Classifications

• • 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
• • 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
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
  • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
• • 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
  • C08G18/08—Processes
  • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
  • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
  • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
  • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
• • 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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
  • C08G18/348—Hydroxycarboxylic acids
• • 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
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
• • 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
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6633—Compounds of group C08G18/42
  • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
• • 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
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
• • 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
• • 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
  • C09D175/06—Polyurethanes from polyesters
• • 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
  • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
  • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
• • 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
  • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
  • D06N3/0065—Organic pigments, e.g. dyes, brighteners
• • 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

Definitions

• the present invention relates to a urethane resin composition and a laminate having a layer formed using the urethane resin composition.
• Urethane resin is widely used in the production of synthetic leather (including artificial leather), coating agents, adhesives, gloves, clothing, etc. due to its mechanical strength and good texture.
• solvent-based urethane resins containing N,N-dimethylformamide (DMF) have been the mainstream, but with DMF regulations in Europe, stricter VOC emission regulations in China and Taiwan, and major apparel manufacturers.
• urethane resin aqueous dispersions polyurethane dispersions
• the method for producing an aqueous urethane resin dispersion involves producing a urethane prepolymer having isocyanate groups in a solvent such as acetone or methyl ethyl ketone, then neutralizing it with amine, adding water to phase inversion emulsification, and elongating the chain.
• a manufacturing method is known which further includes a step of removing the solvent (for example, see Patent Document 1). Since such conventional methods use amines as neutralizing agents, off-odor caused by residual amines has often been a problem. This residual amine is also said to be the cause of urethane discoloration when used for a long period of time. Therefore, in order to solve the above problem, a method for producing an aqueous urethane resin dispersion in which only a nonionic component is dispersed without using a neutralized amine has been proposed (see, for example, Patent Document 2).
• the manufacturing method described in Patent Document 2 can solve the above-mentioned problems of off-odor and discoloration, and can also omit the solvent removal step. Moreover, the urethane resin aqueous dispersion obtained by the manufacturing method described in Patent Document 2 has good drying properties and can be formed into a film, so that thermal energy consumption during film formation can be suppressed.
• the production method described in Patent Document 2 above can solve the problems in the production method when using an amine as a neutralizing agent, and can also produce an aqueous urethane resin dispersion with a high resin solid content. Can be done.
• Patent Document 2 the manufacturing method described in Patent Document 2 can form a film without any problems when drying the urethane resin aqueous dispersion alone in terms of film-forming properties, but when the urethane resin aqueous dispersion is It was confirmed that film-forming properties were not good when other components such as colorants containing .
• a colorant or the like When attempting to form a film by adding a colorant or the like to the urethane resin aqueous dispersion obtained by the manufacturing method described in Patent Document 2, cracking and deterioration of mechanical properties such as tensile strength were occasionally observed.
• the present invention uses a urethane resin aqueous dispersion and a colorant that can form a film that does not cause problems with odor or discoloration, and does not cause cracks or deterioration of mechanical properties such as tensile strength when formed.
• An object of the present invention is to provide a urethane resin composition containing the following.
• the present inventors conducted intensive studies and found that, in a urethane resin composition containing an aqueous urethane resin dispersion and a colorant, the particle size of the aqueous urethane resin dispersion and the colorant.
• the inventors have discovered that the above-mentioned problems can be solved by using a urethane resin composition in which the ratio of the particle diameters of
• a urethane resin composition containing a urethane resin aqueous dispersion (A) having an oxyethylene structure and a colorant (B) containing a pigment,
• the particle diameter (D50) that gives a cumulative value of 50% in the volume frequency particle size distribution measurement of the urethane resin aqueous dispersion (A) and the cumulative value of 50% in the volume frequency particle size distribution measurement of the colorant (B).
• a urethane resin composition having a value of [D50 of (B)/D50 of (A)], which is a ratio with a particle diameter (D50), of 2/3 or less.
