CN101994263B - 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
CN101994263B
CN101994263B CN201010259032.5A CN201010259032A CN101994263B CN 101994263 B CN101994263 B CN 101994263B CN 201010259032 A CN201010259032 A CN 201010259032A CN 101994263 B CN101994263 B CN 101994263B
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carboxyl
polyurethane resin
leather
carboxylic acid
ester groups
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CN101994263A (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

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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

Manufacture method and the leather material of material for leather
Technical field
The present invention relates to leather manufacture method and the leather material of material, particularly, the present invention relates to use waterborne polyurethane resin manufacture, be suitable as manufacture method and the leather material of the leather material of dermatine or synthetic leather use.
Background technology
All the time, as the substitute of natural leather, produce dermatine that the multiple fiber base material of being made up of polyurethane resin and nonwoven fabric forms and by polyurethane resin and fabric or compile the synthetic leather that fiber base material that thing makes forms.Such dermatine, synthetic leather are for example by being called the method manufacture 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 obtaining 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, be dried.
But, because the most inflammabilities of organic solvent such as a large amount of dimethyl formamides that use in this wet type freezing method are strong, toxicity is also high, so, there is the danger of breaking out of fire, and also worry the problem of the environmental pollution of deterioration and atmosphere, the water quality etc. of operating environment.In addition, in order to solve such problem, also incorporate into the manufacture method of the operation that reclaims the organic solvent producing, but still have the problem that produces huge cost of idleness and labor intensive.In addition, in the dermatine that uses the organic solvent solution of polyurethane resin to obtain, synthetic leather, remain organic solvent in leather inside, so the problem that also exists skin barrier etc. to impact human body.Therefore, the problem that the polyurethane resin that is bonded to fiber base material is changed from type of organic solvent hydrotropism polyurethane resin is studied.
The manufacture method of the dermatine of this use waterborne polyurethane resin etc., due to not with an organic solvent, so, reclaim aspect needed cost and the enhancement of environment aspect excellence of the improvement of operating environment, atmosphere pollution, water pollution etc. can remove, but while comparison with the dermatine that uses the organic solvent solution of polyurethane resin to obtain, synthetic leather, cannot obtain having dermatine, the synthetic leather of gratifying feel and physical property.As the major reason of this problem, can be set forth in after the inner impregnation waterborne polyurethane resin of fiber base material, to utilize hot blast to carry out xeothermic when dry, along with the movement of the water from fiber base material surface evaporation, waterborne polyurethane resin moves to fiber base material surface, and so-called migration (migrate) occurs.; due to such migration occurring; in the manufacture method of dermatine etc. that uses waterborne polyurethane resin; waterborne polyurethane resin moves to the surface of fiber base material; be formed on fiber base material inside almost not set have the state of polyurethane resin, thereby obtain Boardy Feeling, lack dermatine, the synthetic leather of piloerection sense.Therefore,, in the manufacture method of dermatine etc. that uses waterborne polyurethane resin, in order to solve migration problem, carrying out various investigations.
For example, a kind of manufacture method of leather sample goods is disclosed in Japanese Patent Publication 55-51076 communique (patent documentation 1), in fiber base cloth, impregnation has been given heat coagulable synthetic resin emulsion by adding Thermogelling agent, makes this synthetic resin emulsion solidify in hot water.
But, in this method, preventing animal migration although can improve, part flows out and solidifies containing immersion liquid in bath, and this jello solidifying is attached to the surface of machining object again, has the problem of the feel variation of the leather material obtaining.And, in this method, along with polyurethane resin concentration declines, heat setting solidity reduces, cause part easily in hot water, to flow out containing immersion liquid, there is the problem of the further variation of feel of the leather material obtaining.
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 has been supplied with to nonwoven tablet, and carry out heat drying in the nonionic emulsion after forced emulsification.
But, in this method, prevent animal migration although can improve, according to the concentration of inorganic salts coordinating, there will be the problem in processing such as processing the bad stability of bathing.In addition, owing to remaining non-ionic surface active agent and inorganic salts in fiber base material, so the leather obtaining is low with wiriness, the abrasion resistance of material, friction firmness is also insufficient.
In addition, a kind of manufacture method of fiber sheet-like composite is disclosed in TOHKEMY 2000-290879 communique (patent documentation 3), in fibrous material matrix, impregnation or coating are the aqueous resin composition that the aqueous polyurethane resin of 40～90 ℃ and associative form tackifier form by heat freezing temperature, utilize water vapour to make this aqueous resin composition thermocoagulation.
But, in this method, prevent animal migration although can improve, owing to remaining non-ionic surface active agent, associative form tackifier in fibrous material matrix, so material still wiriness for the leather obtaining, abrasion resistance is low, friction firmness is also insufficient.
In addition, the manufacture method of a kind of leather flaky material is disclosed in TOHKEMY 2003-138131 communique (patent documentation 4), supply with the non-ionic surface active agent that comprises HLB10～18 and the carboxylic acid type polyurethane resin of inorganic salts to fibrous material, make its thermocoagulation.
But, in this method, also same with the method for recording in above-mentioned patent documentation 2 and 3, produce the problem that surfactant and inorganic salts bring, material still wiriness for the leather obtaining, friction firmness are also insufficient.
In addition, in the method for recording in above-mentioned patent documentation 2～4, although the residues such as non-ionic surface active agent, associative form tackifier can be by repeatedly washing or the operation such as Warm Wash and to remove to a certain degree, be difficult to remove completely, so still can not avoid above-mentioned problem.And, repeatedly wash or the operation such as Warm Wash can cause manufacturing procedure number to increase, involve economy problems.Therefore, require to reduce as far as possible washing or the operation of Warm Wash and can easily remove residue and obtain the manufacture method of the leather material with sufficient feel and physical property.
In addition, the manufacture method of a kind of leather material is disclosed in TOHKEMY 2006-36960 communique (patent documentation 5), in fiber base material, impregnation comprises polyurethane resin, the ammonium salt of carboxylic acid and the mixed liquor of water with carboxyl, is dried afterwards.
But, in this method, although can solve the problem of migration, the new problems such as the foul smell that the ammonia that has occurred producing when dry causes.In addition, during as ammonium carboxylate salt, there is causing due to the carboxylic acid that heat drying volatilizees the problem of corrosion of equipment at the ammonium salt that uses the carboxylic acid that the carbon numbers such as ammonium formate or ammonium acetate are few, need to improve manufacturing process.On the other hand, in the time using the ammonium salt of the carboxylic acid that carbon number is many, when heat drying the volatilization of carboxylic acid few, but if obtain the animal migration that prevents of object, must use in a large number.In addition, if for improve resin the durability such as heat resistance and and with polycarbodiimide compound, because it reacts with ammonium carboxylate salt, so even if use in a large number ammonium carboxylate salt, be also difficult to obtain preventing fully animal migration.
