JPH0473274A - Leathery sheetlike material - Google Patents

Abstract

PURPOSE:To obtain a leathery sheetlike material capable of holding excellent slimy feeling for a long period by impregnating a fiber substrate with a polyurethane elastomer composed of a specific polyester-based polyol, a polylactone- based polyol and an organic diisocyanate. CONSTITUTION:A polyurethane solution prepared by reacting (A) a polyester- based polyol containing 5-6C alkanediol units derived from 1, 5-pentanediol which may be substituted with methyl group and dicarboxylic acid units and a polylactone-based polyol containing beta-methyl-delta-valerolactone units at a weight ratio within the range of (5:95)-(85-15) with (B) an organic diisocyanate as a polyurethane-based resin contained in a leathery sheet is applied onto a release paper and heated to form a polyurethane film. A bonding polyurethane liquid is then applied thereto and a fiber substrate is subsequently laminated thereto by heating to afford the objective durable leathery sheetlike material having excellent slimy feeling.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a leather-like sheet material. For more details,
The present invention relates to a leather-like sheet material made of a polyurethane resin containing a polyurethane elastomer' having a polyester polyol component with a specific structure and a polylactone polyol component as essential components, and a fiber substrate.

The leather-like sheet material of the present invention has an excellent texture such as a unique slimy feel, and is also highly durable, so it can be applied to applications where ordinary synthetic leather and artificial leather are used. For example, it is useful as a material for shoes, bags, bags, clothing, etc.

[Conventional technology]

BACKGROUND ART Conventionally, so-called silver-finished or suede-like synthetic leathers and artificial leathers have been known as leather-like sheet materials made of a fiber base and a polyurethane resin. It has been proposed that the polyurethane resin is a polymethylvalerolactone-based polyurethane resin fr-j. That is, Kokai No. 60-26019 describes that poly(β-methyl-δ-valerolactone)-based polyurethane resins have excellent hydrolysis resistance and can be used for artificial leather. JP-A-63-315676 discloses a polymethylvalerolactone polyol or a mixed polymer polyol of polymethylvalerolactone polyol and polybutylene adipate polyol or polyethylene butylene adipate polyol, which is obtained by reacting an organic diisocyanate with 1,4-butanediol. It is described that synthetic leather made by forming a layer made of a polyurethane resin on a base material has excellent hydrolysis resistance and light resistance. Furthermore, Japanese Patent Application Laid-open No. 1-132885 discloses that one of the soft segments that can constitute a polyurethane that can be impregnated or coated on a fiber substrate to produce a leather-like sheet-like material.
One example is poly(β-methyl-δ-valerolactone).

On the other hand, it has also been proposed to use poly(3-methylpentamethylene adipate)-based polyurethane resin as the polyurethane-based resin used for leather-like sheet materials.

That is, JP-A No. 61-207675 uses a polyurethane obtained by reacting a polymer diol mainly composed of poly(3-methylpentamethylene adipate) diol, 4,4'-diphenylmethane diisocyanate, and a low-molecular diol. It is stated that a leather-like sheet material produced by a wet coagulation method has excellent hydrolysis resistance and surface smoothness, and has a soft texture. It is said that polymer diols other than poly(3-methylpentamethylene adipate) diol, such as glycols, can be used in combination with poly(3-methylpentamethylene adipate) diol in an amount of about 15 m or less by weight of the total polymer diol. .

[Problem to be solved by the invention]

In recent years, the trend toward luxury, sensibility, and fashion in consumer life has been remarkable.
Even in leather-like sheet materials such as synthetic leather and artificial leather, requirements for properties that were not required in the past are becoming stricter.

The inventors of the present invention focused on the slimy feeling of leather-like sheet materials and found that
From the polyurethane obtained by reacting polymethylvalerolactone diol with an organic diisocyanate as described in Japanese Patent No. 32885, a leather-like sheet-like material having a firm, sticky and good slimy feel can be obtained. It turns out there isn't. Furthermore, a mixed polymer of polymethylvalerolactone diol such as poly(β-methyl-δ-valerolactone) diol and polybutylene adipate diol was prepared according to the description in JP-A No. 63-315676.
Leather-like sheet materials produced using polyurethane obtained by reacting diols with organic diisocyanates and chain extenders may have a good slimy feel, but on the other hand, hydrolysis resistance is reduced. It was found that various properties such as sliminess deteriorate significantly over time.

In addition, poly(3-methylpentamethylene adipate) diol as described in the above-mentioned Japanese Patent Application Laid-Open No. 61-207675 or a mixed polymer diol of 90:10 in a weight ratio of 4,4
It has been found that a leather-like sheet material with a good slimy feel cannot be obtained from polyurethane obtained by reacting with '-diphenylmethane diincyanate and low molecular weight di-ol. The purpose of the product is to provide a leather-like sheet-like material made of a polyurethane resin with two fiber bases, which has a good sliminess and is durable enough to prevent the good sliminess of swords and thighs from deteriorating over time. An object of the present invention is to provide a leather-like article having excellent properties.

[Means for Solving the Problems] According to the present invention, the above object is to provide a leather-like sheet-like article comprising an ffl fiber substrate and a polyurethane resin, in which the polyurethane resin is substituted with (A) a methyl group. A polyester polyol containing an alkanediol unit having 5 to 6 carbon atoms derived from 1,5-bentanediol and a dicarboxylic acid unit, and β-methyl-δ
- a polymer polyol consisting of a polylactone polyol containing valerolactone units, in which the weight ratio of the polyester polyol to the polylactone polyol is within the range of 5:95 to 85:15; and (B) an organic diinthate; This is achieved by providing a leather-like sheet material characterized by containing a polyurethane elastomer obtained by reacting the following.

The above polyester polyol [hereinafter referred to as polyester polyol (A-1)], which is one of the essential components of the polymer polyol in the present invention, has the above specific alkanediol unit and dicarboxylic acid unit as essential components. as a unit, and has an average of two or more alcohol dispersion groups in the molecular chain end.

