JPH06207381A - Polyurethane and leather-like sheet - Google Patents

Abstract

(57) [Abstract] [Purpose] An industrially applicable polyurethane resin with an improved dyeing property by introducing a dyeing seat of an acid dye into polyurethane and a soft texture and durability using the polyurethane resin. Provided is a leather-like sheet that can be dyed with an excellent acid dye. [Structure] A polymer diol (B) having a number average molecular weight of 500 to 3000 selected from the group consisting of a polyester diol (A) consisting of a tertiary amino group-containing diol and a dicarboxylic acid, a polyester, a polycarbonate, a polylactone and a polyether, and a low A leather-like sheet comprising a fibrous substrate and a polyurethane comprising a molecular diol (C) and an organic diisocyanate (D).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane and leather-like sheet excellent in dyeability with an acid dye. More specifically, various physical properties such as mechanical properties and durability obtained by blending and reacting a polyester diol containing a specific component constituting a polyurethane resin as an essential component,
The present invention relates to a polyurethane resin having excellent processability and capable of being dyed with an acid dye, and a leather-like sheet having excellent dyeability with an acid dye containing the polyurethane and a fibrous substrate.

[0002]

2. Description of the Prior Art Polyurethane has excellent mechanical properties, and a surface finish of a fibrous base material obtained by impregnating and / or applying a solution of polyurethane to a fibrous base material and then dry- or wet-coagulating or impregnating and depositing a polymer substance. Leather-like sheet materials having a polyurethane resin film as a layer are used in various fields. However, conventional polyurethane cannot be dyed because it does not have a dyeing seat required for dyeing an acid dye or a cationic dye. Further, although disperse dyes can be dyed, due to the looseness of the amorphous structure of polyurethane, the dye is difficult to stay inside the resin, that is, the dyeing fastness is extremely poor, and due to washing or rubbing, Color fading and fading were easily observed, which was not practical.

As an attempt to remedy these drawbacks, the introduction of dyeing seats into polyurethane resins has been carried out,
For example, it is known to obtain a polyurethane dyeable to an acid dye by using a low molecular weight compound having a tertiary nitrogen atom or a piperazine ring as a chain extender. For example,
JP-A-48-55995 and JP-B-44-163.
No. 86 discloses that a polyurethane having good dyeability can be obtained by completing the reaction of an unreacted isocyanate group with a monohydric alcohol or amine having a tertiary or quaternary nitrogen atom in the molecule. ing. However, according to the method of the publication, a monohydric alcohol or amine having a dyeing seat is monofunctional and is introduced at the terminal of a polyurethane polymer molecule. Therefore, if a large amount of alcohol or amine is used to enhance the dyeability, the molecular weight of the polyurethane becomes too small, the viscosity of the polyurethane solution becomes too low, and not only the process passability deteriorates, but also the mechanical performance of the resin is lowered. It is not preferable because it decreases. Also, if the polyurethane molecule is made large enough to satisfy the mechanical performance and process passability (solution viscosity), it is possible to introduce as much monohydric alcohol or amine as is necessary to secure a sufficient dyeing seat. However, it was difficult to carry out industrially in any case.

JP-A-48-22602 describes a general formula

[Chemical 1] (However, R is an aliphatic alkyl group) N-
Substituted diethanolamine, aromatic diisocyanate or aliphatic diisocyanate, and molecular weight of 500-
It is 5,000, and it is disclosed that artificial leather can be obtained by using a polyurethane synthesized from polyester glycol or polyether glycol having at least two active hydrogen atoms in the molecule. The artificial leather obtained by the method of the publication is excellent in dyeability, light resistance and functionality, and asserts its superiority.

However, the polyurethane obtained by the method of this publication uses the N-substituted diethanolamine shown in Chemical formula 1 above as a chain extender. Thus, when a diol having a branched structure in the molecule is used as a chain extender, it cannot form a strong hard segment due to its steric hindrance, and the mechanical properties of polyurethane are not only weak. In addition, it is inferior in heat resistance and solvent resistance, and is completely unsuitable for application to artificial leather. Not only that, when the glycol having a molecular weight of 500 to 5000, which is an essential component of polyurethane, is a polyether glycol, it is inferior in wet coagulability, and it is difficult to obtain an artificial leather with a good texture. I had a problem.