Like this, in the manufacture method of dermatine etc. that uses waterborne polyurethane resin, thereby the foul smell that not yet obtain at present fully preventing migration, set polyurethane resin and not existing causes due to the gas producing in operation equably on fiber base material and the burn into manufacture of device have the method for material for the leather of sufficient feel and quality, the countermeasure of the VOC that need to produce in operation.
Summary of the invention
The present invention completes in view of the existing problem of above-mentioned prior art, and its object is the leather material that the manufacture method of a kind of leather material is provided and is obtained by this manufacture method.Although this leather is also to have considered the manufacture method of the leather material of the use aqueous polyurethane resin of carrying capacity of environment and VOC problem by the manufacture method of material, but can prevent fully migration, and, there is not the foul smell that causes due to the gas producing in operation and the corrosion of device, can effectively and reliably obtain yet excellent leather material of the physical property such as soft and abrasion resistance and friction firmness.
In order to reach above-mentioned purpose, the present inventor conducts in-depth research repeatedly, found that: after the mixed liquor that comprises specific waterborne polyurethane resin, inorganic acid salt and water by impregnation in fiber base material, be dried, can there is not migration and local existence in waterborne polyurethane resin in dry, polyurethane resin is anchored to the inside of fiber base material equably, the leather material that can obtain possessing soft feel and abundant physical property, based on this opinion, has completed the present invention.
, leather of the present invention is as described below by the manufacture method of material.
(1) manufacture method of material for a kind of leather, the ammonium salt that comprises polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid by impregnation in fiber base material and (C) mixed liquor of water, be dried afterwards, obtain leather material.
(2) manufacture method of material for the leather as described in above-mentioned (1), in described mixed liquor, (A) there is 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) manufacture method of material for the leather as described in above-mentioned (1) or (2), (B) inorganic acid in the ammonium salt of inorganic acid is sulfuric acid and/or phosphoric acid.
(4) manufacture method of material for the leather as described in any one in above-mentioned (1)～(3), the ammonium salt that comprises polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) pH of the mixed liquor of water are 5.0～7.0.
(5) manufacture method of material for the leather as described in any one in above-mentioned (1)～(4), the ammonium salt that comprises 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 are 30～80 ℃.
(6) manufacture method of material for the leather as described in any one in above-mentioned (1)～(5), (A) polyurethane resin that has carboxyl and/or a carboxylic acid ester groups obtains by following method, make (a) organic diisocyanate, (b) polyalcohol and (c) there is carboxyl and the compound of more than 2 active hydrogen reaction, by the isocyanate group end prepolymer neutralization with carboxyl obtaining, by self-emulsifying in water after emulsion dispersion, use (d) to there is the polyamine compounds of more than 2 amino and/or imino group, the reaction of generation chain, thereby obtain having the polyurethane resin of carboxyl and/or carboxylic acid ester groups.
(7) manufacture method of material for the leather as described in any one in above-mentioned (1)～(6), (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.
In addition, leather of the present invention is obtained by the manufacture method of the present invention described in any one in above-mentioned (1)～(7) with material.
According to the present invention, the leather material that the manufacture method of a kind of leather material is provided and is obtained by this manufacture method.Although this leather is also to have considered the manufacture method of the leather material of the use aqueous polyurethane resin of carrying capacity of environment and VOC problem by the manufacture method of material, but can prevent fully migration, and, there is not the foul smell that causes due to the gas producing in operation and the corrosion of device, can effectively and reliably obtain yet excellent leather material of the physical property such as soft and abrasion resistance and friction firmness.
The specific embodiment
Below, by preferred embodiment describing the present invention in detail.
The manufacture method of material for leather of the present invention, the ammonium salt that comprises polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid by impregnation in fiber base material and (C) mixed liquor of water, be dried afterwards, obtain leather material.
The polyurethane resin that (A) of the present invention like this has carboxyl and/or carboxylic acid ester groups is in polyurethane resin skeleton, to have carboxyl and/or the carboxylic acid ester groups polyurethane resin as hydrophilic component.There is the polyurethane resin of carboxyl and/or carboxylic acid ester groups as such (A), preferably use the polyurethane resin with carboxyl and/or carboxylic acid ester groups obtaining by following method, make (a) organic diisocyanate, (b) polyalcohol and (c) there is carboxyl and the compound of more than 2 active hydrogen reaction, by the isocyanate group end prepolymer neutralization with carboxyl obtaining, by self-emulsifying in water after emulsion dispersion, use (d) to there is the polyamine compounds of more than 2 amino and/or imino group, the reaction of generation chain, thereby obtain having the polyurethane resin of carboxyl and/or carboxylic acid ester groups.
As such (a) organic diisocyanate, be not particularly limited, can use aliphatic diisocyanate, ester ring type vulcabond and the aromatic diisocyanate with 2 isocyanate group.As such (a) organic diisocyanate, for example, can enumerate hexamethylene diisocyanate, the aliphatic diisocyanate compounds such as trimethyl hexamethylene diisocyanate, isophorone diisocyanate, hydrogenation of benzene dimethyl vulcabond, dicyclohexyl methyl hydride diisocyanate, norbornene alkyl diisocyanate, 1, the ester ring type diisocyanate cpds such as 3-bis-(isocyanato-methyl) cyclohexane, benzal vulcabond, methyl diphenylene diisocyanate, naphthalene diisocyanate, tolidine vulcabond, xyxylene vulcabond, the 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 material with without flavescence, thereby be applicable to using, be particularly suitable for using hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, norbornene alkyl diisocyanate and 1,3-bis-(isocyanato-methyl) cyclohexane.
In addition, as (b) polyalcohol, as long as there are 2 above hydroxyls, be not particularly limited, except can using polyester polyol, polycarbonate polyol, polyether polyol etc., can also use the 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--6-caprolactone glycol, poly-adipic acid (3-methyl isophthalic acid, 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-Isosorbide-5-Nitrae-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, random copolymer or the block copolymer etc. of ethylene oxide and propylene oxide and ethylene oxide and butylene oxide.
In addition, such (b) polyalcohol can use separately a kind or combine two or more use.And, as the mean molecule quantity of such (b) polyalcohol, be preferably 500～5000, more preferably 1000～3000.In addition, from giving the viewpoint of leather material with sufficient durability by the polyurethane resin with carboxyl and/or carboxylic acid ester groups obtaining, as above-mentioned (b) polyalcohol, preferably use polycarbonate polyol or polyether polyol.
