CN106687489A - Aqueous polyurethane-resin dispersion and uses thereof - Google Patents
Aqueous polyurethane-resin dispersion and uses thereof Download PDFInfo
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- CN106687489A CN106687489A CN201580048323.0A CN201580048323A CN106687489A CN 106687489 A CN106687489 A CN 106687489A CN 201580048323 A CN201580048323 A CN 201580048323A CN 106687489 A CN106687489 A CN 106687489A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
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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
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
Provided is an aqueous polyurethane-resin dispersion which comprises an aqueous medium and, dispersed therein, a polyurethane resin obtained by reacting at least polyols, an acidic-group-containing polyol, a polyisocyanate, and a chain extender, wherein the polyols comprise a high-molecular-weight diol having a number-average molecular weight of 1,000-30,000 and a high-molecular-weight triol having a number-average molecular weight of 300-30,000 and the chain extender comprises a compound having, in the molecule, three or more functional groups reactive with an isocyanato group. This aqueous polyurethane-resin dispersion is useful especially as a coating material for synthetic leathers.
Description
Technical field
The present invention relates to aqueous polyurethane resin dispersion and the smears containing the aqueous polyurethane resin dispersion.
In addition, being directed to use with the synthetic leather that aqueous polyurethane resin dispersion is obtained.
Background technology
Synthetic leather by bonding agent for example by being applied to fiber base material and the previously fabricated urethane resin film of lamination
Dry process and obtain.In this case, above-mentioned urethane resin film is for example antiseized by the way that the polyaminoester emulsion of water system is applied to
Property base material on and heating make its drying and obtain.
In dry process, for bonding epidermal area and the bonding agent of fibrous substrate layer, various researchs have been carried out.
For example, it is proposed that following methods：It is non-using having as aqueous polyurethane resin dispersion used in bonding agent
The nonionic system aqueous polyurethane resin dispersion of ionic hydrophilic group, so as to the outward appearance of synthetic leather, feel and viscous can be improved
Connect intensity (with reference to Japanese Unexamined Patent Publication 2003-336028 publications).
In addition, it is proposed that following methods：As aqueous polyurethane resin dispersion used in bonding agent, using containing soft
It is less than 50 DEG C of waterborne polyurethane resin and the aqueous polyurethane resin dispersion of carbamate system thickener to change temperature, from
And the in apparent good order and condition of synthetic leather is made, improve adhesive strength and feel (with reference to Japanese Unexamined Patent Publication 2009-298154 publications).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-336028 publications
Patent document 2：Japanese Unexamined Patent Publication 2009-298154 publications
The content of the invention
Invent problem to be solved
For synthetic leather smears, in order to keep feel, it is desirable to flexibility, it is proposed that above-mentioned to improve hand
The method of sense.But, there is solvent resistance and light resistance in the synthetic leather of polyurethane resin dispersion that used so far
Insufficient problem.In addition, it is not known that following smears, the smears possess it is sufficiently sunproof simultaneously, can change
The surface state of the synthetic leathers such as kind flexibility, or the problem in terms of other physical property such as solvent resistance can be eliminated, using the teaching of the invention it is possible to provide
With film that is high-level, balancedly meeting these various characteristics.
The problem of the present invention is to provide a kind of aqueous polyurethane resin dispersion and synthetic leather smears, and it can be carried
For the film that flexibility or solvent resistance while excellent in light-resistance are also excellent.
For solving the scheme of problem
The present invention is completed to solve above-mentioned problem, specifically, with following compositions.
(1) a kind of aqueous polyurethane resin dispersion, the aqueous polyurethane resin dispersion is that polyurethane resin is scattered in
In water-medium, the polyurethane resin be at least make polyalcohol, the polyalcohol containing acidic-group, polyisocyanates and
Obtained from chain extender reaction,
Above-mentioned polyalcohol is at least containing the high molecular weight diol and number-average molecular weight that number-average molecular weight is 1000～30000
300～30000 HMW triol,
Above-mentioned chain extender contains there are more than 3 to have reactive functional group with NCO in a molecule
Compound.
(2) aqueous polyurethane resin dispersion described in (1) as described above, wherein, the quality of HMW triol relative to
The ratio of the gross mass of high molecular weight diol and HMW triol is 1 mass %～30 mass %.
(3) aqueous polyurethane resin dispersion described in (1) or (2) as described above, wherein, chain extender contains in a molecule
In have more than 3 with NCO have reactivity functional group compound and in a molecule with 2 with it is different
Cyanic acid ester group has the compound of the functional group of reactivity.
(4) aqueous polyurethane resin dispersion any one of (1)～(3) as described above, wherein, in chain extender,
There is the content of compound of more than 3 functional groups with NCO with reactivity in a molecule relative to one
There is the compound of more than 3 functional groups with NCO with reactivity and in a molecule with 2 in individual molecule
Individual and NCO has the ratio of the total content of the compound of the functional group of reactivity with molar ratio computing as 10：90～40：
60。
(5) aqueous polyurethane resin dispersion any one of (1)～(4) as described above, wherein, HMW triol
For polyoxyalkylene triols.
(6) aqueous polyurethane resin dispersion described in (5) as described above, wherein, HMW triol is that have oxidation third
The HMW triol of alkene unit and/or ethylene oxide unit as repetitive.
(7) aqueous polyurethane resin dispersion any one of (1)～(6) as described above, wherein, high molecular weight diol
For PCDL.
(8) a kind of synthetic leather smears, it contains the aqueous polyurethane tree any one of above-mentioned (1)～(7)
Fat dispersion.
(9) a kind of synthetic leather, the synthetic leather at least has：Fiber base material；Bonding is not passed through by bond layer or
Oxidant layer and lamination are in the epidermal area of above-mentioned fiber base material；With lamination in the coating layer of above-mentioned epidermal area,
Above-mentioned coating layer is to be dried the smears described in above-mentioned (8).
(10) a kind of manufacture method of synthetic leather, it uses the aqueous polyurethane any one of above-mentioned (1)～(7)
Resin dispersion forms epidermal area.
(11) a kind of urethane resin film, it is by containing the aqueous polyurethane tree any one of above-mentioned (1)～(7)
What the aqueous resin dispersion of fat dispersion was dried.
(12) a kind of synthetic leather, it uses the urethane resin film described in above-mentioned (11) as epidermal area.
The effect of invention
According to the present invention it is possible to provide a kind of aqueous polyurethane resin dispersion and synthetic leather smears, it can be carried
For while excellent in light-resistance, the also excellent film of flexibility or solvent resistance.
It is aqueous poly- in water-medium that the aqueous polyurethane resin dispersion of the present invention is that polyurethane resin is scattered in
Urethane resin dispersion, the polyurethane resin is at least with polyalcohol, the polyalcohol containing acidic-group, polyisocyanates and chain extension
Agent is used as constituent, and above-mentioned polyalcohol is at least equal containing the high molecular weight diol sum that number-average molecular weight is 1000～30000
Molecular weight is 300～30000 HMW triol, and above-mentioned chain extender contains in a molecule with more than 3 and isocyanide
Perester radical has the compound of the functional group of reactivity.
(polyalcohol)
In the present invention, above-mentioned polyalcohol is at least containing the high molecular weight diol sum that number-average molecular weight is 1000～30000
Average molecular weight is 300～30000 HMW triol.
<High molecular weight diol>
As long as the glycol that above-mentioned high molecular weight diol number-average molecular weight is 1000～30000 is just not particularly limited, example
Such as, PTMEG, polyester-diol, PCDL, polyether polyester glycol, polyether polycarbonate glycol, polyester can be enumerated
PCDL etc..They can only using one kind, it is also possible to shares two or more.Wherein, from obtaining excellent wear resistance
Polyurethane resin from the aspect of, preferred PCDL and/or polyester-polycarbonate glycol.
The number-average molecular weight of above-mentioned high molecular weight diol be 1000～30000, preferred number average molecular weight be 1000～
10000, more preferably number-average molecular weight is 1000～5000.
PCDL is the high molecular weight diol that diol monomer is linked by carbonic acid ester bond.
PCDL can be by using the phosgenation of diol monomer and phosgene or using diol monomer and carbonic ester
Ester-interchange method manufacturing.Particularly, due to there is no being mixed into, being difficult to for chlorine in the PCDL for being obtained by ester-interchange method
Coloring, thus be preferred.
As the diol monomer of the raw material for becoming PCDL, straight chain aliphatic diols, Branched fatty can be enumerated
Race's glycol, the glycol containing alicyclic structure, the glycol containing aromatic ring structure.
As above-mentioned straight chain aliphatic diols, for example can enumerate ethylene glycol, 1,3-PD, BDO, 1,5-
Pentanediol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,10- decanediols, 1,11- hendecanes two
Alcohol, 1,12- dodecanediols etc..
As above-mentioned branched aliphatic glycol, for example, can enumerate Isopropanediol, 1,3-BDO, 2- methyl isophthalic acids, 3- third
Glycol, 1,4- pentanediols, 2- methyl isophthalic acids, 4- butanediols, neopentyl glycol, 1,5- hexylene glycols, 2- methyl isophthalic acids, 5- pentanediols, 3- first
Base -1,5- pentanediols, 2- methyl isophthalic acids, 8- ethohexadiols etc..
As the above-mentioned glycol containing alicyclic structure, for example can enumerate 1,3- ring pentanediols, 1,3- cyclohexanediols, Isosorbide-5-Nitrae-
Cyclohexanediol, 1,3- cyclohexanedimethanols, 1,4 cyclohexane dimethanol etc..
As the above-mentioned glycol containing aromatic ring structure, for example can enumerate catechol, hydroquinones, resorcinol,
1,3- benzene dimethanols, 1,4- benzene dimethanols, bisphenol-A etc..
Above-mentioned diol monomer can only using one kind, it is also possible to shares two or more.
As above-mentioned diol monomer, from the flexibility of resulting polyurethane resin it is more excellent from the aspect of, it is preferably straight
Chain fatty race glycol and/or branched aliphatic glycol.
Above-mentioned straight chain aliphatic diols and branched aliphatic glycol can only using one kind, it is also possible to share two or more.
