WO2018110105A1 - 水性ウレタン樹脂組成物、及び、合成皮革 - Google Patents
水性ウレタン樹脂組成物、及び、合成皮革 Download PDFInfo
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- WO2018110105A1 WO2018110105A1 PCT/JP2017/038610 JP2017038610W WO2018110105A1 WO 2018110105 A1 WO2018110105 A1 WO 2018110105A1 JP 2017038610 W JP2017038610 W JP 2017038610W WO 2018110105 A1 WO2018110105 A1 WO 2018110105A1
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- urethane resin
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- resin composition
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- synthetic leather
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- 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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- 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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- 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
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
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- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- 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
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
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- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—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
Definitions
- the present invention relates to an aqueous urethane resin composition in which a urethane resin is dispersed in an aqueous medium.
- Polyurethane resin is widely used for the production of synthetic leather (including artificial leather) because of its mechanical strength and good texture.
- a solvent-based urethane resin containing N, N-dimethylformamide (DMF) has been mainly used so far.
- DMF N, N-dimethylformamide
- Patent Document 1 water-based urethane resin compositions in which a urethane resin is dispersed in water have been widely studied (for example, see Patent Document 1).
- Patent Document 1 As the skin layer of the synthetic leather, although the replacement from the solvent system to the water system is gradually increasing in the market, the water system of the urethane resin for the intermediate layer is still advanced. Not. This is mainly because the peel strength of the aqueous urethane resin is insufficient compared to the solvent-based urethane resin.
- the problem to be solved by the present invention is to provide an aqueous urethane resin composition excellent in peel strength, hydrolysis resistance, and light resistance.
- the present invention is a reaction product of a polyol (a1) containing a polyol (a1-1) having an anionic group and an aromatic polyisocyanate (a2), and the concentration of the anionic group is 0.35 mmol / g or less.
- An aqueous urethane resin composition containing a urethane resin (A) and an aqueous medium (B) is provided.
- the present invention is a synthetic leather in which at least a base fabric (i), an adhesive layer (ii), and an outer skin layer (iii) are laminated, wherein the adhesive layer (ii) is as defined in claims 1 to 4.
- a synthetic leather characterized in that it is formed of any one of the water-based urethane resin compositions described in any one of the above items.
- the aqueous urethane resin composition of the present invention is excellent in peel strength, hydrolysis resistance, and light resistance.
- the aqueous urethane resin composition of the present invention can be suitably used for the production of synthetic leather, and in particular, can be suitably used as a resin for forming an intermediate layer of synthetic leather. Therefore, it can be used for applications requiring high durability such as automobile interior materials, furniture, and sports shoes, which have been difficult to replace from solvent to water.
- the aqueous urethane resin composition of the present invention is a reaction product of a polyol (a1) containing a polyol (a1-1) having an anionic group and an aromatic polyisocyanate (a2), and the concentration of the anionic group is 0.00. It contains a urethane resin (A) that is 35 mmol / g or less and an aqueous medium (B).
- the polyol (a1-1) having an anionic group is a raw material for obtaining an anionic urethane resin.
- 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2- A polyol having a carboxyl group such as dimethylolbutyric acid or 2,2-valeric acid; a polyol having a sulfonyl group such as 3,4-dimethylolbutanesulfonic acid or 3,6-dimethylol-2-toluenesulfonic acid may be used. It can. These compounds may be used alone or in combination of two or more.
- the concentration of the anionic group of the polyurethane resin (A) can be easily adjusted within the range described in the present invention, and more excellent hydrolysis resistance can be obtained.
- the polyol (a1) preferably has a range of 0.05 to 10% by mass, more preferably 0.1 to 6.2% by mass, still more preferably 0.5 to 3% by mass. A range of ⁇ 2.7% by weight is particularly preferred.
- polystyrene resin examples include polyether polyol, polyester polyol, polycarbonate polyol, dimer diol, acrylic polyol, polybutadiene polyol, and the like. . These polyols may be used alone or in combination of two or more. Among these, it is preferable to use polyether polyol and / or polycarbonate polyol from the point that hydrolysis resistance can be further improved.
