CN107164971A - The preparation method of leather and application - Google Patents
The preparation method of leather and application Download PDFInfo
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- CN107164971A CN107164971A CN201710271573.1A CN201710271573A CN107164971A CN 107164971 A CN107164971 A CN 107164971A CN 201710271573 A CN201710271573 A CN 201710271573A CN 107164971 A CN107164971 A CN 107164971A
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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
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
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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
- D06N3/0056—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
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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
- D06N3/0056—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
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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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
- D06N2209/00—Properties of the materials
- D06N2209/04—Properties of the materials having electrical or magnetic properties
- D06N2209/046—Anti-static
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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
- D06N2209/00—Properties of the materials
- D06N2209/04—Properties of the materials having electrical or magnetic properties
- D06N2209/048—Electromagnetic interference shielding
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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
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
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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
- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/105—Resistant to abrasion, scratch
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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
- D06N2209/00—Properties of the materials
- D06N2209/12—Permeability or impermeability properties
- D06N2209/126—Permeability to liquids, absorption
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- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
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- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1678—Resistive to light or to UV
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- D—TEXTILES; PAPER
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- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention relates to a kind of preparation method of leather, comprise the following steps：S101：Graphene is dissolved in acid solution, and in heating 3h~5h at 110 DEG C~130 DEG C；S102：Polyethyl acrylate and tourmaline powder are added in the product that S101 is obtained, the pH value for stirring and adjusting product is 5.8~6.3；S103：Polyurethane resin and polyvinyl alcohol are added in the product that S102 is obtained and is stirred；S104：The obtained products of S103 are coated in leather base cloth, leather is obtained.Using graphene as additive application in the preparation process of leather, thus obtained leather and fur products and especially skin summer sleeping mat have excellent wear-resisting scratch resistance, it is antistatic, inhale ripple, antibacterial, mould proof, anti-UV agings, flame-retardant smoke inhibition, electromagnetic shielding, the function such as far infrared health care；So as to the grade of General Promotion leather, the function in terms of the comfortableness of China's cowhide mat, durability, antimildew and antibacterial is lifted.
Description
Technical field
The present invention relates to chemical technology field, and in particular to a kind of preparation method of leather and application.
Background technology
It is well known that graphene be carbon atom each other with sp2 keys and the two-dimensional material of honeycomb crystal lattice arrangement form,
It can infinitely extend in two-dimensional space, and be considered as material most thin on universe, be also considered as most solid material.Graphene
With not penetrability, excellent mechanical performance, the transparency and electric conductivity etc., and it is considered as the preferable material of separation application
Material, turns into the study hotspot of physics, chemistry, biology and materials science field at present.
China is as artificial leather synthetic leather big producer, and in recent years, leather industry is developed rapidly, and leather and fur products is also increasingly
It is widely used in daily life, such as sofa, clothes are up to popular in recent years summer sleeping mat and cushion.Wherein, it is cool
Seat is indispensable as the suitable to people of all ages reducing temperature of heatstroke prevention good merchantable brand of summer and autumn high temperature season.At present, commodity summer sleeping mat is substantially all to be natural fine
Summer sleeping mat is tieed up, mainly has straw mat, bamboo mat, linen mat, rattan seat and cow leather mat etc., is made by natural fiber material.Wherein, (1) grass
Seat：Cheap, material is soft, but cooling property is poor, not enough feel nice and cool, and is easily caused human allergy, easily gives birth to acarid.(2) bamboo mat：Lead
Hot coefficient is high, feels nice and cool, old man, child and Low people should not use.(3) linolenic summer sleeping mat：Moisture absorption is ventilative, antibacterial, but not enough
Nice and cool and excessively soft, planarization is poor.(4) rattan peel summer sleeping mat.Good toughness, not easy to break, soft abrasion-resistant, elasticity are good, foldable,
Service life is long, and comfortable, radiating is nice and cool, and absorbing sweat does not glue body, is not damaged by worms, but price is higher.(5) cowhide mat：Thermal capacity is big,
Thermal diffusivity is relatively good, and moisture-proof function is excellent, has the disadvantage there is adhesion sense when skin has sweat, and price is higher.Conventionally employed natural leather
Although the skin summer sleeping mat being made has smooth, refrigerant, water vapor permeability good, the advantages of cosmetic variation is more and durable in use also have not
Preferably wash easily decolouring, the weak point such as keeping and maintenance trouble.The incongruent main harm of colorfastness to rubbing：The lighter easily causes dirt
The light clothing of dye, the composition that severe one is easily caused in top finishing layer is absorbed after human contact, so as to produce shadow to health
Ring, the service life of product may also be directly influenced in addition.In addition, along with the continuous improvement of people's material and culture level,
Consumer is light to leather and fur products, thin, soft, it is comfortable pursue, also require that accordingly the summer sleeping mat used have light, waterproof, breathe freely,
The excellent ground such as wear-resisting, fast light combination property.
