JP3128373B2 - Polyurethane and leather-like sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Polyurethane has excellent mechanical properties, and is impregnated and / or coated with a solution of polyurethane on a fibrous substrate, and is subjected to dry or wet coagulation or impregnated and deposited with a polymer material to finish the surface of the fibrous substrate. Leather-like sheets 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 necessary for dyeing an acid dye, a cationic dye, or the like. In the case of disperse dyes, dyeing is possible, but due to the looseness of the amorphous structure of the polyurethane, the dye is difficult to stay inside the resin, that is, the dyeing fastness is extremely poor, due to washing and friction, etc. Discoloration and fading were easily seen and were not practical.

In an attempt to improve these drawbacks, dyed seats have been introduced into polyurethane resins.
For example, it is known to obtain a polyurethane dyeable to an acid dye by using a low molecular 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 unreacted isocyanate groups using a monohydric alcohol or amine having a tertiary or quaternary nitrogen atom in the molecule. ing. 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, when 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 viscosity of the polyurethane solution becomes too low, so that not only the process passability is deteriorated but also the mechanical performance of the resin becomes poor. It is not preferable because it decreases. In addition, if polyurethane molecules are 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 necessary to secure a sufficient dyeing seat. In any case, there were difficulties in implementing it industrially.

Japanese Patent Application Laid-Open No. 48-22602 discloses a general formula

Embedded image (Where R is an aliphatic alkyl group)
Substituted diethanolamine, aromatic diisocyanate or aliphatic diisocyanate, and a molecular weight of 500 to
It is disclosed that an artificial leather can be obtained 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 this publication is shown to be excellent in dyeability, light resistance and functionality, and claims its superiority.

[0005] However, the polyurethane obtained by the method of this publication uses the N-substituted diethanolamine represented by the above formula 1 as a chain extender. When a diol having a branched structure in the molecule is used as a chain extender, the physical properties of the polyurethane become fragile because a strong hard segment cannot be formed due to steric hindrance. However, it is inferior in heat resistance, solvent resistance, etc., and is completely poor for application to artificial leather. Not only that, when the glycol having a molecular weight of 500 to 5,000, which is an essential component constituting polyurethane, is a polyether glycol, the wet coagulability is inferior, and it is difficult to obtain an artificial leather having a good texture, and the method is industrially practiced. Had difficulties.

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

Embedded image (However, R ¹ and R ² are hydrogen, —CH ₂ CH ₂ NH ₂ or —CH ₂ CH ₂ CH ₂ NH ₂ ) This publication applies to polyester and polyether polymer isocyanate compounds, This shows that the dyeability of the disperse dye is good for the acid dye as well as the acid dye, and it claims superiority.

[0007] However, the polyurethane obtained by the method of this publication uses N-substituted diethanolamine containing a cyclic structure and diol as a part of the chain extender. When a low molecular weight compound having a cyclic structure in the molecule is used as a chain extender, a rigid hard segment cannot be formed due to steric hindrance, so that the mechanical properties of polyurethane are weak. In addition, it is inferior in heat resistance, solvent resistance, etc., and is completely poor for application to artificial leather. Not only that, when the glycol having a molecular weight of 500 to 5,000, which is an essential component constituting polyurethane, is a polyether glycol, the wet coagulability is inferior, and it is difficult to obtain an artificial leather having a good texture, and the method is industrially practiced. Had difficulties.

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

Embedded image (However, R ³ has 2 to 1 carbon atoms which may have a branch.
2 alkylene chain, comprising units of R ⁴ is an alkyl group, R ⁵ is an alkylene group made together with the alkyl group or R ^4,, R ⁶ is an alkyl group, x is an integer of from 2 to 6) Elastic filaments made of polyurethane are disclosed, but the polyurethane is also not satisfactory.

As an attempt to prevent the deterioration of the physical properties of polyurethane due to the introduction of a tertiary amino group-containing compound as described above, JP-B-50-17237 discloses an organic polyisocyanate, a high molecular weight polyvalent hydroxy compound and a polyfunctional compound. In the process of producing a polyurethane elastomer from a low molecular weight compound, a terminal hydroxyl group obtained by reacting an organic diisocyanate, a diol having a tertiary nitrogen and a high molecular weight polyhydroxy compound of at least 7 mol% or more of the diol. A method for producing a dyeable polyurethane elastic body characterized by adding a semipolymer and performing block copolymerization is disclosed. It shows that the polyurethane produced by the publication can impart dyeability without affecting the properties of the elastic yarn, and claims its superiority. However, in the method according to the publication, the diol having a tertiary nitrogen is allowed to react with a high-molecular-weight polyvalent hydroxy compound and to undergo a polyurethane-forming reaction via a semipolymer having a terminal hydroxyl group, so that the polyurethane production process becomes complicated. It is too much, and a great deal of labor is required for process control, which not only makes industrial use difficult, but also has a large variation in the quality of the obtained polyurethane, and there is a difficulty in using it for a leather sheet.

