JP3142097B2 - Leather-like sheet with silver surface dyeable with acid dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a leather-like sheet having excellent dyeability. In more detail, the specific components that make up the polyurethane resin are blended in a specific composition and in a specific order, and the physical properties obtained by mixing and reacting are excellent in various physical properties such as durability, processing suitability, and acid dye. The present invention relates to a leather-like sheet having a clear layer of a dyeable polyurethane resin and a colored layer containing a pigment on its surface.

[0002]

2. Description of the Related Art Conventionally, coloring with a dye has provided a deeper color tone because of its clear hue and transparency, as compared with coloring with a pigment, and has a wide variety of colors. Therefore, a leather-like sheet material in which a skin layer is made of polyurethane colored by a dye is known.

For example, JP-A-59-100778 and JP-A-59-100779 disclose a polycarbonate-based cross-linked polyurethane layer, a polycarbonate / polyethylene glycol-based polyurethane colored layer, and a polycarbonate-based polyurethane layer on a substrate layer surface. A leather-like sheet having a laminated structure is disclosed. However, since the leather-like sheet of the publication uses a polycarbonate / polyethylene glycol-based polyurethane for the coloring layer, good coloring can be obtained with a metal-containing complex dye, but sufficient coloring cannot be obtained with an acid dye. There are cases. Further, since polyethylene glycol is used for the colored layer, the color is often faded due to oxidative deterioration.

[0004] As an attempt to improve such disadvantages, 3
It is known to obtain a polyurethane dyeable to an acid dye by introducing a dyeing seat into a polyurethane resin by using a low molecular compound having a graded nitrogen atom or a piperazine ring as a chain extender. For example, JP-A-48-5599
No. 5 and Japanese Examined Patent Publication No. 44-16386 show that a monohydric alcohol or amine having a tertiary or quaternary nitrogen atom in the molecule is used to complete the reaction of the unreacted isocyanate group to thereby improve the dyeability. It is disclosed that a polyurethane can be obtained. However, according to the method of the publication, monohydric alcohols or amines having a dyeing seat are monofunctional and introduced at the end of the polyurethane polymer molecule. Therefore, if a large amount of alcohol or amine is used to enhance the dyeing properties, the molecular weight of the polyurethane becomes too small and the mechanical performance is reduced, and if the molecular weight of the polyurethane is increased so that sufficient mechanical performance can be obtained, the sufficient It is impossible to introduce as much monohydric alcohol or amine as necessary to secure a proper dyeing seat, and in any case, there is a problem in industrial implementation.

[0005] JP-A-48-22602 discloses that N-
An artificial leather excellent in dyeability using a polyurethane using a substituted diethanolamine as a chain extender is disclosed. However, in the polyurethane obtained by the method of this publication, since N-substituted diethanolamine is used as a chain extender, a strong hard segment is not formed due to steric hindrance, and the mechanical properties of the polyurethane are weak. Not only that, heat resistance and solvent resistance are poor. Furthermore, in the case of dyeing, there is a problem that the texture becomes hard, the folding wrinkles become large, and the appearance becomes poor, probably because of the poor balance of the polyurethane.

Japanese Patent Publication No. 47-19189 discloses a process for producing a polyurethane having good dyeing properties using an N-substituted diethanolamine having a cyclic structure and a diol as a part of a chain extender. However, the polyurethane obtained by the method of this publication is disclosed in
Since a cyclic amine having a large steric hindrance is used as a chain extender as in JP-A-8-22602, a strong hard segment is not formed due to the steric hindrance, and not only the mechanical properties of the polyurethane become fragile, but also There is a problem that heat resistance and solvent resistance are poor.

The present inventors have disclosed in Japanese Patent Application No. 5-2505 an OH-terminated prepolymer obtained by reacting a tertiary amino group-containing diol, a polymer diol and a diisocyanate at a specific ratio with a diisocyanate and a low molecular chain extender. A leather-like sheet which can be dyed with an acid dye using a polyurethane obtained by the reaction was proposed. However, although the leather-like sheet is excellent in dyeing properties and various physical properties, when a silver-coated sheet having a surface layer consisting of only a dry surface layer without laminating a porous layer, Due to the transparency of the surface layer, the color of the fibrous base material layer may be seen through, and a plaque may appear, resulting in low commercial value.