• the urethane resin aqueous dispersion (A) contains a urethane prepolymer (a1) having an isocyanate group which is a reaction product of a polyol, a polyisocyanate, and a compound having an oxyethylene structure, water (a2), and a chain.
• the urethane resin composition according to [1] which contains an extender (a3) as an essential raw material.
• the urethane resin composition according to [1] or [2], wherein the pigment is carbon black.
• the urethane resin composition according to [3], wherein the carbon black has a volatile content of 1% or more.
• the particle diameter (D50) that is 50% of the cumulative value in the volume frequency particle size distribution measurement of the colorant (B) is 180 nm or less, and the cumulative value in the volume frequency particle size distribution measurement of the colorant (B)
• the colorant (B) further contains a polymeric dispersant, and the polymeric dispersant has an acid value of 30 mgKOH/g or more and an amine value of 10 mgKOH/g or less, [1] ⁇
• the ratio of breaking strength (MD direction)/breaking strength (TD direction) of the film formed using the urethane resin composition is 1.6 or less, and the breaking elongation (MD direction)/breaking elongation
• a laminate comprising a fibrous base material and a skin layer formed from the urethane resin composition according to any one of [1] to [7] on at least one surface of the fibrous base material. .
• the laminate according to [8] further comprising a surface treatment layer using a surface treatment agent on the surface of the skin layer.
• the laminate according to [8] or [9] wherein the form of the fibrous base material is one selected from the group consisting of nonwoven fabric, knitted fabric, and woven fabric.
• a urethane resin aqueous dispersion and a colorant can be used to form a film that does not cause problems with odor or discoloration, and does not cause cracks or deterioration of mechanical properties such as tensile strength when formed.
• a urethane resin composition containing the following can be provided.
• the urethane resin composition of the present invention contains a urethane resin aqueous dispersion (A) and a colorant (B).
• the urethane resin aqueous dispersion (A) has an oxyethylene structure.
• the colorant (B) contains a pigment.
• the urethane resin composition of the present invention has a particle diameter (D50) that is 50% in cumulative value in the volume frequency particle size distribution measurement of the urethane resin aqueous dispersion (A) and a particle diameter (D50) that is 50% in the volume frequency particle size distribution measurement of the colorant (B).
• the value of [D50 of (B)/D50 of (A)], which is the ratio to the particle diameter (D50) that gives a cumulative value of 50%, is 2/3 or less.
• the urethane resin composition of the present invention can further contain other components such as a leveling agent and an antifoaming agent in addition to the urethane resin aqueous dispersion (A) and the colorant (B).
• the urethane resin aqueous dispersion (A) is an aqueous dispersion of urethane resin (X).
• the content of the urethane resin (X) in the aqueous dispersion is preferably in the range of 50 to 70% by mass.
• Urethane resin (X) is a general term for polymer compounds having a urethane bond (-NHCOO-), and is generally produced by reacting a polyol and a polyisocyanate (crosslinking/curing reaction).
• the urethane resin aqueous dispersion (A) used in the present invention has an oxyethylene structure.
• the urethane resin aqueous dispersion (A) has an isocyanate group-containing urethane prepolymer (a1), water (a2), and a chain extender (a3) as essential raw materials, and is formed using these essential raw materials. It is preferable that the The urethane prepolymer (a1) is preferably a reaction product of a polyol (a1-2), a polyisocyanate (a1-3), and a compound having an oxyethylene structure (a1-4).
• the content of the urethane resin (X) is preferably in the range of 50 to 70% by mass, as described above.
• the drying properties of the urethane resin water dispersion are improved due to the high so-called solid content in the water alone, so there are no cracks in the urethane resin film during and/or after drying, resulting in excellent film formation. You can get sex.
• the solid content is high, it is possible to reduce the amount of heat required during drying.
• the content of the urethane resin (X) is more preferably in the range of 52 to 68% by mass, and even more preferably in the range of 54 to 65% by mass, from the standpoint of obtaining even better film-forming properties.
