CN109963980B - Synthetic leather - Google Patents

Synthetic leather Download PDF

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Publication number
CN109963980B
CN109963980B CN201780070043.9A CN201780070043A CN109963980B CN 109963980 B CN109963980 B CN 109963980B CN 201780070043 A CN201780070043 A CN 201780070043A CN 109963980 B CN109963980 B CN 109963980B
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polyol
hot
mass
synthetic leather
moisture
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CN109963980A (en
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竹田伸吾
藤原丰邦
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DIC Corp
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DIC Corp
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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
    • 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • 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
    • C08G18/28—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1692—Weather resistance

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention provides a synthetic leather having a layer formed from a moisture-curable polyurethane hot-melt resin composition containing a hot-melt urethane prepolymer (i) which is a reaction product of a polyol (A) containing an alicyclic polyester polyol (a1) and a polyisocyanate (B). The above polyol (a) preferably further contains polyoxypropylene glycol (a 2). The moisture-curable polyurethane hot-melt resin composition preferably further contains a hindered amine compound (ii) and a triazole compound (iii). The synthetic leather of the present invention is excellent in weather resistance and adhesive strength, and can be suitably used as split leather.

Description

Synthetic leather
Technical Field
The present invention relates to synthetic leather having a cured product layer of a moisture-curable polyurethane hot-melt resin composition.
Background
Moisture-curable polyurethane hot-melt resin compositions are widely used for producing synthetic leathers because they are excellent in mechanical strength, flexibility, adhesiveness, and the like. Among them, split leather having a split leather layer, an adhesive layer and a skin layer has an appearance and texture similar to those of natural leather, and thus, the demand for split leather has been increasing with the recent increase in the price of natural leather.
As a resin composition for forming the adhesive layer of the split leather, for example, a composition containing a hot-melt urethane prepolymer using an aliphatic polyester polyol or the like as a raw material is disclosed (for example, see patent document 1).
However, further improvement in adhesive strength is desired for the composition. In recent years, in split leather applications, various colored skin layers have been used in some cases from the viewpoint of design properties, and for example, in the case of using a light colored skin layer, excellent weather resistance is also required for the adhesive layer so as not to cause discoloration with time so as not to impair the appearance. However, in reality, a material having both excellent weather resistance and adhesive strength has not yet been found.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-297985
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide synthetic leather with a cured product layer of a moisture-curing polyurethane hot-melt resin composition with excellent weather resistance and adhesive strength.
Means for solving the problems
The present invention provides a synthetic leather having a layer formed from a moisture-curable polyurethane hot-melt resin composition containing a hot-melt urethane prepolymer (i) which is a reaction product of a polyol (A) containing an alicyclic polyester polyol (a1) and a polyisocyanate (B).
ADVANTAGEOUS EFFECTS OF INVENTION
The synthetic leather of the present invention has a layer having a high adhesive strength (particularly initial adhesive strength) and excellent weather resistance.
Detailed Description
The synthetic leather of the present invention has a layer formed of a moisture-curable polyurethane hot-melt resin composition containing a hot-melt urethane prepolymer (i) which is a reaction product of a polyol (a) containing an alicyclic polyester polyol (a1) and a polyisocyanate (B).
The alicyclic polyester polyol (a1) is an essential component in view of obtaining excellent weather resistance and adhesive strength. In order to obtain excellent initial adhesion strength, an aromatic polyester polyol using an aromatic compound such as phthalic acid as a raw material is generally used. However, when an aromatic polyester polyol is used, there is a problem that discoloration occurs particularly by irradiation with sunlight over time. On the other hand, in the present invention, by using the alicyclic polyester polyol (a1), a cured product layer having good initial strength due to cohesive force and excellent weather resistance (particularly resistance to discoloration even under sunlight irradiation with time) can be obtained. In the examples of the present invention, the results of the weather resistance test by the QUV accelerated weather resistance tester (manufactured by Q-LAB Corporation) equipped with a UVA-340 lamp having a short wavelength region of 295 to 365nm, which most faithfully simulates sunlight, are shown.