Based on this, a kind of more preferable leather of each side's surface properties how is effectively provided, to conform better to consumer demand
It is particularly important.
The content of the invention
For defect of the prior art, the present invention is intended to provide preparation method and the application of a kind of leather.Using this hair
The technical scheme of bright offer, using graphene as additive application in the preparation process of leather, thus obtained leather and fur products
And especially skin summer sleeping mat has excellent wear-resisting scratch resistance, antistatic, suction ripple, antibacterial, mould proof, anti-UV agings, flame-retardant smoke inhibition, electromagnetism
The functions such as shielding, far infrared health care；So as to the grade of General Promotion leather, the comfortableness of lifting China cowhide mat is resistance to
With property, the function in terms of antimildew and antibacterial.
Therefore, the present invention provides following technical scheme：
In a first aspect, the present invention provides a kind of preparation method of leather, comprise the following steps：S101：Graphene is dissolved in
In acid solution, and in heating 3h~5h at 110 DEG C~130 DEG C；S102：Polyethyl acrylate is added in the product that S101 is obtained
And tourmaline powder, 100min~300min is stirred at 85 DEG C~90 DEG C afterwards, the pH value of regulation product is 5.8~6.3；
S103：Polyurethane resin and polyvinyl alcohol are added in the product that S102 is obtained and is stirred；S104：The production that S103 is obtained
Thing is coated in leather base cloth, obtains leather.
In the further embodiment of the present invention, in S101, acid solution is specially：Solute is sulfuric acid and phosphoric acid, and sulphur
The mass ratio of acid and phosphoric acid is 1：The mass ratio of (0.5~0.8), solute and solvent is (3~5)：100；Graphene and acid solution
Mass ratio be (1~3)：10.
In the further embodiment of the present invention, in S103, polyurethane resin is by PPG and isocyanates system
It is standby to form；Wherein, the mol ratio of PPG and isocyanates is (1.2~2)：1.
In the further embodiment of the present invention, PPG includes PTMG, and poly- tetrahydrochysene furan
Mutter ether glycol number-average molecular weight be 5000~10000；Isocyanates includes 2,4,4- trimethyl hexamethylene diisocyanates.
In the further embodiment of the present invention, in S103, also include after stirring：Stirred in S103
Oxammonium hydrochloride and tetradecanoic acid butyl ester are added in product afterwards, and it is 7.5~8.0 to adjust pH value, is afterwards 1500rpm in rotating speed
~2500rpm, temperature is stirring 30min~50min under conditions of 55 DEG C~60 DEG C；Wherein, graphene, oxammonium hydrochloride and 14
The mass ratio of alkanoic acid butyl ester is followed successively by 1：(1~3)：(2~5).
The present invention further embodiment in, graphene, polyurethane resin, polyvinyl alcohol, polyethyl acrylate with
The mass ratio of tourmaline powder is (0.18~0.23)：100：(3~5)：(1~3)：(1~2).
In the further embodiment of the present invention, the number-average molecular weight of polyvinyl alcohol is 10000~30000, alcoholysis degree
For 78%~90%；The number-average molecular weight of polyethyl acrylate is 8000~20000.
In the further embodiment of the present invention, in S103, polyurethane resin and polyvinyl alcohol and the bar stirred are added
Part is specially：Add after polyurethane resin and polyvinyl alcohol, be 65 DEG C~75 DEG C in temperature, rotating speed is 2500rpm~3500rpm
Under conditions of stir 3h~6h.
In the further embodiment of the present invention, leather base cloth includes looped fabric, woven fabric, non-woven fabrics, woven fabric non-woven fabrics
With the one or more in corium；Wherein, corium includes ox-hide.