• the urethane resin aqueous dispersion (A) can be produced, for example, by reacting a polyol (a1-2), a polyisocyanate (a1-3), and a compound (a1-4) having an oxyethylene structure to form a urethane resin having an isocyanate group. It can be produced through the steps of obtaining the polymer (a1), then dispersing the urethane prepolymer (a1) in water (a2), and then reacting with the chain extender (a3) to obtain the urethane resin (X). can.
• polyether polyol for example, polyether polyol, polyester polyol, polyacrylic polyol, polycarbonate polyol, polybutadiene polyol, etc. can be used. These polyols may be used alone or in combination of two or more.
• a material other than the raw material used as the compound having an oxyethylene structure (a1-4) described later is used.
• the number average molecular weight of the polyol (a1-2) is preferably in the range of 500 to 100,000, more preferably in the range of 800 to 10,000, from the viewpoint of the mechanical strength of the resulting film. .
• the number average molecular weight of polyol (a1-2) is a value measured by gel permeation column chromatography (GPC).
• the proportion of polyol (a1-2) to be used is more preferably in the range of 40 to 90% by mass, based on the total mass of the raw materials constituting the urethane resin (X), from the viewpoint of obtaining even better mechanical strength. A range of 80% by mass is more preferred.
• polyisocyanate (a1-3) examples include aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidated diphenylmethane polyisocyanate; hexamethylene diisocyanate; , lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, or other aliphatic polyisocyanates or alicyclic polyisocyanates can be aromatic polyisocyanates such as phenylene diisocyan
• the proportion of polyisocyanate (a1-3) used is more preferably in the range of 5 to 40% by mass based on the total mass of the raw materials constituting the urethane resin (X), from the viewpoint of obtaining even better mechanical strength. A range of 10 to 35% by mass is more preferred.
• Examples of the compound (a1-4) having an oxyethylene structure include polyether polyols having an oxyethylene structure such as polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, and polyethylene glycol dimethyl ether. Can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use polyethylene glycol and/or polyethylene glycol dimethyl ether because the hydrophilicity can be controlled more easily.
• the number average molecular weight of the compound (a1-4) having an oxyethylene structure is preferably in the range of 200 to 10,000 from the viewpoint of obtaining even better emulsifying properties and water dispersion stability.
• the range is more preferably from 300 to 3,000, and even more preferably from 300 to 2,000.
• the number average molecular weight of the compound (a1-4) having an oxyethylene structure is a value measured by gel permeation column chromatography (GPC).
• the proportion of the compound having an oxyethylene structure (a1-4) is determined from the viewpoint of obtaining even better emulsifying properties, water dispersion stability, and film-forming properties. It is preferably 5% by mass or less, more preferably 2% by mass or less, even more preferably 0.25 to 2% by mass, and particularly preferably 0.5 to 1.8% by mass based on the total mass.
• ion exchange water, distilled water, etc. can be used as the water used in the present invention. These waters may be used alone or in combination of two or more.
• chain extender (a3) those having a molecular weight of less than 500 (preferably in the range of 50 to 450) can be used, and specifically, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene Glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerin, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4 Chain extenders with hydroxyl groups such as '-dihydroxydiphenyl ether and trimethylolpropane; ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2- Cyclohexanediamine, 1,3-cyclohexanedia
• the chain extender (a3) has the following advantages: it can easily extend the chain even at a relatively low temperature of 30°C or less, it can suppress energy consumption during reaction, it has even better mechanical strength due to the introduction of a urea group, and From the viewpoint of obtaining film-forming properties, it is preferable to use a chain extender having an amino group (hereinafter abbreviated as "amine chain extender"), and even if the urethane resin (X) is highly solidified, It is more preferable to use an amine chain extender having a molecular weight in the range of 30 to 250, more preferably in the range of 40 to 250, in order to obtain even better emulsifying properties and water dispersion stability. In addition, when two or more types of chain extenders are used in combination, the above molecular weight indicates the average value, and the average value may be included in the above preferable molecular weight range.
