CN109963980A - Synthetic leather - Google Patents
Synthetic leather Download PDFInfo
- Publication number
- CN109963980A CN109963980A CN201780070043.9A CN201780070043A CN109963980A CN 109963980 A CN109963980 A CN 109963980A CN 201780070043 A CN201780070043 A CN 201780070043A CN 109963980 A CN109963980 A CN 109963980A
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- China
- Prior art keywords
- hot melt
- mentioned
- synthetic leather
- polyalcohol
- carbamate prepolymer
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/40—High-molecular-weight compounds
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1692—Weather resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a kind of synthetic leather, it is characterized in that, it has the layer formed by the wet-cured type polyurethane-hot melt resin combination containing hot melt carbamate prepolymer (i), and hot melt carbamate prepolymer (i) is the reactant of the polyalcohol (A) comprising alicyclic polyester polyalcohol (a1) and polyisocyanates (B).Above-mentioned polyalcohol (A) preferably also includes polyoxypropylene glycol (a2).Above-mentioned wet-cured type polyurethane-hot melt resin combination preferably also contains hindered amine compound (ii), triazole compounds (iii).The weatherability and adhesive strength of synthetic leather of the invention are excellent, can be suitable as split leather.
Description
Technical field
The present invention relates to the synthetic leathers of the solidified material layer with wet-cured type polyurethane-hot melt resin combination.
Background technique
Wet-cured type polyurethane-hot melt resin combination is used extensively because mechanical strength, flexibility, cementability etc. are excellent
In manufacture synthetic leather.Wherein, have the appearance, quality and natural leather phase of the split leather of double-layer fur, adhesive layer and epidermis
Closely, therefore, the price along with natural leather in recent years is surging, and demand is also increasing.
As the resin combination for the adhesive layer for forming above-mentioned split leather, disclose for example comprising aliphatic polyester is polynary
Alcohol etc. is used as the composition of the hot melt carbamate prepolymer of raw material (referring for example to patent document 1).
However, seeking further increasing for adhesive strength for the composition.In addition, used on the way in split leather,
In recent years from the viewpoint of design, the epidermis of various colours is used sometimes, for example, the case where using light epidermis
Under, in order not to damage beauty, the excellent weather resistance that time dependent discoloration does not occur is also sought to for adhesive layer.However, actual conditions
It is the material that not yet discovery has both excellent weather resistance and adhesive strength.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2009-297985 bulletin
Summary of the invention
Problems to be solved by the invention
Project to be solved by this invention is to provide the wet-cured type polyurethane heat excellent with weatherability and adhesive strength
The synthetic leather of the solidified material layer of cladding resin composition.
Means for solving the problems
The present invention provides a kind of synthetic leather, which is characterized in that it has by containing hot melt carbamate prepolymer (i)
The layer that is formed of wet-cured type polyurethane-hot melt resin combination, the hot melt carbamate prepolymer (i) is includes alicyclic ring
The polyalcohol (A) of formula polyester polyol (a1) and the reactant of polyisocyanates (B).
The effect of invention
Synthetic leather of the invention has the layer that adhesive strength (especially initial bond strenght) is strong and has excellent weather resistance.
Specific embodiment
Synthetic leather of the invention has by the wet-cured type polyurethane-hot melt containing hot melt carbamate prepolymer (i)
The layer that resin combination is formed, hot melt carbamate prepolymer (i) are to include the more of alicyclic polyester polyalcohol (a1)
The reactant of first alcohol (A) and polyisocyanates (B).
Above-mentioned alicyclic polyester polyalcohol (a1) be from obtain excellent weatherability and adhesive strength consider necessary at
Point.Consider from excellent initial bond strenght is obtained, usually using using the aromatic compound of phthalic acid etc as original
The aromatic polyester polyol of material.However, using aromatic polyester polyol, especially because sunlight through when
It irradiates and there are problems that changing colour.It on the other hand,, can by using alicyclic polyester polyalcohol (a1) in the present invention
Obtain based on cohesiveness good initial strength and weatherability (especially even if sunlight through when irradiate under resistance to discoloration
Performance) excellent solidified material layer.It should be noted that showing in the embodiment of the present invention using equipped with most loyal simulation
The UVA-340 lamp of the i.e. 295~365nm in short wavelength region of sunlight, QUV promotion weathering tester (Q-LAB
Corporation system) result of atmospheric exposure test that is carried out.