Second aspect, the leather that the method provided using the present invention is prepared.
The third aspect, application of the leather that the present invention is prepared in leather and fur products or leather and fur products additive is prepared.
The above-mentioned technical proposal of the present invention has advantages below compared with prior art：
(1) applicant has found by numerous studies：Using graphene as additive application in the preparation process of leather, by
This obtained leather and fur products and especially skin summer sleeping mat have excellent wear-resisting scratch resistance, antistatic, suction ripple, antibacterial, mould proof, anti-UV old
The functions such as change, flame-retardant smoke inhibition, electromagnetic shielding, far infrared health care；So as to the grade of General Promotion leather, lifting China ox-hide
Function in terms of the comfortableness of summer sleeping mat, durability, antimildew and antibacterial.
(2) leather that the present invention is prepared has excellent colorfastness to rubbing.It is well known that using colorfastness to rubbing compared with
The leather and fur products of difference, the lighter easily causes the pollution to light clothing, and the composition that severe one is easily caused in top finishing layer is connect by human body
Absorb after touch, so as to produce influence to health；In addition, the shortcoming may also directly influence the service life of product.
(3) leather that the present invention is prepared has excellent water suction vapour.The bad leather and fur products of conventional absorbent vapour
User's skin can be made uncomfortable, and lose cooling feeling, so as to can not embody the peculiar function of leather and fur products；Water suction vapour official post is obtained
The sweat of product surface is not volatile, and then is possible to produce various bacteriums, and it is unfavorable to health to be used for a long time；Absorb water vapour
Difference also results in human sweat and stayed for a long time in product surface, so that top finishing layer is easy to fall off.
(4) leather and fur products that the present invention is prepared has excellent resistance to colour fastness to water.Leather and fur products price general charged ratio
Costly, if consumer accidentally splashes water or liquid on leather and fur products, poor resistance to colour fastness to water can make
Will produce on leather and fur products water stain, and be difficult cleaning；And the later stage maintenance of such leather and fur products is difficult, because simply
Water is wiped and is likely to bring irremediable spot to leather and fur products, and then adds the cost of upkeep of consumer.
(5) applicant is by investigating discovery：Once consumer chooses traditional cowhide mat of low price, and traditional ox
Skin summer sleeping mat, which is bought back home, has slept soon, with regard to whole skin allergy.The identification of commission quality testing department is found afterwards：Traditional cowhide mat is adopted
Chromatograph is applied with resin, ox-hide pore is blocked, it is impossible to ventilative absorbing sweat, and businessman is to reduce cost, from harmful change
Learn product and complete process for tanning, formaldehyde severe overweight causes a hidden trouble to health.And the preparation method provided using the present invention, will
Graphene etc. is made an addition in the preparation process of leather, and thus obtained leather and fur products gas permeability and wearability are greatly improved, even
Negative oxygen ion can be distributed, plays a part of purifying the air of a room.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Embodiment
The embodiment to technical solution of the present invention is described in detail below.Following examples are only used for clearer
Explanation technical scheme, therefore be only used as example, and can not be limited the scope of the invention with this.
Experimental method in following embodiments, is conventional method unless otherwise specified.
Test material used, is to be commercially available from conventional reagent shop unless otherwise specified in following embodiments.
Quantitative test in following examples, is respectively provided with three repetition experiments, and data are the average value of three repetition experiments
Or mean+SD.
Polyethyl acrylate used in the present invention is purchased from Jinan Xin Senyuan Chemical Co., Ltd.s, PTMG purchase
From the open chemical materials Co., Ltd in Shanghai, polyvinyl alcohol is purchased from Shenzhen uncle along Chemical Co., Ltd..
The present invention provides a kind of preparation method of leather, comprises the following steps：
S101：Graphene is dissolved in acid solution, and in heating 3h~5h at 110 DEG C~130 DEG C.Wherein, acid solution has
Body is：Solute is sulfuric acid and phosphoric acid, and the mass ratio of sulfuric acid and phosphoric acid is 1：The mass ratio of (0.5~0.8), solute and solvent is
(3~5)：100；The mass ratio of graphene and acid solution is (1~3)：10.