The above specific alkanediol unit, which is one of the essential constituent units of the polyester polyol (A-1), has 1
A unit obtained by removing two hydrogen atoms contained in two hydroxyl groups from 1,5-bentanediol which may be substituted with 1,5-methyl groups [hereinafter, such a unit is referred to as an alkanediol unit (1)] - formula % formula % (1) (wherein, R represents a hydrogen atom or a methyl group, and m is 0 to
represents an integer of 2, n represents an integer of 2 to 4, where the sum of m and n is 4)/)0 The alkylene diol unit (1) has the formula % % of 3-methyl-1,5-bentanediol in the 1st position (hereinafter referred to as MPD unit), the resulting leather-like sheet material is particularly excellent in sliminess and durability; Due to the good coagulation properties of polyurethane elastomers in non-solvents, it is possible to produce flexible leather-like sheets with uniform micropores in the polyurethane resin phase when using a wet method. This is desirable because

The polyester polyol (A-1) may contain one or more diol units other than the alkanediol unit (+). Examples of such diol units include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, neopentyl glycol, etc. saturated aliphatic diol; 1,
Saturated alicyclic diols such as 4-cyclohexanediol; units obtained by removing two hydrogen atoms contained in two hydroxyl groups from diols such as divalent aromatic alcohols such as xylylene glycol, etc. . The content of diol units other than the alkanediol unit (I) is not particularly limited as long as the action and effects of the present invention are not impaired, but in general, the content of diol units other than the alkanediol unit (I) is
The molar fraction of each diol unit contained in the polyester polyol (A-1) with respect to the total diol units and the number of carbon atoms in each diol unit be within a range such that the sum of the products of Mi represents the number of carbon atoms in each type of diol unit, and Mi is the i-th number of diol units contained in the polyester polyol.
(representing the molar fraction of diol units of the fourth class) is preferably within a range that satisfies the relationship shown below.

There are no particular restrictions on the type of dicarboxylic acid units constituting the polyester polyol (A-1), and any dicarboxylic acid units constituting polyester polyols such as those used in the production of ordinary polyurethane may be used. Such dicarboxylic acid units include, for example, saturated aliphatic dicarboxylic acids such as adipic acid, pimelic acid, superric acid, azelaic acid, and sebacic acid; and aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid. Examples include units in which 02 hydroxyl groups are removed from a carboxyl group. Among these dicarboxylic acid units, adipic acid units, azelaic acid units, sebacic acid units, etc. are often used in leather-like sheets that have particularly good properties such as sliminess and durability. desirable. The number of dicarboxylic acid units constituting the polyester polyol (A-1) may be one, or two or more.

The polyester polyol (A-1) is essentially composed of a diol unit containing at least one alkanediol unit (1) as described above and a dicarboxylic acid unit.
However, other units may be included as long as the amount is within a range that does not impair the functions and effects of the present invention. Examples of such units that may be optionally included include trivalent or higher-valent units obtained by removing the hydrogen atoms in the hydroxyl groups from trivalent or higher-valent polyhydric alcohols such as glycerin, pentaerythritol, and trimethylolpropane.

The molecular weight of the polyester polyol (A-1) is not particularly limited, but a range of molecular weights possessed by polyester polyols used as raw materials for the production of ordinary polyurethanes is preferably employed. Among them, the number average molecular weight is 500 to 10,000. Especially from 800
5000 is the polyester polyol (A
-1) and the polyurethane elastomer obtained therefrom have good handling properties, and the resulting leather-like sheet material has a slimy feel and its durability9. The method for producing the polyester polyol (A-1) in the present invention is not particularly limited, and the method for producing the polyester polyol (A-1) in the present invention is not particularly limited, and the method for producing the polyester polyol (A-1) in the present invention is not particularly limited, and the method for producing the polyester polyol (A-1) in the present invention is not particularly limited. For example, polyester polyol (AI) can be prepared by manufacturing a diol having a structure corresponding to a desired diol unit, a dicarboxylic acid having a structure corresponding to a desired dicarboxylic acid unit, or a methyl ester thereof; using an ester-forming derivative such as ethyl ester in a desired ratio at 150-250°C in the presence of an esterification catalyst and/or transesterification catalyst.
It can be produced by esterification or transesterification, and then condensation polymerization of the resulting oxidized product at 200 to 300° C. under reduced pressure.

The above polylactone polyol [hereinafter referred to as polylactone polyol (A-2)], which is one of the essential components of the polymer polyol in the present invention, has a β-methyl-δ-valerolactone unit as an essential constituent unit. The β-methyl-δ-valerolactone unit constituting the 0-polylactone polyol (A-2), which contains alcoholic hydroxyl groups on average of two or more sides at the end of the molecular chain, is β-methyl-δ-valerolactone. It is a unit represented by the formula % in the ring-opened form. Polylactone polyol (A
-2) May contain lactone units other than ldβ-methyl-δ-valerolactone units. Such optional lactone units include, for example, units in the ring-opened form of lactones that do not have gA@, such as δ-valerolactone and ε-caprolactone; α-methyl-δ-valerolactone, γ- Ring-opened forms of lactones with side chains other than β-methyl-δ-valerolactone, such as methyl-δ-valerolactone, δ-methyl-δ-valerolactone, β, β, δ-trimethyl-C-prolactone Examples include units. The content of lactone units other than β-methyl-δ-valerolactone units is not limited to buckwheat as long as the action and effects of the present invention are not impaired, but generally, the content of lactone units in the polylactone polyol (A-2) is It is desirable that the molar ratio is 60 or less based on all the lactone units contained.

The molecular weight of the polylactone-based polyol (A-2) is not particularly limited, but a range of molecular weights possessed by polylactone-based polyols commonly used as raw materials for producing polyurethane is preferably employed. Among them, the number average molecular weight is 500 to 10,000, especially 800 to 5.
000 is a polylactone polyol (A-2
) and the polyurethane elastomer obtained therefrom are generally desirable because they are easy to handle, and the resulting leather-like sheet material often has particularly good sliminess and durability.

