CN101994263A - Method for producing leather material and leather material - Google Patents

Method for producing leather material and leather material Download PDF

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Publication number
CN101994263A
CN101994263A CN2010102590325A CN201010259032A CN101994263A CN 101994263 A CN101994263 A CN 101994263A CN 2010102590325 A CN2010102590325 A CN 2010102590325A CN 201010259032 A CN201010259032 A CN 201010259032A CN 101994263 A CN101994263 A CN 101994263A
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Prior art keywords
carboxyl
leather
polyurethane resin
carboxylic acid
ester groups
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CN2010102590325A
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CN101994263B (en
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木部佳延
西野正和
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Nicca Chemical Co Ltd
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Nicca Chemical Co Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
    • D06M11/62—Complexes of metal oxides or complexes of metal salts with ammonia or with organic amines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
    • D06N3/08—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products with a finishing layer consisting of polyacrylates, polyamides or polyurethanes or polyester
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/106—Roughness, anti-slip, abrasiveness
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/108—Slipping, anti-blocking, low friction
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing
    • D06N2211/106—Footwear
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/14—Furniture, upholstery
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/18—Medical, e.g. bandage, prostheses, catheter
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/26—Vehicles, transportation

Abstract

The present invention provides a method for producing leather material by dipping fiber base material in a mixed liquor containing (A) polyurethane resin with carboxyl and/or carboxylate, (B) aminium salt of inorganic acid and (C) water, then drying to obtain the leather material.

Description

Leather is with the manufacture method and the leather material of material
Technical field
The present invention relates to manufacture method and the leather material of leather, particularly, the present invention relates to use the waterborne polyurethane resin manufacturing, be suitable as manufacture method and the leather material of the leather of dermatine or synthetic leather use with material with material.
Background technology
All the time, as the substitute of natural leather, produce dermatine that the multiple fiber base material of being made by polyurethane resin and nonwoven fabric constitutes and by polyurethane resin and fabric or compile the synthetic leather that fiber base material that thing makes constitutes.Such dermatine, synthetic leather are for example by being called the method manufacturing of wet type freezing method, in the method, in order to make it be similar to natural leather, the organic solvent solution of impregnation or coating polyurethane resin in fiber base material, make the product that obtains by being poor solvent with respect to polyurethane resin and having in the solidification liquid (normally water) of intermiscibility with this organic solvent, it is solidified, then wash, drying.
But, because a large amount of most inflammabilities of using of organic solvents such as dimethyl formamide are strong in this wet type freezing method, toxicity is also high, so, have the danger of breaking out of fire, and also worry the deterioration of operating environment and the environmental pollution problems of atmosphere, water quality etc.In addition,, also incorporate into the manufacture method of the operation that reclaims the organic solvent that produces, but still have the problem that produces huge cost of idleness and labor intensive in order to solve such problem.In addition, in the dermatine that obtains owing to the organic solvent solution that uses polyurethane resin, the synthetic leather, organic solvent is arranged in that leather is inner residual, so the problem that also exists skin barrier etc. that human body is impacted.Therefore, the polyurethane resin that will be bonded to fiber base material is studied from the problem that type of organic solvent hydrotropism polyurethane resin changes.
The manufacture method of the dermatine of this use waterborne polyurethane resin etc., because not with an organic solvent, so, reclaim aspect the needed cost and the enhancement of environment aspect excellence of the improvement of operating environment, atmosphere pollution, water pollution etc. can removing, but the dermatine that obtains with the organic solvent solution that uses polyurethane resin, synthetic leather be relatively the time, dermatine, the synthetic leather that can't obtain having gratifying feel and rerum natura.Major reason as this problem, after can being set forth in the inner impregnation waterborne polyurethane resin of fiber base material, when utilizing hot blast to carry out xeothermic drying, along with moving from the water of fiber base material surface evaporation, waterborne polyurethane resin moves to the fiber base material surface, and so-called migration (migrate) promptly takes place.Promptly, because such migration takes place, in the manufacture method of the dermatine that uses waterborne polyurethane resin etc., waterborne polyurethane resin moves to the surface of fiber base material, be formed on fiber base material inside almost not set the state of polyurethane resin is arranged, thereby obtain Boardy Feeling, lack dermatine, the synthetic leather of piloerection sense.Therefore, in the manufacture method of the dermatine that uses waterborne polyurethane resin etc.,, carrying out various investigations in order to solve migration problem.
For example, a kind of manufacture method of leather sample goods is disclosed in Japanese Patent Publication 55-51076 communique (patent documentation 1), impregnation has been given heat coagulable synthetic resin emulsion by adding the Thermogelling agent in fiber base cloth, and this synthetic resin emulsion is solidified.
But, in this method, preventing animal migration though can improve, part contains immersion liquid and flows out in bath and solidify, and this jello that solidifies is attached to the surface of machining object once more, has the leather that the obtains problem of the feel variation of material.And, in this method,, cause part to contain immersion liquid and in hot water, flow out easily along with polyurethane resin lowering of concentration, thermocoagulation reduction, there is the leather that the obtains problem of the further variation of feel of material.
In addition, in Japanese kokai publication hei 6-316877 communique (patent documentation 2), disclose a kind of manufacture method of dermatine, the aqueous resin composition that is dissolved with inorganic salts in will the nonionic emulsion behind forced emulsification is supplied with to the nonwoven tablet, and carries out heat drying.
But, in this method, prevent animal migration though can improve, according to the concentration of the inorganic salts that cooperate, the problem in the processing such as bad stability of bath can appear handling.In addition, owing to residual in fiber base material non-ionic surface active agent and inorganic salts are arranged, wiriness, the abrasion resistance of material are low, the friction firmness is also insufficient so the leather that obtains is used.
In addition, a kind of manufacture method of fiber sheet-like composite is disclosed in TOHKEMY 2000-290879 communique (patent documentation 3), impregnation or coating are the aqueous resin composition that 40～90 ℃ aqueous polyurethane resin and associative form tackifier constitute by heat freezing temperature in the fibrous material matrix, utilize water vapour to make this aqueous resin composition thermocoagulation.
But, in this method, prevent animal migration though can improve owing to residual in the fibrous material matrix non-ionic surface active agent, associative form tackifier are arranged, so the leather that obtains with material still wiriness, abrasion resistance is low, the friction firmness is also insufficient.
In addition, the manufacture method of a kind of leather with flaky material disclosed in TOHKEMY 2003-138131 communique (patent documentation 4), comprise the non-ionic surface active agent of HLB10～18 and the carboxylic acid type polyurethane resin of inorganic salts to the fibrous material supply, make its thermocoagulation.
But, in this method, also with above-mentioned patent documentation 2 and 3 in the method for record same, produce the problem that surfactant and inorganic salts brought, the leather that obtains is also insufficient with material still wiriness, friction firmness.
In addition, in the method for in above-mentioned patent documentation 2～4, putting down in writing, though residues such as non-ionic surface active agent, associative form tackifier can be by washing repeatedly or operation such as Warm Wash and to remove to a certain degree, be difficult to remove fully, so still can not avoid above-mentioned problem.And, wash repeatedly or operation such as Warm Wash can cause the manufacturing procedure number to increase, involve economy problems.Therefore, require to reduce the operation of washing or Warm Wash as far as possible and can easily remove residue and obtain having the manufacture method of the leather of sufficient feel and rerum natura with material.
In addition, disclose the manufacture method of a kind of leather with material in TOHKEMY 2006-36960 communique (patent documentation 5), impregnation comprises the polyurethane resin with carboxyl, the ammonium salt of carboxylic acid and the mixed liquor of water in fiber base material, carries out drying afterwards.
But, in this method, though can solve the problem of migration, the new problems such as foul smell that the ammonia that has produced when having occurred owing to drying causes.In addition, during as ammonium carboxylate salt, the problem of corrosion of equipment occurs causing, need improve manufacturing process owing to the carboxylic acid that heat drying volatilizees at the ammonium salt that uses the few carboxylic acid of carbon numbers such as ammonium formate or ammonium acetate.On the other hand, when using the ammonium salt of the many carboxylic acids of carbon number, during heat drying the volatilization of carboxylic acid few, but if obtain the animal migration that prevents of purpose, must use in a large number.In addition, if for durability such as the heat resistance that improves resin and use polycarbodiimide compound, because itself and ammonium carboxylate salt react, so, also be difficult to be prevented fully animal migration even use ammonium carboxylate salt in a large number.
Like this, in the manufacture method of the dermatine that uses waterborne polyurethane resin etc., not obtaining as yet at present fully preventing moves, thereby the foul smell that causes owing to the gas that produces in the operation of set polyurethane resin and not existing and the burn into manufacturing of device have the method for the leather usefulness material of sufficient feel and quality, the countermeasure of the VOC that need produce in operation equably on fiber base material.
Summary of the invention
The present invention finishes in view of above-mentioned existing in prior technology problem, and its purpose is to provide the manufacture method of a kind of leather with material and the leather material that is obtained by this manufacture method.Although this leather also is to have considered that the leather of use aqueous polyurethane resin of carrying capacity of environment and VOC problem is with the manufacture method of material with the manufacture method of material, but can prevent migration fully, and, there are not the foul smell that causes owing to the gas that produces in the operation and the corrosion of device, can be effectively and obtain soft reliably and the also excellent leather materials of rerum naturas such as abrasion resistance and friction firmness.