In addition, there is carboxyl and the compound of more than 2 active hydrogen as (c), for example, can enumerate 2,2-dihydromethyl propionic acid, 2,2-dimethylolpropionic acid etc.And, there is carboxyl and the compound of more than 2 active hydrogen as such, also can use the dihydroxylic alcohols with carboxyl to react with aromatic dicarboxylic acid, aliphatic dicarboxylic acid etc. and the polyester polyol with pendant type carboxyl that obtains.In addition, also can mix and not have the dihydroxylic alcohols of carboxyl to replace the above-mentioned dihydroxylic alcohols with carboxyl to react as diol component.In addition, such have carboxyl and the compound of more than 2 active hydrogen can be used singly or in combination of two or more thereof.
In addition, making (a) organic diisocyanate, (b) polyalcohol and (c) there is carboxyl and the compound of more than 2 active hydrogen reaction and manufacturing while thering is the isocyanate group end prepolymer of carboxyl, as required, can use the low-molecular-weight chain extender with more than 2 reactive hydrogen atom.
As such low-molecular-weight chain extender with more than 2 reactive hydrogen atom, preferred molecular weight is, below 400, to be particularly preferably below 300.In addition, as such low-molecular-weight chain extender, for example, can enumerate ethylene glycol, propylene glycol, season pentanediol, 1,4-butanediol, 1, the low molecular weight polyols such as 6-hexylene glycol, trimethylolpropane, pentaerythrite, D-sorbite, the 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 more than 2 reactive hydrogen atom can be used singly or in combination of two or more thereof.
In the present invention, there is the concrete grammar of the isocyanate group end prepolymer of carboxyl as manufacture, be not particularly limited, for example, can be by manufactures such as the isocyanates polyaddition reaction methods of the so-called single-step method of existing known one-part form, multisection type.Reaction temperature is now preferably 40～150 ℃.In addition, while carrying out such reaction, as required, can add the 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 the organic solvent with isocyanates radical reaction.As such organic solvent, for example, can use acetone, MEK, toluene, oxolane, diox, dimethyl formamide, 1-METHYLPYRROLIDONE etc.
In addition, in the present invention, there is the neutralization of the isocyanate group end prepolymer of carboxyl, can before or after modulation has the isocyanate group end prepolymer of carboxyl, use suitable known method to carry out.The compound that the neutralization of the isocyanate group end prepolymer with carboxyl is like this used 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, the amines such as N-diethyl monoethanolamine, triethanolamine, potassium hydroxide, NaOH, ammonia etc.In these above-claimed cpds, the particularly preferably tertiary amines such as trimethylamine, triethylamine, Tri-n-Propylamine, tri-n-butylamine.
In addition, in the present invention, the emulsification machine that the corrective that makes the isocyanate group end prepolymer with carboxyl uses when emulsion dispersion in water is not particularly limited, and for example, can enumerate mixer for well-distribution, homogenizer, dispersion machine etc.In addition, the corrective that makes the isocyanate group end prepolymer with carboxyl is in water when emulsion dispersion, do not use especially emulsifying agent, temperature range in room temperature～40 ℃, make corrective emulsion dispersion in water of the isocyanate group end prepolymer with carboxyl, preferably suppress as far as possible reacting of isocyanate group and water.And, in the time carrying out emulsion dispersion like this, as required, can add the 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, by the corrective making the isocyanate group end prepolymer with carboxyl in water after emulsion dispersion, use (d) to there is the polyamine compounds of more than 2 amino and/or imino group, generation chain reaction, thus (A) that obtain object has the emulsified dispersed liquid of the polyurethane resin of carboxyl and/or carboxylic acid ester groups.
There is the polyamine compounds of more than 2 amino and/or imino group as such (d), for example, can enumerate the 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; The 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; The water-soluble amine derivatives such as the single ketones imines of di-primary amine; Grass acid dihydrazide, 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, the hydrazine derivates such as 1 '-(Isosorbide-5-Nitrae-butylidene) two hydrazines.The polyamine compounds that these have more than 2 amino and/or imino group, can be used singly or in combination of two or more thereof.
In addition, in the present invention, there is the chain reaction of the corrective of the isocyanate group end prepolymer of carboxyl, can be undertaken by add the polyamine compounds that (d) have more than 2 amino and/or imino group in the emulsion dispersion thing of the corrective of the above-mentioned isocyanate group end prepolymer with carboxyl.The emulsion dispersion thing that in addition, also can add by having at (d) corrective of the above-mentioned isocyanate group end prepolymer with carboxyl in the polyamine compounds of more than 2 amino and/or imino group carries out.Chain reaction is preferably carried out with 20～40 ℃ of reaction temperatures, conventionally completes with 30～120 minutes.While thering is the isocyanate group end prepolymer of carboxyl in manufacture with an organic solvent, for example, after chain reaction finishes, preferably remove organic solvent by decompression distillation etc.
In the present invention, there is 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 less than above-mentioned in limited time lower, although can obtain the leather material of soft feel, has the tendency of abrasion resistance variation; On the other hand, if be greater than the above-mentioned upper limit, the tendency that has the Boardy Feeling of the leather that obtains material, declines with the tack of fiber.Here, the value of 100% modulus be according to JIS K6251 (2004), use that dumbbell shaped No. 3 shape test films are measured, the value of distance between bench marks definite elongation tensile stress (MPa) of (when elongation is 2 times) when extending 100%.
In addition, in the present invention, there is 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 is less than above-mentioned in limited time lower, exists (A) that obtain to have the tendency of the storage stability variation of the polyurethane resin of carboxyl and/or carboxylic acid ester groups; On the other hand, if be greater than the above-mentioned upper limit, the heat freezing temperature producing while mixing with the ammonium salt of (B) inorganic acid increases, and has the tendency that prevents the deleterious of migration while manufacturing 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 preventing viewpoint, preferably sulfuric acid and/or the phosphoric acid of the effect excellence of moving.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, from the security processed, volatilization problem dry and dry after easily remove by washing and in the residual few viewpoint of leather in material, preferred use is selected from least a kind in ammonium sulfate, diammonium hydrogen phosphate and 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, mix the ammonium salt of (B) inorganic acid in (A) has the emulsified dispersed liquid of polyurethane resin of carboxyl and/or carboxylic acid ester groups time, 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 from keeping (A) to there is the viewpoint of the stability of the emulsified dispersed liquid of the polyurethane resin of carboxyl and/or carboxylic acid ester groups, preferably mix the ammonium salt of (B) inorganic acid with the state of the aqueous solution.