As above-mentioned alicyclic polyester polyalcohol (a1), the ester ring type chemical combination for example with 2 or more hydroxyls can be enumerated
The reactant of the reactant of object and aliphatic polybasic acids, the aliphatic compound with 2 or more hydroxyls and ester ring type polyacid
Deng.It should be noted that the reactant can be obtained by well known esterification.
As the above-mentioned ester ring type compound with 2 or more hydroxyls, such as pentamethylene glycol, hexamethylene two can be used
Alcohol, cyclohexanedimethanol, hydrogenated bisphenol A, their alkylene oxide addition product etc..These compounds can be used alone, can also be with
Two or more is applied in combination.Among these, from the viewpoint of it can obtain superior weatherability and adhesive strength, preferably make
Use cyclohexanedimethanol.
As above-mentioned aliphatic polybasic acids, can be used for example succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid,
Decanedioic acid, decane diacid, dodecanedioic acid, eicosane diacid, citraconic acid, itaconic acid, citraconic anhydride, itaconic anhydride etc..These
Compound may be used singly or in combination of two or more.
As the above-mentioned aliphatic compound with 2 or more hydroxyls, can be used for example ethylene glycol, 1,3-PD,
1,4-butanediol, 1,5-PD, 1,6- hexylene glycol, 1,7- heptandiol, 1,8- ethohexadiol, 1,9- nonanediol, 1, the 10- last of the ten Heavenly stems two
Alcohol, 1,12- dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1,3-BDO, 2,2- diethyl-
1,3-PD, 2,2- diethylpropanediol, 3- methyl-1,5- pentanediol, 2- ethyl -2- butyl -1,3-PD, 2- first
The chemical combination such as base -1,8- ethohexadiol, 2,4- diethyl -1,5-PD, trimethylolethane, trimethylolpropane, pentaerythrite
Object.These compounds may be used singly or in combination of two or more.It is superior resistance to from that can obtain among these
, it is preferable to use 1,6- hexylene glycol, 1 from the perspective of time property and adhesive strength, 8- ethohexadiol, 1,10- decanediol, neopentyl glycol,
3- methyl-1,5- pentanediol further increase cohesiveness from and with branched structure, can obtain superior weather-proof
From the perspective of property and adhesive strength, more preferably neopentyl glycol and/or 3- methyl-1,5- pentanediol.
As above-mentioned ester ring type polyacid, can be used for example cyclohexane dicarboxylic acid, cyclopentane dicarboxylic acid, hexamethylene two oneself
Two acid esters etc..These compounds may be used singly or in combination of two or more.It is more excellent from that can obtain among these
, it is preferable to use two adipate ester of cyclohexane dicarboxylic acid and/or hexamethylene from the perspective of different weatherability and adhesive strength.
As the number-average molecular weight of above-mentioned alicyclic polyester polyalcohol (a1), from superior weatherability and viscous can be obtained
From the perspective of connecing intensity, preferably 400~10000 range, more preferably 500~5000 range, further preferably
600~3000 range.It should be noted that the number-average molecular weight expression of above-mentioned alicyclic polyester polyalcohol (a1) passes through gel
Value measured by permeation chromatography (GPC) method.
As the content of above-mentioned alicyclic polyester polyalcohol (a1), from superior weatherability and adhesive strength can be obtained
From the perspective of, it is preferably 10 mass % or more, the preferably range of 20~80 mass %, more excellent in above-mentioned polyalcohol (A)
It is selected as the range of 30~70 mass %, the range of further preferably 30~50 mass %.