• the proportion of the chain extender (a1) used is such that even better mechanical strength, film-forming properties, emulsifying properties, and water dispersion stability can be obtained, and that the urethane resin (X) can be more easily solidified. From this point of view, it is more preferably in the range of 0.1 to 30% by mass, particularly preferably in the range of 0.5 to 10% by mass, based on the total mass of the raw materials constituting the urethane resin (X).
• emulsifiers that can be used when dispersing a urethane prepolymer in water to obtain a urethane resin include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, and polyoxyethylene sorbitol tetra.
• Nonionic emulsifiers such as oleate and polyethylene/polypropylene copolymers; fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, Anionic emulsifiers such as alkanesulfonate sodium salts and alkyldiphenylethersulfonic acid sodium salts; cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts can be used. These emulsifiers may be used alone or in combination of two or more.
• urethane resin water dispersion (A) As a method for producing the urethane resin aqueous dispersion according to the present invention, for example, the above polyol (a1-2), the above polyisocyanate (a1-3), and the above oxyethylene group-containing compound (a1-4) are reacted. to obtain a urethane prepolymer (a1) having an isocyanate group (hereinafter abbreviated as "prepolymer step"), and then disperse the urethane prepolymer (a1) in the water (a2) (hereinafter “prepolymer step").
• prepolymer step a urethane prepolymer having an isocyanate group
• the urethane resin (X) is then reacted with the chain extender (a3) to obtain the urethane resin (X) (hereinafter abbreviated as the "chain extension step”).
• chain extension step A method for producing a urethane resin aqueous dispersion, which is an aqueous dispersion, is mentioned.
• the prepolymer step can be performed without a solvent.
• the prepolymer process was generally carried out in an organic solvent such as methyl ethyl ketone or acetone, but a desolvation process was required to distill off the organic solvent after the emulsification process, making it difficult to carry out at actual production sites. This would have required several days of production. Furthermore, it is difficult to completely distill off the organic solvent in the desolvation step, and in many cases a small amount of organic solvent remains, making it difficult to be completely environmentally friendly.
• the prepolymer step can be carried out without a solvent, thereby obtaining an aqueous urethane resin dispersion completely free of organic solvents, and
• the production process can also be labor-saving.
• the molar ratio of the sum of the hydroxyl groups possessed by the polyol (a1-2) and the hydroxyl groups possessed by the compound (a1-4) having an oxyethylene group and the isocyanate groups possessed by the polyisocyanate (a1-3) [Isocyanate group/hydroxyl group] is preferably in the range of 1.1 to 3, and more preferably in the range of 1.2 to 2, from the viewpoint of obtaining even better film forming properties and mechanical strength. preferable.
• the reaction in the prepolymer step may be carried out, for example, at 50 to 120°C for 1 to 10 hours.
• the prepolymer process is carried out using a reaction vessel equipped with stirring blades; a kneader, a continuous kneader, a tapered roll, a single screw extruder, a twin screw extruder, a triple screw extruder, a universal mixer, a plastomill, a bodeda type kneader, etc.
• Kneading machines Rotary dispersion mixers such as TK Homo Mixer, Filmix, Ebara Milder, Clearmix, Ultra Turrax, Cavitron, and Biomixer; Ultrasonic dispersion equipment; There are no moving parts such as in-line mixers, and the fluid itself This can be done by using a device that can mix by the flow of water.
• the emulsification step is preferably carried out at a temperature at which water does not evaporate, for example in the range of 10 to 90° C.
• the emulsification step can be carried out using the same equipment as the prepolymer step. Among them, it is possible to stably obtain an aqueous dispersion of urethane resin with a small amount of oxyethylene groups introduced, reacted with a chain extender, and having the same average particle size as the conventional method, and urethane resin It is preferable to use a kneader because a urethane resin aqueous dispersion with a high content can be easily obtained.