Further, JP-A-4-178416 and JP-A-4-178417 disclose radical polymerizable unsaturated compounds in the presence of a mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group. A method for producing a polyurethane resin in which a macromonomer (A) having a diol group at one end obtained by radical polymerization of a monomer having a bond, a polyol (B), and a polyisocyanate (C) are reacted, and the polyurethane resin is produced. A polyurethane resin composition is disclosed. These publications disclose 3-mercapto-1,2-propanediol as a mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group as dimethylaminomethyl (ethyl) as a monomer having a radical 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 claims its superiority. However, the polyurethane resins obtained by the methods of these publications are not particularly limited in the reaction order, or because each component in the resin does not have a controlled sequence structure,
During polymerization, it is difficult to obtain a sufficient viscosity or a balance of various properties such as heat resistance, cold resistance, strength, etc. of the obtained polyurethane resin. 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 an acid dye-dyeing seat into a polyurethane, to improve the dyeing properties, and to apply an industrially applicable polyurethane resin and a flexible resin using the polyurethane. An object of the present invention is to provide a leather-like sheet which can be dyed with an acid dye having excellent texture and durability.

[0012]

According to the present invention, there is provided a polyester diol (A) comprising a tertiary amino group-containing diol and a dicarboxylic acid, a polyester, a polycarbonate, a polylactone, and a polyether having a number average molecular weight of 500. It is 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.

In the present invention, in order to improve the dyeability of the polyurethane, a tertiary amino group-containing diol is used not as a hard segment (chain extender) or a molecular end of the polyurethane but as a part of the composition of the soft segment of the polyurethane. It is introduced into the diol (A) to form an acidic dyeing seat. 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 amount of the tertiary amino group-containing diol is not particularly limited, and varies depending on the molecular weight, required dyeability, and the dye used, but it is 1 to 1000 μeq / g, preferably 1. 5 to 500 µe
q / g, more preferably 2 to 200 μeq / g.

The tertiary amino group-containing diol used in the production of the polyester diol containing a tertiary amino group in the present invention includes, for example, the following.

Embedded image (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 a phenyl group, n Is an integer of 1 to 10.

[0015]

Embedded image (However, R ⁹ is an aliphatic alkyl group or a phenyl group)

Embedded image

[0016]

Embedded image (However, R ³ has 2 to 1 carbon atoms which may have a branch.
2 is an 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, the tertiary amino group-containing diol may be an alkyl of tertiary amino group-containing acrylic acid and / or methacrylic acid in the presence of a compound containing two hydroxyl groups and one thiol group. A tertiary amino group-containing diol (macromonomer having a diol group at one end) obtained by radical polymerization of 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,
(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 initiators such as azobisisobutyronitrile, azobisisovaleronitrile, banzoyl peroxide and the like.
In addition, butyl acrylate, methyl methacrylate, butyl methacrylate, and so on within a range not to impair the object of the present invention.
Methacrylates containing no perfluoroalkyl such as ethyl acrylate, acrylates, and other copolymerizable vinyl monomers can be used in combination. The molecular weight when using such a macromonomer as a tertiary amino group-containing diol is not particularly limited,
Although it depends on the monomer used, it is preferably from 400 to 20,000, particularly preferably from 500 to 4,000. If it is too large exceeding 20,000, a polymer having no hydroxyl group is likely to be produced at the time of production, which makes it difficult to effectively use it as a polyester diol, which may be a problem in industrial production.

The tertiary amino group-containing polyester diol (A) can be obtained, for example, by reacting a dibasic acid with the above-mentioned tertiary amino group-containing low molecular weight diol or macromonomer. Examples of the dibasic acid include aromatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and brassic acid, aromatic dibasic acids such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. One of the basic acids or a combination thereof can be used. Among them, aliphatic dibasic acids, especially adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, etc., have a methylene chain length of 4-8.
Is more preferably used. As the diol, a tertiary amino group-containing low molecular diol 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 diol that can be used at that time may be, for example, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol,
A kind of aliphatic diol such as heptanediol, octanediol, nonanediol, decanediol, dodecanediol, alicyclic diol such as cyclohexanediol, hydrogenated xylylene glycol, xylylene glycol, or aromatic diol such as A mixture of two or more kinds is used. Among them, aliphatic diols having 4 or more carbon atoms, particularly those having a carbon chain length of 5 to 9 such as methylpentanediol, hexanediol, heptanediol, methyloctanediol, and nonanediol, are used. One or a mixture of two or more aliphatic diols is suitably 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 from 500 to 3,000, but is more preferably from 700 to 2,500.
If 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 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. Here, the number average molecular weight of the polyester diol (A) when a macromonomer is used as a raw material of the polyesterdiol is calculated from the number average molecular weight and the content of the macromonomer. The average molecular weight of a substantial main chain portion is referred to.

