CN109722918A - Polyurethane resin composition, overlay film and synthetic leather - Google Patents
Polyurethane resin composition, overlay film and synthetic leather Download PDFInfo
- Publication number
- CN109722918A CN109722918A CN201811256346.2A CN201811256346A CN109722918A CN 109722918 A CN109722918 A CN 109722918A CN 201811256346 A CN201811256346 A CN 201811256346A CN 109722918 A CN109722918 A CN 109722918A
- Authority
- CN
- China
- Prior art keywords
- polyurethane resin
- mass parts
- mentioned
- resin composition
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The problem to be solved by the present invention is to provide the polyurethane resin compositions of a kind of resistance to acidity of oil, low-temperature bending and mechanical strength.The present invention provides a kind of polyurethane resin composition, it is characterized in that, its contain chain extender (Y) using polyalcohol (X), with amino and polyisocyanates (Z) as must raw material polyurethane resin, above-mentioned polyalcohol (X) includes the polycarbonate polyol (A) using the glycol that carbon atom number is 8~11 as raw material of 1~50 mass %.In addition, the present invention provides: a kind of overlay film, which is characterized in that it is formed using above-mentioned polyurethane resin composition；And a kind of synthetic leather, which is characterized in that it has the overlay film.Polyurethane resin composition of the invention can be adapted to be used as material used in the manufacture of synthetic leather, dress material, support pads, grinding pad etc., may be particularly well suited for the material as synthetic leather.
Description
Technical field
The present invention relates to polyurethane resin compositions.
Background technique
Polyurethane resin is just being widely used in the various fields such as synthetic leather, processing and forming sheet material.Especially, in quilt
In the case where the component of the long-time services such as the synthetic leather for automobile interior materials, it is desirable that higher durability.
The assessment item of above-mentioned durability is varied, can enumerate heat resistance, humidity resistance, light resistance, chemically-resistant medicament
Property, wear resistance etc., in particular, in recent years to the resistance to acidity of oil of synthetic leather part requirement, resistance to sun-proof frequently contacted with human body
The chemically-resistants medicament such as oiliness.As excellent materials such as above-mentioned resistance to acidity of oil, such as disclose comprising polycarbonate-based poly- ammonia
The resin combination of ester resin, polyether system polyurethane resin and acrylic resin (for example, referring to patent document 1).
But the material as synthetic leather, above-mentioned resistance to acidity of oil etc. is not only needed, also to imagine makes in cold district
With and improve the demand levels of the bendability under low temperature, in addition it is also necessary to the excellent machine for obtaining excellent wear resistance
Tool intensity.But not yet find to have both the material of these characteristics at present.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2012-1693 bulletin
Summary of the invention
Subject to be solved by the invention
The problem to be solved by the present invention is to provide the poly- of a kind of resistance to acidity of oil, low-temperature bending and mechanical strength
Urethane resin combination.
The method used for solving the problem
The present invention provides a kind of polyurethane resin composition, which is characterized in that it contains with polyalcohol (X), has amino
Chain extender (Y) and polyisocyanates (Z) as must raw material polyurethane resin, above-mentioned polyalcohol (X) include 1 mass %~
50 mass % using carbon atom number be 8~11 glycol as raw material polycarbonate polyol (A).
In addition, the present invention provides: a kind of overlay film, which is characterized in that it is formed using above-mentioned polyurethane resin composition；
And a kind of synthetic leather, which is characterized in that it has the overlay film.
The effect of invention
Resistance to acidity of oil, low-temperature bending and the mechanical strength of polyurethane resin composition of the invention.
Therefore, polyurethane resin composition of the invention can be adapted to be used as synthetic leather, dress material, support pads, grinding pad
Deng manufacture used in material, the material of synthetic leather can be particularly suited for use as.
Specific embodiment
Polyurethane resin composition of the invention contains with polyalcohol (X), chain extender (Y) and polyisocyanic acid with amino
Polyurethane resin of the ester (Z) as necessary raw material, above-mentioned polyalcohol (X) is comprising 1~50 mass % with carbon atom number for 8~11
Polycarbonate polyol (A) of the glycol as raw material.
Above-mentioned polycarbonate polyol (A) is necessary ingredient especially in terms of obtaining excellent low-temperature bending.Separately
Outside, the usage amount of above-mentioned polycarbonate polyol (A) is necessary for 1~50 mass % in polyalcohol (X).If above-mentioned polycarbonate
The usage amount of polyalcohol (A) is lower than 1 mass % in above-mentioned polyalcohol (X), then can not obtain required low-temperature bending, separately
Outside, if more than 50 mass %, although sufficient low-temperature bending can be obtained, resistance to acidity of oil can not be obtained.As above-mentioned
The usage amount of polycarbonate polyol (A), from the viewpoint of sufficiently obtaining superior low-temperature bending and resistance to acidity of oil, more
It is preferred that the range for being 3~40 mass % in polyalcohol (X).
For the glycol for being 8~11 as the carbon atom number of the raw material of above-mentioned polycarbonate polyol (A), such as it can lift
Out: 2,4- dimethyl -1,5- pentanediol, 2,3- dimethyl -1,5- pentanediol, 2- ethyl -1,5- pentanediol, 2- methyl-1,6-
Hexylene glycol, 3- methyl-1,6- hexylene glycol, 1,7- nonanediol, 2- ethyl -1,6-HD, 2- methyl-1,7- nonanediol, 3- first
Base -1,7- nonanediol, 4- methyl-1,7- nonanediol, 1,8- ethohexadiol, 2- methyl-1, the carbon such as 8- ethohexadiol, 1,9- nonanediol are former
The glycol that subnumber is 8~9；2- methyl-1,8- ethohexadiol, 3- methyl-1,8- ethohexadiol, 4- methyl-1,8- ethohexadiol, 1,10-
Decanediol, 2- methyl-1,10- decanediol, 3- methyl-1,10- decanediol, 4- methyl-1,10- decanediol, 1,11- hendecane two
The glycol etc. that the carbon atom numbers such as alcohol are 10~11.These glycol can be used alone, and also two or more kinds may be used.
As the raw material of above-mentioned polycarbonate polyol (A), among above-mentioned, from obtaining superior resistance to acidity of oil, low
From the perspective of warm bendability and mechanical strength, the glycol of straight-chain and the glycol with branched structure is preferably used in combination.