- the number average molecular weight of the polyol (a1) is preferably in the range of 500 to 10,000, and more preferably in the range of 800 to 10,000, from the viewpoints of obtaining more excellent peel strength, mechanical strength of the film, and hydrolysis resistance. A range of 5,000 is more preferred.
- the number average molecular weight of the said polyol (a1) shows the value measured by the gel permeation column chromatography (GPC) method.
- the polyol may be used in combination with a chain extender (having no carboxyl group) as necessary.
- a chain extender for example, a chain extender having a hydroxyl group, a chain extender having an amino group, or the like can be used. These may be used alone or in combination of two or more. Among these, it is preferable to use a chain extender having a hydroxyl group from the viewpoint that much more excellent light resistance can be obtained.
- chain extender having a hydroxyl group examples include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Aliphatic polyol compounds such as sucrose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc. Aromatic polyol compounds; water and the like can be used. These chain extenders may be used alone or in combination of two or more. Among these, it is preferable to use an aliphatic polyol compound from the viewpoint that discoloration can be easily suppressed and further excellent light resistance can be obtained.
- chain extender having an amino group examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4. '-Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, etc. Can be used. These chain extenders may be used alone or in combination of two or more.
- the amount used in the case of using the chain extender (a3) is 0.5 to 40% by mass in the total mass of the core material constituting the urethane resin (A) from the viewpoint that the durability of the film can be further improved.
- the range is preferable, and the range of 1 to 20% by mass is more preferable.
- the aromatic polyisocyanate (a2) has a strong intermolecular force and is an essential component for obtaining an excellent peel strength due to the packing effect.
- Examples of the aromatic polyisocyanate (a2) include phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, and the like. These aromatic polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use toluene diisocyanate from the viewpoint that the crystallinity is moderately weak and further excellent peel strength can be obtained.
- the amount used in the case of using toluene diisocyanate as the aromatic polyisocyanate (a2) it is preferably 50% by mass or more in the aromatic polyisocyanate (a2) from the viewpoint that a further excellent peel strength can be obtained. 70 mass% or more is more preferable.
- an aliphatic or alicyclic polyisocyanate may be used in combination as long as the effects of the present invention are not hindered.
- aliphatic or alicyclic polyisocyanate examples include fats such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate.
- Aliphatic or alicyclic polyisocyanates can be used. These polyisocyanates may be used alone or in combination of two or more.
- Examples of the method for producing the urethane resin (A) include a method in which the polyol (a1), the aromatic polyisocyanate (a2) and, if necessary, the chain extender (a3) are charged and reacted together. Can be mentioned. These reactions include, for example, a method in which the reaction is performed at a temperature of 50 to 100 ° C. for 3 to 10 hours.
- the molar ratio of the total hydroxyl group and / or amino group of the polyol and the isocyanate group of the aromatic polyisocyanate (a2) [(isocyanate Group) / (total of hydroxyl group and amino group)] is preferably in the range of 0.8 to 1.2, more preferably in the range of 0.9 to 1.1.
- the urethane resin (A) When producing the urethane resin (A), it is preferable to deactivate the isocyanate group remaining in the urethane resin (A). When deactivating the isocyanate group, it is preferable to use an alcohol having a hydroxyl group such as methanol. The amount of alcohol used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A).
- an organic solvent may be used.
- the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetate compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; dimethylformamide and N-methylpyrrolidone Amide compounds and the like can be used.
- These organic solvents may be used alone or in combination of two or more. The organic solvent is preferably removed by a distillation method or the like when obtaining an aqueous urethane resin composition.
- the urethane resin (A) obtained by the above method must have an anionic group concentration of 0.35 mmol / g or less. By being in this range, it is possible to prevent poor hydrolysis resistance derived from the hydrophilic group while maintaining the water dispersibility and peel strength of the urethane resin (A).
- the concentration of the anionic group of the urethane resin (A) is preferably 0.25 mmol / g or less from the viewpoint of obtaining further excellent hydrolysis resistance, and is 0.05 to 0.22 mmol / kg. The range of is more preferable.
- the concentration of the anionic group of the urethane resin (A) is determined by the number of moles of the anionic group derived from the polyol (a1-1) having the anionic group as the total of each raw material constituting the urethane resin (A). The value divided by mass is shown.
