamine, diethylethanolamine, aminoethylethanolamine and the like.
- the self-crosslinking polyhydroxy polyurethane resin of the present invention used above may be an aqueous dispersion emulsified in water by a surfactant according to a conventional method.
- the resin composition for the skin material used in the present invention is suitable for spraying and coating on the thermoplastic polyolefin resin sheet of the topcoat layer formed by the resin composition.
- various conventionally known binder resins can be mixed and used.
- the binder resin used is preferably one that can chemically react with the polyisocyanate group generated by dissociation of the masking agent in the self-crosslinking polyhydroxypolyurethane resin, but has no reactivity. But it can be used in the present invention.
- binder resins conventionally used for the surface of thermoplastic polyolefin resins can be used, and are not particularly limited.
- acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl butyral resin, epoxy resin, polyamide resin Etc. can be used.
- the amount used may be determined in view of the functionality, but it can be used in the range of 5 to 90% by mass.
- the resin composition for the skin material used in the present invention is blended with various coating additives such as a coating surface adjusting agent, a fluidity adjusting agent, an ultraviolet absorber, a dispersing agent, and an anti-settling agent, if necessary. May be.
- the skin material made of the thermoplastic polyolefin resin of the present invention has a top coat layer in which the above-mentioned resin composition for skin material is applied directly or via a primer layer on a thermoplastic polyolefin resin sheet.
- the thermoplastic polyolefin resin sheet include low density to high density polyethylene (LDPE, LLDPE, HDPE, etc.), polypropylene, polypropylene such as propylene-ethylene copolymer, ethylene-propylene rubber (EPR), ethylene-butene rubber (EBR).
- At least one resin sheet selected from the group consisting of thermoplastic polyolefin resins such as ethylene-propylene-diene terpolymer (EDPM).
- EDPM ethylene-propylene-diene terpolymer
- a polypropylene resin and a polyolefin-based thermoplastic elastomer are preferable.
- thermoplastic polyolefin resin sheets made of the materials listed above are inactive on the surface and often have poor adhesion to the coating on the surface, so the surface is physically treated by corona discharge treatment, etc.
- those chemically activated may be used in the present invention.
- the above-described resin composition for skin material is directly applied, or after the primer layer is applied, the above-mentioned resin composition for skin material is applied to form a top coat It is preferable to provide a layer.
- a chlorinated polyolefin resin, a polyester resin and a polyisocyanate compound, a polyurethane resin and a polyisocyanate compound, or the like can be used as a material for forming the primer layer.
- the skin material made of thermoplastic polyolefin resin of the present invention uses the resin composition for skin material comprising the self-crosslinking type polyhydroxy polyurethane resin of the present invention described above, and adding a matting agent as necessary.
- a primer layer is formed on the thermoplastic polyolefin resin sheet directly or on the sheet with the above-described compound, etc., and then the skin material is applied by a known coating method such as brush coating, spraying, roll coating, gravure, or dipping. Apply the resin composition.
- a top coat layer having good surface characteristics is formed by coating so that the thickness after drying becomes about 3 to 20 ⁇ m, followed by heat treatment at a temperature of 80 to 170 ° C. after drying. That is, by the heat treatment, the masking agent of the self-crosslinking polyhydroxypolyurethane resin in the resin composition for the skin material is dissociated, and the generated isocyanate group reacts with the free hydroxyl group in the polyhydroxypolyurethane resin so that the self-crosslinking film (Topcoat layer) is formed.
- the skin material made of the thermoplastic polyolefin resin of the present invention thus obtained is processed into a predetermined shape by vacuum forming into various products or parts.
- the skin material made of the thermoplastic polyolefin resin of the present invention uses the self-crosslinking polyhydroxypolyurethane resin of the present invention, and its topcoat layer is a self-crosslinking film, so its surface properties are scratch resistance, Excellent wear resistance, chemical resistance, and heat resistance. If necessary, a matting agent can be used to provide a uniform matting effect.
- thermoplastic polyolefin resin of the present invention It is useful from the viewpoint of greenhouse gas reduction to use the skin material made of the thermoplastic polyolefin resin of the present invention. That is, since the 5-membered cyclic carbonate compound used in the synthesis of the polyhydroxy polyurethane resin used in the present invention can use carbon dioxide as a synthesis raw material, carbon dioxide can be incorporated into the resin. For this reason, the skin material made of the thermoplastic polyolefin resin of the present invention makes it possible to provide environmentally friendly products that could not be achieved with conventional products.
- the weatherstrip material of the present invention is a material for coating and / or impregnating a polymer elastic material to form a surface treatment layer in a sliding contact portion that is in sliding contact with other components.
- a self-crosslinking polyhydroxyurethane resin of the present invention a diorganopolysiloxane having an average polymerization degree of 5,000 to 10,000 and / or a silicone oil having a kinematic viscosity of 100 to 10,000 CS.
- the self-crosslinking polyhydroxy polyurethane resin of the present invention used above has an isocyanate group masked in its structure as described above.
- the self-crosslinking polyhydroxypolyurethane resin can be obtained, for example, by reacting with a hydroxyl group in the polyhydroxypolyurethane resin using a modifier having at least one free isocyanate group and a masked isocyanate group. it can.
- the polyhydroxy polyurethane resin is preferably a resin derived from a reaction between a 5-membered cyclic carbonate compound and an amine compound. Since the 5-membered cyclic carbonate compound is obtained by reacting an epoxy compound with carbon dioxide, it becomes a material that contributes to environmental conservation.
- the weather strip material of the present invention may further contain a binder resin other than the self-crosslinking polyhydroxyurethane resin of the present invention.
- the modification rate of the self-crosslinking polyhydroxypolyurethane resin of the present invention with a modifier is preferably 2 to 60%, and more preferably 5 to 40%. Depending on the ratio of the modification rate, performances such as wear resistance, chemical resistance and heat resistance after heat treatment can be controlled to some extent. If the modification rate is less than 2%, characteristics such as heat resistance and chemical resistance necessary for weather strips obtained by sufficient crosslinking may not be obtained. On the other hand, if the modification rate exceeds 60%, the bending whitening property suitable as a weather strip is impaired due to overcrosslinking, and the possibility that the dissociated isocyanate group remains without reacting in the resin is preferable. Absent.
- Modification rate (%) ⁇ 1 ⁇ (hydroxyl group of resin after modification ⁇ hydroxyl group of resin before modification) ⁇ ⁇ 100
- the self-crosslinking polyhydroxypolyurethane resin of the present invention used above is obtained by combining a modifier and a polyhydroxypolyurethane resin at 0 to 150 ° C. in the presence or absence of an organic solvent and a catalyst.
- a modifier Preferably, it can be easily obtained by reacting at a temperature of 20 to 80 ° C. for 30 minutes to 3 hours.
- the reaction is carried out at a temperature lower than the dissociation temperature of the masking agent, so that the structure of the modified self-crosslinked polyhydroxy polyurethane resin has a masked isocyanate group.
- the diorganopolysiloxane blended in the self-crosslinking polyhydroxypolyurethane resin of the present invention, which constitutes the material for weatherstrip of the present invention, has an average polymerization degree of 5,000 to 10,000. Use. Such is a straight-chain non-fluid rubbery silicone that is readily available from the market. Since the organopolysiloxane (silicone) having an average polymerization degree in such a range has a high viscosity, in the film formed by the weatherstrip material of the present invention containing such an organopolysiloxane (silicone), It is considered that the orientation (bleed) proceeds slowly.
- the inventors of the present invention can form a surface treatment layer using the weather strip material of the present invention at the sliding contact portion that is in sliding contact with the other parts of the polymer elastic body material, which is a base material. It is inferred that it has become possible to maintain the performance over the entire period.
- Examples of commercially available products include high viscosity series of silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., and any of these can be used in the present invention.
- KF96H-6,000 cs to KF96H-50,000 cs, more preferably KF96H-10,000 cs to KF96H-30,000 cs may be used.
- the material for weatherstrips of the present invention is obtained by replacing, in addition to the diorganopolysiloxane (silicone), a silicone oil having a low kinematic viscosity having a kinematic viscosity in the range of 100 to 10,000 CS with the self-crosslinking of the present invention. Formulated with polyhydroxypolyurethane resin.