It is other as being able to use other than above-mentioned alicyclic polyester polyalcohol (a1) as above-mentioned polyalcohol (A)
Polyalcohol can be used the polyester polyol for example other than above-mentioned alicyclic polyester polyalcohol (a1), polyether polyol, gather
Carbonate polyol, polybutadiene polyol, dimer diol, acrylic polyol etc..These polyalcohols can individually make
With two or more can also be applied in combination.Among these, when being applied in combination with above-mentioned alicyclic polyester polyalcohol (a1), from energy
It is enough to mitigate the high viscosity for being originated from above-mentioned (a1), the coating realized by lowering viscousity is improved, can be improved the beauty of split leather
, it is preferable to use polyether polyol, more preferably polyoxypropylene glycol (a2) from the perspective of sight and manufacture stability.
As content when using above-mentioned polyoxypropylene glycol (a2), from maintaining weatherability and adhesive strength and can be into one
It walks from the perspective of improving low viscosity, is preferably the range of 5~90 mass % in polyalcohol (A), is more preferably 10~80
The range of the range of quality %, further preferably 30~70 mass %.
In addition, when using polyoxypropylene glycol (a2), from weatherability, adhesive strength and low viscosity can be further increased
From the perspective of the balance of property, aliphatic polyester polyols and/or polytetramethylene glycol is preferably applied in combination.
As the number-average molecular weight of above-mentioned other polyalcohols, from the standpoint of mechanical strength, preferably 500~10000
Range, more preferably 700~5000 range.In addition, using polyoxypropylene glycol (a2) as above-mentioned other polyalcohols
In the case where, as its number-average molecular weight, from the viewpoint of it can further increase low viscosity, preferably 1100~5000
Range, more preferably 1500~3000 range.It should be noted that above-mentioned other polyalcohols number-average molecular weight indicate with
The number-average molecular weight of above-mentioned alicyclic polyester polyalcohol (a1) is worth obtained from equally measuring.
As above-mentioned polyisocyanates (B), it is different that polymethylene polyphenyl Quito isocyanates, diphenyl methane two can be used
Cyanate, carbodiimide modified methyl diphenylene diisocyanate isocyanates, benzene dimethylene diisocyanate, two isocyanide of benzene
The aromatic polyisocyanates such as acid esters, toluene di-isocyanate(TDI), naphthalene diisocyanate；Hexamethylene diisocyanate, hexamethylene
Diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, tetramethylxylene diisocyanate
The aliphatic such as ester or alicyclic polyisocyanates etc..These polyisocyanates may be used alone, can also be used in combination 2 kinds with
On.Among these, it is preferable to use aromatic series polyisocyanic acid from the viewpoint of it can obtain excellent reactivity and peel strength
Ester, more preferably methyl diphenylene diisocyanate.
As the dosage of above-mentioned polyisocyanates (B), in the total matter for the raw material for constituting hot melt carbamate prepolymer (i)
It is preferably range, the range of more preferably 10~30 mass % of 5~40 mass % in amount.
Above-mentioned hot melt carbamate prepolymer (i) is that above-mentioned polyalcohol (A) and above-mentioned polyisocyanates (B) occurs instead
Obtained from answering, have can in air, to be coated in the substrate of wet-cured type polyurethane-hot melt resin combination and exist
Moisture react and formed the isocyanate group of cross-linked structure.
It, can be for example, by equipped with above-mentioned polyisocyanate cyanogen as the manufacturing method of above-mentioned hot melt carbamate prepolymer (i)
Above-mentioned polyalcohol (A) is put into the reaction vessel of acid esters (B), makes its isocyanates possessed by above-mentioned polyisocyanates (B)
Base phase is reacted to manufacture under the conditions of reaching excessive for hydroxyl possessed by above-mentioned polyalcohol (A).