Examples of the alicyclic polyester polyol (a1) include a reaction product of an alicyclic compound having 2 or more hydroxyl groups and an aliphatic polybasic acid, and a reaction product of an aliphatic compound having 2 or more hydroxyl groups and an alicyclic polybasic acid. The reactants may be obtained by a known esterification reaction.
Examples of the alicyclic compound having 2 or more hydroxyl groups include cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol a, and alkylene oxide adducts thereof. These compounds may be used alone, or 2 or more of them may be used in combination. Among these, cyclohexanedimethanol is preferably used from the viewpoint that more excellent weather resistance and adhesive strength can be obtained.
Examples of the aliphatic polybasic acid include succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanedioic acid, citraconic acid, itaconic acid, citraconic anhydride, and itaconic anhydride. These compounds may be used alone, or 2 or more of them may be used in combination.
Examples of the aliphatic compound having 2 or more hydroxyl groups include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1, 3-butanediol, 2-diethyl-1, 3-propanediol, 2-diethylpropanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol, 2-methyl-1, 8-octanediol, 2, 4-diethyl-1, 5-pentanediol, trimethylolethane, trimethylolpropane, pentaerythritol, and the like. These compounds may be used alone, or 2 or more of them may be used in combination. Among these, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, neopentyl glycol, and 3-methyl-1, 5-pentanediol are preferably used from the viewpoint of obtaining more excellent weather resistance and adhesive strength, and neopentyl glycol and/or 3-methyl-1, 5-pentanediol are more preferably used from the viewpoint of further improving cohesive force by having a branched structure and obtaining more excellent weather resistance and adhesive strength.
Examples of the alicyclic polybasic acid include cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and cyclohexanediadipate. These compounds may be used alone, or 2 or more of them may be used in combination. Among these, cyclohexane dicarboxylic acid and/or cyclohexane diadipate are preferably used from the viewpoint of obtaining more excellent weather resistance and adhesive strength.
The number average molecular weight of the alicyclic polyester polyol (a1) is preferably in the range of 400 to 10000, more preferably in the range of 500 to 5000, and even more preferably in the range of 600 to 3000, from the viewpoint of obtaining more excellent weather resistance and adhesive strength. The number average molecular weight of the alicyclic polyester polyol (a1) is a value measured by a Gel Permeation Chromatography (GPC) method.
The content of the alicyclic polyester polyol (a1) is preferably 10% by mass or more, preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably 30 to 50% by mass in the polyol (a), from the viewpoint of obtaining more excellent weather resistance and adhesive strength.
As the polyol (a), for example, a polyester polyol, a polyether polyol, a polycarbonate polyol, a polybutadiene polyol, a dimer diol, an acrylic polyol, or the like other than the alicyclic polyester polyol (a1) can be used as another polyol which can be used in addition to the alicyclic polyester polyol (a 1). These polyhydric alcohols may be used alone, or 2 or more kinds may be used in combination. Among these, when used in combination with the alicyclic polyester polyol (a1), a polyether polyol is preferably used, and polyoxypropylene glycol (a2) is more preferred, from the viewpoint that the high viscosity derived from (a1) can be alleviated, the coatability by lowering the viscosity can be improved, and the appearance and production stability of split leather can be improved.
The content of the polyoxypropylene glycol (a2) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 30 to 70% by mass of the polyol (a), from the viewpoint of maintaining weather resistance and adhesive strength and further improving low viscosity.
In addition, when polyoxypropylene glycol (a2) is used, it is preferable to use an aliphatic polyester polyol and/or polytetramethylene glycol in combination from the viewpoint that the balance among weather resistance, adhesive strength and low viscosity can be further improved.
The number average molecular weight of the other polyol is preferably in the range of 500 to 10000, more preferably 700 to 5000, from the viewpoint of mechanical strength. In addition, when polyoxypropylene glycol (a2) is used as the other polyol, the number average molecular weight is preferably in the range of 1100 to 5000, more preferably in the range of 1500 to 3000, from the viewpoint of further improving the low viscosity. The number average molecular weight of the other polyol is a value measured in the same manner as the number average molecular weight of the alicyclic polyester polyol (a 1).