Japanese Patent Publication No. 47-19189 is characterized in that a high molecular isocyanate compound having an isocyanate group at the terminal is reacted with a chain extender containing 5 to 50 mol% of the compound represented by Chemical formula 2. A method for producing a polyurethane having good dyeability is disclosed.

[Chemical 2] (However, R ¹ and R ² are hydrogen, —CH ₂ CH ₂ NH ₂ or —CH ₂ CH ₂ CH ₂ NH ₂ ) In the publication, it is applied to polyester, polyether-based polymer isocyanate compounds, It shows superior dyeability to disperse dyes as well as acid dyes, and claims superiority.

However, the polyurethane obtained by the method of this publication uses N-substituted diethanolamine and diol containing a cyclic structure as part of the chain extender. Thus, when a low molecular weight compound having a cyclic structure in the molecule is used as a chain extender, it is not possible to form a strong hard segment due to its steric hindrance, and the mechanical properties of polyurethane become fragile. Not only is it inferior in heat resistance and solvent resistance, but it is completely unsuitable for application to artificial leather. Not only that, when the glycol having a molecular weight of 500 to 5000, which is an essential component of polyurethane, is a polyether glycol, it is inferior in wet coagulability, and it is difficult to obtain an artificial leather with a good texture. I had a problem.

Further, in Japanese Patent Publication No. 41-11651, a linear polyhydroxyl compound having a hydroxyl group at the end is reacted with an excess of diisocyanate and a chain extender composed of diamine, hydrazine, hydrazide and a mixture thereof. Obtained and formula

[Chemical 3] (However, R ³ has 2 to 1 carbon atoms which may have a branch.
2 alkylene chain, R ⁴ is an alkyl group, R ⁵ is an alkyl group, or an alkylene group formed together with R ⁴ , R ⁶ is an alkyl group, and x is an integer of 2 to 6). Although elastic filaments made of polyurethane are disclosed, the polyurethane is not satisfactory either.

As an attempt to prevent the deterioration of the physical properties of polyurethane due to the introduction of the tertiary amino group-containing compound as described above, Japanese Patent Publication No. 50-17237 discloses an organic polyisocyanate, a high molecular weight polyhydroxy compound and a polyfunctional compound. In the process of producing a polyurethane elastic body from a low molecular weight compound, it has a terminal hydroxyl group obtained by reacting an organic diisocyanate, a diol having a tertiary nitrogen and at least 7 mol% or more of a high molecular weight polyhydric compound of the diol. Disclosed is a method for producing a dyeable polyurethane elastic body, which comprises adding a semipolymer and performing block copolymerization. It is shown that the polyurethane produced according to this publication can impart dyeability without affecting the properties of the elastic yarn, and asserts its superiority. However, in the method according to this publication, a diol having a tertiary nitrogen is reacted with a polyhydric compound having a high molecular weight and is allowed to participate in a polyurethane-forming reaction via a semipolymer having a terminal hydroxyl group, which complicates the production process of polyurethane. However, not only is it difficult to use industrially because it requires too much labor for process control, but also the quality of the obtained polyurethane varies greatly, and it is difficult to use it for leather sheets.

Further, in JP-A-4-178416 and JP-A-4-178417, radical polymerizable unsaturated in the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group. A method for producing a polyurethane resin, which comprises reacting a macromonomer (A) having a diol group at one end, a polyol (B), and a polyisocyanate (C) obtained by radically polymerizing a monomer having a bond, and the resin. A polyurethane resin composition is disclosed. In these publications, 3-mercapto-1,2-propanediol is used as a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group, and dimethylaminomethyl (ethyl) is used as a monomer having a radically polymerizable unsaturated bond. ) Examples of tertiary amino group-containing (meth) acrylates such as (meth) acrylate,
It shows that it has excellent adhesion to the obtained polyurethane steel sheet and asserts its superiority. However, the polyurethane resin obtained by the method of those publications, because the reaction sequence is not particularly limited, or because each component in the resin does not have a controlled array structure,
During polymerization, it is difficult to obtain a polyurethane resin with sufficient viscosity, and it is difficult to obtain a polyurethane resin with sufficient balance of physical properties such as heat resistance, cold resistance and strength. Even if it can be used as an adhesive, artificial leather It could not be applied to the production of such sheets.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to introduce a dyeing seat of an acid dye into polyurethane, which has improved dyeability and is industrially applicable, and a flexible resin using the polyurethane resin. An object is to provide a leather-like sheet that can be dyed with an acid dye having excellent texture and excellent durability.