- the orientation (bleed) of the silicone to the surface of the film can be controlled, so that the range of selection of the silicone material can be expanded.
- the amount of low viscosity silicone oil used relative to high viscosity silicone is preferably about 100: 3 to 20.
- the silicone oil may or may not have an active hydrogen group that reacts with a polyisocyanate that is a crosslinking agent used in the synthesis of the polyurethane resin used in the present invention.
- CS centistokes [cSt] that is 1 / 100th of Stokes.
- the above-mentioned diorganopolysiloxane and / or silicone oil constituting the weather strip material of the present invention is 1 to 100 parts by mass, preferably 100 parts by mass with respect to 100 parts by mass of the self-crosslinking polyhydroxypolyurethane resin of the present invention. Is blended in the range of 3 to 70 parts by mass, more preferably 10 to 30 parts by mass. If the blending amount is less than 1 part by mass, the added effect is too small. On the other hand, if the blending amount exceeds 100 parts by mass, the coating tends to be weak, which is not preferable.
- the material for weatherstrip of the present invention uses organic fine powder and / or inorganic fine powder in combination of one or more kinds in order to improve the matte, abrasion and lubricity of the formed surface treatment layer. It is preferable to do.
- the organic fine powder is not particularly limited, and examples thereof include acrylic resin particles, styrene resin particles, styrene-acrylic resin particles, phenol resin particles, melamine resin particles, acrylic-polyurethane resin particles, polyurethane resin particles, and polyester. Resin particles, nylon resin particles, silicone resin particles, polyethylene resin particles, and the like can be used. These powders preferably have an average particle size in the range of 1 to 50 ⁇ m.
- the shape of the particle is preferably spherical or substantially spherical.
- the inorganic fine powder examples include talc, mica, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, carbon fiber, glass fiber, metal fiber, carbon black, titanium oxide, molybdenum, and magnesium hydroxide. Bentonite, graphite and the like can be used.
- the average particle size of these powders is 10 ⁇ m or less in accordance with the object of the present invention, but a powder having a particle size as small as possible is more preferable.
- the addition amount of the inorganic or organic fine particles as mentioned above is 1 to 150 parts by mass, preferably 3 to 60 parts by mass with respect to 100 parts by mass of the self-crosslinking polyhydroxy polyurethane resin of the present invention. . If the amount is less than 1 part by mass, the effect of addition cannot be sufficiently obtained.
- the weatherstrip material mainly composed of the self-crosslinking type polyhydroxypolyurethane resin of the present invention is basically an organic solvent solution or an aqueous dispersion (solution) containing the above-mentioned self-crosslinking type polyhydroxypolyurethane resin. is there.
- Preferred organic solvents used when the weatherstrip material is an organic solvent solution include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone and the like.
- the resin concentration in the organic solvent is preferably 3 to 60% by mass. When the resin concentration is less than 3% by mass, the film formability is inferior and the film thickness is insufficient, resulting in insufficient strength. On the other hand, if the resin concentration exceeds 60% by mass, the formation of the film after drying may be incomplete, and problems such as residual organic solvent in the film may occur.
- the weatherstrip material of the present invention is used as an aqueous dispersion (solution), it is preferably prepared as follows. First, the hydroxyl group or NH group in the self-crosslinking polyhydroxy polyurethane resin of the present invention is half-esterified or half-amidated with an acid anhydride to introduce a carboxyl group into the resin. Thereafter, the carboxyl group is preferably neutralized with ammonia, an organic amine compound, an inorganic base or the like to form a carboxylate and used as a self-emulsifying aqueous dispersion. Examples of the acid anhydride used at this time include phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, and the like.
- the self-crosslinking polyhydroxypolyurethane resin may be an aqueous dispersion emulsified in water with a surfactant according to a conventional method.
- the weatherstrip material of the present invention is used to improve adhesion and film formability when a surface treatment layer is formed by applying it to a polymer elastic body as a weatherstrip substrate.
- various conventionally known binder resins may be mixed.
- the binder resin used is preferably one that can chemically react with the isocyanate group generated by dissociation of the masking agent in the self-crosslinking polyhydroxypolyurethane resin essential in the present invention. Even those that do not have can be used.
- binder resins are not particularly limited, and any binder resin conventionally used for surface treatment of weatherstrips can be used.
- acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl butyral resin, epoxy resin, polyamide resin Etc. can be used.
- the amount used may be determined in view of the functionality, but it can be used in the range of 5 to 90% by mass.
- various additives for coating materials such as a coating surface modifier, a fluidity modifier, an ultraviolet absorber, a dispersant, an anti-settling agent, etc., may be appropriately added to the weather strip material of the present invention as necessary. Also good.
- a surface treatment layer having excellent functionality can be obtained.
- a weather strip can be formed. Specifically, by coating and / or impregnating the polymer elastic body with the material of the present invention, a surface treatment layer having excellent functionality can be easily formed in the sliding contact portion of the base material that is in sliding contact with other components. Can do.
- the weatherstrip material of the present invention is applied to the polymer elastic body by a known application method such as brush coating, spraying, roll coating, gravure, or dipping so that the thickness after drying is about 10 to 100 ⁇ m.
- the surface treatment layer can be formed by heat treatment at a temperature of about 50 to 170 ° C. That is, when heat-treated, the masking agent for the masked isocyanate group in the molecule of the self-crosslinking polyhydroxypolyurethane resin is dissociated to form an isocyanate group, and the isocyanate group is contained in the self-crosslinking polyhydroxypolyurethane resin. By reacting with the free hydroxyl group, a self-crosslinking film is formed. As a result, a film is formed on the polymer elastic body for weather strip, and a weather strip product having a surface treatment layer with excellent functionality is obtained.
- the weatherstrip material of the present invention comprises the self-crosslinking polyhydroxy polyurethane resin of the present invention and a specific diorganopolysiloxane and / or a specific silicone oil.
- a weather strip excellent in lubricity, wear resistance, heat resistance, weather resistance and uniform matte effect can be obtained.
- the self-crosslinking polyhydroxypolyurethane resin used in the present invention is useful from the viewpoint of reducing greenhouse gases because carbon dioxide can be incorporated into the resin during synthesis. It is possible to provide a weather strip that could not be used for environmental conservation.
- the mixture was heated and stirred at 80 ° C. for 30 hours while bubbling carbon dioxide gas at a rate of 0.5 liter / min.
- the obtained solution was gradually added to 300 parts of n-hexane with high-speed stirring at 300 rpm, and the resulting powdery product was filtered through a filter, further washed with methanol, N-methylpyrrolidone and Sodium iodide was removed.
- the powder was dried in a drier to obtain 118 parts (yield 95%) of a white powder 5-membered cyclic carbonate compound (1-A).
- Example 1 (Production of self-crosslinking polyhydroxypolyurethane resin solution) A reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser was replaced with nitrogen, and 100 parts of the 5-membered cyclic carbonate compound obtained in Production Example 4 was added thereto so that the solid content was 35%. N-methylpyrrolidone was added to and uniformly dissolved. Next, 27.1 parts of hexamethylenediamine was added and stirred for 10 hours at a temperature of 90 ° C. until the hexamethylenediamine could not be confirmed. Next, 20 parts of the modifier of Production Example 1 (solid content 50%) was added and reacted at 90 ° C. for 3 hours. After confirming that the absorption of the isocyanate group by the infrared absorption spectrum disappeared, the self-crosslinked polyhydroxypolyurethane resin solution of this example was obtained.
- Examples 2 to 6 (Production of self-crosslinking polyhydroxy polyurethane resin solution)
- the 5-membered cyclic carbonate compound, polyamine compound, and modifier shown in Table 1 were combined and reacted in the same manner as in Example 1.
- 2 to 6 self-crosslinking polyhydroxypolyurethane resin solutions were obtained.
- polyester polyurethane resin used in the comparative example was synthesized as follows.