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.When the concentration of the ammonium salt of (B) inorganic acid in the above-mentioned aqueous solution is less than the aqueous solution of above-mentioned lower limit, animal migration while preventing from being dried in order to bring into play, while mixing in (A) has the emulsified dispersed liquid of polyurethane resin of carboxyl and/or carboxylic acid ester groups, need to add a large amount of above-mentioned aqueous solution, follow in this, the concentration that (A) in mixed liquor has the polyurethane resin of carboxyl and/or carboxylic acid ester groups declines.Therefore, for the polyurethane resin with carboxyl and/or carboxylic acid ester groups that makes requirement anchors in fiber base material, must be in fiber base material a large amount of mixed liquor of impregnation, dry in the amount of moisture of volatilization increase, so, exist extend 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 be greater than above-mentioned upper in limited time, while existing the emulsified dispersed liquid that there is the polyurethane resin of carboxyl and/or carboxylic acid ester groups with (A) to mix, produce precipitate etc., damage 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 the effect as solvent when the ammonium salt of inorganic acid mixing (A), is applicable to using ion exchange water or distilled water.
In the present invention, the ammonium salt that preparation comprises polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) method of the mixed liquor of water are not particularly limited, and can suitably use known method.
In addition, in above-mentioned mixed liquor, there is 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, preferably (A): (B)=100: 0.1～100: 50, more preferably 100: 1～100: 40.Above-mentioned match ratio is greater than at 100: 0.1 o'clock, and the match ratio of inorganic acid ammonium salt is less than at 0.1 o'clock, has the tendency that prevents migration effect variation in drying process; Be less than at 100: 50 o'clock in match ratio, the match ratio of inorganic acid ammonium salt is greater than at 50 o'clock, has the tendency of mixed liquor gelation under the temperature atmosphere in summer.Wherein, the solid state component in the present invention refers to the residual component under the condition of 105 ℃ of temperature, by 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 refers to, adds the above-mentioned mixed liquor of 50g in 100mL glass beaker processed, and content limit is stirred by the slowly heating in the hot bath of 95 ℃ of this beaker, the content temperature while solidifying that loses flowability in limit.Heat freezing temperature lower than above-mentioned lower in limited time, there is the tendency of mixed liquor gelation under the temperature atmosphere in summer.Higher than on above-mentioned in limited time, thermocoagulation can not show observantly, so there is the tendency that prevents animal migration variation in drying process.
In addition, there is the content of the polyurethane resin of carboxyl and/or carboxylic acid ester groups as (A) in above-mentioned mixed liquor, with the mass conversion of solid state component, be preferably 5～40 quality %, 10～30 quality % more preferably.The content with the polyurethane resin of carboxyl and/or carboxylic acid ester groups is less than above-mentioned in limited time lower, in order to make the polyurethane resin set of necessary amount, need to be in fiber base material a large amount of above-mentioned mixed liquor of impregnation, so, amount of moisture dry and volatilization increases, and has the tendency of prolongation drying time, economy variation.On the other hand, the content with the polyurethane resin of carboxyl and/or carboxylic acid ester groups is greater than above-mentioned upper prescribing a time limit, and has the tendency of the bad stability of above-mentioned mixed liquor.
The mixed liquor that comprises the polyurethane resin with carboxyl and/or carboxylic acid ester groups of the prior art is in the time of aobvious acidity, emulsion stability declines, so, be difficult to use in the manufacture of leather material, even if but the pH value of mixed liquor of the present invention is in an acid side (preferably 5.0～7.0, more preferably 5.5～6.8, particularly preferably 6.0～6.5), the emulsification with the polyurethane resin of carboxyl and/or carboxylic acid ester groups is also stablized, and can be used in the manufacture of leather material.
And, as fiber base material of the present invention, be not particularly limited, be applicable to using fabric, compile thing or nonwoven fabric etc.As the raw material of such fiber base material, in order to obtain approaching feel and the quality of natural leather, applicable utilization has been used the fiber base material of polyamide fiber, polyester fiber.
In addition, in the above-mentioned nonwoven fabric using, use the viewpoint of the feel of material from improving the leather obtaining as above-mentioned fiber base material, the rugosity of the line of nonwoven fabric is preferably below 2.0dtex.When the rugosity of the line of nonwoven fabric is greater than 2.0dtex, will there is the tendency that feel becomes thick and stiff, quality suffers damage of leather material.
In addition, as the density of such nonwoven fabric, be preferably 0.2～0.7g/cm 3, 0.30～0.55g/cm more preferably 3.The density of nonwoven fabric is less than above-mentioned in limited time lower, will there is the tendency of the abrasion resistance variation of the leather material obtaining, in addition, if make a large amount of polyurethane resin sets in order to make up this problem, there is the tendency that feel becomes thick and stiff, quality suffers damage of the leather material obtaining.On the other hand, the density of nonwoven fabric is greater than above-mentioned in limited time upper, has the tendency that feel becomes thick and stiff, quality suffers damage of the leather material obtaining.
Use in the manufacture method of material at leather of the present invention, not damaging in the scope of the object of the invention, in order to give flexibility (adaptability) of operation, can be comprising (A) and have the ammonium salt of the polyurethane resin of 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, organosilicone surfactants, fluorine class surfactant etc.; The various stabilization agents such as antioxidant, fast light stabilizing agent, ultraviolet screener; Mineral oils, silicone based etc. various defoamers; The colouring agents such as polyurethane-reinforcement catalyst, plasticizer, pigment, up time extend agent etc.Such additive can be used singly or in combination of two or more thereof.
In addition, in such additive, particularly 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 obtain making polyurethane resin evenly to anchor at the effect in above-mentioned fiber base material.As such penetrant, as long as normally used material, be not particularly limited, but particularly 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, not damaging in the scope of the object of the invention, in order to give flexibility (adaptability) of operation, can be comprising (A) and have the ammonium salt of the polyurethane resin of carboxyl and/or carboxylic acid ester groups, (B) inorganic acid and (C) add in the mixed liquor of water and the crosslinking agent of carboxyl reaction.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, by comprise (A) and have carboxyl and/or carboxylic acid ester groups polyurethane resin, (B) inorganic acid ammonium salt and (C) mixed liquor of water containing after in being immersed in fabric, compiling the fiber base materials such as thing, nonwoven fabric, be dried.
As the method for the above-mentioned mixed liquor of impregnation in above-mentioned fiber base material, be not particularly limited, for example, preferably adopt the existing known method such as impregnation processing, spraying processing being formed by dip-nip mode, also can suitably select concentration and the treatment conditions etc. of above-mentioned mixed liquor.In addition, also can be at fabric, compile the fiber base materials such as thing, nonwoven fabric in the impregnation ammonium salt that comprises 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 to pre-treatment.In such pretreatment procedure, in order to regulate the bonding force of fiber base material and polyurethane resin composition, preferably use the macromolecule aqueous solution being formed by polyvinyl alcohol, carboxymethyl cellulose etc., silicone based dryingagent, fluorine class dryingagent etc., fiber base material is processed.