[0012]

The present invention has a number average molecular weight of 500 selected from the group consisting of polyester diol (A) consisting of tertiary amino group-containing diol and dicarboxylic acid, polyester, polycarbonate, polylactone and polyether. It is a leather-like sheet composed of a polyurethane comprising a polymer diol (B), a low-molecular diol (C) and an organic diisocyanate (D) of up to 3000 and a fibrous substrate.

In the present invention, in order to improve the dyeability of polyurethane, a polyester containing a tertiary amino group-containing diol as a part of the composition of the soft segment rather than at the polyurethane hard segment (chain extender) or molecular end is used. It is introduced into the diol (A) and used as a dyeing seat for acid dyes. That is, the polyurethane used in the present invention can introduce a necessary amount of dyeing seat without any adverse effect on the molecular weight or the crystallinity of the hard segment. Therefore, the compounding amount of the tertiary amino group-containing diol is not particularly limited, and varies depending on the molecular weight, the required dyeability, and the dye used, but the tertiary amino group is 1 to 1000 μeq / g with respect to polyurethane, and particularly 1. 5 to 500 μe
It is preferably q / g, and more preferably 2 to 200 μeq / g.

Examples of the tertiary amino group-containing diol used in the present invention for producing the tertiary amino group-containing polyester diol include the following.

[Chemical 4] (However, Y is H or a lower alkyl group having 1 to 6 carbon atoms, R ⁷ is the same or different lower alkylene group having 2 to 6 carbon atoms, R ⁸ is a lower alkyl group having 1 to 6 carbon atoms or phenyl group, n Is an integer of 1 to 10)

[0015]

[Chemical 5] (However, R ⁹ is an aliphatic alkyl group or a phenyl group)

[Chemical 6]

[0016]

[Chemical 7] (However, R ³ has 2 to 1 carbon atoms which may have a branch.
2 alkylene chain, R ⁴ is an alkyl group, R ⁵ is an alkyl group, or an alkylene group formed together with R ⁴ , R ⁶ is an alkyl group, and x is an integer of 2 to 6)

In the present invention, as the tertiary amino group-containing diol, a tertiary amino group-containing acrylic acid and / or methacrylic acid alkyl in the presence of a compound having two hydroxyl groups and one thiol group is used. A tertiary amino group-containing diol (a macromonomer having a diol group at one end) obtained by radically polymerizing an ester can be used. Such a macromonomer can be obtained by a known method. For example, in the presence of 3-mercapto-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-n-propylamino) 1-methylethyl acrylate, dimethylaminoethyl Monomers such as acrylates can be polymerized using an initiator such as azobisisobutyronitrile, azobisisovaleronitrile, vanzoyl peroxide.
Further, butyl acrylate, methyl methacrylate, butyl methacrylate, within a range that does not impair the object of the present invention,
There is no problem with using perfluoroalkyl-free methacrylates such as ethyl acrylate, acrylates, and other copolymerizable vinyl monomers in combination. There is no particular limitation on the molecular weight when such a macromonomer is used as a tertiary amino group-containing diol,
Depending on the monomer used, 400 to 20,000, preferably 500 to 4,000, is particularly preferable. If it exceeds 20,000 and is too large, a polymer having no hydroxyl group is likely to be produced during production, and it may be difficult to be effectively used for polyester diol, which may be a difficulty in industrial production.