- a reaction vessel equipped with a stirrer, a thermometer, a gas introduction pipe and a reflux condenser was replaced with nitrogen, 150 parts of polybutylene adipate having an average molecular weight of about 2,000, and 15 parts of 1,4-butanediol, Dissolved in a mixed organic solvent consisting of 200 parts methyl ethyl ketone and 50 parts dimethylformamide.
- polyester polyurethane resin used in the comparative example was synthesized as follows. A reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser was replaced with nitrogen, and 150 parts of polybutylene adipate having an average molecular weight of about 2,000 and 15 parts of 1,4-butanediol were added to 250 parts. In dimethylformamide. Thereafter, 62 parts of water-added MDI (methylenebis (1,4-cyclohexane) -diisocyanate) dissolved in 171 parts of dimethylformamide was gradually added dropwise while stirring well at 60 ° C.
- MDI methylenebis (1,4-cyclohexane
- This solution had a viscosity of 3.2 MPa ⁇ s (25 ° C.) at a solid content of 35%.
- the film obtained from this solution had a breaking strength of 45 MPa, a breaking elongation of 480%, and a heat softening temperature of 110 ° C.
- This solution has a solid content of 35% and a viscosity of 1.6 MPa ⁇ s (25 ° C.).
- a film obtained from this solution has a breaking strength of 21 MPa and a breaking elongation of 250%, and the heat softening temperature is 135. ° C.
- ⁇ Comparative Example 3-2> Polycarbonate polyurethane resin
- the polycarbonate polyurethane resin used in the comparative example was synthesized as follows. Similar to Comparative Example 2-2, 150 parts of polycarbonate diol (Ube Industries, Ltd.) having an average molecular weight of about 2,000 and 15 parts of 1,4-butanediol were dissolved in 250 parts of dimethylformamide. . Thereafter, 62 parts of water-added MDI dissolved in 171 parts of dimethylformamide was gradually added dropwise with stirring at 60 ° C., and the mixture was reacted at 80 ° C. for 6 hours.
- polycarbonate diol Ube Industries, Ltd.
- This solution had a viscosity of 1.6 MPa ⁇ s (25 ° C.) at a solid content of 35%.
- the film obtained from this solution had a breaking strength of 21 MPa, a breaking elongation of 250%, and a thermal softening temperature of 135 ° C.
- thermo softening point About each film, the thermal softening point was evaluated according to JISK7206 (Vicat softening point measuring method). The results are shown in Table 2.
- Examples 7 to 14 Comparative Examples 4 to 9> (Manufacture of artificial leather) Using the resin solutions prepared in Example 1, Example 2, Example 5, Example 6, Example 6, Comparative Example 1, Comparative Example 2-2, and Comparative Example 3-2, respectively, were used as artificial leather paints. Using this, artificial leather was produced and evaluated by the following method. Tables 3-1 and 3-2 show the composition and evaluation results.
- Thermal softening point At the time of production of the above synthetic leather, a film obtained by coating on a release paper and heating and drying (150 ° C./10 minutes) was measured according to JIS K7206 (Vicat softening point measurement method). The results are shown in Table 3-2.
- Examples 15 to 22, Comparative Examples 10 to 15 (Production of skin material) Using the resin solutions obtained in Examples 1 to 4, Comparative Example 1, Comparative Example 2-1, and Comparative Example 3-1, topcoat layer-forming paints having the formulations shown in Tables 4 and 5 were prepared. did. And the sheet
- thermoplastic polyolefin base sheet that was corona-discharge treated and the surface was activated to a wetting index of 45 dyn / cm was used.
- chlorinated polypropylene [Super Clon (trade name), manufactured by Nippon Paper Industries Co., Ltd.] was applied with a 120 mesh gravure roll so that the thickness after drying would be 3 ⁇ m, at 100 ° C.
- the primer layer was formed by drying for 2 minutes.
- the topcoat layer-forming paint described in Table 2 was applied with a 120 mesh gravure roll so that the thickness after drying was 5 ⁇ m. Then, after drying at 150 ° C. for 3 minutes, aging at 80 ° C.
- Beef oil (Nacalai Tech Co., Ltd.) was applied to the surface of the skin coating at a radius of 2 cm and left for 5 days in an 80 ° C. atmosphere. Then, the beef oil was removed, and a cellophane cellophane tape peeling test on the coated surface was conducted. Evaluation was made according to the same criteria as in the case of scratching.
- Examples 23 to 30, Comparative Examples 16 to 21 (Production of Weather Strip Material) Using the resin solutions (paints) of Examples 1 to 4, Comparative Example 1, Comparative Example 2-1, and Comparative Example 3-1, paints having the formulations shown in Tables 6 and 7 were prepared. Then, it was coated on an EPDM rubber sheet using an air spray gun and dried at 140 ° C. for 10 minutes to form a 20 ⁇ m film on the sheet. The EPDM rubber sheet having the coating surface obtained as described above was used as a measurement sample for evaluating the surface treatment layer (coating surface) formed by each weather strip material.
- the contact angle of water in the film part of the measurement sample obtained above was measured with a contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd.), and the contact angle of water on the coating surface formed using each weather strip material and did.
- a polyhydroxypolyurethane resin which is a useful material that is considered to contribute to solving problems such as global warming and resource depletion, but whose application development has not progressed, can be effectively used for industrial use.
- a polyhydroxy polyurethane resin can be provided.
- the product formed is an environmentally friendly product that incorporates carbon dioxide and can contribute to the reduction of greenhouse gases, but it also has heat resistance, chemical resistance, and wear resistance. Performance and other performances are also satisfactory. Therefore, its utilization is expected from the standpoint of global environmental conservation.
- the artificial leather of the present invention uses a resin composition containing the self-crosslinking polyhydroxypolyurethane resin as a main component, so that the masked isocyanate group dissociated by the heat in the structure and the polyisocyanate in the resin. Since the hydroxyl group of the hydroxypolyurethane resin reacts to become a crosslinked resin, it is possible to provide artificial leather excellent in scratch resistance, abrasion resistance, chemical resistance and heat resistance. As a result, it is possible to provide environmentally friendly artificial leather products that could not be achieved with conventional products. As a result, it can contribute to solving problems such as global warming and resource depletion that have become global issues in recent years. it can.
- the topcoat layer of the thermoplastic polyolefin resin sheet is formed using the resin composition containing the self-crosslinking polyhydroxypolyurethane resin as a main component.
- the topcoat layer is formed as a self-crosslinking film because the masked isocyanate group in the resin is dissociated by heat and the dissociated isocyanate group reacts with the free hydroxyl group in the polyhydroxypolyurethane resin. Excellent scratch resistance, wear resistance, chemical resistance, and heat resistance, and a uniform matte effect.
- global warming and resource depletion have become a global issue in recent years. It can contribute to solving such problems.
- the weatherstrip material of the present invention is a resin composition comprising a self-crosslinking polyhydroxypolyurethane resin and an additive, a masked isocyanate group that is dissociated by heat in the structure of the resin, and the resin Since it reacts with the hydroxyl group therein to form a cross-linked resin, it has excellent lubricity, abrasion resistance, heat resistance, weather resistance, and even a uniform matte effect. As a result, the surface treatment layer formed using the weatherstrip material has excellent performance.
- the self-crosslinking polyhydroxypolyurethane resin used in the present invention is a useful material that contributes to solving problems such as global warming and resource depletion in which carbon dioxide is incorporated and fixed in the resin. Weatherstrip materials are also able to provide environmentally friendly products that could not be achieved with conventional products, and expansion of use from this point is expected.