- the concentration of the aromatic ring of the urethane resin (A) is preferably in the range of 0.1 to 2.5 mmol / kg from the viewpoint of obtaining even better peel strength. A range of 0.0 mmol / kg is more preferable.
- the molecular weight of benzene or naphthalene having no substituent is used as the molecular weight of the aromatic ring.
- the weight average molecular weight of the urethane resin (A) is preferably in the range of 2,000 to 150,000, more preferably in the range of 4,000 to 100,000, from the viewpoint of obtaining even better peel strength. More preferably, the range of 6,000 to 70,000 is still more preferable, and the range of 13,000 to 70,000 is particularly preferable. In addition, the weight average molecular weight of the said urethane resin (A) shows the value obtained by measuring similarly to the number average molecular weight of the said polyol (a1).
- aqueous medium (B) for example, water, an organic solvent miscible with water, a mixture thereof, or the like can be used.
- organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n- and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycol solvents such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ether solvents: lactam solvents such as N-methyl-2-pyrrolidone and the like can be used.
- These aqueous media may be used alone or in combination of two or more.
- the content of the aqueous medium (B) is preferably in the range of 20 to 90% by mass in the aqueous urethane resin composition from the viewpoint of workability, coating property, and storage stability, and preferably 40 to 80% by mass. % Range is more preferred.
- the aqueous urethane resin composition used in the present invention contains the urethane resin (A) and the aqueous medium (B) as essential components, but may contain other additives as necessary.
- Examples of the other additives include a urethanization catalyst, a neutralizing agent, a crosslinking agent, a silane coupling agent, a thickening agent, a filler, a thixotropic agent, a tackifier, a wax, a heat stabilizer, and a light resistance stabilizer.
- Fluorescent whitening agent, foaming agent, pigment, dye, conductivity imparting agent, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam, flame retardant, water absorbent, moisture absorbent, deodorant , Foam stabilizers, antiblocking agents, hydrolysis inhibitors, and the like can be used. These additives may be used alone or in combination of two or more.
- the aqueous urethane resin composition of the present invention is excellent in peel strength, hydrolysis resistance, and light resistance. Therefore, the water-based urethane resin of the present invention can be suitably used for the production of synthetic leather, and can be particularly suitably used as a resin for forming an intermediate layer of synthetic leather. Therefore, it can be used for applications requiring high durability such as automobile interior materials, furniture, and sports shoes, which have been difficult to replace from solvent to water.
- the synthetic leather has at least a base fabric (i), an adhesive layer (ii), and a skin layer (iii).
- Specific examples include the following configurations. (1) Base fabric (i), adhesive layer (ii), skin layer (iii) (2) Base fabric (i), adhesive layer (ii), intermediate layer, skin layer (iii) (3) Base fabric (i), wet porous layer, adhesive layer (ii), skin layer (iii) (4) Base fabric (i), wet porous layer, adhesive layer (ii), intermediate layer, skin layer (iii)
- Examples of the base fabric include polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, glass fiber, carbon fiber, and a blend thereof.
- Nonwoven fabrics, woven fabrics, knitted fabrics, and the like made of fibers can be used.
- wet porous layer one formed by a known wet film forming method using a solvent-based urethane resin composition can be used.
- Examples of the material for forming the intermediate layer and the skin layer (iii) include known water-based urethane resins, solvent-based urethane resins, solvent-free urethane resins, water-based acrylic resins, silicone resins, polypropylene resins, and polyester resins. Can be used. These resins may be used alone or in combination of two or more.
- a skin layer-forming resin is applied to a release-treated substrate, dried and processed to obtain a skin layer (iii), and then this skin
- the adhesive layer (ii) may be formed by coating the water-based urethane resin composition of the present invention on the skin layer (iii), bonding it to the base fabric (i), and drying it.
- Examples of the method for applying the aqueous urethane resin of the present invention include a method using an applicator, a roll coater, a spray coater, a T-die coater, a knife coater, a comma coater and the like.
- Examples of the method for drying the water-based urethane resin composition include a method of performing the treatment at 40 to 130 ° C. for 1 to 10 minutes.
- the thickness of the intermediate layer (ii) to be obtained is appropriately determined depending on the use for which the synthetic leather is used, and is in the range of 0.5 to 100 ⁇ m, for example.