S102：Polyethyl acrylate and tourmaline powder are added in the product that S101 is obtained, afterwards at 85 DEG C~90 DEG C
100min~300min is stirred, the pH value of regulation product is 5.8~6.3.
S103：Polyurethane resin and polyvinyl alcohol are added in the product that S102 is obtained and is stirred.Wherein, polyurethane
Resin is prepared from by PPG and isocyanates；The mol ratio of PPG and isocyanates is (1.2~2)：1；
PPG includes PTMG, and the number-average molecular weight of PTMG is 5000~10000；It is different
Cyanate includes 2,4,4- trimethyl hexamethylene diisocyanates.The condition of stirring is specially：Temperature is 65 DEG C~75 DEG C, is turned
Speed is 2500rpm~3500rpm, and the time is 3h~6h.
S104：The obtained products of S103 are coated in leather base cloth, leather is obtained.Wherein, leather base cloth includes looped fabric, shuttle
Weave cotton cloth, the one or more in non-woven fabrics, woven fabric non-woven fabrics and corium；Wherein, corium includes ox-hide.
Preferably, in S103, also include after stirring：Hydrochloric acid hydroxyl is added in product after being stirred in S103
Ammonia and tetradecanoic acid butyl ester, and it is 7.5~8.0 to adjust pH value, is afterwards 1500rpm~2500rpm in rotating speed, temperature is 55 DEG C
30min~50min is stirred under conditions of~60 DEG C；Wherein, the mass ratio of graphene, oxammonium hydrochloride and tetradecanoic acid butyl ester is successively
For 1：(1~3)：(2~5).
Preferably, the mass ratio of graphene, polyurethane resin, polyvinyl alcohol, polyethyl acrylate and tourmaline powder is
(0.18~0.23)：100：(3~5)：(1~3)：(1~2).
Preferably, the number-average molecular weight of polyvinyl alcohol is 10000~30000, and alcoholysis degree is 78%~90%；Polyacrylic acid
The number-average molecular weight of ethyl ester is 8000~20000.
Illustrated with reference to embodiment：
Embodiment one
The present invention provides a kind of preparation method of leather, comprises the following steps：
S101：Graphene is dissolved in acid solution, and in heating 5h at 110 DEG C.Wherein, acid solution is specially：Solute is
Sulfuric acid and phosphoric acid, and the mass ratio of sulfuric acid and phosphoric acid is 1：0.8, the mass ratio of solute and solvent is 3：100；Graphene is molten with acid
The mass ratio of liquid is 2：10.
S102：Polyethyl acrylate and tourmaline powder that number-average molecular weight is 20000 are added in the product that S101 is obtained,
100min is stirred at 90 DEG C afterwards, the p H values of regulation product are 6.3.
S103：Polyurethane resin and polyvinyl alcohol are added in the product that S102 is obtained and it is 65 DEG C in temperature, rotating speed is
3h is stirred under conditions of 3500rpm.Wherein, polyurethane resin is 2 by mol ratio：1 PTMG and 2,4,4-
Trimethyl hexamethylene diisocyanate is prepared from；The number-average molecular weight of PTMG is 5000, polyvinyl alcohol
Number-average molecular weight be 10000, alcoholysis degree is 90%.Graphene, polyurethane resin, polyvinyl alcohol, polyethyl acrylate and electricity
The mass ratio of gas stone flour is 0.18：100：5：1：2.
S104：The obtained products of S103 are coated on ox-hide, leather is obtained.
Embodiment two
The present invention provides a kind of preparation method of leather, comprises the following steps：
S101：Graphene is dissolved in acid solution, and in heating 3h at 130 DEG C.Wherein, acid solution is specially：Solute is
Sulfuric acid and phosphoric acid, and the mass ratio of sulfuric acid and phosphoric acid is 1：0.5, the mass ratio of solute and solvent is 5：100；Graphene is molten with acid
The mass ratio of liquid is 1：10.
S102：Polyethyl acrylate and tourmaline powder that number-average molecular weight is 8000 are added in the product that S101 is obtained,
300min is stirred at 85 DEG C afterwards, the pH value of regulation product is 5.8.