[0008]

In recent years, there has been a remarkable trend in consumerism toward higher-grade consumerism, emphasis on sensitivity, and emphasis on fashion. The same is true in the field of leather-like sheet materials such as artificial leather and synthetic leather, and there is a demand for fashionable materials having clear colors and excellent looks. At present, a leather-like sheet having a tone with silver is mainly manufactured by a method such as a dry method or a wet method, and at that time, a pigment is mainly used for coloring. Therefore, the color was not clear and could not sufficiently respond to the demands of consumers. Further, even if a resin that can be colored with a dye is used, a resin that satisfies all of the physical properties, durability, and coloring properties has not been obtained. An object of the present invention is to have a silver surface that can be colored with an acidic dye having no problem as described above,
An object of the present invention is to provide a leather-like sheet having a high-grade appearance, excellent flexibility and durability.

[0009]

According to the present invention, there is provided a fibrous base material comprising a polyurethane colored layer containing a pigment and a tertiary amino group-containing diol (A), a polyester, a polycarbonate, a polylactone, and a polyether. Substantially obtained by reacting at least one selected polymer diol (B) and organic diisocyanate (C1) in a quantitative relationship such that the equivalent ratio of NCO / OH is 0.5 to 0.99. OH-terminated intermediate diol (D), low-molecular diol (E) and diphenylmethane-4,4 '
-A leather-like sheet having a silver surface which can be dyed with an acid dye, in which a clear layer made of polyurethane obtained by reacting with diisocyanate (C2) is sequentially laminated.

In the present invention, the tertiary amino group-containing diol (A) is used not in the hard segment (chain extender) or the molecular terminal but in the soft segment in order to improve the dyeability of the polyurethane used for the grain surface layer. Into an intermediate diol (D), which serves as a dyeing seat for an acid dye. That is, the polyurethane used in the present invention can introduce a required amount of dyed seat without any adverse effect on the molecular weight or the crystallinity of the hard segment. Therefore, the blending amount of the tertiary amino group-containing diol (A) is not particularly limited, and varies depending on its molecular structure, required dyeability, dye used, etc. / G, especially 1.5 to
500 μeq / g, more preferably 2 to 200 μeq
/ G range.

The tertiary amino group-containing diol (A) used in the present invention includes, for example, the following.

Embedded image (Where Y is H or a lower alkyl group having 1 to 6 carbon atoms, R ¹ is the same or different lower alkylene group having 2 to 6 carbon atoms, R ² is a lower alkyl group having 1 to 6 carbon atoms or a phenyl group, m , N is an integer from 1 to 10)

[0012]

Embedded image (However, R ³ is an aliphatic alkyl group or a phenyl group)

[0013]

Embedded image

[0014]

Embedded image (However, R ⁴ has 2 to 1 carbon atoms which may have a branch.
An alkylene chain of 2, R ⁵ is an alkyl group, R ⁶ is an alkyl group, or an alkylene group formed together with R ⁵ , R ⁷ is an alkyl group, and x is an integer of 2 to 6.)

In the present invention, the tertiary amino group-containing diol (A) is used in the presence of a compound containing two hydroxyl groups and one thiol group in the presence of a tertiary amino group-containing acrylic acid and / or methacrylic acid. A tertiary amino group-containing diol obtained by radical polymerization of an acid alkyl ester can be used.

Such a tertiary amino group-containing diol can be obtained by a known method. For example, 3-mercapto-
In the presence of 1,2-propanediol, as an alkyl ester of tertiary amino group-containing acrylic acid and / or methacrylic acid, for example, diisopropylaminoethyl methacrylate, t-butylmethylaminoethyl methacrylate, 2- (di-n- Propylamino) -1-methylethyl methacrylate, dimethylaminoethyl methacrylate, diisopropylaminoethyl acrylate, t
-Butylmethylaminoethyl acrylate, 2- (di-
Monomers such as (n-propylamino) -1-methylethyl acrylate and dimethylaminoethyl acrylate can be polymerized using an initiator such as azobisisobutyronitrile, azobisisovaleronitrile, and benzoyl peroxide. . In addition, butyl acrylate, methyl methacrylate, butyl methacrylate, methacrylate containing no perfluoroalkyl such as ethyl acrylate, acrylate, and even other copolymerizable vinyl monomers can be used in combination without impairing the object of the present invention. No problem.