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Abstract
Description
従来、袋物、鞄、靴、家具、衣料、車両内装材、電化製品などに擬革が使用されているが、この擬革用樹脂としてポリウレタン系樹脂が広く使用されている。上記「擬革」とは、天然皮革に似せて製造される皮革状製品の総称で、一般的には、人工皮革、合成皮革、塩化ビニルレザーに大別される。
近年におけるゴミ問題及び環境問題の深刻化に鑑み、車両内装材(インストルメントパネル、ドアトリムなど)や家電部品においては、使用後における廃材をできるだけ低減するため、その構成部材に対し、リサイクル化が強く要望されている。この観点から、上記部材の形成材料には、熱可塑性ポリオレフィン樹脂、例えば、ポリプロピレン樹脂(PP樹脂と略す)、ABS樹脂、AS樹脂、ポリオレフィン系熱可塑性エラストマー(TPO樹脂と略す)などが使用されている。しかしながら、これら熱可塑性ポリオレフィン樹脂は、表面の、接着性、耐擦傷性、耐摩耗性、耐薬品性が従来使用されていた塩化ビニル樹脂などに比べて劣るという問題があり、これらの問題を改善するために、表面に機能性を付与する必要がある。また、高級感を与える意匠性を実現するために、或いは、自動車内装材においては運転者への防眩性の配慮などを考慮して、熱可塑性ポリオレフィン基材に種々の塗装を施すことが行われている。
従来、自動車や建築物の、グラスラン、ドアウェザーストリップ、ボディサイドウェザーストリップ、インサイドシール、アウトサイドシールなどのウェザーストリップの形成材料としては、クロロプレンゴム、スチレン-ブタジエンゴム、ニトリルゴム、EPDMゴムなどの高分子弾性体材料が用いられている。そして、これらの表面には、滑性、耐摩耗性、離型性、耐熱性、耐水性、耐候性などの性能を持たせるため、塗布又は含浸などの方法によって表面処理層を形成することが行われている。
(変性剤)
<有機ポリイソシアネート化合物>
本発明の自己架橋型ポリヒドロキシポリウレタン樹脂を製造する際に用いる変性剤の構成成分について説明する。該変性剤としては、有機ポリイソシアネート化合物とマスキング剤との反応生成物が用いられる。この際に使用する有機ポリイソシアネート化合物は、脂肪族或いは芳香族化合物中に少なくとも2個のイソシアネート基を有する有機化合物であり、従来からポリウレタン樹脂の合成原料として広く使用されている。これらの公知の有機ポリイソシアネート化合物はいずれも本発明において有用である。特に好ましい有機ポリイソシアネート化合物を挙げれば、以下の通りである。
本発明で使用される変性剤は、上記した有機ポリイソシアネート化合物とマスキング剤との反応生成物であるが、マスキング剤としては、下記のものが使用できる。アルコール系、フェノール系、活性メチレン系、酸アミド系、イミダゾール系、尿素系、オキシム系、ピリジン系の化合物などであり、これらを単独あるいは混合して使用してもよい。具体的なマスキング剤の例としては下記のものがある。
上記に列挙した有機ポリイソシアネート化合物と、上記に列挙したマスキング剤とを反応させて、本発明で用いる、少なくとも一個の遊離イソシアネート基を有し、かつ、他はマスキングされたイソシアネート基を有する変性剤を合成する。合成方法は特に限定されないが、上記マスキング剤と上記有機ポリイソシアネート化合物とを、1分子中でイソシアネート基が1個以上過剰になる官能基比で、有機溶媒及び触媒の存在下又は不存在下で、0~150℃、好ましくは20~80℃の温度で、30分~3時間反応させることによって容易に得ることができる。
本発明の自己架橋型ポリヒドロキシポリウレタン樹脂は、ポリヒドロキシポリウレタン樹脂を上記したような特定の変性剤によって変性されて得られる。その際に用いるポリヒドロキシポリウレタン樹脂は、5員環環状カーボネート化合物とアミン化合物との反応によって得られるが、以下に、当該反応に用いる各成分について説明する。
本発明で使用する5員環環状カーボネート化合物は、下記[式-A]で示されるように、エポキシ化合物と二酸化炭素とを反応させて製造することができる。さらに詳しくは、エポキシ化合物を、有機溶媒の存在下又は不存在下、及び触媒の存在下、40℃~150℃の温度で、常圧又は僅かに高められた圧力下、10~20時間、二酸化炭素と反応させることによって得られる。
上記したようなエポキシ化合物と、二酸化炭素の反応において使用される触媒としては、塩基触媒及びルイス酸触媒が挙げられる。
塩基触媒としては、トリエチルアミン、トリブチルアミンなどの第三級アミン類、ジアザビシクロウンデセン、ジアザビシクロオクタン及びピリジンなどの環状アミン類、リチウムクロライド、リチウムブロマイド、フッ化リチウム、塩化ナトリウムなどのアルカリ金属塩類、塩化カルシウムなどのアルカリ土類金属塩類、テトラブチルアンモニウムクロライド、テトラエチルアンモニウムブロマイド、ベンジルトリメチルアンモニウムクロライドなどの四級アンモニウム塩類、炭酸カリウム、炭酸ナトリウムなどの炭酸塩類、酢酸亜鉛、酢酸鉛、酢酸銅、酢酸鉄などの金属酢酸塩類、酸化カルシウム、酸化マグネシウム、酸化亜鉛などの金属酸化物、テトラブチルホスホニウムクロリドなどのホスホニウム塩類が挙げられる。
上記反応に使用するアミン化合物としては、ジアミンが好ましく、従来ポリウレタン樹脂の製造に使用されているものがいずれも使用でき、特に限定されない。例えば、メチレンジアミン、エチレンジアミン、トリメチレンジアミン、1,3-ジアミノプロパン、ヘキサメチレンジアミン、オクタメチレンジアミンなどの脂肪族ジアミン;フェニレンジアミン、3,3’-ジクロロ-4,4’-ジアミノジフェニルメタン、4,4’-メチレンビス(フェニルアミン)、4,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルスルホン、メタキシリレンジアミン、パラキシリレンジアミンなどの芳香族ジアミン;1,4-シクロヘキサンジアミン、4,4’-ジアミノシクロヘキシルメタン、1,4’-ジアミノメチルシクロヘキサン、イソホロンジアミンなどの脂環族ジアミン;モノエタノールジアミン、エチルアミノエタノールアミン、ヒドロキシエチルアミノプロピルアミンなどのアルカノールジアミンが挙げられる。
また、本発明に用いるポリヒドロキシポリウレタン樹脂は、その数平均分子量(GPCで測定した標準ポリスチレン換算値)が、2,000~100,000程度であることが好ましく、より好ましくは5,000~70,000程度のものを用いる。
本発明の自己架橋型ポリヒドロキシポリウレタン樹脂は、それぞれ上述のようにして得られる、変性剤と、ポリヒドロキシポリウレタン樹脂とを反応させることで得られる。詳しくは、上記ポリヒドロキシポリウレタン樹脂中の水酸基と、該変性剤中の少なくとも一個の遊離したイソシアネート基とが反応することによって合成できる。
変性率(%)={1-(変性後の樹脂の水酸基÷変性前の樹脂の水酸基)}×100
上記のようにして得ることのできる本発明の自己架橋型ポリヒドロキシポリウレタン樹脂は、そのまま、フィルム・成型材料、各種コーティング材、各種塗料、各種バインダーなどとして用いることができ、これにより、耐摩耗性、耐薬品性、耐熱性に優れた製品等が得られる。各種用途や皮膜の形成に際しては、樹脂特性の調整などを目的として、自己架橋型ポリヒドロキシポリウレタン樹脂に、従来公知の各種樹脂をバインダー樹脂等として混合して樹脂材料として使用することもできる。この際に使用するバインダー樹脂としては、自己架橋型ポリヒドロキシポリウレタン樹脂の構造中のマスキング部分が解離することによって生成するイソシアネート基と、化学的に反応し得るものが好ましい。しかし、上記のような反応性を有していない樹脂であっても、目的に応じて適宜に本発明の自己架橋型ポリヒドロキシポリウレタン樹脂と併用して樹脂材料とすることができる。
(擬革用樹脂組成物)