The method for producing polylactone-based polyester (A-2) according to the present invention is not particularly limited, and publicly available means for producing polylactone can be applied. For example, the polylactone polyol (A-2) is a compound containing 21 or more active hydrogen atoms in the molecule, using a lactone having a structure corresponding to a desired lactone unit as a polymerization initiator, and lithium, sodium, n- It can be produced by ring-opening polymerization at 10 to 200°C in the presence of a polymerization catalyst such as butyllithium or sulfuric acid. Examples of compounds containing two or more active hydrogen atoms in the molecule used as polymerization initiators include ethylene glycol, 1
, 2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol,
1,9-nonanediol, 1,10-decanediol,
2 carbon atoms such as 3-methyl-1,5-bentanediol, neopentyl glycol, natsutalene glycol, diethylene glycol, tetraethylene glycol, glycerin, trimethylolfuropane, triethanolamine, etc.
-22 polyhydric alcohols; average molecular weight 200-200
Polyoxyalkylene glycols having an oxyalkylene group having 2 to 12 carbon atoms or an oxine chloroalkylene group having 4 to 10 carbon atoms as a repeating constituent unit, such as polyoxyethylene glycol and polyoxypropylene glycol; ethylenediamine, 1.4 -C2-C12 polyamines such as -butanediamine, 1,6-hexanediamine, p-phenylenediamine, and piperazine.

In the present invention, the above-mentioned polyester polyol (A-1) and polylactone polyol (
It is essential to use A-2) in a weight ratio within the range of 5:95 to 85:15. If the weight ratio of the polyester polyol (A-1) and polylactone polyol (A-2) in the polymer polyol is outside the above range, a leather-like sheet material with good sliminess cannot be obtained. The weight ratio of polyester polyol (A1) and polylactone polyol (A-2) is 20:80 to 8
It is preferable that the ratio is within the range of 0:20 because the sliminess and durability of the leather-like sheet obtained are particularly good. In the present invention, the above polyester polyol (A -1) and the polylactone polyol (A-2), other polymer polyols may be used together with the essential polymer polyols. Such optional polymer polyols include, for example, polyester polyols (
Polyester polyols other than A-1); poly(,-
polylactone-based polyols other than polylactone-based polyol (A-2), such as (caprolactone) diol; polyether-based polyols, such as polyoxypropylene diol, polyoxytetramethylene diol; polycarbonate-based polyols, such as poly(hexamethylene carbonate) diol, etc. can be mentioned. Examples of the above-mentioned polyester polyols that may be used optionally include ethylene glycol, propylene glycol, 1.4
-butanediol, 1,6-hexanediol, 1.4
- at least one diol such as cyclohexanediol, xylylene glycol, neopentyl glycol and an aliphatic or aromatic dicarboxylic acid such as adipine, pimelic acid, superric acid, azelaic acid, sebacic acid, inphthalic acid, terephthalic acid, etc. Examples include condensation polymers with at least one kind. The amount of the polymer polyol used is not particularly limited as long as it does not impair the action and effect of the present invention, but it may be used in an amount of 50% by weight based on the total amount of the polymer polyol used. This is numerically preferable because the properties such as the sliminess and durability of the resulting leather-like sheet material are often particularly good.

The organic diisocyanate μ used for producing the polyurethane elastomer in the present invention may be any organic diisocyanate that is commonly used for producing polyurethane. Examples of such organic diisocyanates include aromatic diisocyanates such as 4.4' diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and xylylene diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, 4.4'-dicyclohexylmethane diisocyanate, and water. Examples include aliphatic or alicyclic diisocyanates such as added tolylene diisocyanate and hydrogenated xylylene diisocyanate. Among these organic diisocyanates, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, inphorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate are particularly popular in industrial applications due to their high versatility. It is advantageous for use in

In the present invention, in order to produce a polyurethane elastomer, a polymer polyol and an organic diisocyanate are conveniently used as essential raw materials, but a chain extender may also be used in combination if desired. Such a chain extender may be any chain extender that is used for the production of ordinary polyurethane, and is usually a low-molecular compound with a molecular weight of 400 or less having two or more active hydrogen atoms in the molecule. Used for convenience. Typical examples of such low molecular weight compounds include ethylene glycol, fluoropylene gelicol, 4-butanediol, 1,6-hexanediol, 3-methyl-1,
5-bentanediol, 1,9-nonanediol, 2-
Aliphatic diols such as methyl-1,8-octanediol; cycloaliphatic diols such as 1,4-cyclohexanediol; dihydric aromatic alcohols such as xylylene glycol; diethylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol , polyalkylene glycols such as tripropylene glycol; diols such as carboxyl group-containing diols such as dimethylolpropionic acid; aliphatic and alicyclic compounds such as ethylene diamine, propylene diamine, xylylene diamine, inphorone diamine, phenylene diamine, tolylene diamine, etc. Heterocyclic compounds containing two imino groups in the cyclic structure such as piperazine; Dihydrazides such as adipic acid dihydrazide and isophthalic acid dihydrazide; Hydrazine; trimethylolpropane, pentaerythritol, glycerin, etc. Examples include trihydric or higher alcohols. As the chain extender, at least one of the above-mentioned diols, diamines, heterocyclic compounds containing two imino groups in the cyclic structure, and low molecular weight compounds having two active hydrogen atoms in the molecule such as dihydrazide and hydrazine is used. It is common to use one ingredient alone or in combination with at least one of the above trihydric or higher alcohols.

