JPH10226970A - Leather-like sheet and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a leather-like sheet excellent in fretting flaw resistance and wear resistance on the surface, flexing resistance and slipperiness and to provide a method for producing the sheet. SOLUTION: A layer C comprising a two-pack type polyurethane resin (a) having 20,000-100,000 number-average molecular weight and a two-pack type polyurethane resin (b) having 130,000-280,000 number-average molecular weight crosslinked with a polyisocyanate-based curing agent is laminated through an adhesive layer B consisting essentially of a polyurethane to a substrate layer A containing a polymer consisting essentially of an elastic polymer in a fiber assembly. The blending ratio of the polyurethane (a) and the polyurethane (b) is 0.05-4 by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a leather-like sheet excellent in surface scratch resistance, abrasion resistance, flex resistance and slipperiness, and a method for producing the same.

[0002]

2. Description of the Related Art Various leather-like sheets having a high surface strength have been conventionally provided. For example, a leather-like sheet is known in which a coat layer made of a polyurethane containing fine particles having a Brinell hardness of 20 to 100 is formed on the base layer. On the base layer, the outermost surface is 1
Forming a coat layer having a silicon-modified urethane layer as a surface layer on a leather-like sheet or a base layer on which a coat layer of a one-component urethane having a modulus of 100% / 100 kg / cm ² or more is formed, and sliding the surface. There is also known a leather-like sheet having improved scratch resistance.

[0003]

However, among the conventionally proposed methods, Brinell hardness of 20 to 10 is used.
In the case of polyurethane containing 0 fine particles,
There is a drawback that glossiness is easily adversely affected, and scratch resistance, when exposed on the surface, leads to accelerated scratching. 100 kg / cm at 100% modulus
^In the leather-like sheet on which ^two or more one-pack type urethane layers were formed, although the scratch resistance was considerably improved, almost no effect was recognized on instantaneous scratches. Similarly, even if the outermost surface of the coat layer is a silicon-modified urethane layer, it has almost no effect on instantaneous abrasions and cannot be an effective means. The present invention provides a leather-like sheet excellent in abrasion resistance, abrasion resistance, bending resistance and slipperiness of the outermost surface, and a method for producing the same.

[0004]

Means for Solving the Problems The inventors of the present invention focused on the resin composition constituting the surface and the release paper for dry surface forming, and as a result of intensive studies, as a result, the fiber aggregate was mainly composed of an elastic polymer. On the surface of the polymer-containing base layer (A), a two-pack polyurethane resin (a) having a number average molecular weight of 20,000 to 100,000 and a two-pack polyurethane resin (b) having a number average molecular weight of 130,000 to 280,000 ) And a polyurethane resin layer containing a polyisocyanate curing agent in a solid content ratio of 10 to 75% by weight based on the total weight of the resins (a) and (b) is provided on the outermost surface, so that the surface has scratch resistance and scratch resistance. It has been found that the properties, abrasion resistance, bending resistance and slipperiness are greatly improved, and the present invention has been completed. In order to further improve the releasability, the mixed resin solution is applied onto a release paper having a polyolefin-based outermost coating layer, so that the release paper and the two-component polyurethane layer have been separated without peeling. The inventor has found that it is possible to improve the occurrence of the defect and completed the present invention.

That is, the leather-like sheet of the present invention comprises an adhesive layer (B) made of a resin mainly composed of a polyurethane resin on a base layer (A) containing a polymer mainly composed of an elastic polymer in a fiber assembly. ), The number average molecular weight is from 20,000 to 10
10,000 two-pack polyurethane resin (a) and a number average molecular weight of 1
A 30,000-280,000 two-component polyurethane resin (b) is laminated with a layer (C) made of a resin cross-linked by a polyisocyanate-based curing agent, and further comprises a polyurethane (a) and a polyurethane (b). Blend weight ratio of 0.0
5 to 4.