S103：Polyurethane resin and polyvinyl alcohol are added in the product that S102 is obtained and it is 75 DEG C in temperature, rotating speed is
6h is stirred under conditions of 2500rpm.Wherein, polyurethane resin is 1.2 by mol ratio：1 PTMG and 2,4,
4- trimethyl hexamethylene diisocyanates are prepared from；The number-average molecular weight of PTMG is 10000, polyethylene
The number-average molecular weight of alcohol is 10000, and alcoholysis degree is 78%.Graphene, polyurethane resin, polyvinyl alcohol, polyethyl acrylate with
The mass ratio of tourmaline powder is 0.23：100：3：3：1.
S104：The obtained products of S103 are coated on ox-hide, leather is obtained.
Embodiment three
The present invention provides a kind of preparation method of leather, comprises the following steps：
S101：Graphene is dissolved in acid solution, and in heating 4h at 120 DEG C.Wherein, acid solution is specially：Solute is
Sulfuric acid and phosphoric acid, and the mass ratio of sulfuric acid and phosphoric acid is 1：0.7, the mass ratio of solute and solvent is 4：100；Graphene is molten with acid
The mass ratio of liquid is 3：10.
S102：Polyethyl acrylate and tourmaline powder that number-average molecular weight is 15000 are added in the product that S101 is obtained,
200min is stirred at 88 DEG C afterwards, the pH value of regulation product is 6.0.
S103：Polyurethane resin and polyvinyl alcohol are added in the product that S102 is obtained and it is 70 DEG C in temperature, rotating speed is
5h is stirred under conditions of 3000rpm.Wherein, polyurethane resin is 1.5 by mol ratio：1 PTMG and 2,4,
4- trimethyl hexamethylene diisocyanates are prepared from；The number-average molecular weight of PTMG is 8000, polyethylene
The number-average molecular weight of alcohol is 20000, and alcoholysis degree is 88%.Graphene, polyurethane resin, polyvinyl alcohol, polyethyl acrylate with
The mass ratio of tourmaline powder is 0.2：100：4：2：1.
S104：The obtained products of S103 are coated on ox-hide, leather is obtained.
Example IV
The present invention provides a kind of preparation method of leather, comprises the following steps：
S101：Graphene is dissolved in acid solution, and in heating 3h at 130 DEG C.Wherein, acid solution is specially：Solute is
Sulfuric acid and phosphoric acid, and the mass ratio of sulfuric acid and phosphoric acid is 1：0.5, the mass ratio of solute and solvent is 5：100；Graphene is molten with acid
The mass ratio of liquid is 1：10.
S102：Polyethyl acrylate and tourmaline powder that number-average molecular weight is 8000 are added in the product that S101 is obtained,
300min is stirred at 85 DEG C afterwards, the pH value of regulation product is 5.8.
S103：Polyurethane resin and polyvinyl alcohol are added in the product that S102 is obtained and it is 75 DEG C in temperature, rotating speed is
6h is stirred under conditions of 2500rpm.Wherein, polyurethane resin is 1.2 by mol ratio：1 PTMG and 2,4,
4- trimethyl hexamethylene diisocyanates are prepared from；The number-average molecular weight of PTMG is 10000, polyethylene
The number-average molecular weight of alcohol is 10000, and alcoholysis degree is 78%.Then oxammonium hydrochloride and 14 is added in the product that stirring 6h is obtained
Alkanoic acid butyl ester, and adjust pH value for 7.5, is afterwards 2500rpm in rotating speed, and temperature is to stir 50min under conditions of 55 DEG C；Its
In, the mass ratio of graphene, oxammonium hydrochloride and tetradecanoic acid butyl ester is followed successively by 1：3：2.
S104：The obtained products of S103 are coated on ox-hide, leather is obtained.
In the present embodiment, graphene, polyurethane resin, polyvinyl alcohol, the mass ratio of polyethyl acrylate and tourmaline powder
For 0.23：100：3：3：1.
Embodiment five
The present invention provides a kind of preparation method of leather, comprises the following steps：
S101：Graphene is dissolved in acid solution, and in heating 4h at 120 DEG C.Wherein, acid solution is specially：Solute is
Sulfuric acid and phosphoric acid, and the mass ratio of sulfuric acid and phosphoric acid is 1：0.7, the mass ratio of solute and solvent is 4：100；Graphene is molten with acid
The mass ratio of liquid is 3：10.
S102：Polyethyl acrylate and tourmaline powder that number-average molecular weight is 15000 are added in the product that S101 is obtained,
200min is stirred at 88 DEG C afterwards, the pH value of regulation product is 6.0.