The polyester diol (A) containing a tertiary amino group can be obtained, for example, by reacting a dibasic acid with the low molecular diol or macromonomer containing a tertiary amino group. Examples of dibasic acids include aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and brassic acid, and aromatic dibasic acids such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. It is possible to use one type of basic acid or a combination thereof. Among them, aliphatic dibasic acids, especially adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, etc., have a methylene chain length of 4 to 8
The dibasic acid of is more preferably used. As the diol, a low-molecular diol containing a tertiary amino group may be used, but other low-molecular diols can be mixed and used as long as the object of the present invention is not impaired. The low molecular weight diols that can be mixed at that time are, for example, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol,
Aliphatic diol such as heptane diol, octane diol, nonane diol, decane diol, dodecane diol, alicyclic diol such as cyclohexane diol, hydrogenated xylylene glycol, xylylene glycol, etc. A mixture of two or more kinds is used, and among them, an aliphatic diol having a carbon number of 4 or more, particularly methylpentanediol, hexanediol, heptanediol, methyloctanediol, nonanediol having a carbon chain length of 5 to 9 is used. One kind or a mixture of two or more kinds of aliphatic diols is preferably used in terms of physical properties such as water resistance.

The number average molecular weight of the polyester diol (A) containing a tertiary amino group is 500 to 3000, and more preferably 700 to 2500 is selected.
When it is less than 400, the flexibility of the polyurethane resin tends to be lost, or the heat resistance tends to decrease, which is not preferable. If it exceeds 3,000, it is inevitable that the concentration of the urethane group is decreased, and it is difficult to obtain a polyurethane resin having a good balance of mechanical properties, flexibility, cold resistance, heat resistance and durability. This is not preferable because of the difficulty in industrial production of diol. The number average molecular weight of the polyester diol (A) when a macromonomer is used as a raw material for the polyester diol is calculated theoretically from the number average molecular weight and the content of the macromonomer. The average molecular weight of the substantial main chain portion.

The polymer diol (B) is polyester,
It is selected from the group consisting of polycarbonate, polylactone and polyether. Its number average molecular weight is 500-300
Although it is 0, the range of 700 to 2500 is more preferably selected. If it is less than 500, the flexibility of the leather-like sheet material tends to be lost, or the texture tends to deteriorate, which is not preferable. If it exceeds 3,000, the concentration of urethane groups will inevitably decrease, and not only is it difficult to obtain a leather-like sheet material with well-balanced feeling, flexibility, cold resistance, heat resistance, and durability, There are difficulties in industrial production of the polymer diol, which is not preferable. More preferably, it substantially contains polycarbonate. The blending ratio varies depending on the required durability, flexibility, etc.,
It is preferable that the content is 10% or more, further 20% or more. Further, there is no limitation to mix and use a low-molecular diol having a molecular weight of less than 500 within a range not impairing the object of the present invention, but a low-molecular linear diol such as ethylene glycol, butanediol, hexanediol, xylylene, or the like. It is preferable that substantially no components such as an aromatic diol such as glycol which are usually used as a chain extender are substantially contained in terms of mechanical properties, flexibility, cold resistance and the like of the polyurethane resin.

The polyester diol used in the present invention can be obtained, for example, by reacting a dibasic acid with a diol. Examples of dibasic acids include aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and brassic acid, and aromatic dibasic acids such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. It is possible to use one type of basic acid or a combination thereof. Among them, aliphatic dibasic acids, particularly adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and other dibasic acids having a methylene chain length of 4 to 8 are more preferably used. Aliphatic diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol and dodecanediol, which may be substituted with lower alcohols. Aliphatic diols such as diols, cyclohexane diols, hydrogenated xylylene glycols, etc., and aromatic diols such as xylylene glycols, etc. are used alone or as a mixture of two or more thereof. The aliphatic diol is particularly resistant to one or a mixture of two or more aliphatic diols having a carbon chain length of 5 to 9 such as methylpentanediol, hexanediol, heptanediol, methyloctanediol and nonanediol. It is preferably used in terms of sex.