• the chain extension step is a step of increasing the molecular weight of the urethane prepolymer (a1) by reacting the isocyanate groups of the urethane prepolymer (a1) with the chain extender (a3) to obtain the urethane resin (X). .
• the temperature during the chain elongation step is preferably 50° C. or lower from the viewpoint of productivity.
• the molar ratio of the isocyanate groups possessed by the urethane prepolymer (a1) to the total of the hydroxyl groups and amino groups possessed by the chain extender (a3) [(hydroxyl groups and amino groups)/isocyanate groups] is more From the standpoint of obtaining even better film-forming properties and mechanical strength, the range is preferably from 0.8 to 1.1, more preferably from 0.9 to 1.
• the chain extension step can be performed using the same equipment as the prepolymer step.
• the particle diameter (D50) that is 50% in the cumulative value in the volume frequency particle size distribution measurement of the urethane resin aqueous dispersion (A) and 50% in the cumulative value in the volume frequency particle size distribution measurement of the colorant (B) is determined.
• a urethane resin composition is defined in which the value of [D50 of (B)/D50 of (A)], which is the ratio to the particle diameter (D50), is 2/3 or less.
• the ratio of the average particle diameter (D50) of the urethane resin aqueous dispersion (A) and the colorant (B) [D50 of (B)/D50 of (A)] is within the above range, the urethane resin and the colorant
• the difference in the particle size distribution of the colorant can be increased, and the particle size of the colorant can be decreased. This is preferable because it is considered that the generation of aggregates during film formation is suppressed and cracks are less likely to occur.
• D50 represents a particle diameter (average particle diameter) that gives a cumulative value of 50% in volume frequency particle size distribution measurement.
• the particle size (D50) of the urethane resin aqueous dispersion (A) is determined as follows (the measurement of the particle size (D50) of the colorant (B) will be described later).
• the particle diameter (D50) of the urethane resin aqueous dispersion (A) is preferably in the range of 10 to 1000 nm, more preferably in the range of 50 to 500 nm, from the standpoint of obtaining even better film forming properties.
• the molecular weight of the urethane resin (X) varies depending on the use and required performance, but may be appropriately selected in the number average molecular weight range of 5,000 to 50,000, preferably 5,000 to 15,000.
• the colorant (B) contains a pigment.
• the colorant (B) is not particularly limited in form as long as it contains a pigment, and the pigment alone may be used as the colorant, or the pigment may be used in combination with other components.
• the colorant (B) further contains a polymeric dispersant, and for example, it is more preferable that the pigment is a colorant whose surface is treated with a polymeric dispersant.
• Pigments included in the colorant include inorganic pigments and organic pigments.
• inorganic pigments it is more preferable to use carbon black.
• inorganic pigments other than carbon black include oxides, hydroxides, sulfides, ferrocyanides, chromates, carbonates, silicates, phosphates, and metal powders. It will be done.
• organic pigments include nitrosos, dyeing lakes, azo lakes, insoluble azos, monoazos, disazos, condensed azos, benzimidazolones, phthalocyanines, anthraquinones, perylenes, quinacridones, and dioxazines. , isoindolines, azomethines, pyrrolopyrroles, and the like. From the viewpoint of ensuring flexibility, pigments with small particle diameters are preferred.
• the pigment is carbon black, and in particular, it is more preferable that the volatile content of carbon black is 1% or more.
• the volatile content of carbon black is as high as in the above range, the amount of functional groups (OH and COOH) on the carbon black surface is large, which makes it easier to maintain compatibility with the urethane resin during film formation, and prevents particle aggregation. This is preferable because it is thought to be less likely to cause oxidation.
• the volatile content of carbon black refers to the volatile content (loss of weight) when heated at 950° C. for 7 minutes, for example, and this value can be known from a product catalog or the like.
• the colorant (B) can be prepared by mixing and dispersing a pigment and a polymeric dispersant in an aqueous medium.
