JPH07150479A - Leathery sheet and its production - Google Patents

Abstract

PURPOSE:To obtain a leathery sheet having a feel close to natural leather, excellent in resistances to light, hydrolysis, wear and oleic acid and flame retardancy, also having dry texture, mattoned appearance and moderate surface slipperiness, and to provide a method for producing such a leathery sheet. CONSTITUTION:This leathery sheet can be obtained by laminating the surface of a natural leather with a resin surface skin layer predominant in a non- yellowing polycarbonate-based urethane resin via an adhesive layer consisting of a polycarbonate-based urethane resin-predominant resin. It is preferable that the surface skin layer be prepared by incorporating 100 pts.wt. of a non- yellowing polycarbonate-based urethane resin-predominant resin with 3-50 pts.wt. of spherical fine particle powder consisting of e.g. crosslinked synthetic resin <=10mum in average particle diameter.

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 suitable as an interior material for vehicles, a skin material for furniture, and the like, more specifically, light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, and flame resistance. The present invention relates to a leather-like sheet which has excellent smoothness, a matte appearance, and a suitable surface smoothness.

[0002]

2. Description of the Related Art Conventionally, a sheet made of natural leather or a resin made of synthetic resin such as urethane resin or vinyl chloride resin on a base cloth as a material sheet for interior materials such as vehicle materials and skin materials for furniture. Synthetic leather, artificial leather provided with a skin layer,
Leather-like sheets such as PVC leather are used.

[0003]

In the above material sheet, the natural leather is excellent in hygroscopicity, moisture release and the like and has a high-class appearance. There is a problem that the usable part is extremely limited and very expensive, and if it is scratched, it cannot be used. Further, there is a problem that the surface strength is particularly insufficient. Further, leather-like sheets such as synthetic leather, artificial leather, and vinyl chloride leather are often used as substitutes for natural leather, but these leather-like sheets are cheaper than natural leather, but on the other hand, as a base material. Since it uses a woven or non-woven fabric, it is inferior to natural leather in terms of texture,
The surface wear strength was also insufficient.

Therefore, as a leather-like sheet having a texture closer to that of natural leather, a raw leather such as cowhide, sheepskin and horseskin is sliced as a base material and the surface of the floor leather which is the remaining portion after separating the silver surface layer is cut. A leather-like sheet provided with a resin skin layer made of a urethane resin or the like has also been proposed, but in such a leather-like sheet, although the texture and the like are superior to the above-mentioned sheet based on a woven or non-woven fabric, It does not satisfy various properties such as light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, etc. required for vehicle interior materials, furniture skin materials, etc.
Similar to the above-mentioned sheet based on knitted fabric or nonwoven fabric, the surface abrasion strength was insufficient.

The above-mentioned surface abrasion strength is improved by adding an additive such as silicone oil, which imparts surface lubricity, to a synthetic resin such as urethane resin or vinyl chloride resin, which generally forms a skin layer. However, on the other hand, during use, the silicone oil bleeds on the surface and deteriorates the quality of the leather-like sheet. In addition, since the silicone oil added to the synthetic resin has a lustering effect, it is necessary to perform a surface treatment for matting and adjust the gloss, and furthermore, a surface treatment for matting during use. The surface treatment agent used in the above procedure falls off, resulting in the problem that the quality of the leather-like sheet is further degraded.

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, on the surface of the floor leather taken from the raw leather, a skin layer made of a specific urethane type resin and a specific urethane type resin adhesive layer were formed. It has excellent light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, flame resistance and surface abrasion resistance, and has a texture very similar to that of natural leather. It was found that a leather-like sheet without deterioration can be obtained, and further, by adding a specific additive to the above-mentioned skin layer, a leather-like sheet having a dry texture and a matte appearance and surface smoothness is obtained. They have found that they can be obtained and have completed the present invention.

