WO2018105261A1

WO2018105261A1 - Synthetic leather

Info

Publication number: WO2018105261A1
Application number: PCT/JP2017/038608
Authority: WO
Inventors: 宏之千々和; 保之片上; 美和上口
Original assignee: Dic株式会社
Priority date: 2016-12-05
Filing date: 2017-10-26
Publication date: 2018-06-14
Also published as: TW201829876A; JPWO2018105261A1; JP6455644B2

Abstract

The present invention provides a synthetic leather in which a base fabric (i), a bonding layer (ii), an intermediate layer (iii) and a skin layer (iv) are sequentially laminated, and which is characterized in that the intermediate layer (iii) is formed from a polyurethane resin composition containing a polyurethane resin (X) that is a reaction product of a polyol (A) containing 70% by mass or more of a polycarbonate polyol (a-1), an aliphatic or alicyclic polyisocyanate (B) and a chain extender (C). It is preferable that the bonding layer (ii) is formed from a polyurethane resin composition that contains a polyurethane resin (D-1) having a hydroxyl group and a crosslinking agent (D-2), said polyurethane resin (D-1) being a reaction product of the polyol (A) containing 70% by mass or more of a polycarbonate polyol (a-1), the aliphatic or alicyclic polyisocyanate (B) and the chain extender (C). The present invention provides a synthetic leather which is free from deformation or the like even in cases where a sunscreen cream gets thereon.

Description

Synthetic leather

The present invention relates to a synthetic leather that does not cause deformation or the like even when sunscreen cream is attached.

Polyurethane resins are widely used in various fields such as films, adhesives, automobile interior materials, and abrasives because they have excellent mechanical strength. Among them, in recent years, since the excellent texture can be obtained due to the flexibility of the polyurethane resin, many studies have been made for synthetic leather applications (see, for example, Patent Document 1).

Polyurethane resins used for the production of the synthetic leather (including artificial leather) have recently been required to have high durability especially for automobile interior materials. Above all, in vehicle interior materials, in addition to conventional durability (heat resistance, light resistance, hydrolysis resistance, etc.), excellent chemical resistance to sunscreen cream is required. However, the fact is that no material having excellent chemical resistance to sunscreen cream has yet been found.

Japanese Patent Laid-Open No. 2007-1000028

The problem to be solved by the present invention is to provide a synthetic leather which does not cause deformation or the like even when sunscreen cream adheres.

The present invention relates to a synthetic leather in which a base fabric (i), an adhesive layer (ii), an intermediate layer (iii), and a skin layer (iv) are sequentially laminated, and the intermediate layer (iii) is a polycarbonate polyol. Polyurethane containing polyol (X) containing 70% by mass or more of (x-1), aliphatic or alicyclic polyisocyanate (Y), and polyurethane resin (W) which is a reaction product of chain extender (Z) It is intended to provide a synthetic leather characterized by being formed by a resin composition.

The synthetic leather of the present invention does not cause deformation or the like even when sunscreen cream adheres (hereinafter abbreviated as “chemical resistance”).

The synthetic leather of the present invention is a synthetic leather in which a base fabric (i), an adhesive layer (ii), an intermediate layer (iii), and an outer skin layer (iv) are sequentially laminated, and the intermediate layer (iii) Polyurethane resin (W) which is a reaction product of polyol (X) containing 70% by mass or more of polycarbonate polyol (x-1), aliphatic or alicyclic polyisocyanate (Y), and chain extender (Z) It is formed by the polyurethane resin composition containing this.

The skin layer (iv) can be formed by a known method using a known material. For example, a solvent-based urethane resin, a water-based urethane resin, a solvent-free urethane resin, a silicone resin, a polypropylene resin, a polyester resin, or the like is used. be able to.

The intermediate layer (iii) is a reaction product of a polyol (X) containing 70% by mass or more of a polycarbonate polyol (x-1), an aliphatic or alicyclic polyisocyanate (Y), and a chain extender (Z). It is formed by the polyurethane resin composition containing the polyurethane resin (W) which is. By forming the intermediate layer (iii) from this specific polyurethane resin composition, excellent chemical resistance can be exhibited regardless of the type of the adhesive layer (ii) or the skin layer (iv). .

The polyurethane resin composition used for the intermediate layer (iii) is: 1) use a specific amount or more of polycarbonate polyol (x-1) having excellent chemical resistance; 2) lower cohesive force than aromatic polyisocyanate. Since an aliphatic or cycloaliphatic polyisocyanate (Y) is used, it can be relaxed between the polymers of the polyurethane resin when sunscreen is attached, and there is no deformation such as swelling, and the shape of the synthetic leather is maintained. It is thought that it was possible. Moreover, it is thought that the effect improved more by introduce | transducing this specific polyurethane resin composition into the intermediate | middle layer (iii) close | similar to the skin layer (iv).

The synthetic leather of the present invention has excellent chemical resistance against various sunscreens by forming the intermediate layer (iii) with a specific polyurethane resin. For example, Neutrogena (registered trademark), which is known as sunscreen cream, has an ultraviolet absorbent having a hydroxyl group such as 2-hydroxy-4-methoxybenzophenone and 3,3,5-trimethylcyclohexyl salicylate contained in synthetic leather. The chemical resistance test using this becomes a very severe test because it leads to poor chemical resistance due to the affinity with the urethane bond in the polyurethane resin to be constituted. However, the synthetic leather of the present invention exhibits excellent chemical resistance even when the Neutrogena is used.

As the polycarbonate polyol (x-1), for example, a reaction product of a carbonate ester and / or phosgene and a compound having two or more hydroxyl groups can be used.

Examples of the carbonate ester include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate. These compounds may be used alone or in combination of two or more.

Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, and 2-methyl. 1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,10-decanediol, 1,12-dodecanediol 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolprop It can be used trimethylol ethane, glycerin and the like. These compounds may be used alone or in combination of two or more.

The number average molecular weight of the polycarbonate polyol (x-1) is preferably in the range of 500 to 8,000, more preferably in the range of 700 to 5,000, from the viewpoint that even better chemical resistance is obtained. More preferably, the range is in the range of 800 to 3,000. The number average molecular weight of the polycarbonate polyol (x-1) is a value measured by a gel permeation chromatography (GPC) method.

The polyol (X) contains 70% by mass or more of the polycarbonate polyol (x-1) in order to obtain excellent chemical resistance. Other polyols that can be used in addition to the polycarbonate polyol (x-1) include, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene poly Polyether polyols such as tetramethylene glycol; polyester polyols; polyacrylic polyols and the like can be used. These polyols may be used alone or in combination of two or more.

The number average molecular weight of the other polyol is preferably in the range of 500 to 10,000, more preferably in the range of 700 to 5,000. The number average molecular weight of the other polyol is a value obtained by measurement in the same manner as the number average molecular weight of the polycarbonate polyol (x-1).

Examples of the aliphatic or alicyclic polyisocyanate (Y) include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3. -Cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-di (isocyanate methyl) cyclohexane, 1,4-di (isocyanate methyl) cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4 ' It can be used dicyclohexylmethane diisocyanate. These polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use isophorone diisocyanate and / or dicyclohexylmethane diisocyanate from the viewpoint that much more excellent chemical resistance is obtained.

In the aliphatic or alicyclic polyisocyanate (Y), for the purpose of improving the texture of the synthetic leather, an aromatic polyisocyanate may be used in combination as long as the effects of the present invention are not impaired.

Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl- 2,5-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4- Phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3, Diethylbenzene diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate 1-methyl-naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2′-diisocyanate, biphenyl-2,4′-diisocyanate Biphenyl-4,4′-diisocyanate, 3-3′-dimethylbiphenyl-4,4′-diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, diphenylmethane-2,4-dii Or the like can be used cyanate. These aromatic polyisocyanates may be used alone or in combination of two or more.

As the chain extender (Z), for example, a chain extender having an amino group, a chain extender having a hydroxyl group, or 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 a chain extender (c-1) having an amino group from the viewpoint of obtaining even better chemical resistance.

Examples of the chain extender having an amino group 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. Among these, it is preferable to use isophorone diamine and / or dicyclohexylmethane diamine from the viewpoint that much more excellent chemical resistance is obtained.

Examples of the chain extender having a hydroxyl group 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.

As a method for producing the polyurethane resin (W), for example, after the polyol (X) and preferably an organic solvent are charged and stirred, the polyisocyanate (Y) and further a chain extender (Z) are added. Examples thereof include a method of reacting at 50 to 100 ° C. for 3 to 10 hours. After the polyurethane resin is produced, an alcohol such as ethanol, methanol, or butanol may be added for the purpose of deactivating the remaining isocyanate groups.

Examples of the organic solvent include ketone solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl-n-propyl ketone, acetone, and methyl isobutyl ketone; Ester solvents such as methyl, ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate and sec-butyl acetate; alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol can be used. These organic solvents may be used alone or in combination of two or more. The amount used in the case of using the organic solvent is preferably in the range of 30 to 90% by mass in the polyurethane resin composition, for example, from the viewpoint of production stability, coating property, and film forming property. A range of ˜80 mass% is more preferred.

The weight average molecular weight of the polyurethane resin (W) obtained by the above method is in the range of 5,000 to 500,000 from the standpoint of further improving chemical resistance and film formability. The range of 10,000 to 300,000 is more preferable. The weight average molecular weight of the polyurethane resin (W) is a value measured in the same manner as the number average molecular weight of the polycarbonate polyol (x-1).

The content of the alicyclic structure in the polyurethane resin (W) is preferably in the range of 4,500 to 7,000 mol / kg from the standpoint that even better chemical resistance is obtained. A range of ˜6,000 mol / kg is more preferred. In addition, content of the said alicyclic structure is content of the alicyclic structure with respect to the total mass of the said polyol (X), aliphatic or alicyclic polyisocyanate (Y) used for a raw material, and the said chain extender (Z). Show.

The urethane bond content in the polyurethane resin (W) is preferably in the range of 500 to 900 mol / kg, more preferably in the range of 700 to 800 mol / kg, from the viewpoint of obtaining even better chemical resistance. More preferred. In addition, content of the said urethane bond shows content of the urethane bond with respect to the total mass of the said polyol (X) used for a raw material, aliphatic or alicyclic polyisocyanate (Y), and the said chain extender (Z).

The polyurethane resin composition used in the present invention contains the polyurethane resin (W) as an essential component, but may contain other additives as necessary.

Examples of the other additives include surfactants, pigments, catalysts, flame retardants, plasticizers, softeners, stabilizers, waxes, antifoaming agents, dispersants, penetrants, fillers, antifungal agents, and antibacterial agents. UV absorbers, antioxidants, weathering stabilizers, fluorescent brighteners, anti-aging agents, thickeners, and the like can be used. These additives may be used alone or in combination of two or more.

The adhesive layer (ii) can be formed by a known method using a known material. For example, a solvent-based urethane resin, a water-based urethane resin, a solvent-free urethane resin, a silicone resin, a polypropylene resin, a polyester resin, or the like is used. be able to.

As the adhesive layer (ii), a polyol (A) containing 70% by mass or more of a polycarbonate polyol (a-1), an aliphatic or an aliphatic resin is used from the viewpoint of obtaining even more excellent chemical resistance among those described above. Formed by a polyurethane resin composition comprising a cyclic polyisocyanate (B) and a polyurethane resin (D-1) having a hydroxyl group, which is a reaction product of a chain extender (C), and a crosslinking agent (D-2) It is preferable to use one.

The polyol (A), aliphatic or alicyclic polyisocyanate (B), and chain extender (C) used as raw materials for the polyurethane resin (D-1) are used for forming the intermediate layer (iii). The same raw material as the polyurethane resin (W) can be used.

As a method for producing the polyurethane resin (D-1), for example, the polyol (A), and preferably an organic solvent are charged and stirred, and then the polyisocyanate (B) and a chain extender (C) are added. Examples thereof include a method of reacting at 50 to 100 ° C. for 3 to 10 hours. Moreover, the molar ratio of the total of the hydroxyl group and amino group which the said polyol (A) and the said chain extender (C) have, and the isocyanate group which the said polyisocyanate (B) has at the time of performing this urethanation reaction (NCO / OH + NH) is in the range of 0.4 to 0.9 from the viewpoint that it exhibits good crosslinking with the crosslinking agent (X-2) described later, and further excellent adhesion and chemical resistance can be obtained. The range of 0.5 to 0.8 is more preferable.

The weight average molecular weight of the polyurethane resin (D-1) obtained by the above method is 2,000 to 300,000 from the standpoint of obtaining more excellent chemical resistance, film formability, and adhesiveness. The range is preferable, and the range of 5,000 to 30,000 is more preferable. The weight average molecular weight of the polyurethane resin (D-1) is a value measured in the same manner as the number average molecular weight of the polycarbonate polyol (x-1).

The urethane bond content in the polyurethane resin (D-1) is preferably in the range of 500 to 900 μmol / g, and more preferably in the range of 750 to 850 μmol / g from the viewpoint of obtaining even better chemical resistance. A range is more preferred. In addition, content of the said urethane bond shows content of the urethane bond with respect to the total mass of the said polyol (A) used for a raw material, aliphatic or alicyclic polyisocyanate (B), and the said chain extender (C).

As the crosslinking agent (D-2), for example, a polyisocyanate crosslinking agent, a melamine crosslinking agent, or the like can be used. These crosslinking agents may be used alone or in combination of two or more. Among these, it is preferable to use a polyisocyanate crosslinking agent from the viewpoint of exhibiting good crosslinking with the polyurethane resin (D-1) and obtaining further excellent adhesion and chemical resistance.

Examples of the polyisocyanate crosslinking agent include polyisocyanates such as tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate; and these trimethylolpropanes. These isocyanurates, these burettes, these adducts, polymethylene polyphenyl polyisocyanate, and the like can be used. These crosslinking agents may be used alone or in combination of two or more.

The content of the cross-linking agent (D-2) is such that the polyurethane resin (D-1) can form a good cross-link, and more excellent adhesion and chemical resistance can be obtained. It is preferably in the range of 0.1 to 40 parts by weight, more preferably in the range of 0.2 to 20 parts by weight with respect to 100 parts by weight of the solid content of (D-1).

The polyurethane resin composition contains the polyurethane resin (D-1) and a crosslinking agent (D-2), and if necessary, other additives that can be used for the intermediate layer (iii). You may contain.

Examples of the base fabric (i) 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, Nonwoven fabrics, woven fabrics, knitted fabrics and the like made of these blended fibers can be used.

As a method for producing the synthetic leather of the present invention, for example, after forming a skin layer (iv) on a release-treated substrate by a known method, the polyurethane resin is formed on the skin layer (iv). After the composition is applied and dried, an intermediate layer (iii) is obtained, and then an adhesive layer (ii) is formed on the intermediate layer (iii) by a known method, and the adhesive layer (ii) ) And the base fabric (i).

Examples of the coating method of the resin composition when forming the layers (ii) to (iv) include a method using a gravure coater, knife coater, pipe coater, comma coater, roll coater, applicator and the like. .

The drying after coating the resin composition may be performed, for example, for 1 to 60 minutes using a drier adjusted to 80 to 120 ° C., for example.

The film thickness after drying of the layers (ii) to (iv) is appropriately determined depending on the intended use, and is, for example, in the range of 0.001 to 10 mm.

A surface treatment layer (v) may be provided on the skin layer (iv) as necessary.

As described above, the synthetic leather of the present invention has excellent chemical resistance that does not cause deformation or the like even when sunscreen cream (particularly Neutrogena) adheres.

Hereinafter, the present invention will be described in more detail with reference to examples.

[Synthesis Example 1] Synthesis of polyurethane resin for intermediate layer (W-1) Polycarbonate diol (number average molecular weight: 2,6) using 1,6-hexanediol as a raw material in a reactor having a stirrer, a reflux tube and a thermometer. 000, abbreviated as “PC-1”.) 324 parts by mass was added, and the pressure was reduced to 0.095 MPa, followed by dehydration at 120 to 130 ° C. After cooling to 50 ° C., 278 parts by mass of N, N-dimethylformamide (hereinafter abbreviated as “DMF”), 4,4′-dicyclohexylmethane diisocyanate (hereinafter abbreviated as “H12MDI”). 93 parts by mass and 0.2 parts by mass of stannous octylate were added and reacted at 75 ° C. to obtain an organic solvent solution of urethane prepolymer having an isocyanate group. Next, 773 parts by mass of DMF was added thereto, cooled to 35 ° C., 30 parts by mass of isophoronediamine (hereinafter abbreviated as “IPDA”) was added, and the polyurethane resin was chain-extended by mixing and stirring. . Next, 1.5 parts by mass of N, N-dibutylamine was added and mixed to obtain an intermediate layer polyurethane resin (W-1) composition.

[Synthesis Example 2] Synthesis of polyurethane resin for intermediate layer (W-2) 1,4-butanediol and 1,6-hexanediol (molar ratio: 70 / m) were added to a reactor having a stirrer, a reflux tube, and a thermometer. Polycarbonate polyol using 30) as a raw material (number average molecular weight; 2,000, abbreviated as “PC-2”) 275 parts by mass, polyester polyol using 1,6-hexanediol and adipic acid as raw materials (number average molecular weight) : 2,000, hereinafter abbreviated as “PEs-1”.) 49 parts by mass was added, the pressure was reduced to 0.095 MPa, and dehydration was performed at 120 to 130 ° C. Then, it cools to 50 degreeC, 278 mass parts of DMF, 93 mass parts of H12MDI, and 0.2 mass part of stannous octylate are added, and it is made to react at 75 degreeC, The urethane prepolymer which has an isocyanate group An organic solvent solution was obtained. Next, 773 parts by mass of DMF was added thereto, cooled to 35 ° C., 30 parts by mass of IPDA were added, and the polyurethane resin was chain-extended by mixing and stirring. Next, 1.5 parts by mass of N, N-dibutylamine was added and mixed to obtain an intermediate layer polyurethane resin (W-2) composition.

[Synthesis Example 3] Synthesis of polyurethane resin for intermediate layer (W-3) Polycarbonate polyol (number average molecular weight; 1, 1, hexanediol) as a raw material was added to a reactor having a stirrer, a reflux tube and a thermometer. 000, abbreviated as “PC-3”.) 235 parts by mass, polyester polyol using 1,4-butanediol and adipic acid as raw materials (number average molecular weight: 1,000, hereinafter abbreviated as “PEs-2”). ) 78 parts by mass was added, the pressure was reduced to 0.095 MPa, and dehydration was performed at 120 to 130 ° C. Thereafter, the mixture was cooled to 50 ° C., 278 parts by mass of DMF, 104 parts by mass of isophorone diisocyanate (hereinafter abbreviated as “IPDI”), and 0.2 parts by mass of stannous octylate were added and reacted at 75 ° C. By doing so, an organic solvent solution of a urethane prepolymer having an isocyanate group was obtained. Next, 773 parts by mass of DMF was added thereto, the mixture was cooled to 35 ° C., 30 parts by mass of 4,4′-dicyclohexyldiamine (hereinafter abbreviated as “H12MDA”) was added, and the mixture was agitated to obtain a polyurethane resin. Was chain extended. Next, 1.5 parts by mass of N, N-dibutylamine was added and mixed to obtain a polyurethane resin (W-3) composition for intermediate layer.

[Synthesis Example 4] Synthesis of polyurethane resin for intermediate layer (W-4) To a reactor having a stirrer, a reflux tube, and a thermometer, 339 parts by mass of PC-2 was added, and the pressure was reduced to 0.095 MPa, and 120-130 Dehydration was performed at ° C. Thereafter, the mixture was cooled to 50 ° C., 277 parts by mass of DMF, 75 parts by mass of IPDI, and 0.2 parts by mass of stannous octylate were added and reacted at 75 ° C., whereby the urethane prepolymer having an isocyanate group was reacted. An organic solvent solution was obtained. Next, 774 parts by mass of DMF was added thereto, cooled to 35 ° C., 32 parts by mass of H ₁₂ MDA was added, and the polyurethane resin was chain-extended by mixing and stirring. Next, 1.5 parts by mass of N, N-dibutylamine was added and mixed to obtain an intermediate layer polyurethane resin (W-4) composition.

Synthesis Example 5 Synthesis of Intermediate Layer Polyurethane Resin (W-5) In a reactor having a stirrer, a reflux tube, and a thermometer, 245 parts by mass of PC-1 and polyoxytetramethylene glycol (number average molecular weight: 1) , 000 (hereinafter abbreviated as “PEt-1”) was added in an amount of 105 parts by mass, and the pressure was reduced to 0.095 MPa, followed by dehydration at 120 to 130 ° C. Then, it cools to 50 degreeC, 284 mass parts of DMF, 76 mass parts of IPDI, 0.2 mass part of stannous octylates are added, and it is made to react at 75 degreeC, The urethane prepolymer which has an isocyanate group An organic solvent solution was obtained. Next, 767 parts by mass of DMF was added thereto, cooled to 35 ° C., 22 parts by mass of H12MDA was added, and the polyurethane resin was chain-extended by mixing and stirring. Next, 1.5 parts by mass of N, N-dibutylamine was added and mixed to obtain an intermediate layer polyurethane resin (W-5) composition.

[Synthesis Example 6] Synthesis of polyurethane resin for intermediate layer (W-6) To a reaction apparatus having a stirrer, a reflux tube and a thermometer, 1,4-butanediol and 1,6-hexanediol (molar ratio: 90 / Polycarbonate polyol using 10) as a raw material (number average molecular weight; 2,000, abbreviated as “PC-4”) was added in 363 parts by mass, and the pressure was reduced to 0.095 MPa, followed by dehydration at 120 to 130 ° C. Then, it cools to 50 degreeC, 290 mass parts of DMF, 71 mass parts of H12MDI, and 0.2 mass part of stannous octylate are added, and it is made to react at 75 degreeC, By the urethane prepolymer which has an isocyanate group An organic solvent solution was obtained. Next, 761 parts by mass of DMF was added thereto, the mixture was cooled to 35 ° C., 14 parts by mass of IPDA was added, and the polyurethane resin was chain-extended by mixing and stirring. Next, 1.5 parts by mass of N, N-dibutylamine was added and mixed to obtain a polyurethane resin (W-6) composition for intermediate layer.

[Synthesis Example 7] Synthesis of polyurethane resin for intermediate layer (W-7) To a reaction apparatus having a stirrer, a reflux tube and a thermometer, 243 parts by mass of PC-4 and 81 parts by mass of PEs-1 were added. Dehydration was performed at 120 to 130 ° C. under reduced pressure to 095 MPa. Then, it cools to 50 degreeC, 278 mass parts of DMF, 93 mass parts of H12MDI, and 0.2 mass part of stannous octylate are added, and it is made to react at 75 degreeC, The urethane prepolymer which has an isocyanate group An organic solvent solution was obtained. Next, 773 parts by mass of DMF was added thereto, cooled to 35 ° C., 30 parts by mass of IPDA were added, and the polyurethane resin was chain-extended by mixing and stirring. Next, 1.5 parts by mass of N, N-dibutylamine was added and mixed to obtain an intermediate layer polyurethane resin (W-7) composition.

[Synthesis Example 8] Synthesis of polyurethane resin for intermediate layer (W-8) To a reactor having a stirrer, a reflux tube and a thermometer, 1,5-pentanediol and 1,6-hexanediol (molar ratio: 50 / 50) was a polycarbonate polyol (number average molecular weight: 2,000, abbreviated as “PC-5”) 339 parts by mass, depressurized to 0.095 MPa and dehydrated at 120 to 130 ° C. Thereafter, the mixture was cooled to 50 ° C., 277 parts by mass of DMF, 75 parts by mass of IPDI, and 0.2 parts by mass of stannous octylate were added and reacted at 75 ° C., whereby the urethane prepolymer having an isocyanate group was reacted. An organic solvent solution was obtained. Next, 774 parts by mass of DMF was added thereto, cooled to 35 ° C., 32 parts by mass of H12MDA was added, and the mixture was stirred to extend the polyurethane resin. Next, 1.5 parts by mass of N, N-dibutylamine was added and mixed to obtain an intermediate layer polyurethane resin (W-8) composition.

[Comparative Synthesis Example 1] Synthesis of polyurethane resin for intermediate layer (W'-1) To a reactor having a stirrer, a reflux tube, and a thermometer, 198 parts by mass of PC-1 and 132 parts by mass of PEs-1 were added. Dehydration was performed at 120 to 130 ° C. under reduced pressure to 0.095 MPa. Then, it cools to 50 degreeC, 273 mass parts of DMF, 86 mass parts of H12MDI, and 0.2 mass part of stannous octylate are added, and it is made to react at 75 degreeC, The urethane prepolymer which has an isocyanate group An organic solvent solution was obtained. Next, 774 parts by mass of DMF was added thereto, cooled to 35 ° C., 31 parts by mass of H12MDA was added, and the polyurethane resin was chain-extended by mixing and stirring. Next, 1.5 parts by mass of N, N-dibutylamine was added and mixed to obtain an intermediate layer polyurethane resin (W′-1) composition.

[Comparative Synthesis Example 2] Synthesis of polyurethane resin for intermediate layer (W'-2) In a reaction apparatus having a stirrer, a reflux tube and a thermometer, 197 parts by mass of PC-1, polyoxytetramethylene glycol (number average molecular weight) : 2,000, hereinafter referred to as “PEt-2”) was added in an amount of 131 parts by mass, and the pressure was reduced to 0.095 MPa, followed by dehydration at 120 to 130 ° C. Then, it cools to 50 degreeC, 273 mass parts of DMF, 80 mass parts of IPDI, 0.2 mass part of stannous octylates are added, and it is made to react at 75 degreeC, The urethane prepolymer which has an isocyanate group An organic solvent solution was obtained. Next, 778 parts by mass of DMF was added thereto, cooled to 35 ° C., 37 parts by mass of H12MDA was added, and the mixture was stirred to extend the polyurethane resin. Next, 1.5 parts by mass of N, N-dibutylamine was added and mixed to obtain an intermediate layer polyurethane resin (W′-2) composition.

[Preparation Example 1] Preparation of skin layer compounding liquid 100 parts by mass of a solvent-based urethane resin (“Crisbon NY-331” manufactured by DIC Corporation) and 20 parts by mass of a black pigment (“DILAC L-1770S” manufactured by DIC Corporation) The mixture was stirred at 2,000 rpm for 2 minutes with a mixer, and then defoamed using a vacuum defoamer to obtain a skin layer compounding liquid.

[Adjustment Example 2] Preparation of Compounding Solution for Adhesive Layer Polycarbonate urethane resin (PC-1,4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”)), 1,4-butanediol (hereinafter, “ BG ".) 100 parts by mass, cross-linking agent (adduct of hexamethylene diisocyanate, hereinafter abbreviated as" HDI adduct "), 10 parts by mass, catalyst (" Crisbon "manufactured by DIC Corporation) Accelerator T-81E ") 1 part by mass was mixed with a homomixer to obtain a mixed solution for the adhesive layer.

[Example 1]
On the release paper ("EK-100D" manufactured by Lintec Co., Ltd.), after applying the skin layer mixture liquid obtained in Preparation Example 1 with a knife coater (application thickness 150 μm), using a hot air dryer The skin layer was obtained by drying at 70 ° C. for 2 minutes and then at 120 ° C. for 2 minutes. Further, the intermediate layer polyurethane resin (W-1) composition obtained in Synthesis Example 1 was applied onto this skin layer using a knife coater (application thickness 150 μm), and then a hot air dryer was used. And dried at 70 ° C. for 2 minutes and then at 120 ° C. for 2 minutes. Subsequently, after apply | coating the compounding liquid for adhesion layers obtained by the preparation example 2 with a knife coater (application | coating thickness 150 micrometers), it is dried at 70 degreeC for 2 minutes using a hot air dryer, and then for 2 minutes at 120 degreeC. Thus, an adhesive layer was obtained. Finally, a non-woven fabric substrate (basis weight 300 g / m ² ) is stacked on the adhesive layer, and thermocompression bonded with a hot roll press (roll temperature 130 ° C., press linear pressure 8 MPa / m ² , feed rate 1 m / min), Synthetic leather was obtained.

[Examples 2 to 8, Comparative Examples 1 and 2]
Synthetic leather was obtained in the same manner as in Example 1 except that the polyurethane resin composition for the intermediate layer used in the intermediate layer (iii) was changed as shown in Tables 1 and 2.

[Synthesis Example 9] Synthesis of polyurethane resin (D-1-1) for adhesive layer Polycarbonate diol (number average molecular weight; starting from 1,6-hexanediol) in a reactor having a stirrer, a reflux pipe, and a thermometer 2,000, abbreviated as “PC-1”.) 437 parts by mass was added, and the pressure was reduced to 0.095 MPa, followed by dehydration at 120 to 130 ° C. After cooling to 50 ° C., 340 parts by mass of N, N-dimethylformamide (hereinafter abbreviated as “DMF”), 73 parts by mass of isophorone diisocyanate (hereinafter abbreviated as “IPDI”), octylic acid The organic solvent solution of the urethane prepolymer which has an isocyanate group was obtained by adding 0.2 mass part of stannous and making it react at 75 degreeC. Next, 636 parts by mass of DMF was added thereto, cooled to 40 ° C., 10 parts by mass of isophoronediamine (hereinafter abbreviated as “IPDA”) was added, and the polyurethane resin was chain-extended by mixing and stirring. . Next, 6.0 parts by mass of monoethanolamine was added and mixed to obtain a polyurethane resin (X-1-1) composition. Immediately before coating to form an adhesive layer, the polyurethane resin (D-1-1) composition was mixed with 10% by mass of an HDI adduct to obtain a polyurethane resin composition.

[Synthesis Example 10] Synthesis of polyurethane resin for adhesive layer (D-1-2) 426 parts by mass of PC-2 was added to a reactor having a stirrer, a reflux tube and a thermometer, and the pressure was reduced to 0.095 MPa and 120 Dehydration was performed at ˜130 ° C. After cooling to 50 ° C., 340 parts by mass of N, N-dimethylformamide (hereinafter abbreviated as “DMF”) and 4,4′-dicyclohexylmethane diisocyanate (hereinafter abbreviated as “H12MDI”). 84 parts by mass and 0.2 parts by mass of stannous octylate were added and reacted at 75 ° C. to obtain an organic solvent solution of urethane prepolymer having an isocyanate group. Next, 636 parts by mass of DMF was added thereto, cooled to 40 ° C., 9 parts by mass of isophoronediamine (hereinafter abbreviated as “IPDA”) was added, and the polyurethane resin was chain-extended by mixing and stirring. . Next, 6.0 parts by mass of monoethanolamine was added and mixed to obtain a polyurethane resin (D-1-2) composition. Immediately before coating to form an adhesive layer, the polyurethane resin (D-1-2) composition was mixed with 10% by mass of an HDI adduct to obtain a polyurethane resin composition.

[Synthesis Example 11] Synthesis of polyurethane resin for adhesive layer (D-1-3) To a reactor having a stirrer, a reflux pipe, and a thermometer, 326 parts by mass of PC-1 and 109 parts by mass of PEs-1 were added. Dehydration was performed at 120 to 130 ° C. under reduced pressure to 0.095 MPa. Thereafter, the mixture was cooled to 50 ° C., 338 parts by mass of N, N-dimethylformamide (hereinafter abbreviated as “DMF”), 73 parts by mass of IPDI, and 0.2 parts by mass of stannous octylate were added, and 75 ° C. The organic solvent solution of the urethane prepolymer which has an isocyanate group was obtained by making it react. Next, 638 parts by mass of DMF was added thereto, the mixture was cooled to 40 ° C., 12 parts by mass of 4,4′-dicyclohexylmethanediamine (hereinafter abbreviated as “H12MDA”) was added, and the mixture was stirred to obtain polyurethane. The resin was chain extended. Next, 6.0 parts by mass of monoethanolamine was added and mixed to obtain a polyurethane resin (D-1-3) composition. Immediately before coating to form an adhesive layer, the polyurethane resin (D-1-3) composition was mixed with 10% by mass of an HDI adduct to obtain a polyurethane resin composition.

[Synthesis Example 12] Synthesis of polyurethane resin (D-1-4) for adhesive layer To a reactor having a stirrer, a reflux tube, and a thermometer, 320 parts by mass of PC-2 and 107 parts by mass of PEs-2 were added. Dehydration was performed at 120 to 130 ° C. under reduced pressure to 0.095 MPa. Thereafter, the mixture was cooled to 50 ° C., 340 parts by mass of N, N-dimethylformamide (hereinafter abbreviated as “DMF”), 84 parts by mass of H12MDI, and 0.2 parts by mass of stannous octylate were added, and 75 ° C. The organic solvent solution of the urethane prepolymer which has an isocyanate group was obtained by making it react. Next, 636 parts by mass of DMF was added thereto, cooled to 40 ° C., 10 parts by mass of IPDA were added, and the polyurethane resin was chain-extended by mixing and stirring. Next, 6.0 parts by mass of monoethanolamine was added and mixed to obtain a polyurethane resin (D-1-4) composition. Immediately before coating to form an adhesive layer, the polyurethane resin (D-1-4) composition was mixed with 10% by mass of an HDI adduct to obtain a polyurethane resin composition.

[Example 9]
On the release paper ("EK-100D" manufactured by Lintec Co., Ltd.), after applying the skin layer mixture liquid obtained in Preparation Example 1 with a knife coater (application thickness 150 μm), using a hot air dryer The skin layer was obtained by drying at 70 ° C. for 2 minutes and then at 120 ° C. for 2 minutes. Further, the intermediate layer polyurethane resin (W-1) composition obtained in Synthesis Example 1 was applied onto this skin layer using a knife coater (application thickness 150 μm), and then a hot air dryer was used. And dried at 70 ° C. for 2 minutes and then at 120 ° C. for 2 minutes. Subsequently, after apply | coating the compounding liquid for adhesive layers for the adhesive layers obtained by the synthesis example 9 with a knife coater (application | coating thickness 150 micrometers), it uses a hot air dryer for 2 minutes at 70 degreeC, and then it is 2 at 120 degreeC. The adhesive layer was obtained by drying for minutes. Finally, a non-woven fabric substrate (basis weight 300 g / m ² ) is stacked on the adhesive layer, and thermocompression bonded with a hot roll press (roll temperature 130 ° C., press linear pressure 8 MPa / m ² , feed rate 1 m / min), Synthetic leather was obtained.

[Examples 10 to 12]
Synthetic leather was obtained in the same manner as in Example 9, except that the polyurethane resin composition used for the intermediate layer (iii) and the adhesive layer (ii) was changed as shown in Table 3.

[Measurement method of number average molecular weight]
The number average molecular weights of the polyols and the like used in the synthesis examples and the like are values measured under the following conditions by gel permeation chromatography (GPC) method.

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 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared 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

[Chemical resistance evaluation method]
An amount of 1.5 g of a sunscreen cream (“Ultra Sheer DRY-TOUCH SUNLOCK SPF45” manufactured by Neutrogena) was uniformly applied to the skin layer of the synthetic leather obtained in Examples and Comparative Examples in a 10 cm × 10 cm frame. Then, the synthetic leather was visually observed and the chemical resistance was evaluated as follows.
“5”: No change is observed in the swelling or surface shape of the synthetic leather film.
“4”: Slight changes are observed in the swelling and surface shape of the synthetic leather film.
“3”: The film is partially expanded and part of the surface shape is changed.
“2”: The film expands everywhere or changes in the surface shape are observed.
“1”: The film is significantly expanded and the surface shape is changed.

In Tables 1 to 3, “content of (x-1) (mass%)”, “content of polycarbonate polyol (mass%)”, and “content of (a-1) (mass%)” Indicates the value rounded to the first decimal place.

The synthetic leather of the present invention was found to have excellent chemical resistance.

On the other hand, Comparative Examples 1 and 2 are embodiments in which the amount of the polycarbonate polyol of the polyurethane resin (X) used for the intermediate layer (iii) is less than the range specified in the present invention, but the chemical resistance was poor. .

Claims

A synthetic leather in which a base fabric (i), an adhesive layer (ii), an intermediate layer (iii), and a skin layer (iv) are sequentially laminated,
Reaction product of polyol (X), aliphatic or cycloaliphatic polyisocyanate (Y), and chain extender (Z) in which the intermediate layer (iii) contains 70% by mass or more of polycarbonate polyol (x-1) A synthetic leather formed of a polyurethane resin composition containing a polyurethane resin (W).
Reaction product of polyol (A), aliphatic or cycloaliphatic polyisocyanate (B), and chain extender (C) containing 70 mass% or more of polycarbonate polyol (a-1) in the adhesive layer (ii) The synthetic leather according to claim 1, wherein the synthetic leather is formed of a polyurethane resin composition comprising a hydroxyl group-containing polyurethane resin (D-1) and a crosslinking agent (D-2).
The synthetic leather according to claim 1 or 2, wherein the polyisocyanate (Y) and the alicyclic polyisocyanate (B) are isophorone diisocyanate and / or dicyclohexylmethane diisocyanate, respectively.
The synthetic leather according to any one of claims 1 to 3, wherein the chain extender (Z) and the chain extender (C) are chain extenders having an amino group.
The synthetic leather according to claim 4, wherein the chain extender having an amino group is isophoronediamine and / or dicyclohexylmethanediamine.