A kind of pliability is high, the automobile-used artificial leather of hydrolysis and preparation method thereof
Technical field
The present invention relates to a kind of leather processing fields, and in particular to a kind of pliability is high, hydrolysis automobile-used artificial leather and
Preparation method.
Background technique
In recent years, with the blowout of Chinese automobile yield, especially middle-to-high end car accounting cumulative year after year, cause user couple
Automobile human-subject test is promoted rapidly, and consequent is that the requirement to automobile is continuously improved.More and more users are no longer only
It is confined to the visual demand to vehicle configuration appearance, the design of automobile interior decoration and its becomes new for user's bring pleasure of the senses
Focus.Interior trim automobile carry user during, be unquestionably with the longest part of user's intimate contact, in addition to base
This decoration function, whether enough comforts can be provided for user, whether can be permanent keep initial color, flower
Whether the designs such as line and sense of touch may generate the use feeling that adverse effect will all directly affect user to user's body health
By.
Therefore, selecting which kind of interior material just seems particularly critical.In very long automobile interior decoration development process, polychlorostyrene second
Alkene (PVC) and polyurethane (PU) material rely on the design color texture expressive force and excellent materialization of its great impact force
The interior material of most mainstream in industry can be become, this also makes its design scheme become the mainstream scheme for substituting corium in industry.But
PVC and PU material causes two kinds of materials to fail to welcome new milestone formula development always since certain defect is individually present.
For PVC material as most widely used at present corium alternative materials, the excellent degree of performance is self-evident.So
And with the continuous improvement that user vehicle requires interior trim comfort, although feel is improved covering with paint scheme and constantly updated, still
It is difficult to meet the needs of user is to product, finds new solution and have become the objective reality that main engine plants have to face.
PU material has the performances such as excellent feel, wear-resisting, resistant to bending, low temperature resistant, but in automobile interior decoration application process, sunlight and temperature
Degree bring light-heat aging and water oxygen effect make PU material itself that hydrolysis phenomena occur.Material will result directly in it once hydrolyzing
Physical property is breached a dyke the falling in of formula.For state-of-the art, the performances such as hydrolysis of PU material are hardly resulted in into one
Step is promoted.
Application for a patent for invention CN108797143A disclose it is a kind of applied to automotive interior section with wear-resisting epidermis
The automobile-used artificial leather of lightweight, the surface treatment agent layer being sequentially distributed from top to bottom, wear-resisting epidermis, foaming layer, glue layer, base fabric
Layer;The wear-resisting epidermis includes: 80-100 parts of PVC resin powder, 50-100 parts of plasticizer, 1-20 parts of heat stabilizer, levelling agent
0.01-20 parts, 0.01-20 parts of antiager, 0.1-30 parts of anti-wear agent, wherein anti-wear agent include: 5-50 parts of hollow glass micropearl,
5-50 parts of hollow ceramic microspheres, adjacent 80-100 parts, 30-90 parts of polyvinyl chloride powder of class plasticizer of benzene.By adding tiny balloon, and
Decentralized processing is carried out to tiny balloon in advance, solves the technical problem that existing PVC artificial leather is not wear-resisting and density is big, is obtained
Not only wearability with higher, but also the PVC artificial leather with lightweight characteristic.But the hydrolytic resistance of automotive interior material
It is the very important factor of user, the problem of the invention application is not concerned with this respect.
Application for a patent for invention CN108642895A discloses a kind of aqueous coating automobile artificial leather and preparation method thereof, presses
According to mass fraction, coating material includes: waterborne, polycarbonate 100, levelling agent 0.5-2, wetting agent 1-3, thickener 1-2, defoaming
Agent 0.2-1, hand feeling agent 0.5-2, silica 0-8;Foaming layer includes: the polyvinyl chloride resin 50-100 of the degree of polymerization 1300, the degree of polymerization
2500 polyvinyl chloride resin 50-100, DINP70-90, stearic acid 0-0.5 is plasticized accelerant A CR0-3, stabilizer 3-5, three oxidations two
Antimony 10-20, foaming agent 3-6, surfactant 0.5-2, calcium carbonate 20-60;Nonfoamed layer includes: the polyvinyl chloride resin 50- of the degree of polymerization 1300
100, polyvinyl chloride resin 50-100, DINP70-90, the stearic acid 0-1 of the degree of polymerization 2500 are plasticized accelerant A CR0-3, stabilizer 3-5,
Antimony oxide 3-10, ultraviolet absorber 0.1-1, antioxidant 0-0.5.Solvent type finishing agent is replaced using aqueous coating agent, is subtracted
Few VOC emission, product have preferable surface color fastness, weather-resistant performance, low temperature resistant cold brittleness, anti-tortuosity and heat-resisting
Property.But the invention application pliability is poor, feel is poor, user experience is poor, meanwhile, material cost is high, so that the cost of vehicle mentions
It is high.
Currently, raising of the user vehicle to automobile human-subject test, causes it to get over the performance requirements such as automobile interior decoration comfort level
Come it is higher, PVC artificial leather feel and in terms of be difficult to meet user demand;And completely new interior design is also right
The performances such as wear-resisting, resistant to bending and low temperature resistant of PVC artificial leather propose requirements at the higher level.To seek more excellent feel, material development
Personnel and interior design teacher apply PU artificial leather in automobile interior decoration, PU artificial leather by splendid feel and pliability by
It greatly promotes, but due to itself group of PU material and molecule segment design reasons, there are hydrolysis problems for the material, hydrolyze bring
Negative effect makes life of product be affected.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, it is high, hydrolysis automobile-used that the present invention provides a kind of pliability
Artificial leather.
A kind of pliability is high, hydrolysis automobile-used artificial leather, by surface treatment agent layer, the epidermis being sequentially distributed from top to bottom
Layer, foaming layer, glue layer and base cloth layer composition.