The polycarbonate diol can be obtained, for example, by reacting a carbonate compound with a diol. As the carbonate compound, dimethyl carbonate, diphenyl carbonate, ethylene carbonate and the like can be used. As the diol, ethylene glycol optionally substituted with a lower alcohol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol,
Aliphatic diols such as heptanediol, octanediol, nonanediol, decanediol and dodecanediol, alicyclic diols such as cyclohexanediol and hydrogenated xylylene glycol, and aromatic diols such as xylylene glycol. Mixtures of one or more species are used, among which aliphatic diols are
In particular, one or a mixture of two or more aliphatic diols having a carbon chain length of 4 to 9 such as butanediol, methylpentanediol, hexanediol, heptanediol, methyloctanediol and nonanediol is preferable in terms of flexibility. Used.

Polylactone diols are, for example, poly-
ε-caprolactone diol, poly-trimethyl-ε-
Examples include caprolactone diol and poly-β-methyl-δ-valerolactone diol. Examples of the polyether diol include polytetramethylene glycol, polypropylene glycol, polyethylene glycol and the like.

As the low molecular weight diol (C), 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 also one or a mixture of two or more such as diethylene glycol. Among them, aliphatic diols, especially ethylene glycol and butane diol, are preferably used from the viewpoint of the balance of the texture, flexibility, cold resistance, heat resistance and the like of the leather-like sheet material. The amount used is not particularly limited, but it usually depends on the 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, but it is usually (A). + (B), the equivalent ratio of (C) / (A) + (B) is 0.5 to 7, and 1 to 5.5 is obtained. In many cases, it is suitable in terms of cold resistance and heat resistance.

The organic diisocyanate (D) is, for example, diphenylmethane-4,4'-diisocyanate,
Aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate, meta or paraphenylene diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, hydrogenated MDI, etc. The non-aromatic diisocyanate of and the like are used. Among them, diphenylmethane-4,4′-diisocyanate is preferable because it has good surface properties and texture of the sheet-like product obtained by coagulating with a non-solvent. The amount used varies depending on the reaction solvent, the water content in the raw material, etc., but is usually an isocyanate group (NCO) from (D) and an amino group-containing polyester diol (A), a polymer diol (B) and a low molecular diol. Equivalent ratio of hydroxyl group (OH) from (C) (NCO
/ OH) is 0.95 to 1.2, especially 0.97 to 1.
It is preferably 1.

Further, a catalyst is not always necessary when carrying out the polymerization method used in the present invention, but catalysts used in the production of ordinary polyurethane, for example, metal compounds such as titanium tetraisopropoxide, dibutyltin dilaurate and tin octate. A tertiary amine such as tetramethylbutanediamine or 1,4-diaza (2,2,2) bicyclooctane can be used.

As the solvent for the polyurethane obtained by the method used in the present invention, there are used commonly used solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, ethyl acetate, methylethylketone, and tetrahydrofuran. The polyurethane obtained by the method used in the present invention is various additives used in conventional polyurethanes in use, for example, phosphorus compounds, flame retardants such as halogen-containing compounds, antioxidants, ultraviolet absorbers, pigments and dyes. , A plasticizer, a surfactant and the like can be added.

