JP3400281B2 - Leather-like sheet and method for producing the same - Google Patents

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 having excellent surface abrasion resistance, abrasion resistance, bending resistance and slippage, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, various leather-like sheets having high surface strength have been provided. For example, a leather-like sheet is known in which a coat layer made of polyurethane containing fine particles having a Brinell hardness of 20 to 100 is formed on the outermost surface of a base layer. The outermost surface is 1 on the base layer.
To form a coat layer having a silicone-modified urethane layer as a surface layer on a leather-like sheet having a coat layer formed of a one-component urethane having a 00% modulus of 100 kg / cm ² or more, or a base layer, and sliding the surface. A leather-like sheet having improved scratch resistance is also known.

[0003]

However, among the methods conventionally proposed, the Brinell hardness of 20 to 10 is used.
In the case of a polyurethane containing 0 fine particles,
It has a drawback that it tends to have an adverse effect on the glossiness, and in terms of scratch resistance, when exposed to the surface, it promotes scratches. 100 kg / cm at 100% modulus
^In the leather-like sheet having ^two or more one-pack type urethane layers formed, scratch resistance was considerably improved, but almost no effect was recognized against instantaneous scratches. Similarly, even if the outermost surface of the coat layer is a silicone-modified urethane layer, it is hardly effective against instantaneous scratches and cannot be an effective means. The present invention provides a leather-like sheet having excellent scratch resistance, abrasion resistance, bending resistance and slipperiness on the outermost surface, and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have paid attention to the resin composition constituting the surface and the release paper for dry surface-making, and as a result of diligent study, as a result, the fiber assembly was mainly composed of an elastic polymer. On the surface of the base layer (A) containing a polymer, 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. ) And a polyurethane resin layer containing a polyisocyanate curing agent in a solid content ratio of 10 to 75% by weight with respect to the total weight of the resins (a) and (b) is provided on the outermost surface, the surface has scratch resistance and scratch resistance. The inventors have found that the properties, abrasion resistance, flex resistance and slippage are greatly improved, and have completed the present invention. In order to further improve the releasability, by coating the mixed resin solution on a release paper whose outermost surface coating layer is made of polyolefin, the release paper and the two-component polyurethane layer have not been peeled until now. The inventors have found that it is possible to improve the fact that a defect has occurred, and have completed the present invention.

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

The method for producing a leather-like sheet of the present invention is
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 a release paper and dried to form a layer (C), and then a fiber is formed through an adhesive layer (B). The release paper is peeled off after the assembly is adhered to a base layer containing a polymer mainly composed of an elastic polymer to cause a curing reaction.

The present invention will be described in detail below. The base layer (A) of the leather-like sheet of the present invention is a sheet containing a polymer mainly composed of an elastic polymer in a fiber assembly.

The fiber assembly 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 of natural fibers or fibers of a special form, for example, ultrafine fibers such as polyester, polyamide, polyacrylonitrile, etc., or ultrafine fiber generating fibers composed of at least two kinds of polymers. For example, an extractable or degradable fiber having a sea-island structure having a cross section such that the sea component is dissolved or decomposed by a solvent or a decomposing agent such as sodium hydroxide into an island component, or mechanically or a treating agent. As a result, there is a split-type fiber or the like in which separation occurs at the polymer interface and fibrillates into ultrafine fibers made of each polymer.

As the polymer constituting the ultrafine fibers, 6
-Nylon, melt-spinnable polyamides such as 66-nylon, polyethylene terephthalate, polybutylene terephthalate, melt-spinnable polyesters such as cationic dyeable modified polyethylene terephthalate, polyolefins represented by polypropylene, etc. At least one polymer selected from Further, the component extracted or decomposed and removed by the extractable or degradable fiber is a polymer having a different solubility or degradability in a solvent or a degrading agent from the ultrafine fiber component and having a small compatibility with the ultrafine fiber component. , And a polymer having a smaller melt viscosity or a smaller surface tension than the ultrafine fiber component under spinning conditions, for example, polyethylene, polystyrene, polyethylene propylene copolymer,
It is at least one polymer selected from polymers such as modified polyester.