As and with above-mentioned straight-chain glycol with branched structure glycol when the two molar ratio [(C8-C11
Straight chain)/(C8-C11 branch)], it is excellent from the viewpoint of obtaining superior resistance to acidity of oil, low-temperature bending and mechanical strength
It is selected as 10/90~90/10 range, more preferably 10/90~70/30 range.
About above-mentioned polycarbonate polyol (A), specifically, can be used makes the two of above-mentioned carbon atom number 8~11
Product obtained from alcohol is reacted with carbonic ester and/or phosgene as well known method.In addition, above-mentioned glycol can also basis
Need and and with carbon atom number be 2~7 glycol.As the use ratio for the glycol that carbon atom number is 8~11, preferably all
80 mass % or more, more preferably 90 mass % or more in glycol.
As above-mentioned carbonic ester, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, carbonic acid Asia second can be used for example
Ester, propylene carbonate etc..These compounds can be used alone, and also two or more kinds may be used.
As the number-average molecular weight of above-mentioned polycarbonate polyol (A), from obtaining superior mechanical strength and low temperature is curved
From the perspective of song, preferably 1500~3500 range.It should be noted that the number of above-mentioned polycarbonate polyol (A)
Average molecular weight indicates the value measured by gel permeation chromatography (GPC) method.
Above-mentioned polyalcohol (X) is used as essential component containing above-mentioned polycarbonate polyol (A), but can also contain as needed
There are other polyalcohols.
As above-mentioned other polyalcohols, it can be used for example: polycarbonate polyol other than above-mentioned (A), poly-
Ethoxylated polyhydric alcohol, polyester polyol, polyacrylic polyalcohol, polybutadiene polyol, hydrogenated butadiene polymer polyalcohol etc..These
Polyalcohol can be used alone, and also two or more kinds may be used.Among them, from by with above-mentioned polycarbonate polyol (A) simultaneously
With and from the perspective of obtaining superior resistance to acidity of oil, low-temperature bending and mechanical strength, it is preferable to use in addition to above-mentioned (A) with
Outer polycarbonate polyol.
As the polycarbonate polyol other than above-mentioned (A), it is not particularly limited as long as there is structural carbonate,
From the viewpoint of obtaining superior resistance to acidity of oil, low-temperature bending and mechanical strength, it is preferable to use for example with propylene glycol, fourth
Glycol, pentanediol, hexylene glycol, 3- methyl-1, the glycol that the carbon atom numbers such as 5- pentanediol, neopentyl glycol are 4~6 is as raw material
Polycarbonate polyol etc..In above-mentioned polycarbonate polyol, as diol component, other glycol can be used together, but above-mentioned
The use ratio of the glycol of carbon atom number 4~6 is preferably the 80 mass % or more, more preferably 90 mass % or more in glycol.
It is more excellent from obtaining as the usage amount in the case where the polycarbonate polyol used other than above-mentioned (A)
Resistance to acidity of oil, be preferably the model of 30~95 mass % in polyalcohol (X) from the perspective of low-temperature bending and mechanical strength
It encloses, more preferably the range of 55~90 mass %.
As the number-average molecular weight of above-mentioned other polyalcohols, go out from the viewpoint for making overlay film obtain good mechanical strength
Hair, preferably 600~50000 range are using the poly- carbonic acid other than above-mentioned (A) as above-mentioned other polyalcohols
In the case where ester polyol, from the viewpoint of obtaining superior resistance to acidity of oil, low-temperature bending and mechanical strength, number is equal
Molecular weight is preferably 1500~3500 range.It should be noted that the number-average molecular weight of above-mentioned others polyalcohol indicates logical
Cross value obtained from the measurement of gel permeation chromatography (GPC) method.
From the viewpoint of obtaining excellent mechanical strength and resistance to acidity of oil, the above-mentioned chain extender (Y) with amino is must
The ingredient of palpus.
The number-average molecular weight of the above-mentioned chain extender (Y) with amino is 50~550, be can be used for example: ethylenediamine, 1,2-
Propane diamine, 1,6- hexamethylene diamine, piperazine, 2,5- lupetazin, isophorone diamine, 1,2- cyclohexane diamine, 1,3-
Cyclohexane diamine, 1,4- cyclohexane diamine, 4,4 '-dicyclohexylmethane diamine, 3,3 '-dimethyl -4,4 '-dicyclohexyl methyl hydride
Diamines, hydrazine etc..These chain extenders can be used alone, and also two or more kinds may be used.Among them, from obtaining superior machine
, it is preferable to use the chain extender with alicyclic structure from the perspective of tool intensity and resistance to acidity of oil.
As the usage amount of above-mentioned chain extender (Y), from the viewpoint of obtaining excellent mechanical strength and resistance to acidity of oil,
Polyalcohol (X), chain extender (Y) and polyisocyanates (Z) total quality in, the preferably range of 1~15 mass %, more preferably
For the range of 3~10 mass %.
As above-mentioned polyisocyanates (Z), it can be used for example: 1,3- phenylene diisocyanate and Isosorbide-5-Nitrae-benzene diisocyanate
Ester, 1- methyl -2,4- phenylene diisocyanate, 1- methyl -2,6- phenylene diisocyanate, 1- methyl -2,5- phenylene diisocyanate, 1-
Methyl -2,6- phenylene diisocyanate, 1- methyl -3,5- phenylene diisocyanate, 1- ethyl -2,4- phenylene diisocyanate, 1- isopropyl
Base -2,4- phenylene diisocyanate, 1,3- dimethyl -2,4- phenylene diisocyanate, 1,3- dimethyl -4,6- phenylene diisocyanate,
1,4- dimethyl -2,5- phenylene diisocyanate, di-ethylbenzene diisocyanate, diisopropyl phenylene diisocyanate, methyl -3 1-,
5- di-ethylbenzene diisocyanate, 3- methyl-1,5- diethylbenzene -2,4- diisocyanate, 1,3,5- triethylbenzene -2,4- two
Isocyanates, naphthalene-1,4-disocyanate, naphthalene -1,5- diisocyanate, 1- methyl-naphthalene -1,5- diisocyanate, naphthalene -2,6-
Diisocyanate, naphthalene -2,7- diisocyanate, 1,1- dinaphthyl -2,2 '-diisocyanate, biphenyl -2,4 '-diisocyanate,
Biphenyl -4,4 '-diisocyanate, 3,3 '-dimethyl diphenyls -4,4 '-diisocyanate, 4,4 '-diphenylmethane diisocyanates
The aromatic polyisocyanates such as ester, 2,2 '-methyl diphenylene diisocyanates, diphenyl methane -2,4- diisocyanate；Four is sub-
Methyl diisocyanate, 1,5- pentamethylene diisocyanate, 1,6- hexamethylene diisocyanate, ten dimethylenes, two isocyanide
Acid esters, trimethyl hexamethylene diisocyanate, 1,3- cyclopentylene diisocyanate, 1,3- cyclohexylene diisocyanate,
1,4 cyclohexalene diisocyanate, 1,3- bis- (isocyanatomethyl) hexamethylene, 1,4- bis- (isocyanatomethyl) hexamethylene,
Lysine diisocyanate, isophorone diisocyanate, 4,4- dicyclohexyl methyl hydride diisocyanate, 2,4 '-dicyclohexyls
Methane diisocyanate, 2,2 '-dicyclohexyl methyl hydride diisocyanates, 3,3 '-dimethyl -4,4 '-dicyclohexyl methyl hydride two are different
The aliphatic such as cyanate or ester ring type polyisocyanates etc..These polyisocyanates can be used alone, also can be used together 2 kinds with
On.