In the case of a silver-leathered leather-like sheet having a surface layer of the above-mentioned polyurethane on the surface, it is not always necessary that the constituent fibers are dyed, and the fiber substrate is particularly limited to a fiber material dyed with an acid dye. Although not limited to this, in order to prevent the cut surface of the leather-like sheet from becoming discolored, it is preferable to use a fiber that is dyed with an acid dye. In the case of a fiber-puffed suede-like leather-like sheet, there is no particular limitation as long as it is composed of fibers dyeable with an acid dye, and synthetic fibers such as polyamide, tertiary amino group-modified polyester, etc., or natural fibers such as Any of knitted fabrics, woven fabrics, non-woven fabrics, three-dimensionally entangled ultrafine fiber bundles having an average fineness of 0.1 denier or less and the like can be used. Above all, a non-woven fabric composed of an ultrafine fiber bundle having a three-dimensionally entangled average fineness of 0.1 denier or less, and further 0.005 to 0.1 denier can be suitably applied. This can be derived from a polyamide ultrafine fiber-generating fiber from two or more polymer components including a known polyamide resin. The polyamid-type ultrafine fiber-generating fiber used in the present invention is a polyamide resin such as 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon, or a spinnable polyamide having an aromatic group. It is at least one type of polyamide selected from On the other hand, the other polymer constituting the ultrafine fiber-generating fiber is not particularly limited, is a resin having a different solubility to a polyamide resin and a solvent, a resin having a low affinity with the polyamide resin, and that of the polyamide resin under spinning conditions. Any resin may be used as long as it has a lower melt viscosity or is a resin, for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-α-olefin copolymer. Polymer, polystyrene, styrene-isoprene copolymer, hydrogenated product of styrene-isoprene copolymer, stellene-butadiene copolymer, stellene-
It is selected from hydrogenated products of butadiene copolymer. Fibers composed of polyamide and other polymers are mixed at a predetermined mixing ratio and melted in the same dissolution system to form a mixed system and spinning, or in a separate dissolution system and joined at the spinning machine head. A method of spinning by forming a mixed system by repeating splitting a plurality of times, a method of dissolving by a separate dissolving system, and a method of spinning by defining the fiber shape in the spinneret part of the spinning machine; % To 80% by weight, and the polyamide ultrafine fiber component in the fiber is 5 or more, preferably 5
A polyamide ultrafine fiber-generating fiber in the range of 0 to 800 is obtained. If necessary, the ultrafine fiber-generating fiber may have a fineness of 2 to 15 denier through an ordinary fiber treatment process such as drawing and heat setting, and an average fineness of the polyamide ultrafine fiber component (calculated value)
The fiber has a denier of 0.2 or less, preferably 0.005 to 0.1 denier.

The ultrafine fiber generating fiber is defibrated with a card to form a random web or a cross wrap web through a web bar, and the obtained fiber web is laminated to have a desired weight and thickness. Then, the fiber web is subjected to a fiber entanglement treatment using a needle punch, a water jet, an air jet or the like by a conventionally known method to obtain a fiber entangled nonwoven fabric.

Then, the sheet-like material is a composition solution obtained by adding a coagulation regulator, a release agent, a plasticizer, a stabilizer, an antioxidant, a light-proofing agent, a colorant, etc. to the solution of polyurethane if necessary. , Is impregnated and / or applied on a fibrous substrate, and is wet- or dry-coagulated. In the case of ultrafine fiber generation type fibers, the fiber entangled non-woven fabric is treated with a solvent of other resin constituting the fiber and a non-solvent of the fiber before or after the impregnation and application of the polyurethane composition liquid. Get the body. The amount of the polyurethane resin in the sheet material is not particularly limited, but the weight fraction is 10 to 60%, especially 15 to
Often used at 45%. If the amount of urethane used is small, the texture is rather flat, and if it is less than 10%, it becomes remarkable. If the amount of urethane is large, it will become hard and the texture will not bulge easily. The tendency becomes remarkable when it is used in excess of 60%.

Further, the sheet-like material is provided with a porous or non-porous coating layer obtained from the above polyurethane on the surface, if necessary, to obtain a silver-tone leather-like sheet, or at least one surface thereof is provided. It can be made into a fiber-like napped suede-like leather-like sheet by applying a brushing treatment. Further, if necessary, it is possible to perform slice division into an arbitrary thickness in the thickness direction at an arbitrary stage.

[0032]

The thus-obtained leather sheet material of the present invention is useful for various purposes such as clothing, shoes, bags, furniture, vehicle interior materials and sundries. Various desirable mechanical properties of the polyurethane resin, acid dyes without loss of processability, dyeable with so-called acid dyes such as complex salt dyes, and without impairing the desirable properties in the leather-like sheet manufacturing process, Although a leather-like sheet material having a good texture was obtained, its mechanism of action is not clear, but a tertiary amino group-containing polyester diol (A), polymer diol (B), low molecular weight diol (C), organic diisocyanate (D) ) And a soft segment and a hard segment constituting the polyurethane resin while maintaining a desirable microphase separation state, because the tertiary amino group serving as the dyeing seat of the acid dye is introduced, the polyurethane resin is Impregnation,
It is considered that the above-mentioned preferable characteristics are imparted to the leather sheet material serving as the coat layer.