In addition,,, be not particularly limited as carry out dry method after the above-mentioned mixed liquor of the inner impregnation of fiber base material with in the manufacture method of material at leather of the present invention, for example, can use and utilize the dry type of hot blast dry; Use the wet type of high velocity vapor generator (Ha イ テ Application パ Le チ ヤ mono-ス チ mono-マ mono-, H.T.S.), high pressure steam generator (H.P.S.) dry; Microwave irradiation formula is dry etc., and from the aspect of continuous processability, applicable use utilizes the dry type of hot blast dry.These drying meanss can be used singly or in combination of two or more thereof.And, state in the use while utilizing the dry type of hot blast dry, preferably its treatment temperature is that 60～190 ℃, processing time are 1～20 minute, particularly preferably treatment temperature is that 100～170 ℃, processing time are 2～5 minutes.By such being dried, can be at the inner set polyurethane resin of fiber base material.
Operation like this, after the mixed liquor of the ammonium salt that impregnation comprises polyurethane resin that (A) have carboxyl and/or carboxylic acid ester groups, (B) inorganic acid in fiber base material and (C) water, be dried, can obtain leather material of the present invention.
Use in material at such leather of the present invention, set solid state component amount as leather with the polyurethane resin in material etc., be not particularly limited, at leather, with in material, the composition that preferably has a polyurethane resin of carboxyl and/or carboxylic acid ester groups from (A) is 10～90 quality %, is 0.5～7.0 quality % left and right from the composition of the ammonium salt of (B) inorganic acid.
In addition, leather of the present invention can dye with material.Such colouring method is not particularly limited, and can adopt any means of the first impregnation poststaining method dyeing after set polyurethane resin in fiber base material and the first colouring method of rear impregnation that makes polyurethane resin set after fiber base material is dyeed.
And leather material of the present invention, can form epidermal area, make the leather material with the grain of 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 on processing release paper and be coated with epidermal area material, form epidermal area thereby moisture is evaporated, coating adhesive thereon again, directly fit with material with leather of the present invention, transpiring moisture, or the processing release paper transfer printing of laminating after moisture evaporation; On processing release paper, be coated with epidermal area material, thereby make moisture evaporation form epidermal area, utilize heat by the thermal transfer of epidermal area and the laminating of leather of the present invention material; In the gunite that directly sprays epidermal area material on material for leather of the present invention; Utilize heliogravure coating machine, knife type coater, unfilled corner wheel coating machine (comma coater), Pneumatic scraper coating machine etc. at the direct rubbing method etc. that is coated with epidermal area material on material for leather of the present invention.In the method for such formation epidermal area, the viewpoint of the physical property face of the epidermal area obtaining from further raising, most preferably processing release paper transfer printing.Material and adhesive for the epidermal area using in such processing release paper transfer printing, as long as can fit with material with leather of the present invention, but from feel aspect and physical property aspect, optimization polyurethane resin, in addition, from the aspect of VOC free and carrying capacity of environment, the preferably material of water-based or solvent-free class.
In addition, the purposes as leather of the present invention with material, can be in the fields such as vehicle, furniture, clothing, footwear, bag, bag, sandals (sandale), groceries, grinding.
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 being obtained by each embodiment and each comparative example uses material by following method evaluation.
(1) prevent animal migration
For the leather material being obtained by each embodiment and each comparative example, use scanning electron microscope [Scanning Electron Microscope S-2400 (HITACHI)], observe the cross section of leather material with the multiplying powers of 60 times, the set state of the polyurethane resin that compares the set state of the polyurethane resin existing at nonwoven fabric central portion and exist in nonwoven surface portion, evaluates according to following benchmark.
5 grades: with in material section, completely there is no difference at central portion and surface element resin fixed amount at leather, do not move.
4 grades: with in material section, almost there is no difference at central portion and surface element resin fixed amount at leather, do not move.
3 grades: at leather, with in material section, in central portion and slightly difference of surface element resin fixed amount, in full depth, 10% part of shared central portion can not be confirmed resin set.
2 grades: with in material section, have sizable difference at central portion and surface element resin fixed amount at leather, in full depth, 30% part of shared central portion can not be confirmed resin set.
1 grade: at leather, with in material section, in central portion and surface element resin fixed amount, there were significant differences, and in full depth, 50% part of shared middle body can not be confirmed resin set.
(2) abrasion test
For the leather material being obtained by each embodiment and each comparative example, according to the coning of JIS L1096 (1999), utilize taper abrasion testing machine [peace field essence mechanism is done institute and produced], use the soft CS-10 of wheel, apply loading 500g, wear and tear after 1000 times and 3000 times, leather is now expressed as to abrasion loss by the reduction of the weight of material.Wherein, abrasion loss is fewer, and leather is more excellent with the abrasion resistance of material.
(3) friction firmness
For the leather material being obtained by each embodiment and each comparative example, according to JIS L0849 (2004), by learning vibration shape frictional testing machine [Daiei chemistry essence mechanism is done institute and produced], applying loading 200g, rub 100 times, measure wet friction firmness.In the mensuration of above-mentioned friction firmness, use and pollute with the relatively dustiness of cotton canequim of the progressive series of greys, evaluate according to following benchmark.
5 grades: can not confirm to pollute.
4 grades: confirm slightly to pollute.
3 grades: clearly confirm to pollute.
2 grades: confirm to pollute remarkable a little.
1 grade: confirm significantly to pollute.
(4) there is noresidue
For the leather material being obtained by each embodiment and each comparative example, about the content of the composition beyond nonwoven fabric and polyurethane resin in material for leather residues such as () surfactants, utilize using methyl alcohol as the special extractor of Suo Gesi profit that extracts solvent, extract 3 hours with 70 ℃, measure extracted amount now, be that more than 1.0 quality % goods have been evaluated as residue by extracted amount, the goods that extracted amount are less than to 1.0 quality % are evaluated as noresidue.
(5) feel
By sense of touch, according to following benchmark, the feel of material for the leather being obtained by each embodiment and each comparative example with 5 Phase Evaluations of 5 grades (softnesses) to 1 grade (thick and stiff).
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 slightly lack the feel of rebound elasticity.
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).
(6) foul smell while being dried
In each embodiment and each comparative example, ammonia when sensory evaluation utilizes air drier to be dried and sour foul smell.
A: without foul smell.
B: slightly foul smell.