S103：Polyurethane resin and polyvinyl alcohol are added in the product that S102 is obtained and it is 70 DEG C in temperature, rotating speed is
5h is stirred under conditions of 3000rpm.Wherein, polyurethane resin is 1.5 by mol ratio：1 PTMG and 2,4,
4- trimethyl hexamethylene diisocyanates are prepared from；The number-average molecular weight of PTMG is 8000, polyethylene
The number-average molecular weight of alcohol is 20000, and alcoholysis degree is 88%.Then oxammonium hydrochloride and 14 is added in the product that stirring 5h is obtained
Alkanoic acid butyl ester, and adjust pH value for 8.0, is afterwards 1500rpm in rotating speed, temperature be stirring 30min under conditions of 60 DEG C~
50min；Wherein, the mass ratio of graphene, oxammonium hydrochloride and tetradecanoic acid butyl ester is followed successively by 1：1：5.
S104：The obtained products of S103 are coated on ox-hide, leather is obtained.
In the present embodiment, graphene, polyurethane resin, polyvinyl alcohol, the mass ratio of polyethyl acrylate and tourmaline powder
For 0.2：100：4：2：1.
In addition, the advantage in order to further highlight the above-mentioned technical proposal that the present invention is provided, carries out comparative testing below.Need
It is noted that following contrast tests are on the basis of embodiment five, obtained by changing relevant parameter.
Comparative example one
The present invention provides a kind of preparation method of leather, comprises the following steps：
S101：Graphene is dissolved in the aqueous solution, and in heating 4h at 120 DEG C.
S102：Polyethyl acrylate and tourmaline powder that number-average molecular weight is 15000 are added in the product that S101 is obtained,
200min is stirred at 88 DEG C afterwards, the pH value of regulation product is 6.0.
S103：Polyurethane resin and polyvinyl alcohol are added in the product that S102 is obtained and it is 70 DEG C in temperature, rotating speed is
5h is stirred under conditions of 3000rpm.Wherein, polyurethane resin is 1.5 by mol ratio：1 PTMG and 2,4,
4- trimethyl hexamethylene diisocyanates are prepared from；The number-average molecular weight of PTMG is 8000, polyethylene
The number-average molecular weight of alcohol is 20000, and alcoholysis degree is 88%.Then oxammonium hydrochloride and 14 is added in the product that stirring 5h is obtained
Alkanoic acid butyl ester, and adjust pH value for 8.0, is afterwards 1500rpm in rotating speed, temperature be stirring 30min under conditions of 60 DEG C~
50min；Wherein, the mass ratio of graphene, oxammonium hydrochloride and tetradecanoic acid butyl ester is followed successively by 1：1：5.
S104：The obtained products of S103 are coated on ox-hide, leather is obtained.
In this comparative example, graphene, polyurethane resin, polyvinyl alcohol, the mass ratio of polyethyl acrylate and tourmaline powder
For 0.2：100：4：2：1.
Comparative example two
The present invention provides a kind of preparation method of leather, comprises the following steps：
S101：Graphene is dissolved in acid solution, and in heating 4h at 120 DEG C.Wherein, acid solution is specially：Solute is
The mass ratio of sulfuric acid, solute and solvent is 4：100；The mass ratio of graphene and acid solution is 3：10.
S102：Polyethyl acrylate and tourmaline powder that number-average molecular weight is 15000 are added in the product that S101 is obtained,
200min is stirred at 88 DEG C afterwards, the pH value of regulation product is 6.0.
S103：Polyurethane resin and polyvinyl alcohol are added in the product that S102 is obtained and it is 70 DEG C in temperature, rotating speed is
5h is stirred under conditions of 3000rpm.Wherein, polyurethane resin is 1.5 by mol ratio：1 PTMG and 2,4,
4- trimethyl hexamethylene diisocyanates are prepared from；The number-average molecular weight of PTMG is 8000, polyethylene
The number-average molecular weight of alcohol is 20000, and alcoholysis degree is 88%.Then oxammonium hydrochloride and 14 is added in the product that stirring 5h is obtained
Alkanoic acid butyl ester, and adjust pH value for 8.0, is afterwards 1500rpm in rotating speed, temperature be stirring 30min under conditions of 60 DEG C~
50min；Wherein, the mass ratio of graphene, oxammonium hydrochloride and tetradecanoic acid butyl ester is followed successively by 1：1：5.