In order to reach above-mentioned purpose, the present inventor furthers investigate repeatedly, found that: carry out drying comprise the mixed liquor of specific waterborne polyurethane resin, inorganic acid salt and water by impregnation in fiber base material after, migration can not take place and local the existence in waterborne polyurethane resin in drying, polyurethane resin is anchored to the inside of fiber base material equably, can access the leather material that possesses soft hand feeling and abundant rerum natura,, finish the present invention based on this opinion.
That is, leather of the present invention is as described below with the manufacture method of material.
(1) a kind of leather is with the manufacture method of material, comprises the ammonium salt of polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) mixed liquor of water by impregnation in fiber base material, carries out drying afterwards, obtains the leather material.
(2) as the manufacture method of above-mentioned (1) described leather with material, in described mixed liquor, (A) have the polyurethane resin of carboxyl and/or carboxylic acid ester groups and (B) match ratio of the ammonium salt of inorganic acid, with the mass conversion of solid state component, (A): (B)=100: 0.1～100: 50.
(3) as the manufacture method of above-mentioned (1) or (2) described leather with material, (B) inorganic acid in the ammonium salt of inorganic acid is sulfuric acid and/or phosphoric acid.
(4) as each described leather in above-mentioned (1)～(3) with the manufacture method of material, comprise the ammonium salt of polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) pH of the mixed liquor of water be 5.0～7.0.
(5) as each described leather in above-mentioned (1)～(4) with the manufacture method of material, comprise the ammonium salt of polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) heat freezing temperature of the mixed liquor of water be 30～80 ℃.
(6) as each described leather in above-mentioned (1)～(5) with the manufacture method of material, (A) polyurethane resin with carboxyl and/or carboxylic acid ester groups obtains by following method, make (a) organic diisocyanate, (b) polyalcohol and the compound reaction that (c) has carboxyl and 2 above active hydrogens, with the terminal prepolymer neutralization of the isocyanate group that obtains with carboxyl, after emulsification disperses in water by self-emulsifying, use (d) to have the polyamine compounds of amino more than 2 and/or imino group, increase chain reaction, thereby obtain having the polyurethane resin of carboxyl and/or carboxylic acid ester groups.
(7) as each described leather in above-mentioned (1)～(6) with the manufacture method of material, (A) have 0.5～4.0 quality % that adds up to of carboxyl-content in the polyurethane resin of carboxyl and/or carboxylic acid ester groups and carboxylic acid ester groups content.
In addition, leather of the present invention is obtained by each described manufacture method of the present invention in above-mentioned (1)～(7) with material.
According to the present invention, provide the manufacture method of a kind of leather with material and the leather material that obtains by this manufacture method.Although this leather also is to have considered that the leather of use aqueous polyurethane resin of carrying capacity of environment and VOC problem is with the manufacture method of material with the manufacture method of material, but can prevent migration fully, and, there are not the foul smell that causes owing to the gas that produces in the operation and the corrosion of device, can be effectively and obtain soft reliably and the also excellent leather materials of rerum naturas such as abrasion resistance and friction firmness.
The specific embodiment
Below, by preferred embodiment describing the present invention in detail.
Leather of the present invention is with the manufacture method of material, comprises the ammonium salt of polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) mixed liquor of water by impregnation in fiber base material, carries out drying afterwards, obtains the leather material.
The polyurethane resin that (A) of the present invention like this has carboxyl and/or carboxylic acid ester groups is to have carboxyl and/or the carboxylic acid ester groups polyurethane resin as hydrophilic component in the polyurethane resin skeleton.The polyurethane resin that has carboxyl and/or carboxylic acid ester groups as such (A), the preferred polyurethane resin that obtains by following method that uses with carboxyl and/or carboxylic acid ester groups, make (a) organic diisocyanate, (b) polyalcohol and the compound reaction that (c) has carboxyl and 2 above active hydrogens, with the terminal prepolymer neutralization of the isocyanate group that obtains with carboxyl, after emulsification disperses in water by self-emulsifying, use (d) to have the polyamine compounds of amino more than 2 and/or imino group, increase chain reaction, thereby obtain having the polyurethane resin of carboxyl and/or carboxylic acid ester groups.
(a) organic diisocyanate as such is not particularly limited, and can use aliphatic diisocyanate, ester ring type vulcabond and aromatic diisocyanate with 2 isocyanate group.As such (a) organic diisocyanate, for example, can enumerate hexamethylene diisocyanate, aliphatic diisocyanate compounds such as trimethyl hexamethylene diisocyanate, isophorone diisocyanate, hydrogenation of benzene dimethyl vulcabond, dicyclohexyl methyl hydride diisocyanate, norbornene alkyl diisocyanate, 1, ester ring type diisocyanate cpds such as 3-two (isocyanato-methyl) cyclohexane, the benzal vulcabond, methyl diphenylene diisocyanate, naphthalene diisocyanate, the tolidine vulcabond, the xyxylene vulcabond, aromatic diisocyanate compounds such as durol dimethyl vulcabond etc.These diisocyanate cpds can be used singly or in combination of two or more thereof.In such (a) organic diisocyanate, aliphatic diisocyanate compound and ester ring type diisocyanate cpd can be given leather and use material with no flavescence, thereby be fit to use, be particularly suitable for using hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, norbornene alkyl diisocyanate and 1,3-two (isocyanato-methyl) cyclohexane.
In addition, as (b) polyalcohol,, be not particularly limited as long as have hydroxyl more than 2, except can using polyester polyol, polycarbonate polyol, polyether polyol etc., can also use polyether ester type polyalcohol with ehter bond and ester bond.
As such polyester polyol, for example, can enumerate polyethylene adipate, poly-adipic acid butylidene ester, poly-adipic acid ethylidene butylidene ester, poly-adipic acid hexa-methylene isophthalic acid ester ester, poly-succinic ethylidene ester, polytetramethylene succinate, poly-decanedioic acid ethylidene ester, polytetramethylene sebacate, poly--the 6-caprolactone glycol, poly-adipic acid (3-methyl isophthalic acid, the 5-pentylidene) ester, 1, the condensation polymer of 6-hexylene glycol and dimeric dibasic acid, 1, the co-condensation polymer of 6-hexylene glycol and adipic acid and dimeric dibasic acid, the condensation polymer of nonanediol and dimeric dibasic acid, the co-condensation polymer of ethylene glycol and adipic acid and dimeric dibasic acid etc.
In addition, as above-mentioned polycarbonate polyol, for example, can enumerate polymerized thylene carbonate butyl ester type glycol, polyhexamethylene carbonate type glycol, poly-carbonic acid-1,4-cyclohexanedimethyleterephthalate ester type glycol, poly-carbonic acid-1,6-hexylene glycol ester type polyalcohol etc.
In addition, as above-mentioned polyether polyol, for example, can enumerate homopolymers, block copolymer, the random copolymer of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, the random copolymer of ethylene oxide and propylene oxide and ethylene oxide and butylene oxide or block copolymer etc.
In addition, such (b) polyalcohol can use a kind or make up more than 2 kinds and use separately.And the mean molecule quantity as such (b) polyalcohol is preferably 500～5000, more preferably 1000～3000.In addition, from giving leather with the viewpoint of material,, preferably use polycarbonate polyol or polyether polyol as above-mentioned (b) polyalcohol by the polyurethane resin that obtains with carboxyl and/or carboxylic acid ester groups with sufficient durability.
In addition, as the compound that (c) has carboxyl and 2 above active hydrogens, for example, can enumerate 2,2-dihydromethyl propionic acid, 2,2-dimethylolpropionic acid etc.And,, also can use reactions such as dihydroxylic alcohols with carboxyl and aromatic dicarboxylic acid, aliphatic dicarboxylic acid and the polyester polyol that obtains with pendant type carboxyl as such compound with carboxyl and 2 above active hydrogens.In addition, also can mix the dihydroxylic alcohols that does not have carboxyl replaces above-mentioned dihydroxylic alcohols with carboxyl to react as diol component.In addition, such compound with carboxyl and 2 above active hydrogens can be used singly or in combination of two or more thereof.
In addition, when making isocyanate group end prepolymer with carboxyl in that (a) organic diisocyanate, (b) polyalcohol and the compound that (c) has carboxyl and 2 above active hydrogens are reacted, as required, can use low-molecular-weight chain extender with 2 above reactive hydrogen atoms.
As such low-molecular-weight chain extender with 2 above reactive hydrogen atoms, preferred molecular weight is below 400, to be preferably below 300 especially.In addition, as such low-molecular-weight chain extender, for example, can enumerate ethylene glycol, propylene glycol, season pentanediol, 1,4-butanediol, 1, low molecular weight polyols such as 6-hexylene glycol, trimethylolpropane, pentaerythrite, D-sorbite, low-molecular-weight polyamines such as ethylenediamine, propane diamine, hexamethylene diamine, diaminourea cyclohexyl-methane, piperazine, 2-methyl piperazine, isophorone diamine, diethylenetriamines, trien etc.And such low-molecular-weight chain extender with 2 above reactive hydrogen atoms can be used singly or in combination of two or more thereof.