- the synthetic leather After the synthetic leather is produced, it may be aged at 30 to 100 ° C. for 1 to 10 days, if necessary.
- Example 1 ⁇ Preparation of aqueous urethane resin composition>
- PTMG1000 polytetramethylene glycol (number average molecular weight: 1,000, hereinafter abbreviated as “PTMG1000”) 500 mass in a nitrogen stream.
- DMPA 2,2-dimethylolpropionic acid
- TDI toluene diisocyanate
- 1,3-BG 1,3-butanediol
- aqueous urethane resin composition (nonvolatile content: 40% by mass, concentration of anionic group (carboxyl group, the same shall apply hereinafter); 0.17 mmol / g).
- Example 2 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, polycarbonate diol ("DURANOL T5652" number average molecular weight: 2,000, hereinafter "PC", manufactured by Asahi Kasei Chemicals Corporation) under a nitrogen stream. 500 parts by mass, DMPA 8 parts by mass, methyl ethyl ketone 394 parts by mass, mixed uniformly, then TDI 68 parts by mass, then dibutyltin dilaurate 0.1 parts by mass, and 70 ° C. for about 4 hours Reacted. Next, 14 parts by mass of 1,3-BG was added and reacted at 70 ° C.
- PC polycarbonate diol
- Example 3 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 500 parts by mass of polypropylene glycol (number average molecular weight: 2,000, hereinafter abbreviated as “PPG2000”) under nitrogen flow. Add 9 parts by weight of 1,4-butanediol (hereinafter abbreviated as “1,4-BG”), 10 parts by weight of DMPA, and 400 parts by weight of methyl ethyl ketone, mix uniformly, add 78 parts by weight of TDI, and then add dibutyltin. 0.1 part by mass of dilaurate was added and reacted at 70 ° C.
- PPG2000 polypropylene glycol
- 1,4-BG 1,4-butanediol
- Example 4 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 500 parts by mass of polytetramethylene glycol (number average molecular weight: 2,000, hereinafter referred to as “PTMG2000”), ethylene glycol under a nitrogen stream (Hereinafter abbreviated as “EG”) 3 parts by mass, 12 parts by mass of DMPA and 403 parts by mass of methyl ethyl ketone were added and mixed uniformly, then 79 parts by mass of TDI was added, and then 0.1 part by mass of dibutyltin dilaurate was added. The reaction was carried out at about 4 hours for about 4 hours.
- PTMG2000 polytetramethylene glycol
- EG ethylene glycol under a nitrogen stream
- Example 5 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube, 500 parts by mass of PTMG2000, polyester polyol (reaction product of 1,4-butanediol and adipic acid, Average molecular weight: 1,000, hereinafter abbreviated as “PEs”) 50 parts by mass, trimethylolpropane (hereinafter abbreviated as “TMP”) 0.2 parts by mass, DPMA 10 parts by mass, methyl ethyl ketone 435 parts by mass, After mixing uniformly, 79 parts by mass of TDI was added, then 0.1 part by mass of dibutyltin dilaurate was added, and the mixture was reacted at 70 ° C.
- PEs polyester polyol (reaction product of 1,4-butanediol and adipic acid, Average molecular weight: 1,000, hereinafter abbreviated as “PEs”) 50 parts by mass, trimethyl
- Example 6 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 500 parts by mass of polypropylene glycol (number average molecular weight: 1,000, hereinafter abbreviated as “PPG1000”) in a nitrogen stream, After 18 parts by weight of DMPA and 472 parts by weight of methyl ethyl ketone were added and mixed uniformly, 115 parts by weight of TDI and 41 parts by weight of 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”) were added, followed by dibutyltin dilaurate.
- PPG1000 number average molecular weight: 1,000, hereinafter abbreviated as “PPG1000”
- Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
- Examples 1 to 8 which are synthetic leathers using the aqueous urethane resin composition of the present invention, are excellent in peel strength, hydrolysis resistance, and light resistance.
- Comparative Example 1 was an embodiment using alicyclic polyisocyanate instead of aromatic polyisocyanate (a2), but the peel strength was poor.
- Comparative Example 2 was an embodiment in which the concentration of the anionic group of the urethane resin (A) exceeded the range specified in the present invention, but the hydrolysis resistance was poor.