As the polyisocyanate (B), aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, xylylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate. These polyisocyanates may be used alone, or 2 or more kinds may be used in combination. Among these, aromatic polyisocyanates are preferably used, and diphenylmethane diisocyanate is more preferably used, from the viewpoint of obtaining excellent reactivity and peel strength.
The amount of the polyisocyanate (B) used is preferably in the range of 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total mass of the raw materials constituting the hot-melt urethane prepolymer (i).
The hot-melt urethane prepolymer (i) is obtained by reacting the polyol (a) with the polyisocyanate (B), and has an isocyanate group capable of reacting with moisture present in the air or in a substrate to be coated with the moisture-curable polyurethane hot-melt resin composition to form a crosslinked structure.
The hot-melt urethane prepolymer (i) can be produced, for example, by charging the polyol (a) into a reaction vessel containing the polyisocyanate (B) and reacting the polyol (a) under such conditions that the isocyanate group of the polyisocyanate (B) is in excess of the hydroxyl group of the polyol (a).
The equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group of the polyisocyanate (B) to the hydroxyl group of the polyol (a) in producing the hot-melt urethane prepolymer (i) is preferably in the range of 1.1 to 5, and more preferably in the range of 1.5 to 3, from the viewpoint of obtaining more excellent peel strength.
The content of the isocyanate group (hereinafter abbreviated as "NCO%") in the hot-melt urethane prepolymer (i) obtained by the above method is preferably in the range of 1.7 to 5, more preferably in the range of 1.8 to 3, from the viewpoint of obtaining more excellent peel strength. The NCO% of the hot-melt urethane prepolymer (i) is a value measured by a potentiometric titration method based on JIS K1603-1: 2007.
The moisture-curable polyurethane hot-melt resin composition used in the present invention contains the above hot-melt urethane prepolymer as an essential component, but may contain other additives as required.
As the above-mentioned other additives, for example, weather resistant stabilizers, curing catalysts, tackifiers, plasticizers, fillers, dyes, pigments, fluorescent brighteners, silane coupling agents, waxes, thermoplastic resins, and the like can be used. These additives may be used alone, or 2 or more of them may be used in combination. Among these, a weather resistant stabilizer is preferably used from the viewpoint of obtaining more excellent weather resistance.
As the weather-resistant stabilizer, for example, a hindered amine compound (ii), a triazole compound (iii), a hindered phenol compound, a phosphorus compound, or the like can be used. These weather-resistant stabilizers may be used alone or in combination of 2 or more. Among these, from the viewpoint of obtaining more excellent weather resistance, the hindered amine compound (ii) is preferably used, and the hindered amine compound (ii) and the triazole compound (iii) are more preferably used.
Examples of the hindered amine compound (ii) which can trap radicals generated by photodegradation include bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (1, 2, 2, 6, 6-pentamethylpiperidin-4-yl) sebacate, tetrakis (2, 2, 6, 6-tetramethyl-4-piperidyl) 1, 2, 3, 4-butanetetracarboxylate, tetrakis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) 1, 2, 3, 4-butanetetracarboxylate, (mixed 2, 2, 6, 6-tetramethyl-4-piperidyl/tridecyl) 1, 2, 3, 4-butanetetracarboxylate, (mixed 1, 2, 2, 6, 6-pentamethyl-4-piperidyl/tridecyl) 1, 2, 3, 4-butanetetracarboxylate, 8-acetyl-3-dodecyl-7, 7, 9, 9-tetramethyl-1, 3, 8-triazaspiro [ 4.5 ] decane-2, 4-dione, and the like. These compounds may be used alone, or 2 or more of them may be used in combination.
The content of the hindered amine compound (ii) is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.05 to 5 parts by mass, and still more preferably in the range of 0.1 to 3 parts by mass, based on 100 parts by mass of the hot-melt urethane prepolymer (i), from the viewpoint of obtaining more excellent weather resistance.