本発明の擬革は、上述した、5員環環状カーボネート化合物とアミン化合物との反応から誘導された、その構造中にマスキングされたイソシアネート基を有する本発明の自己架橋型ポリヒドロキシポリウレタン樹脂を主成分とする樹脂組成物(以下、擬革用樹脂組成物と呼ぶ)を、基布に充填或いは積層せしめたことを特徴とする。該樹脂のマスキングされたイソシアネート基は、有機ポリイソシアネート基とマスキング剤との反応生成物であり、熱処理することによりマスキングされた部分が解離されてイソシアネート基を生成し、自己架橋型ポリヒドロキシポリウレタン樹脂の構造中の水酸基と反応して自己架橋するものである。このため、該樹脂を用いることで、表面の耐擦傷性、耐摩耗性、耐薬品性、耐熱性に優れる擬革を得ることができる。本発明で使用する地球環境保全の観点から特に好適な自己架橋型ポリヒドロキシポリウレタン樹脂は、5員環環状カーボネート化合物が、エポキシ化合物と二酸化炭素との反応物であり、かつ、その構造中に二酸化炭素を1~25質量%の範囲で含むものである。また、擬革用樹脂組成物は、さらに他の樹脂を含むものであってもよい。
本発明の擬革は、先に説明した本発明の自己架橋型ポリヒドロキシポリウレタン樹脂を主成分とする擬革用樹脂組成物を、基布に充填或いは積層せしめてなることを特徴とする。本発明の擬革の製造方法については、本発明の範囲内であれば何ら限定されるものではなく、公知の人工皮革、合成皮革の製法を利用できる。また、本発明の擬革には、基布の上に可塑剤入りの塩化ビニル樹脂層を設け、これを基材シートとし、該基材シートの上に、本発明を特徴づける自己架橋型ポリヒドロキシポリウレタン樹脂を主成分とする擬革用樹脂組成物からなる層を形成したものも含まれる。
(表皮材用樹脂組成物)
本発明の熱可塑性ポリオレフィン樹脂製の表皮材は、熱可塑性ポリオレフィン樹脂シートと、該シート上に直接又はプライマー層を介して形成されてなるトップコート層を有し、かつ、該トップコート層が、上述した、分子中にマスキングされたイソシアネート基を含有する自己架橋型ポリヒドロキシポリウレタン樹脂を主成分としてなる樹脂組成物(以下、表皮材用樹脂組成物と呼ぶ)によって形成されたものであることを特徴とする。より具体的には、熱可塑性ポリオレフィン樹脂シート上に、上記特定の構成からなる表皮材用樹脂組成物を直接塗布してトップコート層を形成し、或いは、上記樹脂シート上にプライマー層を形成し、該プライマー層上に上記特定の構成からなる表皮材用樹脂組成物を塗布してトップコート層を形成して構成される。そして、該トップコート層を、分子中にマスキングされたイソシアネート基を含有する自己架橋型ポリヒドロキシポリウレタン樹脂を主成分としてなる表皮材用樹脂組成物によって形成してなることを特徴とする。また、表皮材用樹脂組成物は、艶消剤として、有機系微粉末及び無機系微粉末から選ばれる一種又は二種以上の組み合わせからなる物質を配合してなるものであってもよい。さらに、他の樹脂を含むものであってもよい。
本発明においては、本発明の自己架橋型ポリヒドロキシポリウレタン樹脂に、必要に応じて艶消剤を加えてなる表皮材用樹脂組成物を用いてトップコート層を形成することも好ましい。該艶消剤としては、有機系微粉末及び/又は無機系微粉末を一種又は二種以上を組み合わせて使用できる。この場合に使用する有機系微粉末としては、特に制限されるものではなく、例えば、アクリル樹脂粒子、スチレン樹脂粒子、スチレン-アクリル樹脂粒子、フェノール樹脂粒子、メラミン樹脂粒子、アクリル-ポリウレタン樹脂粒子、ポリウレタン樹脂粒子、ポリエステル樹脂粒子、ナイロン樹脂粒子、シリコーン樹脂粒子、ポリエチレン樹脂粒子などが挙げられる。これら粉末の平均粒径は0.1~10μmの範囲が好ましく、形状としては、形成される塗膜の艶消性が特に優れることから、球状又は略球状が実用上好ましい。
本発明で使用する表皮材用樹脂組成物は、基本的には、本発明の自己架橋型ポリヒドロキシポリウレタン樹脂を含んでなる有機溶剤溶液又は水分散体(溶液)である。有機溶剤溶液とする場合に用いる有機溶剤としては、例えば、ジメチルホルムアミド、ジメチルスルホキシド、ジメチルアセトアミド、N-メチルピロリドン、N-エチルピロリドンなどが挙げられる。また、有機溶剤中における樹脂の濃度は3~60質量%であることが好ましい。樹脂濃度が3質量%未満では、成膜性に劣るとともに、皮膜の厚みが不足し、そのため強度不足が生じる恐れがあるので好ましくない。一方、樹脂濃度が60質量%を超えると、乾燥後の皮膜の形成が不完全になる恐れがあるとともに、皮膜中への有機溶剤の残留などの問題が生じる恐れがあるので好ましくない。
また、本発明で用いる表皮材用樹脂組成物には、上述した艶消剤以外にも、該樹脂組成物によって形成したトップコート層の、熱可塑性ポリオレフィン樹脂シートに対するスプレー適正及びコーティング適正、成膜性の向上のために、従来公知の各種バインダー樹脂を混合して使用することができる。この際、使用するバインダー樹脂としては、自己架橋型ポリヒドロキシポリウレタン樹脂中のマスキング剤が解離して生成するポリイソシアネート基と化学的に反応し得るものが好ましいが、反応性を有していないものでも本発明に使用することができる。
本発明の熱可塑性ポリオレフィン樹脂製の表皮材は、熱可塑性ポリオレフィン樹脂シート上に、上記した表皮材用樹脂組成物を直接又はプライマー層を介して塗布したトップコート層を有してなる。上記熱可塑性ポリオレフィン樹脂シートとしては、低密度~高密度ポリエチレン(LDPE、LLDPE、HDPEなど)、ポリプロピレン、プロピレン-エチレン共重合体などのポリプロピレン、及びエチレン-プロピレンゴム(EPR)、エチレン-ブテンゴム(EBR)、エチレン-プロピレン-ジエンターポリマー(EDPM)などの熱可塑性ポリオレフィン樹脂からなる群から選ばれた少なくとも1種の樹脂シートが挙げられる。優れた機械的強度とともに良好な柔軟性及び弾性を有するために、ポリプロピレン樹脂、ポリオレフィン系熱可塑性エラストマーであることが好ましい。
本発明の熱可塑性ポリオレフィン樹脂製の表皮材は、先に説明した本発明の自己架橋型ポリヒドロキシポリウレタン樹脂を含み、必要に応じて艶消剤を添加してなる表皮材用樹脂組成物を用い、下記のようにして得ることができる。まず、熱可塑性ポリオレフィン樹脂シート上に、直接、又は該シート上に上記した化合物等によってプライマー層を形成した後、刷毛塗り、スプレー、ロールコート、グラビア、浸漬などの公知の塗布方法で上記表皮材用樹脂組成物を塗布する。この際、乾燥後の厚みが3~20μm程度になるように塗布し、乾燥後、80~170℃の温度で加熱処理することで、良好な表面特性を有するトップコート層が形成される。すなわち、加熱処理することにより、表皮材用樹脂組成物中の自己架橋型ポリヒドロキシポリウレタン樹脂のマスキング剤が解離し、生成したイソシアネート基がポリヒドロキシポリウレタン樹脂中の遊離水酸基と反応して自己架橋皮膜(トップコート層)が形成される。このようにして得られる本発明の熱可塑性ポリオレフィン樹脂製の表皮材は、真空成形によって所定の形状に加工されて、種々の製品或いは部品になる。
本発明のウェザーストリップ用材料は、高分子弾性体材料に被覆及び/又は含浸させて、他部品と摺接する摺接部に表面処理層を形成するための材料であって、バインダー樹脂に、上記した本発明の自己架橋型ポリヒドロキシウレタン樹脂と、平均重合度5,000~10,000のジオルガノポリシロキサン及び/又は動粘度が100~10,000CSのシリコーンオイルとを含有してなることを特徴とする。上記で用いる本発明の自己架橋型ポリヒドロキシポリウレタン樹脂は、先に述べた通り、その構造中にマスキングされたイソシアネート基を有する。該自己架橋型ポリヒドロキシポリウレタン樹脂は、例えば、少なくとも1個の遊離のイソシアネート基と、マスキングされたイソシアネート基とを有する変性剤を用い、ポリヒドロキシポリウレタン樹脂中の水酸基と反応させることで得ることができる。さらに、このポリヒドロキシポリウレタン樹脂は、5員環環状カーボネート化合物とアミン化合物との反応から誘導された樹脂であることが好ましい。該5員環環状カーボネート化合物は、エポキシ化合物と二酸化炭素を反応させて得られるため、環境保全性にも資する材料となる。また、本発明のウェザーストリップ用材料は、さらに、本発明の自己架橋型ポリヒドロキシウレタン樹脂以外のバインダー樹脂を含むものであってもよい。