As above-mentioned polyisocyanates (Z), from excellent low-temperature bending and polyurethane resin composition can be taken into account
From the perspective of screening characteristics, the aliphatic polyisocyante of 10 mass % or more, more preferably 10~50 mass % are preferably comprised
Range, further preferably contain in the range of 13~40 mass %.In addition, as above-mentioned polyisocyanates (Z), from energy
From the perspective of enough taking into account superior low-temperature bending and the screening characteristics of polyurethane resin composition, it is more that aliphatic is preferably used in combination
Isocyanates and ester ring type polyisocyanates.
As the usage amount of above-mentioned polyisocyanates (Z), from the viewpoint of obtaining excellent mechanical strength, reactivity,
Polyalcohol (X), chain extender (Y) and polyisocyanates (Z) total quality in, the preferably range of 7~60 mass % is more excellent
It is selected as the range of 10~45 mass %.
It as the manufacturing method of above-mentioned polyurethane resin, such as can enumerate: by by above-mentioned polyalcohol (X), above-mentioned chain extension
Agent (Y) and above-mentioned polyisocyanates (Z) put into together and make its react and the method that is manufactured, reaction for example preferably 30~
It is carried out 3~10 hours at a temperature of 100 DEG C.In addition, above-mentioned reaction can carry out in aftermentioned solvent.
As isocyanate group possessed by above-mentioned polyisocyanates (Z) relative to hydroxyl possessed by above-mentioned polyalcohol (X)
The molar ratio [(isocyanate group)/(hydroxyl and amino)] of amino possessed by base and above-mentioned chain extender (Y), preferably 0.6~2
Range, more preferably 0.8~1.2 range.
As the number-average molecular weight of polyurethane resin obtained from the method as more than, covered from can further improve
From the perspective of the mechanical strength and flexibility of film, preferably 5000~1000000 range, more preferably 10000~
500000 range.It should be noted that the number-average molecular weight of above-mentioned polyurethane resin indicates to pass through gel permeation chromatography (GPC)
It is worth obtained by method measurement.
Above-mentioned polyurethane resin composition contains above-mentioned polyurethane resin as essential component, but can also contain as needed
There are other ingredients.
As above-mentioned other ingredients, can be used for example: solvent, pigment, fire retardant, plasticizer, softening agent, stabilization
It is agent, wax, defoaming agent, dispersing agent, penetrant, surfactant, filler, mould inhibitor, antibacterial agent, ultraviolet absorbing agent, anti-oxidant
Agent, weathering stabilizers, fluorescent whitening agent, antiaging agent, thickener etc..These ingredients can be used alone, and also can be used together 2 kinds
More than.
As above-mentioned solvent, it can be used for example: water, n,N-Dimethylformamide, n,N-dimethylacetamide, N- first
The ketone solvents such as base -2-Pyrrolidone, methyl ethyl ketone, methyl n-propyl ketone, acetone, methyl iso-butyl ketone (MIBK)；Methyl formate, formic acid second
The ester solvents such as ester, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, sec-butyl acetate；Methanol,
Alcoholic solvents such as ethyl alcohol, isopropanol, butanol etc..These solvents can be used alone, and also two or more kinds may be used.
As the content of above-mentioned solvent, from the viewpoint of workability and viscosity, in polyurethane resin composition, preferably
For the range of 30~90 mass %.
Polyurethane resin composition of the invention is coated on substrate and is made it dry and obtains overlay film.
As above-mentioned base material, the fibrous substrate comprising non-woven fabrics, woven fabric, braided fabric etc. can be used for example；Resin film
Deng.As the substance for constituting above-mentioned fibrous substrate, can be used for example: polyester fiber, nylon fiber, acrylic fiber,
The chemical fibres such as polyurethane fiber, typel, rayon fiber, acid fiber by polylactic；Cotton, fiber crops, silk, wool, they mixed
Spin fiber etc..
As above-mentioned resin film, it can be used for example: polyethylene terephthalate film, polycarbonate membrane, acrylic acid
Resin film, COP (cyclic olefin polymer) film, TAC (triacetyl cellulose) film etc..
It can implement antistatic processing, demoulding processing, hydrophobic processing, water suction to the surface of above-mentioned substrate as needed
Processing, antibacterial deodourizing processing, antibacterial processing, ultraviolet light block the processing such as processing.
It as the method for being coated with polyurethane resin composition of the invention on above-mentioned substrate, such as can enumerate: utilize painting
The coating method of cloth device, bar coater, knife type coater, T- mould coating machine, roll coater etc..
As the method for keeping the above-mentioned polyurethane resin composition being applied dry, such as can enumerate at 50~140 DEG C
At a temperature of make it dry 30 seconds~10 minutes methods.
As the thickness of gained overlay film, suitably determined according to used purposes, for example, the model of 0.001~10mm
It encloses.
Go out in the case where being used for leather-like sheet from the viewpoint for obtaining superior wear resistance as above-mentioned overlay film
It sends out, 100% modulus obtained in tension test under conditions of crosshead speed is 10mm/ seconds is preferably 9MPa or more, more
The preferably range of 11~20MPa.It should be noted that the measuring method of above-mentioned 100% modulus value of above-mentioned overlay film is recorded in
In embodiment.