The molecular weight of the tertiary amino group-containing diol (A) is not particularly limited, but is preferably from 400 to 20,000, more preferably from 500 to 400, depending on the monomer used.
0 is preferred. If it is too large, exceeding 20,000, a polymer having no hydroxyl group is likely to be produced during the production, which makes it difficult to be effectively used for polyurethane, which may be a problem in industrial production.

The polymer diol (B) used in the present invention is selected from the group consisting of polyester, polycarbonate, polylactone and polyether. Its number average molecular weight is 500-3000, more preferably 70-3000.
A range of 0 to 2500 is selected. If it is less than 500, the flexibility of the polyurethane tends to be impaired, or the heat resistance tends to decrease, which is not preferable. If it exceeds 3,000, it is difficult to obtain a polyurethane resin having a good balance of mechanical properties, flexibility, cold resistance, heat resistance, and durability. -There are difficulties in industrial production of diols, which is not preferred. There is no particular limitation on the use of a low-molecular diol having a molecular weight of less than 500 as long as the object of the present invention is not impaired, but low-molecular linear diols such as ethylene glycol, butanediol and hexanediol, and xylylene It is preferable that a component generally used as a chain extender such as an aromatic diol such as glycol is not substantially contained in view of mechanical properties, flexibility, and cold resistance of the polyurethane resin.

The polyester diol used in the present invention can be obtained by reacting an alkane diol with a dicarboxylic acid or an ester-forming derivative thereof under the conditions employed in a usual polyester formation reaction.
Alkanediols include ethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-
Nonanediol, 1,10-decanediol, and the like. In consideration of durability, physical properties, and the like, the alkane diol is particularly preferably an alkane diol having 6 to 10 carbon atoms. If the number of carbon atoms is less than 6, the resulting polyurethane may have poor durability, especially wet heat resistance. On the other hand, if the number of carbon atoms is larger than 10, the obtained polyurethane becomes hard, and the texture of the leather-like sheet may become poor or the cold resistance may become poor.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid. These dicarboxylic acids can be used alone or in combination of two or more. Among them, aliphatic dibasic acids, especially adipic acid, azelaic acid and sebacic acid are preferably used. These dicarboxylic acids may be used in the form of an ester-forming derivative. Examples of such ester-forming derivatives include lower alkyl esters such as methyl and ethyl esters of the above dicarboxylic acids. The above dicarboxylic acids or ester-forming derivatives thereof may be used alone or as a mixture of two or more.

The polycarbonate diol is produced by a transesterification reaction between an alkylene glycol and a carbonate or a reaction between phosgene or chloroformate and an alkylene glycol. As the alkylene glycol, for example, ethylene glycol, 1,4-
Butanediol, 1,6-hexanediol, 1,9-
Nonanediol, 1,10-decanediol, linear alkylene glycol having 2 to 10 carbon atoms which may have an oxygen atom interposed in the alkylene portion such as 1,10-decanediol, diethylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol , 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol and the like, branched alkylene glycols having 4 to 10 carbon atoms or the like are used alone or as a mixture of two or more. Examples of the carbonate include diphenyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate.

Polylactone diols include, for example, poly-
ε-caprolactone diol, poly-β-methyl-δ-
Valerolactone diol and the like. These polylactone diols are produced by ring-opening polymerization of lactone using alkylene glycol or the like as an initiator. Examples of the polyether diol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

The organic diisocyanate (C1) is, for example, diphenylmethane-4,4'-diisocyanate,
Aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate, meta- or para-phenylene diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4 ' -Non-aromatic diisocyanates such as dicyclohexylmethane diisocyanate are used. Among them, diphenylmethane-4,
In the case of 4'-diisocyanate, isophorone diisocyanate, 2,4- or 2,6-tolylene diisocyanate, and hexamethylene diisocyanate, the obtained sheet-like material is preferable because of its good surface properties and feeling.