In the present invention, have the concrete grammar of the terminal prepolymer of isocyanate group of carboxyl, be not particularly limited as manufacturing, for example, can be by the so-called single-step method of existing known one-part form, the manufacturings such as isocyanates polyaddition reaction method of multisection type.The reaction temperature of this moment is preferably 40～150 ℃.In addition, when carrying out such reaction, as required, can add catalysts such as dibutyl tin laurate, stannous octoate, 2 ethyl hexanoic acid dibutyl tin, triethylamine, triethylenediamine, N-methylmorpholine.In addition, in reaction or after reaction finishes, can add not organic solvent with the isocyanates radical reaction.As such organic solvent, for example, can use acetone, MEK, toluene, oxolane, diox, dimethyl formamide, N-Methyl pyrrolidone etc.
In addition, in the present invention, have the neutralization of the terminal prepolymer of isocyanate group of carboxyl, can before or after modulation has the terminal prepolymer of isocyanate group of carboxyl, use suitable known method to carry out.The employed compound of neutralization of the terminal prepolymer of the isocyanate group with carboxyl like this is not particularly limited, for example, can enumerate trimethylamine, triethylamine, Tri-n-Propylamine, tri-n-butylamine, N-methyl-diethanol amine, N, N-dimethyl monoethanolamine, N, amines such as N-diethyl monoethanolamine, triethanolamine, potassium hydroxide, NaOH, ammonia etc.In these above-claimed cpds, tertiary amines such as preferred especially trimethylamine, triethylamine, Tri-n-Propylamine, tri-n-butylamine.
In addition, in the present invention, the emulsification machine that the corrective of the terminal prepolymer of the isocyanate group with carboxyl is used when emulsification disperses in water is not particularly limited, and for example, can enumerate homogeneous blender, homogenizer, dispersion machine etc.In addition, when making the corrective of the terminal prepolymer of the isocyanate group with carboxyl emulsification disperseing in water, do not use emulsifying agent especially, temperature range in room temperature～40 ℃, corrective emulsification in water of the terminal prepolymer of isocyanate group with carboxyl is disperseed, preferably suppress the reaction of isocyanate group and water as far as possible.And, when carrying out the emulsification dispersion like this, as required, can add reaction suppressors such as phosphoric acid, sodium dihydrogen phosphate, sodium hydrogen phosphate, p-methyl benzenesulfonic acid, adipic acid, chlorobenzoyl chloride.
And, in the present invention, after emulsification disperses in water at the corrective that makes the terminal prepolymer of isocyanate group with carboxyl, use (d) to have the polyamine compounds of amino more than 2 and/or imino group, increase chain reaction, thereby (A) that obtain purpose has the emulsified dispersed liquid of the polyurethane resin of carboxyl and/or carboxylic acid ester groups.
The polyamine compounds that has amino more than 2 and/or imino group as such (d), for example, can enumerate diamines such as ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diaminourea cyclohexyl-methane, piperazine, hydrazine, 2-methyl piperazine, isophorone diamine, norbornane diamines, diaminodiphenyl-methane, toluenediamine, xyxylene diamines; Polyamines such as diethylenetriamines, trien, tetren, two propylamine, three (2-amino-ethyl) amine of imino group; Be derived from di-primary amine and monocarboxylic amino amides; Water-soluble amine derivatives such as the single ketones imines of di-primary amine; Oxalic acid two hydrazides, malonic acid two hydrazides, amber acid dihydrazide, glutaric acid two hydrazides, adipic dihydrazide, sebacic dihydrazide, Malaysia acid dihydrazide, fumaric acid two hydrazides, itaconic acid two hydrazides, 1,1 '-ethylidene hydrazine, 1,1 '-trimethylene hydrazine, 1, hydrazine derivates such as 1 '-(1, the 4-butylidene) two hydrazines.The polyamine compounds that these have amino more than 2 and/or imino group can be used singly or in combination of two or more thereof.
In addition, in the present invention, have carboxyl the terminal prepolymer of isocyanate group corrective increase chain reaction, can disperse to add in the thing polyamine compounds that (d) have amino more than 2 and/or imino group by emulsification and carry out at the corrective of the above-mentioned terminal prepolymer of isocyanate group with carboxyl.In addition, the emulsification of corrective that also can be by adding the above-mentioned terminal prepolymer of isocyanate group with carboxyl in the polyamine compounds that has amino more than 2 and/or imino group at (d) disperses thing to carry out.Increase chain reaction and preferably carry out for 20～40 ℃, finished with 30～120 minutes usually with reaction temperature.When manufacturing has the terminal prepolymer of the isocyanate group of carboxyl under with an organic solvent the situation, for example, after increasing chain reaction and finishing, preferably remove organic solvent by decompression distillation etc.
In the present invention, have the value of 100% modulus (100%modulus) of the polyurethane resin of carboxyl and/or carboxylic acid ester groups as (A), be preferably 0.5～20MPa, 2～6MPa more preferably.The value of 100% modulus is prescribed a time limit down less than above-mentioned, though can access the leather of soft feel material, has the tendency of abrasion resistance variation; On the other hand, if greater than the above-mentioned upper limit, the tendency that then exists the leather obtain to descend with the Boardy Feeling of material, with the tack of fiber.Here, the value of 100% modulus be according to JIS K6251 (2004), use that No. 3 shape test films of dumbbell shaped are measured, distance between bench marks is from the value of definite elongation tensile stress (MPa) of elongation 100% o'clock (when elongation is 2 times).
In addition, in the present invention, have the carboxyl-content in the polyurethane resin of carboxyl and/or carboxylic acid ester groups and the total of carboxylic acid ester groups content as (A), be preferably 0.5～4.0 quality %, 1.0～2.0 quality % more preferably.The aggregate value of carboxyl-content and carboxylic acid ester groups content less than above-mentioned down in limited time, exist (A) that obtain to have the tendency of storage stability variation of the polyurethane resin of carboxyl and/or carboxylic acid ester groups; On the other hand, if greater than the above-mentioned upper limit, the heat freezing temperature that produces when mixing with the ammonium salt of (B) inorganic acid increases, and has the tendency that prevents the deleterious of moving when making leather with material.
As the inorganic acid in (B) of the present invention inorganic acid ammonium salt, can enumerate perchloric acid, carbonic acid, sulfuric acid, persulfuric acid, sulfurous acid, phosphoric acid, nitric acid etc.In such inorganic acid, from viewpoint, preferably sulfuric acid and/or the phosphoric acid of the effect excellence that prevents to move.As the ammonium salt of concrete (B) inorganic acid, for example, can enumerate ammonium persulfate, ammonium perchlorate, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium sulfite, ammonium bisulfite, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium persulfate, ammonium nitrate etc.In such (B) inorganic acid ammonium salt, remove by washing easily from the security handled, volatilization problem the drying and dry back and at leather with the residual few viewpoint in the material, preferred use is selected from least a kind in ammonium sulfate, diammonium hydrogen phosphate and the ammonium dihydrogen phosphate (ADP).In addition, diammonium hydrogen phosphate can use separately, but preferably phosphoric acid ammonium dihydrogen and diammonium hydrogen phosphate are also with using.
Use in the manufacture method of material at leather of the present invention, when in (A) has the emulsified dispersed liquid of polyurethane resin of carboxyl and/or carboxylic acid ester groups, mixing the ammonium salt of (B) inorganic acid, the ammonium salt of (B) inorganic acid can be blended in the emulsified dispersed liquid of polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups with solid (powder) state, but, preferably mix the ammonium salt of (B) inorganic acid with the state of the aqueous solution from keeping (A) to have the viewpoint of stability of emulsified dispersed liquid of the polyurethane resin of carboxyl and/or carboxylic acid ester groups.
In the aqueous solution of such (B) inorganic acid ammonium salt, the concentration of inorganic acid ammonium salt is preferably 1～50 quality %, 10～30 quality % more preferably.The concentration of the ammonium salt of (B) inorganic acid in the above-mentioned aqueous solution is during less than the aqueous solution of above-mentioned lower limit, animal migration when preventing drying in order to bring into play, when in (A) has the emulsified dispersed liquid of polyurethane resin of carboxyl and/or carboxylic acid ester groups, mixing, need to add a large amount of above-mentioned aqueous solution, follow in this, (A) in the mixed liquor has the lowering of concentration of the polyurethane resin of carboxyl and/or carboxylic acid ester groups.Therefore, for the polyurethane resin with carboxyl and/or carboxylic acid ester groups that makes requirement anchors in the fiber base material, must be in fiber base material a large amount of mixed liquor of impregnation, the amount of moisture that volatilizees in the drying increases, so, exist prolong drying time, the tendency of economy variation.On the other hand, the concentration of (B) inorganic acid ammonium salt in the above-mentioned aqueous solution goes up in limited time greater than above-mentioned, has when emulsified dispersed liquid that (A) has a polyurethane resin of carboxyl and/or carboxylic acid ester groups mixes generation precipitate etc., damages the tendency of the stability of emulsified dispersed liquid.