In the case where stating overlay film in use and obtaining synthetic leather, preferably using above-mentioned overlay film as the epidermis of synthetic leather
Layer or top coating.
As the manufacturing method of above-mentioned synthetic leather, such as can enumerate: by the surface-treated layer formed on processing release paper and
The method that above-mentioned overlay film is bonded by well known method.As the material of the above-mentioned surface-treated layer of formation, such as can make
With solvent system polyurethane resin, aqueous polyurethane resin, water system acrylic resin etc..In addition, above-mentioned fitting as needed may be used
To use well known bonding agent.
More than, resistance to acidity of oil, low-temperature bending and the mechanical strength of polyurethane resin composition of the invention.Cause
This, polyurethane resin composition of the invention can be adapted in the manufacture for being used as synthetic leather, dress material, support pads, grinding pad etc.
Used material can be particularly suited for use as the material of synthetic leather.
Embodiment
Hereinafter, the present invention is described in more detail using embodiment.
[embodiment 1]
In 4 mouthfuls of flasks through nitrogen displacement with blender, reflux condensing tube and thermometer, polycarbonate two is added
Alcohol (with 1,9- nonanediol (C9 straight chain) and 2- methyl-1,8- ethohexadiol (C9 branch) is used as raw material, [C9 straight chain/C9 branch] (with
Under be denoted as molar ratio)=65/35, number-average molecular weight: 2000, hereinafter referred to as " PC1 ") 10 mass parts, polycarbonate glycol (with
1,4-butanediol (C4) and 1,6- hexylene glycol (C6) are used as raw material, and [C4/C6] (being denoted as molar ratio below)=90/10, number are divided equally
Son amount: 2000, hereinafter referred to as " other PC1 ") 180 mass parts, polytetramethylene glycol (number-average molecular weight: 2000, following letter
It is denoted as " PTMG ") 10 mass parts, it is dehydrated at degree of pressure reduction 0.095MPa with 120~130 DEG C.After dehydration, while being cooled to
50 DEG C, n,N-Dimethylformamide (hereinafter referred to as " DMF ") 130 mass parts are added in side, are sufficiently stirred.After stirring, add
Enter 4,4 '-dicyclohexyl methyl hydride diisocyanates (hereinafter referred to as " H12MDI ") 33 mass parts, hexamethylene diisocyanate
0.1 mass parts of (hereinafter referred to as " HDI ") 9 mass parts and stannous octoate, react it at 75 DEG C, thus obtain at molecule end
Hold the organic solvent solution with the carbamate prepolymer of isocyanate group.Next, in above-mentioned carbamate pre-polymerization
328 mass parts of DMF, 153 mass parts of ethyl acetate are added in the organic solvent solution of object, are cooled to 35 DEG C, isophorone is added
Diamines (hereinafter referred to as " IPDA ") 12 mass parts, are stirred mixing, thus extend polyurethane resin.Next, being added
1 mass parts of N, N- dibutylamine, 153 mass parts of isopropanol, are mixed, thus obtain polyurethane resin composition.
[embodiment 2]
In 4 mouthfuls of flasks through nitrogen displacement with blender, reflux condensing tube and thermometer, polycarbonate two is added
Alcohol (with 1,9- nonanediol (C9 straight chain) and 2- methyl-1,8- ethohexadiol (C9 branch) is used as raw material, [C9 straight chain/C9 branch] (with
Under be denoted as molar ratio)=15/85, number-average molecular weight: 2000, hereinafter referred to as " PC2 ") 39 mass parts, other 156 mass of PC1
Part, it is dehydrated at degree of pressure reduction 0.095MPa with 120~130 DEG C.After dehydration, while being cooled to 50 DEG C, DMF 128 is added in side
Mass parts are sufficiently stirred.After stirring, 37 mass parts of H12MDI and 0.1 mass of 6 mass parts of HDI and stannous octoate is added
Part, its reaction is made at 75 DEG C, is thus obtained in the organic of carbamate prepolymer of the molecular end with isocyanate group
Solvent solution.Next, 324 mass parts of DMF, acetic acid are added in the organic solvent solution of the above urethane prepolymer
151 mass parts of ethyl ester are cooled to 35 DEG C, and 12 mass parts of IPDA are added, is stirred mixing, thus extends polyurethane resin.
Next, N is added, 1 mass parts of N- dibutylamine, 151 mass parts of isopropanol are mixed, thus obtain polyurethane resin group
Close object.
[embodiment 3]
In 4 mouthfuls of flasks through nitrogen displacement with blender, reflux condensing tube and thermometer, 167 matter of PC2 is added
Part, other 124 mass parts of PC1 are measured, is dehydrated at degree of pressure reduction 0.095MPa with 120~130 DEG C.After dehydration, side is cooling
To 50 DEG C, 124 mass parts of DMF are added in side, are sufficiently stirred.After stirring, isophorone diisocyanate (following letter is added
It is denoted as " IPDI ") 0.1 mass parts of 34 mass parts and 6 mass parts of HDI and stannous octoate, react it at 75 DEG C, thus
To the organic solvent solution of the carbamate prepolymer in molecular end with isocyanate group.Next, in above-mentioned amino
325 mass parts of DMF, 150 mass parts of ethyl acetate are added in the organic solvent solution of urethane prepolymer, is cooled to 35 DEG C, adds
Enter 4,4 '-dicyclohexylmethane diamine (hereinafter referred to as " H12MDA ") 18 mass parts, is stirred mixing, thus makes polyurethane
Resin elongation.Next, N is added, 1 mass parts of N- dibutylamine, 150 mass parts of isopropanol are mixed, thus obtain poly- ammonia
Ester resin composition.