[0033]

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

Example 1 As the tertiary amino group-containing polyester diol (A),
260 parts by weight of a polyester diol having a number average molecular weight of 2000, in which the diol component is a mixture of N-methyldiethanolamine and 3-methyl-1,5-pentanediol in an equimolar amount, and the dicarboxylic acid component is sebacic acid,
As the polymer diol (B), 620 parts by weight of polyhexylene carbonate having a number average molecular weight of 2000, 580 parts by weight of polybutylene adipate having a number average molecular weight of 2000, and polytetramethylene glycol 5 having a number average molecular weight of 2000
40 parts by weight, 217 parts by weight of ethylene glycol as the low molecular diol (D), diphenylmethane-4,4'-diisocyanate 11 as the organic diisocyanate (C) 11
49 parts by weight and 10100 parts by weight of DMF were placed in a reactor and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain a polyurethane solution having a concentration of 25% and a weight average molecular weight of 360,000. DMF9 was added to 100 parts by weight of the obtained polyurethane solution.
2 parts by weight, 1.5 parts by weight of Chris Bon Assister SD7 (trademark: Dainippon Ink Co., Ltd.) and 1.5 parts by weight of Chris Bon Assister SD14 (trademark: Dainippon Ink Co., Ltd.) were added to prepare an impregnating solution.

A web was prepared using staple fibers of ultrafine fiber-generating fibers (60-nylon is an ultrafine fiber component) obtained by melt spinning 60 parts by weight of 6-nylon and 40 parts by weight of highly fluid polyethylene. It was a needle punch entangled nonwoven fabric. This entangled nonwoven fabric was impregnated with the above impregnating liquid and then put into a 25% aqueous solution of DMF to coagulate.
Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet-like material having a thickness of 1.4 mm. The sheet-like material was divided into two, and the divided surfaces were buffed with sandpaper to have a thickness of 0.56 mm. Further, the surface at the time of coagulation was treated with an emery buffing machine to form a nap surface. When the sheet-like material having the napped surface was dyed under the following conditions,
A leather-like sheet material which is dyed in a bright color and has a good texture is obtained, and the superiority of the present invention is clear. further,
When the leather-like sheet was exposed to an atmosphere of 70 ° C. and a relative humidity of 95%, no change was observed until the 5th week.
Deterioration of the polyurethane was observed at the 7th week, but this was practically sufficient. Dye Kayacyl Blue HRL Dye concentration 5.0 g / liter Ammonium acetate 0.6 g / liter Formic acid 1.0 g / liter Bath ratio 50: 1

Comparative Example 1 The number average molecular weight of 2 was used as the polymer diol (B) without using the tertiary amino group-containing polyester diol (A).
713 parts by weight of polyhexylene carbonate and 667 parts by weight of polybutylene adipate having a number average molecular weight of 2000, 620 parts by weight of polytetramethylene glycol having a number average molecular weight of 2000, and 217 parts by weight of ethylene glycol as a low molecular weight diol (D). As the organic diisocyanate (C), 1150 parts by weight of diphenylmethane-4,4'-diisocyanate and 10100 parts by weight of DMF were charged into a reactor and reacted under a nitrogen stream at a predetermined temperature for a predetermined time, a concentration of 25% and a weight average molecular weight. 350,000 (polystyrene equivalent) polyurethane solution was obtained. Using the obtained polyurethane solution, an impregnating liquid was prepared in the same manner as in Example 1. Furthermore, when a sheet-like material having a raised surface impregnated with the above impregnating liquid in an entangled nonwoven fabric was dyed under the following conditions, the fiber part was dyed, but the polyurethane part was hardly dyed and looked unattractive. Example 1
In comparison with, the effect of using the tertiary amino group-containing polyester diol (A) of the present invention is clear.