In addition, (C) of the present invention water has the polyurethane resin of carboxyl and/or carboxylic acid ester groups and (B) has effect as solvent during the ammonium salt of inorganic acid mixing (A), is fit to use ion exchange water or distilled water.
In the present invention, preparation comprise the ammonium salt of polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) method of the mixed liquor of water be not particularly limited, can suitably use known method.
In addition, in above-mentioned mixed liquor, have the polyurethane resin of carboxyl and/or carboxylic acid ester groups and (B) match ratio of the ammonium salt of inorganic acid as (A), with the mass conversion of solid state component, preferred (A): (B)=100: 0.1～100: 50, more preferably 100: 1～100: 40.Above-mentioned match ratio was greater than 100: 0.1 o'clock, and promptly there was the tendency that prevents the migration effect variation in the drying process in the match ratio of inorganic acid ammonium salt less than 0.1 o'clock; Less than 100: 50 o'clock, promptly the match ratio of inorganic acid ammonium salt was greater than 50 o'clock in match ratio, had the tendency of mixed liquor gelation under the temperature atmosphere in summer.Wherein, the solid state component among the present invention refers under the condition of 105 ℃ of temperature, with the residual component of sample heating after 3 hours.
The heat freezing temperature of above-mentioned mixed liquor is preferably 30～80 ℃, more preferably 40～70 ℃.The heat freezing temperature here is meant, adds the above-mentioned mixed liquor of 50g in 100mL glass system beaker, and the content limit is stirred with the slowly heating in 95 ℃ hot bath of this beaker in the limit, the content temperature when solidifying that loses flowability.Heat freezing temperature be lower than above-mentioned down in limited time, have the tendency of mixed liquor gelation under the temperature atmosphere in summer.Be higher than above-mentioned in limited time, thermocoagulation can not show observantly, so there is the tendency that prevents the animal migration variation in the drying process.
In addition, have the content of the polyurethane resin of carboxyl and/or carboxylic acid ester groups,, be preferably 5～40 quality %, 10～30 quality % more preferably with the mass conversion of solid state component as (A) in the above-mentioned mixed liquor.Content with polyurethane resin of carboxyl and/or carboxylic acid ester groups is prescribed a time limit down less than above-mentioned, in order to make the polyurethane resin set of necessary amount, need be in fiber base material a large amount of above-mentioned mixed liquor of impregnation, so, dry and amount of moisture volatilization increases, exist prolong drying time, the tendency of economy variation.On the other hand, the content with polyurethane resin of carboxyl and/or carboxylic acid ester groups is gone up in limited time greater than above-mentioned, has the tendency of the bad stability of above-mentioned mixed liquor.
The mixed liquor of the polyurethane resin with carboxyl and/or carboxylic acid ester groups that comprises of the prior art is when showing acid, emulsion stability descends, so, be difficult to use in the manufacturing of leather with material, even but the pH value of mixed liquor of the present invention is in an acid side (preferred 5.0～7.0, more preferably 5.5～6.8, preferred especially 6.0～6.5), emulsification with polyurethane resin of carboxyl and/or carboxylic acid ester groups is also stablized, and can be used in the manufacturing of leather with material.
And, as fiber base material of the present invention, be not particularly limited, be fit to use fabric, compile thing or nonwoven fabric etc.As the raw material of such fiber base material, in order to obtain feel and the quality near natural leather, the fiber base material of polyamide fiber, polyester fiber has been used in suitable utilization.
In addition, in the above-mentioned nonwoven fabric that uses as above-mentioned fiber base material, the leather that obtains from raising is with the viewpoint of the feel of material, and the rugosity of the line of nonwoven fabric is preferably below the 2.0dtex.Will there be the tendency that feel become thick and stiff, quality suffer damage of leather with material in the rugosity of the line of nonwoven fabric during greater than 2.0dtex.
In addition, the density as such nonwoven fabric is preferably 0.2～0.7g/cm 3, 0.30～0.55g/cm more preferably 3The density of nonwoven fabric is prescribed a time limit down less than above-mentioned, will there be the leather that the obtains tendency of the abrasion resistance variation of material, in addition, if make a large amount of polyurethane resin sets, then there is the leather obtain the tendency that feel becomes thick and stiff, quality suffers damage with material in order to remedy this problem.On the other hand, the density of nonwoven fabric goes up in limited time greater than above-mentioned, has the leather that the obtains tendency that feel becomes thick and stiff, quality suffers damage with material.
Use in the manufacture method of material at leather of the present invention, in the scope of not damaging the object of the invention, in order to give flexibility (adaptability) of operation, can be at the ammonium salt that comprises polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) add various additives in the mixed liquor of water.As such additive, for example, can enumerate the various penetrants of lower alcohol, glycolic solvents, alcohols non-ionic surface active agent, acetylenediol class special surface activating agent, silicone based surfactant, fluorine class surfactant etc.; Various stabilization agents such as antioxidant, fast light stabilizing agent, ultraviolet screener; Mineral oils, silicone based etc. various defoamers; Colouring agents such as polyurethane-reinforcement catalyst, plasticizer, pigment, up time prolong agent etc.Such additive can be used singly or in combination of two or more thereof.
In addition, in such additive, especially preferably add penetrant.This is because by using penetrant, can make the above-mentioned mixed liquor of the rapid impregnation of above-mentioned fiber base material, and can access and make polyurethane resin evenly anchor at effect in the above-mentioned fiber base material.As such penetrant, so long as normally used material is not particularly limited, but especially preferably use lower alcohol, glycolic solvents, alcohols non-ionic surface active agent etc.
In addition, use in the manufacture method of material at leather of the present invention, in the scope of not damaging the object of the invention, in order to give flexibility (adaptability) of operation, can be at the ammonium salt that comprises polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) add crosslinking agent with carboxyl reaction in the mixed liquor of water.As such crosslinking agent, for example, can Lie Ju oxazoline class crosslinking agent, epoxies crosslinking agent, isocyanates crosslinking agent, Carbodiimides crosslinking agent, aziridines crosslinking agent, blocked isocyanate class crosslinking agent, aqueous dispersion isocyanates crosslinking agent, melamine class crosslinking agent etc.These crosslinking agents can be used singly or in combination of two or more thereof.
Use in the manufacture method of material at leather of the present invention, the ammonium salt that will comprise polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) mixed liquor of water contain be immersed in fabric, compile in the fiber base materials such as thing, nonwoven fabric after, carry out drying.
Method as the above-mentioned mixed liquor of impregnation in above-mentioned fiber base material, be not particularly limited, for example, the preferred existing known method such as the impregnation processing be made up of the dip-nip mode, spraying processing that adopt also can suitably be selected the concentration of above-mentioned mixed liquor and treatment conditions etc.In addition, also can be at fabric, compile impregnation in the fiber base materials such as thing, nonwoven fabric and comprise the ammonium salt of polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) before the mixed liquor of water, fiber base material is carried out pre-treatment.In such pretreatment procedure, in order to regulate the bonding force of fiber base material and polyurethane resin composition, the preferred macromolecule aqueous solution that is made of polyvinyl alcohol, carboxymethyl cellulose etc., silicone based dryingagent, the fluorine class dryingagents etc. of using are handled fiber base material.
In addition, with in the manufacture method of material,, be not particularly limited, for example, can use the dry type drying of utilizing hot blast as after the above-mentioned mixed liquor of the inner impregnation of fiber base material, carrying out dry method at leather of the present invention; Use the high velocity vapor generator (Ha イ テ Application パ Le チ ヤ one ス チ one マ one, H.T.S.), the wet type drying of high pressure steam generator (H.P.S.); Microwave irradiation formula dryings etc., from the aspect of continuous processability, suitable use utilizes the dry type drying of hot blast.These drying meanss can be used singly or in combination of two or more thereof.And, state the dry type of utilizing hot blast in the use when dry, preferably its treatment temperature is that 60～190 ℃, processing time are 1～20 minute, special preferred process temperature is that 100～170 ℃, processing time are 2～5 minutes.By such drying, can be at the inner set polyurethane resin of fiber base material.
Operation like this, impregnation comprises the ammonium salt of polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) carries out drying after the mixed liquor of water in fiber base material, can access leather material of the present invention.
Use in the material at such leather of the present invention, as the set solid state component amount of leather with the polyurethane resin in the material etc., be not particularly limited, with in the material, preferably the composition that has a polyurethane resin of carboxyl and/or carboxylic acid ester groups from (A) is 10～90 quality %, is about 0.5～7.0 quality % from the composition of the ammonium salt of (B) inorganic acid at leather.
In addition, leather of the present invention can dye with material.Such colouring method is not particularly limited, and can adopt any means of first impregnation poststaining method that dyes behind the set polyurethane resin in fiber base material and the first colouring method of back impregnation that makes the polyurethane resin set after fiber base material is dyeed.