A polyurethane elastomer obtained by reacting a polymer polyol consisting of a polyester polyol (A-1) and a polylactone polyol (A-2) with an organic diisocyanate and, if necessary, a chain extender [hereinafter referred to as polyurethane elastomer (E)] Although there are no particular restrictions on the viscosity of the solution, it is possible to improve the passability of the leather-like sheet material through the production process, and the resulting leather-like sheet material has particularly good sliminess and durability. Since this is often the case, the solid content in the dimethylformamide solvent added at 30°C is 25%.
The viscosity of the solution is 5 to 2000 voids, especially 50 to 90
Regarding the specific operation method for producing the polyurethane elastomer (E), which is generally preferred to have 0 voids, known urethanization reaction techniques are used. For example, the above polyester polyol (A-1)% polylactone polyol (A-2)
'Z Mix any polymer polyol and chain extender if necessary, preheat to about 40-100°C, then add organic diisocyanate and react at 50-140°C for several hours, and if necessary add the already used The desired polyurethane elastomer can be obtained by mixing the same or different type of chain extender and reacting at 20 to 140°C for several hours. In the urethanization reaction, a well-developed urethanization reaction catalyst such as an organic tin compound, an organic titanium compound, a tertiary amine, etc. may be used as desired. Further, the above reaction may be carried out in the presence of an organic solvent that is inert to organic solvents. Examples of the organic solvent include aromatic hydrocarbons such as toluene; esters such as ethyl acetate;
amides such as dimethylformamide; ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetone;
Cyclic ethers such as tetrahydrofuran; halogenated hydrocarbons such as trichloroethylenenato are used alone or in any mixture. These exemplified organic solvents may be used in combination with alcohols such as ingropanol, ethanol, and methanol. When the reaction is carried out in the presence of an organic solvent, the amount of organic solvent used should be adjusted so that the solid content at the end of the reaction is 10 to 60 t's even if it is 5 to 90 t's. is common.

Polyurethane elastomer obtained as above (
E) is used alone or in a mixture with a polyurethane elastomer other than the polyurethane elastomer (E),
The leather-like sorted material of the present invention is used as a polyurethane-based resin composed of a fiber substrate and #. As the polyurethane elastomer that can optionally be used in combination with the polyurethane elastomer (E), it is possible to use ordinary polyurethane elastomers such as those used with Vc fiber substrates to produce ordinary artificial leathers or synthetic leathers. As the front side of such an optionally used oligourethane elastomer, ethylene glycol, propylene glycol, 1,4-phthanediol,
At least one low molecular weight diol such as 1,6-hexanediol, 1,4-cyclohexanediol, quinrylene glycol, neopentyl glycol and adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid. Polyester polyols that are condensation polymers with at least one aliphatic or aromatic dicarboxylic acid such as acid; polyether polyols such as polyquine propylene polyol and polyoxytetramethylene polyol; poly(ε-caprolactone) ) Polylactone polyols such as polyols; polyurethane elastomers obtained by urethanizing in a conventional manner using polymer polyols such as polycarbonate polyols, organic diisocyanates, and chain extenders if necessary. The amount of polyurethane elastomer that may be used optionally and [7
There is no particular restriction on the amount as long as the action and effects of the present invention are not impaired, but it may be less than 50% by weight relative to the overall view of the polyurethane resin that constitutes the leather-like notebook of the present invention together with the fiber base. This is numerically preferable because both the sliminess and durability of the resulting leather-like sorted material are often particularly good.

The fiber base constituting the leather-like sheet material of the present invention is a two-dimensional fiber aggregate such as a woven fabric, a knitted fabric, a non-woven fabric, or a three-dimensional It is a fiber aggregate. The fibers that make up the fiber base include natural fibers such as cotton, silk, hemp, wool, and asbestos; recycled fibers such as viscose rayon fiber and steel ammonia rayon fiber; semi-synthetic fibers such as acetate fiber; and polyamide fiber (nylon 6). fibers, nylon 66 fibers, aromatic nylon fibers, etc.), polyvinyl alcohol fibers,
Synthetic fibers such as polyvinylidene chloride fibers, polyester fibers, polyacrylonitrile fibers, polyurethane fibers, poly(alkylene paraoxybenzoate) fibers, etc.
Cotton or two or more types can be used, especially cotton,
Polyamide fiber (nylon 6 fiber, nylon 66 fiber,
Aromatic nylon fibers), polyvinyl alcohol fibers, polyester fibers, polyurethane fibers, etc. are preferably used. These fibers may be ordinary fibers or may be specially shaped fibers such as fine fibers and porous fibers. Note that the fiber substrate may be obtained by impregnating the above-mentioned fiber aggregate with an elastic polymer such as a polyurethane elastomer other than the polyurethane elastomer (E).

The leather-like sheet material of the present invention has a so-called silver-finished or polymer suede-like form in which a layer of polyurethane resin is coated on a fiber base, and has a fiber base impregnated with a polyurethane resin. , so-called fibrous suede-like form. In a leather-like sheet material having a form in which a layer made of a polyurethane resin is coated on a fiber substrate, adhesive l and /Or a mesothelial layer may be present. For example, polyurethane is suitably used as the resin constituting the adhesive layer or the intermediate skin layer. The polyurethane resin containing the polyurethane elastomer (E) may be blended with various additives such as those used in synthetic leather or artificial leather, depending on the purpose of the leather-like sheet material. can. Examples of such additives include colorants such as pigments and dyes, inorganic fillers, hiding agents, softeners, antioxidants, ultraviolet absorbers, surface active agents, coagulation regulators, and lubricants.

The leather-like sheet material of the present invention is manufactured according to publicly known methods, such as wet methods and dry methods, which are employed to produce ordinary synthetic leather and artificial leather. can do.

As a method for producing a leather-like sheet material by a dry method, for example, the following transfer method can be adopted. 1st,
A solution of polyurethane resin containing polyurethane elastomer (E) k is applied onto the release paper using a doctor knife, and dried with hot air at 90 to 110°C for 2 to 3 minutes2 to form a resin layer for the skin on the release paper. Let it form. A solution of an adhesive resin such as polyurethane is applied onto the resin layer on the release paper, and a fibrous substrate is further bonded thereon using a laminating roll, and heated at 90 to 110°C for 2 to 3 hours.
Dry with hot air for a minute. Next, the obtained laminate was heated to 40~
After lasing at 60° C. for 2 to 3 days, the release paper is peeled off, and if necessary, the surface is finished several times with a gravure roll to obtain the leather-like article of the present invention. In addition, in applying the solution of the polyurethane resin containing the polyurethane elastomer ('E) above onto the release paper, it is not necessarily uniform depending on the use of the resulting leather-like sheet material, but it is usually formed. The solution concentration and application amount are adopted such that the thickness of the resin layer for the epidermis is 10 to 100 μm. As a solution of the resin for the above-mentioned adhesive, a solution of 30 to 50% by weight resin at 11% was added to 60% by weight.
When coating the resin layer for the skin with a coating amount of ~150 y7rrr, an adhesive layer with a thickness of several tens of microns is formed after drying. Furthermore, instead of the above-mentioned release paper, a resin film having release properties may be used, and as a method for forming the m# layer for the skin on the release paper or resin film, instead of hot air drying, It is also possible to adopt a method of coagulating polyurethane resin by immersing a release paper or resin film coated with a polyurethane resin solution in a non-solvent of the polyurethane resin. The manufacturing method includes, for example, impregnating and/or coating a fiber base with a bath solution of a polyurethane resin, and then immersing it in a non-solvent of the polyurethane resin to form a layer made of the polyurethane resin. A method consisting of the following can be adopted.