[0006] The method for producing a leather-like sheet of the present invention comprises:
Two-component polyurethane resin (a) having a number average molecular weight of 20,000 to 100,000, two-component polyurethane resin (b) having a number average molecular weight of 130,000 to 280,000, and the total weight of the resins (a) and (b) A polyurethane resin containing a polyisocyanate curing agent having a solid content ratio of 10 to 75% by weight is coated on release paper, dried to form a layer (C), and then the fiber is passed through an adhesive layer (B). It is characterized in that the release paper is peeled off after the assembly is adhered to a base layer containing a polymer mainly composed of an elastic polymer, and a curing reaction is performed.

Hereinafter, the present invention will be described in detail. The base layer (A) of the leather-like sheet of the present invention is a sheet in which a fiber aggregate contains a polymer mainly composed of an elastic polymer.

[0008] The fiber aggregate used in the production of the base layer (A) of the present invention includes ordinary fibers such as synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyolefin and polyvinyl alcohol, and chemical fibers such as regenerated cellulose. It is made from natural fibers or fibers of a special form, for example ultrafine fibers such as polyester, polyamide, polyacrylonitrile, or ultrafine fiber-generating fibers composed of at least two polymers. For example, extractable or degradable fibers having a sea-island structure in which the sea component is dissolved or decomposed by a solvent or a decomposing agent such as sodium hydroxide to fibrillate into island components, or mechanically or a treating agent For example, split-type fibers that cause separation at the polymer interface and fibrillate into ultrafine fibers made of each polymer are exemplified.

As the polymer constituting the ultrafine fiber, 6 is used.
-Melt-spinnable polyamides such as nylon and 66-nylon, melt-spinnable polyesters such as polyethylene terephthalate, polybutylene terephthalate and cationic dyeable modified polyethylene terephthalate, and polyolefins represented by polypropylene, etc. And at least one polymer selected from the group consisting of: In addition, the component that is extracted or decomposed and removed by the extractable or degradable fiber is a polymer having a different solubility or decomposability to a solvent or a decomposer from the ultrafine fiber component and having low compatibility with the ultrafine fiber component. A polymer having a lower melt viscosity or a lower surface tension than the ultrafine fiber component under spinning conditions, and, for example, polyethylene, polystyrene, polyethylene propylene copolymer,
It is at least one kind of polymer selected from polymers such as modified polyester.

The weight ratio of the sea component to the island component of the ultrafine fiber is 1: 2 to 2: 1, and the preferred denier of the island component after the extraction of the sea component is 0 in terms of texture and fullness. .0
A range of 1 to 0.0001 denier is preferred. These fibers are made into a web and entangled with a needle punch or a high-speed fluid flow to form a nonwoven fabric. The basis weight of the nonwoven fabric is 300 to 15
00 g / m ² , more preferably 500 to 10
Was 00g / m ^2, becomes rubber-like due to insufficient amount fiber in the case of less than 300 g / m ^2, the inflexible leather-like sheet in the case of more than 1500 g / m ^2. Further, the thickness is preferably 0.8 to 4 mm, more preferably 1 to 4 mm.
When the thickness is less than 0.8 mm or more than 4 mm, the balance at the time of forming the surface is poor, and the rubber-like or inflexible material is not obtained.

Next, the fiber entangled nonwoven fabric is impregnated with an elastic resin liquid and gelled by heating and drying, or immersed in a liquid containing a non-solvent of the elastic resin and wet-solidified to form a dense foamed sponge. I do. As the elastic resin to be impregnated here, for example, at least one kind of polymer diol selected from polyester diol having an average molecular weight of 500 to 3000, composite diol such as polyether diol, polycarbonate diol or polyester polyether diol, and 4,4 '-Diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HD
At least one diisocyanate selected from aromatic, alicyclic, and aliphatic diisocyanates such as I) and at least one low-molecular compound having two or more active hydrogen atoms and a molecular weight of 300 or less Compounds of, for example, ethylene glycol, propylene glycol,
Diols such as 1.4 butanediol, hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, xylene glycol, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine, phenylenediamine, Polyurethane obtained by reacting with at least one selected from diamines such as tolylenediamine, hydrazines such as adipic hydrazide and isophthalic dihydrazide, and hydrazides. Particularly preferably,
A polyurethane obtained by reacting a chain extender mainly composed of 1,4-butanediol or 3-methyl-1,5-pentanediol at a predetermined molar ratio, and a modified product thereof.