And leather material of the present invention can form epidermal area, make the leather material of the grain that has leather.As the method that forms such epidermal area, it can be existing known any means, be not particularly limited, for example, can be set forth in coating epidermal area material on the processing release paper, thereby make water evaporates form epidermal area, coating adhesive thereon again, directly fit transpiring moisture, the processing release paper transfer printing of perhaps after water evaporates, fitting with material with leather of the present invention; Coating epidermal area material on processing release paper, thus make water evaporates form epidermal area, utilize heat with epidermal area and leather of the present invention thermal transfer with the material applying; Leather of the present invention with material on directly the ejection epidermal area with the gunite of material; Utilize heliogravure coating machine, knife type coater, unfilled corner wheel coating machine (comma coater), pneumatic knife type coater etc. leather of the present invention with material on the coating epidermal area with the direct rubbing method of material etc.In the method for such formation epidermal area, the viewpoint of the rerum natura face of the epidermal area that obtains from further raising, most preferably processing release paper transfer printing.The epidermal area that in such processing release paper transfer printing, uses material and adhesive, as long as can fit with material with leather of the present invention, but from feel aspect and rerum natura aspect, the optimization polyurethane resin, in addition, from the aspect of VOC free and carrying capacity of environment, the material of preferred water-based or solvent-free class.
In addition, as the purposes of leather of the present invention, can be used for fields such as vehicle, furniture, clothing, footwear, bag, bag, sandals (sandale), groceries, grinding with material.
Embodiment
Below, further specifically describe the present invention based on embodiment and comparative example, but the present invention is not limited by following embodiment.
Wherein, the leather that is obtained by each embodiment and each comparative example uses material by following method evaluation.
(1) prevents animal migration
For the leather material that obtains by each embodiment and each comparative example, use scanning electron microscope [Scanning Electron Microscope S-2400 (HITACHI)], observe the cross section of leather with 60 times multiplying powers with material, relatively the set state of the set state of the polyurethane resin that exists at the nonwoven fabric central portion and the polyurethane resin that exists in nonwoven surface portion is estimated according to following benchmark.
5 grades: with in the material section, do not have difference fully at leather, do not move at central portion and surface element resin fixed amount.
4 grades: with in the material section, almost do not have difference at leather, do not move at central portion and surface element resin fixed amount.
3 grades: with in the material section, variant slightly at central portion and surface element resin fixed amount, 10% part of shared central portion can not be confirmed the resin set in full depth at leather.
2 grades: with in the material section, at central portion and surface element resin fixed amount sizable difference is arranged at leather, 30% part of shared central portion can not be confirmed the resin set in full depth.
1 grade: with in the material section, there were significant differences in central portion and surface element resin fixed amount at leather, and 50% part of shared middle body can not be confirmed the resin set in full depth.
(2) abrasion test
For the leather material that obtains by each embodiment and each comparative example, coning according to JIS L1096 (1999), utilize taper abrasion testing machine [the smart mechanism work in peace field is produced], use the soft CS-10 of wheel, apply loading 500g, wear and tear after 1000 times and 3000 times, the leather of this moment is expressed as the abrasion amount with the reduction of the weight of material.Wherein, the abrasion amount is few more, and leather is excellent more with the abrasion resistance of material.
(3) friction firmness
For by each embodiment and the leather material that each comparative example obtains, according to JIS L0849 (2004),, rub 100 times by learning vibration shape frictional testing machine [the smart mechanism work of Daiei chemistry is produced], applying loading 200g, measure the wet friction firmness.In the mensuration of above-mentioned friction firmness, use and pollute the dustiness that compares the cotton canequim with the progressive series of greys, estimate according to following benchmark.
5 grades: can not confirm to pollute.
4 grades: confirm to have slightly pollution.
3 grades: clearly confirm to pollute.
2 grades: confirm to pollute remarkable a little.
1 grade: confirm significantly to pollute.
(4) noresidue is arranged
For the leather material that obtains by each embodiment and each comparative example, about the content of leather with the nonwoven fabric in the material and the composition beyond the polyurethane resin residues such as () surfactants, utilization is with the Suo Gesi profit special extractor of methyl alcohol as the extraction solvent, extracted 3 hours with 70 ℃, measure the extracted amount of this moment, with extracted amount is that goods more than the 1.0 quality % have been evaluated as residue, and extracted amount is evaluated as noresidue less than the goods of 1.0 quality %.
(5) feel
By sense of touch,, estimate the feel of the leather usefulness material that obtains by each embodiment and each comparative example with 5 stages of 5 grades (softnesses) to 1 grade (thick and stiff) according to following benchmark.
5 grades: soft and be rich in the feel of rebound elasticity.
4 grades: soft and be imbued with the feel of rebound elasticity.
3 grades: soft but lack the feel of rebound elasticity slightly.
2 grades: thick and stiff slightly and be similar to the feel of paper (paper is such).
1 grade: thick and stiff and be similar to the feel of paper (paper is such).
Foul smell when (6) dry
In each embodiment and each comparative example, the foul smell of ammonia when sensory evaluation utilizes air drier to carry out drying and acid.
A: no foul smell.
B: foul smell is arranged slightly.
C: towards the such strong foul smell of nose
[synthesis example and comparison synthesis example]
Below, the comparison synthesis example of the waterborne polyurethane resin that uses in the synthesis example of the polyurethane resin that uses among expression the present invention and the comparative example with carboxyl and carboxylic acid ester groups.
(synthesis example 1)
Having mixer, reflux condensing tube, add the poly-carbonic acid-1 of 157.0g in the four-hole boiling flask of thermometer and nitrogen ingress pipe, 6-hexylene glycol ester type polyalcohol (mean molecule quantity 2000), 7.5g season pentanediol, 1.3g trimethylolpropane, 9.5g 2, the 2-dihydromethyl propionic acid, 0.001g dibutyl tin laurate and 105g MEK, after evenly mixing, add the 69.7g isophorone diisocyanate, with 80 ℃ of reactions 300 minutes, the content that obtains with respect to the free isocyanate groups of nonvolatile component was 1.9 quality %'s, methyl ethyl ketone solution with terminal prepolymer of isocyanate group of carboxyl.
After being cooled to above-mentioned solution below 50 ℃, add the 6.8g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after will neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 421.9g water, and the corrective emulsification of the terminal prepolymer of isocyanate group with carboxyl is disperseed, and obtains dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution that adds water hydrazine and 1.1g diethylenetriamines of the 60 quality % that are dissolved with 5.2g in the 20g water, 35 ℃ carry out increasing chain reaction in 60 minutes after, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin of nonvolatile component 35.0 quality %, viscosity 120mPas (BM viscosimeter, No. 2 rotors, 60rpm), pH value 7.8, average grain diameter 90nm with carboxyl and carboxylic acid ester groups.
This has carboxyl-content in the polyurethane resin of carboxyl and carboxylic acid ester groups and the aggregate value of carboxylic acid ester groups content is 1.3 quality %, and 100% modulus value is 2MPa.And this has the water dispersion of the polyurethane resin of carboxyl and carboxylic acid ester groups, even 90 ℃ of also not gelations of heating, is not have heat coagulable water dispersion.
(synthesis example 2)
Having mixer, reflux condensing tube, add the poly-carbonic acid-1 of 178.0g in the four-hole boiling flask of thermometer and nitrogen ingress pipe, 6-hexylene glycol ester type polyalcohol (mean molecule quantity 2000), 0.9g trimethylolpropane, 9.3g 2, the 2-dihydromethyl propionic acid, 0.001g dibutyl tin laurate and 105g MEK, after evenly mixing, add the 56.9g dicyclohexyl methyl hydride diisocyanate, with 80 ℃ of reactions 420 minutes, the content that obtains with respect to the free isocyanate groups of nonvolatile component was 1.2 quality %'s, methyl ethyl ketone solution with terminal prepolymer of isocyanate group of carboxyl.
After being cooled to above-mentioned solution below 50 ℃, add the 6.7g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after will neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 424.4g water, and the corrective emulsification of the terminal prepolymer of isocyanate group with carboxyl is disperseed, and obtains dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution that adds water hydrazine and 0.7g diethylenetriamines of the 60 quality % that are dissolved with 3.3g in the 20g water, 35 ℃ carry out increasing chain reaction in 60 minutes after, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin of nonvolatile component 35.0 quality %, viscosity 70mPas (BM viscosimeter, No. 1 rotor, 60rpm), pH value 7.6, average grain diameter 120nm with carboxyl and carboxylic acid ester groups.
This has carboxyl-content in the polyurethane resin of carboxyl and carboxylic acid ester groups and the aggregate value of carboxylic acid ester groups content is 1.3 quality %, and 100% modulus value is 5MPa.And this has the water dispersion of the polyurethane resin of carboxyl and carboxylic acid ester groups, even 90 ℃ of also not gelations of heating, is not have heat coagulable water dispersion.
(synthesis example 3)
In the four-hole boiling flask that has mixer, reflux condensing tube, thermometer and nitrogen ingress pipe, add 2 of 141.9g polytetramethylene glycol (mean molecule quantity 2000), 30.8g, 2-dihydromethyl propionic acid, 0.001g dibutyl tin laurate and 105g MEK, after evenly mixing, add the 72.3g hexamethylene diisocyanate, with 80 ℃ of reactions 180 minutes, the content that obtains with respect to the free isocyanate groups of nonvolatile component was the methyl ethyl ketone solution of the terminal prepolymer of isocyanate group 3.1 quality %, that have carboxyl.