Further, the epidermis is made of WPU resin, crosslinking agent, levelling agent, defoaming agent, thickener and mill base;Institute
Foaming layer is stated to be made of polyvinyl chloride resin, plasticizer, heat stabilizer, foaming agent, levelling agent and antiager.
Further, by weight, the epidermis layer is by 100 parts of WPU resins, 2-7 parts of crosslinking agents, 0.1-2 parts of levellings
Agent, 0.1-2 parts of defoaming agents, 1-5 parts of thickeners and 2-6 parts of mill bases are made.
Further, the WPU resin is according to 53504 test method of DIN, and when 100% modulus condition, stretching is slightly
1-35MPa。
Further, the WPU resin includes the aliphatic polyurethane for being not limited to polycarbonate type or polyether-type, alicyclic ring
One or more of adoption urethane, aromatic urethane.
Further, the crosslinking agent is aqueous sealing end or uncapped aliphatic, alicyclic, aromatic poly-isocyanate
One of.
Further, the levelling agent is polydimethylsiloxane, polymethylphenylsiloxane, dimethyl silicone polymer, gathers
One or more of ether polyester modified organic siloxane, alkyl-modified organosiloxane.
Further, the defoaming agent is organic silicon defoaming agent;The thickener is methylcellulose, hydroxypropyl methyl
One or more of cellulose, sodium carboxymethylcellulose and hydroxyethyl cellulose.
Further, the mill base is aqueous color paste, includes but are not limited to the inorganic mill base based on metal oxide
Or organic mill base based on azo, condensed ring class and organic macromolecule class.
Further, by weight, the foaming layer is steady by 100 parts of polyvinyl chloride resins, 75-95 parts of plasticizer, 1-20 parts of heat
Determine agent, 0.1-2 parts of foaming agents, 0.1-3 parts of levelling agents and 0.1-5 parts of antiagers to be made.
Further, the polyvinyl chloride resin is resin of the K value between 65-80.
Further, the plasticizer is phthalic ester plasticizer, fatty diacid ester plasticizer, inclined benzene
One or more of three acid ester type plasticizers, epoxidized vegetable oil class plasticizer.
Further, the plasticizer include dioctyl phthalate, n-butyl phthalate, glutarate,
Adipate ester, suberate, sebacate, dodecanedioic acid ester, tridecanedioate, trioctyl trimellitate (TOTM), epoxyoleic acid
Butyl ester, epoxyoleic acid monooctyl ester, epoxyoleic acid last of the ten Heavenly stems ester etc..
Further, the heat stabilizer is calcium stearate, castor oil calcium, zinc stearate, barium stearate and Lanthanum Stearate
One or more of.
Further, the foaming agent is AC foaming agent.
Further, the antiager is benzophenone antiager, benzotriazole antiager and triazines
One or more of antiager.
Further, the antiager includes ESCALOL 567,2- hydroxyl -4- n-octyloxy
Benzophenone, 2- hydroxyl -4- dodecyloxy benzophenones, 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, 2- (2- hydroxyl -
3- tert-butyl -5- aminomethyl phenyl) the chloro- benzotriazole of -5-, 2- (bis- (2,4- the 3,5-dimethylphenyl) -1,3,5- triazine -2- of 4,6-
Base) -5- octyloxy phenol, one or more of 2,4,6- tri- (2- hydroxyl -4- n-butoxyphenyl).
Further, the surface treatment agent layer is the one or more of polyurethane or acrylic compounds inorganic agent;The glue
Water layer is the one or more of PVC or modified grafting PVC;The base cloth layer is looped fabric.
The present invention also provides the preparation methods of a kind of pliability height, the automobile-used artificial leather of hydrolysis, comprising the following steps:
(1) epidermis slurry premixes: the WPU resin, levelling agent, defoaming agent and mill base are mixed;Thickener, dispersion is added
Stirring;Crosslinking agent is added, slurries I is stirred to obtain in dispersion;Slurries I is sieved, epidermis slurry is obtained;
(2) foamed slurry premixes: polyvinyl chloride resin, plasticizer, heat stabilizer, foaming agent, levelling agent and antiager are mixed
It closes, dispersion stirs to get slurries II;By slurries II vacuum defoamation, sieving, foaming layer slurry is obtained;
(3) prepared by artificial leather: by release paper cladding process, by the base cloth layer, glue layer, foaming layer slurry and epidermis
Slurry according to being sequentially prepared PVC artificial leather semi-finished product from top to bottom, then to PVC artificial leather semi-finished product surface treatment agent layer
Coating, obtains artificial leather.
Further, the step (1), by the WPU resin, levelling agent, defoaming agent and mill base by metering mixing, dispersion
The condition of stirring is, under the conditions of 100-300rpm, dispersion stirring 5-15min;Then under the conditions of 200-400rpm, dispersion is stirred
Mix 5-15min.
Further, the step (1), by thickener by metered, the condition for dispersing stirring is, in 100-300rpm
Under the conditions of, dispersion stirring 5-15min;Then under the conditions of 500-600rpm, dispersion stirring 5-15min.
Further, the step (1), by crosslinking agent by metered, the condition for dispersing stirring is, in 100-300rpm
Under the conditions of, dispersion stirring 5-15min;Then under the conditions of 500-600rpm, dispersion stirring 20-40min.
Further, the step (1), slurries cross 50-150 mesh.
Further, the step (2), dispersion stirring condition is, under the conditions of 200-1000rpm, dispersion stirring 10-
30min;Then under the conditions of 500-1500rpm, dispersion stirring 10-50min;Again under the conditions of 2000-3000rpm, dispersion is stirred
Mix 10-50min.
Further, the step (2), vacuum defoamation condition are vacuum defoamation 10- under the conditions of -0.15--0.01MPa
50min。
Further, the step (2), vacuum defoamation mixing speed are 100-500rpm.
Further, the slurries after deaeration are crossed 50-150 mesh by the step (2).
Further, the preparation method of high, hydrolysis the automobile-used artificial leather of a kind of pliability, comprising the following steps:
(1) epidermis slurry premixes: the WPU resin, levelling agent, defoaming agent and mill base being mixed, in 100-300rpm item
Under part, dispersion stirring 5-15min;Then under the conditions of 200-400rpm, dispersion stirring 5-15min;Thickener is added, in 100-
Under the conditions of 300rpm, dispersion stirring 5-15min;Then under the conditions of 500-600rpm, dispersion stirring 5-15min;Crosslinking is added
Agent, under the conditions of 100-300rpm, dispersion stirring 5-15min;Then under the conditions of 500-600rpm, dispersion stirring 20-40min
Obtain slurries I;By slurries I through 50-150 mesh net filtration, epidermis slurry is obtained;
(2) foamed slurry premixes: polyvinyl chloride resin, plasticizer, heat stabilizer, foaming agent, levelling agent and antiager are mixed
It closes, under the conditions of 200-1000rpm, dispersion stirring 10-30min;Then under the conditions of 500-1500rpm, dispersion stirring 10-
50min;Again under the conditions of 2000-3000rpm, dispersion stirring 10-50min obtains slurries II;By slurries II, in -0.15--
10-50min is stirred in vacuum defoamation under the conditions of 0.01MPa, 100-500rpm;By the slurries after deaeration through 50-150 mesh screen mistake
Filter, obtains foaming layer slurry;
(3) prepared by artificial leather: by release paper cladding process, by the base cloth layer, glue layer, foaming layer slurry and epidermis
Slurry according to being sequentially prepared PVC artificial leather semi-finished product from top to bottom, then to PVC artificial leather semi-finished product surface treatment agent layer
Coating, is embossed through high temperature, obtains artificial leather.
It is compared with the prior art, the beneficial effects of the present invention are:
1. selecting polyurethane material as product epidermis imparts the comfortable feel of product, high-flexibility and high abrasion
Property, while the epidermis slurry that is prepared of suitable component and foamed slurry makes product resistant to bending and resistance to low temperature also obtains
A degree of promotion.
2. material is that environmentally protective class material provides when with user's long-time intimate contact for the health of user
Guarantee, suitable preparation method, the reasonable order of addition of each component impart the excellent antioxygenic property of material and water-fast
Performance is solved, product yellowing resistance and durability is enable to get a promotion.
3. matching example by regulation polyurethane, screening suitable K is worth polyvinyl chloride resin, keeps polyurethane surface layer and PVC foam layer attached
Put forth effort significantly to be promoted, product stability is guaranteed.
4. PVC foam material substitution polyurethane foam is selected to support as product bottom, comprehensive product is greatly reduced
There is the probability of hydrolysis phenomena, further enhances the stability of product, be that life of product is extended.
5. inventive formulation designs, raw material are easy to access, compared with the preparation of full PU artificial leather, simplify operation stream
Journey shortens the production time, improves production efficiency.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and is used to explain the present invention together with embodiments of the present invention,
It is not construed as limiting the invention, in the accompanying drawings:
Fig. 1 is the present inventor's fabricate-leather structure chart, and in figure, 1-5 is respectively represented, surface treatment agent layer, epidermis, foaming layer,
Glue layer and base cloth layer.
Specific embodiment
The invention will now be further described with reference to specific embodiments, the advantages and features of the present invention will be with description and
It is apparent, but these examples are merely exemplary, it is not intended to limit the scope of the present invention in any way.Those skilled in the art
Member it should be understood that without departing from the spirit and scope of the invention can details to technical solution of the present invention and form into
Row modifications or substitutions, but these modifications and replacement are fallen within the protection scope of the present invention.
Embodiment 1
(1) epidermis slurry premix: take 100 part of 100% modulus 5-7MPa polycarbonate type aliphatic polyurethane, 0.5 part
Polydimethylsiloxane levelling agent, 0.5 part of defoaming agent and 2 parts of metal oxide-type mill bases, at 100 rpm, dispersion stirring
5min;Under the conditions of 200rpm, dispersion stirring 5min;By 1 part of methylcellulose thickener by metered after being uniformly dispersed,
Under the conditions of 100rpm, dispersion stirring 5min;After slurry viscosity obviously increases, under the conditions of 500rpm, dispersion stirring 5min;Dispersion
By 3 parts of aqueous endcap fatty adoption isocyanate crosslinkings by metered after uniformly, at 100 rpm, dispersion stirring
5min;Under the conditions of 500rpm, dispersion stirring 20min;After being uniformly dispersed by slurries through 50 mesh shine net filtration, both the epidermis
Layer slurry.
(2) foamed slurry premixes: take the polyvinyl chloride resin that 100 parts of K values are 75 to paste, 90 parts of plasticizer phthalic acid dioctyl ester,
15 parts of heat stabilizer calcium stearate, 0.5 part of AC foaming agent, 0.1 part of levelling agent polydimethylsiloxane, antiager 2- hydroxyl -4-
0.5 part of methoxy benzophenone, mixing, under the conditions of 200rpm, dispersion stirring 10min;Then under the conditions of 500rpm, dispersion
Stir 10min;Again under the conditions of 2000rpm, dispersion stirring 10min;The slurries that will be stirred, in -0.15MPa, 100rpm item
10min is stirred in vacuum defoamation under part;Slurries after deaeration are arrived into the foaming layer slurry through 50 mesh net filtrations.
(3) prepared by artificial leather: by release paper cladding process, by the base fabric, foaming layer slurry and epidermis slurry in glue
PVC artificial leather semi-finished product are prepared according to described put in order under water layer fixed function, then to PVC artificial leather semi-finished product table
Surface treatment agent coating, then be embossed through high temperature to get the automobile-used artificial of the tool good hand, high-flexibility and high hydrolytic resistance
Leather.Product is numbered, S1 is denoted as.
Embodiment 2
(1) epidermis slurry premixes: take the polycarbonate type aliphatic polyurethane of 85 part of 100% modulus 5-7MPa, 15 parts
100% modulus 30-35MPa polycarbonate type aliphatic polyurethane, 1 part of polymethylphenylsiloxane levelling agent, 1 part of defoaming agent and
4 parts of azo mill bases, under the conditions of 200rpm, dispersion stirring 10min;Under the conditions of 300rpm, dispersion stirring 10min;Dispersion
By 2 parts of hydroxypropyl methyl cellulose thickeners by metered after uniformly, under the conditions of 200rpm, dispersion stirring 10min;Slurries
After viscosity obviously increases, under the conditions of 500rpm, dispersion stirring 10min;It is after being uniformly dispersed that 4 parts of aqueous endcap fatty adoptions are different
Isocyanate cross-linking agent is by metered, under the conditions of 200rpm, dispersion stirring 10min;Under the conditions of 500rpm, dispersion stirring
30min;After being uniformly dispersed by slurries through 100 mesh shine net filtration, both the epidermis slurry.
(2) foamed slurry premixes: take the polyvinyl chloride resin that 100 parts of K values are 70 to paste, 87 parts of plasticizer trioctyl trimellitate (TOTM), and heat
15 parts of stabilizer zinc stearate, 1 part of AC foaming agent, 1 part of levelling agent dimethyl silicone polymer, antiager 2- (2- hydroxy-5-methyl
Base phenyl) 2 parts of benzotriazole, mixing, under the conditions of 500rpm, dispersion stirring 20min;Then under the conditions of 1000rpm, dispersion
Stir 30min;Again under the conditions of 2000rpm, dispersion stirring 20min;The slurries that will be stirred, in -0.1MPa, 300rpm condition
30min is stirred in lower vacuum defoamation;Slurries after deaeration are arrived into the foaming layer slurry through 100 mesh net filtrations.
(3) prepared by artificial leather: by release paper cladding process, by the base fabric, foaming layer slurry and epidermis slurry in glue
PVC artificial leather semi-finished product are prepared according to described put in order under water layer fixed function, then to PVC artificial leather semi-finished product table
Surface treatment agent coating, then be embossed through high temperature to get the automobile-used artificial of the tool good hand, high-flexibility and high hydrolytic resistance
Leather.Product is numbered, S2 is denoted as.
Embodiment 3
(1) epidermis slurry premixes: take the polycarbonate type aliphatic polyurethane of 60 part of 100% modulus 5-7MPa, 40 parts
100% modulus 20-25MPa polycarbonate type aliphatic polyurethane, 1.5 parts of dimethyl silicone polymer levelling agents, 1.5 parts of defoaming agents
With 4 parts of condensed ring class mill bases, under the conditions of 300rpm, dispersion stirring 15min;Under the conditions of 400rpm, dispersion stirring 15min;Point
By 4 parts of sodium carboxymethyl cellulose thickeners by metered after dissipating uniformly, under the conditions of 300rpm, dispersion stirring 15min;Slurries
After viscosity obviously increases, under the conditions of 600rpm, dispersion stirring 15min;By 5 uncapped aliphatic polyurethanes after being uniformly dispersed
Crosslinking agent is by metered, under the conditions of 300rpm, dispersion stirring 15min;Under the conditions of 600rpm, dispersion stirring 40min;Point
Dissipate uniformly after by slurries through 150 mesh shine net filtration, both the epidermis slurry.
(2) foamed slurry premixes: taking the polyvinyl chloride resin that 100 parts of K values are 75 to paste, 80 parts of plasticizer epoxyoleic acid butyl ester, heat is steady
Determine 20 parts of agent castor oil calcium, 1 part of AC foaming agent, 2 parts of levelling agent polydimethylsiloxane, antiager 2- hydroxyl -4- n-octyloxy
3 parts of benzophenone mixing, under the conditions of 400rpm, dispersion stirring 20min;Then under the conditions of 800rpm, dispersion stirring
30min;Again under the conditions of 2000rpm, dispersion stirring 20min;The slurries that will be stirred, it is true under the conditions of -0.1MPa, 500rpm
50min is stirred in empty deaeration;Slurries after deaeration are arrived into the foaming layer slurry through 150 mesh net filtrations.
(3) prepared by artificial leather: by release paper cladding process, by the base fabric, foaming layer slurry and epidermis slurry in glue
PVC artificial leather semi-finished product are prepared according to described put in order under water layer fixed function, then to PVC artificial leather semi-finished product table
Surface treatment agent coating, then be embossed through high temperature to get the automobile-used artificial of the tool good hand, high-flexibility and high hydrolytic resistance
Leather.Product is numbered, S3 is denoted as.
Embodiment 4
(1) epidermis slurry premixes: take the polycarbonate type aliphatic polyurethane of 70 part of 100% modulus 2-4MPa, 30 parts
100% modulus 30-35MPa polycarbonate type aliphatic polyurethane, 2 parts of polyether polyester azo polyether polyeste levelling agents, 2 parts disappear
Infusion and 5 parts of organic macromolecule class mill bases, under the conditions of 300rpm, dispersion stirring 15min;Under the conditions of 400rpm, dispersion is stirred
Mix 15min;By 5 parts of hydroxyethylcellulose thickeners by metered after being uniformly dispersed, under the conditions of 300rpm, dispersion stirring
15min;After slurry viscosity obviously increases, under the conditions of 600rpm, dispersion stirring 15min;By 5 uncapped rouge after being uniformly dispersed
Ring race polyurethane cross-linking agent is by metered, under the conditions of 300rpm, dispersion stirring 15min;Under the conditions of 600rpm, dispersion is stirred
Mix 40min;After being uniformly dispersed by slurries through 150 mesh shine net filtration, both the epidermis slurry.
(2) foamed slurry premixes: take the polyvinyl chloride resin that 100 parts of K values are 70 to paste, 85 parts of plasticizer phthalic acid N-butyl,
17 parts of heat stabilizer barium stearate, 0.6 part of AC foaming agent, 3 parts of levelling agent polymethylphenylsiloxane, antiager 2- hydroxyl-
4 parts of 4- dodecyloxy benzophenones, mixing, under the conditions of 800rpm, dispersion stirring 30min;Then in 1500rpm condition
Under, dispersion stirring 50min;Again under the conditions of 3000rpm, dispersion stirring 50min;The slurries that will be stirred, -0.8MPa,
50min is stirred in vacuum defoamation under the conditions of 500rpm;Slurries after deaeration are arrived into the foaming layer through 150 mesh net filtrations
Slurry.
(3) prepared by artificial leather: by release paper cladding process, by the base fabric, foaming layer slurry and epidermis slurry in glue
PVC artificial leather semi-finished product are prepared according to described put in order under water layer fixed function, then to PVC artificial leather semi-finished product table
Surface treatment agent coating, then be embossed through high temperature to get the automobile-used artificial of the tool good hand, high-flexibility and high hydrolytic resistance
Leather.Product is numbered, S4 is denoted as.
Embodiment 5
(1) epidermis slurry premixes: taking the polyether-type aliphatic polyurethane of 70 part of 100% modulus 5-7MPa, 30 part of 100% mould
Measure 30-35MPa polyether-type cycloaliphatic polyurethane, 1.5 parts of dimethyl silicone polymer levelling agents, 1.5 parts of defoaming agents and 4 parts of metal oxygens
Compound class mill base, under the conditions of 300rpm, dispersion stirring 15min;Under the conditions of 400rpm, dispersion stirring 15min;It is uniformly dispersed
Afterwards by 4 parts of sodium carboxymethyl cellulose thickeners by metered, under the conditions of 300rpm, dispersion stirring 15min;Slurry viscosity is bright
After aobvious increase, under the conditions of 600rpm, dispersion stirring 15min;By 5 uncapped aliphatic polyurethane crosslinking agents after being uniformly dispersed
By metered, under the conditions of 300rpm, dispersion stirring 15min;Under the conditions of 600rpm, dispersion stirring 40min;It is uniformly dispersed
Afterwards by slurries through 150 mesh shine net filtration, both the epidermis slurry.
(2) foamed slurry premixes: take the polyvinyl chloride resin that 100 parts of K values are 75 to paste, 80 parts of plasticizer adipate ester, and heat stabilizer
20 parts of Lanthanum Stearate, 1 part of AC foaming agent, 2 parts of levelling agent polyester modified organic siloxane, antiager 2- (the tertiary fourth of 2- hydroxyl -3-
Base -5- aminomethyl phenyl) 3 parts of the chloro- benzotriazole of -5-, mixing, under the conditions of 400rpm, dispersion stirring 20min;Then exist
Under the conditions of 800rpm, dispersion stirring 30min;Again under the conditions of 2000rpm, dispersion stirring 20min;The slurries that will be stirred ,-
50min is stirred in vacuum defoamation under the conditions of 0.1MPa, 500rpm;By the slurries after deaeration through 150 mesh net filtrations to get described in
Foaming layer slurry.
(3) prepared by artificial leather: by release paper cladding process, by the base fabric, foaming layer slurry and epidermis slurry in glue
PVC artificial leather semi-finished product are prepared according to described put in order under water layer fixed function, then to PVC artificial leather semi-finished product table
Surface treatment agent coating, then be embossed through high temperature to get the automobile-used artificial of the tool good hand, high-flexibility and high hydrolytic resistance
Leather.Product is numbered, S5 is denoted as.
Embodiment 6
(1) epidermis slurry premixes: taking the polyether-type cycloaliphatic polyurethane of 50 part of 100% modulus 2-4MPa, 50 part of 100% mould
Measure 20-25MPa polyether-type aliphatic polyurethane, 2 parts of polyether polyester azo polyether polyeste levelling agents, 2 parts of defoaming agents and 5 parts of idols
Nitrogen class mill base, under the conditions of 300rpm, dispersion stirring 15min;Under the conditions of 400rpm, dispersion stirring 15min;After being uniformly dispersed
By 5 parts of hydroxyethylcellulose thickeners by metered, under the conditions of 300rpm, dispersion stirring 15min;Slurry viscosity obviously increases
After adding, under the conditions of 600rpm, dispersion stirring 15min;After being uniformly dispersed by 5 uncapped cycloaliphatic polyurethane crosslinking agents based on
Amount is added, under the conditions of 300rpm, dispersion stirring 15min;Under the conditions of 600rpm, dispersion stirring 40min;It will after being uniformly dispersed
Slurries through 150 mesh shine net filtration, both the epidermis slurry.
(2) foamed slurry premixes: taking the polyvinyl chloride resin that 100 parts of K values are 75 to paste, 90 parts of last of the ten Heavenly stems ester of plasticizer epoxyoleic acid, heat is steady
Determine 15 parts of agent Lanthanum Stearate, 0.5 part of AC foaming agent, 0.1 part of levelling agent alkyl-modified organosiloxane, antiager 2- (4,6-
Bis- (2,4- 3,5-dimethylphenyl) -1,3,5-triazines -2- bases) 0.5 part of -5- octyloxy phenol, mixing, under the conditions of 200rpm, dispersion
Stir 10min;Then under the conditions of 500rpm, dispersion stirring 10min;Again under the conditions of 2000rpm, dispersion stirring 10min;It will
The slurries being stirred, 10min is stirred in vacuum defoamation under the conditions of -0.15MPa, 100rpm;By the slurries after deaeration through 50 meshes
Net filtration to get arrive the foaming layer slurry.
(3) prepared by artificial leather: by release paper cladding process, by the base fabric, foaming layer slurry and epidermis slurry in glue
PVC artificial leather semi-finished product are prepared according to described put in order under water layer fixed function, then to PVC artificial leather semi-finished product table
Surface treatment agent coating, then be embossed through high temperature to get the automobile-used artificial of the tool good hand, high-flexibility and high hydrolytic resistance
Leather.Product is numbered, S6 is denoted as.
Embodiment 7
(1) epidermis slurry premixes: taking the polyether-type aliphatic polyurethane of 90 part of 100% modulus 2-4MPa, 10 part of 100% mould
Measure 30-35MPa polyether-type aromatic urethane, 0.5 part of polydimethylsiloxane levelling agent, 0.5 part of defoaming agent and 2 parts of condensed ring class colors
Slurry, at 100 rpm, dispersion stirring 5min;Under the conditions of 200rpm, dispersion stirring 5min;By 1 part of first after being uniformly dispersed
Base cellulose thickener is by metered, at 100 rpm, dispersion stirring 5min;After slurry viscosity obviously increases,
Under the conditions of 500rpm, dispersion stirring 5min;By 3 parts of aqueous endcap fatty adoption isocyanate crosslinkings by metering after being uniformly dispersed
It is added, at 100 rpm, dispersion stirring 5min;Under the conditions of 500rpm, dispersion stirring 20min;It will slurry after being uniformly dispersed
Liquid through 50 mesh shine net filtration, both the epidermis slurry.
(2) foamed slurry premixes: take the polyvinyl chloride resin that 100 parts of K values are 70 to paste, 85 parts of plasticizer sebacate, and heat stabilizer
17 parts of barium stearate, 0.6 part of AC foaming agent, 3 parts of levelling agent alkyl-modified organosiloxane, antiager 2,4, (the 2- hydroxyl of 6- tri-
Base -4- n-butoxyphenyl) 4 parts, mixing, under the conditions of 800rpm, dispersion stirring 30min;Then under the conditions of 1500rpm,
Dispersion stirring 50min;Again under the conditions of 3000rpm, dispersion stirring 50min;The slurries that will be stirred, in -0.8MPa, 500rpm
Under the conditions of vacuum defoamation stir 50min;Slurries after deaeration are arrived into the foaming layer slurry through 150 mesh net filtrations.
(3) prepared by artificial leather: by release paper cladding process, by the base fabric, foaming layer slurry and epidermis slurry in glue
PVC artificial leather semi-finished product are prepared according to described put in order under water layer fixed function, then to PVC artificial leather semi-finished product table
Surface treatment agent coating, then be embossed through high temperature to get the automobile-used artificial of the tool good hand, high-flexibility and high hydrolytic resistance
Leather.Product is numbered, S7 is denoted as.
Embodiment 8
(1) epidermis slurry premixes: take the polycarbonate type aliphatic polyurethane of 30 part of 100% modulus 5-7MPa, 70 parts
100% modulus 30-35MPa polyether-type aliphatic polyurethane, 1 part of polymethylphenylsiloxane levelling agent, 1 part of defoaming agent and 4 parts
Organic macromolecule class mill base, under the conditions of 200rpm, dispersion stirring 10min;Under the conditions of 300rpm, dispersion stirring 10min;Point
By 2 parts of hydroxypropyl methyl cellulose thickeners by metered after dissipating uniformly, under the conditions of 200rpm, dispersion stirring 10min;Slurry
After fluid viscosity obviously increases, under the conditions of 500rpm, dispersion stirring 10min;It is after being uniformly dispersed that 4 aqueous endcap fatty adoptions are different
Isocyanate cross-linking agent is by metered, under the conditions of 200rpm, dispersion stirring 10min;Under the conditions of 500rpm, dispersion stirring
30min;After being uniformly dispersed by slurries through 100 mesh shine net filtration, both the epidermis slurry.
(2) foamed slurry premixes: taking the polyvinyl chloride resin that 100 parts of K values are 75 to paste, 90 parts of plasticizer tridecanedioate, heat is steady
Determine 15 parts of agent castor oil calcium, 0.5 part of AC foaming agent, 0.1 part of levelling agent polymethylphenylsiloxane, antiager 2,4,6- tri-
0.5 part of (2- hydroxyl -4- n-butoxyphenyl), mixing, under the conditions of 200rpm, dispersion stirring 10min;Then in 500rpm item
Under part, dispersion stirring 10min;Again under the conditions of 2000rpm, dispersion stirring 10min;The slurries that will be stirred, -0.15MPa,
10min is stirred in vacuum defoamation under the conditions of 100rpm;Slurries after deaeration are starched through 50 mesh net filtrations to get to the foaming layer
Material.
(3) prepared by artificial leather: by release paper cladding process, by the base fabric, foaming layer slurry and epidermis slurry in glue
PVC artificial leather semi-finished product are prepared according to described put in order under water layer fixed function, then to PVC artificial leather semi-finished product table
Surface treatment agent coating, then be embossed through high temperature to get the automobile-used artificial of the tool good hand, high-flexibility and high hydrolytic resistance
Leather.Product is numbered, S8 is denoted as.
Embodiment 9
(1) epidermis slurry premixes: taking the polyether-type aromatic urethane of 20 part of 100% modulus 2-4MPa, 80 part of 100% mould
Measure 20-25MPa polyether-type aromatic urethane, 1 part of polymethylphenylsiloxane levelling agent, 1 part of defoaming agent and 4 parts of metal oxidations
Species mill base, under the conditions of 200rpm, dispersion stirring 10min;Under the conditions of 300rpm, dispersion stirring 10min;After being uniformly dispersed
By 2 parts of hydroxypropyl methyl cellulose thickeners by metered, under the conditions of 200rpm, dispersion stirring 10min;Slurry viscosity is bright
After aobvious increase, under the conditions of 500rpm, dispersion stirring 10min;4 aqueous endcap fatty adoption isocyanates are handed over after being uniformly dispersed
Join agent by metered, under the conditions of 200rpm, dispersion stirring 10min;Under the conditions of 500rpm, dispersion stirring 30min;Dispersion
Uniformly after by slurries through 100 mesh shine net filtration, both the epidermis slurry.