The weight ratio of the sea component to the island component of this ultrafine fiber is 1: 2 to 2: 1. As a preferable denier of the island component after extracting the sea component, in terms of texture and fullness, 0 .0
A range of 1 to 0.0001 denier is preferred. These fibers are used as webs and entangled by needle punching or high-speed fluid flow to form a nonwoven fabric. Nonwoven fabric weight is 300 to 15
00 g / m ² is preferable, and 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
When the thickness is less than 0.8 mm or more than 4 mm, the balance at the time of making a surface is poor, and it becomes rubber-like or inflexible.

Next, the fiber-entangled non-woven fabric is impregnated with an elastic resin liquid and gelled by heating and drying, or by immersing in a liquid containing a non-solvent of the elastic resin and wet coagulation to form a dense foam sponge. To do. Examples of the elastic resin impregnated here include at least one polymer diol selected from composite diols having an average molecular weight of 500 to 3000, such as polyester diol, polyether diol, polycarbonate diol, polyester polyether diol, and the like; '-Diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HD
I) such as at least one kind of diisocyanate selected from aromatic, alicyclic and aliphatic diisocyanates and at least one kind of low molecular weight compound having two or more active hydrogen atoms and having a molecular weight of 300 or less. A compound of, for example, ethylene glycol, propylene glycol,
1.4-butanediol, hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, diols such as xylene glycol, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine, phenylenediamine, A polyurethane obtained by reacting with at least one selected from diamines such as tolylenediamine, hydrazine such as adipic acid hydrazide and isophthalic acid dihydrazide, hydrazides and the like. 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, other elastic resin such as polyester elastomer and elastic resin such as acrylic resin may be used.
A polymer composition obtained by mixing these may also be used. But,
The above-mentioned polyurethane is preferably used because of its flexibility, elastic recovery property, 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 in which the molar ratio of the polymer diol and the low molecular weight compound is 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 dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, diphenylsulfone, N, N'-dimethylimidazolinone, etc., and dimethylformamide is particularly preferably used. The concentration of polyurethane in the dissolved or diluted polyurethane liquid is preferably 5 to 30% by weight,
It is particularly preferably 10 to 20% by weight.

The impregnated polyurethane liquid is coagulated and dewashed in a non-solvent of polyurethane, or after gelling and coagulation by a dry method, it is immersed in a liquid such as Perkren, trichlene, toluene or the like to prepare multi-component fibers ( The base layer is prepared by forming (ultrafine fiber-generating fiber) into a bundle of ultrafine fibers. Note that the order of ultrafine and impregnation with the elastic polymer may be reversed. The thickness of the base layer can be arbitrarily selected depending on the intended use of the obtained leather-like sheet and is not particularly limited, but is preferably 0.5 to 3 from the viewpoint of balance with the surface layer.
mm, and more preferably 0.5 to 2 mm. The specific gravity of the base layer is preferably 0.2 to 0.7 g /
cm ³ , and more preferably 0.3 to 0.5 g / cm ^3.
Is the range. The weight ratio of the fibers constituting the base layer and the elastic polymer is preferably 90:10 to 40:60.

In the present invention, the type of polyurethane constituting the crosslinked elastic polymer resin constituting the surface layer (C) is not particularly limited, and examples thereof include polyester type, polyether type, polycarbonate type, blends thereof or modifications thereof. Examples thereof include a body, and in consideration of durability and physical properties, a polyether type or a polycarbonate type is preferable.

The resin constituting the surface layer (C) includes 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. ), Which is a cross-linked product of the blended product of (a) and polyurethane (a) and polyurethane (b).
/ (B) is preferably from 0.05 to 4, and when it is less than 0.05, there is a defect that abrasion resistance, abrasion resistance and slidability are good, but bending resistance is bad. When (a) / (b) exceeds 4, tackiness on the outermost surface is excessive and slipperiness deteriorates.
In addition, there is a drawback that blocking occurs due to high surface tackiness.