[0007]

The leather-like sheet of the present invention, which has been made to solve the above problems, has a yellow-free sheet formed on the surface of a natural leather substrate via an adhesive layer made of a polycarbonate-based urethane resin. It is characterized in that a resin skin layer mainly composed of a modified polycarbonate-based urethane resin is laminated, and further 100 wt% of a resin mainly composed of a non-yellowing type polycarbonate urethane resin which forms the resin skin layer. 3 to 50 parts by weight of a spherical fine powder having an average particle size of 10 μm or less is contained in each part.

Further, in the method for producing a leather-like sheet of the present invention, a step of coating a resin solution mainly composed of a non-yellowing type polycarbonate urethane resin on a release paper, and drying and gelling the resin skin layer is formed. , A step of applying an adhesive consisting of a polycarbonate-based urethane resin to the resin skin layer and / or a natural leather base material, and a resin surface layer mainly composed of a non-yellowing type polycarbonate urethane resin and a natural leather base material are pressure bonded by a pressure bonding roll. And a step of performing.

The present invention will be described below with reference to the drawings. FIG. 1 is a partially enlarged cross-sectional view showing an embodiment of the leather-like sheet of the present invention, and FIG. 4 is a process drawing showing an example of the method for manufacturing the leather-like sheet of the present invention.

The natural leather base material 2 which is the base material of the leather-like sheet 1 of the present invention is limited to floor leather which is the remaining portion obtained by slicing raw leather such as cowhide, sheepskin and horseskin to separate the silver surface layer. Without
Even so-called natural leather with a silver surface can be used. When a natural leather with a silver surface is used, a material that cannot be used as an interior material as it is due to a scratch or the like is usually used. The natural leather substrate 2 used as the substrate preferably has a thickness of 0.8 mm or more. If the thickness of the natural leather substrate is too thin, the tensile strength of the product as a product will be poor, and there is a risk of breakage during processing or use.

The non-yellowing type polycarbonate urethane resin to be the resin skin layer 3 of the present invention is a polymer obtained by reacting a polycarbonate diol component with a non-yellowing type diisocyanate component and a low molecular chain extender.

The polycarbonate diol component is a polyalkylene polycarbonate diol having an average molecular weight of 500 to 5,000. To further improve oleic acid resistance and abrasion resistance, polyethylene carbonate diol,
One or more polyalkylene polycarbonate diols selected from polybutylene carbonate diols and polyhexamethylene carbonate polyols, or polysiloxane carbinols mainly containing these and having hydroxyl groups bonded to both ends of linear polysiloxanes; A mixture of an organopolysiloxane having an isocyanate group and a non-reactive functional group at one end and two hydroxyl groups at the other end can be particularly preferably used.

As the non-yellowing type diisocyanate component,
Aliphatic and alicyclic diisocyanates can be used, but in order to further improve oleic acid resistance and abrasion resistance, isophorone diisocyanate or a cyclohexyl diisocyanate mainly containing isophorone diisocyanate and / or a mixture with dicyclohexylmethane diisocyanate is particularly preferable. It can be preferably used.

As the low molecular weight chain extender, aliphatic diols, alicyclic diols, alicyclic diamines, hydrazine derivatives and the like can be used. These low molecular weight chain extenders may be used alone or as a mixture of two or more kinds.

The non-yellowing type polycarbonate urethane resin of the present invention is obtained by reacting the above-mentioned polycarbonate diol component, the non-yellowing type diisocyanate component and the low molecular chain extender in a desired ratio. Further, the above urethane resin has a 100% modulus of 20.
~ 200kg / cm ² can be used, but 100%
A modulus of 40 to 150 kg / cm ² is suitable. If the 100% modulus is too low, the mechanical strength will decrease, and conversely, if the 100% modulus is too high, the texture will be hard.

The non-yellowing type polycarbonate urethane resin used in the present invention is a non-yellowing type urethane resin as long as it does not impair various properties such as light resistance, hydrolysis resistance, abrasion resistance and oleic acid resistance. A copolymer with a urethane resin other than the polycarbonate-based urethane resin, a mixture, or the like can also be used. Further, non-yellowing type polycarbonate-based urethane resin used in the present invention, or a copolymer or mixture mainly composed of non-yellowing type polycarbonate-based urethane resin, an antioxidant, an ultraviolet absorber, if necessary,
It is also possible to add various additives such as pigments, dyes, surfactants, antistatic agents, flame retardants, antiblocking agents, fillers, crosslinking agents, and collagen powder.