After being cooled to above-mentioned solution below 50 ℃, add the 22.1g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after will neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 402.6g water, and the corrective emulsification of the terminal prepolymer of isocyanate group with carboxyl is disperseed, and obtains dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution that adds water hydrazine and 1.8g diethylenetriamines of the 60 quality % that are dissolved with 8.6g in the 20g water, 35 ℃ carry out increasing chain reaction in 60 minutes after, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin of nonvolatile component 35.0 quality %, viscosity 50mPas (BM viscosimeter, No. 1 rotor, 60rpm), pH value 7.9, average grain diameter 150nm with carboxyl and carboxylic acid ester groups.
This has carboxyl-content in the polyurethane resin of carboxyl and carboxylic acid ester groups and the aggregate value of carboxylic acid ester groups content is 4.2 quality %, and 100% modulus value is 8MPa.And this has the water dispersion of the polyurethane resin of carboxyl and carboxylic acid ester groups, even 90 ℃ of also not gelations of heating, is not have heat coagulable water dispersion.
(synthesis example 4)
Having mixer, reflux condensing tube, add the poly-carbonic acid-1 of 157.0g in the four-hole boiling flask of thermometer and nitrogen ingress pipe, 6-hexylene glycol ester type polyalcohol (mean molecule quantity 2000), 7.5g season pentanediol, 1.3g trimethylolpropane, 9.5g 2, the 2-dihydromethyl propionic acid, 0.001g dibutyl tin laurate and 105g MEK, after evenly mixing, add the 69.7g isophorone diisocyanate, with 80 ℃ of reactions 300 minutes, the content that obtains with respect to the free isocyanate groups of nonvolatile component was 1.9 quality %'s, methyl ethyl ketone solution with terminal prepolymer of isocyanate group of carboxyl.
After being cooled to above-mentioned solution below 50 ℃, add the 8.6g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after will neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 420.1g water, and the corrective emulsification of the terminal prepolymer of isocyanate group with carboxyl is disperseed, and obtains dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution that adds water hydrazine and 1.1g diethylenetriamines of the 60 quality % that are dissolved with 5.2g in the 20g water, 35 ℃ carry out increasing chain reaction in 60 minutes after, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin of nonvolatile component 35.0 quality %, viscosity 180mPas (BM viscosimeter, No. 2 rotors, 60rpm), pH value 9.5, average grain diameter 70nm with carboxyl and carboxylic acid ester groups.
This has carboxyl-content in the polyurethane resin of carboxyl and carboxylic acid ester groups and the aggregate value of carboxylic acid ester groups content is 1.3 quality %, and 100% modulus value is 2MPa.And this has the water dispersion of the polyurethane resin of carboxyl and carboxylic acid ester groups, even 90 ℃ of also not gelations of heating, is not have heat coagulable water dispersion.
(synthesis example 5)
Having mixer, reflux condensing tube, add the poly-carbonic acid-1 of 146.1g in the four-hole boiling flask of thermometer and nitrogen ingress pipe, 6-hexylene glycol ester type polyalcohol (mean molecule quantity 2000), 2.9g 1, the 4-butanediol, 1.7g trimethylolpropane, 11.1g 2, the 2-hydroxymethyl propionic acid, 0.001g dibutyl tin laurate and 105g MEK, after evenly mixing, add the 83.2g dicyclohexyl methyl hydride diisocyanate, with 80 ℃ of reactions 240 minutes, the content that obtains with respect to the free isocyanate groups of nonvolatile component was 3.8 quality %'s, methyl ethyl ketone solution with terminal prepolymer of isocyanate group of carboxyl.
After being cooled to above-mentioned solution below 50 ℃, add the 7.9g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after will neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 403.3g water, and the corrective emulsification of the terminal prepolymer of isocyanate group with carboxyl is disperseed, and obtains dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution that adds water hydrazine and 1.3g diethylenetriamines of the 60 quality % that are dissolved with 7.7g in the 20g water, 35 ℃ carry out increasing chain reaction in 60 minutes after, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin of nonvolatile component 35.0 quality %, viscosity 40mPas (BM viscosimeter, No. 1 rotor, 60rpm), pH value 8.0, average grain diameter 40nm with carboxyl and carboxylic acid ester groups.
This has carboxyl-content in the polyurethane resin of carboxyl and carboxylic acid ester groups and the aggregate value of carboxylic acid ester groups content is 1.5 quality %, and 100% modulus value is 18MPa.And this has the water dispersion of the polyurethane resin of carboxyl and carboxylic acid ester groups, even 90 ℃ of also not gelations of heating, is not have heat coagulable water dispersion.
(synthesis example 6)
Having mixer, reflux condensing tube, add the poly-carbonic acid-1 of 134.3g in the four-hole boiling flask of thermometer and nitrogen ingress pipe, 6-hexylene glycol ester type polyalcohol (mean molecule quantity 2000), 3.5g 1, the 4-butanediol, 3.8g trimethylolpropane, 10.9g 2, the 2-dihydromethyl propionic acid, 0.001g dibutyl tin laurate and 105g MEK, after evenly mixing, add the 92.6g dicyclohexyl methyl hydride diisocyanate, with 80 ℃ of reactions 210 minutes, the content that obtains with respect to the free isocyanate groups of nonvolatile component was 4.2 quality %'s, methyl ethyl ketone solution with terminal prepolymer of isocyanate group of carboxyl.
After being cooled to above-mentioned solution below 50 ℃, add the 7.8g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after will neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 405.0g water, and the corrective emulsification of the terminal prepolymer of isocyanate group with carboxyl is disperseed, and obtains dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution that adds water hydrazine and 2.0g diethylenetriamines of the 60 quality % that are dissolved with 6.9g in the 20g water, 35 ℃ carry out increasing chain reaction in 60 minutes after, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin of nonvolatile component 35.0 quality %, viscosity 230mPas (BM viscosimeter, No. 2 rotors, 60rpm), pH value 8.7, average grain diameter 90nm with carboxyl and carboxylic acid ester groups.
This has carboxyl-content in the polyurethane resin of carboxyl and carboxylic acid ester groups and the aggregate value of carboxylic acid ester groups content is 1.5 quality %, and 100% modulus value is 23MPa.And this has the water dispersion of the polyurethane resin of carboxyl and carboxylic acid ester groups, even 90 ℃ of also not gelations of heating, is not have heat coagulable water dispersion.
(relatively synthesis example 1)
Having mixer, reflux condensing tube, the polytetramethylene glycol (mean molecule quantity 1000) that adds 76.1g in the four-hole boiling flask of thermometer and nitrogen ingress pipe, 16.9g polyoxyethylene polypropylene glycol random copolymer glycol (mean molecule quantity 1000, oxyethylene group content 70 quality %), 1.5g 1, the 4-butanediol, 1.9g trimethylolpropane, 0.001g dibutyl tin laurate and 60g MEK, after evenly mixing, add the 40.4g dicyclohexyl methyl hydride diisocyanate, with 80 ℃ of reactions 300 minutes, the content that obtains with respect to the free isocyanate groups of nonvolatile component was the methyl ethyl ketone solution of the terminal prepolymer of isocyanate group of 2.1 quality %.
After being cooled to above-mentioned solution below 30 ℃, add 0.1g phosphoric acid ester in the last of the ten Heavenly stems and 6.0g polyoxyethylene triphenylethylene base phenyl ether (HLB=15), after evenly mixing, use distribution blade slowly to add 254.0g water, carry out Phase inversion emulsification, dispersion, obtain dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution that is dissolved with 2.0g piperazine hexahydrate and 0.8g diethylenetriamines in the 11.3g water, 35 ℃ carry out increasing chain reaction in 90 minutes after, under reduced pressure, carry out desolventizing with 35 ℃, obtain the water dispersion of the stabilized aqueous polyurethane resin of nonvolatile component 35.0 quality %, viscosity 50mPas (BM viscosimeter, No. 1 rotor, 60rpm), pH value 8.0, average grain diameter 550nm.
The aggregate value of carboxyl-content in this waterborne polyurethane resin and carboxylic acid ester groups content is 0.0 quality %, and 100% modulus value is 2MPa.And gelation takes place at 45 ℃ in the water dispersion of this waterborne polyurethane resin, is to have heat coagulable water dispersion.
Below, the proterties that in table 1, gather and represent synthesis example 1～6, compares synthesis example 1.