• the polymeric dispersant is not particularly limited, but for example, a polymeric pigment dispersant described in JP-A No. 2022-75758 can be used. More specifically, for example, as the polymeric dispersant, those described below can be suitably used.
• a comb-shaped polymeric pigment dispersant having a pigment affinity group in the main chain and/or multiple side chains and having multiple side chains constituting a solvation moiety (2) Pigment in the main chain Polymer pigment dispersant having multiple pigment-affinity moieties consisting of affinity groups (3) Linear polymer pigment dispersant having a pigment-affinity moiety consisting of pigment-affinity groups at one end of the main chain
• the above-mentioned pigment affinity group refers to a functional group that has a strong adsorption force to the surface of a pigment.
• a tertiary amino group, a quaternary ammonium group, a basic nitrogen atom A heterocyclic group, a hydroxyl group, a carboxyl group;
• examples of the hydrosol include a phenyl group, a lauryl group, a stearyl group, a dodecyl group, an oleyl group, and the like.
• Each of the above-mentioned polymeric pigment dispersants may be used alone, or two or more types may be used in combination.
• polymeric dispersants the viewpoint of ensuring affinity between the pigment and urethane resin (X) in the dispersion when the urethane resin aqueous dispersion (A) and colorant (B) are mixed to form a paint. It is preferable to use a polymer dispersant having an acid value of 30 mgKOH/g or more and an amine value of 10 mgKOH/g or less.
• the particle diameter (D50) of the colorant (B) is determined as follows.
• the particle diameter (D50) of the colorant (B) is preferably 180 nm or less. Further, the particle diameter (D95) at which the cumulative value of the colorant (B) is 95% in volume frequency particle size distribution measurement is preferably 350 nm or less. It is more preferable that the particle size (D50) of the colorant (B) is 180 nm or less, and the particle size (D95) of the colorant (B) is 350 nm or less. When the 50% particle size (D50) and 95% particle size (D95) in the cumulative particle size distribution of the colorant (B) are within the above ranges, the particle size of the colorant can be prevented from becoming too large and the generation of aggregates can be prevented. can be suppressed.
• the amount of the colorant (B) in the urethane resin composition is within the range of 10 to 40 parts by mass based on 100 parts by mass of the resin solid content of the urethane resin (X) in the urethane resin aqueous dispersion (A). It is preferably within the range of 10 to 20 parts by mass, and more preferably within the range of 10 to 20 parts by mass.
• the amount of the colorant (B) is below the above upper limit, it is possible to effectively prevent problems such as deterioration of coating film strength and generation of cracks due to an increase in particles in the coating film.
• the amount of the colorant (B) is equal to or more than the above lower limit value, it is possible to effectively prevent the problem that the color development and hiding properties of the coating film deteriorate.
• the urethane resin composition of the present invention may be leveled, if necessary, within a range that does not impair the physical properties of the polyurethane resin obtained by curing.
• Other components such as antifoaming agents, antifoaming agents, and thickening agents may also be contained.
• additives examples include emulsifiers, neutralizers, thickeners, urethanization catalysts, fillers, flame retardants, leveling agents, antiblocking agents, film forming aids, antifoaming agents, foaming agents, etc. be able to. These additives may be used alone or in combination of two or more.
• the urethane resin composition of the present invention can be used, for example, as a coating agent for fibrous base materials.
• the coating agent is an agent that forms a film on the surface of a base material, and includes the concept of a surface treatment agent.
• the layer made of the urethane resin composition can be formed not only as a skin layer but also as an adhesive layer or an intermediate layer. It is also possible to further form a surface treatment layer using a surface treatment agent on the surface of the layer formed by the urethane resin composition to obtain a laminate having a skin layer and a surface treatment layer on the surface of the fibrous base material. .
• a film formed using a urethane resin composition does not cause problems with odor or discoloration, and does not cause cracking or deterioration of mechanical properties such as tensile strength. It also shows good results when evaluating mechanical properties such as breaking strength and breaking elongation.