As shown in FIG. 3, the resin skin layer 3 of the present invention has an average particle diameter of 10 μm with respect to 100 parts by weight of a resin mainly comprising a non-yellowing type polycarbonate urethane resin forming the resin skin layer 3. The following spherical fine powder A is added to 3 to 50
It is preferable to include the amount by weight. By doing so, the obtained leather-like sheet can be provided with a dry texture, a matte appearance and surface smoothness.

The spherical fine powder A is, for example, silica fine powder, glass fine powder, inorganic fine spherical powder such as glass fine hollow spheres, crosslinked vinyl chloride resin fine powder, crosslinked acrylic resin fine powder, crosslinked olefin. One or more kinds selected from crosslinked synthetic resin fine powders such as fine resin powder, fine phenol resin powder, fine melamine resin powder, fine urea resin powder and fine benzoguanamine resin powder can be used.
The spherical fine powder of the crosslinked synthetic resin is preferable from the viewpoints of the adhesiveness with the urethane resin, the retention of the spherical fine powder (prevention of falling), and the like. Among the spherical fine powders of crosslinked synthetic resin, urea-based resin fine powders, melamine-based resin fine powders, phenol-based resin fine powders, and benzoguanamine-based resin fine powders are particularly preferable in terms of chemical resistance and solvent resistance. Specifically as the above urea resin fine powder, melamine resin fine powder, phenol resin fine powder, benzoguanamine resin fine powder,
Phenol-formaldehyde condensate, melamine-formaldehyde condensate, urea-formaldehyde condensate,
Examples thereof include benzoguanamine-melamine-formaldehyde condensate.

It is necessary that the average particle size of the spherical fine powder A is 10 μm or less. If the average particle size is larger than 10 μm, the surface becomes rough and the slipperiness is reduced, and the wear resistance is improved. In addition to not contributing, the smooth texture and matte appearance of natural leather cannot be obtained. The apparent bulk density of the spherical fine powder A used is 0.1 to 0.6 g /
It is preferably in the range of cm ³ . Apparent bulk density is 0.
If it is less than 1 g / cm ³ , the strength of the spherical fine powder tends to be low, and the film strength tends to be low, which does not contribute to the improvement of wear resistance. Also, the apparent bulk density is 0.6 g / cm ^3.
The larger, the smaller the bulk of the spherical fine powder,
You will no longer be able to obtain a silky texture and a matte appearance similar to natural leather.

The above-mentioned spherical fine powder A is added in an amount of 3 to 50 parts by weight based on 100 parts by weight of a resin mainly composed of a non-yellowing type polycarbonate urethane resin forming the resin skin layer 3. If the amount of the spherical fine powder A added is small, the effect of imparting lubricity cannot be obtained, so that it does not contribute to the improvement of abrasion resistance, and a dry texture and a matte appearance similar to natural leather cannot be obtained. On the other hand, if the amount of the spherical fine powder A added is too large, the resin content ratio in the coating decreases, so that the coating strength and abrasion resistance decrease.

The above-mentioned resin composition mainly composed of non-yellowing type polycarbonate urethane resin is dissolved in a solvent such as methyl ethyl ketone, toluene, dimethylformamide, etc., and used for release paper or the like, knife coater, comma doctor, roll coater, reverse roll coater. , Coated by various means such as rotary screen coater,
It is dried and gelled to form the resin skin layer 3. The thickness of the film at this time is 10 to 100 μm, preferably 20 to
It is 60 μm. If the film is too thin, the strength will be insufficient and the natural leather base material may be exposed due to wear,
If the film is too thick, the texture will be hard.