[embodiment 4]
In 4 mouthfuls of flasks through nitrogen displacement with blender, reflux condensing tube and thermometer, 30 mass of PC1 is added
Part is (using 1,6-HD (C6) as raw material, [C6]=100, number-average molecular weight: 2000, hereinafter referred to as " other PC2 ") 170
Mass parts are dehydrated at degree of pressure reduction 0.095MPa with 120~130 DEG C.After dehydration, while being cooled to 50 DEG C, DMF is added in side
131 mass parts, are sufficiently stirred.After stirring, 32 mass parts of H12MDI and 13 mass parts of HDI and stannous octoate 0.1 is added
Mass parts, react it at 75 DEG C, thus obtain in carbamate prepolymer of the molecular end with isocyanate group
Organic solvent solution.Next, in the organic solvent solution of the above urethane prepolymer be added 331 mass parts of DMF,
154 mass parts of ethyl acetate are cooled to 35 DEG C, and 13 mass parts of IPDA are added, is stirred mixing, thus makes polyurethane resin
Elongation.Next, N is added, 1 mass parts of N- dibutylamine, 154 mass parts of isopropanol are mixed, thus obtain polyurethane tree
Oil/fat composition.
[embodiment 5]
In 4 mouthfuls of flasks through nitrogen displacement with blender, reflux condensing tube and thermometer, 29 mass of PC1 is added
Part, (with 1,4-butanediol (C4) and 1,6- hexylene glycol (C6) is used as raw material to polycarbonate glycol, and [C4/C6] (is denoted as mole below
Than)=70/30, number-average molecular weight: 2000, hereinafter referred to as " other PC3 ") 164 mass parts, at degree of pressure reduction 0.095MPa
It is dehydrated with 120~130 DEG C.After dehydration, while being cooled to 50 DEG C, 125 mass parts of DMF are added in side, are sufficiently stirred.It stirs
After mixing, 30 mass parts of IPDI and 0.1 mass parts of 10 mass parts of HDI and stannous octoate are added, its reaction is made at 75 DEG C, by
This obtains the organic solvent solution for the carbamate prepolymer for having isocyanate group in molecular end.Next, above-mentioned
330 mass parts of DMF, 152 mass parts of ethyl acetate are added in the organic solvent solution of carbamate prepolymer, are cooled to 35
DEG C, 19 mass parts of H12MDA are added, is stirred mixing, thus extends polyurethane resin.Next, N, bis- fourth of N- is added
1 mass parts of base amine, 152 mass parts of isopropanol, are mixed, thus obtain polyurethane resin composition.
[embodiment 6]
In 4 mouthfuls of flasks through nitrogen displacement with blender, reflux condensing tube and thermometer, 28 mass of PC2 is added
Part, other 159 mass parts of PC3, are dehydrated at degree of pressure reduction 0.095MPa with 120~130 DEG C.After dehydration, while being cooled to
50 DEG C, 122 mass parts of DMF are added in side, are sufficiently stirred.After stirring, 31 mass parts of IPDI and 8 mass parts of HDI are added
With 0.1 mass parts of stannous octoate, its reaction is made at 75 DEG C, thus obtains the amino first that there is isocyanate group in molecular end
The organic solvent solution of acid esters prepolymer.Next, DMF is added in the organic solvent solution of the above urethane prepolymer
320 mass parts, 147 mass parts of ethyl acetate are cooled to 35 DEG C, and 18 mass parts of H12MDA are added, are stirred mixing, thus
Extend polyurethane resin.Next, N is added, 1 mass parts of N- dibutylamine, 147 mass parts of isopropanol are mixed, thus
Obtain polyurethane resin composition.
[comparative example 1]
In 4 mouthfuls of flasks through nitrogen displacement with blender, reflux condensing tube and thermometer, 118 matter of PC1 is added
Part, other 78 mass parts of PC3 are measured, is dehydrated at degree of pressure reduction 0.095MPa with 120~130 DEG C.After dehydration, side is cooling
To 50 DEG C, 127 mass parts of DMF are added in side, are sufficiently stirred.After stirring, 31 mass parts of IPDI and 8 mass of HDI is added
Part and 0.1 mass parts of stannous octoate, react it at 75 DEG C, thus obtain the amino for having isocyanate group in molecular end
The organic solvent solution of urethane prepolymer.Next, being added in the organic solvent solution of the above urethane prepolymer
329 mass parts of DMF, 152 mass parts of ethyl acetate are cooled to 35 DEG C, and 17 mass parts of H12MDA are added, are stirred mixing,
Thus extend polyurethane resin.Next, N is added, 1 mass parts of N- dibutylamine, 152 mass parts of isopropanol are mixed,
Thus polyurethane resin composition is obtained.
[comparative example 2]
In 4 mouthfuls of flasks through nitrogen displacement with blender, reflux condensing tube and thermometer, other PC2 are added
190 mass parts are dehydrated at degree of pressure reduction 0.095MPa with 120~130 DEG C.After dehydration, while being cooled to 50 DEG C, side is added
127 mass parts of DMF, are sufficiently stirred.After stirring, 40 mass parts of H12MDI and 6 mass parts of HDI and stannous octoate is added
0.1 mass parts, react it at 75 DEG C, thus obtain the carbamate prepolymer for having isocyanate group in molecular end
Organic solvent solution.Next, 325 mass of DMF is added in the organic solvent solution of the above urethane prepolymer
Part, 151 mass parts of ethyl acetate are cooled to 35 DEG C, and 14 mass parts of IPDA are added, is stirred mixing, thus makes polyurethane tree
Rouge elongation.Next, N is added, 1 mass parts of N- dibutylamine, 151 mass parts of isopropanol are mixed, thus obtain polyurethane
Resin combination.
[comparative example 3]
In embodiment 1, polyurethane resin composition is not got similarly in addition to this using IPDA.
[measuring method of number-average molecular weight]
The number-average molecular weight of polyalcohol used in Examples and Comparative Examples etc. indicates to pass through gel permeation chromatography (GPC) method
The value measured under the following conditions.
Measurement device: high speed GPC device (TOSOH Co., Ltd's system " HLC-8220GPC ")
Column: following columns of TOSOH Co., Ltd are connected in series and are used.
" TSKgel G5000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G4000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G3000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G2000 " (7.8mmI.D. × 30cm) × 1 piece
Detector: RI (differential refractometer)
Column temperature: 40 DEG C
Eluent: tetrahydrofuran (THF)
Flow velocity: 1.0mL/ minutes
Injection rate: 100 μ L (tetrahydrofuran solution that sample solution concentration is 0.4 mass %)
Standard sample: standard curve is made using following standard polystyrens.