Abstract
Description
(1)基布(i)、接着層(ii)、表皮層(iii)
(2)基布(i)、接着層(ii)、中間層、表皮層(iii)
(3)基布(i)、湿式多孔層、接着層(ii)、表皮層(iii)
(4)基布(i)、湿式多孔層、接着層(ii)、中間層、表皮層(iii)
<水性ウレタン樹脂組成物の調製>
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、ポリテトラメチレングリコール(数平均分子量:1,000、以下「PTMG1000」と略記する。)500質量部、2,2-ジメチロールプロピオン酸(以下「DMPA」と略記する。)15質量部、メチルエチルケトン428質量部を加え、均一に混合した後、トルエンジイソシアネート(以下「TDI」と略記する。)117質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-ブタンジオール(以下「1,3-BG」と略記する。)を11質量部加え、70℃で約1時間反応させて反応を終了させ、ウレタンポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にN,N-ジメチルエタノールアミン10質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水964質量部を加えた後、メチルエチルケトンを減圧下留去することによって、水性ウレタン樹脂組成物(不揮発分;40質量%、アニオン性基(カルボキシル基、以下同じ。)の濃度;0.17mmol/g)を得た。
表皮層用の水性ウレタン樹脂組成物(DIC株式会社製「ハイドランWLS-210」)を100質量部、水分散性黒色顔料(DIC株式会社製「ダイラックHS-9530」)を10質量部、会合型増粘剤(DIC株式会社製「ハイドラン アシスター T10」)を1質量部からなる配合液をフラット離型紙(味の素株式会社製「DN-TP-155T」)上に乾燥後の膜厚が30μmとなる様に塗布し、70℃で2分間、さらに120℃で2分間乾燥させた。次いで、前記調整例にて得られた水性ウレタン樹脂組成物を100質量部、会合型増粘剤(DIC株式会社製「ハイドラン アシスター T10」)を1質量部、ポリイソシアネート系架橋剤(DIC株式会社製「ハイドラン アシスター C5」)を9質量部からなる配合液を乾燥後の膜厚が50μmとなるように塗布し、70℃で3分間乾燥させた。乾燥後直ちにT/R起毛布を貼り合わせた後、120℃で2分間熱処理し、50℃で2日間熟成させてから離型紙を剥離して合成皮革を得た。
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、ポリカーボネートジオール(旭化成ケミカルズ株式会社製「DURANOL T5652」数平均分子量:2,000、以下「PC」と略記する。)500質量部、DMPA8質量部、メチルエチルケトン394質量部を加え、均一に混合した後、TDI68質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-BGを14質量部加え、70℃で約1時間反応させて反応を終了させ、ウレタンポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にトリエチルアミン6質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水886質量部を加えた後、メチルエチルケトンを減圧下留去することによって、水性ウレタン樹脂組成物(不揮発分;40質量%、アニオン性基の濃度;0.11mmol/g)を得た。これを用いて実施例1と同様に合成皮革を得た。
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、ポリプロピレングリコール(数平均分子量:2,000、以下「PPG2000」と略記する。)500質量部、1,4-ブタンジオール(以下「1,4-BG」と略記する。)9質量部、DMPA10質量部、メチルエチルケトン400質量部を加え、均一に混合した後、TDI78質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-BGを4質量部加え、70℃で約1時間反応させて反応を終了させ、ウレタンポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にN,N-ジメチルエタノールアミン7質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水901質量部を加えた後、メチルエチルケトンを減圧下留去することによって、水性ウレタン樹脂組成物(不揮発分;40質量%、アニオン性基の濃度;0.13mmol/g)を得た。これを用いて実施例1と同様に合成皮革を得た。
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、ポリテトラメチレングリコール(数平均分子量:2,000、以下「PTMG2000」)500質量部、エチレングリコール(以下「EG」と略記する。)3質量部、DMPA12質量部、メチルエチルケトン403質量部を加え、均一に混合した後、TDI79質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-BGを11質量部加え、70℃で約1時間反応させて反応を終了させ、ウレタンポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にトリエチルアミン9質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水907質量部を加えた後、メチルエチルケトンを減圧下留去することによって、水性ウレタン樹脂組成物(不揮発分;40質量%、アニオン性基の濃度;0.15mmol/g)を得た。これを用いて実施例1と同様に合成皮革を得た。