The polymer diol (B) is a 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, a range of 700 to 2500 is more preferably selected. If it is less than 500, the leather-like sheet tends to lose its flexibility or its hand is unfavorably reduced. If it exceeds 3000, it may be difficult to obtain a leather-like sheet having a good balance of feeling, flexibility, cold resistance, heat resistance and durability, probably because the urethane group concentration is inevitably reduced. There is a problem in industrial production of the polymer diol, which is not preferable. More preferably, it is preferable to substantially contain polycarbonate. The mixing ratio varies depending on the required durability, flexibility, etc.,
It is preferred that the content is 10% or more, more preferably 20% or more. 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, 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 the dibasic acid include aromatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and brassic acid, aromatic dibasic acids such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. One of the basic acids or a combination thereof can be used. Among these, aliphatic dibasic acids, especially dibasic acids having a methylene chain length of 4 to 8, such as adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, etc., are more preferably used. Examples of the diol include aliphatic alcohols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, and dodecanediol which may be substituted with a lower alcohol. diol, cyclohexane diol, hydrogenated Kishirirengu Ricoh <br/> Le, alicyclic diols such as, xylylene glycol, one or a mixture of two or more such aromatic diols such as are used, inter alia carbons in length Is an aliphatic diol having a carbon chain length of 5 to 9, such as methylpentanediol, hexanediol, heptanediol, methyloctanediol, and nonanediol, or a mixture of two or more aliphatic diols. It is preferably used in terms of water resistance.

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, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, which may be substituted with a lower alcohol,
One or two or more 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 more than one species are used, of 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 are preferably used in terms of flexibility and the like. Used.

The polylactone diol is, 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 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 aliphatic diols such as decane diol and dodecane diol, cyclohexane diol, hydrogenated xylylene glycol, and aromatic diols such as xylylene glycol, and one or a mixture of two or more kinds such as diethylene glycol. Among them, aliphatic diols, in particular, ethylene glycol and butanediol are particularly preferably used in terms of balance of feeling, flexibility, cold resistance and heat resistance of the leather-like sheet. The amount used is not particularly limited, but it varies depending on the molecular structure, the blending amount of the component (A), the molecular weight of the polymer diol (B), the type of the organic diisocyanate, and the NCO / OH equivalent ratio. + (B), leather-like sheet-like material having an equivalent ratio of (C) / (A) + (B) of from 0.5 to 7, preferably from 1 to 5.5. Often, 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 para-phenylene diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, hydrogenated MDI, etc. And the like are used. Of these, diphenylmethane-4,4'-diisocyanate is preferred because the surface properties and feel of the sheet obtained by coagulation with a non-solvent are good. The amount used varies depending on the reaction solvent, moisture contained in the raw materials, etc., but is usually an isocyanate group (NCO) and an amino group-containing polyester diol (A) from (D), a polymer diol (B) and a low molecular diol. (C) equivalent ratio of hydroxyl group (OH) (NCO
/ OH) 0.95 to 1.2, especially 0.97 to 1.
It is preferably 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 polyurethane, for example, metal compounds such as titanium tetraisopropoxide, dibutyltin dilaurate and tin octate And tertiary amines such as tetramethylbutanediamine and 1,4-diaza (2,2,2) bicyclooctane.

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

In the case of a silver-coated leather-like sheet having a surface layer of the above-mentioned polyurethane on its surface, the fiber base material does not necessarily have to be dyed with constituent fibers, and is particularly limited to a fiber material dyed with an acid dye. Although it is not a thing, what consists of the fiber dye | stained with an acidic dye is preferable in order not to produce the discoloration of the cut surface of a leather-like sheet | seat. In addition, in the case of a fiber-napped suede-like leather-like sheet, there is no particular limitation as long as it is made of a fiber that can be dyed with an acid dye, and a synthetic fiber such as a polyamide, a tertiary amino group-modified polyester, or a natural fiber such as Any of knitted fabrics, woven fabrics, nonwoven fabrics obtained from wool or the like, and three-dimensionally entangled ultrafine fiber bundles having an average fineness of 0.1 denier or less can be used. Above all, a nonwoven fabric composed of a bundle of ultrafine fibers having an average fineness of 0.1 denier or less and more preferably 0.005 to 0.1 denier entangled three-dimensionally 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 term polyamide bromide poles fine fiber-generating fibers to be used in the present invention is a polyamide resin, such as 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon, soluble spinnability with other aromatic groups It is at least one kind of polyamide selected from polyamide. 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 for the polyamide resin, and that of a polyamide resin under spinning conditions. it may be any resin that have a smaller melt viscosity, such as polyethylene, polypropylene, ethylene - propylene copolymer, ethylene - vinyl acetate copolymer, ethylene - acrylic acid ester alcohol copolymer, ethylene -α- olefin copolymers, polystyrene, styrene - isoprene copolymer, styrene - isoprene copolymer hydrogenation product, scan Ji Ren - butadiene copolymer, scan Ji Ren -
It is selected from hydrogenated butadiene copolymers. The fibers comprising polyamide and other polymers are mixed at a predetermined mixing ratio, and melting in the same melting system, a method of spinning to form a mixed system, and molten in another separate melting systems, spinning machine joining the head portion - a method of spinning to form a mixed system is repeated several times divided, were molten in separate melting systems, by a method of spinning defining the fiber shape at a spinning machine mouthpiece, in the fibers The polyamide resin component occupies 40 to 80% by weight, and the polyamide ultrafine fiber component in the fiber is 5 or more, preferably 50 to 8%.
Polyamide ultrafine fiber generating fibers in the range of 00 fibers are obtained. The microfiber-generating fiber is fineness of 2 to 15 denier through normal fiber processing steps such as drawing and heat setting, if necessary.
The average fineness (calculated value) of the polyamide ultrafine fiber component is 0.2 denier or less, preferably 0.005 to 0.1 denier.

The microfiber-generating fiber is defibrated with a card, and a random web or a cross-wrap web is formed through a webber. The obtained fiber web is laminated to a desired weight and thickness. Next, the fiber web is subjected to a fiber entanglement treatment by a needle punch, a water jet, an air jet or the like by a conventionally known method to obtain a fiber entangled nonwoven fabric.

[0030] Then, coagulation adjusting agent if necessary to a solution of Polyurethane, mold release agents, plasticizers, stabilizers, antioxidants, light
The composition is prepared by adding a stabilizer , a colorant, and the like, and is impregnated and / or coated on a fibrous substrate, and then wet-coagulated or dry-coagulated. In the case of microfiber-generating fibers, prior to impregnation and application of the polyurethane composition liquid to the fiber-entangled nonwoven fabric, or after impregnation and application, the fiber is treated with a solvent for the other resin that composes the fiber and a non-solvent for the fiber to produce a microfiber structure. Get the body. The amount of the polyurethane resin in the sheet is not particularly limited,
It is often used at a weight fraction of 10 to 60%, especially 15 to 45%. If the amount of urethane used is small, the texture is rather stiff, and if it is less than 10%, it becomes remarkable. If the amount of urethane is large, it becomes hard,
It tends to have a texture without swelling. When the content exceeds 60%, the tendency becomes remarkable.

Further, the sheet-like material may be further provided with a porous or non-porous coating layer obtained from the above-mentioned polyurethane, if necessary, to give a leather-like sheet with silver, or at least one surface thereof. By raising the skin, it is possible to obtain a fiber-napped suede-like leather-like sheet. Further, if necessary, it can be slice-divided into an arbitrary thickness in the thickness direction at an arbitrary stage.

[0032]

The leather- like sheet of the present invention thus obtained is useful for various uses such as clothing, shoes, bags, furniture, vehicle interior materials, and miscellaneous goods. Polyurethane resin its desired mechanical various physical properties, acid dyes without losing the proper processing, and can stain-called acid dyes such as metal-containing complex salt dye, without compromising the desirable properties in the manufacturing process of the leather-like sheet, excellent Although the mechanism of action of obtaining a leather-like sheet having a natural texture is not clear, tertiary amino group-containing polyester diol (A), polymer diol (B), low molecular diol (C), organic diisocyanate (D) The soft segment and the hard segment constituting the polyurethane resin maintain a desirable microphase separation state, and are impregnated with the polyurethane resin because a tertiary amino group serving as a dyeing seat for an acid dye has been introduced. ,
It is considered that the desirable properties as described above were imparted to the leather sheet material used as the coat layer.

[0033]

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.