(standard polystyren)
TOSOH Co., Ltd's system " TSKgel standard polystyren A-500 "
TOSOH Co., Ltd's system " TSKgel standard polystyren A-1000 "
TOSOH Co., Ltd's system " TSKgel standard polystyren A-2500 "
TOSOH Co., Ltd's system " TSKgel standard polystyren A-5000 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-1 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-2 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-4 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-10 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-20 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-40 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-80 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-128 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-288 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-550 "
[measuring method of mechanical strength]
40 mass parts of DMF will be cooperated in 100 mass parts of polyurethane resin composition obtained in Examples and Comparative Examples
Made of fluid,matching be coated on flat processing release paper (Lintec Co. Ltd. system, " EK-100D ") so that the film thickness after dry at
It is 30 microns, is dried at 90 DEG C 2 minutes, further dried 2 minutes at 120 DEG C and make overlay film.Next, by resulting
Overlay film is cut to the short strip shape of width 5mm, length 50mm, uses (Co., Ltd. island cupping machine " AUTOGRAPH AG-I "
Saliva production is made), under 23 DEG C of temperature of atmosphere, stretched with the condition that crosshead speed is 10mm/ seconds, measurement test piece
100% modulus (MPa).Distance between chuck at this time is set as 40mm.It is evaluated as follows by resulting 100% modulus value mechanical strong
Degree.
" A ": 5MPa or more
" B ": less than 5MPa
[measuring method of resistance to acidity of oil]
Overlay film is made by method same as above-mentioned [measuring method of mechanical strength].Next, the overlay film is cut off
For width 5mm, length 50mm short strip shape and test piece, taken out after being impregnated 24 hours in oleic acid under room temperature, by surface
The oleic acid of attachment is gently wiped away with paper wiping cloth (rags).Then, using cupping machine " AUTOGRAPH AG-I " (Shimano Inc's system
Make made), it is that distance is drawn between 10mm/ seconds, chuck for the condition of 40mm with crosshead speed under 23 DEG C of temperature of atmosphere
It stretches, measurement test piece stretches stress when 100%.By the stress divided by measurement in above-mentioned [measuring method of mechanical strength]
Conservation rate of the value as 100% modulus value, evaluates resistance to acidity of oil as follows obtained by 100% modulus value.
" A ": conservation rate is 40% or more
" B ": conservation rate is 30% more than and less than 40%
" C ": conservation rate is less than 30%
[measuring method of low-temperature bending]
40 mass of DMF will be cooperated in 100 mass parts of polyurethane resin composition obtained in Examples and Comparative Examples
Fluid,matching made of colorant " ダ イ ラ ッ Network L-1770S " 20 mass parts of part, 30 mass parts of methyl ethyl ketone and the manufacture of DIC company
It is coated on processing release paper, so that the film thickness after dry becomes 30 microns, it is 2 minutes dry at 90 DEG C, further done at 120 DEG C
Dry 2 minutes, overlay film is made on processing release paper.Next, being coated with the polyurethane resin manufactured by DIC company on the overlay film
The polyisocyanate crosslinker of " CRISVON TA-205FT " 100 mass parts, 60 mass parts of DMF and the manufacture of DIC company
The cooperation that " Burnock DN-950 " 12 mass parts, tin catalyst " Accel T-81E " 1 mass parts of DIC company manufacture are constituted
Liquid makes it dry 1 minute so that the film thickness after dry becomes 60 microns at 100 DEG C.Next, mounting polyester base fabric, is used
It after 120 DEG C of laminating machine crimps it, is cured 3 days at 40 DEG C, removes processing release paper, obtain synthetic leather.
The synthetic leather is carried out with deflectometer (Co., Ltd.'s An Tianjing mechanism makees made, " deflectometer with cryostat, ")
Pliability test (- 30 DEG C, 100 times/per minute), measure synthetic leather surface rupture until number, following progress
Evaluation.
" A ": 20000 times or more
" B ": 10000 times more than and less than 20000 times
" C ": less than 10000 time
[table 1]
[table 2]
Abbreviation in table 1~2 is illustrated.
" Mn ": number-average molecular weight
" NCO ": polyisocyanates
Known to: the resistance to acidity of oil of polyurethane resin composition, that is, Examples 1 to 6, low-temperature bending and machinery of the invention
Excellent strength.Especially, although above-mentioned low-temperature bending is the very harsh test at -30 DEG C, have of the invention
The synthetic leather of the overlay film of polyurethane resin composition should not still rupture.
On the other hand, comparative example 1 is that the usage amount of polycarbonate polyol (A) exceeds the side of range given to this invention
Formula, mechanical strength and resistance to acidity of oil are bad.
Comparative example 2 is the mode without using polycarbonate polyol (A), and resistance to acidity of oil and low-temperature bending are insufficient.
Comparative example 3 is without the mode using the chain extender (Y) with amino, and mechanical strength and resistance to acidity of oil are bad.
Claims (8)
1. a kind of polyurethane resin composition, which is characterized in that its contain with polyalcohol (X), the chain extender (Y) with amino and
Polyisocyanates (Z) as must raw material polyurethane resin, the polyalcohol (X) include 1 mass of mass %~50 % with
Polycarbonate polyol (A) of the glycol that carbon atom number is 8~11 as raw material.
2. polyurethane resin composition according to claim 1, wherein the glycol in the polycarbonate polyol (A)
Glycol comprising straight-chain and the glycol with branched structure.
3. polyurethane resin composition according to claim 2, wherein the glycol of the straight-chain has branch with described
The range that the molar ratio of the glycol of structure, i.e. (C8-C11 straight chain)/(C8-C11 branch) are 10/90~90/10.
4. polyurethane resin composition described in any one of claim 1 to 3, wherein the polycarbonate polyol
(A) range that number-average molecular weight is 1500~3500.
5. polyurethane resin composition according to any one of claims 1 to 4, wherein the polyalcohol (X) is also contained
Using the glycol that carbon atom number is 4~6 as the polycarbonate polyol (B) of raw material.
6. polyurethane resin composition according to any one of claims 1 to 5, wherein the polyisocyanates (Z) contains
There is the aliphatic polyisocyante of 10 mass % or more.
7. a kind of overlay film, which is characterized in that its using the polyurethane resin composition described in any one of claim 1~6 and
It is formed.