Further, when used as a single polyurethane resin having a number average molecular weight of less than 100,000, there is a problem in passingability in sewing and other processes because there is considerable tack after the surface is made. When used, the tack after fabrication is good, but there is a problem that abrasion resistance and flex resistance are deteriorated. Further, when it is used as a single polyurethane resin having a number average molecular weight of 100,000 to 130,000, scratch resistance is not sufficient, and tack is generated, which causes a problem in sewing and other process passability.

Further, 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 drawback that tack remains, and a polyurethane having a number average molecular weight of 100,000 to 130,000 is used. 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 drawback that the bending resistance becomes poor.
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 drawback that tack remains, and a polyurethane having a number average molecular weight of more than 280,000 is present. Even in the case of blending resins, there is a drawback that the bending resistance becomes poor. 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, and the blending 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 blended resin does not affect the effect even if a resin having a molecular weight distribution outside the claimed range, such as a polyurethane-based pigment ink, is added within 20% by weight of the total resin.

As the polyisocyanate curing agent to be added, an adduct of trimethylolpropane (TMP) and tolylene diisocyanate (TDI), TMP and 4,
4'-methylenebis (cyclohexyl isocyanate)
Examples include organic polyisocyanates such as (HMDI) adduct, TMP and HDI adduct, TMP and IPDI adduct, and HMDI trimer. As the organic polyisocyanate used in the present invention, two or more different organic polyisocyanates may be used in combination, and in particular, an aliphatic or alicyclic polyisocyanate may be used in combination with an aromatic polyisocyanate. If the amount of polyisocyanate curing agent added to the polyurethane resin solution is less than 10% by weight of the solid content, the abrasion resistance and abrasion resistance will deteriorate, and if it exceeds 75%, the bending resistance will deteriorate.
A range of 75% is good. More preferably, 20 to 50%
Is the range. If necessary, various additives such as antioxidants, ultraviolet absorbers, pigments, dyes, surfactants, antistatic agents, flame retardants, anti-adhesives, fillers, etc. and collagen within a range that does not hinder the reaction of the curing agent. Powder or the like can also be added.

The type of polyurethane constituting the intermediate layer (D) and the adhesive layer (B) may be polyester type, polyether type, polycarbonate type, or blends or modified products thereof, but the present invention is not particularly limited. Polyurethane resin is good. Further, the purpose of providing the intermediate layer (D) is to adjust the thickness of the face-making layer and is not always necessary. 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 onto a release paper coated with a polyolefin resin. In addition, there are release papers coated with alkyd resin, amino acrylate resin, acrylic resin on the outermost surface, but these release papers in the present invention have the disadvantage that they are difficult to peel off because they have too good adhesion with the coating resin. There is. Therefore, it is preferable in the present invention that the outermost surface coating layer of the release paper is made of polyolefin resin.

The coating method is a knife coater on release paper,
Comma coater, roll coater, reverse coater,
A method of applying by a 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 is too strong and the texture is deteriorated. Further, the thickness of the total dry surface-forming layer from the outermost surface layer (C) to the adhesive layer (B) after drying is preferably 10 μm to 200 μm,
Particularly, 50 μm to 100 μm is preferable. Film thickness is 10 μm
If it is less than the range, uneven coating may occur, and the film thickness is 2
If it exceeds 00 μm, the texture becomes hard.

[0022]

EXAMPLES 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. Parts and% in the examples relate to weight unless otherwise specified. Further, in the following examples and comparative examples, the scratch resistance, abrasion resistance, flex resistance and slippage were measured or evaluated according to the following methods.

[Scratch resistance] The scratch resistance of the leather-like sheets obtained in Examples and Comparative Examples is about 2 kg with nails.
The condition of whitening scratches after rubbing at a speed of about 30 to 50 km per hour was determined by adjusting so as to apply the load. The condition of whitening scratches is evaluated as follows. ◯: No whitening scratches. B: Whitening scratches appear thin. X: Whitening scratches are noticeable.

[Abrasion Resistance Reduction] The abrasion resistance reduction was measured according to the Taber abrasion test (JIS K7204). That is, a circular test piece having a diameter of 12 cm was cut out from the leather-like sheet obtained in each of Examples and Comparative Examples. A wear wheel (H-22) is applied to the surface of this circular test piece to produce a load of 1 kgf.
A circular test piece is rotated 1000 times to perform a wear test,
The Taber abrasion amount (weight reduced by abrasion) mg was obtained by subtracting the weight of the specimen after the abrasion test from the weight of the specimen before the abrasion test.