C: rush the such strong foul smell of nose
[synthesis example and relatively synthesis example]
The comparison synthesis example of the waterborne polyurethane resin using in the synthesis example of the polyurethane resin with carboxyl and carboxylic acid ester groups using in expression the present invention below, and comparative example.
(synthesis example 1)
With mixer, reflux condensing tube, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, add 157.0g to gather carbonic acid-1, 6-hexylene glycol ester type polyalcohol (mean molecule quantity 2000), 7.5g season pentanediol, 1.3g trimethylolpropane, 2 of 9.5g, 2-dihydromethyl propionic acid, 0.001g dibutyl tin laurate and 105g MEK, after evenly mixing, add 69.7g isophorone diisocyanate, with 80 ℃ of reactions 300 minutes, obtaining with respect to the content of the free isocyanate groups of nonvolatile component is 1.9 quality %'s, there is the methyl ethyl ketone solution of the isocyanate group end prepolymer of carboxyl.
After below above-mentioned solution is cooled to 50 ℃, add 6.8g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 421.9g water, make the corrective emulsion dispersion of the isocyanate group end prepolymer with carboxyl, obtain dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution of add water hydrazine and the 1.1g diethylenetriamines of the 60 quality % that are dissolved with 5.2g in 20g water, carry out after chain reaction in 60 minutes at 35 ℃, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin with carboxyl and carboxylic acid ester groups of nonvolatile component 35.0 quality %, viscosity 120mPas (BM viscosimeter, No. 2 rotors, 60rpm), pH value 7.8, average grain diameter 90nm.
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, be not there is heat coagulable water dispersion.
(synthesis example 2)
With mixer, reflux condensing tube, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, add 178.0g to gather carbonic acid-1, 6-hexylene glycol ester type polyalcohol (mean molecule quantity 2000), 0.9g trimethylolpropane, 2 of 9.3g, 2-dihydromethyl propionic acid, 0.001g dibutyl tin laurate and 105g MEK, after evenly mixing, add 56.9g dicyclohexyl methyl hydride diisocyanate, with 80 ℃ of reactions 420 minutes, obtaining with respect to the content of the free isocyanate groups of nonvolatile component is 1.2 quality %'s, there is the methyl ethyl ketone solution of the isocyanate group end prepolymer of carboxyl.
After below above-mentioned solution is cooled to 50 ℃, add 6.7g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 424.4g water, make the corrective emulsion dispersion of the isocyanate group end prepolymer with carboxyl, obtain dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution of add water hydrazine and the 0.7g diethylenetriamines of the 60 quality % that are dissolved with 3.3g in 20g water, carry out after chain reaction in 60 minutes at 35 ℃, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin with carboxyl and carboxylic acid ester groups of nonvolatile component 35.0 quality %, viscosity 70mPas (BM viscosimeter, No. 1 rotor, 60rpm), pH value 7.6, average grain diameter 120nm.
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, be not there is heat coagulable water dispersion.
(synthesis example 3)
In the four-hole boiling flask with 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 72.3g hexamethylene diisocyanate, with 80 ℃ of reactions 180 minutes, obtaining with respect to the content of the free isocyanate groups of nonvolatile component was the methyl ethyl ketone solution of 3.1 isocyanate group end prepolymers quality %, that have carboxyl.
After below above-mentioned solution is cooled to 50 ℃, add 22.1g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 402.6g water, make the corrective emulsion dispersion of the isocyanate group end prepolymer with carboxyl, obtain dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution of add water hydrazine and the 1.8g diethylenetriamines of the 60 quality % that are dissolved with 8.6g in 20g water, carry out after chain reaction in 60 minutes at 35 ℃, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin with carboxyl and carboxylic acid ester groups of nonvolatile component 35.0 quality %, viscosity 50mPas (BM viscosimeter, No. 1 rotor, 60rpm), pH value 7.9, average grain diameter 150nm.
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, be not there is heat coagulable water dispersion.
(synthesis example 4)
With mixer, reflux condensing tube, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, add 157.0g to gather carbonic acid-1, 6-hexylene glycol ester type polyalcohol (mean molecule quantity 2000), 7.5g season pentanediol, 1.3g trimethylolpropane, 2 of 9.5g, 2-dihydromethyl propionic acid, 0.001g dibutyl tin laurate and 105g MEK, after evenly mixing, add 69.7g isophorone diisocyanate, with 80 ℃ of reactions 300 minutes, obtaining with respect to the content of the free isocyanate groups of nonvolatile component is 1.9 quality %'s, there is the methyl ethyl ketone solution of the isocyanate group end prepolymer of carboxyl.
After below above-mentioned solution is cooled to 50 ℃, add 8.6g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 420.1g water, make the corrective emulsion dispersion of the isocyanate group end prepolymer with carboxyl, obtain dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution of add water hydrazine and the 1.1g diethylenetriamines of the 60 quality % that are dissolved with 5.2g in 20g water, carry out after chain reaction in 60 minutes at 35 ℃, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin with carboxyl and carboxylic acid ester groups of nonvolatile component 35.0 quality %, viscosity 180mPas (BM viscosimeter, No. 2 rotors, 60rpm), pH value 9.5, average grain diameter 70nm.
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, be not there is heat coagulable water dispersion.
(synthesis example 5)
With mixer, reflux condensing tube, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, add 146.1g to gather carbonic acid-1, 6-hexylene glycol ester type polyalcohol (mean molecule quantity 2000), 1 of 2.9g, 4-butanediol, 1.7g trimethylolpropane, 11.1g 2, 2-hydroxymethyl propionic acid, 0.001g dibutyl tin laurate and 105g MEK, after evenly mixing, add 83.2g dicyclohexyl methyl hydride diisocyanate, with 80 ℃ of reactions 240 minutes, obtaining with respect to the content of the free isocyanate groups of nonvolatile component is 3.8 quality %'s, there is the methyl ethyl ketone solution of the isocyanate group end prepolymer of carboxyl.
After below above-mentioned solution is cooled to 50 ℃, add 7.9g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 403.3g water, make the corrective emulsion dispersion of the isocyanate group end prepolymer with carboxyl, obtain dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution of add water hydrazine and the 1.3g diethylenetriamines of the 60 quality % that are dissolved with 7.7g in 20g water, carry out after chain reaction in 60 minutes at 35 ℃, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin with carboxyl and carboxylic acid ester groups of nonvolatile component 35.0 quality %, viscosity 40mPas (BM viscosimeter, No. 1 rotor, 60rpm), pH value 8.0, average grain diameter 40nm.
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, be not there is heat coagulable water dispersion.