The above-mentioned triazole compound (iii) can prevent discoloration, for example, using N, N-bis (2-ethylhexyl) - [ (1, 2, 4-triazol-1-yl) methyl ] amine; 2- [ 2-hydroxy-3, 5-bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ' -tert-amyl-5 ' -isobutylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ' -isobutyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ' -isobutyl-5 ' -propylphenyl) -5-chlorobenzotriazole And benzotriazole compounds such as 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, and 2- [2 ' -hydroxy-5 ' - (1, 1, 3, 3-tetramethyl) phenyl ] benzotriazole. These triazole compounds may be used alone, or 2 or more triazole compounds may be used in combination. Among these, from the viewpoint of obtaining more excellent weather resistance, the benzotriazole compound is preferably used.
The content of the triazole compound (iii) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the hot-melt urethane prepolymer (i), from the viewpoint of obtaining more excellent weather resistance.
Next, the synthetic leather of the present invention will be described.
The synthetic leather of the present invention has a layer formed of the moisture-curable polyurethane hot-melt resin composition and having excellent weather resistance. Accordingly, since the layer is not discolored due to deterioration with time by sunlight or the like, the range of applications of split leather, which is required to be increased particularly compared with the conventional art, can be widened.
The split leather comprises a split leather, an adhesive layer and a skin layer, and the moisture-curable polyurethane hot-melt resin composition can be suitably used as the adhesive layer of the split leather. Hereinafter, a method for producing split leather using the moisture-curable polyurethane hot-melt resin composition for an adhesive layer will be described.
As the double skin, known products can be used, and for example, a double skin composed of a layer obtained by removing the epidermis and papilla layer from natural leather such as cow, horse, sheep, goat, deer, kangaroo, and the like can be used. These split skins are preferably used as products obtained through a known tanning process, tanning process and dyeing/finishing process. The thickness of the double skin is suitably determined depending on the application, and is, for example, in the range of 0.1 to 2 mm.
Examples of the method for forming the adhesive layer on the split skin include the following methods: a method of applying the moisture-curable polyurethane hot-melt resin composition melted at 50 to 130 ℃ to the split skin; a method in which the moisture-curable polyurethane hot-melt resin composition melted at, for example, 50 to 130 ℃ is applied to a release paper, and then the cured product layer is bonded to the two-layer skin; a method in which the moisture-curable polyurethane hot-melt resin composition melted at 50 to 130 ℃, for example, is applied to a skin layer formed on a release paper, and then the cured product layer is bonded to the two-layer skin.
In any of the above methods, examples of the method for applying the moisture-curable polyurethane hot-melt resin composition include a method using a roll coater, a knife coater, a spray coater, a gravure coater, a comma coater, a T-die coater, an applicator, and the like.
After the application of the moisture-curable polyurethane hot-melt resin composition, curing can be performed by a known method.
The thickness of the cured product layer (adhesive layer) of the moisture-curable urethane hot-melt resin composition is, for example, in the range of 5 to 200 μm.
As the resin for forming the skin layer, known materials can be used, and for example, a solvent-based urethane resin, an aqueous urethane resin, a solvent-free urethane resin, a solvent-based acrylic resin, an aqueous acrylic resin, and the like can be used. These resins may be used alone, or 2 or more kinds may be used in combination.
The heating method for removing the solvent from the resin for forming the skin layer includes, for example, a method of heating at a temperature of 50 to 120 ℃ for 2 to 20 minutes.
The thickness of the skin layer is, for example, in the range of 5 to 100 μm.
Examples
The present invention will be described in more detail below with reference to examples.
[ example 1]
40 parts by mass of an alicyclic polyester polyol (a product obtained by reacting neopentyl glycol, 3-methyl-1, 5-pentanediol, and cyclohexanedicarboxylic acid, and having a number average molecular weight of 1000, hereinafter abbreviated to "alicyclic PEs 1") and 60 parts by mass of polyoxypropylene glycol (a number average molecular weight of 2000, hereinafter abbreviated to "PPG 2000") were put into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, and mixed, and then dehydrated until the water content in the flask became 0.05% by mass or less by heating under reduced pressure at 100 ℃.
Subsequently, the flask was cooled to 90 ℃ and 26.5 parts by mass of 4, 4' -diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") melted at 70 ℃ was added thereto, and the mixture was reacted at 110 ℃ for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to thereby obtain a hot-melt urethane prepolymer having an NCO% of 2.4% by mass.