変性率(%)={1-(変性後の樹脂の水酸基÷変性前の樹脂の水酸基)}×100
本発明のウェザーストリップ用材料を構成する、上記で説明した本発明の自己架橋型ポリヒドロキシポリウレタン樹脂に配合されるジオルガノポリシロキサンには、その平均重合度5,000~10,000のものを用いる。このようなものとしては、直鎖状の流動性のないゴム状シリコーンがあり、容易に市場から入手可能である。平均重合度がこのような範囲であるオルガノポリシロキサン(シリコーン)は高粘度であるため、このようなものを含んでなる本発明のウェザーストリップ用材料によって形成した皮膜では、皮膜表面へのシリコーンの配向(ブリード)が緩やかに進むと考えられる。
本発明のウェザーストリップ用材料は、上記ジオルガノポリシロキサン(シリコーン)に代えて、或いは加えて、動粘度が100~10,000CSの範囲の、動粘度の低いシリコーンオイルを、本発明の自己架橋型ポリヒドロキシポリウレタン樹脂に配合する。上記高粘度のシリコーンに加えて、このような粘度の低いシリコーンオイルを少量添加すると、皮膜表面へのシリコーンの配向(ブリード)を制御できるため、シリコーン材料の選択の幅を広げることができる。高粘度のシリコーンに対する低粘度のシリコーンオイルの使用量としては、100:3~20程度とすることが好ましい。該シリコーンオイルとしては、本発明で使用するポリウレタン樹脂の合成の際に用いられる架橋剤であるポリイソシアネートと反応する活性水素基を有しているものでも、有していないものでもよい。なお、本発明においてCSとは、ストークスの100分の1のセンチストークス[cSt]を意味する。
また、本発明のウェザーストリップ用材料は、形成した表面処理層の艶消し、摩耗性・滑性の向上のため、有機系微粉末及び/又は無機系微粉末を一種又は二種以上組み合わせて使用することが好ましい。有機系微粉末としては、特に制限されるものではなく、例えば、アクリル樹脂粒子、スチレン樹脂粒子、スチレン-アクリル樹脂粒子、フェノール樹脂粒子、メラミン樹脂粒子、アクリル-ポリウレタン樹脂粒子、ポリウレタン樹脂粒子、ポリエステル樹脂粒子、ナイロン樹脂粒子、シリコーン樹脂粒子、ポリエチレン樹脂粒子などが使用できる。これら粉末は、その平均粒径が、1~50μmの範囲のものが好ましい。また、形成した塗膜の表面性向上及び艶消性が特に優れることから、粒子の形状は、球状又は略球状が実用上好ましい。
トリメチロールプロパンとヘキサメチレンジイソシアネート3量体付加物[コロネートHL(商品名)、日本ポリウレタン社製、NCO=12.9%、固形分75%]100部、酢酸エチルを24.5部、100℃でよく攪拌しながら、ε-カプロラクタムを25.5部添加し、5時間反応させた。得られた変性剤の赤外吸収スペクトル(堀場製作所 FT-720)によれば、2,270cm-1に遊離イソシアネート基による吸収は残っており、この遊離イソシアネート基を定量すると、固形分50%で理論値が2.1%であるのに対し実測値は1.8%であった。
ヘキサメチレンジイソシアネートと水の付加体(ジュラネート24A-100(商品名)、旭化成社製、NCO=23.0%)100部、酢酸エチル132部を80℃でよく攪拌しながら、メチルエチルケトオキシムを32部添加し、5時間反応させた。得られた変性剤の赤外吸収スペクトルによれば、2,270cm-1に遊離イソシアネート基による吸収は残っており、この遊離イソシアネート基を定量すると、固形分50%で理論値が2.9%であるのに対し、実測値は2.6%であった。
トリメチロールプロパンとトリレンジイソシアネート3量体付加物[コロネートL(商品名)、日本ポリウレタン社製、NCO=12.5%、固形分75%]100部、酢酸エチルを67.3部、80℃でよく攪拌しながら、メチルエチルケトオキシムを17.3部添加し、5時間反応させた。得られた変性剤の赤外吸収スペクトルによれば、2,270cm-1に遊離イソシアネート基による吸収は残っており、この遊離イソシアネート基を定量すると、固形分50%で理論値が2.3%であるのに対し、実測値は2.0%であった。
攪拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器中に、下記式Aで表される2価エポキシ化合物[エピコート828(商品名)、ジャパンエポキシレジン(株)製、エポキシ当量187g/mol]100部、N-メチルピロリドンを100部、ヨウ化ナトリウムを1.5部加え、均一に溶解させた。
製造例4で用いた2価エポキシ化合物Aの代わりに、下記式Bで表わされる2価エポキシ化合物[YDF-170(商品名)、東都化成社製、エポキシ当量172g/mol]を使い、製造例4と同様に反応させ、白色粉末の5員環環状カーボネート化合物(1-B)121部(収率96%)を得た。
製造例4で用いた2価エポキシ化合物Aの代わりに、下記式C[EX-212(商品名)、ナガセケムテックス(株)製、エポキシ当量151g/mol]を使い、製造例4と同様に反応させ、無色透明の液状5員環環状カーボネート化合物(1-C)111部(収率86%)を得た。
撹拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器を窒素置換し、これに製造例4で得られた5員環環状カーボネート化合物100部を、固形分が35%になるようにN-メチルピロリドンを加えて均一に溶解した。次に、ヘキサメチレンジアミンを27.1部加え、90℃の温度で10時間撹拌し、ヘキサメチレンジアミンが確認できなくなるまで反応させた。次に、製造例1の変性剤を20部(固形分50%)添加し、90℃で3時間反応させた。赤外吸収スペクトルによるイソシアネート基の吸収が消失したことを確認し、本実施例の自己架橋型ポリヒドロキシポリウレタン樹脂溶液を得た。
以下、実施例1と同様に、表1に示した5員環環状カーボネート化合物、ポリアミン化合物、変性剤をそれぞれ組み合わせて、実施例1と同様の方法で反応させて、表1に記載の実施例2~6の自己架橋型ポリヒドロキシポリウレタン樹脂溶液を得た。
実施例1で用いた製造例1の変性剤を使用しない以外は実施例1と同様にして、ポリヒドロキシポリウレタン樹脂溶液を使用した。
下記のようにして、比較例で用いるポリエステルポリウレタン樹脂を合成した。撹拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器を窒素置換し、平均分子量約2,000のポリブチレンアジペートを150部と、1,4-ブタンジオールを15部とを、200部のメチルエチルケトンと、50部のジメチルホルムアミドからなる混合有機溶剤中に溶解した。その後、60℃でよく撹拌しながら、62部の水添加MDI(メチレンビス(1,4-シクロヘキサン)-ジイソシアネート)を、171部のジメチルホルムアミドに溶解したものを徐々に滴下し、滴下終了後80℃で6時間反応させた。この溶液は、固形分35%で3.2MPa・s(25℃)の粘度を有していた。
下記のようにして、比較例で用いるポリエステルポリウレタン樹脂を合成した。撹拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器を窒素置換し、平均分子量約2,000のポリブチレンアジペート150部と、1,4-ブタンジオール15部とを、250部のジメチルホルムアミド中に溶解した。その後、60℃でよく撹拌しながら62部の水添加MDI(メチレンビス(1,4-シクロヘキサン)-ジイソシアネート)を、171部のジメチルホルムアミドに溶解したものを徐々に滴下し、滴下終了後80℃で6時間反応させた。この溶液は、固形分35%で3.2MPa・s(25℃)の粘度を有していた。また、この溶液から得られたフィルムは破断強度45MPaで、破断伸度480%を有し、熱軟化温度は110℃であった。