Further, another elastic resin such as a polyester elastomer and an elastic resin such as an acrylic resin may be used.
Further, a polymer composition obtained by mixing these may be used. But,
The above-mentioned polyurethane is preferably used from the viewpoint of flexibility, elastic recovery, sponge forming property and the like. The polymer concentration of the elastic body when impregnating the nonwoven fabric is preferably 10 to 50%,
The Young's modulus is preferably in the range of 1 to 15 kg / mm ² . Further, as the polyurethane, a polyurethane having a molar ratio of the polymer diol to the low-molecular compound in the range of 1: 1 to 1: 7 is preferable. This polyurethane is dissolved or diluted with a solvent to impregnate the fiber-entangled nonwoven fabric. The solvent used here is dimethylsulfoxide, sulfolane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, diphenylsulfone, N, N'-dimethylimidazolinone, and dimethylformamide is particularly preferably used. The polyurethane concentration in the dissolved or diluted polyurethane liquid is preferably 5 to 30% by weight,
Particularly preferably, it is 10 to 20% by weight.

The impregnated polyurethane liquid is coagulated and dewashed in a non-solvent of polyurethane, or gelled and coagulated by a dry method, and then immersed in a liquid such as perchrene, trichlene or toluene to obtain multicomponent fibers ( The base layer is prepared by converting the ultrafine fiber-generating fibers into ultrafine fiber bundle-shaped fibers. Note that the order of ultrafineness and impregnation with the elastic polymer may be reversed. The thickness of the base layer can be arbitrarily selected depending on the use of the obtained leather-like sheet, and is not particularly limited, but is preferably 0.5 to 3 in terms of balance with the surface-forming layer.
mm, more preferably in the range of 0.5 to 2 mm. The specific gravity of the base layer is preferably 0.2 to 0.7 g /
cm ³ , more preferably 0.3 to 0.5 g / cm ³
Range. The weight ratio of the fibers constituting the base layer to the elastic polymer is preferably in the range of 90:10 to 40:60.

In the present invention, the kind of the polyurethane constituting the crosslinked elastic polymer resin constituting the surface layer (C) is not particularly limited. For example, polyester-based, polyether-based, polycarbonate-based or blends thereof or modified thereof However, in consideration of durability and physical properties, a polyether type or a polycarbonate type is preferable.

The resin constituting the surface layer (C) is a two-component polyurethane resin (a) having a number average molecular weight of 20,000 to 100,000 and a two-component polyurethane resin (b) having a number average molecular weight of 130,000 to 280,000. A) a blend of polyurethane (a) and polyurethane (b) in weight ratio (a)
The value of / (b) is preferably from 0.05 to 4, and if it is less than 0.05, the scratch resistance, abrasion resistance and sliding properties are good, but the bending resistance is poor. When (a) / (b) exceeds 4, the tackiness on the outermost surface is too large, resulting in poor slipperiness.
In addition, there is a disadvantage that blocking occurs due to high surface tackiness.

Further, if a polyurethane resin having a number-average molecular weight of less than 100,000 is used alone, there is a problem in passing through sewing and other processes due to a considerable tack after the surface is formed. When used, the tack after forming is good, but there is a problem that the abrasion resistance and the bending resistance are reduced. In addition, when used as a single polyurethane resin having a number average molecular weight of 100,000 to 130,000, scratch resistance is not sufficient, and tackiness appears, so that there is a problem in sewing and other processability.