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、PTMG2000を500質量部、ポリエステルポリオール(1,4-ブタンジオールとアジピン酸との反応物、数平均分子量:1,000、以下「PEs」と略記する。)50質量部、トリメチロールプロパン(以下「TMP」と略記する。)0.2質量部、DPMA10質量部、メチルエチルケトン435質量部を加え、均一に混合した後、TDI79質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-BGを14質量部加え、70℃で約1時間反応させて反応を終了させ、ウレタンポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にN,N-ジメチルエタノールアミン7質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水979質量部を加えた後、メチルエチルケトンを減圧下留去することによって、水性ウレタン樹脂組成物(不揮発分;40質量%、アニオン性基の濃度;0.12mmol/g)を得た。これを用いて実施例1と同様に合成皮革を得た。
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、ポリプロピレングリコール(数平均分子量:1,000、以下「PPG1000」と略記する。)500質量部、DMPA18質量部、メチルエチルケトン472質量部を加え、均一に混合した後、TDIを115質量部、4,4‘-ジフェニルメタンジイソシアネート(以下「MDI」と略記する。)41質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-ブタンジオールを34質量部加え、70℃で約1時間反応させて反応を終了させ、ウレタンポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にトリエチルアミン14質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水1063質量部を加えた後、メチルエチルケトンを減圧下留去することによって、水性ウレタン樹脂組成物(不揮発分;40質量%、アニオン性基の濃度;0.19mmol/g)を得た。これを用いて実施例1と同様に合成皮革を得た。
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、PTMG1000を500質量部、DMPA15質量部、メチルエチルケトン450質量部を加え、均一に混合した後、イソホロンジイソシアネート(以下「IPDI」と略記する。)149質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-BGを11質量部加え、70℃で約1時間反応させて反応を終了させ、ウレタンポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にN,N-ジメチルエタノールアミン10質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水1012質量部を加えた後、メチルエチルケトンを減圧下留去することによって、水性ウレタン樹脂組成物(不揮発分;40質量%、アニオン性基の濃度;0.16mmol/g)を得た。これを用いて実施例1と同様に合成皮革を得た。
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4ツ口フラスコに、窒素気流下、PTMG1000を500質量部、DMPA34質量部、メチルエチルケトン460質量部を加え、均一に混合した後、TDIを144質量部を加え、次いでジブチル錫ジラウレート0.1質量部を加え、70℃で約4時間反応させた。次いで、1,3-BGを14質量部加え、70℃で約1時間反応させて反応を終了させ、ウレタンポリマーのメチルエチルケトン溶液を得た。次いで、前記方法で得られたウレタンポリマーのメチルエチルケトン溶液にN,N-ジメチルエタノールアミン22質量部を加え、前記ウレタンポリマー中のカルボキシル基を中和した後、イオン交換水1036質量部を加えた後、メチルエチルケトンを減圧下留去することによって、水性ウレタン樹脂組成物(不揮発分;40質量%、アニオン性基の濃度;0.36mmol/g)を得た。これを用いて実施例1と同様に合成皮革を得た。
実施例及び比較例で用いたポリオール等の数平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー(GPC)法により、下記の条件で測定した値を示す。
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度0.4質量%のテトラヒドロフラン溶液)
標準試料:下記の標準ポリスチレンを用いて検量線を作成した。
東ソー株式会社製「TSKgel 標準ポリスチレン A-500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A-2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F-1」
東ソー株式会社製「TSKgel 標準ポリスチレン F-2」
東ソー株式会社製「TSKgel 標準ポリスチレン F-4」
東ソー株式会社製「TSKgel 標準ポリスチレン F-10」