The intermediate diol (D) having an OH terminal substantially constitutes a substantially soft segment of the obtained polyurethane, and comprises the component (A), the polymer diol (B) and the organic diisocyanate (C1). And NC
It is obtained by reacting in a quantitative relationship such that the equivalent ratio of O / OH becomes 0.5 to 0.99. The equivalent ratio of NCO / OH is 0.5
If the amount is less than the above, the amount of the urethane bond incorporated into the intermediate diol having an OH end substantially varies depending on the blending amount of the component (A), the molecular weight of the polymer diol (B), and the type of the organic diisocyanate (C1). It is difficult to balance the feeling, flexibility, cold resistance and heat resistance of the leather-like sheet because the molecular weight is too small or the molecular weight is too small, and the effect of the present invention cannot be sufficiently obtained. Also NCO
When the equivalent ratio of / OH exceeds 0.99, it differs substantially depending on the blending amount of the component (A), the molecular weight of the polymer diol (B), and the type of the organic diisocyanate (C1). Either the amount of urethane bonds incorporated in the diol is too large, or the molecular weight of the intermediate diol (D) is too large, or the surface property, texture, flexibility, cold resistance and heat resistance of the leather-like sheet material It is difficult to achieve balance, which is not preferable.

Examples of the low molecular weight diol (E) include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, which may be substituted with a lower alcohol. Aliphatic diols such as decane diol and dodecane diol, alicyclic diols such as cyclohexane diol and hydrogenated xylylene glycol, aromatic diols such as xylylene glycol, and one or a mixture of two or more kinds such as diethylene glycol are used. But,
Among them, aliphatic diols, especially ethylene glycol and butanediol, are suitably used in terms of balance of feeling, flexibility, cold resistance and heat resistance of the leather-like sheet.

The amount of the low molecular weight diol (E) is not particularly limited, but depends on its molecular structure, the amount of the component (A), the molecular weight of the polymer diol (B), the type of organic diisocyanate, and the NCO / OH equivalent ratio. Leather-like sheet usually having an equivalent ratio of (E) / (B) of 0.5 to 7.0, especially 1.0 to 5.5, relative to polymer diol (B). In many cases, it is suitable in terms of feeling, flexibility, cold resistance and heat resistance of the product.

The amount of diphenylmethane-4,4'-diisocyanate (C2) used is not particularly limited, and the viscosity of the polyurethane solution, the tertiary amino group-containing diol (A), the polymer diol (B) and the organic diisocyanate (C1) can be used. Although it depends on the equivalent ratio of NCO / OH, the reaction solvent, the water content in the polymer diol (B) and the low molecular weight diol (E), etc., the N from the (C1) and (C2) is usually different.
Equivalent ratio N of hydroxyl groups from CO and amino group-containing diol (A), polymer diol (B) and low molecular weight diol (E)
CO / OH 0.95-1.2, especially 0.97-
It is preferably 1.1.

A catalyst is not always necessary when the polymerization method used in the present invention is carried out, but catalysts used in the production of ordinary polyurethanes, for example, titanium tetraisopropoxide, dibutyltin dilaurate, tin octate, etc. Tertiary amines such as a metal compound, tetramethylbutanediamine, and 1,4-diaza (2,2,2) bicyclooctane can be used.

Examples of the solvent for the polyurethane obtained by the method used in the present invention include dimethylformamide,
Commonly used solvents such as dimethylacetamide, N-methylpyrrolidone, toluene, ethyl acetate, methyl ethyl ketone and tetrahydrofuran are used.

When the polyurethane obtained by the method used in the present invention is used, various additives used in conventional polyurethanes such as a flame retardant such as a phosphorus compound and a halogen-containing compound, an antioxidant, an ultraviolet absorber, Pigments,
Dyes, plasticizers, surfactants and the like can be added.

The thickness of the polyurethane clear layer of the present invention is preferably in the range of 5 to 100 μm, more preferably 10 to 50 μm. 5 μm clear layer
If it is thinner, a good tint may not be obtained even when dyed. On the other hand, if the thickness is larger than 100 μm, the obtained leather sheet-like material may have inconvenience such as a hard feel or a bad wrinkle feeling. The polyurethane clear layer basically contains no pigment, but may be added in a small amount as long as the effect of the present invention is not impaired.