Resin skin layer 3 obtained as described above
Is a natural leather substrate 2 serving as a substrate via an adhesive layer 4 made of a resin mainly composed of a polycarbonate-based urethane resin.
Is stacked with. The polycarbonate-based urethane resin constituting the adhesive layer 4 is obtained by reacting an alkylene polycarbonate diol component with an aliphatic, alicyclic or aromatic diisocyanate component, and particularly, an alkylene polycarbonate diol component and an aromatic diisocyanate. Those obtained by reacting the components are preferred. Further, a copolymer or a mixture with a urethane resin other than the polycarbonate-based urethane resin can be used as long as the physical properties are not deteriorated. The polycarbonate-based urethane resin preferably has a 100% modulus of 15 to 50 kg / cm ² .

If necessary, the adhesive layer 4 made of the above polycarbonate urethane resin contains an antioxidant, an ultraviolet absorber, a pigment, a dye, a surfactant, an antistatic agent, a flame retardant, an antisticking agent, and a filler. Various additives such as a crosslinking agent and collagen powder may be added.

The leather-like sheet 1 of the present invention may be provided with a resin skin layer 3 directly on a natural leather substrate 2 via an adhesive layer 4 as shown in FIGS. As shown in FIG. 2, an intermediate layer 5 is provided between the natural leather substrate 2 and the resin skin layer 3.
May be provided.

The intermediate layer 5 is preferably made of a polycarbonate urethane resin obtained by reacting an alkylene polycarbonate diol component with an aliphatic, alicyclic or aromatic diisocyanate component, and even a non-foamed layer is foamed. It may be a layer. Alternatively, a separately manufactured microporous film or the like may be bonded via an adhesive layer.

The urethane resin used as the intermediate layer 5 may be either a non-yellowing type or a yellowing type, but if a yellowing type is used, the oleic acid resistance of the obtained leather-like sheet is further improved. improves. The urethane resin used for the mid layer 5 has a 100% modulus of 40 to 15
The range of 0 kg / cm ² is preferable. Further, the intermediate layer 5 may include an antioxidant, an ultraviolet absorber, and
Various additives such as pigments, dyes, surfactants, antistatic agents, flame retardants, anti-adhesive agents, fillers, cross-linking agents, and collagen powder may be added.

The leather-like sheet 1 of the present invention is a vehicle interior material,
It is suitably used as a material for parts such as skin materials of furniture where light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, and flame resistance are required. Needless to say, the leather-like sheet of the present invention can be used as a material for bags, bags, shoes, etc. other than the above.

Next, a method for manufacturing the leather-like sheet 1 of the present invention will be described. First, a resin mainly composed of the non-yellowing type polycarbonate urethane resin and various additives, a urethane resin solution obtained by dissolving methyl ethyl ketone, toluene, a solvent such as dimethylformamide,
The release paper 6 is coated with a coating means 9 such as a knife coater, comma doctor, roll coater, reverse roll coater or rotary screen coater, dried and gelled to form the resin skin layer 3. At this time,
If a release paper with a tie pattern is used as the release paper 6, the tie pattern can be given to the surface of the obtained leather-like sheet 1. When the spherical fine powder A is added to the resin skin layer 3, 100 parts by weight of a resin mainly composed of the non-yellowing type polycarbonate-based urethane resin is added to the above-mentioned resin solution mainly composed of the non-yellowing type polycarbonate-based urethane resin. On the other hand, a spherical fine powder having an average particle size of 10 μm or less may be used in an amount of 3 to 50 parts by weight.

On the resin skin layer 3 obtained as described above, the adhesive layer 4 made of the above polycarbonate urethane resin is formed by the coating means 9 '. Specific examples of the coating means 9 ′ at this time include a knife coater, a comma doctor, a roll coater, a reverse roll coater, a rotary screen coater, and the like, like the coating means 9 described above. Although the adhesive is applied to the adhesive surface of the resin skin layer 3 in FIG. 4, the adhesive may be the adhesive surface of the natural leather base material 2 or the adhesive surface of the resin skin layer 3 and the natural leather base material 2. It may be applied to both of the adhesive surfaces.