[table 1]
Synthesis example 1 Synthesis example 2 Synthesis example 3 Synthesis example 4 Synthesis example 5 Synthesis example 6 Compare synthesis example 1
Nonvolatile component (quality %) 35.0 35.0 35.0 35.0 35.0 35.0 35.0
Viscosity (mPas) 120 70 50 180 40 230 50
The pH value 7.8 7.6 7.9 9.5 8.0 8.7 8.0
Average grain diameter (nm) 90 120 150 70 40 90 550
Carboxyl-content (quality %) 1.3 1.3 4.2 1.3 1.5 1.5 0.0
100% modulus (MPa) 2 5 8 2 18 23 2
Emulsifying agent (having or not) Do not have Do not have Do not have Do not have Do not have Do not have Have
Heat freezing temperature (℃) ＞90 ＞90 ＞90 ＞90 ＞90 ＞90 45
[embodiment 1～10 and comparative example 1～6]
(embodiment 1)
Water dispersion, the 20 quality % aqueous solution of 17.5g ammonium sulfate, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, the Nicca Chemical Co., Ltd of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups that obtains in the 100g synthesis example 1 produce] the 50 quality % aqueous solution and 16.5g water, the preparation mixed liquor.The content that the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of ammonium sulfate be that 100: 10, pH value are 6.2, heat freezing temperature is 57 ℃, have a polyurethane resin of carboxyl and carboxylic acid ester groups is 25 quality %.
Use bar shaped calender (slit mangle), at the nonwoven fabric of making by polyester fiber (0.5dtex, density 0.3g/cm 3) in this mixed liquor of impregnation, make its absorption (pick up) 250 quality %, utilize air drier [TABAI SAFETYOVEN SPH-200] to carry out 3 minutes dryings, then carry out 3 minutes dryings afterwards with 150 ℃ with 100 ℃, obtain dermatine.Again the dermatine (leather material) that obtains is dyeed with following condition, and carry out RC and soap, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
＜dyeing condition 〉
Dyeing machine: MINI-COLOR dyeing machine [Co., Ltd.'s texam skill is ground]
Dyestuff:
Kayalon Microester Blue DX-LS conc[Nippon Kayaku K. K] 0.10%o.w.f.
Kayalon Microester Yellow DX-LS[Nippon Kayaku K. K] 2.00%o.w.f.
Kayalon Microester Red DX-LS[Nippon Kayaku K. K] 0.80%o.w.f.
Dyeing assistant: NICCA SUNSOLT RM-340[Nicca Chemical Co., Ltd] 0.5g/L
PH regulator agent: 90 quality % acetic acid 0.3cc/L
Bath raio: (1: 20)
Dyeing condition: 130 ℃ * 60 minutes (2 ℃/minute of programming rates).
＜RC condition 〉
RC bathes: NaOH 2g/L
Sodium dithionite (hydrosulfite) 2g/L
Bath raio: (1: 20)
RC condition: 80 ℃ * 20 minutes (2 ℃/minute of programming rates).
(embodiment 2)
Water dispersion, the 30 quality % aqueous solution of 23.3g ammonium sulfate, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, the Nicca Chemical Co., Ltd of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups that obtains in the 100g synthesis example 1 produce] the 50 quality % aqueous solution and 10.7g water, the preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of ammonium sulfate be that 100: 20, pH value are 6.0, heat freezing temperature is 45 ℃, have carboxyl and a carboxylic acid ester groups is 25 quality %.
Except using such mixed liquor, handle similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
(embodiment 3)
Water dispersion, the 40 quality % aqueous solution of 30.6g ammonium sulfate, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, the Nicca Chemical Co., Ltd of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups that obtains in the 100g synthesis example 1 produce] the 50 quality % aqueous solution and 31.4g water, the preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of ammonium sulfate be that 100: 35, pH value are 5.8, heat freezing temperature is 59 ℃, have carboxyl and a carboxylic acid ester groups is 21 quality %.
The such mixed liquor of impregnation makes it absorb 300 quality %, in addition, handles similarly to Example 1, obtains dermatine dyeing processing cloth (through the leather material of dyeing processing).
(embodiment 4)
Evenly mix the water dispersion of the polyurethane resin that obtains in the 100g synthesis example 1, the 40 quality % aqueous solution and the 1.8g water of 1.8g ammonium sulfate, the preparation mixed liquor with carboxyl and carboxylic acid ester groups.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of ammonium sulfate be that 100: 2, pH value are 6.8, heat freezing temperature is 70 ℃, have carboxyl and a carboxylic acid ester groups is 34 quality %.
The such mixed liquor of impregnation makes it absorb 185 quality %, in addition, handles similarly to Example 1, obtains dermatine dyeing processing cloth (through the leather material of dyeing processing).
(embodiment 5)
Water dispersion, the 20 quality % aqueous solution of 17.5g ammonium sulfate, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, the Nicca Chemical Co., Ltd of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups that obtains in the 100g synthesis example 2 produce] the 50 quality % aqueous solution and 16.5g water, the preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of ammonium sulfate be that 100: 10, pH value are 6.3, heat freezing temperature is 55 ℃, have carboxyl and a carboxylic acid ester groups is 25 quality %.
Except using such mixed liquor, handle similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
(embodiment 6)
Water dispersion, the 20 quality % aqueous solution of 17.5g ammonium sulfate, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, the Nicca Chemical Co., Ltd of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups that obtains in the 100g synthesis example 3 produce] the 50 quality % aqueous solution and 16.5g water, the preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of ammonium sulfate be that 100: 10, pH value are 6.2, heat freezing temperature is 52 ℃, have carboxyl and a carboxylic acid ester groups is 25 quality %.
Except using such mixed liquor, handle similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
(embodiment 7)
Water dispersion, the 20 quality % aqueous solution of 17.5g ammonium sulfate, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, the Nicca Chemical Co., Ltd of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups that obtains in the 100g synthesis example 4 produce] the 50 quality % aqueous solution and 16.5g water, the preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of ammonium sulfate be that 100: 10, pH value are 6.2, heat freezing temperature is 66 ℃, have carboxyl and a carboxylic acid ester groups is 25 quality %.
Except using such mixed liquor, handle similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
(embodiment 8)
Evenly mix water dispersion, the 17.5g diammonium hydrogen phosphate/ammonium dihydrogen phosphate (ADP) (mass ratio 50/50) of the polyurethane resin that obtains in the 100g synthesis example 1 with carboxyl and carboxylic acid ester groups the 20 quality % aqueous solution, the Carbodilite E-02[Carbodiimides crosslinking agent of 1.0g, trade name, day spin Co., Ltd. clearly and produce], the TEXPORT BG[alcohols penetrant of 6.0g, trade name, Nicca Chemical Co., Ltd produce] the 50 quality % aqueous solution and 15.5g water, the preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of inorganic acid ammonium salt be that 100: 10, pH value are 6.3, heat freezing temperature is 45 ℃, have carboxyl and a carboxylic acid ester groups is 25 quality %.
Except using such mixed liquor, handle similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
(embodiment 9)
Water dispersion, the 20 quality % aqueous solution of 17.5g ammonium sulfate, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, the Nicca Chemical Co., Ltd of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups that obtains in the 100g synthesis example 5 produce] the 50 quality % aqueous solution and 16.5g water, the preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of ammonium sulfate be that 100: 10, pH value are 6.3, heat freezing temperature is 55 ℃, have carboxyl and a carboxylic acid ester groups is 25 quality %.
The such mixed liquor of impregnation makes it absorb 125 quality %, in addition, handles similarly to Example 1, obtains dermatine dyeing processing cloth (through the leather material of dyeing processing).
(embodiment 10)
Water dispersion, the 20 quality % aqueous solution of 17.5g ammonium sulfate, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, the Nicca Chemical Co., Ltd of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups that obtains in the 100g synthesis example 6 produce] the 50 quality % aqueous solution and 16.5g water, the preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of ammonium sulfate be that 100: 10, pH value are 6.2, heat freezing temperature is 50 ℃, have carboxyl and a carboxylic acid ester groups is 25 quality %.
The such mixed liquor of impregnation makes it absorb 125 quality %, in addition, handles similarly to Example 1, obtains dermatine dyeing processing cloth (through the leather material of dyeing processing).
(comparative example 1)
Water dispersion, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, the Nicca Chemical Co., Ltd of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups that obtains in the 100g synthesis example 1 produce] the 50 quality % aqueous solution and 34.0g water, the preparation mixed liquor.The polyurethane resin content that the match ratio of the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the ammonium salt of inorganic acid is that 100: 0, pH value are 7.5, heat freezing temperature is more than 90 ℃, have carboxyl and a carboxylic acid ester groups is 25 quality %.
Except using such mixed liquor, handle similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
(comparative example 2)
Water dispersion, the 10 quality % aqueous solution of 17.5g sulfuric acid, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, the Nicca Chemical Co., Ltd of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups that obtains in the 100g synthesis example 1 produce] the 50 quality % aqueous solution and 16.5g water, the preparation mixed liquor.The polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of sulfuric acid are that 100: 5, heat freezing temperature are, polyurethane resin content with carboxyl and carboxylic acid ester groups is 25 quality % below 10 ℃.
In addition, above-mentioned mixed liquor is when adding the 10 quality % aqueous solution of sulfuric acid, and moment is observed and separate out precipitate from mixed liquor, so, the manufacturing failure of dermatine dyeing processing cloth.And, the mensuration difficulty of pH.