東ソー株式会社製「TSKgel 標準ポリスチレン F-20」
東ソー株式会社製「TSKgel 標準ポリスチレン F-40」
東ソー株式会社製「TSKgel 標準ポリスチレン F-80」
東ソー株式会社製「TSKgel 標準ポリスチレン F-128」
東ソー株式会社製「TSKgel 標準ポリスチレン F-288」
東ソー株式会社製「TSKgel 標準ポリスチレン F-550」
実施例及び比較例で得られた合成皮革を、島津オートグラフ「AG-1」(株式会社島津製作所製)を使用して、フルスケール5kg、ヘッドスピード20mm/分の条件にて剥離強度を測定し、以下のように評価した。
「A」;0.15MPa以上
「B」;0.1MPa以上0.15MPa未満
「C」;0.1MPa未満
実施例及び比較例で得られた合成皮革を70℃、湿度95%の条件下で5週間放置した。その後、[剥離強度の測定方法]と同様の方法にて剥離強度を測定し、放置前後の剥離強度の保持率を算出し、以下のように評価した。
「A」;70%以上
「B」;50%以上70%未満
「C」;50%未満
実施例及び比較例で得られた合成皮革を、スガ試験機株式会社製フェードメーター「U48AU」(63℃、湿度50%)で100時間光照射した。その後の合成皮革を目視観察し、以下のように評価した。
「A」;外観に変化なし。
「B」;外観に軽度の黄変が確認される。
「C」;外観に大きな黄変が確認される。
Claims (5)
- アニオン性基を有するポリオール(a1-1)を含むポリオール(a1)と芳香族ポリイソシアネート(a2)との反応物であり、アニオン性基の濃度が0.35mmol/g以下であるウレタン樹脂(A)、及び、水性媒体(B)を含有する水性ウレタン樹脂組成物。
- 前記芳香族ポリイソシアネート(a2)が、トルエンジイソシアネートを含むものである請求項1記載の水性ウレタン樹脂組成物。
- 前記ウレタン樹脂(A)中の芳香環の濃度が、0.1~2.5mmol/kgの範囲である請求項1又は2記載の水性ウレタン樹脂組成物。
- 前記ウレタン樹脂(A)の重量平均分子量が、2,000~150,000の範囲である請求項1~3のいずれか1項記載の水性ウレタン樹脂組成物。
- 少なくとも、基布(i)、接着層(ii)、及び、表皮層(iii)を積層する合成皮革であって、前記接着層(ii)が、請求項1~4のいずれか1項記載の水性ウレタン樹脂組成物により形成されたものであることを特徴とする合成皮革。
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CN201780070204.4A CN109937219B (zh) | 2016-12-12 | 2017-10-26 | 水性聚氨酯树脂组合物和合成皮革 |
EP17879686.8A EP3553103A4 (en) | 2016-12-12 | 2017-10-26 | WATER-BASED URETHANE RESIN COMPOSITION AND FAUX LEATHER |
US16/347,061 US11795267B2 (en) | 2016-12-12 | 2017-10-26 | Aqueous urethane resin composition and synthetic leather |
JP2018524854A JP6428966B2 (ja) | 2016-12-12 | 2017-10-26 | 水性ウレタン樹脂組成物、及び、合成皮革 |
KR1020197009985A KR102168393B1 (ko) | 2016-12-12 | 2017-10-26 | 수성 우레탄 수지 조성물, 및, 합성 피혁 |
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WO2020116305A1 (ja) * | 2018-12-04 | 2020-06-11 | Dic株式会社 | 合成皮革 |
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WO2021124661A1 (ja) * | 2019-12-20 | 2021-06-24 | Dic株式会社 | ウレタン樹脂水分散体、合成皮革、及び、合成皮革の製造方法 |
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KR102499140B1 (ko) * | 2020-02-14 | 2023-02-13 | 디아이씨 가부시끼가이샤 | 우레탄 수지 조성물, 및 다공체의 제조 방법 |
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EP3553103A4 (en) | 2020-08-19 |
TW201829519A (zh) | 2018-08-16 |
TWI733938B (zh) | 2021-07-21 |
JP6428966B2 (ja) | 2018-11-28 |
US20200071452A1 (en) | 2020-03-05 |
JPWO2018110105A1 (ja) | 2018-12-13 |
EP3553103A1 (en) | 2019-10-16 |
KR102168393B1 (ko) | 2020-10-21 |
US11795267B2 (en) | 2023-10-24 |
CN109937219B (zh) | 2022-06-28 |
CN109937219A (zh) | 2019-06-25 |
KR20190051017A (ko) | 2019-05-14 |
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