As isocyanide possessed by the above-mentioned polyisocyanates (B) when manufacturing above-mentioned hot melt carbamate prepolymer (i)
The equivalent proportion (isocyanate group/hydroxyl) of perester radical and hydroxyl possessed by above-mentioned polyalcohol (A), it is superior from that can obtain
From the perspective of peel strength, preferably 1.1~5 range, more preferably 1.5~3 range.
As obtained from the above method heat carbamate prepolymer (i) isocyanate group containing ratio (with
Under be abbreviated as " NCO% "), it is preferably 1.7~5 range, more excellent from the viewpoint of it can obtain superior peel strength
It is selected as 1.8~3 range.It should be noted that the NCO% expression of above-mentioned hot melt carbamate prepolymer (i) is based on
JISK1603-1: 2007, and the value measured using potential difference titration.
Wet-cured type polyurethane-hot melt resin combination used in the present invention contains above-mentioned hot melt carbamate pre-polymerization
Object can contain other additives as essential component as needed.
As above-mentioned other additives, such as weathering stabilizers can be used, curing catalysts, tackifier, plasticizer, fill out
Fill material, dyestuff, pigment, fluorescent whitening agent, silane coupling agent, wax, thermoplastic resin etc..These additives can individually make
With two or more can also be applied in combination.Among these, from the viewpoint of it can obtain superior weatherability, it is preferable to use
Weathering stabilizers.
As above-mentioned weathering stabilizers, such as hindered amine compound (ii) can be used, triazole compounds (iii), be obstructed
Phenolic compounds, phosphorus compound etc..These weathering stabilizers may be used singly or in combination of two or more.These it
In, it is preferable to use hindered amine compound (ii), more preferable use are obstructed from the viewpoint of it can obtain superior weatherability
Amine compounds (ii) and triazole compounds (iii).
Above-mentioned hindered amine compound (ii) captures the free radical generated by light deterioration, and it is double that such as decanedioic acid can be used
(2,2,6,6- tetramethyl -4- piperidyl) ester, decanedioic acid bis- (1,2,2,6,6- pentamethvl -4- base) esters, four (2,2,6,6-
Tetramethyl -4- piperidyl) 1,2,3,4- butane tetracarboxylic acid esters, four (1,2,2,6,6- pentamethyl -4- piperidyl) 1,2,3,4- fourths
Alkane tetrabasic ester, (mixing 2,2,6,6- tetramethyl -4- piperidyls/tridecyl) 1,2,3,4- butane tetracarboxylic acid esters, (mixing 1,
2,2,6,6- pentamethyl -4- piperidyls/tridecyl) 1,2,3,4- butane tetracarboxylic acid esters, dodecyl -7 8- acetyl group -3-,
7,9,9- tetramethyls -1,3,8- thriazaspiro (4.5) decane-2,4-diones etc..These compounds can be used alone, can also be with
Two or more is applied in combination.
As the content of above-mentioned hindered amine compound (ii), from the viewpoint of it can obtain superior weatherability, phase
For above-mentioned 100 mass parts of hot melt carbamate prepolymer (i), the preferably range of 0.01~10 mass parts, more preferably
The range of the range of 0.05~5 mass parts, further preferably 0.1~3 mass parts.
Above-mentioned triazole compounds (iii) can prevent from changing colour, such as use N, bis- (2- ethylhexyl)-[(1,2,4- tri- N-
Azoles -1- base) methyl] amine；2- [bis- (alpha, alpha-dimethylbenzyl) phenyl of 2- hydroxyl -3,5-] -2H- benzotriazole, 2- (2 '-hydroxyls -
3 ', 5 '-di-tert-butyl-phenyls) -5- chlorobenzotriazole, 2- (2 '-hydroxyls -3 '-tert-butyl -5 '-aminomethyl phenyl) -5- chlorobenzene and three
Azoles, 2- (2 '-hydroxyls -3 '-tertiary pentyl -5 '-isobutyl phenenyl) -5- chlorobenzotriazole, 2- (2 '-hydroxyls -3 '-isobutyl group -5 ' -
Aminomethyl phenyl) -5- chlorobenzotriazole, 2- (2 '-hydroxyls -3 '-isobutyl group -5 '-propyl phenyl) -5- chlorobenzotriazole, 2- (2 ' -
Hydroxyl -3 ', 5 '-di-tert-butyl-phenyls) benzotriazole, 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole, 2- [2 '-hydroxyls -
5 '-(1,1,3,3- tetramethyl) phenyl] benzotriazole cpds such as benzotriazole etc..These triazole compounds can individually make
With two or more can also be applied in combination.Among these, from the viewpoint of it can obtain superior weatherability, it is preferable to use
Benzotriazole cpd.