Next, a solvent-based polyurethane resin ("CRISPON TF-50P-C" manufactured by DIC) was applied onto the release paper so that the dried film thickness became 30 μm, and dried at 120 ℃ for 10 minutes to obtain a skin layer. Next, the hot-melt urethane prepolymer melted at 110 ℃ for 1 hour was applied onto the skin layer to a thickness of 30 μm using a comma coater, and then a split leather was obtained by bonding a split leather obtained by removing the skin layer and the nipple layer from a natural cow leather and manufacturing leather, and then left to stand at a temperature of 23 ℃ and a relative humidity of 65% for 3 days.
Examples 2 to 4 and comparative examples 1 to 2
Split leather was obtained in the same manner as in example 1, except that hot-melt urethane prepolymers were obtained according to the kinds and blending amounts of the polyol (a) and the polyisocyanate (B) shown in table 1.
[ example 5]
A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with 40 parts by mass of alicyclic PEsl and 200060 parts by mass of PPG, and the mixture was heated at 100 ℃ under reduced pressure to dehydrate the flask to a water content of 0.05% by mass or less.
Subsequently, the flask was cooled to 90 ℃ and 26.5 parts by mass of MDI melted at 70 ℃ was added, and the mixture was reacted at 110 ℃ for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, thereby obtaining a hot-melt urethane prepolymer having an NCO% of 2.4 mass%. To this was added 0.5 mass% of bis (1, 2, 2, 6, 6-pentamethylpiperidin-4-yl) sebacate ("SANOL LS-765" manufactured by Sanko K.K., hereinafter abbreviated as "LS-765") to obtain a moisture-curable polyurethane hot-melt resin composition.
Next, a solvent-based polyurethane resin ("CRISPON TF-50P-C" manufactured by DIC) was applied onto the release paper so that the dried film thickness became 30 μm, and dried at 120 ℃ for 10 minutes to obtain a skin layer. Next, the moisture-curable polyurethane hot-melt resin composition melted at 110 ℃ for 1 hour was applied onto the skin layer to a thickness of 30 μm using a comma coater, and then a split leather was obtained by bonding two layers of leather produced by removing the skin layer and the nipple layer from bovine natural leather and leaving them to stand at a temperature of 23 ℃ and a relative humidity of 65% for 3 days.
[ example 6]
A moisture-curable polyurethane hot-melt resin composition was obtained in the same manner as in example 1 except that 0.5% by mass of a benzotriazole compound ("Tinuvin (registered trademark) 234" manufactured by BASF corporation, hereinafter abbreviated as "T234") was further added to the above-mentioned moisture-curable polyurethane hot-melt resin composition, and split leather was produced.
[ examples 7 to 9]
Split leather was obtained in the same manner as in example 6, except that the moisture-curable polyurethane hot-melt resin compositions were obtained according to the kinds and blending amounts of the polyol (a), the polyisocyanate (B), the hindered amine compound (ii), and the triazole compound (iii) shown in table 2.
[ method for measuring number average molecular weight ]
The number average molecular weights of the polyols and the like used in the examples and comparative examples represent values measured by a Gel Permeation Chromatography (GPC) method under the following conditions.
A measuring device: high-speed GPC apparatus (HLC-8220 GPC, manufactured by Tosoh corporation)
Column: the following columns from Tosoh corporation were used in series.
"TSKgel G5000" (7.8 mmI.D.. times.30 cm). times.1 roots
"TSKgel G4000" (7.8mm I.D.. times.30 cm). times.1 roots
"TSKgel G3000" (7.8 mmI.D.. times.30 cm). times.1 roots
"TSKgel G2000" (7.8 mmI.D.. times.30 cm). times.1 roots
A detector: RI (differential refractometer)
Column temperature: 40 deg.C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100 μ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: the standard curve was made using the following standard polystyrene.