The polyurethane colored layer located between the polyurethane clear layer and the fibrous base material is used for the leather sheet of the present invention having substantially no porous coating layer. This is an essential layer for hiding from the layer. That is, if the surface clear layer is simply dyed with an acid dye, the mixed state of the fibers and the resin constituting the fibrous base material can be seen through the surface, resulting in poor appearance. The polyurethane used for the polyurethane colored layer does not necessarily need to be dyed with an acid dye and does not need to have a tertiary amino group, but preferably has the same physical properties as the clear layer. It is preferable to use a polyurethane having the same kind of soft segments as the polyurethane used. Further, when the same polyurethane as the polyurethane used for the clear layer is used, the polyurethane colored layer is also dyed with an acid dye, so that a deeper color tone is obtained, which is preferable.

It is also preferable to blend a polyfunctional polyisocyanate in the polyurethane colored layer in order to improve the adhesion to the fibrous substrate and the peel strength. This method is particularly effective when a chain extender is not used for polyurethane synthesis,
Examples of such polyfunctional polyisocyanates include adducts of organic diisocyanates such as tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate with tri- to tetrahydric alcohols such as trimethylolpropane, glycerin, and pentaerythritol. The added amount of the polyfunctional polyisocyanate is preferably in the range of 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the polyurethane. If the addition amount is less than 5 parts by weight, the effect of improving peel strength is difficult to be obtained, and if it is more than 50 parts by weight, depending on the color difference between the pigment and the dye to be combined and the dyeing concentration, the pigment color is strong and the transparency is high. May be inferior, and the texture may be hard.

When a segmented polyurethane is used as the polyurethane for the polyurethane colored layer, the adhesion to the fibrous substrate and the peel strength may not be sufficiently obtained. In such a case, an adhesive consisting of a combination of a polyurethane and a polyfunctional polyisocyanate that does not use the chain extender may be interposed between the polyurethane colored layer and the fibrous substrate. In this case, the adhesive layer may be a clear layer containing no pigment.

The thickness of the polyurethane coloring layer is 5 to 100 μm.
m, more preferably 10 to 50 μm. When the thickness is less than 5 μm, even if the amount of the pigment added is large, the color unevenness due to the fibrous substrate may not be able to be concealed, and the thickness unevenness of the colored layer may easily affect the color unevenness, resulting in poor appearance. is there. On the other hand, if the thickness is larger than 100 μm, the obtained leather-like sheet may have poor texture, wrinkle and the like.

The amount of the pigment used in the polyurethane colored layer depends on the thickness of the colored layer and the clear layer, the kind and color of the pigment, and is not particularly limited as long as the object of the present invention is attained. Usually, it is preferred that the weight ratio of the pigment content / the resin content is 0.01 or more. For example, when the thickness of the polyurethane colored layer is 10 to 50 μm, the weight ratio is preferably in the range of 0.01 to 0.70, and more preferably in the range of 0.02 to 0.30. If the weight ratio is less than 0.01, the color unevenness of the fibrous substrate cannot be concealed even if the thickness of the colored layer is increased, resulting in poor appearance and impaired commercial value. Also, when the weight ratio is large, the tint of the pigment is strongly affected even by dyeing with an acid dye, and the dyeing effect with the acid dye may not be sufficiently obtained. If the colored layer is made as thin as about 5 μm and the clear layer is made thicker, there is no particular problem in texture, physical properties, dyeing properties, and concealing properties even if the amount of pigment added is increased to about 1.5.

The fibrous substrate is made of synthetic fibers such as polyamide, polyester, vinylon and polyacrylonitrile;
Artificial fibers such as rayon, cupra, acetate, silk,
Any of knitted fabrics, woven fabrics, and nonwoven fabrics made of natural fibers such as cotton, wool, and hemp can be used. Among them, a three-dimensional entangled nonwoven fabric, in particular, a nonwoven fabric made of an ultrafine fiber bundle having an average fineness of 0.1 denier or less, and more preferably 0.005 to 0.1 denier, can be suitably applied. The fibers constituting the fibrous substrate are not necessarily dyed, but are preferably made of fibers dyed with an acid dye in order to prevent the cross section of the leather-like sheet from having a different color.