In the case of a blend of a polyurethane resin having a number-average molecular weight of 100,000 to 130,000 and a polyurethane resin having a number-average molecular weight of 20,000 to 100,000, there is a disadvantage that tack is left, and a polyurethane having a number-average molecular weight of 100,000 to 130,000 has a disadvantage. In the case of a blend of a resin and a polyurethane resin having a number average molecular weight of 130,000 to 280,000, there is a disadvantage that bending resistance is deteriorated.
Also, in the case of a blend of a polyurethane resin having a number average molecular weight of less than 20,000 and a polyurethane resin having a number average molecular weight of 130,000 to 280,000, there is a disadvantage that tack remains, and a polyurethane having a number average molecular weight of more than 280,000 has a disadvantage. Even in the case of a resin blend, there is a disadvantage that bending resistance is deteriorated. Accordingly, the polyurethane resins to be blended are a two-component polyurethane resin having a number average molecular weight of 20,000 to 100,000 and a two-component polyurethane resin having a number average molecular weight of 130,000 to 280,000. Further, the blend resin ratio (weight) of the polyurethane (A) / (b) is preferably in the range of 0.05 to 4,
More preferably, (a) / (b) is blended at a ratio of 0.2 to 2. The effect of the blended resin is not affected by the addition of a resin having a molecular weight distribution outside the range of the claims, for example, a polyurethane pigment ink within 20% by weight of the whole resin.

As the polyisocyanate curing agent to be added, an adduct of trimethylolpropane (TMP) and tolylene diisocyanate (TDI),
4'-methylenebis (cyclohexyl isocyanate)
Organic polyisocyanates such as an adduct of (HMDI), an adduct of TMP and HDI, an adduct of TMP and IPDI, and a trimer of HMDI. As the organic polyisocyanate used in the present invention, two or more different organic polyisocyanates may be used in combination, and in particular, an aromatic or alicyclic polyisocyanate may be used in combination with an aromatic polyisocyanate. If the addition amount of the polyisocyanate curing agent to the polyurethane resin solution is less than 10% by weight of the solid content, the abrasion resistance and abrasion resistance deteriorate, and if it exceeds 75%, the bending resistance deteriorates.
A range of 75% is good. More preferably, 20 to 50%
Range. In addition, various additives such as an antioxidant, an ultraviolet absorber, a pigment, a dye, a surfactant, an antistatic agent, a flame retardant, an anti-adhesive, a filler, and collagen as long as the reaction of the curing agent is not hindered. Powders and the like can also be added.

The type of polyurethane constituting the intermediate layer (D) and the adhesive layer (B) includes polyester type, polyether type, polycarbonate type, and blends or modified products thereof. Polyurethane resin is good. The purpose of providing the intermediate layer (D) is to adjust the thickness of the surface-forming layer, and is not necessarily required. The adhesive layer is for bonding the base layer (A) and the layer (C) or the base layer (A) and the intermediate layer (D).

As a method for producing the coating layer, it is preferable to use a method in which a polyurethane resin (c) is applied on release paper coated with a polyolefin resin. There are other release papers coated with alkyd-based resin, aminoacrylate-based resin, and acrylic-based resin on the outermost surface, but these release papers have the disadvantage that in the present invention, it is difficult to peel off because the adhesion to the coating resin is too good. There is. Therefore, in the present invention, it is preferable that the release paper has an outermost surface coating layer made of a polyolefin resin.

The coating method is as follows: a knife coater on release paper;
Comma coater, roll coater, reverse coater,
A method of applying by means such as a rotary screen coater is used. The thickness of the surface layer (C) after drying is 5 μm to 100 μm, preferably 10 μm to 50 μm. If it is 5 μm or less, there is a problem that the abrasion resistance is deteriorated, and if it is more than 100 μm, there is a problem that the surface wins too much and the texture is deteriorated. The thickness of the total dry layer from the outermost surface layer (C) to the adhesive layer (B) after drying is preferably 10 μm to 200 μm,
In particular, 50 μm to 100 μm is preferable. 10 μm thick
When the thickness is less than 2 mm, coating unevenness may occur, and
If it exceeds 00 μm, the texture becomes hard.

[0022]

The embodiments of the present invention will be described below with reference to specific examples, but the present invention is not limited to these examples. In the examples, parts and percentages relate to weight unless otherwise specified. Further, in the following Examples and Comparative Examples, measurement or evaluation of scratch resistance, abrasion resistance, flex resistance, and slip resistance was performed according to the following methods.

[Abrasion resistance] The abrasion resistance of the leather-like sheets obtained in Examples and Comparative Examples was about 2 kg with nails.
And the state of whitening scratches after rubbing at a speed of about 30 to 50 km / h was determined. The evaluation of the condition of the whitening flaw is as follows. ：: No whitening damage. Δ: Whitening scratches appear thin. X: Whitening scratches are conspicuous.

[Wear loss resistance] The wear loss resistance was measured according to the Taber abrasion test (JIS K7204). That is, circular test pieces having a diameter of 12 cm were cut out from the leather-like sheets obtained in the examples and comparative examples. A wear wheel (H-22) was applied to the surface of the circular test piece, and a load of 1 kgf was applied.
Perform a wear test by rotating the circular test piece 1000 times with
The weight of the test piece after the abrasion test was subtracted from the weight of the test piece before the abrasion test to obtain a Taber abrasion amount (weight reduced by abrasion) mg.

[Bending resistance] The bending resistance is determined by the FLEXO test method (JIS K6545).

[Slipperiness] The slipperiness was felt by touching with a hand, good in dry touch, slightly poor when there was a slight tack, and poor when there was a tack.

Example 1 As a base layer (A), 100 parts of 6-nylon and 100 parts of polyethylene were mixed and spun, and then stretched, crimped and cut to obtain 4 dr of 6-nylon as an island component. Raw cotton was produced. A web is made from this raw cotton by random weber and needle punched to obtain a web of 430 g / m ^2.
Entangled non-woven fabric. Then, the sheet was immersed in an aqueous solution of polyvinyl alcohol, dried, and then heat-treated at 135 ° C. to fuse polyethylene as a sea component to form a hard sheet. Thereafter, polyethylene propylene adipate glycol / 4,4-diphenylmethane diisocyanate /
A 13% DMF solution of a polyurethane elastomer obtained by polymerizing ethylene glycol at an equivalent ratio of 1/5/4 was impregnated and immersed in a coagulation bath of 30 parts of 70 parts of water and 30 parts of DMF at 30 ° C. for wet coagulation. Subsequently, this sheet was immersed in perchren to extract polyethylene as a sea component, and a 6-nylon ultrafine fiber bundle (average denier of single fiber, 0.01%) was used.
Thus, a base layer (A) having a porous polyurethane elastomer inside the entangled denier was obtained. This sheet has a basis weight of 37
0 g / m ² , apparent density 0.35 g / cm ³ , thickness 1 mm
Met.

Next, dry molding was performed, and a polyurethane resin solution constituting the surface layer (C) was prepared in the following manner. Two-component polyurethane (a) (a 1,6-hexane polycarbonate polyol as a polyol component, tolylene diisocyanate (TDI) as a diisocyanate compound, and dimethylformamide (D) having a solid content of 70% polymerized from ethylene glycol as a chain extender
MF) solution, 10 parts of a number-average molecular weight: 70,000, two-pack polyurethane (b) (1,6-hexane polycarbonate polyol as a polyol component, and tolylene diisocyanate (TDI) as a diisocyanate compound);
DMF solution having a solid content of 30% polymerized from ethylene glycol as a chain extender, number average molecular weight 170,000) 90
Parts were blended. The blend ratio of this blend was (a) / (b) was 0.26.

With respect to 100 parts of the blend resin (c),
6 parts of a titanium oxide powder as a pigment, 15 parts of a polyisocyanate curing agent (d) (a 75% solids concentration ethyl acetate solution in an adduct of TMP and HDI) (33% solids ratio of curing agent to polyurethane resin), 5 parts of an amine catalyst (e) (solid content: 4%) as a curing accelerator, 40 parts of DMF as a diluting solvent, and 40 parts of methyl ethyl ketone (MEK)
Parts, uniformly mixed to prepare a coating solution, and coated on a release paper (AR-60SG manufactured by Asahi Roll Co., whose surface was coated with a polyolefin resin) at a coating amount of 100 g / m ^{2 with} a comma coater. Apply evenly, 1
The film was dried in a drying oven at 00 to 130 ° C. for 1 minute to obtain a film.

Then, 100 parts of the two-component polyurethane (a) as an adhesive layer (B) and 6 parts of titanium oxide powder
Parts, 8 parts of a polyisocyanate curing agent (d), 5 parts of an amine catalyst (e), 15 parts of DMF, and 15 parts of MEK, and uniformly mixed. The coating was uniformly applied at a coating amount of m ² and dried in a drying oven at 70 ° C. for 1 minute to obtain a film. Then, the base layer (A) was pressed and bonded on the sheet by dry lamination in a state of having an adhesive property immediately after drying. Then, after leaving at 60 ° C. for 48 hours, the release paper was peeled off to obtain a desired leather-like sheet. As shown in Table 1, the obtained sheet was excellent in bending resistance, abrasion resistance and abrasion resistance, and had good sliding properties.

Comparative Example 1 Using the base layer (A) of Example 1, dry molding was performed in the following manner. As a polyurethane resin solution constituting a surface layer, 6 parts of titanium oxide powder as a pigment and 100 parts of a two-component polyurethane (a) were blended with Example 1 without blending the two-component polyurethane (b), and polyisocyanate was cured. 15 parts of an agent (d), 5 parts of an amine catalyst (e) as a curing accelerator, 40 parts of DMF and 40 parts of methyl ethyl ketone (MEK) as a diluting solvent were added and uniformly mixed to prepare a coating solution. The coating solution was uniformly applied on the top with a comma coater at an application amount of 100 g / m ² and dried in a drying oven at 100 to 130 ° C. for 1 minute to obtain a film.

Then, as an adhesive layer (B) thereon, 2
100 parts of liquid type polyurethane (a), titanium oxide powder 6
Parts, 8 parts of a polycisocyanate curing agent (d), 5 parts of an amine catalyst (e), 15 parts of DMF and 15 parts of MEK were uniformly coated with a comma coater at a coating amount of 100 g / m ² , The film was dried in a drying oven at 70 ° C. for 1 minute to obtain a film. Immediately after drying, the sheet was pressed and bonded to the base layer (A) by dry lamination in a state of still having tackiness. Thereafter, after leaving at 60 ° C. for 48 hours, the release paper was peeled off to obtain a leather-like sheet. As shown in Table 1, the obtained sheet had good bending resistance, abrasion resistance and abrasion resistance, but had a tacky tack with poor slipperiness, and the desired sheet could not be obtained.

Comparative Example 2 Using the substrate layer (A) of Example 1, dry molding was performed in the following manner. The polyurethane resin solution constituting the surface layer (C) was prepared by mixing the two-component polyurethane (a) with the two-component polyurethane (a) without blending the two-component polyurethane (a).
With respect to 00 parts, 6 parts of titanium oxide powder as a pigment, 15 parts of a polyisocyanate curing agent (d), 5 parts of an amine catalyst (e) as a curing accelerator, 40 parts of DMF as a diluting solvent,
40 parts of methyl ethyl ketone (MEK) was added and mixed uniformly to prepare a coating solution, and 100 g / m ² was uniformly applied on the release paper with a comma coater.
The coating was dried in a drying oven at １３０130 ° C. for 1 minute to obtain a film. Then, as an adhesive layer (B), 100 parts of a two-component polyurethane (a), 6 parts of titanium oxide powder, 8 parts of a polycisocyanate curing agent (d), 5 parts of an amine catalyst (e), D
A uniform mixture of 15 parts of MF and 15 parts of MEK was uniformly applied at a coating amount of 100 g / m ² with a comma coater, and dried in a drying oven at 70 ° C. for 1 minute to obtain a film. Then, the sheet was pressed and bonded to the base layer (A) by dry lamination in a state having the adhesiveness immediately after drying. Thereafter, after leaving at 60 ° C. for 48 hours, the release paper was peeled off to obtain a leather-like sheet. The obtained leather-like sheet is shown in Table 1.
As shown in Table 2, the scratch resistance, abrasion resistance and slipperiness of the outermost surface were good, but the bending resistance was poor and the target sheet could not be obtained.