S104：The obtained products of S103 are coated on ox-hide, leather is obtained.
In this comparative example, graphene, polyurethane resin, polyvinyl alcohol, the mass ratio of polyethyl acrylate and tourmaline powder
For 0.2：100：4：2：1.
Comparative example three
The present invention provides a kind of preparation method of leather, comprises the following steps：
S101：Graphene is dissolved in acid solution, and in heating 4h at 120 DEG C.Wherein, acid solution is specially：Solute is
Sulfuric acid and phosphoric acid, and the mass ratio of sulfuric acid and phosphoric acid is 1：0.7, the mass ratio of solute and solvent is 4：100；Graphene is molten with acid
The mass ratio of liquid is 3：10.
S102：Polyethyl acrylate and tourmaline powder that number-average molecular weight is 15000 are added in the product that S101 is obtained,
200min is stirred at 88 DEG C afterwards, the pH value of regulation product is 6.0.
S103：Polyurethane resin and polyvinyl alcohol are added in the product that S102 is obtained and it is 70 DEG C in temperature, rotating speed is
5h is stirred under conditions of 3000rpm.Wherein, polyurethane resin is 1.5 by mol ratio：1 PTMG and 2,4,
4- trimethyl hexamethylene diisocyanates are prepared from；The number-average molecular weight of PTMG is 8000, polyethylene
The number-average molecular weight of alcohol is 20000, and alcoholysis degree is 88%.Then oxammonium hydrochloride and 14 is added in the product that stirring 5h is obtained
Alkanoic acid butyl ester, and adjust pH value for 8.0, is afterwards 1500rpm in rotating speed, temperature be stirring 30min under conditions of 60 DEG C~
50min；Wherein, the mass ratio of graphene, oxammonium hydrochloride and tetradecanoic acid butyl ester is followed successively by 1：1：5.
S104：The obtained products of S103 are coated on ox-hide, leather is obtained.
In this comparative example, graphene, polyurethane resin, polyvinyl alcohol, the mass ratio of polyethyl acrylate and tourmaline powder
For 0.2：100：4：2：1.
In addition, the performance of the coating solution in order to preferably evaluate each embodiment, carries out following test：
First, each embodiment and comparative example leather harmful substance contents are determined
Specifically, according to national standard GB20400-2006《Leather and fur limits of harmful substances》Determine each embodiment and contrast
The correlated performance for the leather that example is prepared, it is specific as shown in table 1.
Harmful substance contents are determined in each embodiment of table 1 and comparative example leather
| Decomposable asymmetric choice net is harmful to aromatic amine dyestuff (mg/kg) | Free formaldehyde (mg/kg) | |
| Embodiment one | 13 | 10 |
| Embodiment two | 10 | 8 |
| Embodiment three | 10 | 8 |
| Example IV | 6 | 3 |
| Embodiment five | 5 | 3 |
| Comparative example one | 28 | 16 |
| Comparative example two | 26 | 16 |
| Comparative example three | 28 | 15 |
2nd, the performance characterization for the leather that each embodiment and comparative example are prepared
Specifically, the leatherwork skin summer sleeping mat prepared using each embodiment and comparative example, afterwards according to national standard QB/T
Each embodiment of 4204-2011 People's Republic of China (PRC) light industry standard test is related to the skin summer sleeping mat that comparative example is prepared
Performance, it is specific as shown in table 2.
The performance data of each embodiment of table 2 and comparative example leather
3rd, the test of each embodiment leather mechanical property
Specifically, the film that thickness is 5 μm is made after the leather drying each embodiment and comparative example prepared, afterwards
Its mechanical property is determined, specific data are as shown in table 3：
The mechanical performance data of each embodiment of table 3 and comparative example leather
Certainly, in addition to the data that the embodiment of the present invention one is enumerated to embodiment five, using other material components and match somebody with somebody
Than also possible.