• a film formed using the urethane resin composition of the present invention exhibits a ratio of breaking strength (MD direction)/breaking strength (TD direction) of 1.6 or less, and/or a breaking elongation (MD direction) of 1.6 or less. )/Elongation at break (TD direction) ratio of 1.2 or less.
• the laminate of the present invention has a layer formed using the urethane resin composition of the present invention.
• a layer formed using the urethane resin composition of the present invention can be suitably used as a skin layer of a fibrous base material.
• it can also be suitably used as an adhesive layer, an intermediate layer, or a surface treatment layer on the surface of the skin layer.
• a surface treatment layer using a surface treatment agent may be further formed on the surface of the skin layer formed using the urethane resin composition of the present invention.
• fibrous base materials include natural fibers (vegetable fibers and animal fibers) such as cotton, linen, and silk; chemical fibers such as polyester, nylon, acrylic, and polyurethane. Can be mentioned.
• Examples of the form of the fibrous base material include knitted fabrics, woven fabrics, nonwoven fabrics, and the like.
• articles having a laminate according to the present invention include synthetic leather, artificial leather, natural leather, automobile interior seats using polyvinyl chloride (PVC) leather, sports shoes, clothing, furniture, thermoplastic olefin ( TPO) leather, dashboards, instrument panels, etc.
• PVC polyvinyl chloride
• TPO thermoplastic olefin
• the laminate in the present invention can be manufactured by a known dry film forming method or wet film forming method.
• examples of the dry film forming method include the following method.
• the adhesive layer resin composition is applied onto the dried coating film of the skin layer using a doctor knife, and then pre-dried. Furthermore, after bonding with a nonwoven fabric, it is dried. Thereafter, after aging, the release paper is peeled off to obtain a laminate.
• a wet film forming method After applying a urethane resin composition containing an organic solvent to a base material, by immersing it in water, the solvent in the urethane resin composition is replaced with water, and the solids in the urethane resin composition are precipitated. To form a film. Next, the residual solvent is thoroughly washed away with water, squeezed with a mangle roll or the like, and then dried to obtain a laminate.
• a wet film forming aid may be appropriately added to the urethane resin composition of the present invention in order to adjust the film forming rate and to obtain good surface smoothness.
• wet film forming aids include castor oil, glycerin tripalmitate, silicone oil, and the like. These wet film forming aids can be used alone or in combination of two or more.
• the thickness of the layer made of the urethane resin composition is preferably in the range of 0.1 to 100 ⁇ m, for example.
• surfactant Floren GW-1500 (manufactured by Kyoeisha Chemical, polymer dispersant with high affinity for pigments, solid content 100%)
• Leveling agent BYK-348 (manufactured by BYK, polyether modified polydimethylsiloxane, non-volatile content: >90%)
• antifoaming agent TEGO Foamex 800 (manufactured by EVONIK, polyether siloxane copolymer, non-volatile content 25%)
• thicker Borchi Gel L75N, manufactured by Borchers, 50% solids
• D50 of the urethane resin aqueous dispersion (A) was measured as follows. 1 g of urethane resin aqueous dispersion was diluted with 50 g of water, pretreated with an ultrasonic homogenizer (Nippon Seiki ULTRA HOMOGENIZER US-300E) at 2.5 A for 1 minute, and then subjected to dynamic Particle size distribution was measured using a light scattering device Nanotrac Wave II manufactured by Microtrac Bell Co., Ltd. The results are shown in Tables 1-1 and 1-2 below.
• a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.
• 51 parts by mass of triethylamine was added to the methyl ethyl ketone solution of the urethane prepolymer obtained by the above method to neutralize the carboxyl groups in the urethane prepolymer, and then 1555 parts by mass of ion-exchanged water was added, and then 128 parts by mass of isophorone diamine was added. Parts by mass were added and reacted.
• urethane resin aqueous dispersion (A').