The fibrous substrate is more preferably formed by impregnating the above-mentioned knitted fabric, woven fabric, non-woven fabric, or the like with a polyurethane solution and subjecting it to wet or dry coagulation. In this case, the amount of the polyurethane occupying the fibrous substrate is not particularly limited, but is 3 to 60% by weight, especially 10 to 30% by weight.
And the apparent density of the fibrous substrate is 0.4
It is preferable easily take balanced texture and waist of the leather-like sheet obtained in the range of 0.8 g / cm ^3.

The leather-like sheet material of the present invention can be obtained by laminating a colored layer and a clear layer of a pigment on the above fibrous base material, but in view of smoothness of the surface and easy control of the coating amount. It is advantageous to produce by a so-called dry method. That is, a desired amount of a polyurethane solution for a clear layer is applied and dried on a release paper with a grain, and then a polyurethane composition liquid for a coloring layer to which a pigment is added is applied.If necessary, a polyurethane for an adhesive layer is further applied. It is applied, bonded to a fibrous substrate by a method of wet lamination or dry lamination, aged for a predetermined time, and then the release paper is peeled off to obtain the leather sheet of the present invention. The clear layer or the colored layer is not limited to only one layer, and two or more layers having different compositions or the same composition may be laminated as long as the total thickness of the layers is within the range described above in order to improve clarity and concealment. You can also.

The obtained leather sheet material is subjected to coloring by dyeing, rubbing treatment conventionally performed as a finishing treatment for improving surface touch and appearance, various finishing agents treatment by gravure or spraying, and the like. Can be finished. When such a finishing treatment is performed, it is preferable that the staining treatment is performed prior to the finishing treatment because the dyeing property may be impaired. The leather-like sheet of the present invention thus obtained can have its silver surface layer dyeable with an acid dye, and its excellent mechanical properties, durability, and good texture can be used for clothing, shoes, and the like. It can be used for various uses such as bags, furniture, vehicle interior materials, and miscellaneous goods.

[0041]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
In the examples, the compounds may be represented by the following abbreviations. DMF: N, N-dimethylformamide MEK: Methyl ethyl ketone MDI: Diphenylmethane-4,4'-diisocyanate TDI: Tolylene diisocyanate EG: Ethylene glycol PHC: Polyhexylene carbonate diol PMPA: Polymethylpentane adipate diol PTG: Polytetramethylene glycol PBA: polybutylene adipate diol MDEA: N-methyldiethanolamine

<Production Example of Polyurethane> PU-1 MDEA 4.0 as a tertiary amino group-containing diol (A)
Parts by weight, number average molecular weight 2 as polymer diol (B)
200 parts by weight of PHC having a molecular weight of 2000, 200 parts by weight of PMPA having a number average molecular weight of 2000, 200 parts by weight of PTG having a number average molecular weight of 2000, 63 parts by weight of MDI as an organic diisocyanate (C1) (NCO / 0H = 0.75), and DMF 667 parts by weight The mixture was charged into a three-necked flask equipped with a cooling tube, and reacted at a predetermined temperature and a predetermined time under a nitrogen stream to obtain an intermediate diol (D). After confirming that the isocyanate group had disappeared by the reaction, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured using gel permeation chromatography (hereinafter referred to as GPC). To this intermediate diol, 62 parts by weight of EG as a low molecular weight diol (E) and MDI (C
2) 275 parts by weight were added and reacted, and 334 parts by weight of DMF and 556 parts by weight of MEK were further added and reacted to obtain a polyurethane (PU-1) solution having a concentration of 30% and a weight average molecular weight of 260,000.

PU-2 MDEA 4.0 parts by weight, PHC having a number average molecular weight of 2000
200 parts by weight of PMPA 200 having a number average molecular weight of 2000
Parts by weight, 200 parts by weight of PTG having a number average molecular weight of 2000,
338 parts by weight of MDI, 62 parts by weight of EG, DMF1000
Parts by weight and 556 parts by weight of MEK were charged into a three-necked flask equipped with a Dimroth condenser and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain a concentration of 30% and a weight average molecular weight of 2800.
A polyurethane (PU-2) solution of No. 00 was obtained.