The leather-like sheet material of the present invention may be subjected to various post-treatments such as those applied to ordinary synthetic leather and artificial leather, if necessary. Examples of such technical treatments include embossing, rolling, wrinkling, softening agent treatment, and top coating to improve texture, texture, and surface durability.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

In addition, in the examples, compounds may be indicated by the following abbreviations.

BD: 14-butanediol DMF: N,N-dimethylformamide EG: Ethylene glycol MDI: 44'-diphenylmethane diisocyanate MPD: 3-methyl-1,5-bentanediol PMV
L: β- using ethylene glycol as a polymerization initiator
Ring-opening polymerization of methyl-δ-valerolactone VC
Poly(β-methyl-δ-valerolactone) diol obtained from PCL: Poly(ε-caprolactone) diol obtained by fully ring-opening polymerization of caprolactone using ethylene glycol as an initiator Example Weight ratio of polyester diol with a number average molecular weight of 2000 obtained by total condensation polymerization of I MPD and adipic acid to PMVL with a number average molecular fi of 2000: 50:
Polymer polyol, MDI, and EG (molar ratio of polymer polyol, MDI, and EG: 1:3.2:2.2) consisting of a mixture of 50 and 50% were subjected to an open reaction at 85° C. for about 8 hours in a DMF solvent according to a conventional method. To make; τ2, concentration 25
5 parts by weight DMF of polyurethane elastomer for skin layer
The viscosity of the solution obtained at 30°C is v'1400.
I met Boise.

By diluting the solution with total methylethylgtone,
A polyurethane solution for the skin layer having a solid content of 201% was obtained.

Polyester-based diol 2-process tolylene diincyanate having a number average molecular weight of 1000 obtained by polymerizing MPD and adipic acid was prepared in toluene as a solvent.
The solvent is subjected to a urethanization reaction under reflux, and then L)M
It was diluted with a mixed solvent of F and ethyl acetate to obtain a bath liquid-like polyurethane base for adhesives with a solid content concentration of 45% by weight and a viscosity of 700 voids (30°C). Next, 5.5 parts by weight of an adduct of tolylene diisocyanate of trimethylolpropane as a hardening agent and a desired amount of DMF were added to 100 parts by weight of the base resin to obtain a polyurethane solution for adhesives with a viscosity of 50 voids (30°C). Ta.

On the release paper, use a knife coater to apply polyurethane solution I for the skin layer (solid content concentration: 20 weight jL4) to a dry thickness of 25
A polyurethane film for one layer of the epidermis was formed by applying the film with a diameter of μm and heating and drying it at 100° C. for 3 minutes. Next, apply a polyurethane solution for adhesive on the above film using a knife coater in an amount to give a basis weight of 120 r/pi, and immediately apply the polyester thread as the warp and the rayon thread as the weft. The non-raised surfaces of the raised fabrics obtained by interweaving were laminated together, and then crimped using a laminating roll. The obtained laminate was dried at 100° C. for 2 minutes, cured at 50° C. for 3 days, and then the release paper was peeled off to obtain a leather-like sheet material.

A portion of the obtained leather-like sheet material was treated using a jungle tester under conditions of relative humidity of 95 degrees and temperature of 70 degrees Celsius for 6 weeks (1000 hours).

For each of the leather-like sheet-like materials that have not been subjected to the jungle test and the leather-like sheet-like materials that have been subjected to the jungle test, 10 adult panelists have evaluated the sliminess based on tactile sensation (touch) and visual perception (visual observation). The texture and surface smoothness of the epidermis were evaluated. Regarding the slimy feeling,
Each panel was rated as ``It has a moist and very good slimy feel'', ``It has a good slimy feel'', ``It feels like it has a slight slimy feel'', and ``It has a slimy feel.'' were evaluated on a four-point scale from all<N not done.”
Numerical values corresponding to each rating (3.2.1 and 0, respectively)
The feeling of sliminess was scored. Regarding surface smoothness,
Each panelist evaluated the surface on a four-point scale: "Extremely smooth,""Verysmooth,""Slightlysmooth," and "No smoothness at all." The surface smoothness was scored using the corresponding numerical values (3.2.1 and 0 for roughness, respectively). Table 1 shows the average scores of each panelist for sliminess and surface smoothness.

As is clear from Table 1, the obtained leather-like sheet material has extremely good surface smoothness and a strong moist and slimy feel, making it a sheet with a luxurious feel. be. In addition, the leather-like sheet retains extremely good surface smoothness and a moist and slimy feel even after being subjected to a jungle test, indicating that it is a highly durable sheet with excellent hydrolysis resistance. .

Comparative Example 1 Number average molecular weight 2000 (7) PMVL, MDI! and E
DM of a polyurethane disstomer for skin layer at a concentration of 25% by weight by reacting G (the molar ratio of these is 1:3.4:2.4) in a DMF solvent at 85°C for about 12 hours.
A solution in F was obtained. The viscosity of the solution at 30°C was 380 poise. By diluting this solution with methyl ethyl ketone, a polyurethane solution for the skin layer having a solid content concentration of 20% by weight was obtained. A leather-like sheet material was obtained in the same manner as in Example 1-2, except that the polyurethane solution for the skin layer thus obtained was used.