Furthermore it is also possible to straight chain aliphatic diols are shared with branched aliphatic glycol.
As polyester-polycarbonate glycol, as long as there is the repetitive of ester bond and with carbonic acid ester bond containing intramolecular
Repetitive is just not particularly limited, from maintain obtained by polyurethane resin flexibility while, improve solvent resistance
From the aspect of, preferred main chain does not have the polyester-polycarbonate glycol of alicyclic structure and aromatic ring structure.
There is no the polyester-polycarbonate glycol of alicyclic structure and aromatic ring structure as above-mentioned main chain, for example, can enumerate
From straight-chain hydrocarbons type monomer or the polyester-polycarbonate glycol of branched-chain hydrocarbons type monomer.
As above-mentioned straight-chain hydrocarbons type monomer, for example, can enumerate ethylene glycol, 1,3-PD, BDO, 1,5- penta
The straight-chain hydrocarbons glycol such as glycol, 1,6-HD, 1,9- nonanediols, 1,10- decanediols, 1,11- dodecanediols；In α-acetyl
The lactones such as ester, beta-propiolactone, gamma-butyrolacton, δ-valerolactone, 6-caprolactone；Alpha-hydroxy acetic acid esters, ethylene lactic acid ester, γ-hydroxyl
The 'omega '-hydroxy carboxylic acid esters such as base butyrate, δ-hydroxyl valerate, ε-hydroxycaproic ester；The α such as diester malonate, succinic diester,
Omega dicarboxylic acid diesters；The α such as succinyl oxide, alpha, omega-dicarboxylic acid acid anhydride etc..
As above-mentioned branched-chain hydrocarbons type monomer, the material that there is the side chains such as alkyl in above-mentioned straight-chain hydrocarbons type monomer can be enumerated.
<HMW triol>
In polyurethane resin, polyol component constitutes the part as soft chain segment, by using HMW triol,
The part for forming soft chain segment can be utilized when forming polyurethane resin to be crosslinked.
As long as the triol that above-mentioned HMW triol number-average molecular weight is 300～30000 is just not particularly limited, for example
Can enumerate：Using glycerine, triol of the trimethylolpropane equimolecular quantity less than 300 as construction unit polyether triol, poly-
Ester triol, Merlon triol, polyether polyester triol, polyether polycarbonate triol, polyester-polycarbonate triol etc..Wherein, from
From the aspect of obtaining the more excellent polyurethane resin of flexibility, preferred, polyethers triol.
The number-average molecular weight of above-mentioned HMW triol is 300～30000, and preferred number average molecular weight is 500～20000,
More preferably number-average molecular weight is 1000～20000.
As above-mentioned polyether triol, preferred polyoxyalkylene triols.Wherein, preferably with ethylene oxide unit and/or oxidation
Propylene units as repetitive polyoxyalkylene triols, more preferably polyoxypropylene triol.
<Other polyalcohols>
Except the high molecular weight diol that number-average molecular weight is 1000～30000 and the height that number-average molecular weight is 300～30000
Beyond molecular weight triol, other polyalcohols can also be shared to above-mentioned polyalcohol.
As long as above-mentioned other polyalcohols are not included in the range of above-mentioned high molecular weight diol and HMW triol
Polyalcohol is just not particularly limited.Above-mentioned other polyalcohol preferred number average molecular weights are 500～5000, more preferably number-average molecular weight
For 500～3000.
In addition, being not particularly limited to the species of above-mentioned other polyalcohols, for example, can enumerate PPG, polyester many
First alcohol, polycarbonate polyol, polyether polyester polyalcohol, polyether polycarbonate polyalcohol, polyester polycarbonate polyols etc..It
Can only using one kind, it is also possible to share two or more.Wherein, from obtain the more excellent polyurethane resin of flexibility in terms of
Consider, preferred polyester polycarbonate polyols, further preferred polyester-polycarbonate glycol and/or main chain have alicyclic structure
PCDL, it is special from obtaining while flexibility is maintained, from the aspect of the also excellent polyurethane resin of abrasion performance
There is not preferred main chain the main chain of the polyester-polycarbonate glycol and/or number-average molecular weight of alicyclic structure less than 1000 to have alicyclic ring
The PCDL of structure.
It should be noted that in the present invention, in above-mentioned other polyalcohols the polyalcohol containing acidic-group is not included.
In above-mentioned polyester polycarbonate polyols, ester bond is preferably 1 with the mol ratio of carbonic acid ester bond：9～9：1st, it is more excellent
Elect 3 as：7～7：3rd, particularly preferably 4：6～6：4.It is such scope by making the mol ratio of ester bond and carbonic acid ester bond, can be with
Obtain the more excellent polyurethane resin of flexibility and abrasion performance.
There is the polyester-polycarbonate glycol of alicyclic structure as above-mentioned main chain, can enumerate and be only from main chain there is alicyclic ring
The polyester-polycarbonate glycol of the monomer of structure from main chain there is the monomer and main chain of alicyclic structure not to have alicyclic structure
Monomer polyester-polycarbonate glycol.It is also excellent poly- from while flexibility is further maintained abrasion performance can be obtained
From the aspect of urethane resin, it is preferred from main chain and there is the monomer and main chain of alicyclic structure not to have the monomer of alicyclic structure
Polyester-polycarbonate glycol.Above, " monomer " represents glycol, hydroxycarboxylic acid esters, lactone, dicarboxylic diester, dicarboxylic anhydride, no
Including carbonic ester.
There is the monomer of alicyclic structure as above-mentioned main chain, the main chains such as cyclohexanediol, cyclohexanedimethanol tool can be enumerated
There is the diol monomer of alicyclic structure；There are the hydroxycarboxylic acid esters of alicyclic structure to main chains such as hydroxy cyclohexane carboxylic's esters；To hexamethylene
The main chains such as alkane dicarboxylic diester have dicarboxylic diester of alicyclic structure etc..
There is no the monomer of alicyclic structure as above-mentioned main chain, straight-chain hydrocarbons type monomer, branched-chain hydrocarbons type monomer etc. can be enumerated.
As the example of these monomers, described monomer in the item of high molecular weight diol before can enumerating.
There is the PCDL of alicyclic structure as above-mentioned main chain, can enumerate and be only from main chain there is alicyclic structure
Monomeric diol PCDL or from main chain there is the monomeric diol and main chain of alicyclic structure not have alicyclic structure
Monomeric diol PCDL.From can obtain maintain flexibility while the also excellent polyurethane tree of abrasion performance
From the aspect of fat, it is preferred from main chain and there is the monomeric diol and main chain of alicyclic structure not to have the monomeric diol of alicyclic structure
PCDL.
In addition, the number-average molecular weight of above-mentioned PCDL is preferably smaller than 1000, more preferably 400～990.
There is the monomeric diol of alicyclic structure as above-mentioned main chain, cyclohexanediol, cyclohexanedimethanol etc. can be enumerated main
Chain has the diol monomer of alicyclic structure.
There is no the monomeric diol of alicyclic structure as above-mentioned main chain, straight-chain hydrocarbons type monomeric diol, branched-chain hydrocarbons can be enumerated
Type monomeric diol etc..As the example of these monomers, described monomer in the item of high molecular weight diol before can enumerating.
The quality of above-mentioned high molecular weight diol is relative to above-mentioned high molecular weight diol, above-mentioned HMW triol and other are more
The ratio of the gross mass of first alcohol is preferably 45 mass %～99 mass %, more preferably 51 mass %～85 mass %.By making
The ratio of above-mentioned high molecular weight diol is the scope, can obtain the more excellent polyurethane resin of flexibility and abrasion performance.
The quality of above-mentioned HMW triol is relative to above-mentioned high molecular weight diol, above-mentioned HMW triol and other are more
The ratio of the gross mass of first alcohol is preferably 1 mass %～30 mass %, more preferably 1 mass %～10 mass %.By such
The ratio of above-mentioned HMW triol is set, the more excellent polyurethane resin of flexibility and abrasion performance can be obtained.
The quality of above-mentioned other polyalcohols is relative to above-mentioned high molecular weight diol, above-mentioned HMW triol and other are polynary
The ratio of the gross mass of alcohol is preferably 0～50 mass %, more preferably 10 mass %～40 mass %.It is above-mentioned by being arranged such
The ratio of other polyalcohols, can obtain the more excellent polyurethane resin of flexibility and abrasion performance.
(polyalcohol containing acidic-group)
Polyalcohol containing acidic-group is in a molecule containing the hydroxyl of more than 2 and the acidic-group of more than 1.
As acidic-group, carboxyl, sulfonic group, phosphate, phenolic hydroxyl group etc. can be enumerated.It should be noted that phenolic hydroxyl group and polyalcohol
Hydroxyl distinguished.Particularly, as the polyalcohol containing acidic-group, preferably comprise and have in a molecule 2
The compound of hydroxyl and 1 carboxyl.The above-mentioned polyalcohol containing acidic-group can be used alone one kind, it is also possible to share two kinds
More than.
As the above-mentioned polyalcohol containing acidic-group, 2,2- dihydromethyl propionic acids, 2,2- dihydroxy first can be specifically enumerated
The acid of the dihydroxymethyl such as base butyric acid alkane；The double hydroxyethyl glycine of N, N-, N, the double hydroxyethyl alanine of N-, 3,4- dihydroxy fourths
Alkyl sulfonic acid, 3,6- dihydroxy -2- toluenesulfonic acids etc..Wherein, from easiness aspect is obtained, 2 methylols are preferably comprised
Carbon number be 4～12 alkane acid (dihydroxymethyl alkane acid), in the acid of dihydroxymethyl alkane, more preferably 2,2- dihydroxy first
Base propionic acid.
The acidic-group of the above-mentioned polyalcohol containing acidic-group can be in the following appropriate stage be carried out with nertralizer
It is with, stage：The stage of aftermentioned manufacture polyurethane prepolymer；Polyurethane resin is set to be scattered in the stage front in water-medium；
It is scattered in water-medium simultaneously with polyurethane resin is made；Stage after making polyurethane resin be scattered in water-medium etc..
As above-mentioned nertralizer, trimethylamine, triethylamine, tri-isopropyl amine, tri-n-butylamine, triethanolamine, N- methyl can be enumerated
Diethanol amine, N- ethyldiethanolamines, N- phenyldiethanol-amines, dimethylethanolamine, diethyl ethylene diamine, N-methylmorpholine,
The organic amines such as pyridine, 2- (dimethylamino) -2- methyl isophthalic acids-propyl alcohol (DMAP)；The inorganic base salts such as NaOH, potassium hydroxide
Class, ammonia etc..Wherein, organic amine can be preferably used, can more preferably uses tertiary amine, can most preferably use triethylamine.
(polyisocyanates)
As polyisocyanates, it is not particularly limited, aromatic polyisocyanate, aliphatic polyisocyanic acid can be enumerated
Ester, ester ring type polyisocyanates etc..
As aromatic polyisocyanate, specifically can enumerate 1,3- phenylene diisocyanates, Isosorbide-5-Nitrae-phenylene diisocyanate, 2,
4- toluene di-isocyanate(TDI)s (TDI), 2,6- toluene di-isocyanate(TDI)s, 4,4 '-methyl diphenylene diisocyanate (MDI), 2,4-
Methyl diphenylene diisocyanate, 4,4 '-two isocyanato- biphenyl, the isocyanato- biphenyl of '-two of 3,3 '-dimethyl -4,4,
The isocyanato- diphenyl methane of '-two of 3,3 '-dimethyl -4,4, l,5 naphthylene diisocyanate, 4,4 ', 4 "-triphenylmenthane
Triisocyanate, an isocyanato- phcnylsulfonyl isocyanate, to isocyanato- phcnylsulfonyl isocyanate etc..
As aliphatic polyisocyante, specifically can enumerate ethylidene diisocyanate, tetramethylene diisocyanate,
Hexamethylene diisocyanate (HDI), ten dimethylene diisocyanates, 1,6,11- hendecane triisocyanates, 2,2,4- tri-
Methyl hexamethylene diisocyanate, LDI, the isocyanatomethyl capronates of 2,6- bis-, double (2- isocyanides
Acid group close ethyl) fumarate, double (2- isocyanatoethyls) carbonic esters, the isocyanic acids of 2- isocyanatoethyls -2,6- two
Root closes capronate etc..
As ester ring type polyisocyanates, IPDI (IPDI), 4,4 '-two hexamethylenes can be specifically enumerated
Dicyclohexylmethane diisocyanate (H12MDI), cyclohexylene diisocyanate, methylcyclohexylidene diisocyanate (hydrogenation TDI),
Double (2- isocyanatoethyls) -4- cyclohexene -1,2- dicarboxylic esters, 2,5- norcamphane diisocyanate, 2,6- norcamphanes two
Isocyanates etc..
These polyisocyanates can only using one kind, it is also possible to shares two or more.
The NCO of each molecule of above-mentioned polyisocyanates is usually 2, but does not occur in polyurethane resin
In the range of gelation, it is also possible to using the polyisocyanate as triphenylmethane triisocyanate with more than 3 NCOs
Cyanate.
In above-mentioned polyisocyanates, from the aspect of hardness from after ultraviolet curing is elevated, preferably tie with alicyclic ring
The ester ring type polyisocyanate compound of structure, from the control easily reacted, the physical properties excellent of resulting polyurethane resin
From the aspect of, particularly preferred HMDI (H12MDI).
(chain extender)
As chain extender, have in a molecule more than 3 by using at least one and have instead with NCO
The compound of the functional group of answering property, so as to the part for forming hard segment can be utilized to be crosslinked when polyurethane resin is formed.
As above-mentioned chain extender, it is possible to use conventionally used known compound.Wherein, preferably will be in a molecule
There is the compound of reactive functional group with NCO and in a molecule with 2 and isocyanide with more than 3
The compound that perester radical has the functional group of reactivity is shared.By having more than 3 and isocyanide in a molecule
Perester radical has the compound of the functional group of reactivity and has reactivity with NCO with 2 in a molecule
The compound of functional group shared, can obtain while flexibility is maintained, solvent resistance and light resistance it is also more excellent
Polyurethane resin.
There are more than 3 chemical combination with NCO with reactive functional group in a molecule as above-mentioned
Thing, for example, can enumerate the triamine compounds such as diethylenetriamines, double (2- aminopropyls) amine, double (3- aminopropyls) amine；Three
Ethylene tetra, tri propylidene tetramine, N- (benzyl) trien, N, N " '-(dibenzyl) trien, N- (benzyls
Base)-N " ' the tetramine compound such as-(2- ethylhexyls) trien；The amine of tetren, 4 sub-propyl-5-amine etc. five
Compound；The hexamine compound such as penten, five inferior propyl hexamine；Polyethylene imine, polypropylneimine etc. are polynary
Amine etc..
Wherein, from the reactive aspect with polyurethane prepolymer, preferred diethylenetriamines, triethylene four
Amine, double (2- aminopropyls) amine, double (3- aminopropyls) amine, tri propylidene tetramine, tetren, 4 sub-propyl-5-amine,
The polyamine or these mixture with 2 amino and more than 1 imino group such as penten, five inferior propyl hexamine.
There is 2 compounds with NCO with reactive functional group, example in a molecule as above-mentioned
Hydrazine, ethylenediamine, 1,4- tetra-methylenedimines, 2- methyl isophthalic acids, 5- pentanediamines, 3- methyl isophthalic acids, 5- pentanediamines, 1,6- can such as be enumerated
Hexamethylene diamine, 1,4- hexamethylene diamines, 3- amino methyl -3,5,5- trimethyl cyclohexylamines, 1,3- double (amino methyl) hexamethylene, benzene diformazans
Diol compounds such as the diamine compounds such as amine, piperazine, 2,5- lupetazins, 1,4- butanediols, 1,6-HD etc..
Wherein, from the reactive aspect with polyurethane prepolymer, it is preferably selected from by hydrazine, ethylenediamine, Isosorbide-5-Nitrae-four
Methylene diamine, 2- methyl isophthalic acids, 5- pentanediamines, 3- methyl isophthalic acids, more than a kind in 5- pentanediamines, the group of 1,6- hexamethylene diamines composition
Compound, it is more excellent from obtaining while flexibility is maintained, from the aspect of the also more excellent polyurethane resin of solvent resistance
Select 1,6- hexamethylene diamines (HDA).
It is above-mentioned that there are more than 3 to have the compound of reactive functional group with NCO with a molecule
The ratio for stating the compound in a molecule with 2 functional groups with NCO with reactivity is excellent with molar ratio computing
Elect 10 as：90～40：60th, more preferably 20：80～30：70.It is such scope by the ratio for making chain extender, is obtained soft
The soft and more excellent polyurethane resin of abrasion performance.
(water-medium)
In the present invention, polyurethane resin is scattered in water-medium.As above-mentioned water-medium, water, water can be enumerated
With the blending agent of hydrophilic organic solvent etc..
As above-mentioned water, for example, can enumerate clear water, ion exchange water, distilled water, ultra-pure water etc..Wherein, it is contemplated that obtain
Obtain easiness, make particle become unstable etc. because of the impact of salt, preferably use ion exchange water.
As above-mentioned hydrophilic organic solvent, for example, can enumerate the ketones such as acetone, ethyl methyl ketone；N- crassitudes
The pyrrolidinone compounds such as ketone, N- ethyl pyrrolidones；The ethers such as diethyl ether, dimethyl ether；It is methyl alcohol, ethanol, normal propyl alcohol, different
The alcohols such as propyl alcohol, ethylene glycol, diethylene glycol；With the β-alkoxypropan of " the エ Network ア ミ De " of the manufacture of Chu Guangxingchan companies as representative
The amide-types such as acid amides；Tertiary amines containing hydroxyl such as 2- (dimethylamino) -2- methyl isophthalic acids-propyl alcohol (DMAP) etc..
The amount of the above-mentioned hydrophilic organic solvent in as above-mentioned water-medium, preferably 0～20 mass %.
(manufacture method of aqueous polyurethane resin dispersion)
The manufacture method of aqueous polyurethane resin dispersion is not particularly limited, for example, can enumerate following manufacturer
Method.
1st manufacture method is following methods：Raw material is all mixed so as to react, in being scattered in water-medium, thus
To aqueous polyurethane resin dispersion.
2nd manufacture method is following methods：Make polyalcohol, the polyalcohol containing acidic-group and arbitrary other polyalcohols
With polyisocyanates reaction, prepolymer is manufactured, with after, in being scattered in water-medium, will be made in the acidic-group of above-mentioned prepolymer
Chain extender is reacted, and thus obtains aqueous polyurethane resin dispersion.
As the manufacture method of aqueous polyurethane resin dispersion, due to the control for easily carrying out molecular weight, thus it is preferred that
The 2nd above-mentioned manufacture method.
The 2nd above-mentioned manufacture method includes following operation：Make the polyalcohol, polyalcohol containing acidic-group, arbitrary
Other polyalcohols and polyisocyanates react and obtain the operation (α) of prepolymer；Acidic-group in above-mentioned prepolymer is neutralized
Operation (β)；The operation (γ) prepolymer after neutralization being scattered in water-medium；With, make to be scattered in water-medium
The operation (δ) that prepolymer and chain extender are reacted.
When the reaction of above-mentioned operation (α) is carried out, it is also possible to use catalyst.
As above-mentioned catalyst, it is not particularly limited, for example, can enumerates tin (tin) series catalysts (laurate trimethyl
Tin, dibutyl tin laurate etc.), the salt and organic metal of the metal such as lead series catalysts (lead octoate etc.) and organic or inorganic acid
Derivative, amine system catalyst (triethylamine, N-ethylmorpholine, triethylenediamine etc.), the catalysis of diazabicyclo endecatylene system
Agent etc..Wherein, from the aspect of reactivity, preferred dibutyl tin laurate.
Operation (γ) that the above-mentioned prepolymer by after neutralization is scattered in water-medium and above-mentioned make prepolymer and chain extender
The operation (δ) reacted can be while carry out.
(synthetic leather smears)
The present invention aqueous polyurethane resin dispersion can directly or add additive and as the surface of synthetic leather
Synthetic leather used is used with smears.
In synthetic leather smears, other resins can be added as additive.As other resins, can enumerate
Polyester resin, acrylic resin, polyether resin, polycarbonate resin, polyurethane resin, epoxy resin, alkyd resin, polyene
Hydrocarbon resin etc..These can be used alone one kind, it is also possible to share two or more.Other resins are preferably selected from by polyester tree
At least one in fat, acrylic resin, the group of vistanex composition.
Above-mentioned other resins preferably have more than a kind of hydrophilic radical.As hydrophilic radical, can enumerate hydroxyl,
Carboxyl, sulfonic group etc..
In the case that above-mentioned polyester resin and aforesaid propylene acid resin have hydroxyl, as the part in by making resin
Or there is urethane reaction and make these resins elongations and molecular weight in whole hydroxyls and polyisocyanate compound
So-called urethane-modified polyester or urethane-modified acrylic's resinoid, can share these resins.
Above-mentioned polyester resin generally can be manufactured by sour composition with the esterification or ester exchange reaction of alcohol composition.Make
For sour composition, it is possible to use the compound for generally using in the manufacture of polyester resin, for example can enumerate aliphatic polybasic acids,
Alicyclic polyacid, aromatic polyvalent acid etc..
The hydroxyl value of above-mentioned polyester resin be preferably 10mgKOH/g～300mgKOH/g, more preferably 50mgKOH/g～
250mgKOH/g, more preferably 80mgKOH/g～180mgKOH/g.The acid number of above-mentioned polyester resin is preferably 1mgKOH/g
～200mgKOH/g, more preferably 15mgKOH/g～100mgKOH/g, more preferably 25mgKOH/g～60mgKOH/g.
The weight average molecular weight of polyester resin is preferably 500～500,000, more preferably 1,000～300,000, more preferably 1,
500～200,000.In this specification, weight average molecular weight makes the value determined by gel permeation chromatography (polystyrene conversion).
As aforesaid propylene acid resin, the acrylic resin of preferred hydroxyl.The acrylic resin of hydroxyl can
To make hydroxyl by using the known method such as solution polymerization process for example in organic solvent, emulsion polymerization in water
Polymerism unsaturated monomer and can manufacture with other polymerism unsaturated monomer copolymerization of the monomer copolymerization.
As long as the polymerism unsaturated monomer of above-mentioned hydroxyl be in a molecule respectively have more than 1 hydroxyl with
The compound of polymerism unsaturated bond is just not particularly limited, and can enumerate (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) propylene
(methyl) acrylic acid and the carbon atoms such as acid -2- hydroxypropyl acrylates, (methyl) acrylic acid -3- hydroxypropyl acrylates, (methyl) acrylic acid -4- hydroxy butyl esters
Number is the monoesters compound of 2～8 2 yuan of alcohol；The 6-caprolactone modifier of these monoesters compounds；N- hydroxymethyls (methyl) acryloyl
Amine；Allyl alcohol；Molecular end is (methyl) acrylate with polyoxyethylene chain of hydroxyl etc..
The acrylic resin of above-mentioned hydroxyl preferably has cationic functional group.With regard to cationic functional group
Hydroxyl acrylic resin, for example can be by using with the cationic such as tertiary amino, quaternary ammonium salt base functional group
Polymerism unsaturated monomer is manufactured as one kind of polymerism unsaturated monomer.
From the aspects such as storage-stable, the resistance to water of resulting film, the acrylic resin of above-mentioned hydroxyl
Hydroxyl value be preferably 1mgKOH/g～200mgKOH/g, more preferably 2mgKOH/g～100mgKOH/g, more preferably
3mgKOH/g～60mgKOH/g.
In addition, in the case where the acrylic resin of above-mentioned hydroxyl has the acidic groups such as carboxyl, from resulting film
The aspect such as resistance to water set out, the acid number of the acrylic resin of the hydroxyl is preferably 1mgKOH/g～200mgKOH/g, more
Preferably 2mgKOH/g～150mgKOH/g, more preferably 5mgKOH/g～100mgKOH/g.
The weight average molecular weight of the acrylic resin of above-mentioned hydroxyl is preferably 1,000～200,000, more preferably 2,
000～100,000, more preferably 3,000～50,000.
As above-mentioned polyether resin, the polymer with ehter bond or copolymer can be enumerated, polyoxyethylene system can be enumerated
Polyethers, polyoxypropylene system polyethers, polybutylene system polyethers, bisphenol-A or Bisphenol F etc. are gathered by derived from aromatic polyhydroxy compounds
Ether etc..
As above-mentioned polycarbonate resin, the polymer by derived from bisphenol compound can be enumerated, for example, can be enumerated double
Phenol A Merlon etc..
As above-mentioned polyurethane resin, can enumerate by acrylic polyol, PEPA, PPG, poly-
There is amino-formate bond obtained from the reaction of the various polyol components such as carbonate polyol and polyisocyanate compound
Resin.
As above-mentioned epoxy resin, resin obtained from the reaction by bisphenol compound and epoxychloropropane can be enumerated
Deng.As bisphenol compound, for example, can enumerate bisphenol-A, Bisphenol F.
As above-mentioned alkyd resin, the polyacids such as phthalic acid, terephthalic acid (TPA), butanedioic acid and polyalcohol can be enumerated
Further with grease oil fatty acid (soybean oil, linseed oil, coconut oil, stearic acid etc.), natural resin (rosin, amber
Deng) etc. modifying agent reaction obtained from resin.
As said polyolefins resin, can enumerate：Olefinic monomers are made to gather according to conventional with other appropriate monomers
It is legal to be polymerized or copolymerization, resin obtained from moisture dissipates is carried out to resulting vistanex by using emulsifying agent；
Or by carrying out resin obtained from emulsion polymerization together with the monomer that makes olefinic monomers and other appropriate.In addition, according to feelings
Condition, can also be using the so-called chloridized polyolefin modified resin of said polyolefins resin Jing chlorinations.
As above-mentioned olefinic monomers, ethene, propylene, 1- butylene, 3-methyl-1-butene, 4- methyl-1-pentenes can be enumerated
The alpha-olefins such as alkene, 3- Methyl-1-pentenes, 1- heptene, 1- hexenes, 1- decene, 1- dodecylenes, phenylethylene；Butadiene, sub- second
Base ENB, dicyclopentadiene, 1,5- hexadiene equiconjugate diene or non-conjugated diene etc., these monomers can individually make
With, it is also possible to share two or more.
As can with the other monomers of above-mentioned olefinic monomers copolymerization, for example can enumerate vinyl acetate, vinyl alcohol,
Maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride etc., these monomers can be used alone, it is also possible to
Share two or more.
Contain curing agent by making the smears of the present invention, the painting obtained using coating composition or smears can be improved
Film or multilayer film, the resistance to water of coated film etc..
As above-mentioned curing agent, amino resins, polyisocyanate compound, blocked polyisocyanates chemical combination can be enumerated
Thing, melmac, carbodiimides etc..Curing agent can be used alone, it is also possible to share two or more.
As above-mentioned amino resins, can enumerate obtained from the reaction by amino component and aldehyde composition partially or completely
Methylolation amino resins.As amino component, melamine, urea, benzoguanamine, 2,4- diaminourea -6- methyl isophthalic acids can be enumerated,
3,5- triazines, steroidal guanamines, spiral shell guanamines, dicyandiamide etc..As aldehyde composition, formaldehyde, paraformaldehyde, acetaldehyde, benzene first can be enumerated
Aldehyde etc..
As above-mentioned polyisocyanate compound, can enumerate and there is more than 2 NCOs in a molecule
Compound, for example, can enumerate hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate etc..As end-blocking polyisocyanate
Cyanate esters, can enumerate and be obtained by the addition end-capping reagent in the polyisocyanate-based of above-mentioned polyisocyanate compound
The compound for arriving, as end-capping reagent, can enumerate the phenol such as phenol, cresols system；The aliphatic alcohol such as methyl alcohol, ethanol system, malonic acid two
Methyl esters, acetylacetone,2,4-pentanedione isoreactivity methylene base system；The mercaptan such as butanethiol, lauryl mercaptan system；The acyls such as antifebrin, acetamide
Amine system；The lactams systems such as epsilon-caprolactams, δ-valerolactam；The imide series such as succinimide, maleimide, acetyl aldehyde
The oxime such as oxime, acetoxime, methyl ethyl ketone oxime system；The end-capping reagent of the amine systems such as diphenyl aniline, aniline, Ethylenimine etc..
As above-mentioned melmac, the hydroxyl first such as dihydroxymethyl melamine, trimethylol melamine can be enumerated
Base melamine；The alkyl ether compound of these melamine methylols or condensation product；The alkyl ether compound of melamine methylol
Condensation product.
Can add coloring pigment, extender pigment, bright pigment in the smears of the present invention.
As above-mentioned coloring pigment, titanium dioxide, zinc white, carbon black, chrome vermillion, Prussian blue, cobalt blue, azo face can be enumerated
Material, phthalocyanine color, quinacridone pigment, isoindoline pigment, intellectual circle's series pigments, perylene pigment etc..They can be independent
Use, it is also possible to share two or more.As coloring pigment, particularly preferably using titanium dioxide and/or carbon black.
As above-mentioned extender pigment, clay, kaolin, barium sulfate, brium carbonate, calcium carbonate, talcum, titanium dioxide can be enumerated
Silicon, alumina white etc..They can be used alone, it is also possible to share two or more.As extender pigment, particularly preferably using sulfuric acid
Barium and/or talcum, further preferably using barium sulfate.
As above-mentioned bright pigment, can enumerate aluminium, copper, zinc, brass, nickel, aluminum oxide, mica, by titanium dioxide or
The aluminum oxide of iron oxide cladding, the mica coated by titanium dioxide or iron oxide etc..
The present invention smears can as needed alone or in combination two or morely containing thickener, curing catalysts,
The common additive for coatings such as ultra-violet absorber, light stabilizer, defoamer, plasticizer, surface conditioner, sagging inhibitor.
The manufacture method of the smears of the present invention is not particularly limited, it is possible to use known manufacture method.It is general and
Speech, smears can be manufactured by following methods：Aqueous polyurethane resin dispersion and above-mentioned various additives are mixed, addition
Water-medium, is adjusted to fit the viscosity in coating process, thus manufacturing smears.
After by the surface of the synthetic leather coating agent to synthetic leather of the present invention so as to be solidified to form film,
Coated synthetic leather can be obtained.As above-mentioned synthetic leather, it is possible to use known using damp process, dry process etc.
Method manufactured by synthetic leather.
The coating process of synthetic leather smears is not particularly limited, belt coating, spraying coating, roller can be enumerated
Coating, rod coating, spray coating, dip coated etc..As above-mentioned roller coat cloth, can enumerate gravure roll coating, reverse roll coating,
Knife over roll coating etc..
The solidification of synthetic leather smears can be using common solidifications such as air drying, heated-air drying, heat dryings
Method.
As the heating means in above-mentioned heat drying, can add using infrared ray, microwave, steam roller etc. are conventionally used
Thermal means.
(urethane resin film)
The urethane resin film of the present invention can be obtained as follows：By aqueous polyurethane resin dispersion directly or aqueous poly-
Add after additive in urethane resin dispersion, be applied on antistick characteristic base material, be afterwards dried it, solidification, from above-mentioned antiseized
Property base material on peel off, thus obtain above-mentioned urethane resin film.
As above-mentioned additive, it is possible to use the additive same with the additive of above-mentioned smears.Alternatively, it is also possible to add
Plus foaming agent or hollow packing, the urethane resin film of producing foamed.
The thickness of urethane resin film is not particularly limited, preferably 5 μm～500 μm, more preferably 10 μm～300 μ
m。
(synthetic leather epidermal area)
The aqueous polyurethane resin dispersion of the present invention can be used as the epidermal area of synthetic leather.
As using aqueous polyurethane resin dispersion formed synthetic leather epidermal area method, for example can enumerate with
Under three kinds of methods.
First method is that urethane resin film is manufactured using aqueous polyurethane resin dispersion, and viscous with least having
The method for connecing the base material laminating of oxidant layer and fibrous substrate layer.
Second method is that urethane resin film is manufactured using aqueous polyurethane resin dispersion, and fine with least having
The method of the base material laminating of Wiki material, micro- porous layer and bond layer.
The third method is that at least have coating waterborne polyurethane resin point on the base material of fiber base material and micro- porous layer
A prose style free from parallelism and the method for making its drying and forming epidermal area.
In the method for the epidermal area that synthetic leather is formed in above-mentioned use aqueous polyurethane resin dispersion, micro- porous layer can
To be arranged using arbitrary method.
As the forming method of micro- porous layer, for example, can enumerate following methods：Using so-called damp process in fiber base material
Mixture of upper coating polyurethane resin and dimethylformamide (DMF) etc. etc., by DMF etc. water is replaced as, and thus makes polyurethane
Agglomeration, forms micro- porous layer.Alternatively, it is also possible to by with the resin sheet and fiber base for connecting bubble and/or separated foam
Material lamination, so as to form micro- porous layer.
Embodiment
[embodiment 1]
In possessing the reaction unit of mixer and heater, in the presence of dibutyl tin laurate 0.2g, in nitrogen
Under atmosphere, (Yu Buxingchan companies manufacture to make ETERNACOLL (registration mark) UH-300；Number-average molecular weight 3000；Hydroxyl value
37.4mgKOH/g；1,6-HD and carbonic ester is set to carry out PCDL obtained from ester exchange reaction) it is 120.1g, poly-
Propylene triol (manufacture of PPTL and Guang Chun medicines company, number-average molecular weight 1500) 10.10g, ETERNACOLL (registration mark)
(Yu Buxingchan companies manufacture UCC40-150；Number-average molecular weight 1500；Hydroxyl value 72.1mgKOH/g；Ester bond rubs with carbonic acid ester bond
That ratio=4/6；1,4 cyclohexane dimethanol, ε-hydroxycaproic ester and carbonic ester is set to carry out poly- carbonic acid obtained from ester exchange reaction
Esterdiol) 69.90g, 2,2- dihydromethyl propionic acid (DMPA) 10.63g, hydrogenation 4,4 '-dicyclohexyl methyl hydride diisocyanate
(H12MDI) 72.00g reacts 7 hours in N- ethyl pyrrolidones (NEP) 117.7g in 60 DEG C -90 DEG C.Urethane
NCO bases content at the end of reaction is 0.18 mole.Reactant mixture is cooled into 80 DEG C, triethylamine (TEA) is added to
8.460g (being 1 equivalent relative to DMPA) is simultaneously mixed.Under strong agitation reactant mixture 342.6g is added into water
In 416.1g.Then, diethylenetriamines (DETA) aqueous solution 13.2g of 35 mass % is added to carry out chain extension.Further, 35 are added
1,6- hexamethylene diamines (HMDA) aqueous solution 43.7g of quality % carries out chain extension, obtains aqueous polyurethane resin dispersion.DETA/
HMDA=28/72 (mol ratio).Total addition of DETA and HMDA is that the NCO bases at the end of urethane reaction contain
0.9 equivalent of amount.
The molecular weight of resulting aqueous polyurethane resin dispersion is determined, as a result weight average molecular weight (Mw) is
278000.Solid component concentration is 30.4 mass %.The addition of each raw material is shown in table 1.
[embodiment 2]
In possessing the reaction unit of mixer and heater, in the presence of dibutyl tin laurate 0.2g, in nitrogen
Under atmosphere, (Yu Buxingchan companies manufacture to make ETERNACOLL (registration mark) UH-300；Number-average molecular weight 3000；Hydroxyl value
37.4mgKOH/g；1,6-HD and carbonic ester is set to carry out PCDL obtained from ester exchange reaction) it is 119.8g, poly-
Propylene triol (manufacture of PPTL and Guang Chun medicines company, number-average molecular weight 1500) 10.0g, ETERNACOLL (registration mark)
(Yu Buxingchan companies manufacture UCC40-150；Number-average molecular weight 1500；Hydroxyl value 72.1mgKOH/g；Ester bond rubs with carbonic acid ester bond
That ratio=4/6；1,4 cyclohexane dimethanol, ε-hydroxycaproic ester and carbonic ester is set to carry out poly- carbonic acid obtained from ester exchange reaction
Esterdiol) 70.2g, 2,2- dihydromethyl propionic acid (DMPA) 10.61g, hydrogenation 4,4 '-dicyclohexyl methyl hydride diisocyanate
(H12MDI) 71.9g reacts 7 hours in N- ethyl pyrrolidones (NEP) 116.9g in 60 DEG C -90 DEG C.Urethane is anti-
NCO bases content at the end of answering is 0.18 mole.Reactant mixture is cooled into 80 DEG C, triethylamine (TEA) is added to
8.43g (being 1 equivalent relative to DMPA) is simultaneously mixed.Under strong agitation reactant mixture 345.5g is added into water 416.5g
In.Then, diethylenetriamines (DETA) aqueous solution 18.6g of 35 mass % is added to carry out chain extension.Further, 35 mass % are added
1,6- hexamethylene diamines (HMDA) aqueous solution 32.9g carry out chain extension, obtain aqueous polyurethane resin dispersion.DETA/HMDA=39/
61 (mol ratios).Total addition of DETA and HMDA is that 0.9 of the NCO base contents at the end of urethane reaction is worked as
Amount.
The molecular weight of resulting aqueous polyurethane resin dispersion is determined, as a result weight average molecular weight (Mw) is
408000.Solid component concentration is 30.6 mass %.The addition of each raw material is shown in table 1.
[embodiment 3]
In possessing the reaction unit of mixer and heater, in the presence of dibutyl tin laurate 0.2g, in nitrogen
Under atmosphere, (Yu Buxingchan companies manufacture to make ETERNACOLL (registration mark) UH-300；Number-average molecular weight 3000；Hydroxyl value
37.4mgKOH/g；1,6-HD and carbonic ester is set to carry out PCDL obtained from ester exchange reaction) it is 120.3g, poly-
Propylene triol (manufacture of PPTL and Guang Chun medicines company, number-average molecular weight 1500) 10.1g, ETERNACOLL (registration mark)
(Yu Buxingchan companies manufacture UCC40-150；Number-average molecular weight 1500；Hydroxyl value 72.1mgKOH/g；Ester bond rubs with carbonic acid ester bond
That ratio=4/6；1,4 cyclohexane dimethanol, ε-hydroxycaproic ester and carbonic ester is set to carry out poly- carbonic acid obtained from ester exchange reaction
Esterdiol) 70.0g, 2,2- dihydromethyl propionic acid (DMPA) 10.60g, hydrogenation 4,4 '-dicyclohexyl methyl hydride diisocyanate
(H12MDI) 71.9g reacts 7 hours in N- ethyl pyrrolidones (NEP) 116.9g in 60 DEG C -90 DEG C.Urethane is anti-
NCO bases content at the end of answering is 0.18 mole.Reactant mixture is cooled into 80 DEG C, triethylamine (TEA) is added to
8.38g (being 1 equivalent relative to DMPA) is simultaneously mixed.Under strong agitation reactant mixture 343.1g is added into water 415.7g
In.Then, diethylenetriamines (DETA) aqueous solution 8.0g of 35 mass % is added to carry out chain extension.Further, 35 mass % are added
1,6- hexamethylene diamines (HMDA) aqueous solution 44.8g carry out chain extension, obtain aqueous polyurethane resin dispersion.DETA/HMDA=17/
83 (mol ratios).Total addition of DETA and HMDA is that 0.9 of the NCO base contents at the end of urethane reaction is worked as
Amount.
The molecular weight of resulting aqueous polyurethane resin dispersion is determined, as a result weight average molecular weight (Mw) is
220000.Solid component concentration is 30.5 mass %.The addition of each raw material is shown in table 1.
[embodiment 4]
In possessing the reaction unit of mixer and heater, in the presence of dibutyl tin laurate 0.2g, in nitrogen
Under atmosphere, (Yu Buxingchan companies manufacture to make ETERNACOLL (registration mark) UH-300；Number-average molecular weight 3000；Hydroxyl value
37.4mgKOH/g；1,6-HD and carbonic ester is set to carry out PCDL obtained from ester exchange reaction) it is 118.0g, poly-
Propylene triol (manufacture of PPTL and Guang Chun medicines company, number-average molecular weight 1500) 19.9g, ETERNACOLL (registration mark)
(Yu Buxingchan companies manufacture UCC40-150；Number-average molecular weight 1500；Hydroxyl value 72.1mgKOH/g；Ester bond rubs with carbonic acid ester bond
That ratio=4/6；1,4 cyclohexane dimethanol, ε-hydroxycaproic ester and carbonic ester is set to carry out poly- carbonic acid obtained from ester exchange reaction
Esterdiol) 62.0g, 2,2- dihydromethyl propionic acid (DMPA) 10.68g, hydrogenation 4,4 '-dicyclohexyl methyl hydride diisocyanate
(H12MDI) 71.8g reacts 7 hours in N- ethyl pyrrolidones (NEP) 116.7g in 60 DEG C -90 DEG C.Urethane is anti-
NCO bases content at the end of answering is 0.18 mole.Reactant mixture is cooled into 80 DEG C, triethylamine (TEA) is added to
8.37g (being 1 equivalent relative to DMPA) is simultaneously mixed.Under strong agitation reactant mixture 341.5g is added into water 415.7g
In.Then, diethylenetriamines (DETA) aqueous solution 13.2g of 35 mass % is added to carry out chain extension.Further, 35 mass % are added
1,6- hexamethylene diamines (HMDA) aqueous solution 43.7g carry out chain extension, obtain aqueous polyurethane resin dispersion.DETA/HMDA=28/
72 (mol ratios).Total addition of DETA and HMDA is that 0.9 of the NCO base contents at the end of urethane reaction is worked as
Amount.
The molecular weight of resulting aqueous polyurethane resin dispersion is determined, as a result weight average molecular weight (Mw) is
346000.Solid component concentration is 30.3 mass %.The addition of each raw material is shown in table 1.
[comparative example 1]
In possessing the reaction unit of mixer and heater, in the presence of dibutyl tin laurate 0.2g, in nitrogen
Under atmosphere, (Yu Buxingchan companies manufacture to make ETERNACOLL (registration mark) UH-300；Number-average molecular weight 3000；Hydroxyl value
37.4mgKOH/g；Make 1,6-HD and carbonic ester carry out PCDL obtained from ester exchange reaction) 114.2g, three
(Yu Buxingchan companies manufacture hydroxymethyl-propane (molecular weight 134.2) 5.4g, ETERNACOLL (registration mark) UCC40-150；Number
Average molecular weight 1500；Hydroxyl value 72.1mgKOH/g；Mol ratio=4/6 of ester bond and carbonic acid ester bond；Make 1,4 cyclohexane dimethanol,
ε-hydroxycaproic ester and carbonic ester carry out PCDL obtained from ester exchange reaction) 71.6g, 2,2- dihydromethyl propionic acid
(DMPA) 14.08g, hydrogenation 4,4 '-dicyclohexyl methyl hydride diisocyanate (H12MDI) 96.4g are in N- ethyl pyrrolidones
(NEP) react 7 hours in 60 DEG C -90 DEG C in 122.4g.NCO bases content at the end of urethane reacts is rubbed for 0.26
You.Reactant mixture is cooled into 80 DEG C, triethylamine (TEA) 11.01g (being 1 equivalent relative to DMPA) is added to and is gone forward side by side
Row mixing.Reactant mixture 331.3g is added in water 460.7g under strong agitation.Then, two sub- second of 35 mass % are added
Base triamine (DETA) aqueous solution 13.2g carries out chain extension.Further, 1,6- hexamethylene diamines (HMDA) aqueous solution of 35 mass % is added
43.7g carries out chain extension, obtains aqueous polyurethane resin dispersion.DETA/HMDA=28/72 (mol ratio).DETA and HMDA's
Total addition is 0.9 equivalent of the NCO base contents at the end of urethane reaction.
There is gelation in reactant, it is impossible to obtain aqueous polyurethane resin dispersion.Solid component concentration is 28.7 matter
Amount %.The addition of each raw material is shown in table 1.
[comparative example 2]
In possessing the reaction unit of mixer and heater, in the presence of dibutyl tin laurate 0.2g, in nitrogen
Under atmosphere, (Yu Buxingchan companies manufacture to make ETERNACOLL (registration mark) UH-300；Number-average molecular weight 3000；Hydroxyl value
37.4mgKOH/g；Make 1,6-HD and carbonic ester carry out PCDL obtained from ester exchange reaction) 115.8g, three
(Yu Buxingchan companies manufacture hydroxymethyl-propane (molecular weight 134.2) 3.83g, ETERNACOLL (registration mark) UCC40-150；
Number-average molecular weight 1500；Hydroxyl value 72.1mgKOH/g；Mol ratio=4/6 of ester bond and carbonic acid ester bond；Make 1,4- hexamethylene diformazans
Alcohol, ε-hydroxycaproic ester and carbonic ester carry out PCDL obtained from ester exchange reaction) 70.0g, 2,2- dihydroxymethyl
Propionic acid (DMPA) 12.90g, hydrogenation 4,4 '-dicyclohexyl methyl hydride diisocyanate (H12MDI) 86.9g are in N- ethyl pyrrolidones
(NEP) react 7 hours in 60 DEG C -90 DEG C in 120.6g.NCO bases content at the end of urethane reacts is rubbed for 0.23
You.Reactant mixture is cooled into 80 DEG C, triethylamine (TEA) 10.22g (being 1 equivalent relative to DMPA) is added to and is gone forward side by side
Row mixing.Reactant mixture 352.1g is added in water 426.6g under strong agitation.Then, two sub- second of 35 mass % are added
Base triamine (DETA) aqueous solution 16.9g carries out chain extension.Further, 1,6- hexamethylene diamines (HMDA) aqueous solution of 35 mass % is added
49.8g carries out chain extension, obtains aqueous polyurethane resin dispersion.DETA/HMDA=28/72 (mol ratio).DETA and HMDA's
Total addition is 0.9 equivalent of the NCO base contents at the end of urethane reaction.
The molecular weight of resulting aqueous polyurethane resin dispersion is determined, as a result weight average molecular weight (Mw) is
379000.Solid component concentration is 30.1 mass %.The addition of each raw material is shown in table 1.
[comparative example 3]
In possessing the reaction unit of mixer and heater, in the presence of dibutyl tin laurate 0.2g, in nitrogen
Under atmosphere, (Yu Buxingchan companies manufacture to make ETERNACOLL (registration mark) UH-300；Number-average molecular weight 3000；Hydroxyl value
37.4mgKOH/g；Make 1,6-HD and carbonic ester carry out PCDL obtained from ester exchange reaction) 124.3g, three
(Yu Buxingchan companies manufacture hydroxymethyl-propane (molecular weight 134.2) 2.0g, ETERNACOLL (registration mark) UCC40-150；Number
Average molecular weight 1500；Hydroxyl value 72.1mgKOH/g；Mol ratio=4/6 of ester bond and carbonic acid ester bond；Make 1,4 cyclohexane dimethanol,
ε-hydroxycaproic ester and carbonic ester carry out PCDL obtained from ester exchange reaction) 74.0g, 2,2- dihydromethyl propionic acid
(DMPA) 11.97g, hydrogenation 4,4 '-dicyclohexyl methyl hydride diisocyanate (H12MDI) 81.0g are in N- ethyl pyrrolidones
(NEP) react 7 hours in 60 DEG C -90 DEG C in 120.6g.NCO bases content at the end of urethane reacts is rubbed for 0.21
You.Reactant mixture is cooled into 80 DEG C, triethylamine (TEA) 9.51g (being 1 equivalent relative to DMPA) is added to and is carried out
Mixing.Reactant mixture 352.7g is added in water 429.6g under strong agitation.Then, the diethylidene of 35 mass % is added
Triamine (DETA) aqueous solution 15.6g carries out chain extension.Further, 1,6- hexamethylene diamines (HMDA) aqueous solution 46.5g of 35 mass % is added
Chain extension is carried out, aqueous polyurethane resin dispersion is obtained.DETA/HMDA=28/72 (mol ratio).DETA and HMDA's is total
Addition is 0.9 equivalent of the NCO base contents at the end of urethane reaction.
The molecular weight of resulting aqueous polyurethane resin dispersion is determined, as a result weight average molecular weight (Mw) is
336000.Solid component concentration is 30.2 mass %.
[comparative example 4]
In possessing the reaction unit of mixer and heater, in the presence of dibutyl tin laurate 0.2g, in nitrogen
Under atmosphere, (Yu Buxingchan companies manufacture to make ETERNACOLL (registration mark) UH-300；Number-average molecular weight 3000；Hydroxyl value
37.4mgKOH/g；Make 1,6-HD and carbonic ester carry out PCDL obtained from ester exchange reaction) 122.0g, three
(Yu Buxingchan companies manufacture hydroxymethyl-propane (molecular weight 134.2) 3.98g, ETERNACOLL (registration mark) UCC40-150；
Number-average molecular weight 1500；Hydroxyl value 72.1mgKOH/g；Mol ratio=4/6 of ester bond and carbonic acid ester bond；Make 1,4- hexamethylene diformazans
Alcohol, ε-hydroxycaproic ester and carbonic ester carry out PCDL obtained from ester exchange reaction) 73.4g, 2,2- dihydroxymethyl
Propionic acid (DMPA) 10.20g, hydrogenation 4,4 '-dicyclohexyl methyl hydride diisocyanate (H12MDI) 80.4g are in N- ethyl pyrrolidones
(NEP) react 7 hours in 60 DEG C -90 DEG C in 120.1g.NCO bases content at the end of urethane reacts is rubbed for 0.21
You.Reactant mixture is cooled into 80 DEG C, triethylamine 8.08g is added to and is mixed.It is under strong agitation that reaction is mixed
Compound 208.3g is added in water 460g, enters water-filling extension.
Reactant condenses, it is impossible to obtain aqueous polyurethane resin dispersion.The addition of each raw material is shown in table 1.
[comparative example 5]
In possessing the reaction unit of mixer and heater, in the presence of dibutyl tin laurate 0.2g, in nitrogen
Under atmosphere, (Yu Buxingchan companies manufacture to make ETERNACOLL (registration mark) UH-300；Number-average molecular weight 3000；Hydroxyl value
37.4mgKOH/g；Make 1,6-HD and carbonic ester carry out PCDL obtained from ester exchange reaction) 116.8g, three
(Yu Buxingchan companies manufacture hydroxymethyl-propane (molecular weight 134.2) 3.75g, ETERNACOLL (registration mark) UCC40-150；
Number-average molecular weight 1500；Hydroxyl value 72.1mgKOH/g；Mol ratio=4/6 of ester bond and carbonic acid ester bond；Make 1,4- hexamethylene diformazans
Alcohol, ε-hydroxycaproic ester and carbonic ester carry out PCDL obtained from ester exchange reaction) 70.4g, 2,2- dihydroxymethyl
Propionic acid (DMPA) 11.18g, hydrogenation 4,4 '-dicyclohexyl methyl hydride diisocyanate (H12MDI) 81.8g are in N- ethyl pyrrolidones
(NEP) react 7 hours in 60 DEG C -90 DEG C in 119.4g.NCO bases content at the end of urethane reacts is rubbed for 0.22
You.Reactant mixture is cooled into 80 DEG C, triethylamine (TEA) 8.80g (being 1 equivalent relative to DMPA) is added to and is carried out
Mixing.Reactant mixture 330.2g is added in water 408.6g under strong agitation.Then, the diethylidene of 35 mass % is added
Triamine (DETA) aqueous solution 16.2g carries out chain extension.Further, 1,6- hexamethylene diamines (HMDA) aqueous solution 47.5g of 35 mass % is added
Chain extension is carried out, aqueous polyurethane resin dispersion is obtained.DETA/HMDA=28/72 (mol ratio).DETA and HMDA's is total
Addition is 0.9 equivalent of the NCO base contents at the end of urethane reaction.
The molecular weight of resulting aqueous polyurethane resin dispersion is determined, as a result weight average molecular weight (Mw) is
379000.Solid component concentration is 29.6 mass %.The addition of each raw material is shown in table 1.
[table 1]
| UH-300 | PPTL | UCC40-150 | TMP | DMPA | H12MDI | NEP | TEA | 35wt%DETA | 35wt%HMDA | DETA/HMDA | |
| Embodiment 1 | 120.1 | 10.1 | 69.9 | - | 10.6 | 72.0 | 117.7 | 8.4 | 13.2 | 43.7 | 28/72 |
| Embodiment 2 | 119.8 | 10.0 | 70.2 | - | 10.6 | 72.0 | 116.9 | 8.4 | 18.6 | 32.9 | 39/61 |
| Embodiment 3 | 120.3 | 10.1 | 70.0 | - | 10.6 | 72.0 | 116.9 | 8.4 | 8.0 | 44.8 | 17/83 |
| Embodiment 4 | 118.0 | 19.9 | 62.0 | - | 10.6 | 72.0 | 116.7 | 8.4 | 13.2 | 43.7 | 28/72 |
| Comparative example 1 | 114.2 | - | 71.6 | 5.4 | 14.1 | 96.4 | 122.4 | 11.0 | 13.2 | 43.7 | 28/72 |
| Comparative example 2 | 115.8 | - | 70.0 | 3.8 | 13.0 | 86.9 | 120.6 | 10.2 | 16.9 | 49.8 | 28/72 |
| Comparative example 3 | 124.3 | - | 74.0 | 2.0 | 12.0 | 81.0 | 120.6 | 9.5 | 15.6 | 46.5 | 28/72 |
| Comparative example 4 | 122.0 | - | 73.4 | 4.0 | 10.2 | 80.4 | 120.1 | 8.1 | - | - | - |
| Comparative example 5 | 116.6 | - | 70.4 | 3.8 | 11.2 | 81.8 | 119.4 | 8.8 | 16.2 | 47.5 | 28/72 |
Unit：G, DETA/HMDA mol ratio
[calculating of median particle diameter]
For each aqueous polyurethane resin dispersion obtained in embodiment 1～4 and comparative example 2,3,5, using hole field system
Make manufactured laser diffraction/scattering formula particle size distribution device LA-910, with volume reference 0.02 μm～1000 μm are determined
Scope size distribution, calculate median particle diameter.As a result it is shown in table 2.
[measure of viscosity]
For each aqueous polyurethane resin dispersion obtained in embodiment 1～4 and comparative example 2,3,5, make at 20 DEG C
It is measured with Brookfield viscometer.As a result it is shown in table 2.
[making of urethane resin film test film]
It is for about the mode of 0.10mm according to dried thickness, it is each by what is obtained in embodiment 1～4 and comparative example 2,3,5
Aqueous polyurethane resin dispersion is equably applied on glass plate.Next, after placing 16 hours at room temperature, it is dry at 60 DEG C
Dry 1 hour, and then in 120 DEG C of dryings 5 hours, afterwards peel off resulting urethane resin film from glass plate, carry out following
Evaluation.
[measure of elongation when tensile stress, maximum tensile stress, the cut-out of urethane resin film]
Urethane resin film to being made using said method carries out punching press, produces 1A types (JIS specified in ISO 37
No. 3 shapes of dumbbell shaped specified in K 6251) test film (between thickness 0.05mm～0.1mm, width 5mm, the graticule of parallel portion
Apart from 20mm), determined using force cell (" UR-500N-D " of the manufacture of ORIENTEC CORPORATION companies) above-mentioned
The elastic modelling quantity of urethane resin film, maximum point stress, breakaway poing elongation.It should be noted that condition determination is warm to determine
23 DEG C of degree, humidity 50%, draw speed 100mm/ minutes.As a result it is shown in table 2.
[table 2]
As shown in Table 2, the aqueous polyurethane resin dispersion of embodiment 1～4 divides with the waterborne polyurethane resin of comparative example
A prose style free from parallelism is compared, and polyurethane resin disperses as less particle, and viscosity is low, thus operability is excellent.
In addition, as shown in Table 2, the urethane resin film of embodiment 1～4 and the aqueous polyurethane resin dispersion of comparative example
Compare, elastic modelling quantity is low, thus flexibility is excellent, maximum point stress and breakaway poing elongation are big, thus define and extend
And it is difficult to broken urethane resin film.
[evaluation of the solvent resistance of urethane resin film]
Using the urethane resin film made by said method, the evaluation of solvent resistance has been carried out.In evaluation, make each molten
Agent is penetrated into absorbent cotton, and the absorbent cotton is placed in into film upper 0.5 hour, 2.0 hours, 24 hours, surface state to now film, is become
Color is visually observed, and is evaluated with 6 stages.Using ethanol (EtOH), isopropanol (IPA), toluene, acetone as molten
Agent, is evaluated.
Metewand is as described below.
“5”：Change is not observed completely.“4”：Heave or change colour in slightly film surface.“3”：Heave on slightly film surface
And discoloration.“2”：There is heaving or changing colour for a little film surface.“1”：There is heaving and changing colour for a little film surface.“0”：Film surface is molten
Solution.As a result it is shown in table 3.
[evaluation of the gloss of urethane resin film]
It is for about 50 μm of mode according to dried thickness, each water that will be obtained in embodiment 1～4 and comparative example 2,3,5
Property polyurethane resin dispersion homogeneous be applied to electro-deposition coating steel plate on.Next, after room temperature is placed 16 hours, 60
DEG C drying 1 hour, and then in 120 DEG C of dryings 5 hours, make test film.
For resulting test film, using micro-TRI-gloss (manufacture of BYK-Gardner companies), with specific
Determine angle (20 °, 60 °) and determine gloss.As a result it is shown in table 3.
[table 3]
As shown in Table 3, the gloss of the film of each embodiment and comparative example is same degree, and the surface state of the film at initial stage is obtained
Maintain.However, one will appreciate that, the film of embodiment is particularly in the harsh test using acetone, and solvent resistance is improved.
[making of synthetic leather smears]
(without delustring)
Relative to mass % of each aqueous polyurethane resin dispersion 100 obtained in embodiment 1～4 and comparative example 2,3,5,
Addition wetting agent (" BYK-302 " of the manufacture of Bi Ke chemical companies) 0.2 mass %, thickener be (Dow Chemical's manufacture
" RM-8W ") 0.2 mass %, mass % of ion exchange water 1, make the synthetic leather smears without delustring.
(having delustring)
Relative to mass % of each aqueous polyurethane resin dispersion 100 obtained in embodiment 1～4 and comparative example 2,3,5,
Additive (" BYK-302 " of the manufacture of Bi Ke chemical companies) 0.2 mass %, the thickener (" RM- of Dow Chemical's manufacture
8W ") 0.2 mass %, mass % of ion exchange water 1, delustering agent " the Art Pearl C-800 " of manufacture (Gen Shang industrial groups) 15
Quality %, delustering agent (" the ACEMATT OK607 " of the manufacture of Evonik Degussa companies) 0.2 mass %, are formed with delustring
Synthetic leather smears.
[making of coated synthetic leather test film]
According to the mode that dried thickness is 6 μm～7 μm, closed in commercially available polyurethane resin system using bar coater 10#
Surface into leather (black) is coated with the smears without delustring of above-mentioned making.Next, after placing 16 hours at room temperature,
150 DEG C of dryings 1 minute, make the synthetic leather test film without delustring.
According to the mode that dried thickness is 6 μm～7 μm, closed in commercially available polyurethane resin system using bar coater 10#
Surface into leather (black) is coated with the smears for having a delustring of above-mentioned making.Next, after placing 16 hours at room temperature,
150 DEG C of dryings 1 minute, are formed with the synthetic leather test film of delustring.
[evaluation of the flexibility of coated synthetic leather test film]
For synthetic leather test film obtained above, flexibility is have rated.
With regard to flexibility, have rated by hand sense of touch (black with uncoated commercially available polyurethane resin system synthetic leather
Color) flexibility difference.Evaluation of flexibility when identical with uncoated synthetic leather is set to " 5 ", flexibility more it is poor then
Score is lower.
[evaluation of the solvent resistance of coated synthetic leather test film]
With regard to solvent resistance, the test film for making ethanol penetrate into absorbent cotton is placed 24 hours, to synthetic leather now
Surface state has carried out visual valuation.
Metewand is as described below.
“5”：Change is not observed completely.“4”：Heave or change colour in slightly synthetic leather surface.“3”：Slightly synthesize skin
Leather surface is heaved and is changed colour.“2”：There is heaving or changing colour for a little synthetic leather surface.“1”：There is a little synthetic leather surface
Heave and change colour.“0”：Dissolve on synthetic leather surface.As a result it is shown in table 4.
[the sunproof evaluation of coated synthetic leather test film]
Light fastness test is carried out using the method according to ISO 105 (JIS L 0843 are also identical).Specifically, xenon lamp is made
(300nm～400nm) is 60W/m2, synthetic leather test film obtained above is carried out 300 hours irradiating, reach accumulated light
To 65MJ/m2.In addition, the temperature for making the test film in test is 89 ± 3 DEG C.
Metewand is as described below.
“5”：Change is not observed completely.“4”：The slightly coarse or discoloration on synthetic leather surface.“3”：Slightly synthesize skin
The coarse and discoloration on leather surface.“2”：There are the coarse of a little synthetic leather surface or discoloration.“1”：There is a little synthetic leather surface
It is coarse and discoloration.“0”：Synthetic leather surface becomes dressed in rags.As a result it is shown in table 4.
[measure of the gloss of coated synthetic leather test film (having delustring)]
For synthetic leather test film obtained above, using micro-TRI-gloss (manufacture of BYK-Gardner companies)
Gloss is determined to determine 60 ° of angle.
[table 4]
As shown in Table 4, with regard to flexibility and solvent resistance, the synthetic leather test film of each embodiment and the conjunction of each comparative example
Good result is in a ratio of into leather test film.
In addition, 60 ° of the urethane resin film of table 3 of gloss there is no difference, on the other hand, table 4 has delustring
60 ° of synthetic leather test film of gloss have differences.It follows that the smears of each embodiment with the addition of it is same amount of
In the case of delustering agent, compared with the situation of each comparative example, its extinction effect is excellent.
Claims (12)
1. a kind of aqueous polyurethane resin dispersion, the aqueous polyurethane resin dispersion is that polyurethane resin is scattered in water system Jie
In matter, the polyurethane resin is at least to make polyalcohol, the polyalcohol containing acidic-group, polyisocyanates and chain extender
Obtained from reaction,
The polyalcohol is 300 at least containing the high molecular weight diol and number-average molecular weight that number-average molecular weight is 1000～30000
～30000 HMW triol,
The chain extender contains the chemical combination in a molecule with more than 3 functional groups with NCO with reactivity
Thing.
2. aqueous polyurethane resin dispersion as claimed in claim 1, wherein, the quality of HMW triol is relative to high score
The ratio of the gross mass of son amount glycol and HMW triol is 1 mass %～30 mass %.
3. aqueous polyurethane resin dispersion as claimed in claim 1 or 2, wherein, chain extender contains and has in a molecule
There is the compound of more than 3 functional groups with NCO with reactivity and there is 2 and isocyanic acid in a molecule
Ester group has the compound of the functional group of reactivity.
4. the aqueous polyurethane resin dispersion as any one of claims 1 to 3, wherein, in chain extender, at one
There is the content of compound of more than 3 functional groups with NCO with reactivity relative in a molecule in molecule
In have more than 3 with NCO have reactivity functional group compound and in a molecule with 2 with it is different
Cyanic acid ester group has the ratio of the total content of the compound of the functional group of reactivity with molar ratio computing as 10：90～40：60.
5. the aqueous polyurethane resin dispersion as any one of Claims 1 to 4, wherein, HMW triol is poly-
Oxyalkylene triol.
6. aqueous polyurethane resin dispersion as claimed in claim 5, wherein, HMW triol is with propylene oxide list
HMW triol of the first and/or ethylene oxide unit as repetitive.
7. the aqueous polyurethane resin dispersion as any one of claim 1～6, wherein, high molecular weight diol is poly-
Carbonate diol.
8. a kind of synthetic leather smears, it contains the waterborne polyurethane resin dispersion any one of claim 1～7
Body.
9. a kind of synthetic leather, the synthetic leather at least has：Fiber base material；By bond layer or not by bond layer
Lamination is in the epidermal area of the fiber base material；With lamination in the coating layer of the epidermal area,
The coating layer is to be dried the smears described in claim 8.
10. a kind of manufacture method of synthetic leather, its usage right requires the waterborne polyurethane resin any one of 1～7
Dispersion forms epidermal area.
A kind of 11. urethane resin films, it is by the aqueous polyurethane resin dispersion any one of claim 1～7
It is dried.
A kind of 12. synthetic leathers, the urethane resin film described in its usage right requirement 11 is used as epidermal area.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-183051 | 2014-09-09 | ||
| JP2014183051 | 2014-09-09 | ||
| PCT/JP2015/075657 WO2016039396A1 (en) | 2014-09-09 | 2015-09-09 | Aqueous polyurethane-resin dispersion and uses thereof |
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| CN106687489A true CN106687489A (en) | 2017-05-17 |
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| Country | Link |
|---|---|
| JP (1) | JP6597624B2 (en) |
| CN (1) | CN106687489A (en) |
| WO (1) | WO2016039396A1 (en) |
Cited By (5)
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| CN111348937A (en) * | 2020-03-12 | 2020-06-30 | 颜绢英 | Preparation process of ceramic product |
| CN113072856A (en) * | 2021-04-07 | 2021-07-06 | 滁州金桥德克新材料有限公司无锡分公司 | Water-based paint for automotive interior leather |
| CN113166616A (en) * | 2018-12-03 | 2021-07-23 | 东洋纺株式会社 | Polyurethane resin having good adhesion to substrate and adhesive composition using same |
| CN113289045A (en) * | 2021-05-18 | 2021-08-24 | 长春工业大学 | Preparation of super-hydrophilic medical polyurethane foam dressing |
| CN113307932A (en) * | 2021-07-14 | 2021-08-27 | 四川轻化工大学 | Polyhydroxyacetic acid-based polyurethane and preparation method thereof |
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|---|---|---|---|---|
| JP2018062142A (en) * | 2016-10-14 | 2018-04-19 | 宇部興産株式会社 | Laminate and aqueous coating agent |
| JP7192353B2 (en) * | 2017-10-30 | 2022-12-20 | Dic株式会社 | Urethane resin composition, film, and synthetic leather |
| JP7167446B2 (en) * | 2018-02-02 | 2022-11-09 | 東ソー株式会社 | Aqueous polyurethane resin composition, artificial leather using said composition, surface treatment agent for leather |
| JP2019137789A (en) * | 2018-02-13 | 2019-08-22 | 東ソー株式会社 | Thermoplastic polyurethane resin composition, and molding including the resin composition |
| JP7135642B2 (en) * | 2018-09-19 | 2022-09-13 | 東ソー株式会社 | Solvent-free reaction-curable polyurethane resin composition, molding using said resin composition, and coating agent |
| JPWO2022244850A1 (en) * | 2021-05-19 | 2022-11-24 | ||
| JP7093461B1 (en) | 2021-12-13 | 2022-06-29 | 大日精化工業株式会社 | Water-based ink composition for front printing and articles with printing layer |
| WO2023157807A1 (en) * | 2022-02-15 | 2023-08-24 | 東ソー株式会社 | Polyurethane resin composition, artificial leather, synthetic leather, and leather surface treatment agent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003165950A (en) * | 2001-11-29 | 2003-06-10 | Mitsui Chemicals Inc | Aqueous coating material having excellent solvent resistance |
| JP2007092195A (en) * | 2005-09-27 | 2007-04-12 | Dai Ichi Kogyo Seiyaku Co Ltd | Aqueous resin composition for fiber laminate skin, method for producing fiber laminate, and synthetic leather |
| JP4361556B2 (en) * | 2005-09-27 | 2009-11-11 | 第一工業製薬株式会社 | Polyurethane resin aqueous dispersion composition for fiber laminate skin layer, method for producing fiber laminate and synthetic leather |
| JP5984240B2 (en) * | 2011-11-22 | 2016-09-06 | 旭化成株式会社 | Synthetic leather |
| WO2014103689A1 (en) * | 2012-12-25 | 2014-07-03 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and use of same |
-
2015
- 2015-09-09 CN CN201580048323.0A patent/CN106687489A/en active Pending
- 2015-09-09 WO PCT/JP2015/075657 patent/WO2016039396A1/en active Application Filing
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113166616A (en) * | 2018-12-03 | 2021-07-23 | 东洋纺株式会社 | Polyurethane resin having good adhesion to substrate and adhesive composition using same |
| CN113166616B (en) * | 2018-12-03 | 2023-02-03 | 东洋纺株式会社 | Polyurethane resin having good adhesion to substrate and adhesive composition using same |
| CN111348937A (en) * | 2020-03-12 | 2020-06-30 | 颜绢英 | Preparation process of ceramic product |
| CN111348937B (en) * | 2020-03-12 | 2021-03-26 | 福建省德化县腾艺陶瓷有限公司 | Preparation process of ceramic product |
| CN113072856A (en) * | 2021-04-07 | 2021-07-06 | 滁州金桥德克新材料有限公司无锡分公司 | Water-based paint for automotive interior leather |
| CN113289045A (en) * | 2021-05-18 | 2021-08-24 | 长春工业大学 | Preparation of super-hydrophilic medical polyurethane foam dressing |
| CN113289045B (en) * | 2021-05-18 | 2022-07-08 | 长春工业大学 | Preparation of super-hydrophilic medical polyurethane foam dressing |
| CN113307932A (en) * | 2021-07-14 | 2021-08-27 | 四川轻化工大学 | Polyhydroxyacetic acid-based polyurethane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6597624B2 (en) | 2019-10-30 |
| WO2016039396A1 (en) | 2016-03-17 |
| JPWO2016039396A1 (en) | 2017-06-22 |
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Application publication date: 20170517 |