Using the technical scheme that provides of the present invention, using graphene as additive application in the preparation process of leather, by
This obtained leather and fur products and especially skin summer sleeping mat have excellent wear-resisting scratch resistance, antistatic, suction ripple, antibacterial, mould proof, anti-UV old
The functions such as change, flame-retardant smoke inhibition, electromagnetic shielding, far infrared health care；So as to the grade of General Promotion leather, lifting China ox-hide
Function in terms of the comfortableness of summer sleeping mat, durability, antimildew and antibacterial.
In the description of this specification, it is to be understood that reference term " one embodiment ", " some embodiments ", " show
The description of example ", " specific example " or " some examples " etc. mean to combine the specific features of the embodiment or example description, structure,
Material or feature are contained at least one embodiment of the present invention or example.In this manual, above-mentioned term is shown
The statement of meaning property is necessarily directed to identical embodiment or example.Moreover, specific features, structure, material or the spy of description
Point can in an appropriate manner be combined in any one or more embodiments or example.In addition, in the case of not conflicting,
Those skilled in the art can be by the not be the same as Example or example and non-be the same as Example described in this specification or example
Feature is combined and combined.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
1. a kind of preparation method of leather, it is characterised in that comprise the following steps：
S101：Graphene is dissolved in acid solution, and in heating 3h~5h at 110 DEG C~130 DEG C；
S102：Polyethyl acrylate and tourmaline powder are added in the product that the S101 is obtained, is stirred at 85 DEG C~90 DEG C
100min~300min, the pH value that product is adjusted afterwards is 5.8~6.3；
S103：Polyurethane resin and polyvinyl alcohol are added in the product that the S102 is obtained and is stirred；
S104：The obtained products of the S103 are coated in leather base cloth, the leather is obtained.
2. the preparation method of leather according to claim 1, it is characterised in that：
In the S101, in the acid solution：Solute is sulfuric acid and phosphoric acid, and the mass ratio of the sulfuric acid and the phosphoric acid is 1：
The mass ratio of (0.5~0.8), solute and solvent is (3~5)：100；The mass ratio of the graphene and the acid solution is (1
~3)：10.
3. the preparation method of leather according to claim 1, it is characterised in that：
In the S103, the polyurethane resin is prepared from by PPG and isocyanates；
Wherein, the mol ratio of PPG and the isocyanates is (1.2~2)：1；The PPG includes poly- four
Hydrogen furans ether glycol, and the number-average molecular weight of the PTMG is 5000~10000；The isocyanates includes
2,4,4- trimethyl hexamethylene diisocyanates.
4. the preparation method of leather according to claim 3, it is characterised in that：
In the S103, the addition polyurethane resin and polyvinyl alcohol simultaneously stir specially：Add polyurethane resin and
It it is 65 DEG C~75 DEG C in temperature after polyvinyl alcohol, rotating speed is stirring 3h~6h under conditions of 2500rpm~3500rpm.
5. the preparation method of leather according to claim 1, it is characterised in that：
In the S103, described stir also includes afterwards：
Oxammonium hydrochloride and tetradecanoic acid butyl ester are added in product after being stirred in the S103, and it is 7.5 to adjust pH value
~8.0, it is afterwards 1500rpm~2500rpm in rotating speed, temperature is stirring 30min~50min under conditions of 55 DEG C~60 DEG C；
Wherein, the mass ratio of the graphene, the oxammonium hydrochloride and the tetradecanoic acid butyl ester is followed successively by 1：(1~3)：(2~5).
6. the preparation method of leather according to claim 1, it is characterised in that：
The matter of the graphene, the polyurethane resin, the polyvinyl alcohol, the polyethyl acrylate and the tourmaline powder
Amount is than being (0.18~0.23)：100：(3~5)：(1~3)：(1~2).
7. the preparation method of leather according to claim 6, it is characterised in that：
The number-average molecular weight of the polyvinyl alcohol is 10000~30000, and alcoholysis degree is 78%~90%；The polyacrylic acid second
The number-average molecular weight of ester is 8000~20000.
8. according to the preparation method of any one of claim 1~7 leather, it is characterised in that：
The leather base cloth includes the one or more in looped fabric, woven fabric, non-woven fabrics, woven fabric non-woven fabrics and corium；Wherein, institute
Stating corium includes ox-hide.
9. the leather that any one of claim 1~8 methods described is prepared.
10. application of the leather in leather and fur products or leather and fur products additive is prepared in claim 9.
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Application publication date: 20170915 |