[Flex resistance] Flex resistance is determined by the FLEXO test method (JIS K6545).

[Slipping Property] Sliding property is a touch feeling with a hand, good for dry touch, good for slight tack, and bad for 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 give a 4 dr of 6-nylon as an island component. Raw cotton was produced. A web is made from this raw cotton by a random weber and needle punched to 430 g / m ^2.
Made entangled non-woven fabric. Then, it was dipped in an aqueous solution of polyvinyl alcohol, dried and further heat-treated at 135 ° C. to fuse polyethylene as a sea component to form a hard sheet. After that, 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 ⅕ was impregnated and immersed in a coagulation bath of 70 parts of water and 30 parts of DMF at 30 ° C. for wet coagulation. Subsequently, this sheet was immersed in Perkren to extract polyethylene as a sea component, and an ultrafine fiber bundle of 6-nylon (average denier of single fiber, 0.01
A base layer (A) having a porous polyurethane elastomer inside the entanglement of 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, a dry surface is formed, and a polyurethane resin solution constituting the surface layer (C) was prepared in the following manner. Two-component polyurethane (a) (1,6-hexane polycarbonate polyol as a polyol component, tolylene diisocyanate (TDI) as a diisocyanate compound, and dimethylformamide (D) having a solid content concentration of 70% polymerized from ethylene glycol as a chain extender.
MF) solution, 10 parts of number average molecular weight: 70,000, two-component polyurethane (b) (1,6-hexane polycarbonate polyol as a polyol component, and tolylene diisocyanate (TDI) as a diisocyanate compound,
Polymerized from ethylene glycol as a chain extender, DMF solution with a solid concentration of 30%, number average molecular weight 170,000) 90
Parts were blended. The blend ratio (a) / (b) of this blend was 0.26.

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

Then, 100 parts of two-component polyurethane (a) as an adhesive layer (B) and 6 parts of titanium oxide powder were formed thereon.
Parts, 8 parts of the polyisocyanate curing agent (d), 5 parts of the amine-based catalyst (e), 15 parts of DMF and 15 parts of MEK and uniformly mixed, and further 100 g / commercial on the surface layer with a comma coater. A coating amount of m ² was applied uniformly, followed by drying for 1 minute in a drying oven at 70 ° C. to obtain a film. Then, the base layer (A) was pressed and laminated on the sheet by dry lamination immediately after drying in a state of having tackiness. Then, after leaving it 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 slidability.

Comparative Example 1 The substrate layer (A) of Example 1 was used, and a dry-fabricated surface was formed as follows. As the polyurethane resin solution forming the surface layer, 100 parts of the two-component polyurethane (a) without blending the two-component polyurethane (b) with respect to Example 1, 6 parts of titanium oxide powder as a pigment, and polyisocyanate curing The release paper is prepared by adding 15 parts of the agent (d), 5 parts of the amine catalyst (e) as a curing accelerator, 40 parts of DMF and 40 parts of methyl ethyl ketone (MEK) as a diluting solvent, and uniformly mixing them to prepare a coating liquid. This coating solution was applied uniformly on the above with a comma coater at a coating 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
Liquid polyurethane (a) 100 parts, titanium oxide powder 6
Part, polyisocyanate curing agent (d) 8 parts, amine-based catalyst (e) 5 parts, DMF 15 parts and MEK 15 parts were uniformly applied with a comma coater at an application amount of 100 g / m ² . A film was obtained by drying for 1 minute in a drying oven at 70 ° C. Immediately after being dried, the sheet was dried and laminated on the base layer (A) by pressing on the base layer (A). After that, the release paper was peeled off after standing at 60 ° C. for 48 hours 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 tackiness with poor slipperiness, and the intended sheet could not be obtained.

Comparative Example 2 Using the substrate layer (A) of Example 1, a dry surface-making process was carried out in the following manner. The polyurethane resin solution constituting the surface layer (C) was prepared by blending the two-component polyurethane (a) with the two-component polyurethane (b) 1 in comparison with Example 1 described above.
To 00 parts, 6 parts titanium oxide powder as a pigment, 15 parts polyisocyanate curing agent (d), 5 parts amine catalyst (e) as a curing accelerator, 40 parts DMF as a diluting solvent,
40 parts of methyl ethyl ketone (MEK) was added and uniformly mixed to prepare a coating solution, and 100 g / m ² was evenly applied onto the release paper with a comma coater.
A film was obtained by drying in a drying oven at ˜130 ° C. for 1 minute. Then, 100 parts of two-component polyurethane (a), 6 parts of titanium oxide powder, 8 parts of polycisocyanate curing agent (d), 5 parts of amine-based catalyst (e), D as an adhesive layer (B) thereon.
A uniform mixed solution consisting of 15 parts of MF and 15 parts of MEK was applied uniformly with a comma coater at a coating amount of 100 g / m ² , and dried in a drying oven at 70 ° C. for 1 minute to obtain a film. Then, in the state of having the tackiness immediately after drying, the sheet was pressed and bonded to the base layer (A) by dry lamination. After that, the release paper was peeled off after standing at 60 ° C. for 48 hours to obtain a leather-like sheet. The leather-like sheet obtained is shown in Table 1.
As shown in, the abrasion resistance, the abrasion resistance, and the 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 substrate layer (A) of Example 1, a dry surface-making process was carried out as follows. The polyurethane resin solution forming the surface layer was prepared by blending 10 parts of the two-component polyurethane (a) and 90 parts of the two-component polyurethane (b). The blend ratio of this blend is (a) / (b) is 0.26. To 100 parts of this blended 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) were used.
%), And the addition amount of the curing agent was set to be extremely smaller than that in Example 1. Furthermore, 5 parts of an amine-based catalyst (e) (solid content 4%) as a curing accelerator, and DMF40 as a diluting solvent
Parts, 40 parts of methyl ethyl ketone (MEK) are added and uniformly mixed to prepare a coating solution, and the release paper is evenly coated with a comma coater at a coating amount of 100 g / m ² , and a drying oven at 100 to 130 ° C. And dried for 1 minute to obtain a film. Then, 2-component polyurethane (a) 100 parts as the adhesive layer (B) thereon, 6 parts of titanium oxide powder, poly Lee <br/> isocyanate curing agent (d) 8 parts of amine catalyst (e) 5
Part, DMF 15 parts, and MEK 15 parts were uniformly applied with 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, in a state of having tackiness immediately after drying, the sheet was dry laminated and pressed onto the base layer (A) to be laminated. Then, after leaving it 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 flex resistance but poor abrasion resistance, abrasion resistance and slipperiness.

Example 3 Using the substrate layer (A) of Example 1, a dry surface-making process was carried out in the following manner. The polyurethane resin solution forming the surface layer was prepared by blending 10 parts of the two-component polyurethane (a) and 90 parts of the two-component polyurethane (b). The blend ratio (a) / (b) of this blend is 0.26.
To 100 parts of this blended resin (c), 6 parts of titanium oxide powder as a pigment and 50 parts of polyisocyanate curing agent (d)
Part (solid content ratio of curing agent to polyurethane resin 11
0%), and the addition amount of the curing agent was set to an extremely large amount as compared with Example 1. Furthermore, 5 parts of an amine-based catalyst (e) (solid content 4%) as a curing accelerator, and DMF40 as a diluting solvent
Parts and 40 parts of methyl ethyl ketone (MEK) were added and uniformly mixed to prepare a solution, which was uniformly applied onto the release paper with a comma coater at an application amount of 100 g / m ² ,
A film was obtained by drying for 1 minute in a drying oven at 130 ° C. Then, 100 parts of two-component polyurethane (a), 6 parts of titanium oxide powder, 8 parts of polyisocyanate curing agent (d), 5 parts of amine-based catalyst (e), and D as an adhesive layer (B) thereon.
A uniform mixed solution consisting of 15 parts of MF and 15 parts of MEK was evenly applied at 100 g / m ² with a comma coater, and 70 ° C.
It was dried for 1 minute in the drying oven of No. 1 to obtain a film. Then, in a state of having tackiness immediately after drying, the sheet was dry laminated and pressed onto the base layer (A) to be laminated. Then, after leaving it 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 slippage, but not sufficient flex resistance.

Comparative Example 3 Using the substrate layer (A) of Example 1, a dry surface-making process was carried out in the following manner. As a polyurethane resin solution constituting the surface layer (C), a two-component polyurethane (f) was prepared as in Example 1 (1,6-hexane polycarbonate polyol as a polyol component, tolylene diisocyanate (TDI) as a diisocyanate compound, and chain extension). 70% solid content polymerized from ethylene glycol as an agent
Of DMF solution (number average molecular weight 110,000) of
6 parts of titanium oxide powder as a pigment, polyisocyanate curing agent (d), amine catalyst (e) 5 as a curing accelerator
Parts, 40 parts of DMF as a diluting solvent, and 40 parts of methyl ethyl ketone (MEK) were added and uniformly mixed, and a coating liquid of 100 g was applied onto the release paper with a comma coater.
/ M ² and apply evenly in a drying oven at 100-130 ° C.
After drying for a minute, a film was obtained. Then, 100 parts of two-component polyurethane (a), 6 parts of titanium oxide powder, and polyisocyanate curing agent (d) 8 as an adhesive layer (B) thereon.
Parts, 5 parts of amine-based catalyst (e), 15 parts of DMF and MEK
Apply 15 parts of homogeneous solution with comma coater
The coating was uniformly applied at 00 g / m ² and dried in a drying oven at 70 ° C. for 1 minute to obtain a film. Immediately after drying, the sheet was dried and laminated on the base layer (A) by pressing and adhering to the sheet while still sticking. Then 48 at 60 ° C
After being left for a period of time, the release paper was peeled off to obtain a leather-like sheet. As shown in Table 1, the obtained sheet was good in flex resistance and abrasion resistance, but the scuff resistance effect and the slipping effect were not satisfied, and the intended sheet could not be obtained.

[0037]

[Table 1]

The comprehensive evaluation method is as shown below. ◯: Good, Δ: Slightly bad, X: Bad.

[0039]

EFFECTS OF THE INVENTION According to the present invention, a leather-like sheet having excellent scratch resistance, abrasion resistance, bending resistance and slipperiness on the outermost surface can be obtained, and the leather-like sheet of the present invention can be used for sports goods, general shoes, It can be used for bags, bags such as bags, clothing and clothing parts.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-6-81275 (JP, A) JP-A-5-279967 (JP, A) JP-A-5-222681 (JP, A) JP-A-5- 163684 (JP, A) JP 5-163682 (JP, A) JP 2-127574 (JP, A) JP 60-173180 (JP, A) JP 56-112579 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) D06N 3/00-3/18

Claims (6)

(57) [Claims] 1. A number average through a base layer (A) containing a polymer mainly composed of an elastic polymer in a fiber assembly, with an adhesive layer (B) composed of a resin mainly composed of a polyurethane resin interposed therebetween. A layer made of a resin in which 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 are crosslinked with a polyisocyanate curing agent. A leather-like sheet in which (C) is laminated. 2. The blend weight ratio of the polyurethane (a) and the polyurethane (b) is 0.05 to 4.
The leather-like sheet 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-component polyurethane resin (a) having a number average molecular weight of 20,000 to 100,000, a two-component polyurethane resin (b) having a number average molecular weight of 130,000 to 280,000, and the resin (a) ( A polyurethane resin containing a polyisocyanate curing agent in a solid content ratio of 10 to 75% by weight based on the total weight of b) is applied on a release paper and dried to form a layer (C), and then an adhesive layer (B). The release paper is peeled off after being adhered to the base layer (A) containing a polymer mainly composed of an elastic polymer through a fiber to cause a curing reaction. Sheet manufacturing method. 5. The method according to claim 4, wherein the blending weight ratio of the polyurethane (a) and the polyurethane (b) is 0.05 to 4. 6. The production method according to claim 4, wherein the outermost surface coating layer of the release paper is made of polyolefin.