The natural leather substrate 2 and the resin skin layer 3 are laminated via the adhesive layer 4 and then pressure-bonded by the pressure-bonding roll 8. The pressure-bonding roll 8 used at this time is a pair of two rolls 8a and 8b, and it is preferable to use a roll composed of one metal roll and the other rubber roll. If both of them are metal rolls, there is a possibility that the pressure bonding may not be successful when the thickness of the natural leather base material 2 varies. Further, the clearance of the pressure-bonding roll 8 at the time of pressure-bonding is appropriately determined depending on the type and thickness of the natural leather base material 2 used, but is usually about 60 to 90% of the thickness of the natural leather base material 2. It Furthermore,
The pressure at the time of pressure bonding is also appropriately selected depending on the type and thickness of the natural leather substrate 2 used, the type of adhesive, etc., but is usually about 3 to 8 kg / cm ² .

The leather-like sheet 1 of the present invention obtained as described above may be provided with a surface treatment layer if necessary, and may be subjected to processing such as rubbing and embossing.

[0032]

The leather-like sheet of the present invention is formed by laminating a resin skin layer mainly composed of a non-yellowing type polycarbonate urethane resin on a natural leather substrate with an adhesive layer made of the polycarbonate urethane resin interposed therebetween. , Light resistance, hydrolysis resistance, abrasion resistance, olein acid resistance and flame retardancy are excellent, and the treatment according to the present invention, that is, a resin skin layer mainly composed of a non-yellowing type polycarbonate urethane resin is not laminated. It has a texture very similar to that of natural leather for vehicle interiors and furniture skin materials.

When spherical fine powder is contained in the resin skin layer mainly composed of the non-yellowing type polycarbonate urethane resin, a dry texture and a matte tone are obtained without separately providing a surface treatment layer. A leather-like sheet having an appearance can be obtained, and the abrasion resistance of the leather-like sheet is further improved.

[0034]

EXAMPLES The present invention will be described in more detail with reference to the following specific examples, but the present invention is not limited to the examples described below.

[Example 1] On a release paper with a diaphragm pattern, 10
One-component non-yellowing type polycarbonate urethane resin with a 0% modulus of 65 kg / cm ² (Resamine NES9
17% dimethylformamide-toluene solution (containing 15 parts by weight of colorant) of 950, manufactured by Dainichiseika Co., Ltd.) was applied with a knife coater to a dry thickness of 30 μm, and the resulting mixture was heated in an oven at 90 ° C. for 3 minutes. It was dried with hot air to form a resin skin layer. To form an adhesive layer on the resin skin layer, 1
A 50% dimethylformamide-toluene solution of a two-pack type polycarbonate urethane resin (Resamine UD8348, manufactured by Dainichiseika) having a 00% modulus of 25 kg / cm ² was applied with a knife coater to a dry thickness of 60 μm. After drying in an oven at 90 ° C for 2 minutes with hot air, put a 1.3 mm thick floor leather on it and crimp it with a crimping roll consisting of a metal roll on one side and a rubber roll on the other side (clearance of 1.0 mm during crimping). , Pressure 4kg / cm
² ) and leave it for another 48 hours to complete the crosslinking reaction,
The release paper was peeled off to obtain a leather-like sheet of the present invention. The obtained leather-like sheet has the same squeezing and texture as natural leather,
It was wrinkled, had a feeling of volume, and was excellent in light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, and flame retardancy, and was suitable as an interior material for vehicles.