Example 2 Using the base layer (A) of Example 1, dry molding was performed in the following manner. As the polyurethane resin solution constituting the surface layer, 10 parts of the two-component polyurethane (a) and 90 parts of the two-component polyurethane (b) were blended. The blend ratio of this blend is (a) / (b) is 0.26. For 100 parts of this blend resin (c), 6 parts of titanium oxide powder as a pigment and 3 parts of polyisocyanate curing agent (d) (solid content ratio of curing agent to polyurethane resin 6.6)
%), And the amount of the curing agent added was extremely smaller than that in Example 1. Further, 5 parts of an amine catalyst (e) (solid content: 4%) as a curing accelerator and DMF40 as a diluting solvent were used.
And 40 parts of methyl ethyl ketone (MEK) were added and uniformly mixed to prepare a coating solution. The coating liquid was uniformly applied on the release paper at a coating amount of 100 g / m ^{2 with} a comma coater. For 1 minute to obtain a film. Then, 100 parts of a two-component polyurethane (a), 6 parts of titanium oxide powder, 8 parts of a polycisocyanate curing agent (d), and 5 parts of an amine catalyst (e) were formed thereon as an adhesive layer (B).
Parts, 15 parts of DMF and 15 parts of MEK were uniformly applied by a comma coater at an application amount of 100 g / m ² and dried in a drying oven at 70 ° C. for 1 minute to obtain a film. Then, the sheet was pressed and bonded to the base layer (A) by dry lamination in a state having the adhesiveness immediately after drying. Then, after leaving at 60 ° C. for 48 hours, the release paper was peeled off to obtain a desired leather-like sheet. As shown in Table 1, the obtained sheet was a leather-like sheet having good bending resistance but not necessarily good scratch resistance, abrasion resistance and slipperiness.

Example 3 Using the base layer (A) of Example 1, dry molding was performed in the following manner. As the polyurethane resin solution constituting the surface layer, 10 parts of the two-component polyurethane (a) and 90 parts of the two-component polyurethane (b) were blended. The blend ratio of this blend is (a) / (b) is 0.26.
6 parts of titanium oxide powder as a pigment and 100 parts of a polyisocyanate curing agent (d) are added to 100 parts of the blend resin (c).
Part (solid content ratio of curing agent to polyurethane resin 11
0%), and the amount of the curing agent added was much larger than that in Example 1. Further, 5 parts of an amine catalyst (e) (solid content: 4%) as a curing accelerator and DMF40 as a diluting solvent were used.
And 40 parts of methyl ethyl ketone (MEK) were added and uniformly mixed, and the mixture was uniformly coated on the release paper at a coating amount of 100 g / m ^{2 with} a comma coater.
The film was dried in a drying oven at 130 ° C. for 1 minute to obtain a film. Then, 100 parts of a two-component polyurethane (a), 6 parts of titanium oxide powder, 8 parts of a polyisocyanate curing agent (d), 5 parts of an amine catalyst (e),
100 g / m ² of a uniform mixed solution composed of 15 parts of MF and 15 parts of MEK is uniformly applied with a comma coater,
For 1 minute in a drying oven to obtain a film. Then, the sheet was pressed and bonded to the base layer (A) by dry lamination in a state having the adhesiveness immediately after drying. Then, after leaving at 60 ° C. for 48 hours, the release paper was peeled off to obtain a desired leather-like sheet. As shown in Table 1, the obtained sheet was a leather-like sheet having good abrasion resistance, abrasion resistance and slipperiness, but not sufficiently good bending resistance.

Comparative Example 3 Using the substrate layer (A) of Example 1, dry molding was performed in the following manner. As a polyurethane resin solution constituting the surface layer (C), a two-component polyurethane (f) (a 1,6-hexane polycarbonate polyol as a polyol component, a tolylene diisocyanate (TDI) as a diisocyanate compound) and a chain extension as in Example 1 70% of solid content polymerized from ethylene glycol as an agent
100 parts of DMF solution (number average molecular weight 110,000)
6 parts of titanium oxide powder as a pigment, polyisocyanate curing agent (d), and amine catalyst (e) 5 as a curing accelerator
Parts, 40 parts of DMF and 40 parts of methyl ethyl ketone (MEK) were added as a diluting solvent, and the coating liquid mixed uniformly was coated on the release paper with a comma coater in an amount of 100 g.
/ M ² and apply in a drying oven at 100-130 ° C.
After drying for a minute, a film was obtained. Then, 100 parts of a two-component polyurethane (a), 6 parts of titanium oxide powder, and a polyisocyanate curing agent (d) 8 were formed thereon as an adhesive layer (B).
Parts, amine catalyst (e) 5 parts, DMF 15 parts and MEK
15 parts of a uniform solution is applied with a comma coater at an application amount of 1
The coating was uniformly applied at a rate of 00 g / m ² and dried in a drying oven at 70 ° C. for 1 minute to obtain a film. Then, the sheet was pressed and bonded to the base layer (A) by dry lamination in a state of having an adhesive property immediately after drying. Then at 60 ° C for 48
After leaving for a while, the release paper was peeled off to obtain a leather-like sheet. As shown in Table 1, the obtained sheet had good bending resistance and abrasion resistance, but did not satisfy the abrasion resistance effect and the slipping effect, and the intended sheet was not obtained.

[0037]

[Table 1]

The overall evaluation method is as shown below. ：: good, △: slightly poor, ×: bad.

[0039]

Industrial Applicability According to the present invention, a leather-like sheet having excellent outermost surface abrasion resistance, abrasion resistance, flex resistance and slipperiness can be obtained. The leather-like sheet of the present invention can be used for sports goods, general shoes, It can be used for bags such as bags and bags, clothing and clothing parts.

Claims (6)

[Claims] 1. A method according to claim 1, wherein the fiber aggregate comprises a base layer (A) containing a polymer mainly composed of an elastic polymer, and an adhesive layer (B) mainly composed of a polyurethane resin interposed therebetween to form a number average. A layer composed of a two-component polyurethane resin (a) having a molecular weight of 20,000 to 100,000 and a two-component polyurethane resin (b) having a number-average molecular weight of 130,000 to 280,000 cross-linked with a polyisocyanate-based curing agent A leather-like sheet on which (C) is laminated. 2. The blend weight ratio of polyurethane (a) and polyurethane (b) is from 0.05 to 4.
A leather-like sheet as described. 3. The leather-like sheet according to claim 1, wherein a polyurethane intermediate layer (D) is provided between the layer (C) and the adhesive layer (B). 4. A two-pack polyurethane resin (a) having a number average molecular weight of 20,000 to 100,000, a two-pack polyurethane resin (b) having a number average molecular weight of 130,000 to 280,000, and said resin (a) and (a). A polyurethane resin containing a polyisocyanate curing agent having a solid content ratio of 10 to 75% by weight based on the total weight of b) is applied on release paper, dried to form a layer (C), and then an adhesive layer (B) A leather-like material characterized in that the release paper is peeled off after affixing to a base layer (A) containing a polymer mainly composed of an elastic polymer to a fiber assembly through a fiber assembly to cause a curing reaction. Sheet manufacturing method. 5. The method according to claim 4, wherein the blend weight ratio of the polyurethane (a) and the polyurethane (b) is 0.05 to 4. 6. The method according to claim 4, wherein the outermost coating layer of the release paper is made of polyolefin.