Example 2 As a tertiary amino group-containing polyester diol (A),
The diol component is N-methyldiethanolamine, 1,9
A mixture of nonanediol and 2-methyl-1,8-octanediol (molar ratio 50:25:25), dicarboxylic acid component is adipic acid, 200 parts by weight of polyester diol having a number average molecular weight of 2000, polymer As a diol (B), a mixture of 1000 parts by weight of polyhexylene carbonate having a number average molecular weight of 2000 and PNOA having a number average molecular weight of 2000 (the diol component is a mixture of 9-nonanediol and 2-methyl-1,8-octanediol in an equimolar ratio). , Polyester diol whose dicarboxylic acid component is adipic acid), 217 parts by weight as low molecular diol (C), 1160 parts by weight of diphenylmethane-4,4′-diisocyanate as organic diisocyanate (C), and 10140 parts by weight of DMF. To the reactor And, under a stream of nitrogen reacted for a predetermined time at a predetermined temperature, concentration of 25% to obtain a polyurethane solution having a weight average molecular weight of 360,000. The obtained polyurethane solution was used as an impregnating liquid in the same manner as in Example 1. A sheet-like material having a raised surface obtained in the same manner as in Example 1 except that the above-mentioned impregnating liquid was used was dyed under the same conditions. As a result, a leather-like sheet-like material having a good texture was obtained. Thus, the advantages of the present invention are clear. Furthermore, when the leather-like sheet was exposed to an atmosphere of 70 ° C. and a relative humidity of 95%,
No changes were seen by the week. Deterioration of the polyurethane was observed at 10th week, but it was sufficient for practical use.

Example 3 As the tertiary amino group-containing polyester diol (A),
The diol component is a mixture of N-methyldiethanolamine and ethylene glycol in an equimolar amount, the dicarboxylic acid component is adipic acid, and 200 parts by weight of a polyester diol (A) having a number average molecular weight of 2000 and a number average molecular weight as a polymer diol (B) are used. 1800 parts by weight of polyethylene propylene adipate (polyester diol in which the diol component is a mixture of ethylene and propylene in a molar ratio of 85:15 and the dicarboxylic acid component is adipic acid) 1800 parts by weight, and 217 parts by weight of ethylene glycol as a low molecular diol (C) Parts, 1160 parts by weight of diphenylmethane-4,4′-diisocyanate as an organic diisocyanate (D), and 10140 parts by weight of DMF are charged into a reactor and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to give a concentration of 25% and a heavy weight. To obtain a polyurethane solution having an average molecular weight of 350,000. The obtained polyurethane solution was used as an impregnating liquid in the same manner as in Example 1. A sheet-like material having a raised surface obtained in the same manner as in Example 1 except that the above-mentioned impregnating liquid was used was dyed under the same conditions. As a result, a leather-like sheet-like material having a good texture was obtained. Thus, the advantages of the present invention are clear. Further, the leather-like sheet material is
When exposed to an atmosphere of ℃ and 95% relative humidity, no change was observed until the third week. Deterioration of the polyurethane was observed in the 5th week, but its use was limited and practically sufficient for clothing use, for example.

[0039]

EFFECT OF THE INVENTION The leather-like sheet of the present invention is excellent in physical properties such as mechanical properties and durability, suitability for processing, and uses a polyurethane resin which can be dyed with an acid dye, so that it is flexible and excellent in texture and acidity. It is a leather-like sheet that can be dyed with so-called acid dyes such as dyes and complex salt dyes. It has excellent color development and durability and is useful for various applications such as clothing, shoes, bags, furniture, vehicle interior materials, and miscellaneous goods. Is.

Claims (2)

[Claims] 1. A number-average molecular weight selected from the group consisting of polyester diol (A) consisting of tertiary amino group-containing diol and dicarboxylic acid, polyester, polycarbonate, polylactone and polyether is 500 to 3000.
A leather-like sheet comprising a polyurethane comprising a polymer diol (B), a low molecular diol (C) and an organic diisocyanate (D) and a fibrous substrate. 2. A number-average molecular weight selected from the group consisting of polyester diol (A) consisting of tertiary amino group-containing diol and dicarboxylic acid, polyester, polycarbonate, polylactone, polyether is 500 to 3000.
Polyurethane obtained by reacting the polymer diol (B), low molecular diol (C), and organic diisocyanate (D).