[Example 2] On a release paper with a tie pattern, 10
One-component non-yellowing type polycarbonate urethane resin with 0% modulus of 55 kg / cm ² (Crisbon NY3
24S, manufactured by Dainippon Ink and Chemicals, Inc., 18% dimethylformamide-toluene solution (containing 15 parts by weight of colorant) was applied by a knife coater so that the dry thickness was 20 μm, and the mixture was heated in an oven at 90 ° C. for 3 days. It was dried with hot air for a minute to form a resin skin layer. On this resin skin layer, 100% modulus of 55 kg / cm ² of one-pack type yellowing resistant polycarbonate urethane resin (Resamine ME8200LP,
A 21% dimethylformamide-methylethylketone solution (manufactured by Dainichiseika Co., Ltd.) (containing 20 parts by weight of colorant) was applied by a knife coater to a dry thickness of 15 μm, and dried in a hot air oven at 90 ° C. for 3 minutes. To form an intermediate layer. Further, for forming an adhesive layer on the intermediate layer, 1
A 50% dimethylformamide-toluene solution of a two-component polycarbonate urethane resin (Crisbon TA205, manufactured by Dainippon Ink and Chemicals) having a 00% modulus of 25 kg / cm ² was applied with a knife coater to a dry thickness of 50 μm. After drying in an oven at 90 ° C for 2 minutes with hot air, 1.2 mm thick floor leather is put on and pressure-bonded with a pressure roll consisting of a metal roll on one side and a rubber roll on the other side (clearance at the time of pressure bonding 0.8 mm. , Pressure 3.5kg
/ Cm ² ) and left for 48 hours to complete the crosslinking reaction, and the release paper was peeled off to obtain a leather-like sheet of the present invention.
The obtained leather-like sheet has the same squeezing, texture, wrinkle, and volume feeling as natural leather, and has light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, and flame resistance. It was excellent and suitable as an interior material for vehicles.

Example 3 A leather-like sheet of the present invention was obtained in the same manner as in Example 1 except that the base material was replaced with a natural leather with a silver surface having a thickness of 1.3 mm. The leather-like sheet obtained is
It has the same squeezing, texture, wrinkles, and volume as natural leather, and is also excellent in light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, and flame retardancy. Was suitable as.

[Embodiment 4] On a release paper with a squeeze pattern, 10
One-component non-yellowing type polycarbonate urethane resin with 0% modulus of 65 kg / cm ² (Resamine CNU6
50-20, manufactured by Dainichiseika Co., Ltd.) 18% dimethylformamide-toluene solution (containing 15 parts by weight of colorant) is applied with a knife coater to a dry thickness of 30 μm.
The resin skin layer was formed by drying in an oven with hot air at 90 ° C. for 3 minutes. A two-component polycarbonate urethane resin (Resamine UD834) having a 100% modulus of 25 kg / cm ² for forming an adhesive layer on the resin skin layer.
50% dimethylformamide-toluene solution (manufactured by Dainichiseika Co., Ltd.) with a knife coater to a dry thickness of 60 μm, and dried with hot air at 90 ° C. for 2 minutes in an oven to give a thickness of 1 Put a 3 mm floor leather on it and crimp it with a crimping roll consisting of a metal roll on one side and a rubber roll on the other side (clearance at the time of crimping 1.0 mm, pressure 4 kg /
cm ² ), and allowed to stand for 48 hours to complete the crosslinking reaction, and the release paper was peeled off to obtain a leather-like sheet of the present invention. The obtained leather-like sheet has the same squeezing, texture, wrinkles, and volume feeling as natural leather, and has light resistance,
It was excellent in hydrolysis resistance, abrasion resistance, oleic acid resistance, and flame retardancy, and was suitable as an interior material for vehicles.

Example 5 A spherical fine powder of a benzoguanamine-formaldehyde condensate having an average particle size of 2 μm and an apparent bulk density of 0.3 g / cm ³ (Eposter MS, manufactured by Nippon Shokubai Co., Ltd.) was used as a non-yellowing type polycarbonate urethane resin. 10
Example 4 except that 10 parts by weight based on 0 parts by weight was used.
A leather-like sheet of the present invention was obtained in the same manner as in. The obtained leather-like sheet has the same squeezing, texture, wrinkle, and volume feeling as natural leather, and has light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, and flame resistance. Not only was it excellent, but it had a dry texture and a matte appearance.