The samples of the leather-like sheet thus obtained and the samples obtained by subjecting the same to the jungle test were evaluated for sliminess and surface smoothness in the same manner as in Example 1.

Table 2 shows the average scores of each panelist.

Table 2 As is clear from Table 2, although the obtained leather-like sheet material has a reasonably good surface smoothness, it does not have a very moist and slimy feel, so it lacks a luxurious feel. It is.

Comparative Example 2 A polyester diol with a number average molecular weight of 20 obtained by condensation polymerization of BD and adipine
Example 1 except using 00 polyester diol
A solution of a polyurethane elastomer for skin layer having a weight ratio of #25 in DMF was obtained in the same manner as in Section 2. The viscosity of the solution at 30°C was Fi42Q voids.

By diluting the solution with methyl ethyl ketone,
A polyurethane solution for the skin layer having a solid content of 20% by weight was obtained. A leather-like sheet material was obtained in the same manner as in Example 1 except that the thus obtained polyurethane solution for the skin layer was used.

The samples of the leather-like sheet thus obtained and the samples obtained by subjecting the same to the jungle test were evaluated for sliminess and surface smoothness in the same manner as in Example 1.

Table 3 shows the average scores of each panelist.

Table 3 As is clear from Table 3, the obtained leather-like sheet material has good planar smoothness, but does not give a very moist and slimy feeling, and has poor hydrolysis resistance. Inferior, with significant deterioration in surface smoothness and sliminess after the jungle test.

Examples 2 to 5 and Comparative Example 3 Number average molecular weight and mixing ratio of polyester diol and PMVL used to produce polyurethane elastomer for skin layer, and polymer polyol, MDI, and E
A leather-like sheet material was produced in the same manner as in Example 1, except that the conditions shown in Table 4 were adopted as the molar ratio of G. In addition, the concentration 25 obtained by the urethanization reaction
] DM of polyurethane elastomer for skin layer with 1% il
The viscosity of the solution in F was about 400 boids.

For each of the samples of the leather sheet obtained in this way and the samples obtained by subjecting Nana to the jungle test, the sliminess and surface smoothness of the samples in Example 1 were evaluated. Ta.

Table 4 also shows the average evaluation of each panelist.

As is clear from Table 4 below, the leather-like/table-like materials obtained in Examples 2 to 5 were excellent in all of the surface smoothness, slimy feel, and durability. ing. this,'
In contrast to ζ, the leather-like sheet material obtained in Comparative Example 3 hardly feels moist and slimy.

Comparative Example 4 Poly(α-methyl-δ-valerolactone) diol having a number average molecular weight of 2000 obtained by fully ring-opening polymerization of α-methyl-δ-valerolactone using ethylene glycol as a polymerization opening agent Molecule-1] 200-0
A solution of polyurethane elastomer for the skin layer in DMF at a concentration of 25% by weight was prepared by reacting the polymer polyol, MDI and EG in the same manner as in Example 1, except that the same weight was used in place of PMVL. I got it.

The viscosity of the solution at 30° C. was 420 voids.

By diluting the solution with methyl ethyl ketone,
A polyurethane solution for the skin layer having a solid content concentration of 20% by weight was obtained. A leather-like sheet material was obtained in the same manner as in Example 1 except that the thus obtained skin-grade polyurethane solution was used.

The sample of the regular leather-like sheet obtained in this way and the sample obtained by subjecting it to the jungle test had the same slimy feel and surface smoothness as in Cases 1 and 2 of loss of area. was evaluated.

Average evaluation based on each panelist's scoring・Zkoyot'L(
-I, the obtained leather-like note-like proboscis gives a good feeling of surface smoothness and stickiness, but the hydrolysis resistance is 9, and the surface smoothness after the jungle test is It was found that the brightness was reduced, and the whiteness was significantly reduced by 9%.

Comparative Example 5 Opening of γ~methyl-δ-valerolactone using ethylene glycol as an opening agent. ! Poly(γ-methyl-δ-valerolactone) diol with a number average molecular weight of 2000 obtained by polymerization is
[Similarly, polymer polyol,
By reacting MDI and EC, a solution of polyurethane elastomer for skin layer in DMF with a concentration of 25% by weight was obtained.

The viscosity of the solution at 30°C was 390 poise.

By diluting the solution with methyl ethyl ketone,
A polyurethane solution for the skin layer having a solid content of 20% by weight was obtained. A leather-like sheet material was obtained in the same manner as in Example 1 except that the thus obtained polyurethane solution for the skin layer was used.

The samples of the leather-like sheet thus obtained and the samples obtained by subjecting the same to the jungle test were evaluated for sliminess and surface smoothness in the same manner as in Example 1.

According to the average evaluation based on the scores of each panelist, the obtained leather-like sheet material had good surface smoothness and a slimy feel, but it had poor hydrolysis resistance, and after the jungle test, It was found that the surface smoothness and slimy feeling were decreased, and the decrease in the slimy feeling was particularly remarkable.

Example 6 As a polyester diol, a mixture of MPD and BD (mole ratio is 6:4; the sum of the products of the mole fraction of each diol and the number of carbon atoms of the diol is 5.4) and adipic acid are condensed and polymerized. Number average molecular weight 20 obtained by
Example 1 except that 00 polyester diol was used.
A solution of polyurethane elastomer for skin +1 in DMF of 4 times 25% by weight was obtained in the same manner as in . The viscosity V of the solution at 30°C was 400 voids. By diluting the solution with methyl ethyl ketone, a polyurethane solution for the skin layer having a solid content of 20% by weight was obtained. A leather-like sheet material was obtained in the same manner as in Example 1, except that the skin thus obtained and the polyurethane solution for 1 were used.

The leather-like sheet sample thus obtained and the sample obtained by subjecting it to Jungle Test V were evaluated for sliminess and surface smoothness in the same manner as in Example 1. Ta.

Each panelist gave a score of 1 (according to the average evaluation, the obtained leather-like sheet-like material had good surface smoothness and sliminess for the first time, and even after the jungle test, it was found that Good surface smoothness and slimy feel were maintained.