比較例2-1と同様に、平均分子量約2,000のポリカーボネートジオール(宇部興産(株)製)150部と、1,4-ブタンジオール15部とを、200部のメチルエチルケトンと50部のジメチルホルムアミドからなる混合有機溶剤中に溶解した。その後、60℃でよく撹拌しながら、62部の水添加MDIを171部のジメチルホルムアミドに溶解したものを徐々に滴下し、滴下終了後、80℃で6時間反応させた。この溶液は、固形分35%で1.6MPa・s(25℃)の粘度を有し、この溶液から得られたフィルムは破断強度21MPaで破断伸度250%を有し、熱軟化温度は135℃であった。
下記のようにして、比較例で用いるポリカーボネートポリウレタン樹脂を合成した。比較例2-2と同様に、平均分子量約2,000のポリカーボネートジオール(宇部興産(株)製)150部と、1,4-ブタンジオール15部とを、250部のジメチルホルムアミド中に溶解した。その後、60℃でよく撹拌しながら62部の水添加MDIを171部のジメチルホルムアミドに溶解したものを徐々に滴下し、滴下終了後80℃で6時間反応させた。この溶液は、固形分35%で1.6MPa・s(25℃)の粘度を有していた。また、この溶液から得られたフィルムは破断強度21MPaで、破断伸度250%を有し、熱軟化温度は135℃であった。
上記実施例1~4及び比較例1、比較例2-1の各樹脂溶液を使用して、キャスティング法によりフィルムをそれぞれ作製し、得られた各フィルムについて下記の特性を下記の方法で判定し、自己架橋型ポリヒドロキシポリウレタン樹脂の特性を評価した。キャスティング条件は、100℃で3分間乾燥後、160℃で30分間加熱処理をした。
各フィルムについて、JIS K7311に準じて、機械物性(引張強さ、伸び)を評価した。結果を表2に示した。
各フィルムについて、JIS K7206(ビカット軟化点測定法)準じて、熱軟化点を評価した。結果を表2に示した。
各フィルムについて、JIS K7311に準じて、摩耗性を評価した。結果を表2に示した。
JIS K5600-6-1に準じ、50℃のトルエンに10分間浸漬した前後での各フィルムの外観変化について観察し、耐溶剤性を評価した。結果を表2に示した。
各フィルム中における二酸化炭素の固定化の有無によって、○×で評価した。結果を表2に示した。
先に調製した実施例1、実施例2、実施例5、実施例6、比較例1、比較例2-2、比較例3-2の各樹脂溶液をそれぞれ使用して擬革用塗料とし、これを用いて擬革を作製し、下記の方法で評価した。表3-1、3-2に配合と評価結果を示した。
実施例1、2、5、6、比較例1、2-2、3-2で得た樹脂溶液を、厚さ1mmとなるように、ポリスチレン-ポリエステル繊維からなる不織布上に塗布し、25℃のDMF10%の水溶液中に浸漬し凝固させた。洗浄後、加熱乾燥(150℃/10分)し、多孔層シートを有する人工皮革を得た。
織布上に、接着剤層としてポリウレタン系樹脂溶液[レザミンUD-602S(商品名)、大日精化工業(株)製]を、乾燥時の厚さが10μmとなるように塗布及び加熱乾燥して、擬革用基材シートを作製した。一方、実施例1、2、5、6、比較例1、2-2、3-2で得た樹脂溶液を、それぞれ離型紙上に塗布及び加熱乾燥(150℃/10分)させ、約15μmの厚さのフィルムを形成し、これを上記で得た基材シートに貼り合せて合成皮革を得た。
上記で得た各人工皮革及び各合成皮革の各擬革を用いて、下記の方法及び基準で評価した。
(風合い)
各擬革について、手の感触により、下記の基準で判定した。結果を表3-1及び表3-2に示した。
○;軟らかい
△;やや硬い
×;硬い
上記で得た各合成皮革表面に、トルエンをそれぞれ滴下し、常に濡れている状態を保つため溶剤を追加滴下し、1時間後に拭き取った。下記の基準で判定し、結果を表3-2に示した。
○;塗布面に滴下痕が全く見られない。
△;僅かに滴下痕や膨潤など変化が認められるが目立たない。
×;表面状態(膨潤など)の変化が明らかに認められる。
上記で得た各合成皮革について、平面摩耗試験機を用い、6号帆布を荷重1kgfで、擦り傷が発生するまでの回数を測定した。そして、下記の基準で判定し、結果を表3-2に示した。
○;5000回以上
△;2000回以上~5000回未満
×;2000回未満
上記した合成皮革の作製時、離型紙上に塗布及び加熱乾燥(150℃/10分)させて得られたフィルムを、JIS K7206(ビカット軟化点測定法)に準じて測定した。結果を表3-2に示した。
各擬革について、使用した樹脂中における二酸化炭素の固定化の有無によって、○×で評価した。結果を表3-1及び表3-2に示した。
実施例1~4、比較例1、比較例2-1、比較例3-1で得た各樹脂溶液を使用し、表4、5に記載の配合からなるトップコート層形成用塗料をそれぞれ作製した。そして、下記の方法で表面にトップコート層を有する表皮材の評価用シートを形成した。そして、これを用いて、その成形性、グロス値、接着性、耐擦傷性、耐油性、耐薬品性、耐表面摩耗性、環境対応性について、下記の方法でそれぞれ評価した。
コロナ放電処理をして、濡れ指数45dyn/cmに表面を活性化した熱可塑性ポリオレフィンの基材シートを用いた。該基材シートに、塩素化ポリプロピレン[スーパークロン(商品名)、日本製紙(株)製]を、120メッシュのグラビアロールにて、乾燥後の厚みが3μmになるように塗布し、100℃で2分間乾燥して、プライマー層を形成した。この塗膜の上に、表2に記載のトップコート層形成用塗料を120メッシュのグラビアロールにて乾燥後の厚みが5μmになるように塗布した。その後、150℃で3分間乾燥し、80℃で24時間熟成後、表面温度160℃の凸引型真空成形機で成形して、トップコート層が表面に形成されてなる成形品(表皮材)を得た。得られた成形品を用いて、下記の基準で評価を行った。結果を表4及び表5にまとめて示した。
(成形性)
真空成形後のシート表面を目視で観察し、評価した。
○;良好(成型割れや白化現象なし)
×;不良(成型割れ又は白化現象のどちらかが認められる)
真空成形後のシート表面を、JIS K5600に準じたグロスメーターにて測定し、グロス値が1.2以下(業界の求める基準値)のものを合格とした。
真空成形後の表皮塗膜面の碁盤目セロハンテープ剥離試験を行って評価した。
○;良好(塗布面に剥離部分がない)
×;不良(塗布面に剥離部位がある)
真空成形後の表皮塗膜面を爪でこすり、傷跡や白化が生じないかを目視判定で評価した。
○;良好(塗布面の爪傷・白化を判別し難い)
×;不良(塗布面の爪傷・白化跡が明瞭に判別できる)
表皮塗膜面に牛油(ナカライテク(株))を2cm半径に塗布し、80℃雰囲気で5日間放置した後に、牛油を除去し、塗布面の碁盤目セロハンテープ剥離試験を行って、耐擦傷性の場合と同様の基準で評価した。
表皮塗膜面にエタノールをそれぞれ滴下し、常に濡れている状態を保つため溶剤を追加滴下し、1時間後に拭き取った。
○;塗布面に滴下痕が全く見られない。
△;僅かに滴下痕が認められるが目立たない。
×;滴下痕が明らかに認められる。
平面摩耗試験機を用い、6号帆布を荷重1kgfで擦り、傷が発生するまでの回数を測定した。
○;5000回以上
△;2000回以上~5000回未満
×;2000回未満
使用した樹脂中における二酸化炭素の固定化の有無によって、○×で評価した。
実施例1~4、比較例1、比較例2-1、比較例3-1の各樹脂溶液(塗料)を使用して、表6及び7に記載の配合の塗料を作製した。そして、EPDMゴムシート上に、エアースプレーガンを用いて塗工し、140℃で10分間乾燥させ、シート上に20μmの皮膜を形成した。上記のようにして得られた塗膜面を有するEPDMゴムシートを、各ウェザーストリップ用材料によって形成した表面処理層(塗膜面)を評価するための測定用試料とした。
上記で得られたウェザーストリップ材料(塗料)及び上記した各測定用試料について、静止摩擦係数、動摩擦係数、接触角、接着性、摩耗耐久性、耐候性などを以下方法でそれぞれ測定し、実施例及び比較例の材料について評価した。評価結果を表6及び7にまとめて示した。
各ウェザーストリップ用材料(塗料)の、ガラス部材との静止摩擦係数、動摩擦係数を、表面性試験機(新東科学製)で評価した。