(comparative example 3)
Evenly mix water dispersion, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, Nicca Chemical Co., Ltd's production that 100g compares the waterborne polyurethane resin that obtains in the synthesis example 1] the 50 quality % aqueous solution and 34.0g water, the preparation mixed liquor.The match ratio of the waterborne polyurethane resin in the above-mentioned mixed liquor and the ammonium salt of inorganic acid is that 100: 0, pH value are 8.0, heat freezing temperature is that 45 ℃, waterborne polyurethane resin content are 25 quality %.
Except using such mixed liquor, handle similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
(comparative example 4)
Evenly mix water dispersion, the 20 quality % aqueous solution of 17.5g ammonium sulfate, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, Nicca Chemical Co., Ltd's production that 100g compares the waterborne polyurethane resin that obtains in the synthesis example 1] the 50 quality % aqueous solution and 16.5g water, the preparation mixed liquor.The match ratio of the waterborne polyurethane resin in the above-mentioned mixed liquor and the ammonium salt of inorganic acid is that 100: 10, pH value are 6.5, heat freezing temperature is that 45 ℃, waterborne polyurethane resin content are 25 quality %.
Except using such mixed liquor, handle similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
(comparative example 5)
Evenly mix water dispersion, the 10 quality % aqueous solution of 17.5g calcium chloride, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, Nicca Chemical Co., Ltd's production that 100g compares the waterborne polyurethane resin that obtains in the synthesis example 1] the 50 quality % aqueous solution and 16.5g water, the preparation mixed liquor.The waterborne polyurethane resin in the above-mentioned mixed liquor and the match ratio of calcium chloride are that 100: 5, pH value are 8.1, heat freezing temperature is that 35 ℃, waterborne polyurethane resin content are 25 quality %.
Except using such mixed liquor, handle similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
(comparative example 6)
Water dispersion, the 10 quality % aqueous solution of 17.5g ammonium formate, the TEXPORT BG[alcohols penetrant of 6.0g, trade name, the Nicca Chemical Co., Ltd of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups that obtains in the 100g synthesis example 1 produce] the 50 quality % aqueous solution and 16.5g water, the preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in the above-mentioned mixed liquor and the match ratio of ammonium formate be that 100: 5, pH value are 7.9, heat freezing temperature is 45 ℃, have carboxyl and a carboxylic acid ester groups is 25 quality %.
Except using such mixed liquor, handle similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
The evaluation result of the dermatine dyeing processing cloth (through the leather material of dyeing processing) that in table 2, obtains among the expression embodiment 1～10, the evaluation result of the dermatine dyeing processing cloth (through the leather material of dyeing processing) that in table 3, obtains in the expression comparative example 1,3～6.
[table 2]
[table 3]
Figure BSA00000238132900271
The leather that obtains in embodiment 1～9 is used in the material, migration unconfirmed, and resin is fixed to nonwoven fabric inside equably.Owing to prevent migration in this wise, the leather material of the abrasion resistance of the demonstration excellence that can access that feel is very soft, the abrasion amount when in the wear-resistant test 1000 times and 3000 times does not change almost.When 100% modulus of the polyurethane resin with carboxyl and carboxylic acid ester groups is big (embodiment 10), the leather that obtains is with the wiriness of material, and it is poor slightly that 3000 times antifriction decreases in the test, but prevent the animal migration excellence, is enough under the situation of feel use thinking little of.In addition, the leather that obtains in embodiment 1～10 is with in the material, can confirm at leather few with residue residual in the material, as can be known because residue and also little to the influence of friction firmness.
On the other hand, at the ammonium salt that does not contain inorganic acid, only use the leather that obtains in the comparative example 1 of polyurethane resin, can confirm when drying, to take place obviously migration, wiriness with in the material with carboxyl and carboxylic acid ester groups.And, in the abrasion resistance test of the leather that in comparative example 1, obtains,, when abrasion 3000 times, can observe tangible abrasion amount though the abrasion resistance when making it abrasion 1000 times is good with material, confirm that abrasion resistance is insufficient.
In addition, in comparative example 2, use aqueous sulfuric acid to replace the ammonium salt of inorganic acid, can not make the leather material, can confirm that flexibility (adaptability) of operation is insufficient because of mixed liquor generation gelation.
In addition, the leather that obtains in the ammonium salt that does not use inorganic acid, a comparative example with heat coagulable waterborne polyurethane resin 3 that use utilizes surfactant emulsification to obtain can be confirmed to have thermocoagulation, and significantly move when drying with in the material.In addition, the leather that obtains in comparative example 3 is with the wiriness of material, in the abrasion resistance test, though the abrasion resistance when making it abrasion 1000 times is good, can observe tangible abrasion amount when abrasion 3000 times, confirms that abrasion resistance is insufficient.
And, utilize the leather that obtains in the comparative example 4 of the ammonium salt that surfactant emulsification obtains with in the material in use with heat coagulable waterborne polyurethane resin and inorganic acid, can confirm with comparative example 3 in the leather that obtains with the same result of material, for utilizing the heat coagulable waterborne polyurethane resin that has that surfactant emulsification obtains, the effect that preventing of can not obtaining being brought by the ammonium salt of inorganic acid moved etc.
In addition, use calcium chloride water replace inorganic acid ammonium salt, use in the leather usefulness material that obtains in the comparative example 5 of the mixed liquor that mixes with the waterborne polyurethane resin that utilizes surfactant emulsification to obtain, because calcium chloride water makes heat freezing temperature descend, prevent that animal migration from improving slightly, but when using material compared, prevent that animal migration is insufficient with the leather that obtains among the embodiment 1～10.In addition, the leather that obtains in the comparative example 5 is with the wiriness of material, and in the abrasion resistance test, though the abrasion resistance when making it abrasion 1000 times is good, can observe tangible abrasion amount when abrasion 3000 times, confirms that abrasion resistance is insufficient.In addition, can confirm has a surfactant in that leather is residual in material, can confirm that residue is big to the influence of friction firmness.
In addition, the leather that obtains in the comparative example 6 of the ammonium salt that uses the aqueous solution replacement inorganic acid that is made of the formic acid ammonium salt is with in the material, though the animal migration of preventing, abrasion resistance, friction firmness, residue, feel aspect excellence, but can confirm when drying the strong foul smell that produces owing to decomposition, the volatilization of ammonium formate.And the formic acid that produce this moment is the reason of corrosion of equipment, and if formic acid and ammonia emit to atmosphere, will become environmental problem.
As described above described, according to the present invention, provide the manufacture method of a kind of leather with material and the leather material that obtains by this manufacture method.Although this leather also is to have considered that the leather of use aqueous polyurethane resin of carrying capacity of environment and VOC problem is with the manufacture method of material with the manufacture method of material, but can prevent migration fully, and, there are not the foul smell that causes owing to the gas that produces in the operation and the corrosion of device, can be effectively and obtain soft reliably and the also excellent leather materials of rerum naturas such as abrasion resistance and friction firmness.
Therefore, manufacture method of the present invention is particularly useful with the industrially preparing making method of material as leather, in addition, the leather material that obtains by manufacture method of the present invention, leather is with there not being organic solvent residual in the material, can eliminate the harmful effect to human body such as skin barrier, thus can be directly used in the industrial fields such as vehicle, furniture, clothing, bag, footwear, bag, groceries, grinding, can also as epidermal area is set, stable and leather excellent quality uses with material.

Claims (8)

1. a leather is characterized in that with the manufacture method of material:
Comprise the ammonium salt of polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) mixed liquor of water by impregnation in fiber base material, carry out drying afterwards, obtain the leather material.
2. the leather as claimed in claim 1 manufacture method of material is characterized in that:
In described mixed liquor, (A) have the polyurethane resin of carboxyl and/or carboxylic acid ester groups and (B) match ratio of the ammonium salt of inorganic acid, with the mass conversion of solid state component, (A): (B)=100: 0.1～100: 50.
3. the leather as claimed in claim 1 manufacture method of material is characterized in that:
(B) inorganic acid in the ammonium salt of inorganic acid is sulfuric acid and/or phosphoric acid.
4. the leather as claimed in claim 1 manufacture method of material is characterized in that:
Comprise the ammonium salt of polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) pH of the mixed liquor of water be 5.0～7.0.
5. the leather as claimed in claim 1 manufacture method of material is characterized in that:
Comprise the ammonium salt of polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) heat freezing temperature of the mixed liquor of water be 30～80 ℃.
6. the leather as claimed in claim 1 manufacture method of material is characterized in that:
(A) polyurethane resin with carboxyl and/or carboxylic acid ester groups obtains by following method, the compound reaction that makes (a) organic diisocyanate, (b) polyalcohol and (c) have carboxyl and 2 above active hydrogens, with the terminal prepolymer neutralization of the isocyanate group that obtains with carboxyl, after emulsification disperses in water by self-emulsifying, use (d) to have the polyamine compounds of amino more than 2 and/or imino group, increase chain reaction, thereby obtain having the polyurethane resin of carboxyl and/or carboxylic acid ester groups.
7. the leather as claimed in claim 1 manufacture method of material is characterized in that:
(A) has 0.5～4.0 quality % that adds up to of carboxyl-content in the polyurethane resin of carboxyl and/or carboxylic acid ester groups and carboxylic acid ester groups content.
8. leather material that obtains by each described manufacture method in the claim 1～7.
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