8. a kind of synthetic leather, which is characterized in that it is with overlay film as claimed in claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017209204 | 2017-10-30 | ||
| JP2017-209204 | 2017-10-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109722918A true CN109722918A (en) | 2019-05-07 |
| CN109722918B CN109722918B (en) | 2022-09-02 |
Family
ID=66295436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811256346.2A Active CN109722918B (en) | 2017-10-30 | 2018-10-26 | Polyurethane resin composition, coating film, and synthetic leather |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7192353B2 (en) |
| CN (1) | CN109722918B (en) |
| TW (1) | TWI822704B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113840856A (en) * | 2019-05-14 | 2021-12-24 | Dic株式会社 | Urethane resin composition and synthetic leather |
| CN114599701A (en) * | 2019-10-28 | 2022-06-07 | Dic株式会社 | Urethane resin composition, adhesive, and synthetic leather |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022097333A1 (en) * | 2020-11-05 | 2022-05-12 | Dic株式会社 | Laminate and synthetic leather |
| EP4241988A4 (en) * | 2020-11-05 | 2024-09-18 | Dainippon Ink & Chemicals | Laminate and synthetic leather |
Citations (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03234813A (en) * | 1989-02-03 | 1991-10-18 | Asahi Chem Ind Co Ltd | Production of copolycarbonate-based urethane elastic fiber |
| JPH05272072A (en) * | 1992-03-24 | 1993-10-19 | Kuraray Co Ltd | Leathery sheet-like material |
| JPH07179554A (en) * | 1993-12-22 | 1995-07-18 | Kuraray Co Ltd | Polyurethane and its production |
| JP2001323042A (en) * | 2000-05-17 | 2001-11-20 | Ube Ind Ltd | Segmented polyurethane having high stiffness and high elongation |
| JP2002347057A (en) * | 2001-05-25 | 2002-12-04 | Nhk Spring Co Ltd | Manufacturing method of thermoplastic polyurethane foam |
| WO2005049685A1 (en) * | 2003-11-18 | 2005-06-02 | Sanyo Chemical Industries Ltd. | Polyurethane resin for artificial leather and porous sheet material |
| JP2005171228A (en) * | 2003-11-18 | 2005-06-30 | Sanyo Chem Ind Ltd | Polyurethane resin composition for synthetic leather and porous sheet material |
| JP2006022227A (en) * | 2004-07-08 | 2006-01-26 | Bando Chem Ind Ltd | Polyurethane and belt for electrophotographic device |
| JP2006096852A (en) * | 2004-09-29 | 2006-04-13 | Sanyo Chem Ind Ltd | Aqueous polyurethane resin emulsion |
| WO2007105713A1 (en) * | 2006-03-16 | 2007-09-20 | Showa Denko K.K. | Heat curable resin composition, overcoating agent for flexible circuit board, and surface protective film |
| JP2008106415A (en) * | 2006-09-28 | 2008-05-08 | Toray Ind Inc | Sheet body |
| JP2011063696A (en) * | 2009-09-16 | 2011-03-31 | Ube Industries Ltd | Modified urethane resin curable composition and cured product thereof |
| CN102272186A (en) * | 2009-01-20 | 2011-12-07 | 昭和电工株式会社 | (Poly)carbonate polyol and carboxyl group-containing polyurethane using the (poly)carbonate polyol as starting material |
| CN102307921A (en) * | 2009-02-06 | 2012-01-04 | 宇部兴产株式会社 | Polyurethane resin aqueous dispersion and manufacturing method thereof |
| JP2013033131A (en) * | 2011-08-02 | 2013-02-14 | Tokuyama Corp | Photochromic laminate and production method of the same |
| WO2014104134A1 (en) * | 2012-12-26 | 2014-07-03 | 三菱化学株式会社 | Polycarbonate diol and polyurethane using same |
| WO2015015889A1 (en) * | 2013-07-29 | 2015-02-05 | 東洋紡株式会社 | Carboxyl group-containing polyester and thermosetting resin composition comprising same |
| WO2015098271A1 (en) * | 2013-12-25 | 2015-07-02 | Dic株式会社 | Porous body and polishing pad |
| JP2015143316A (en) * | 2013-04-22 | 2015-08-06 | 三菱化学株式会社 | Polycarbonate diol and method of producing the same, and polyurethane using the same |
| WO2016039396A1 (en) * | 2014-09-09 | 2016-03-17 | 宇部興産株式会社 | Aqueous polyurethane-resin dispersion and uses thereof |
| WO2016039395A1 (en) * | 2014-09-09 | 2016-03-17 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, and polyurethane resin film and synthetic leather obtained using same |
| WO2016063761A1 (en) * | 2014-10-24 | 2016-04-28 | 東レ株式会社 | Sheet-like article |
| WO2016063685A1 (en) * | 2014-10-20 | 2016-04-28 | Dic株式会社 | Adhesive composition and adhesive sheet |
| JP2016084463A (en) * | 2014-10-24 | 2016-05-19 | 三洋化成工業株式会社 | Polyurethane resin aqueous dispersion |
| JP2016121211A (en) * | 2014-12-24 | 2016-07-07 | Dic株式会社 | Urethane resin composition, and leather-like sheet |
| CN106905503A (en) * | 2015-12-21 | 2017-06-30 | Dic株式会社 | Polyurethane resin composition and synthetic leather |
| WO2017115549A1 (en) * | 2015-12-28 | 2017-07-06 | 日華化学株式会社 | Aqueous-dispersion type polycarbonate-based polyurethane resin composition, textile product treated with same, and process for producing aqueous-dispersion type polycarbonate-based polyurethane resin composition |
| CN107208363A (en) * | 2015-03-03 | 2017-09-26 | Dic株式会社 | The manufacture method of leather-like sheet |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6323205B2 (en) * | 2014-06-23 | 2018-05-16 | 三菱ケミカル株式会社 | Polyurethane for synthetic leather |
-
2018
- 2018-09-26 JP JP2018180232A patent/JP7192353B2/en active Active
- 2018-10-19 TW TW107136900A patent/TWI822704B/en active
- 2018-10-26 CN CN201811256346.2A patent/CN109722918B/en active Active
Patent Citations (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03234813A (en) * | 1989-02-03 | 1991-10-18 | Asahi Chem Ind Co Ltd | Production of copolycarbonate-based urethane elastic fiber |
| JPH05272072A (en) * | 1992-03-24 | 1993-10-19 | Kuraray Co Ltd | Leathery sheet-like material |