(2) foamed slurry premixes: taking the polyvinyl chloride resin that 100 parts of K values are 75 to paste, 90 parts of plasticizer tridecanedioate, heat is steady
Determine 15 parts of agent barium stearate, 0.5 part of AC foaming agent, 0.1 part of levelling agent polydimethylsiloxane, antiager 2- hydroxyl -4- 12
0.5 part of alkoxy benzophenone, mixing, under the conditions of 200rpm, dispersion stirring 10min;Then under the conditions of 500rpm, dispersion
Stir 10min;Again under the conditions of 2000rpm, dispersion stirring 10min;The slurries that will be stirred, in -0.15MPa, 100rpm item
10min is stirred in vacuum defoamation under part;Slurries after deaeration are arrived into the foaming layer slurry through 50 mesh net filtrations.
(3) prepared by artificial leather: by release paper cladding process, by the base fabric, foaming layer slurry and epidermis slurry in glue
PVC artificial leather semi-finished product are prepared according to described put in order under water layer fixed function, then to PVC artificial leather semi-finished product table
Surface treatment agent coating, then be embossed through high temperature to get the automobile-used artificial of the tool good hand, high-flexibility and high hydrolytic resistance
Leather.Product is numbered, S9 is denoted as.
Embodiment 10
(1) epidermis slurry premixes: take the polycarbonate type aliphatic polyurethane of 10 part of 100% modulus 5-7MPa, 90 parts
100% modulus 30-35MPa polycarbonate type aliphatic polyurethane, 1 part of polymethylphenylsiloxane levelling agent, 1 part of defoaming agent and
4 parts of azo mill bases, under the conditions of 200rpm, dispersion stirring 10min;Under the conditions of 300rpm, dispersion stirring 10min;Dispersion
By 2 parts of hydroxypropyl methyl cellulose thickeners by metered after uniformly, under the conditions of 200rpm, dispersion stirring 10min;Slurries
After viscosity obviously increases, under the conditions of 500rpm, dispersion stirring 10min;By 4 aqueous endcap fatty adoption isocyanides after being uniformly dispersed
Acid esters crosslinking agent is by metered, under the conditions of 200rpm, dispersion stirring 10min;Under the conditions of 500rpm, dispersion stirring
30min;After being uniformly dispersed by slurries through 100 mesh shine net filtration, both the epidermis slurry.
(2) foamed slurry premixes: take the polyvinyl chloride resin that 100 parts of K values are 70 to paste, 85 parts of plasticizer suberate, and heat stabilizer
17 parts of Lanthanum Stearate, 0.6 part of AC foaming agent, 3 parts of levelling agent dimethyl silicone polymer, antiager 2- (4,6- bis- (2,4- diformazans
Base phenyl) -1,3,5-triazines -2- base) 4 parts of -5- octyloxy phenol, mixing, under the conditions of 800rpm, dispersion stirring 30min;Then
Under the conditions of 1500rpm, dispersion stirring 50min;Again under the conditions of 3000rpm, dispersion stirring 50min;The slurries that will be stirred,
50min is stirred in vacuum defoamation under the conditions of -0.8MPa, 500rpm;Slurries after deaeration are arrived through 150 mesh net filtrations
The foaming layer slurry.
(3) prepared by artificial leather: by release paper cladding process, by the base fabric, foaming layer slurry and epidermis slurry in glue
PVC artificial leather semi-finished product are prepared according to described put in order under water layer fixed function, then to PVC artificial leather semi-finished product table
Surface treatment agent coating, then be embossed through high temperature to get the automobile-used artificial of the tool good hand, high-flexibility and high hydrolytic resistance
Leather.Product is numbered, S10 is denoted as.
Comparative example 1
Its preparation process the difference is that only the performance of epidermis addition polyurethane: not adding 100% with embodiment 1
Modulus, the aqueous polyurethane of mechanical property 5-7MPa, and add the poly- ammonia of 100% modulus mechanical property 40-45MPa of equivalent
Ester.Product is numbered, B1 is denoted as.
Comparative example 2
Its preparation process the difference is that only the composition of foaming layer PVC with embodiment 1: the PVC that K value is 75 is not added,
And add polyvinyl chloride resin of the equivalent K value between 60-65.Product is numbered, B2 is denoted as.
Comparative example 3
Its preparation process is with embodiment 1, and difference is only in epidermis layer component.Epidermis selects commercially available PVC slurry, to production
Product are numbered, and are denoted as B3.
Comparative example 4
Its preparation process only forms in epidermis different with embodiment 1, difference: 100% modulus 5- in epidermis
The polycarbonate type aliphatic polyurethane of 7MPa is 160 parts, and polydimethylsiloxane levelling agent is 5 parts, methylcellulose thickener
It is 0.5 part, is denoted as B4.
Comparative example 5
Its preparation process is with embodiment 1, and for difference only when epidermis slurry premixes, each component order by merging is different.Tool
Body is as follows:
(1) epidermis slurry premixes: taking the polycarbonate type aliphatic polyurethane of 100 part of 100% modulus 5-7MPa, 1 part of first
Base cellulose thickener and 2 parts of metal oxide-type mill bases, at 100 rpm, dispersion stirring 5min;In 200rpm condition
Under, dispersion stirring 5min;By 0.5 part of polydimethylsiloxane levelling agent and 3 parts of aqueous endcap fatty adoption isocyanides after being uniformly dispersed
Acid esters crosslinking agent is by metered, at 100 rpm, dispersion stirring 5min;After slurry viscosity obviously increases, in 500rpm
Under the conditions of, dispersion stirring 5min;By 0.5 part of defoaming agent by metered after being uniformly dispersed, at 100 rpm, dispersion stirring
5min;Under the conditions of 500rpm, dispersion stirring 20min;After being uniformly dispersed by slurries through 50 mesh shine net filtration, both the epidermis
Layer slurry.
(2) foamed slurry premixes: take the polyvinyl chloride resin that 100 parts of K values are 75 to paste, 90 parts of plasticizer, and 15 parts of heat stabilizer, hair
0.5 part of infusion, 0.1 part of levelling agent, 0.5 part of antiager, mixing, under the conditions of 200rpm, dispersion stirring 10min;Then exist
Under the conditions of 500rpm, dispersion stirring 10min;Again under the conditions of 2000rpm, dispersion stirring 10min;The slurries that will be stirred ,-
10min is stirred in vacuum defoamation under the conditions of 0.15MPa, 100rpm;By the slurries after deaeration through 50 mesh net filtrations to get described in
Foaming layer slurry.
(3) prepared by artificial leather: by release paper cladding process, by the base fabric, glue, foaming layer slurry and epidermis slurry
PVC artificial leather semi-finished product are prepared according to described put in order, then PVC artificial leather semi-finished product are coated with surface treating agent,
It is embossed again through high temperature to get the automobile-used artificial leather of the tool tool good hand, high-flexibility and high hydrolytic resistance.To product into
Row number is denoted as B5.
The evaluation of 1 hydrolytic resistance of experimental example
Product in above-described embodiment 1-10 and comparative example 1-5 is cut into identical size, sample is in 80 DEG C of 75% humidity
8 weeks are stood in environment, appearance is observed after taking-up, gray scale grading is carried out to aged samples with Color-EYE 7000A, is placed in
It is detected on folding tester, requires to grade to sample according to following table, up to 5 grades.
Grade |
Description |
5 |
Surface is unchanged, without any bending trace |
4 |
There is slight folding line in surface slight change |
3 |
Surface occurs rolling over white or push up white |
2 |
Surface significant change, surface covering cracking fade |
1 |
Surface seriously changes, skin breakage |
2 hand valuation of experimental example
Tester directly uses hand contact product, evaluates its feel, and all tests are evaluated by same people.
The evaluation of the rigid softness of experimental example 3
Along the sample for respectively taking 5 200mm × 25mm through broadwise, sample epidermis is placed on platform, pressing plate pressure along graduated scale upwards
On sample, pressing plate is slowly moved to test equipment slope one end, until sample front end is in contact with 45 ° of slopes, record is tried
Sample moving distance, test value is bigger, and hardness is higher.
The evaluation of experimental example 4Taber abrasion resistance
Product in above-described embodiment and comparative example is cut into identical size, is placed on Taber abrasion wear test machine and carries out
Test.It requires to grade to sample according to following table, up to 5 grades.
Grade |
Description |
5 |
Surface is almost unchanged, texture free of losses, gloss slight change |
4 |
Surface slight change, texture slight loss, gloss change greatly |
3 |
Surface significant change, texture significantly sacrificing, gloss change very greatly |
2 |
Surface seriously changes, and texture loss is serious |
1 |
Foaming layer, base fabric or PPF exposure, texture completely disappear |
The evaluation of 5 bending resistance of experimental example
Along the sample for respectively taking 3 70mm × 45mm through broadwise, sample epidermis side is folded inward, makes two long side alignment,
It is mounted in upper fixture, the two corners that sample is not clamped are foldable outwardly, and are mounted on lower fixture.Experiment number is set, after test
For sample in 10 times of amplifications microscopic observations, ranking method is identical as 1 ranking method of experimental example, and up to 5 grades.
The evaluation of 6 resistance to low temperature of experimental example
Product in above-described embodiment and comparative example is cut into identical size, is placed on folding tester and is examined
It surveys, is tested in low temperature environment.Ranking method is identical as 1 ranking method of experimental example, and up to 5 grades.
Experimental result is as follows:
The performance test results of embodiment and comparative example product
It can be seen that selection polyurethane material conduct in the present invention in conjunction with above-described embodiment comparative example and 1 test result of table
Epidermis with good hand, high-flexibility and high hydrolytic resistance automobile-used artificial leather, relative to do not use polyurethane material,
And use artificial leather of the PVC material as epidermis, i.e., product and the comparison of 3 product of comparative example in embodiment, feel, pliability,
The performances such as wear-resisting, resistant to bending and low temperature resistant are more excellent, illustrate that WPU imparts the multinomial Optimality of product as product epidermis
Energy.Comparative example 1 and comparative example 2 select waterborne, polycarbonate type aliphatic polyurethane as epidermis, also have relative to comparative example 3
There is certain pliability advantage.But resistant to bending and cold tolerance is very poor, illustrates the lower WPU resin of 100% modulus value of thrust and PVC
Foaming layer has higher adhesive force, makes to be not readily separated between layers, assigns that product is higher resistant to bending and cold resistance.Simultaneously
Also illustrate that polyvinyl chloride resin pastes and cold tolerance resistant to bending to product and also has strong influence.
Integration test result is it is found that the application has following advantages:
1. product of the present invention has good hand, pliability high;
2. product of the present invention hydrolytic resistance is high;
3. product of the present invention has excellent wear-resisting, resistant to bending, resistance to low temperature;
4. preparation method of the present invention is simple, it is easy to industrialize, there is good industrial prospect.
The technical means disclosed in the embodiments of the present invention is not limited only to above-mentioned disclosed technological means, further includes by the above skill
Technical solution composed by art feature any combination.The foregoing is a specific embodiment of the present invention, it is noted that for this
For the those of ordinary skill of technical field, without departing from the principle of the present invention, if the improvement can also be made and repaired
Decorations, these also will be regarded as protection scope of the present invention.