Example 1 As a tertiary amino group-containing polyester diol (A),
A diol component comprising a mixture of equimolar amounts of N-methyldiethanolamine and 3-methyl-1,5-pentanediol, a dicarboxylic acid component comprising sebacic acid, 260 parts by weight of a polyester diol having a number average molecular weight of 2,000,
620 parts by weight of polyhexylene carbonate having a number average molecular weight of 2,000, 580 parts by weight of polybutylene adipate having a number average molecular weight of 2,000, and polytetramethylene glycol 5 having a number average molecular weight of 2,000 as the polymer diol (B)
40 parts by weight, 217 parts by weight of ethylene glycol as the low molecular weight diol (D), and diphenylmethane-4,4'-diisocyanate 11 as the organic diisocyanate (C)
49 parts by weight 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 to obtain a polyurethane solution having a concentration of 25% and a weight average molecular weight of 360,000. DMF 9 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 (trade name: Dai Nippon Ink Co., Ltd.) and 1.5 parts by weight of Chris Bon Assister SD14 (trade name: Dai Nippon Ink Co., Ltd.) were added to obtain an impregnating liquid.

A web is formed by using staple fibers of ultrafine fiber generating type fibers (6-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. A needle punch entangled nonwoven fabric was used. This impregnated nonwoven fabric was impregnated with the above impregnating solution, and then poured into a 25% aqueous solution of DMF to coagulate.
Then, the mixture was treated in hot toluene to dissolve and remove the polyethylene component, thereby obtaining a sheet having a thickness of 1.4 mm. This sheet was divided into two parts, and the divided surfaces were buffed with sandpaper to a thickness of 0.56 mm. Further, the surface at the time of solidification was treated with an emery buffing machine to form a napped surface. When the sheet-like material having the napped surface was dyed under the following conditions,
A leather-like sheet which is dyed in a vivid color and has a good texture is obtained, and the superiority of the present invention is apparent. 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 fifth week.
Deterioration of the polyurethane was observed at the seventh week, but it was practically sufficient. Dye Kayacyl Blue HRL Dye concentration 5.0 g / l Ammonium acetate 0.6 g / l Formic acid 1.0 g / l Bath ratio 50: 1

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

Example 2 As a tertiary amino group-containing polyester diol (A),
The diol component is N-methyldiethanolamine, 1, 9
A mixture of 2-nonanediol and 2-methyl-1,8-octanediol (molar ratio, 50:25:25), wherein the dicarboxylic acid component is adipic acid, 200 parts by weight of a polyester diol having a number average molecular weight of 2,000, and a polymer As diol (B), 1000 parts by weight of polyhexylene carbonate having a number average molecular weight of 2,000 and PNOA having a number average molecular weight of 2,000 (a mixture having a diol component of 9-nonanediol and 2-methyl-1,8-octanediol in an equimolar ratio) , 800 parts by weight of a polyester diol having a dicarboxylic acid component of adipic acid) 217 parts by weight of ethylene glycol as a low molecular weight diol (C), 1160 parts by weight of diphenylmethane-4,4′-diisocyanate as an organic diisocyanate (C), and 10140 parts by weight of DMF Into 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 impregnation liquid in the same manner as in Example 1. A sheet-like material having a napped surface obtained in the same manner as in Example 1 was dyed under the same conditions except that the above-mentioned impregnating liquid was used, and a leather-like sheet having a good texture was dyed in a vivid color. Thus, the advantages of the present invention are clear. Further, when the leather-like sheet was exposed to an atmosphere of 70 ° C. and a relative humidity of 95%,
No change was seen until week. At the tenth week, the polyurethane was deteriorated, but it was practically sufficient.

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

[0039]

The leather-like sheet of the present invention is excellent in various physical properties such as mechanical properties and durability, processing suitability, and is made of a polyurethane resin which can be dyed with an acid dye. It is a leather-like sheet that can be dyed with so-called acid dyes such as dyes and gold-containing complex dyes. It has excellent coloring and durability, and is useful for various uses such as clothing, shoes, bags, furniture, vehicle interior materials, and miscellaneous goods. It is.

Claims (2)

(57) [Claims] 1. A polyester diol (A) comprising a tertiary amino group-containing diol and a dicarboxylic acid, and a number average molecular weight selected from the group consisting of polyester, polycarbonate, polylactone and polyether of from 500 to 3,000.
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 polyester diol (A) comprising a tertiary amino group-containing diol and a dicarboxylic acid, a number average molecular weight selected from the group consisting of polyester, polycarbonate, polylactone and polyether is 500 to 3000.
A polyurethane obtained by reacting a polymer diol (B), a low molecular diol (C), and an organic diisocyanate (D).