(synthesis example 6)
With mixer, reflux condensing tube, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, add 134.3g to gather carbonic acid-1, 6-hexylene glycol ester type polyalcohol (mean molecule quantity 2000), 1 of 3.5g, 4-butanediol, 3.8g trimethylolpropane, 10.9g 2, 2-dihydromethyl propionic acid, 0.001g dibutyl tin laurate and 105g MEK, after evenly mixing, add 92.6g dicyclohexyl methyl hydride diisocyanate, with 80 ℃ of reactions 210 minutes, obtaining with respect to the content of the free isocyanate groups of nonvolatile component is 4.2 quality %'s, there is the methyl ethyl ketone solution of the isocyanate group end prepolymer of carboxyl.
After below above-mentioned solution is cooled to 50 ℃, add 7.8g triethylamine, carry out 30 minutes neutralization reactions with 40 ℃.Then, the solution after neutralizing is cooled to below 30 ℃, uses distribution blade slowly to add 405.0g water, make the corrective emulsion dispersion of the isocyanate group end prepolymer with carboxyl, obtain dispersion liquid.Then, in above-mentioned dispersion liquid, be added on the polyamines aqueous solution of add water hydrazine and the 2.0g diethylenetriamines of the 60 quality % that are dissolved with 6.9g in 20g water, carry out after chain reaction in 60 minutes at 35 ℃, under reduced pressure, with 35 ℃ of desolventizings, obtain the water dispersion of the stable polyurethane resin with carboxyl and carboxylic acid ester groups of nonvolatile component 35.0 quality %, viscosity 230mPas (BM viscosimeter, No. 2 rotors, 60rpm), pH value 8.7, average grain diameter 90nm.
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, be not there is heat coagulable water dispersion.
(relatively synthesis example 1)
With mixer, reflux condensing tube, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, add the polytetramethylene glycol (mean molecule quantity 1000) of 76.1g, 16.9g polyoxyethylene polypropylene glycol random copolymer glycol (mean molecule quantity 1000, oxyethylene group content 70 quality %), 1 of 1.5g, 4-butanediol, 1.9g trimethylolpropane, 0.001g dibutyl tin laurate and 60g MEK, after evenly mixing, add 40.4g dicyclohexyl methyl hydride diisocyanate, with 80 ℃ of reactions 300 minutes, obtaining with respect to the content of the free isocyanate groups of nonvolatile component is the methyl ethyl ketone solution of the isocyanate group end prepolymer of 2.1 quality %.
After below above-mentioned solution is cooled to 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 11.3g water, carry out after chain reaction in 90 minutes at 35 ℃, under reduced pressure, carry out desolventizing with 35 ℃, obtain the water dispersion of the stable waterborne 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 the carboxyl-content in this waterborne polyurethane resin and carboxylic acid ester groups content is 0.0 quality %, and 100% modulus value is 2MPa.And, there is gelation at 45 ℃ in the water dispersion of this waterborne polyurethane resin, is to have heat coagulable water dispersion.
Below, in table 1, gather the proterties that represents 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 Relatively 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
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) Nothing Nothing Nothing Nothing Nothing Nothing 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 obtaining in 100g synthesis example 1 produce] the 50 quality % aqueous solution and 16.5g water, preparation mixed liquor.The content that the polyurethane resin with carboxyl and carboxylic acid ester groups in 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 being made by polyester fiber (0.5dtex, density 0.3g/cm 3) middle this mixed liquor of impregnation, make it absorb (pick up) 250 quality %, utilize afterwards air drier [TABAI SAFETYOVEN SPH-200] to carry out being dried for 3 minutes, then carry out being dried for 3 minutes with 150 ℃ with 100 ℃, obtain dermatine.Again the dermatine obtaining (leather material) 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 adjusting agent: 90 quality % acetic acid 0.3cc/L
Bath raio: (1: 20)
Dyeing condition: 130 ℃ × 60 minutes (2 ℃/min 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 ℃/min 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 obtaining in 100g synthesis example 1 produce] the 50 quality % aqueous solution and 10.7g water, preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in 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, process 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 obtaining in 100g synthesis example 1 produce] the 50 quality % aqueous solution and 31.4g water, preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in 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, processes 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 with carboxyl and carboxylic acid ester groups obtaining in 100g synthesis example 1, the 40 quality % aqueous solution and the 1.8g water of 1.8g ammonium sulfate, preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in 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, processes 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 obtaining in 100g synthesis example 2 produce] the 50 quality % aqueous solution and 16.5g water, preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in 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, process 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 obtaining in 100g synthesis example 3 produce] the 50 quality % aqueous solution and 16.5g water, preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in 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, process 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 obtaining in 100g synthesis example 4 produce] the 50 quality % aqueous solution and 16.5g water, preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in 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, process similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
(embodiment 8)
Water dispersion, the 20 quality % aqueous solution of 17.5g diammonium hydrogen phosphate/ammonium dihydrogen phosphate (ADP) (mass ratio 50/50), the Carbodilite E-02[Carbodiimides crosslinking agent of 1.0g, trade name, Nisshinbo Co., Ltd. of evenly mixing the polyurethane resin with carboxyl and carboxylic acid ester groups obtaining in 100g synthesis example 1 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, preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in 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, process 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 obtaining in 100g synthesis example 5 produce] the 50 quality % aqueous solution and 16.5g water, preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in 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, processes 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 obtaining in 100g synthesis example 6 produce] the 50 quality % aqueous solution and 16.5g water, preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in 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, processes 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 obtaining in 100g synthesis example 1 produce] the 50 quality % aqueous solution and 34.0g water, preparation mixed liquor.The match ratio of the polyurethane resin with carboxyl and carboxylic acid ester groups in above-mentioned mixed liquor and the ammonium salt of inorganic acid is that 100: 0, pH value are 7.5, heat freezing temperature is that 90 ℃ of polyurethane resin content above, that have carboxyl and carboxylic acid ester groups are 25 quality %.
Except using such mixed liquor, process 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 obtaining in 100g synthesis example 1 produce] the 50 quality % aqueous solution and 16.5g water, preparation mixed liquor.The polyurethane resin with carboxyl and carboxylic acid ester groups in above-mentioned mixed liquor and the match ratio of sulfuric acid are that 100: 5, heat freezing temperature are that 10 ℃ of polyurethane resin content following, that have carboxyl and carboxylic acid ester groups are 25 quality %.