PU-3 200 parts by weight of PHC having a number average molecular weight of 2000, 200 parts by weight of PMPA having a number average molecular weight of 2000, 200 parts by weight of PTG having a number average molecular weight of 2000, 300 parts by weight of MDI, 59 parts by weight of EG, 1440 parts by weight of MMF, and M
EK800 parts by weight was charged into a three-necked flask equipped with a Dimroth condenser, and reacted at a predetermined temperature and a predetermined time under a nitrogen stream,
A polyurethane (PU-3) solution having a concentration of 30% and a weight average molecular weight of 260,000 was obtained.

PU-4 As a tertiary amino group-containing diol (A), a polymer having an average molecular weight of 2,000 obtained from a 1: 1 mixture of dimethylaminoethyl acrylate and butyl acrylate and 3-mercapto-1,2-propanediol Diol 20
0 parts by weight, 300 parts by weight of PHC having a number average molecular weight of 1000 as the polymer diol (B) and a number average molecular weight of 1000
600 parts by weight of organic diisocyanate (C1)
165 parts by weight of a mixture of 2,4-TDI and 2,6-TDI (weight ratio 80:20) (NCO / OH = 0.9
5) and 5490 parts by weight of DMF were charged into a three-necked flask equipped with a Dimroth condenser and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain an intermediate diol (D). After confirming that the isocyanate group reacted and disappeared, the weight average molecular weight (in terms of polystyrene) of the intermediate diol was measured using GPC and found to be 65,000. A low molecular weight diol (E) is added to a DMF solution of the intermediate diol (D).
Of EG and 459 parts by weight of MDI (C2) were added and reacted to obtain a polyurethane solution having a weight average molecular weight of 350,000.

PU-5 As a tertiary amino group-containing diol (A), 1,4 bis (2
-Hydroxyethyl) piperazine (8.7 parts by weight), a polymer diol (B) having a number average molecular weight of 2,000 PHC
200 parts by weight, 367 parts by weight of PBA having a number average molecular weight of 2,000, and MDI6 as an organic diisocyanate (C1)
6.7 parts by weight (NCO / OH = 0.80) and DMF
1767 parts by weight was charged into a three-necked flask equipped with a Dimroth condenser and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain an intermediate diol (D). After confirming that the isocyanate group had reacted and disappeared, the weight average molecular weight (in terms of polystyrene) of the intermediate diol was measured using GPC and found to be 48,000. DM of this intermediate diol
In solution F, 98.3 parts by weight of EG as low molecular diol (E), 437 parts by weight of MDI (C2), and MEK981
A part by weight was added and reacted to obtain a polyurethane (PU-59) solution having a concentration of 30% and a weight average molecular weight of 270000.

PU-6 700 parts by weight of PHC having a number average molecular weight of 2000, 300 parts by weight of PEG having a number average molecular weight of 2000, 375 parts by weight of MDI, 62 parts by weight of EG, 2156 parts by weight of DMF, and M
EK1198 parts by weight was charged into a three-necked flask equipped with a Dimroth condenser and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain a polyurethane (PU-6) solution having a concentration of 30% and a weight average molecular weight of 240,000.

PU-7 1000 parts by weight of PHC having a number average molecular weight of 1,000, 1000 parts by weight of PTG having a number average molecular weight of 1,000, TDI330
Parts by weight, 780 parts by weight of DMF, and 780 parts by weight of toluene were charged into a three-necked flask equipped with a Dimroth condenser and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain a concentration of 60%.
Polyurethane having a weight average molecular weight of 120,000 (PU-
7) A solution was obtained.