上記で得た測定用試料の皮膜部分における水の接触角を、接触角計(協和界面化学社製)で測定し、各ウェザーストリップ用材料を用いて形成した塗膜面の水の接触角とした。
上記で得た測定用試料の皮膜部分に対して、碁盤目セロハンテープ剥離試験による剥離試験を行って、各ウェザーストリップ用材料からなる塗膜面の接着性を、下記の基準で評価した。
○;良好(塗布面に剥離部分がない)
×;不良(塗布面に剥離部分がある)
上記で得た測定用試料の皮膜部分に、9.8Nの荷重を加えたガラス板を当接し、該ガラス板を往復運動させることによる塗膜の裂傷などが生じるまでの往復運動回数を、表面性試験機(新東科学製)で測定した。そして、得られた往復運動回数で、各ウェザーストリップ用材料からなる塗膜面の摩耗耐久性を評価した。
サンシャインカーボンアーク耐候試験機(スガ試験機)を用い、上記で得た測定用試料の皮膜部分に、パネル温度83℃で200時間照射後、その塗膜面の状態を目視で観察し、各ウェザーストリップ用材料からなる塗膜面の耐候性を、下記の基準で評価した。
3:表面状態変化なし。
2:表面状態少し変化あり。
1:大きな変化及び白化現象。
各ウェザーストリップ用材料(塗料)中の樹脂における二酸化炭素の固定化の有無によって、○×で評価した。
Claims (15)
- 5員環環状カーボネート化合物とアミン化合物との反応から誘導された、その構造中にマスキングされたイソシアネート基を有することを特徴とする自己架橋型ポリヒドロキシポリウレタン樹脂。
- 前記5員環環状カーボネート化合物が、エポキシ化合物と二酸化炭素との反応物であって、かつ、その構造中に二酸化炭素を1~25質量%の範囲で含んでなる請求項1に記載の自己架橋型ポリヒドロキシポリウレタン樹脂。
- 前記マスキングされたイソシアネート基は、有機ポリイソシアネート基とマスキング剤との反応生成物であって、熱処理することによりマスキングされた部分が解離されてイソシアネート基を生成し、その構造中の水酸基と反応して自己架橋するものである請求項1又は2に記載の自己架橋型ポリヒドロキシポリウレタン樹脂。
- 請求項1~3のいずれか1項に記載の自己架橋型ポリヒドロキシポリウレタン樹脂の製造方法であって、少なくとも一個の遊離のイソシアネート基と、マスキングされたイソシアネート基とを有する変性剤を用い、該変性剤の遊離のイソシアネート基を、5員環環状カーボネート化合物とアミン化合物との反応から誘導されたポリヒドロキシポリウレタン樹脂中の水酸基と反応させて、その構造中にマスキングされたイソシアネート基を有するポリヒドロキシポリウレタン樹脂を得ることを特徴とする自己架橋型ポリヒドロキシポリウレタン樹脂の製造方法。
- 前記5員環環状カーボネート化合物が、エポキシ化合物と二酸化炭素との反応物であって、かつ、該化合物とアミン化合物との反応から誘導されたポリヒドロキシポリウレタン樹脂中に二酸化炭素を1~25質量%の範囲で含む請求項4に記載の自己架橋型ポリヒドロキシポリウレタン樹脂の製造方法。
- 前記変性剤が、有機ポリイソシアネート化合物とマスキング剤との反応生成物である請求項4又は5に記載の自己架橋型ポリヒドロキシポリウレタン樹脂の製造方法。
- 請求項1~3のいずれか1項に記載の自己架橋型ポリヒドロキシポリウレタン樹脂に、他のバインダー樹脂を混合してなることを特徴とする樹脂材料。
- 請求項1~3のいずれか1項に記載の自己架橋型ポリヒドロキシポリウレタン樹脂を主成分とする樹脂組成物を、基布に充填或いは積層せしめたことを特徴とする擬革。
- 熱可塑性ポリオレフィン樹脂シートと、該シート上に直接又はプライマー層を介して形成されてなるトップコート層とを有してなり、かつ、該トップコート層が、請求項1~3のいずれか1項に記載の自己架橋型ポリヒドロキシポリウレタン樹脂を主成分としてなる樹脂組成物によって形成されたものであることを特徴とする熱可塑性ポリオレフィン樹脂製の表皮材。
- 前記自己架橋型ポリヒドロキシポリウレタン樹脂が、5員環環状カーボネート化合物とアミン化合物との反応から誘導されたポリヒドロキシポリウレタン樹脂を変性剤によって変性してなるものである請求項9に記載の熱可塑性ポリオレフィン樹脂製の表皮材。
- 前記トップコート層を形成する樹脂組成物が、自己架橋型ポリヒドロキシポリウレタン樹脂100質量部に対して、艶消剤として、有機系微粉末及び無機系微粉末から選ばれる一種又は二種以上の組み合わせからなる物質を1~150質量部の割合で配合してなる請求項9又は10に記載の熱可塑性ポリオレフィン樹脂製の表皮材。
- 高分子弾性体材料に被覆及び/又は含浸させて、他部品と摺接する摺接部に表面処理層を形成するためのウェザーストリップ用材料であって、請求項1~3のいずれか1項に記載の自己架橋型ポリヒドロキシポリウレタン樹脂と、平均重合度5,000~10,000のジオルガノポリシロキサン及び/又は動粘度が100~10,000CSのシリコーンオイルを含有してなる樹脂組成物であることを特徴とするウェザーストリップ用材料。
- 前記自己架橋型ポリヒドロキシポリウレタン樹脂が、5員環環状カーボネート化合物とアミン化合物との反応から誘導されたポリヒドロキシポリウレタン樹脂を変性剤によって変性してなるものである請求項12に記載のウェザーストリップ用材料。
- 前記樹脂組成物が、自己架橋型ポリヒドロキシポリウレタン樹脂100質量部に対して、平均重合度5,000~10,000のジオルガノポリシロキサン及び/又は動粘度が100~10,000CSのシリコーンオイルを1~100質量部の割合で配合してなる請求項12又は13に記載のウェザーストリップ用材料。
- 前記樹脂組成物が、自己架橋型ポリヒドロキシポリウレタン樹脂100質量部に対して、有機系微粉末及び無機系微粉末から選ばれる一種又は二種以上の組み合わせからなる添加剤が、1~150質量部の割合で配合されてなる請求項12~14のいずれか1項に記載のウェザーストリップ用材料。
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US8975420B2 (en) | 2009-11-25 | 2015-03-10 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Five-membered cyclocarbonate polysiloxane compound and process for preparation of same |
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WO2012137726A1 (ja) * | 2011-04-04 | 2012-10-11 | 大日精化工業株式会社 | 自己架橋型ポリシロキサン変性ポリヒドロキシポリウレタン樹脂、該樹脂の製造方法、該樹脂を含む樹脂材料および該樹脂を利用した擬革 |
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JP2014080713A (ja) * | 2012-09-27 | 2014-05-08 | Seiren Co Ltd | 合成皮革およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN102958978B (zh) | 2014-11-19 |
KR20130026488A (ko) | 2013-03-13 |
EP2586814A1 (en) | 2013-05-01 |
US20130095715A1 (en) | 2013-04-18 |
US10066048B2 (en) | 2018-09-04 |
KR101476559B1 (ko) | 2014-12-24 |
EP2586814B1 (en) | 2016-01-20 |
EP2586814A4 (en) | 2015-04-22 |
CN102958978A (zh) | 2013-03-06 |
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