In addition, above-mentioned mixed liquor is in the time adding the 10 quality % aqueous solution of sulfuric acid, and moment is observed and from mixed liquor, separates out precipitate, so, the manufacture 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 obtaining in synthesis example 1] the 50 quality % aqueous solution and 34.0g water, preparation mixed liquor.The match ratio of the waterborne polyurethane resin in 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, process 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 obtaining in synthesis example 1] the 50 quality % aqueous solution and 16.5g water, preparation mixed liquor.The match ratio of the waterborne polyurethane resin in 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, process 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 obtaining in synthesis example 1] the 50 quality % aqueous solution and 16.5g water, preparation mixed liquor.Waterborne polyurethane resin in 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, process 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 obtaining in 100g synthesis example 1 produce] the 50 quality % aqueous solution and 16.5g water, preparation mixed liquor.The polyurethane resin content that the polyurethane resin with carboxyl and carboxylic acid ester groups in 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, process similarly to Example 1, obtain dermatine dyeing processing cloth (through the leather material of dyeing processing).
In table 2, represent the evaluation result of the dermatine dyeing processing cloth (through the leather material of dyeing processing) obtaining in embodiment 1～10, in table 3, represent the evaluation result of the dermatine dyeing processing cloth (through the leather material of dyeing processing) obtaining in comparative example 1,3～6.
[table 2]
Figure BSA00000238132900261
[table 3]
Figure BSA00000238132900271
The leather obtaining in embodiment 1～9 is used in material, migration unconfirmed, and resin is fixed to nonwoven fabric inside equably.Owing to preventing in this wise migration, the leather material of the abrasion resistance of the demonstration excellence that the abrasion loss can obtain in very soft, the wear-resistant test of feel 1000 times and 3000 times time does not almost change.In 100% modulus of polyurethane resin with carboxyl and carboxylic acid ester groups when large (embodiment 10), the wiriness of material for the leather obtaining, it is slightly poor that the antifriction of 3000 times damages in test, but prevent animal migration excellence, is enough to use in the situation that thinking little of feel.In addition, the leather obtaining in embodiment 1～10, with in material, can confirm that residue residual in leather material is few, known also little on the impact of friction firmness due to residue.
On the other hand, use in material at the leather that ammonium salt containing inorganic acid, a use do not obtain in having the comparative example 1 of the polyurethane resin of carboxyl and carboxylic acid ester groups, can confirm when dry, to occur obviously to move wiriness.And, in the abrasion resistance test with material of the leather that obtains, although the abrasion resistance while making it abrasion 1000 times is good, in the time of abrasion 3000 times, can observe obvious abrasion loss in comparative example 1, 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 manufacture leather material because of mixed liquor generation gelation, can confirm that flexibility (adaptability) of operation is insufficient.
In addition, not using the leather obtaining in the ammonium salt of inorganic acid, a comparative example with heat coagulable waterborne polyurethane resin 3 that use utilizes surfactant emulsification to obtain with in material, can confirm to there is heat setting solidity, and significantly move when dry.In addition, the wiriness of material for the leather that obtains in comparative example 3 in abrasion resistance test, although the abrasion resistance while making it abrasion 1000 times is good, can be observed obvious abrasion loss in the time of abrasion 3000 times, confirms that abrasion resistance is insufficient.
And, utilize the leather obtaining in the comparative example 4 of the ammonium salt with heat coagulable waterborne polyurethane resin and inorganic acid that surfactant emulsification obtains with in material in use, the same result of leather material that can confirm and obtain in comparative example 3, for utilizing the heat coagulable waterborne polyurethane resin that has that surfactant emulsification obtains, the effect that prevents migration etc. that can not obtain being brought by the ammonium salt of inorganic acid.
In addition, the leather obtaining in using the ammonium salt of calcium chloride water replacement inorganic acid, using the comparative example 5 of the mixed liquor mixing with the waterborne polyurethane resin that utilizes surfactant emulsification to obtain is with in material, because making heat freezing temperature, calcium chloride water declines, prevent that animal migration from improving slightly, but while using material compared with the leather obtaining in embodiment 1～10, prevent that animal migration is insufficient.In addition, the wiriness of material for the leather that obtains in comparative example 5, and in abrasion resistance test although the abrasion resistance while making it abrasion 1000 times is good, can be observed obvious abrasion loss in the time of abrasion 3000 times, confirms that abrasion resistance is insufficient.In addition, can confirm to remain surfactant at leather in material, can confirm that residue is large on the impact of friction firmness.
In addition, the leather obtaining in the comparative example 6 of ammonium salt that uses the aqueous solution replacement inorganic acid being made up of formic acid ammonium salt is with in material, although the animal migration of preventing, abrasion resistance, friction firmness, residue, feel aspect excellence, but can confirm when dry the strong foul smell producing due to decomposition, the volatilization of ammonium formate.And the formic acid now producing is the reason of corrosion of equipment, and if formic acid and ammonia emit to atmosphere, will become environmental problem.
As described above, according to the present invention, the leather material that the manufacture method of a kind of leather material is provided and is obtained by this manufacture method.Although this leather is also to have considered the manufacture method of the leather material of the use aqueous polyurethane resin of carrying capacity of environment and VOC problem by the manufacture method of material, but can prevent fully migration, and, there is not the foul smell that causes due to the gas producing in operation and the corrosion of device, can effectively and reliably obtain yet excellent leather material of the physical property such as soft and 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 being obtained by manufacture method of the present invention, leather is with there is no organic solvent residual in 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 be as the leather materials'use that epidermal area, stable and excellent quality are set.

Claims (6)

1. a manufacture method for material for leather, is characterized in that:
By 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 in the inner impregnation of fiber base material, be dried afterwards, obtain leather material,
The heat freezing temperature of described mixed liquor is 30～70 ℃, and pH is 5.0～6.8.
2. the manufacture method of material for leather as claimed in claim 1, is characterized in that:
In described mixed liquor, (A) there is 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 manufacture method of material for leather as claimed in claim 1, is characterized in that:
(B) inorganic acid in the ammonium salt of inorganic acid is sulfuric acid and/or phosphoric acid.
4. the manufacture method of material for leather as claimed in claim 1, is characterized in that:
(A) polyurethane resin that has carboxyl and/or a carboxylic acid ester groups obtains by following method, make (a) organic diisocyanate, (b) polyalcohol and (c) there is carboxyl and the reaction of the compound of more than 2 active hydrogen, by the isocyanate group end prepolymer neutralization with carboxyl obtaining, by self-emulsifying in water after emulsion dispersion, use (d) to there is the polyamine compounds of more than 2 amino and/or imino group, generation chain is reacted, thereby obtains having the polyurethane resin of carboxyl and/or carboxylic acid ester groups.
5. the manufacture method of material for leather as claimed in claim 1, is characterized in that:
(A) there is 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.
6. the leather material being obtained by the manufacture method described in any one in claim 1～5.
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