Example 1 25 parts by weight of DMF and M based on 100 parts by weight of PU-1
25 parts by weight of EK were added to obtain a clear layer composition liquid. Also, 25 parts by weight of DMF, 25 parts by weight of MEK, and 20 parts by weight of white pigment were added to 100 parts by weight of PU-3 (pigment / resin ratio (P / R) = 0.25) to obtain a colored layer composition liquid. . Polyethylene propylene adipate / DMF / EG in an equivalent ratio of 1/5/4 to a three-dimensional entangled non-woven fabric of ultrafine fiber-generating fibers having polyethylene as a sea component and polyethylene terephthalate as an island component (average single fineness 0.08 dr). Impregnated with DMF solution of polymerized polyurethane, wet-coagulated, extracted and removed polyethylene component, 1.2m thick
m, an apparent density of 0.42 g / cm ³ , was used as a fibrous base material comprising a polyethylene terephthalate ultrafine fiber bundle and a porous polyurethane (polyurethane ratio: 55%). After coating the above clear layer composition liquid at 150 g / cm ² on release paper with a grain, it was dried at 110 ° C. for 2 minutes to obtain a polyurethane clear layer. On top of that, 120 g / cm
^Two coats were applied, bonded to the above fibrous substrate in a wet state, and dried at 100 ° C. for 2 minutes. Further, after aging at 60 ° C. for 2 days, the release paper was peeled off to obtain a leather sheet of the present invention.

The obtained leather sheet was dyed under the following conditions. Table 1 shows the evaluation results. Dye: Kayanol Cyanine Green G Dye concentration: 0.8 g / l Ammonium acetate: 1.0 g / l Acetic acid: 0.2 g / l Bath ratio: 50: 1

Examples 2-5, Comparative Examples 1-5 A leather-like sheet was obtained in the same manner as in Example 1 except that the kind of polyurethane in the clear layer and the colored layer and the amount of the pigment added to the colored layer were changed. Stained. However, Example 5
In the colored layer of (1), a polyfunctional polyisocyanate was added in an amount of 1 to 100 parts by weight of the solid content of PU-7 to improve adhesion.
8 parts by weight were added. The evaluation results are shown in Table 1.

[0052]

[Table 1]

Each evaluation in the table was classified according to the following criteria by sensory evaluation. Dyeing property: A dye having a vivid green color on the silver surface was evaluated as good, while a dye having a low dyeing density and a color with a strong white color of the pigment were evaluated as poor. Transparency: A product having a high transparency and a deep color was considered good. Concealment: A pattern in which the color of the base layer, the pattern of the fiber, the resin, and the like were not seen through was evaluated as good. Texture: flexibility by touch. Good soft ones. Fold wrinkles: The state of wrinkles that appear on the silver surface when the sheet is bent. Fine things are good.

The leather-like sheet materials of Examples 1 to 5 of the present invention are dyed in a vivid color by being dyed with an acid dye, and are excellent in transparency, concealing property of the base layer, and soft texture. It was a leather-like sheet having a fine crease and well-balanced. Although the sheet of Comparative Example 1 was excellent in clarity and transparency due to dyeing, the base layer was visible through the surface because there was no coloring layer with a pigment, and was of no commercial value. The sheet of Comparative Example 2 had no commercial value because the silver surface layer was not dyed. The sheet of Comparative Example 3 had dyeability with an acid dye, but the surface of the silver surface was roughened by dyeing, probably due to poor balance of polyurethane, and there was no transparency, and the texture and folding texture were poor. The sheet of Comparative Example 4 was inferior in dyeability and had no commercial value.

[0055]

The leather-like sheet material of the present invention can be dyed in a desired vivid color with a so-called acid dye such as an acid dye or a gold-containing complex dye, and has various physical properties such as mechanical properties and durability, texture, and the like. It is excellent in breaking creasing and the like. The leather-like sheet material of the present invention is capable of dyeing a product, in addition to dyeing with a raw cloth, and has excellent coloration and durability, and
It is useful for various uses such as shoes, bags, furniture, vehicle interior materials, and miscellaneous goods.

Claims (1)

(57) [Claims] 1. A polyurethane colored layer containing a pigment, a tertiary amino group-containing diol (A) on a surface of a fibrous substrate,
At least one polymer diol (B) selected from the group consisting of polyester, polycarbonate, polylactone, and polyether;
1) was reacted in a quantitative relationship such that the equivalent ratio of NCO / OH was 0.5 to 0.99, and the terminal was substantially OH.
Intermediate diol (D), low molecular weight diol (E) and diphenylmethane-4,4'-diisocyanate (C
A leather-like sheet having a silver surface which can be dyed with an acid dye, on which a clear layer made of polyurethane obtained by reacting 2) is sequentially laminated.