Example 7 As a polyester diol, a mixture of MPD and EG (molar ratio H7: 3; the sum of the products of the mole fraction of each diol and the number of carbon atoms of the diol is 4.8) and adipic acid are condensed and polymerized. A solution of a polyurethane elastomer for the skin layer in DMF having a concentration of 25 tm by weight was obtained in the same manner as in Example IK, except that the polyester diol having a number average molecular weight of 2000 obtained by the method was used.

The viscosity of the solution at 30°C was 400 poise. By diluting the solution with methyl ethyl ketone, a polyurethane solution for the skin layer having a solid content of 20% by weight a was obtained.

A leather-like sheet material was obtained in the same manner as in Example 1 except that the thus obtained polyurethane solution for the skin layer was used.

The samples of the leather-like sheet thus obtained and the samples obtained by subjecting the same to the jungle test were evaluated for sliminess and surface smoothness in the same manner as in Example 1.

According to the average evaluation based on the scores of each panelist, the obtained leather-like 7-sheet material had good surface smoothness and slimy feel. Although the surface smoothness and the feeling of texture are slightly reduced,
v Good and rare.

Example 8 Xt ratio of polyester diol with a number average molecular weight of 1/2000 obtained by condensation polymerization of MPD and adipic acid and PMVL with a number average molecular weight of 2000: 50:
A mixture of polymer polyol, MDI and BD (the molar ratio of polymer polyol, MDI and BD is 1:6:5) was reacted in a DMF solvent at 85° C. for about 7 hours according to a conventional method. A solution of a pure polyurethane elastomer in DMF was obtained. The viscosity of the solution at 30°C was 400 boids.The solution was diluted with DMF so that the solid content concentration was 13 mm, and then added with alcohol-modified silicone oil and polyoxygenate as additives. A mixture with an ethylene/polyoxybrobylene block copolymer with an IT ratio of o, s:1 was prepared in an amount of 20% based on the polyurethane elastomer, and carbon black as a coloring material was prepared in an amount of 1% by weight based on the polyurethane elastomer. A polyurethane elastomer composition liquid was prepared by separating the mixture.

Apply this polyurethane elastomer composition liquid on a polyethylene notebook at a rate of 1500 r/rr! (Polyurethane child:
62S'/m") by a casting method, and then
Temperature 4 consisting of an aqueous solution of 25 parts dimethylformamide
It was immersed in a coagulation solution at 0°C. The coagulated polyurethane elastomer sheet was peeled off from the polyethylene sheet and
A porous polyurethane sheet was obtained by removing the solvent and washing in hot water at ℃ and drying. The basis weight of such a porous polyurethane sheet is 70? / m”, thickness 0.
It was flexible, had a sponge structure with long pores extending substantially perpendicular to the surface, and an extremely smooth surface.

After adhering the surface of this porous sheet that was in contact with the polyethylene sheet to the nylon tricot using a cross-linked polyurethane adhesive, the surface of the porous sheet was sandpapered to a thickness of approximately 0.04 to 0.05 m. When the internal pores were exposed by polishing to a certain extent, a suede-like, leather-like sheet-like material with a beautiful appearance formed by uniform pores was obtained. This leather-like sheet material had a moist and slimy feel, and was a black sheet with a high-quality feel due to its softness and drapability, and was suitable as a material for clothing. Moreover, this leather-like sheet-like material maintained a good texture such as a moist and slimy feeling even after the jungle test.

Comparative Example 6 Polyester-based polyester with a number average molecular weight of 12,000 obtained by copolymerizing MPD and adipic acid.
l:6:5) in a DMF solvent at 85°C for about 9 hours according to a conventional method. A solution of polyurethane elastomer in DMF with a concentration of 25% by weight was obtained. The viscosity of the solution at 30°C was 400 voids. In addition to using the polyurethane elastomer solution obtained in this manner, in Example 8, Aff of the polyurethane elastomer composition liquid, production of a porous polyurethane sheet 2, and production of a leather-like sorted product were carried out. Ta0
The resulting porous polyethylene sheet has a fabric weight of 69″/r
r? It had a thickness of 0.31 m, an apparent density of KO, 25 t/-, and a sponge structure with irregular pores and a surface with many irregularities. Furthermore, the suede-like leather-like sheet material obtained using Zon did not have a moist, slimy feel and did not have a luxurious feel.

Example 9 A polymer polyol, MDI and BD ( The molar ratio of polymer polyol, MDI and BD is 1
9:6.9) in DMF solvent according to a conventional method.
By reacting at ℃ for about 8 hours! 1 degree 25] ji
Consider a solution of i% polyurethane elastomer in DMF. The viscosity of the solution at 30°C was 370 voids.

The solution was made to have a solid content of 13] cf% 7.
Diluted with MF and added a mixture of alcohol-modified silicone oil as an additive and polyoxyethylene/polyoxypropylene block copolymer at a weight ratio of 0.5:1 to the polyurethane elastomer at a weight of 20 parts B. In short, I have described the polyurethane elastomer composition liquid.

This polyurethane elastomer composition liquid was applied onto a polyethylene sheet at a liquid volume of 600 r/m', and then immersed in a coagulating liquid at a temperature of 40°C consisting of an aqueous solution of dimethylformamide'l 5 i i %. The coagulated polyurethane elastomer notebook was peeled off from the polyethylene sheet, solvent removed in hot water, washed, and dried to give a porous polyurethane sheet with good surface smoothness.

This porous sheet was adhered with a polyurethane adhesive to a 1.2-inch thick fiber base material obtained by incorporating polyester polyurethane into a nylon-6 and other paper fiber bundle entangled nonwoven fabric. A grain-finished leather-like sheet material was obtained by embossing.

The obtained leather-like sheet material had a good embossed pattern, and the sheet material had many long and thin folds, and had a moist, slimy feel and a heavy appearance. It was a leather-like sheet with a luxurious feel. Moreover, this leather-like sheet-like material retained the various favorable features mentioned above even after the jungle test.