[Embodiment 6] On a release paper with a squeeze pattern, 10
One-component non-yellowing type polycarbonate urethane resin with 0% modulus of 65 kg / cm ² (Resamine CNU6
60, manufactured by Dainichiseika Co., Ltd.) 18% dimethylformamide-
Toluene solution (containing 15 parts by weight of colorant) has a dry thickness of 2
It was coated with a knife coater so as to have a thickness of 0 μm and dried in an oven at 100 ° C. for 2.5 minutes with hot air to form a resin skin layer. On this resin skin layer, a 20% dimethylformamide-methylethylketone solution (colorant 20% by weight) of a one-component type yellowing-resistant polycarbonate urethane resin (Resamine ME8200LP, manufactured by Dainichiseika Seiki) having a 100% modulus of 55 kg / cm ² Part included) has a dry thickness of 2
It was coated with a knife coater so as to have a thickness of 0 μm, and dried in a oven with hot air at 90 ° C. for 3 minutes to form an intermediate layer. Furthermore, 10 is formed on the intermediate layer for forming an adhesive layer.
A 50% dimethylformamide-toluene solution of a two-pack type polycarbonate urethane resin (Krisbon TA205, manufactured by Dainippon Ink and Chemicals) having a 0% modulus of 25 kg / cm ² was applied with a knife coater to a dry thickness of 50 μm. After drying in an oven at 90 ° C for 2 minutes with hot air, 1.2mm thick floor leather is put on and pressure-bonded with a pressure roll consisting of a metal roll on one side and a rubber roll on the other side (clearance at the time of pressure bonding 1.0mm , Pressure 4kg / cm
² ) and leave it for another 48 hours to complete the crosslinking reaction,
The release paper was peeled off to obtain a leather-like sheet of the present invention. The obtained leather-like sheet has the same squeezing and texture as natural leather,
It has wrinkles and a sense of volume, and is excellent in light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, and flame resistance.
It was suitable as an interior material for vehicles.

[Example 7] Spherical fine powder of melamine-formaldehyde condensate having an average particle size of 1.2 µm and an apparent bulk density of 0.3 g / cm ³ (Eposter S12, manufactured by Nippon Shokubai Co., Ltd.) was used as a non-yellowing type polycarbonate system. Urethane resin 10
Example 4 except that 20 parts by weight based on 0 parts by weight was used.
A leather-like sheet of the present invention was obtained in the same manner as in. The obtained leather-like sheet has the same squeezing, texture, wrinkle, and volume feeling as natural leather, and has light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, and flame resistance. Not only was it excellent, but it had a dry texture and a matte appearance.

[Example 8] A leather-like sheet of the present invention was obtained in the same manner as in Example 5, except that the substrate was replaced with a natural leather with a silver surface having a thickness of 1.3 mm. The leather-like sheet obtained is
It has the same squeezing, texture, wrinkles, and volume as natural leather, and is not only excellent in light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, and flame retardancy, but also is dry. It had a texture and a matte appearance.

Comparative Example 1 On a release paper with a squeeze pattern, 10
One component type yellowing resistant polycarbonate urethane resin (Resamine ME82 with 0% modulus of 55 kg / cm ²
00LP, made by Dainichiseika Co., Ltd.) 21% dimethylformamide-methylethylketone solution (containing 20 parts by weight of colorant)
Was coated with a knife coater so that the dry thickness was 30 μm, and was dried in a oven with hot air at 90 ° C. for 3 minutes to form a resin skin layer. On this resin skin layer, a two-component polycarbonate urethane resin having a 100% modulus of 25 kg / cm ² (Krisbon TA) for adhesive formation.
No. 205, manufactured by Dainippon Ink and Chemicals, Inc.) 50% dimethylformamide-toluene solution was applied with a knife coater to a dry thickness of 60 μmto and dried in an oven at 90 ° C. for 2 minutes, and then a thickness of 1.3 mm On the floor leather, and crimping with a crimping roll, one of which is a metal roll and the other of which is a rubber roll (clearance at the time of crimping 1.0 mm, pressure 4
(kg / cm ² ) and left for 48 hours to complete the crosslinking reaction, and the release paper was peeled off to obtain a leather-like sheet of the present invention. The obtained leather-like sheet was inferior in light resistance and abrasion resistance.