As content when using above-mentioned triazole compounds (iii), go out from the viewpoint that can obtain superior weatherability
Hair, relative to above-mentioned 100 mass parts of hot melt carbamate prepolymer (i), the preferably range of 0.01~10 mass parts, more excellent
It is selected as the range of 0.05~5 mass parts, the range of further preferably 0.1~3 mass parts.
Then, it is illustrated for synthetic leather of the invention.
Synthetic leather of the invention has the excellent weather resistance and hard formed by above-mentioned wet-cured type polyurethane-hot melt resin combination
Different layer.Above-mentioned layer will not change colour because of the deterioration caused by sunlight etc. as a result, therefore, it is compared with the past especially
It is that can widen demand in the utilization scope of increased split leather.
As above-mentioned split leather, have double-layer fur, adhesive layer and epidermis, above-mentioned wet-cured type polyurethane-hot melt resin group
Close the adhesive layer that object can be suitable as split leather.Hereinafter, having used above-mentioned wet-cured type polyurethane-hot melt resin for adhesive layer
The manufacturing method of split leather when composition is illustrated.
As above-mentioned double-layer fur, known object can be used, can be used for example by from ox, horse, sheep, goat, deer, kangaroo etc.
Natural leather among remove the double-layer fur that layer obtained by epidermis and papillaris pars is constituted.It is preferable to use after known for these double-layer furs
Process hides process, product obtained by tanning processes and dyeing/finishing step.As the thickness of above-mentioned double-layer fur, according to using
Purposes is next suitably to be determined, for example, the range of 0.1~2mm.
It as the method for forming above-mentioned adhesive layer on above-mentioned double-layer fur, can include such as following method: above-mentioned two
The method of the above-mentioned wet-cured type polyurethane-hot melt resin combination for example melted with 50~130 DEG C is coated on layer skin；
The above-mentioned wet-cured type polyurethane-hot melt resin combination for example melted with 50~130 DEG C is coated on processing release paper,
Afterwards, the method for which being fitted in into above-mentioned double-layer fur；It is coated on the epidermis being formed on processing release paper for example with 50
~130 DEG C of above-mentioned wet-cured type polyurethane-hot melt resin combinations melted, thereafter fit in the solidified material layer
The method etc. for stating double-layer fur.
In above-mentioned any means, as the method for coating wet-cured type polyurethane-hot melt resin combination, it can enumerate
Such as the method using roll coater, knife, flush coater, gravure coater, comma coater, T- die coating machine, applicator etc..
After being coated with above-mentioned wet-cured type polyurethane-hot melt resin combination, it can use well known method and conserved.
The thickness of solidified material layer (adhesive layer) as above-mentioned wet-cured type carbamate thermoplastic resin composition, such as
For 5~200 μm of range.
As the resin for being used to form above-mentioned epidermis, known object can be used, such as solvent system polyurethane can be used
Resin, aqueous polyurethane resin, solvent-free system's polyurethane resin, solvent system acrylic resin, water system acrylic resin etc..
These resins may be used singly or in combination of two or more.
As in the resin that will be used to form above-mentioned epidermis solvent removal when heating means, can enumerate for example with
The method that 50~120 DEG C of temperature carries out 2~20 minutes.
As the thickness of above-mentioned epidermis, for example, 5~100 μm of range.
Embodiment
Hereinafter, the present invention is described in more detail using embodiment.
[embodiment 1]
Alicyclic ring is put into the four-hole boiling flask for having thermometer, blender, inactive gas introducing port and reflux condenser
Formula polyester polyol (makes neopentyl glycol, 3- methyl-1, product obtained by 5- pentanediol and cyclohexane dicarboxylic acid reaction, number are divided equally
Son amount: 1000, hereinafter abbreviated as " ester ring type PEs1 ") 40 mass parts, polyoxypropylene glycol (number-average molecular weight: 2000, following letter
It is written as " PPG2000 ") it 60 mass parts and is mixed, with 100 DEG C of progress heating under reduced pressure, the moisture being thus dehydrated to flask reaches
Until 0.05 mass % or less.
Then, it will be cooled to 90 DEG C in flask, add 4, the 4 '-diphenylmethane diisocyanates melted with 70 DEG C
Ester (hereinafter abbreviated as " MDI ") 26.5 mass parts are reacted about 3 hours in a nitrogen atmosphere with 110 DEG C until isocyanate group contains
Until amount reaches constant, the hot melt carbamate prepolymer that NCO% is 2.4 mass % is thus obtained.
Then, (DIC is public for coating solvent system polyurethane resin in such a way that the film thickness after drying reaches 30 μm on processing release paper
Take charge of " the CRISVON TF-50P-C " of system), it is made it dry 10 minutes with 120 DEG C, obtains epidermis.Then, it is coated with using comma
Machine is coated with the above-mentioned hot melt amino first that melting in 1 hour has been carried out with 110 DEG C on the epidermis in such a way that thickness reaches 30 μm
After acid esters prepolymer, fitting is from the natural leather of ox removal epidermis and papillaris pars and through double-layer fur obtained by process hides, thereafter, in temperature
It is placed 3 days under conditions of 23 DEG C of degree, relative humidity 65%, obtains split leather.
[embodiment 2~4, comparative example 1~2]
According to the type and use level of such polyalcohol (A) shown in table 1 and polyisocyanates (B), hot melt amino is obtained
In addition to this urethane prepolymer obtains split leather similarly to Example 1.
[embodiment 5]
Alicyclic ring is put into the four-hole boiling flask for having thermometer, blender, inactive gas introducing port and reflux condenser
40 mass parts of formula PEsl, 60 mass parts of PPG2000 simultaneously mix, and with 100 DEG C of progress heating under reduced pressure, are thus dehydrated to flask
Until moisture reaches 0.05 mass % or less.
Then, it will be cooled to 90 DEG C in flask, add with 70 DEG C of 26.5 mass parts of the MDI melted, in nitrogen gas
About 3 hours are reacted until isocyanate group content reaches constant with 110 DEG C under atmosphere, and thus obtaining NCO% is 2.4 mass %
Hot melt carbamate prepolymer.Cooperate (three strains altogether of bis- (1,2,2,6, the 6- pentamethvl -4- base) esters of decanedioic acid thereto
" the SANOL LS-765 " of formula commercial firm, hereinafter abbreviated as " LS-765 ") 0.5 mass %, obtain wet-cured type polyurethane-hot melt
Resin combination.
Then, (DIC is public for coating solvent system polyurethane resin in such a way that the film thickness after drying reaches 30 μm on processing release paper
Take charge of " the CRISVON TF-50P-C " of system), it is made it dry 10 minutes with 120 DEG C, obtains epidermis.Then, it is coated with using comma
It is poly- that machine is coated with the above-mentioned wet-cured type for having carried out melting in 1 hour with 110 DEG C on the epidermis in such a way that thickness reaches 30 μm
After urethane thermoplastic resin composition, fitting from the natural leather of ox removes epidermis and papillaris pars and through double-layer fur obtained by process hides,
Thereafter, it is placed 3 days under conditions of 23 DEG C of temperature, relative humidity 65%, obtains split leather.
[embodiment 6]
In above-mentioned wet-cured type polyurethane-hot melt resin combination, relative to hot melt carbamate prepolymer, into one
Step cooperation benzotriazole cpd (" Tinuvin (registered trademark) 234 " of BASF AG, hereinafter abbreviated as " T234 ") 0.5
In addition to this quality % is operated similarly to Example 1 and is obtained wet-cured type polyurethane-hot melt resin combination, layer is cutd open in production
Leather.
[embodiment 7~9]
According to such polyalcohol (A) shown in table 2, polyisocyanates (B), hindered amine compound (ii) and triazole compounds
(iii) type and use level obtain wet-cured type polyurethane-hot melt resin combination and in addition to this grasp similarly to Example 6
Make to obtain split leather.
[measuring method of number-average molecular weight]
The number-average molecular weight of polyalcohol used in embodiment and comparative example etc. indicates to pass through gel permeation chromatography (GPC)
Method, and the value measured under the following conditions.
Measurement device: high speed GPC device (" HLC-8220GPC " of TOSOH Co., Ltd)
Column: following columns of TOSOH Co., Ltd are used in series.
" 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)
" the TSKgel standard polystyren A-500 " of TOSOH Co., Ltd
" the TSKgel standard polystyren A-1000 " of TOSOH Co., Ltd
" the TSKgel standard polystyren A-2500 " of TOSOH Co., Ltd
" the TSKgel standard polystyren A-5000 " of TOSOH Co., Ltd
" the TSKgel standard polystyren F-1 " of TOSOH Co., Ltd
" the TSKgel standard polystyren F-2 " of TOSOH Co., Ltd
" the TSKgel standard polystyren F-4 " of TOSOH Co., Ltd
" the TSKgel standard polystyren F-10 " of TOSOH Co., Ltd
" the TSKgel standard polystyren F-20 " of TOSOH Co., Ltd
" the TSKgel standard polystyren F-40 " of TOSOH Co., Ltd
" the TSKgel standard polystyren F-80 " of TOSOH Co., Ltd
" the TSKgel standard polystyren F-128 " of TOSOH Co., Ltd
" the TSKgel standard polystyren F-288 " of TOSOH Co., Ltd
" the TSKgel standard polystyren F-550 " of TOSOH Co., Ltd
[evaluation method of weatherability]
After carbamate prepolymer obtained in embodiment and comparative example is melted 1 hour with 110 DEG C, heated in advance
100 μm are coated on the processing release paper placed on to 110 DEG C of hot plates.The coated articles are taken care of 24 hours with 25 DEG C, humidity 50%,
Solidified, thus obtains film.Using the film, using equipped with UVA-340 light bulb (UV exposure: 0.78W/m2, temperature: 45
DEG C) QUV promote weathering tester " QUV/basic " carry out UV exposure experiment, according to UV irradiation front and back discoloration difference
(Δ E) is proceed as follows the evaluation of weatherability.
" 4 ": Δ E is 10 or less.
" 3 ": Δ E is more than 10 and is 13 or less.
" 2 ": Δ E is more than 13 and is 15 or less.
" 1 ": Δ E is more than 15.
[evaluation method of adhesive strength]
After carbamate prepolymer obtained in embodiment and comparative example is melted 1 hour with 120 DEG C, heated in advance
100 μm are coated on the PET film placed on to 110 DEG C of hot plates.PET film is unloaded from hot plate immediately after coating, immediately
Another PET film is bonded with hand roller.After fitting, test film is cut into 1 inch wide, uses digital force gauge (Co., Ltd. イ
" DS2-220N " of マ ァ ダ), the peel strength between PET after measurement fitting 1 minute evaluates initial strength as follows.
" T ": 5N/inch or more
" F ": less than 5N/inch
[measuring method of low viscosity]
After carbamate prepolymer obtained in embodiment and comparative example is melted 1 hour with 120 DEG C, 1ml, benefit are sampled
Melt viscosity is measured with cone and plate viscometer (40P awl, rotor speed: 50rpm), is proceed as follows evaluation.
" T ": less than 4000mPas
" F ": 4000mPas or more
[table 1]
[table 2]
Abbreviation in table 1 is as described below.
" ester ring type PEs2 ": product, number-average molecular weight obtained by reacting 1,4-CHDM with adipic acid: 1000
" aromatic series PEs ": make product obtained by diethylene glycol, neopentyl glycol and terephthalic acid (TPA) anhydride reactant, the equal molecule of number
Amount: 1000
" aliphatic PEs ": product, number-average molecular weight obtained by reacting 1,4-butanediol with adipic acid: 1000)
Known to: synthetic leather of the invention has weatherability, adhesive strength and the excellent poly- ammonia of wet-cured type of low viscosity
The solidified material layer of ester thermoplastic resin composition.
On the other hand, comparative example 1 is the side that alicyclic polyester polyalcohol (a1) is replaced using aromatic polyester polyol
Formula, although adhesive strength is excellent, weatherability and low viscosity are bad.
Comparative example 2 is the mode that alicyclic polyester polyalcohol (a1) is replaced using aliphatic polyester polyols, but is bonded
Intensity is bad.
Claims (8)
1. a kind of synthetic leather, which is characterized in that it has by the poly- ammonia of wet-cured type containing hot melt carbamate prepolymer i
The layer that ester thermoplastic resin composition is formed, the hot melt carbamate prepolymer i are to include alicyclic polyester polyalcohol a1's
The reactant of polyalcohol A and polyisocyanates B.
2. synthetic leather according to claim 1, wherein the polyalcohol A also includes polyoxypropylene glycol a2.
3. synthetic leather according to claim 1 or 2 also contains hindered amine compound ii.
4. synthetic leather according to claim 3, wherein the content of the hindered amine compound ii is relative to 100 mass
Part hot melt carbamate prepolymer i is 0.01 mass parts~10 mass parts range.
5. synthetic leather according to claim 3 or 4 also contains triazole compounds iii.
6. synthetic leather according to claim 5, wherein the content of the triazole compounds iii is relative to 100 mass parts
The hot melt carbamate prepolymer i is 0.01 mass parts~10 mass parts range.
7. synthetic leather according to claim 5 or 6, wherein the triazole compounds iii is benzotriazole cpd.
8. synthetic leather according to any one of claims 1 to 7 is split leather.
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| JP2016-244383 | 2016-12-16 | ||
| JP2016-244382 | 2016-12-16 | ||
| JP2016244382 | 2016-12-16 | ||
| PCT/JP2017/038611 WO2018110106A1 (en) | 2016-12-16 | 2017-10-26 | Synthetic leather |
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| KR (1) | KR102269803B1 (en) |
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| CN110878033A (en) * | 2019-12-05 | 2020-03-13 | 万华化学集团股份有限公司 | Functional color reducing agent and method for stabilizing color number of diisocyanate product |
| CN113195825A (en) * | 2018-12-17 | 2021-07-30 | Dic株式会社 | Synthetic leather |
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| JP6485726B1 (en) * | 2017-09-25 | 2019-03-20 | Dic株式会社 | Synthetic leather manufacturing method |
| CN111108245B (en) * | 2017-09-25 | 2022-12-30 | Dic株式会社 | Method for producing synthetic leather |
| JP6981578B2 (en) * | 2019-09-20 | 2021-12-15 | Dic株式会社 | Moisture-curable polyurethane resin composition, adhesive, and laminate |
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| KR20190045334A (en) | 2019-05-02 |
| TWI680997B (en) | 2020-01-01 |
| CN109963980B (en) | 2021-08-17 |
| TW201825552A (en) | 2018-07-16 |
| WO2018110106A1 (en) | 2018-06-21 |
| JP6355010B1 (en) | 2018-07-11 |
| JPWO2018110106A1 (en) | 2018-12-13 |
| KR102269803B1 (en) | 2021-06-28 |
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