(Standard polystyrene)
TSKgel Standard polystyrene A-500 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-1000 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-2500 manufactured by Tosoh corporation "
"TSKgel Standard polystyrene A-5000" manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-1 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-2 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-4 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-10 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-20 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-40 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-80 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-128 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-288 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-550 manufactured by Tosoh corporation "
[ method for evaluating weather resistance ]
After the urethane prepolymers obtained in examples and comparative examples were melted at 110 ℃ for 1 hour, 100 μm was coated on a release paper placed on a hot plate heated to 110 ℃ in advance. The coated product was stored at 25 ℃ and 50% humidity for 24 hours and cured to obtain a film. Using this film, a lamp equipped with UVA-340 (UV dose: 0.78W/m) was used2And temperature: a UV irradiation test was carried out in a 45 ℃ QUV accelerated weather resistance tester "QUV/basic", and the weather resistance was evaluated in the following manner based on the difference (. DELTA.E) in color change before and after UV irradiation.
"4": Δ E is 10 or less.
"3": Δ E is more than 10 and 13 or less.
"2": Δ E is more than 13 and 15 or less.
"1": Δ E exceeds 15.
[ method for evaluating adhesive Strength ]
After the urethane prepolymers obtained in examples and comparative examples were melted at 120 ℃ for 1 hour, 100 μm was coated on a PET film placed on a hot plate previously heated to 110 ℃. Immediately after coating, the PET film was detached from the hot plate, and another PET film was immediately attached by a hand roller. After the bonding, the test piece was cut into a width of 1 inch, and the peel strength between PET pieces 1 minute after the bonding was measured using a digital force gauge ("DS 2-220N" manufactured by イマァダ), and the initial strength was evaluated as follows.
"T": more than 5N/inch
"F": less than 5N/inch
[ method for measuring Low viscosity ]
The urethane prepolymers obtained in examples and comparative examples were melted at 120 ℃ for 1 hour, sampled by 1ml, and melt viscosity was measured with a cone and plate viscometer (40P cone, rotor speed: 50rpm) and evaluated as follows.
"T": less than 4000mPa s
"F": 4000 mPa.s or more
[ Table 1]
Figure BDA0002057268360000111
[ Table 2]
Figure BDA0002057268360000121
The abbreviations in table 1 are as follows.
"alicyclic PEs 2": product obtained by reacting 1, 4-cyclohexanedimethanol with adipic acid, number average molecular weight: 1000
"aromatic PEs": product obtained by reacting diethylene glycol, neopentyl glycol and terephthalic anhydride, number average molecular weight: 1000
"aliphatic PEs": product obtained by reacting 1, 4-butanediol with adipic acid, number average molecular weight: 1000)
therefore, the following steps are carried out: the synthetic leather of the present invention has a cured product layer of a moisture-curable polyurethane hot-melt resin composition excellent in weather resistance, adhesive strength and low viscosity.
On the other hand, in comparative example 1, in which an aromatic polyester polyol was used instead of the alicyclic polyester polyol (a1), the adhesive strength was excellent, but the weather resistance and the low viscosity were poor.
In comparative example 2, an aliphatic polyester polyol was used instead of the alicyclic polyester polyol (a1), but the adhesive strength was poor.

Claims (8)

1. A synthetic leather having a layer formed from a moisture-curable polyurethane hot-melt resin composition containing a hot-melt urethane prepolymer i, which is a reaction product of a polyol A containing an alicyclic polyester polyol a1 and a polyisocyanate B,
the polyol A further contains polyoxypropylene glycol a2, and the content of polyoxypropylene glycol a2 in the polyol A is in the range of 5 to 90% by mass.
2. The synthetic leather of claim 1 further comprising a hindered amine compound ii.
3. The synthetic leather according to claim 2, wherein a content of the hindered amine compound ii is in a range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the hot-melt urethane prepolymer i.
4. The synthetic leather according to claim 2 or 3, further comprising a triazole compound iii.
5. The synthetic leather according to claim 4, wherein the content of the triazole compound iii is in a range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the hot-melt urethane prepolymer i.
6. The synthetic leather according to claim 4, wherein the triazole compound iii is a benzotriazole compound.
7. The synthetic leather according to claim 5, wherein the triazole compound iii is a benzotriazole compound.
8. The synthetic leather according to any one of claims 1 to 3, which is split leather.
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