Example 10 A polyester diol with a number average molecular weight of 2000 obtained by condensation polymerization of MPD and adipic acid, PMVL with a number average molecular weight of 2000, and a number average molecular weight of 20
Polyurethane in DMF at a concentration of 25 wt.
A solution was obtained. The viscosity of the solution at 30°C was 370 poise.Other than using such a polyurethane solution,
Similarly to Example 9, grain-finished leather-like 7-t-shape'
I got m.

Although the obtained leather forest and sheet-like material were slightly inferior to those obtained in Example 9, they were moist and had a slimy feel, and this slimy feeling was sufficiently maintained even after the jungle test. Ta.

Example 11 A polymer polyol, MDI and ED ( The molar ratio of polymer polyol, MDI and BD is 1
9:6.9) in DMF solvent according to a conventional method.
By reacting at a temperature of about 8 hours, a solution of a polyurethane elastomer (hereinafter referred to as polyurethane elastomer (X)) having a # degree of 25% by weight in DMF was obtained. The viscosity of the solution at 30°C was 380 poise.

Polybutylene adipate with number average molecular weight 2000, MD
By reacting I and BD (mole ratio is 1, 9:6.9) in a DMF solvent at 85° C. for about 7 hours according to a conventional method, a 25% by weight concentration of H+) U L/Tan elastomer [below] A DMF solution of polyurethane elastomer (Y)] was obtained. The viscosity of the solution at 30°C was 360 poise.

The two types of polyurethane elastomer solutions thus obtained were mixed so that the weight ratio of polyurethane elastomer (X) and polyurethane elastomer (Y) was 75:25, and the solid content was 11 to 13. % by weight, and further diluted with DMF to a weight ratio of 0.5:1 between alcohol-modified silicone oil and polyoxyethylene/polyoxypropylene block copolymer as an additive.
A polyurethane elastomer composition liquid was prepared by adding 20% by weight of the mixture to the polyurethane elastomer.

This polyurethane elastomer composition liquid was applied onto a polyethylene sheet at a liquid volume of 600r/i, and then a 25% by weight aqueous solution of dimethylformamide was applied at a temperature of 40°C.
℃#Immersed in solid liquid. The coagulated polyurethane elastomer sheet was peeled off from the polyethylene sheet, the solvent removed in hot water, washed, and dried to obtain a porous polyurethane sheet with excellent surface smoothness.

This porous sheet is made of nylon-6 ultrafine fiber! #
Contains polyester polyurethane in the entangled nonwoven fabric, resulting in a thickness of 12 cm! The fiber base material was coated with a polyurethane adhesive and embossed to form a leather-like patch-like article (8).

The obtained leather-like sheet material was a luxurious-looking leather-like sheet having a moist, slimy feel and a heavy appearance, and retained these good characteristics even after the jungle test.

Comparative Example 7 P M V L , M D with number average molecule 112000
A DMF solution of a polyurethane elastomer having a concentration of 25 tS was obtained by reacting I and BD (molar ratio 1 nia, 9:6.9) in a DMF solvent at 85° C. for about 7 hours according to a conventional method. The viscosity of the solution at 30°C is 39
There was 0 voice.

A polyurethane elastomer ( The mixture was mixed with Y) dissolved in DMF, and then a polyurethane elastomer composition was prepared, a porous polyethylene was produced, and a grain-finished leather-like sheet was produced.

Although the obtained porous polyurethane sheet Vi had very good surface smoothness, the grain-finished leather-like sheet obtained from it did not feel moist or slimy, and after the jungle test, The durability was insufficient, with cracks appearing on the silver surface.

Example 12 A polyester diol having a concentration of 25% by weight was prepared in the same manner as in Example 1 except that a polyester diol having a number average molecular weight of 2000 obtained by condensation polymerization of 175-bentanediol and adipic acid was used as the polyester diol. DMF of polyurethane elastomer for skin layer
A solution was obtained. The viscosity of the solution at 30°C was 400 voids. The solution was diluted with methyl ethyl ketone to obtain a polyurethane solution for the epidermal layer having a solid content concentration of 20 M1i. The epidermis IfI obtained in this way
A leather-like notebook material was obtained in the same manner as in Example 1 except that the polyurethane solution for I was used.

For each of the leather-like notebook samples obtained in this manner and the samples obtained by subjecting them to the jungle test, evaluations of sliminess and surface smoothness similar to those in Actual 8 Row 1 were obtained. went.

Based on the average evaluation based on the scores of each panelist, the obtained leather-like note-like material had a good sliminess, although it was inferior to the leather-like sorted material obtained by Fu et al. in Example 1. Good sliminess was maintained even in the jungle test wheat. Furthermore, the obtained leather-like sheet material had extremely good surface smoothness, and even after the jungle test, the good surface smoothness was maintained.

〔Effect of the invention〕

As is clear from the above embodiments, according to the invention, it has a good slimy feeling, and the good ambery feeling can be maintained by increasing the tube temperature.
To provide a firm leather-like sheet-like material that retains its shank for a long period of time under high humidity and has excellent vine durability. Among the leather-like notes provided by the present invention, the silver-like leather-like sorted ones have extremely good surface smoothness on the silver surface, and those with surface treatment applied to the edges have wrinkles. It has a good appearance in terms of shape, ■, and fixation of the embossed mold. Furthermore, among the leather sphere sheet-like products provided by the present invention, the suede-like leather-like sheet products have a good suede feel. Furthermore, the leather-like sheet-like products provided by the present invention are excellent in secondary processability, such as cutting processability, sewing processability, plowing and embossing properties.

Patent applicant RiRashi Co., Ltd.

Claims (1)

[Claims] In a leather-like sheet material consisting of a fiber substrate and a polyurethane resin, the polyurethane resin contains (A) an alkane having 5 to 6 carbon atoms derived from 1,5-pentanediol which may be substituted with a methyl group. Consisting of a polyester polyol containing a diol unit and a dicarboxylic acid unit and a polylactone polyol containing β-methyl-δ-valerolactone units, the weight ratio of the polyester polyol to the polylactone polyol is 5:95 to 85: A leather-like sheet material comprising a polyurethane elastomer obtained by reacting a polymer polyol within the range of No. 15 with (B) an organic diisocyanate.