• D50 of the urethane resin aqueous dispersion (A') was measured as follows. 1 g of urethane resin aqueous dispersion was diluted with 50 g of water, pretreated with an ultrasonic homogenizer (Nippon Seiki ULTRA HOMOGENIZER US-300E) at 2.5 A for 1 minute, and then subjected to dynamic Particle size distribution was measured using a light scattering device Nanotrac Wave II manufactured by Microtrac Bell Co., Ltd. The results are shown in Tables 1-1 and 1-2 below.
• Example 1 10 g (10 parts by mass) of the aqueous colorant (B-1) was added to 100 g (100 parts by mass) of the urethane resin aqueous dispersion (A) while stirring with a homodisper. Subsequently, 0.1 g of a leveling agent and 0.1 g of an antifoaming agent were added, and a thickener was added so that the viscosity was about 3,000 mPa ⁇ s. Thereafter, the mixture was stirred for 10 minutes to prepare aqueous skin layer resin composition 1 (in the table, "aqueous skin layer resin composition" is also referred to as "aqueous skin layer paint").
• release paper EK-100D manufactured by Lintec Corporation
• Aqueous skin layer resin composition 1 was coated on release paper (“EK-100D” manufactured by Lintec Corporation) using a knife coater to a thickness of 150 ⁇ m, and then heated in a hot air dryer (70°C x 2). minutes ⁇ 120°C x 2 minutes) and evaluated as follows.
• ⁇ A film with dry water was obtained, and there were no cracks in the film.
• ⁇ Water is not dry and/or cracks are observed in the film.
• Aqueous skin layer resin composition 1 was coated on release paper (“EK-100D” manufactured by Lintec Corporation) using a knife coater to a thickness of 150 ⁇ m, and then dried using a hot air dryer. (70°C x 2 minutes ⁇ 120°C x 2 minutes).
• a water-based paint for adhesive layer was applied onto the dried coating film using a knife coater to a thickness of 150 ⁇ m, and dried using a hot air dryer (90 to 100° C. x 3 minutes).
• synthetic leather was produced by bonding the coated surface of the dried coating film to the nonwoven fabric using a hot roll press set at 100 to 130°C.
• the obtained synthetic leather was subjected to a flexibility test (-10°C, 100 times/min) using a flexometer (“Low Temperature Flexiometer” manufactured by Yasuda Seiki Seisakusho Co., Ltd.), and cracks were detected on the surface of the synthetic leather. The number of times until this occurred was measured and evaluated as follows. A: 30,000 times or more B: 10,000 times or more but less than 30,000 times C: Less than 10,000 times
• ⁇ Odor>> A synthetic leather similar to that described in the section of ⁇ Flexibility>> above was produced.
• the obtained synthetic leather was cut to a size of 200 ⁇ 20 cm 2 , placed in a 1 L glass beaker, heated at 80 ⁇ 2°C for 2 hours, then cooled to 60 ⁇ 5°C, and processed according to the following standards. The odor was determined. A minimum of three judges were selected, and if there was a difference of one grade or more between the scores of each judge, the test was re-tested with at least five judges. If the result is grade 3 or lower, it is considered that there is no problem in practical use.
• Examples 2-3 Aqueous skin layer resin compositions 2 and 3 were obtained in the same manner as in Example 1, except that the ingredients were changed as shown in Table 1-1 below.
• the aqueous skin layer resin composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1-1.
• Aqueous skin layer resin compositions 4 to 9 were obtained in the same manner as in Example 1, except that the ingredients were changed as shown in Table 1-2 below.
• the aqueous skin layer resin composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1-2.
• the urethane resin composition of the present invention containing an aqueous urethane resin dispersion and a colorant does not crack during coating film formation and forms a coating film with high strength in both the MD and TD directions. It was found that synthetic leather with good flexibility can be produced. Furthermore, the synthetic leather sheet using the urethane resin composition of the present invention did not have any unusual odor (amine odor).

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• 2023
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