[0044]

The leather-like sheet of the present invention is excellent in light resistance, hydrolysis resistance, abrasion resistance, oleic acid resistance, and flame resistance.
Moreover, since it has the same squeezing, texture, wrinkles, and volume as natural leather, it is suitable as a material for interior materials for vehicles, skin materials for furniture, and the like.

When the spherical fine powder is contained in the resin skin layer mainly composed of the non-yellowing type polycarbonate urethane resin, a dry texture and a matte tone are obtained without separately providing a surface treatment layer. Since a leather-like sheet having an external appearance can be obtained and the abrasion resistance of the leather-like sheet is further improved, a more suitable material can be obtained as a material such as a vehicle interior material and a furniture skin material.

[Brief description of drawings]

FIG. 1 is a partially enlarged sectional view showing an embodiment of a leather-like sheet of the present invention.

FIG. 2 is a partially enlarged cross-sectional view showing another embodiment of the leather-like sheet of the present invention.

FIG. 3 is a partially enlarged sectional view showing another embodiment of the leather-like sheet of the present invention.

FIG. 4 is a process chart showing an example of a method for manufacturing a leather-like sheet of the present invention.

[Explanation of symbols]

 1 ... Leather-like sheet 2 ... Natural leather substrate (floor leather or natural leather with silver surface) 3 ... Resin skin layer A ... Spherical fine powder 4 ... Adhesive layer 5 ... Middle layer 6 ... Release paper 8 ... Crimping roll 9,9 '... Coating means 10, 10' ... Oven

Claims (8)

[Claims] 1. A resin skin layer mainly composed of a non-yellowing type polycarbonate urethane resin is laminated on a surface of a natural leather base material with an adhesive layer composed of a resin mainly composed of polycarbonate urethane resin interposed therebetween. Leather-like sheet. 2. A non-yellowing type polycarbonate urethane resin is a polyol component mainly composed of one or more kinds selected from polyethylene polycarbonate polyol, polybutylene carbonate polyol and polyhexamethylene carbonate polyol, a diisocyanate component mainly composed of isophorone diisocyanate, The leather-like sheet according to claim 1, which is a urethane resin obtained by reacting a low-molecular chain extender. 3. The resin skin layer contains 3 to 50 parts by weight of a spherical fine powder having an average particle diameter of 10 μm or less with respect to 100 parts by weight of a resin mainly composed of a non-yellowing type polycarbonate-based urethane resin forming the resin skin layer. The leather-like sheet according to claim 1 or 2, wherein 4. The apparent bulk density of the spherical fine powder is 0.1.
The leather-like sheet according to claim ^{3, which has} a range of 0.6 g / cm ³ . 5. The leather-like sheet according to claim 3, wherein the spherical fine powder is a spherical fine powder of a crosslinked synthetic resin. 6. The leather-like sheet according to claim 5, wherein the crosslinked synthetic resin is one or more selected from urea resins, melamine resins, phenol resins and benzoguanamine resins. 7. A release paper is coated with a resin solution mainly composed of a non-yellowing polycarbonate urethane resin,
Mainly composed of a non-yellowing type polycarbonate urethane resin, a step of forming a resin skin layer by drying and gelling, a step of applying an adhesive composed of a carbonate urethane resin to a resin skin layer and / or a natural leather substrate, A method for producing a leather-like sheet, comprising a step of pressure-bonding a resin skin layer and a natural leather substrate with a pressure roll. 8. A resin solution containing a non-yellowing type polycarbonate-based urethane resin as a main component, based on 100 parts by weight of a resin containing a non-yellowing type polycarbonate-based urethane resin as a main component,
The method for producing a leather-like sheet according to claim 7, wherein 3 to 50 parts by weight of spherical fine powder having an average particle diameter of 10 µm or less is contained.