| JPH07179554A (en) * | 1993-12-22 | 1995-07-18 | Kuraray Co Ltd | Polyurethane and its production |
| JP2001323042A (en) * | 2000-05-17 | 2001-11-20 | Ube Ind Ltd | Segmented polyurethane having high stiffness and high elongation |
| JP2002347057A (en) * | 2001-05-25 | 2002-12-04 | Nhk Spring Co Ltd | Manufacturing method of thermoplastic polyurethane foam |
| JP2005171228A (en) * | 2003-11-18 | 2005-06-30 | Sanyo Chem Ind Ltd | Polyurethane resin composition for synthetic leather and porous sheet material |
| WO2005049685A1 (en) * | 2003-11-18 | 2005-06-02 | Sanyo Chemical Industries Ltd. | Polyurethane resin for artificial leather and porous sheet material |
| JP2006022227A (en) * | 2004-07-08 | 2006-01-26 | Bando Chem Ind Ltd | Polyurethane and belt for electrophotographic device |
| JP2006096852A (en) * | 2004-09-29 | 2006-04-13 | Sanyo Chem Ind Ltd | Aqueous polyurethane resin emulsion |
| WO2007105713A1 (en) * | 2006-03-16 | 2007-09-20 | Showa Denko K.K. | Heat curable resin composition, overcoating agent for flexible circuit board, and surface protective film |
| JP2008106415A (en) * | 2006-09-28 | 2008-05-08 | Toray Ind Inc | Sheet body |
| CN102272186A (en) * | 2009-01-20 | 2011-12-07 | 昭和电工株式会社 | (Poly)carbonate polyol and carboxyl group-containing polyurethane using the (poly)carbonate polyol as starting material |
| CN102307921A (en) * | 2009-02-06 | 2012-01-04 | 宇部兴产株式会社 | Polyurethane resin aqueous dispersion and manufacturing method thereof |
| JP2011063696A (en) * | 2009-09-16 | 2011-03-31 | Ube Industries Ltd | Modified urethane resin curable composition and cured product thereof |
| JP2013033131A (en) * | 2011-08-02 | 2013-02-14 | Tokuyama Corp | Photochromic laminate and production method of the same |
| WO2014104134A1 (en) * | 2012-12-26 | 2014-07-03 | 三菱化学株式会社 | Polycarbonate diol and polyurethane using same |
| JP2015143316A (en) * | 2013-04-22 | 2015-08-06 | 三菱化学株式会社 | Polycarbonate diol and method of producing the same, and polyurethane using the same |
| WO2015015889A1 (en) * | 2013-07-29 | 2015-02-05 | 東洋紡株式会社 | Carboxyl group-containing polyester and thermosetting resin composition comprising same |
| WO2015098271A1 (en) * | 2013-12-25 | 2015-07-02 | Dic株式会社 | Porous body and polishing pad |
| WO2016039396A1 (en) * | 2014-09-09 | 2016-03-17 | 宇部興産株式会社 | Aqueous polyurethane-resin dispersion and uses thereof |
| WO2016039395A1 (en) * | 2014-09-09 | 2016-03-17 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, and polyurethane resin film and synthetic leather obtained using same |
| WO2016063685A1 (en) * | 2014-10-20 | 2016-04-28 | Dic株式会社 | Adhesive composition and adhesive sheet |
| WO2016063761A1 (en) * | 2014-10-24 | 2016-04-28 | 東レ株式会社 | Sheet-like article |
| JP2016084463A (en) * | 2014-10-24 | 2016-05-19 | 三洋化成工業株式会社 | Polyurethane resin aqueous dispersion |
| JP2016121211A (en) * | 2014-12-24 | 2016-07-07 | Dic株式会社 | Urethane resin composition, and leather-like sheet |
| CN107208363A (en) * | 2015-03-03 | 2017-09-26 | Dic株式会社 | The manufacture method of leather-like sheet |
| CN106905503A (en) * | 2015-12-21 | 2017-06-30 | Dic株式会社 | Polyurethane resin composition and synthetic leather |
| WO2017115549A1 (en) * | 2015-12-28 | 2017-07-06 | 日華化学株式会社 | Aqueous-dispersion type polycarbonate-based polyurethane resin composition, textile product treated with same, and process for producing aqueous-dispersion type polycarbonate-based polyurethane resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113840856A (en) * | 2019-05-14 | 2021-12-24 | Dic株式会社 | Urethane resin composition and synthetic leather |
| CN114599701A (en) * | 2019-10-28 | 2022-06-07 | Dic株式会社 | Urethane resin composition, adhesive, and synthetic leather |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI822704B (en) | 2023-11-21 |
| JP2019081883A (en) | 2019-05-30 |
| CN109722918B (en) | 2022-09-02 |
| JP7192353B2 (en) | 2022-12-20 |
| TW201922832A (en) | 2019-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109722918A (en) | Polyurethane resin composition, overlay film and synthetic leather | |
| KR101966579B1 (en) | Aqueous urethane resin composition and synthetic leather | |
| EP3029110B1 (en) | Leather-like sheet | |
| KR102642770B1 (en) | Urethane resin composition, film, and synthetic leather | |
| JP6780492B2 (en) | Urethane resin composition, film, and leather-like sheet | |
| TW201829876A (en) | Synthetic leather | |
| KR20200036902A (en) | Synthetic Leather | |
| JP4878519B2 (en) | Polyurethane emulsion for artificial leather and artificial leather | |
| JP2021195376A (en) | Polyurethane resin composition, film, and artificial leather | |
| KR20200140898A (en) | Synthetic Leather | |
| JP6528915B1 (en) | Urethane resin composition, film, and synthetic leather | |
| JP2020105445A (en) | Aqueous polyurethane resin, method for manufacturing the same, aqueous polyurethane resin composition and leather material | |
| CN108348019B (en) | Gloves | |
| JP6828854B1 (en) | Urethane resin composition and synthetic leather | |
| KR20210002551A (en) | Synthetic Leather | |
| JP7095816B2 (en) | Urethane resin composition, film, and synthetic leather | |
| JP2020059928A (en) | Resin film and fiber cloth and fiber product obtained by laminating the same | |
| JP2024046144A (en) | Polyurethane for synthetic leather and synthetic leather | |
| TW202144447A (en) | Carbamate resin composition and synthetic leather characterized by comprising a carbamate resin that uses a polyol containing a polycarbonate polyol, a chain extender other than the polyol and a polyisocyanate as essential raw materials | |
| JP2022154112A (en) | Synthetic leather |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |