CN109137552A - Synthetic leather material and preparation method thereof and synthetic leather and preparation method thereof - Google Patents
Synthetic leather material and preparation method thereof and synthetic leather and preparation method thereof Download PDFInfo
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- CN109137552A CN109137552A CN201811177587.8A CN201811177587A CN109137552A CN 109137552 A CN109137552 A CN 109137552A CN 201811177587 A CN201811177587 A CN 201811177587A CN 109137552 A CN109137552 A CN 109137552A
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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
- D06N3/145—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 two or more layers of 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
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
- D06N3/0045—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by applying a ready-made foam layer; obtained by compressing, crinkling or crushing a foam layer, e.g. Kaschierverfahren für Schaumschicht
-
- 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
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
-
- 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
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses a kind of synthetic leather materials and preparation method thereof, and raw material by weight, includes at least: 20~80 parts of blending-type polyurethane raw rubber；3~60 parts of filling system；0.5~40 part of Plasticising system；0.5~25 part of vulcanizing system；0.02~2 part of antioxidant；0.02~3 part of anti-aging agent；0.02~5 part of anti-hydrolysis agent；0.02~3 part of stabilizer and 0.1~8 part of foaming agent.Preparation method includes: to carry out continuous foamed after mixing the various raw materials of synthetic leather material, obtains synthetic leather material.Other raw materials are coated very well by scientific matching and blending-type polyurethane raw rubber, various auxiliary agents is enabled to carry out full and uniform stable distribution and the excellent processing performance of blending-type polyurethane raw rubber itself in the material, it is had excellent performance so that can mutually be closely linked to be formed by foaming between each raw material component with anti-puncture performance and anti-cut, synthetic leather material with long service life.
Description
Technical field
The present invention relates to technical field of synthetic leather, in particular to a kind of synthetic leather material and preparation method thereof and
Synthetic leather and preparation method thereof.
Background technique
Currently, the demand to clothes, shoes leather goods constantly expands, and natural leather is not as people's living standard is continuously improved
By the demand that quantitatively or in kind much can not meet society, and the synthetic leather to come into being is then rich with its source
It is rich, cheap, and modern mechanical high-volume work production is adapted to, at the Ideal Substitute of natural leather.Currently, in product
In the numerous synthetic leather of kind, and with fine air permeability, penetrability, smooth plentiful feel and excellent mechanical strength, spy
The Synthetic Leather for not being approximate natural leather in structure is preferable substitute.But existing Synthetic Leather is anti-
Puncture performance, anti-cut performance and service life are all to be improved.
Summary of the invention
The first purpose of this invention is to provide a kind of synthetic leather material, enables to the conjunction being prepared by it
Finished leather has excellent anti-puncture performance, anti-cut performance and used life.
Second object of the present invention is to provide a kind of preparation method of synthetic leather material, to be obtained by simple process
Above-mentioned synthetic leather material.
Third object of the present invention is to provide a kind of synthetic leather, to improve the anti-puncture performance of existing synthetic leather, resist
Cutting performance and service life.
Fourth object of the present invention is to provide a kind of preparation method of synthetic leather, to be obtained by simple processing step
To the above-mentioned synthetic leather haveing excellent performance.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention provides a kind of synthetic leather material, raw material by weight, is included at least: blending-type polyurethane raw rubber
20~80 parts；3~60 parts of filling system；0.5~40 part of Plasticising system；0.5~25 part of vulcanizing system；0.02~2 part of antioxidant；
0.02~2 part of anti-aging agent；0.02~2 part of anti-hydrolysis agent；0.02~2 part of stabilizer and 0.02~8 part of foaming agent.
The present invention relates to a kind of preparation methods of synthetic leather material comprising: the various raw materials of synthetic leather material are mixed
After carry out continuous foamed, obtain synthetic leather material.
The invention further relates to a kind of synthetic leather comprising synthetic leather material layer made of above-mentioned synthetic leather material, the synthesis
Opposite two surfaces of leather material layer are respectively arranged with surface layer and laminating layer, and optionally, surface layer is aqueous polyurethane layer or solvent-free
Layer of polyurethane, laminating layer are aqueous polyurethane layer or adhesive for solvent-free use.
The invention further relates to the preparation methods of above-mentioned synthetic leather comprising: surface layer is passed through into aqueous polyurethane or solvent-free
Adhesive is bonded with the one side of synthetic leather material layer, then the another side of synthetic leather material is passed through aqueous polyurethane or solvent-free viscous
Mixture is bonded with base fabric；Or the surface that poly- aqueous polyurethane or solvent-free polyester are coated in synthetic leather material layer is dried
It is dry, then by the another side of synthetic leather material layer by being bonded by aqueous polyurethane or adhesive for solvent-free use with base fabric.
The invention further relates to a kind of synthesis leather goods comprising outer layer made of above-mentioned synthetic leather, it is preferable that synthetic leather system
Product are sofa, luggage, clothing, shoes, boots or ball.
By scientific matching between each material composition and blending-type polyurethane raw rubber to antioxidant, anti-aging agent, water resistant
Solution agent, stabilizer, foaming agent etc. are coated well, and that various auxiliary agents are carried out in the material is full and uniform stable
Distribution and the excellent processing performance of blending-type polyurethane raw rubber itself, and further pass through vulcanizing system and blending-type polyurethane
The crosslinked action generated between the ingredients such as raw rubber, so that can be mutually closely linked between each raw material component by foaming
Being formed, there is anti-puncture performance and anti-cut to have excellent performance, synthetic leather material with long service life.
Specific embodiment
It, below will be to embodiment party of the present invention to keep the purposes, technical schemes and advantages of embodiment of the present invention clearer
Technical solution in formula is clearly and completely described.The person that is not specified actual conditions in embodiment or embodiment, according to routine
The condition that condition or manufacturer suggest carries out.Reagents or instruments used without specified manufacturer, being can be by commercially available purchase
Buy the conventional products of acquisition.
Below to a kind of synthetic leather material of embodiment of the present invention and preparation method thereof and synthetic leather and its preparation side
Method is specifically described.
Some embodiments of the present invention are related to a kind of synthetic leather material, and raw material by weight, includes at least: being kneaded
20~80 parts of type polyurethane raw rubber；3~60 parts of filling system；0.5~40 part of Plasticising system；0.5~25 part of vulcanizing system；Antioxygen
0.02~2 part of agent；0.02~2 part of anti-aging agent；0.02~2 part of anti-hydrolysis agent；0.02~2 part of stabilizer；And foaming agent 0.02
~8 parts.
According to some embodiments, by weight, the raw material of synthetic leather material include: blending-type polyurethane raw rubber 40~
60 parts；5~50 parts of filling system；5~30 parts of Plasticising system；5~20 parts of vulcanizing system；0.1~1 part of antioxidant；Anti-aging agent 0.1
~1 part；0.1~1 part of anti-hydrolysis agent；0.1~1 part of stabilizer；And 0.1~4 part of foaming agent.
In some embodiments, by weight, the raw material of synthetic leather material includes: blending-type polyurethane raw rubber 40~50
Part；10~45 parts of filling system；10~25 parts of Plasticising system；10~20 parts of vulcanizing system；0.1~0.8 part of antioxidant；Anti-aging agent
0.1~0.8 part；0.1~0.8 part of anti-hydrolysis agent；0.1~0.8 part of stabilizer；And 0.3~4 part of foaming agent.
In some embodiments, by weight, in the raw material of synthetic leather material, blending-type polyurethane raw rubber can be 20
~80 parts or 40~60 parts or 40~50 parts；Vulcanizing system can be 0.5~25 part or 5~20 parts or 10~20 parts；It fills out
The system of filling can be 3~60 parts or 5~50 parts or 10~45 parts；Plasticising system can be 0.5~40 part or 5~30 parts, or
10~25 parts；Antioxidant can be 0.02~2 part or 0.1~1 part or 0.1~0.8 part；Anti-aging agent can be 0.02~2 part,
Or 0.1~1 part or 0.1~0.8 part；Anti-hydrolysis agent can be 0.02~2 part or 0.1~1 part or 0.1~0.8 part；Stablize
Agent can be 0.02~2 part or 0.1~1 part or 0.1~0.8 part；And foaming agent can be 0.02~8 part or 0.1~4
Part or 0.3~4 part.
Blending-type polyurethane raw rubber its with good covering property, various addition auxiliary agents can be wrapped well
It covers, so that auxiliary agent can be sufficiently combined together between component, blending-type polyurethane raw rubber itself also has excellent
Processing performance.For example, can obtain tensile strength after unsaturated polyether type polyurethane raw rubber and vulcanizing system are vulcanized and tear
The material that resistance to spalling is big and wear-resisting property is excellent.
Further, the preferred mixed milling type unsaturated polyurethanes raw rubber of blending-type polyurethane raw rubber in some embodiments, mixes
Refining type polyurethane raw rubber is synthesized by the mixing of polyalcohol, isocyanates and chain extender.
Specifically, polyalcohol includes polytetrahydrofuran ethoxylated polyhydric alcohol, polyoxypropylene polyol, poly adipate succinic acid ester
Polyalcohol, polyethylene glycol adipate polyalcohol, polyadipate ethylene glycol propylene glycol ester polyalcohol, polyadipate ethylene glycol fourth two
Alcohol ester polyol, polyneopentyl glycol adipate polyalcohol, polyadipate hexylene glycol polyalcohol, polycaprolactone polyol, poly- carbon
The combination of one or more of acid esters polyalcohol.
Preferably, the molecular weight of polyalcohol is 500~5000, preferably 800~3000；The average functionality of polyalcohol is
1.5-4 preferably 1.8-2.5.
In some embodiments, isocyanates includes toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, isophorone
Diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, paraphenylene diisocyanate, 1,4- hexamethylene
Alkane diisocyanate, benzene dimethylene diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, tetramethyl m-phenylenedimethylim-
The combination of one or more of diisocyanate.
In some embodiments, chain extender includes ethylene glycol, 1,4-butanediol, 1,3-BDO, 1,2-PD, methyl
Propylene glycol, neopentyl glycol, 3- methyl-1,5- pentanediol, 1,4- hydroxymethyl-cyclohexane, glycerol α-allyl ether, trihydroxy methyl
Propane mono allyl ether, trimethylolpropane dual-allyl ether, hydroquinone two hydroxy ethyl ether, resorcinol dihydroxyethyl ether,
The combination of one or more of trimethylolpropane, glycerine, diglycol.
Specifically, blending-type polyurethane raw rubber is the polyalcohol, isocyanates and chain extension that will be selected from said combination
Agent is kneaded in rubber mixing machine, and melting temperature is 70~100 DEG C.
Vulcanizing system can make its at a certain temperature can between the other components such as blending-type polyurethane raw rubber into
Row cross-linking reaction so that linear macromolecular forms space net structure, and then improves the anti-puncture performance and anti-cut of material
Performance.Further, in some embodiments, vulcanizing system can be selected from sulfur cross-linking system, peroxide-based curing system with
And any one in isocyanates vulcanizing system.Wherein, sulfur cross-linking system may include sulphur and promotor, sulphur and
The weight ratio of promotor can be 10:1~3, and further, promotor may include zinc dimethyl dithiocarbamate, two
At least one of zine dimethyldithiocarbamate, tetramethylthiuram disulfide and diphenylguanidine.For example, promotor can be with
Select zinc dimethyl dithiocarbamate, zinc dimethyl dithiocarbamate, tetramethylthiuram disulfide or diphenylguanidine
One of；Also it can choose the mixture of zinc dimethyl dithiocarbamate and zinc dimethyl dithiocarbamate, or
The mixture or tetramethylthiuram disulfide and hexichol of zinc dimethyl dithiocarbamate and tetramethylthiuram disulfide
The mixture or zinc dimethyl dithiocarbamate of guanidine, zinc dimethyl dithiocarbamate and tetramethyl autumn are blue
The mixture etc. of nurse.
Further, peroxide-based curing system may include cumyl peroxide, benzoyl peroxide, 1,1- bis-
Tertiary base peroxy -3,3,5- trimethyl-cyclohexane and 2, at least one of 5- dimethyl-bis(t-butylperoxy) hexane.Example
Such as, peroxide-based curing system can be cumyl peroxide or benzoyl peroxide or 1, the tertiary base peroxy-of 1- bis-
3,3,5- trimethyl-cyclohexanes or 2,5- dimethyl-bis(t-butylperoxy) hexane, peroxide-based curing system can also be with
For the mixture or 1 of cumyl peroxide and benzoyl peroxide, the tertiary base peroxy -3,3 of 1- bis-, 5- trimethyl-cyclohexane
It can be peroxidating two with 2,5- dimethyl-bis(t-butylperoxy) hexane mixture or peroxide-based curing system
Isopropylbenzene, benzoyl peroxide and 1, the tertiary base peroxy -3,3 of 1- bis-, the mixture etc. of 5- trimethyl-cyclohexane.
Further, isocyanates vulcanizing system may include 2,4- toluene di-isocyanate(TDI) and toluene di-isocyanate(TDI)
One of dimer or combinations thereof.For example, isocyanates vulcanizing system can be 2,4- toluene di-isocyanate(TDI) or toluene
Diisocyanate dimer, or the mixture of 2,4- toluene di-isocyanate(TDI)s and toluene diisocyanate dimer.
In some embodiments, filling system includes carbon black, precipitated silica, fumed silica, titanium dioxide
Titanium, talcum powder, calcium carbonate, kaolin, clay, zinc oxide, magnesia, mica powder, barium sulfate, aluminium hydroxide, in magnesium hydroxide
Any one or combinations thereof.
In some embodiments, Plasticising system includes dibutyl phthalate (DBP), o-phthalic acid dibutyl ester, adipic acid two
It is pungent rouge, dioctyl sebacate, tricresyl phosphate, coumarone, chlorinated paraffin, any one in TP-95, TP-90B, TP-759
Kind or combinations thereof.
Antioxidant can prevent blending-type polyurethane raw rubber and vulcanizing system from sulfidation generation thermal oxidative degradation occurs, into
And it avoids raw material and thermal oxidative degradation occurs and reduces material property, and the ratio that the cross-linking reaction between raw material is also able to carry out
Relatively sufficiently.Wherein, antioxidant may include one of antioxidant 264, antioxidant 1010 or antioxidant 1076 or in which two kinds
Or two or more combination.
Synthetic Leather and its product are in long-term storage and use process, since by heat, oxygen, ozone, appraise at the current rate gold
Belong to the erosion of ion, mechanical stress, light, the effect of high-energy ray and other chemical substances and mould etc., can it is gradually tacky,
Be hardened embrittlement or cracking.The phenomenon that this physical mechanical property declines at any time, elasticity reduces is called aging.With aging
The progress and development of journey, Synthetic Leather and its product properties can gradually decrease so that completely losing use value.Therefore, prevent
Old agent can enhance Synthetic Leather and its product to the resistivity of above-mentioned various destructions, delay or inhibit aging
Journey, to extend storage period and the service life of Synthetic Leather and its product.Further, anti-aging agent can be N- benzene
Base-α-aniline, N- phenyl-β-naphthylamine, p-phenylenediamine or N-N'- diphenyl-p-phenylenediamine.
Anti-hydrolysis agent can be steric hindrance aromatic series carbon diimine class stabilisers against hydrolysis, with it with hydrolysate carboxylic acid or
Water reacts, and the degradation for preventing self-catalysis from hydrolyzing occurs, and is coated anti-hydrolysis agent simultaneously by blending-type polyurethane raw rubber
It is distributed in the material that final foaming is formed, enables to synthetic leather material and the product comprising the synthetic leather material in high temperature
Hydrolytic resistance when moist and acid or alkali environment, prolongs the service life.Further, anti-hydrolysis agent can be polymerization carbonization
Diimine.
Stabilizer thermal stability and foaming effect in foaming process is good, and obtained synthetic leather material formation is netted
Structure is more stable, is not easy to be destroyed.Further, stabilizer may include: zinc salt main stabilizer, calcium salt and acrylic acid tree
Rouge.
Wherein, zinc salt main stabilizer is steady for the fatty acid zinc salt main stabilizer of arbitrary proportion mixing and phenyl ring class zinc salt master
Determine agent, fatty acid zinc salt main stabilizer be zinc stearate, zinc palmitate, zinc oleate, zinc laurate, heptadecatriene fatty acid zinc or
Any one of pentadecane fatty acid zinc, phenyl ring class zinc salt main stabilizer are any of zinc benzoate or Zinc dodecylbenzenesulphonate
It is a kind of；Acrylic resin is that esters of acrylic acid and methyl acrylic ester and other olefinic type monomers are copolymerized manufactured resin.It needs
What is illustrated is that stabilizer is also possible to commercially available conventional stabilizer.
Further, it is preferable to ground, the foaming agent includes ammonium carbonate, ammonium hydrogen carbonate, sodium bicarbonate, blowing agent AC, foaming
At least one of agent H, foaming agent OBSH or expended microsphere foaming agent or combinations thereof.Foaming agent may include AC foaming agent or
At least one of OBSH foaming agent.For example, foaming agent can be AC foaming agent, or OBSH foaming agent, or
The mixture of the two.
Enable blending-type polyurethane raw rubber sufficiently to antioxidant, anti-aging agent, anti-hydrolysis agent, steady by suitably matching
Determine agent, foaming agent etc. to be coated well, and under the conditions of suitable temperature and vulcanizing system crosslinks reaction, so that material
Expect that structure becomes reticular structure from linear structure, and it is full and uniform stable that various auxiliary agents are carried out in reticular structure
Distribution, and then the material formed after foaming has and has excellent performance with anti-puncture performance and anti-cut, it is with long service life
Feature.
The above are solvent-based systems in manufacturing process 90% for Synthetic Leather in the prior art, largely use dimethyl
The organic solvents such as formamide (DMF).Have the loss of partial solvent in manufacturing process, the loss of solvent first is that resource waste,
On the other hand the pollution of environment and the health problem of working site be will also result in.It is prepared by aqueous and solvent-free raw material
Synthetic leather material is obtained, is reduced environmental pollution, production cost is reduced.
Fire retardant enables to synthetic leather material that can have excellent flame retardant property, further, some embodiments
In, fire retardant can be halogen-free flame retardants, for example, halogen-free flame retardants may include ammonium phosphate, ammonium polyphosphate, melamine and its
Compound, zinc borate, boron-nitrogen compound, montmorillonite, clay, metal hydroxides, organophosphorus compounds, organophosphorus ester
At least one of compound and phosphorus-containing polyol, i.e. halogen-free flame retardants can be one of above-mentioned substance enumerated or two
Kind or three kinds or three kinds or more of mixture.For example, halogen-free flame retardants can be zinc borate, or boron nitrification
Object, or montmorillonite, or the mixture of zinc borate and boron-nitrogen compound, or ammonium phosphate, zinc borate and
The mixture of boron-nitrogen compound.
It can also include the smoke suppressant of 2~20 parts by weight in some embodiments, smoke suppressant can make material carry out
Smoke amount when burning is reduced, and in some embodiments, smoke suppressant includes at least one in iron compound and magnesium-zinc complexes
Kind.For example, smoke suppressant can be individual iron compound or individual magnesium-zinc complexes, or the mixture of the two.Into
One step, smoke suppressant can select Ongard II or ferrocene.
Some embodiments of the present invention further relate to a kind of preparation method of above-mentioned synthetic leather material comprising: it will synthesize
It carries out continuous foamed after the various raw materials mixing of leather material, obtains synthetic leather material.It is enabled to by way of foaming above-mentioned
Various raw materials carry out full cross-linked and distribution at a certain temperature and are combined together to form stable structure.
Further, continuous foamed to be carried out in continuous foamed equipment, that is, commercially available continuous foam maker.Some implementations
In mode, the various raw materials of synthetic leather material will can be passed through mixer after mixing, be then sent through on continuous foam maker and connect
Supervention steeps to obtain synthetic leather material.And synthetic leather material layer can be directly obtained by continuous foamed dose.In addition, using different
The foaming agent of type and different amounts, using continuous foamed technique, the foamed material of available different densities, different-thickness,
The synthetic leather material layer of different feels can be made.
Further, according to some embodiments, continuous foamed temperature can be 140~190 DEG C or 160~180
DEG C or 165~175 DEG C, the continuous foamed time can be 3~30min or 4~25min or 6~20min.By suitably sending out
Bubble temperature can make the cross moulding between various raw materials be sufficiently carried out, so that its structural behaviour is more excellent, suitably
Foamed time can make reaction molding completely, will not be because of the too long generation over cure of foamed time.
Some embodiments of the present invention further relate to a kind of synthetic leather comprising synthetic leather made of above-mentioned synthetic leather material
Opposite two surfaces of material layer, synthetic leather material layer are respectively arranged with surface layer and laminating layer, it is preferable that surface layer is aqueous polyurethane
Layer or no-solvent polyurethane layer, laminating layer are aqueous polyurethane layer or adhesive for solvent-free use.Pass through aqueous and solvent-free raw material
Synthetic leather is prepared, reduces environmental pollution, reduces production cost.
Aqueous polyurethane is that polyester-type aqueous polyurethane, polyether type aqueous polyurethane and aromatic isocyanate type are aqueous poly-
One of urethane is a variety of.No-solvent polyurethane is hydrogen fluorohydrocarbon class compound (HFCs), such as HFC-245fa and HFC-
365mfc。
Some embodiments of the present invention additionally provide a kind of preparation method of above-mentioned synthetic leather comprising: surface layer is led to
It crosses aqueous polyurethane or adhesive for solvent-free use to be bonded with the one side of synthetic leather material layer, then the another side of synthetic leather material layer is led to
It crosses aqueous polyurethane or adhesive for solvent-free use is bonded with base fabric；
Or the surface that poly- aqueous polyurethane or solvent-free polyester are coated in synthetic leather material layer is dried, then will
The another side of synthetic leather material layer by aqueous polyurethane or adhesive for solvent-free use with base fabric by being bonded.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
In the present embodiment, by weight, the raw material of synthetic leather material includes: 80 parts of blending-type polyurethane raw rubber, filling
60 parts of system, 40 parts of Plasticising system, 25 parts of vulcanizing system, 2 parts of antioxidant, 2 parts of anti-aging agent, 2 parts of anti-hydrolysis agent, 2 parts of stabilizer
And 8 parts of foaming agent.
Wherein, blending-type polyurethane raw rubber is that polyalcohol, isocyanates and chain extender carry out being kneaded in rubber mixing machine
It arrives, melting temperature is 70 DEG C.Polyalcohol is polytetrahydrofuran ethoxylated polyhydric alcohol.The molecular weight of polyalcohol is 800；Polyalcohol is averaged
Degree of functionality is 1.8.Isocyanates is toluene di-isocyanate(TDI).Chain extender is ethylene glycol.
Sulfur cross-linking system includes sulphur and promotor, and the weight ratio of sulphur and promotor is 10:3, and promotor is diformazan
Base zinc dithiocarbamate；Antioxidant is antioxidant 264；Anti-aging agent is N- phenyl-α-aniline；Anti-hydrolysis agent can be poly-
Close carbodiimides；Stabilizer is calcium zinc stabilizer KCZ-58；Foaming agent is AC foaming agent.Filling system is carbon black.It is plasticized body
System is dibutyl phthalate (DBP).
In mixer after mixing by above-mentioned various raw materials, it is passed through continuous foam maker and carries out continuous foamed 4min, obtain
To synthetic leather material layer, wherein continuous foamed temperature is 190 DEG C.
Surface layer is bonded by aqueous polyurethane with the one side of synthetic leather material layer, then by the another side of synthetic leather material layer
It is bonded by aqueous polyurethane or adhesive for solvent-free use with base fabric.
Embodiment 2
In the present embodiment, by weight, the raw material of synthetic leather material includes: 20 parts of blending-type polyurethane raw rubber, filling
50 parts of system, 30 parts of Plasticising system, 20 parts of vulcanizing system, 0.03 part of antioxidant, 0.04 part of anti-aging agent, 0.03 part of anti-hydrolysis agent,
0.02 part of stabilizer and 0.05 part of foaming agent.
Wherein, blending-type polyurethane raw rubber is that polyalcohol, isocyanates and chain extender carry out being kneaded in rubber mixing machine
It arrives, melting temperature is 100 DEG C.Polyalcohol is polyethylene glycol adipate polyalcohol.The molecular weight of polyalcohol is 3000；Polyalcohol
Average functionality be 2.5.Isocyanates is isoflurane chalcone diisocyanate.Chain extender is trimethylolpropane diallyl
Ether.
Sulfur cross-linking system includes sulphur and promotor, and the weight ratio of sulphur and promotor is 10:1, and promotor is two sulphur
Change tetra methylthiuram；Antioxidant is antioxidant 1010；Anti-aging agent is N- phenyl-β-naphthylamine；Anti-hydrolysis agent can be polymerization
Carbodiimides；Stabilizer is calcium zinc stabilizer KCZ-58；Foaming agent is OBSH foaming agent.Filling system is precipitation method titanium dioxide
Silicon.Plasticising system is dioctyl sebacate.
In mixer after mixing by above-mentioned various raw materials, it is passed through continuous foam maker and carries out continuous foamed 10min, obtain
To synthetic leather material layer, wherein continuous foamed temperature is 165 DEG C.
Surface layer is bonded by aqueous polyurethane with the one side of synthetic leather material layer, then by the another side of synthetic leather material layer
It is bonded by aqueous polyurethane with base fabric.
Embodiment 3
In the present embodiment, blending-type polyurethane raw rubber is that polyalcohol, isocyanates and chain extender carry out in rubber mixing machine
Mixing obtains, and melting temperature is 85 DEG C.Polyalcohol is that poly adipate succinic acid ester polyalcohol and polyethylene glycol adipate are polynary
The 1:1 mixture of alcohol.The molecular weight of polyalcohol is 4500, and the average functionality of polyalcohol is 4.Isocyanates is toluene diisocyanate
The 1:1 mixture of acid esters and '-diphenylmethane diisocyanate.Chain extender is 1,3 butylene glycol and hydroquinone two hydroxy ethyl ether
1:1 mixture.
By weight, the raw material of synthetic leather material includes: 60 parts of blending-type polyurethane raw rubber, 15 parts of filling system, increases
10 parts of plastomer system, 10 parts of vulcanizing system, 1 part of antioxidant, 1 part of anti-aging agent, 1 part of anti-hydrolysis agent, 1 part of stabilizer and foaming agent 4
Part.
Wherein, sulfur cross-linking system is cumyl peroxide.Antioxidant is antioxidant 264；Anti-aging agent is N-N'- bis-
Phenyl-pphenylenediamine；Anti-hydrolysis agent can be polymerization carbodiimides；Stabilizer is calcium zinc stabilizer KCZ-58；Foaming agent is
AC foaming agent.Filling system is kaolin.Plasticising system is chlorinated paraffin.
In mixer after mixing by above-mentioned various raw materials, it is passed through continuous foam maker and carries out continuous foamed 8min, obtain
To synthetic leather material layer, wherein continuous foamed temperature is 175 DEG C.
Surface layer is bonded by aqueous polyurethane with the one side of synthetic leather material layer, then by the another side of synthetic leather material layer
It is bonded by aqueous polyurethane with base fabric.
Embodiment 4
In the present embodiment, blending-type polyurethane raw rubber is that polyalcohol, isocyanates and chain extender carry out in rubber mixing machine
Mixing obtains, and melting temperature is 95 DEG C.Polyalcohol is polyadipate ethylene glycol butanediol ester polyalcohol.The molecular weight of polyalcohol is
5000；The average functionality of polyalcohol is 1.5.Isocyanates is hexamethylene diisocyanate.Chain extender is trihydroxy methyl third
Alkane.
By weight, the raw material of synthetic leather material includes: 60 parts of blending-type polyurethane raw rubber, 35 parts of filling system, increases
15 parts of plastomer system, 15 parts of vulcanizing system, 20 parts of fire retardant, 3 parts of smoke suppressant, 0.8 part of antioxidant, 0.7 part of anti-aging agent, anti-hydrolysis agent
0.6 part, 0.5 part of stabilizer and 4 parts of foaming agent.
Wherein, sulfur cross-linking system is toluene diisocyanate dimer；Antioxidant is antioxidant 1076；Anti-aging agent is
N- phenyl-α-aniline；Anti-hydrolysis agent can be polymerization carbodiimides；Stabilizer is calcium zinc stabilizer KCZ-5；Foaming agent is AC
Foaming agent；Fire retardant is ammonium phosphate, and smoke suppressant is Ongard II.Filling system is the 1:1 mixture of zinc oxide and magnesia.Increase
Plastomer system is TP-95.
In mixer after mixing by above-mentioned various raw materials, it is passed through continuous foam maker and carries out continuous foamed 12min, obtain
To synthetic leather material layer, wherein continuous foamed temperature is 170 DEG C.
Surface layer is bonded by aqueous polyurethane with the one side of synthetic leather material layer, then by the another side of synthetic leather material layer
It is bonded by aqueous polyurethane with base fabric.
Embodiment 5
In the present embodiment, blending-type polyurethane raw rubber is that polyalcohol, isocyanates and chain extender carry out in rubber mixing machine
Mixing obtains, and melting temperature is 75 DEG C.Polyalcohol is polycaprolactone polyol.The molecular weight of polyalcohol is 1000；Polyalcohol
Average functionality is 2.Isocyanates is paraphenylene diisocyanate.Chain extender is 1,4- hydroxymethyl-cyclohexane.
By weight, the raw material of synthetic leather material includes: 40 parts of blending-type polyurethane raw rubber, 10 parts of filling system, increases
10 parts of plastomer system, 10 parts of vulcanizing system, 10 parts of fire retardant, 10 parts of smoke suppressant, 0.6 part of antioxidant, 0.9 part of anti-aging agent, resistant to hydrolysis
1.1 parts of agent, 0.8 part of stabilizer and 3 parts of foaming agent.
Wherein, sulfur cross-linking system is toluene diisocyanate dimer, and antioxidant is antioxidant 1076；Anti-aging agent is
N- phenyl-α-aniline；Anti-hydrolysis agent can be polymerization carbodiimides；Stabilizer is calcium zinc stabilizer KCZ-5；Foaming agent is AC
Foaming agent；Fire retardant is zinc borate；Smoke suppressant is ferrocene.Filling system is the 1:1 mixture of titanium dioxide and talcum powder.Increase
Plastomer system is the 1:1 mixture of dibutyl phthalate (DBP) and dioctyl sebacate.
In mixer after mixing by above-mentioned various raw materials, it is passed through continuous foam maker and carries out continuous foamed 15min, obtain
To synthetic leather material layer, wherein continuous foamed temperature is 165 DEG C.
Surface layer is bonded by aqueous polyurethane with the one side of synthetic leather material layer, then by the another side of synthetic leather material layer
It is bonded by aqueous polyurethane with base fabric.
Embodiment 6
The present embodiment difference from Example 5 is only that the blowing temperature in the present embodiment is 135 DEG C.
Embodiment 7
The present embodiment difference from Example 5 is only that the blowing temperature in the present embodiment is 190 DEG C.
Embodiment 8
The present embodiment difference from Example 5 is only that the stabilizer used in the present embodiment is zinc stearate and carbon
The mass ratio of the mixture of sour calcium and acrylic resin, zinc stearate and calcium carbonate and acrylic resin is 2:1:1.
Comparative example 1
This comparative example difference from Example 5 is only that this comparative example does not contain antioxidant.
Comparative example 2
This comparative example difference from Example 5 is, in this comparative example, by weight, the raw material of synthetic leather material
Include: 100 parts of blending-type polyurethane raw rubber, 10 parts of filling system, 10 parts of Plasticising system, 30 parts of vulcanizing system, 10 parts of fire retardant,
10 parts of smoke suppressant, 0.6 part of antioxidant, 0.9 part of anti-aging agent, 1.1 parts of anti-hydrolysis agent, 0.8 part of stabilizer and 10 parts of foaming agent.
Test example
The anti-cut power of the synthetic leather of Examples 1 to 8 and comparative example 1~2 and puncture kinetic energy values are tested, anti-cut
Power is tested using ASTM F-1790, is pierced through kinetic energy values using GA68-2008 standard testing and is pierced through kinetic energy values.Test result
As shown in table 1.
| Group | Anti-cut power (N) | It pierces through kinetic energy values (J) |
| Embodiment 1 | 4.5 | 23 |
| Embodiment 2 | 4.4 | 22 |
| Embodiment 3 | 4.6 | 24 |
| Embodiment 4 | 4.5 | 22 |
| Embodiment 5 | 4.8 | 25 |
| Embodiment 6 | 4.1 | 21 |
| Embodiment 7 | 4.2 | 22 |
| Embodiment 8 | 5.0 | 27 |
| Comparative example 1 | 3.9 | 20 |
| Comparative example 2 | 4.0 | 20 |
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of synthetic leather material, which is characterized in that its raw material by weight, includes at least:
20~80 parts of blending-type polyurethane raw rubber；
3~60 parts of filling system；
0.5~40 part of Plasticising system；
0.5~25 part of vulcanizing system；
0.02~2 part of antioxidant；
0.02~3 part of anti-aging agent；
0.02~5 part of anti-hydrolysis agent；
0.02~3 part of stabilizer；And
0.1~8 part of foaming agent.
2. synthetic leather material according to claim 1, which is characterized in that by weight, the original of the synthetic leather material
Material includes:
20~80 parts of blending-type polyurethane raw rubber；
3~60 parts of filling system；
0.5~40 part of Plasticising system；
0.5~25 part of vulcanizing system；
10~70 parts of fire retardant；
2~20 parts of smoke suppressant；
0.02~2 part of antioxidant；
0.02~3 part of anti-aging agent；
0.02~5 part of anti-hydrolysis agent；
0.02~3 part of stabilizer；And
0.1~8 part of foaming agent.
3. synthetic leather material according to claim 2, which is characterized in that the fire retardant is halogen-free flame retardants, it is preferable that
The halogen-free flame retardants include ammonium phosphate, ammonium polyphosphate, melamine and its compound, zinc borate, boron-nitrogen compound, cover it is de-
At least one in soil, clay, metal hydroxides, organophosphorus compounds, organophosphorus compounds and phosphorus-containing polyol
Kind；
Preferably, the smoke suppressant includes at least one of iron compound and magnesium-zinc complexes.
4. described in any item synthetic leather materials according to claim 1~3, which is characterized in that the blending-type polyurethane raw rubber
Gained is synthesized by polyalcohol, isocyanates and chain extender；
Preferably, the polyalcohol includes polytetrahydrofuran ethoxylated polyhydric alcohol, polyoxypropylene polyol, poly adipate succinic acid ester
Polyalcohol, polyethylene glycol adipate polyalcohol, polyadipate ethylene glycol propylene glycol ester polyalcohol, polyadipate ethylene glycol fourth two
Alcohol ester polyol, polyneopentyl glycol adipate polyalcohol, polyadipate hexylene glycol polyalcohol, polycaprolactone polyol, poly- carbon
One or more of acid esters polyalcohol combination, it is preferable that the molecular weight of the polyalcohol be 500~5000, preferably 800~
3000；The average functionality of the polyalcohol is 1.5-4, preferably 1.8-2.5；
Preferably, the isocyanates includes toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, isophorone diisocyanate
Ester, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, paraphenylene diisocyanate, two isocyanide of 1,4- hexamethylene
Acid esters, benzene dimethylene diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, tetramethyl m-phenylenedimethylim- diisocyanate
The combination of one or more of ester；
Preferably, the chain extender include ethylene glycol, 1,4-butanediol, 1,3-BDO, 1,2-PD, methyl propanediol,
Neopentyl glycol, 3- methyl-1,5- pentanediol, 1,4- hydroxymethyl-cyclohexane, glycerol α-allyl ether, trimethylolpropane monoene
Propyl ether, trimethylolpropane dual-allyl ether, hydroquinone two hydroxy ethyl ether, resorcinol dihydroxyethyl ether, trihydroxy methyl
The combination of one or more of propane, glycerine, diglycol.
5. described in any item synthetic leather materials according to claim 1~3, which is characterized in that the vulcanizing system is selected from sulphur
In vulcanizing system, peroxide-based curing system and isocyanates vulcanizing system any one or combinations thereof；
Preferably, the sulfur cross-linking system includes sulphur and promotor, and further preferably, the promotor includes 2- sulfydryl benzene
And thiazole, dibenzothiazyl disulfide, zinc dimethyl dithiocarbamate, zinc dimethyl dithiocarbamate, curing
At least one of tetra methylthiuram and diphenylguanidine；
Preferably, the peroxide-based curing system includes cumyl peroxide, benzoyl peroxide, the tertiary base mistake of 1,1- bis-
Oxygroup -3,3,5- trimethyl-cyclohexane and 2, at least one of 5- dimethyl-bis(t-butylperoxy) hexane；
Preferably, the isocyanates vulcanizing system include 2,4- toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate and
One of toluene diisocyanate dimer or combinations thereof；
Preferably, the filling system includes carbon black, precipitated silica, fumed silica, titanium dioxide, talcum
It is powder, calcium carbonate, kaolin, clay, zinc oxide, magnesia, mica powder, barium sulfate, aluminium hydroxide, any one in magnesium hydroxide
Kind or combinations thereof；
Preferably, the Plasticising system includes dibutyl phthalate (DBP), o-phthalic acid dibutyl ester, adipic acid dibutyl ester, the last of the ten Heavenly stems
Diacid dibutyl ester, tricresyl phosphate, coumarone, chlorinated paraffin, any one or its group in TP-95, TP-90B, TP-759
It closes.
Preferably, the foaming agent includes ammonium carbonate, ammonium hydrogen carbonate, sodium bicarbonate, blowing agent AC, blowing agent H, foaming agent OBSH
Or at least one of expended microsphere foaming agent or combinations thereof.
6. a kind of preparation method of synthetic leather material as claimed in any one of claims 1 to 5, characterized in that it comprises: will
It carries out continuous foamed after the various raw materials mixing of the synthetic leather material, obtains the synthetic leather material.
7. the preparation method of synthetic leather material according to claim 6, which is characterized in that the continuous foamed temperature is
120~190 DEG C, preferably 150~180 DEG C, more preferable 150~175 DEG C, the continuous foamed time be 3~30min, preferably 4~
25min, more preferable 6~20min.
8. a kind of synthetic leather, which is characterized in that it includes that synthetic leather material as described in claim 1~6 any one is made
Synthetic leather material layer, opposite two surfaces of the synthetic leather material layer are respectively arranged with surface layer and laminating layer, it is preferable that described
Surface layer is aqueous polyurethane layer or no-solvent polyurethane layer, and the laminating layer is aqueous polyurethane layer or adhesive for solvent-free use.
9. a kind of preparation method of synthetic leather as claimed in claim 8, characterized in that it comprises: pass through the surface layer
Aqueous polyurethane or adhesive for solvent-free use are bonded with the one side of the synthetic leather material layer, then by the another of the synthetic leather material layer
It is bonded on one side by aqueous polyurethane or adhesive for solvent-free use with base fabric；
Or the surface that poly- aqueous polyurethane or solvent-free polyester are coated in the synthetic leather material layer is dried, then will
The another side of the synthetic leather material layer by aqueous polyurethane or adhesive for solvent-free use with base fabric by being bonded.
10. a kind of synthesis leather goods, which is characterized in that it includes outer layer made of synthetic leather as claimed in claim 8, preferably
Ground, the synthesis leather goods are sofa, luggage, clothing, shoes, boots or ball.
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| CN110983802A (en) * | 2019-12-24 | 2020-04-10 | 兰州科天水性高分子材料有限公司 | Ultra-soft aqueous wet leather base and preparation method thereof |
| CN113774672A (en) * | 2021-05-26 | 2021-12-10 | 加通汽车内饰(常熟)有限公司 | Novel physical foaming agent and application thereof |
| CN114481641A (en) * | 2022-01-24 | 2022-05-13 | 华伦皮塑（苏州）有限公司 | Synthetic leather for flame-retardant electronic competition seat and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110656506A (en) * | 2019-09-16 | 2020-01-07 | 安徽安利材料科技股份有限公司 | Inorganic particle composite polyurethane synthetic leather and preparation method and application thereof |
| CN110983802A (en) * | 2019-12-24 | 2020-04-10 | 兰州科天水性高分子材料有限公司 | Ultra-soft aqueous wet leather base and preparation method thereof |
| CN110983802B (en) * | 2019-12-24 | 2022-08-19 | 兰州科天水性高分子材料有限公司 | Super-soft aqueous wet leather base and preparation method thereof |
| CN113774672A (en) * | 2021-05-26 | 2021-12-10 | 加通汽车内饰(常熟)有限公司 | Novel physical foaming agent and application thereof |
| CN114481641A (en) * | 2022-01-24 | 2022-05-13 | 华伦皮塑（苏州）有限公司 | Synthetic leather for flame-retardant electronic competition seat and preparation method thereof |
| CN114481641B (en) * | 2022-01-24 | 2023-11-24 | 马鞍山瑞高科技有限公司 | Synthetic leather for flame-retardant electronic contest seat and preparation method thereof |
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