CN110592962A - UV-curing-based solvent-free polyurethane-organic silicon synthetic leather and manufacturing method thereof - Google Patents
UV-curing-based solvent-free polyurethane-organic silicon synthetic leather and manufacturing method thereof Download PDFInfo
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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
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/142—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 mixture of polyurethanes with other resins in the same layer
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—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 characterised by the macromolecular diols used
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—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 characterised by the isocyanates used
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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
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a UV-curing-based solvent-free polyurethane-organic silicon synthetic leather and a manufacturing method thereof, and is characterized in that mixed slurry of solvent-free polyurethane containing photosensitive groups and photosensitive polysiloxane is directly injected and coated on a synthetic leather base material, and a semi-finished product is obtained after ultraviolet curing; and then the grains are endowed on the surface of the synthetic leather through vacuum grain suction, so that the environment-friendly polyurethane-organic silicon synthetic leather is obtained. The invention adopts the UV curing technology, on one hand, the organic solvent can be eliminated from the source, and the invention has the characteristics of high production efficiency, low energy consumption, environmental protection and the like; on the other hand, through chemical bonding, the complementary advantages of the polyurethane and the organic silicon in performance can be realized, the synthetic leather has more excellent service performance, the cost of the organic silicon synthetic leather is reduced, and the quality, the ecological grade and the international market competitiveness of the synthetic leather are improved.
Description
Technical Field
The invention relates to a solvent-free polyurethane-organic silicon synthetic leather based on UV curing and a manufacturing method thereof, belonging to the field of synthetic leather manufacturing.
Background
China is a big country for producing and consuming synthetic leather. According to statistics, the annual output of artificial leather and synthetic leather in China in 2017 is about 368 ten thousand tons, which accounts for more than 70% of the total world output.
In recent years, with the increasing living standard of people, the demand of consumers for high-quality and high-environmental ecological synthetic leather is on a continuous rising trend. Meanwhile, besides traditional shoe upper leather, luggage leather and clothing leather, the leather demand of high-end fields such as airplanes, high-speed rails, yachts, automobiles and the like is increased, and the market strongly calls for high-quality ecological synthetic leather to meet the harsh requirements of the high-end fields on environmental protection and safety.
However, at present, solvent type polyurethane is mainly adopted for manufacturing domestic synthetic leather, and comprises a solvent type surface treating agent, a solvent type surface layer, foaming layer resin and a solvent type adhesive, the annual demand of the solvent type surface treating agent is more than 200 ten thousand tons, the annual demand of an organic solvent is more than 340 ten thousand tons, the disordered discharge of toxic solvents such as dimethylformamide, methylbenzene, butanone and the like in the production process is as high as 150 ten thousand tons per year, the physical and mental health of workers is seriously harmed, and meanwhile, the serious environmental pollution and the resource waste are caused; in addition, the residual quantity of VOCs in the product is more than 1000 mg/kg, which can not meet the requirements of high physical property and ecological property in high-end fields.
The UV curing process is the application of the leading edge of photochemical reaction, and can instantly cure ink, coatings, adhesives and the like through the irradiation of ultraviolet light with certain intensity. With the development of science and technology, the fields related to UV curing are also wider, and the UV curing is widely applied to the manufacture of products such as automobiles, electronics, communication, glass, plastics and the like. In recent years, with the increasing maturity of UV curing technology and its advantages, it has been gradually applied to the field of synthetic leather manufacturing. Chinese patent CN105220519B discloses a method for manufacturing solvent-free synthetic leather based on UV curing technology, which comprises the steps of coating solvent-free polyurethane slurry containing photosensitive groups on pretreated base cloth, and curing by ultraviolet light to obtain a semi-finished product; and then the waterborne polyurethane is used as surface resin, and an environment-friendly polyurethane synthetic leather product is obtained through dry-process veneering. Chinese patent CN107675516B describes an organopolysiloxane synthetic leather and a preparation method thereof. The method forms a polysiloxane surface layer through ultraviolet light curing, and then the polysiloxane surface layer is further photo-cured and bonded with a silica gel bonding layer through a photosensitive group or bonded through an addition reaction to prepare a finished product. The transparent or semitransparent photosensitive polysiloxane surface coating endows the synthetic leather with smoothness, dust resistance and the like.
The organic silicon synthetic leather coating has the excellent characteristics of high and low temperature resistance, oxidation resistance, stability, weather resistance, flame retardancy, hydrophobicity, corrosion resistance, no toxicity, no odor, physiological inertia and the like, but has the characteristics of small surface tension and low surface energy, so that the problems of poor recoatability and poor bonding fastness with base cloth usually exist; in addition, the organosilicon material has low film forming strength (less than or equal to 5 MPa), low elongation (less than or equal to 400 percent) and high price. The polyurethane synthetic leather coating has excellent mechanical property and base cloth bonding force, but often has the defects of cold resistance, wear resistance and hydrophobic antifouling property. Therefore, the polyurethane is used for modifying the organic silicon resin to manufacture the synthetic leather, the complementary advantages of the performances of the polyurethane and the organic silicon material can be realized, and a new thought is provided for the development of high-quality ecological synthetic leather. However, there are still few reports on the application of UV curing technology in the field of solvent-free polyurethane modified silicone synthetic leather manufacturing.
Disclosure of Invention
The invention aims to provide a solvent-free polyurethane-organic silicon synthetic leather based on UV curing and a manufacturing method thereof aiming at the defects of the prior art. According to the invention, on the basis of a UV curing technology, the photosensitive polysiloxane and the photosensitive polyurethane are covalently combined, so that the excellent performances of the polyurethane such as mechanical strength, base cloth bonding force and the like and the outstanding performances of cold resistance, wear resistance, weather resistance, hydrophobicity, antifouling and the like which can be endowed by the organosilicon are effectively integrated, and a new thought is provided for the development of high-quality and high-physical-property ecological synthetic leather.
The invention provides a UV-curing-based solvent-free polyurethane-organic silicon synthetic leather and a manufacturing method thereof, which are characterized by comprising the following steps of:
(1) preparation of UV curable solvent-free polyurethane:
adding 45 ~ 75 parts of liquid polyester or polyether diol subjected to vacuum dehydration and 1.0 part of 1, 4-butanediol 1.0 ~ 1.5.5 parts into a reaction kettle, sequentially adding 10 ~ 20 parts of liquid diisocyanate and 0 ~ 0.1.1 parts of organic bismuth catalyst, heating to 75 ~ 85.85 ℃, stirring for reaction for 1 ~ 2 h, adding 0.5 ~ 1.0 part of trimethylolpropane, continuing stirring for reaction for 1 ~ 2 h at 75 ~ 85 ℃, cooling, adding a compound containing a photosensitive group, carrying out end capping at 50 ~ 60 ℃, determining-NCO group by a di-n-butylamine method, completely reacting to obtain a UV-curable solvent-free polyurethane prepolymer containing both a terminal group and a side chain containing the photosensitive group, and sealing and packaging for later use;
(2) preparing UV curing slurry, namely fully and uniformly mixing 12 ~ 80 parts of UV-curable solvent-free polyurethane, 20 ~ 88 parts of photosensitive polysiloxane, 2.0 ~ 5.0.0 parts of photoinitiator, 0.5 ~ 3.0.0 part of surfactant, 5.0 ~ 12 parts of filler and 3.0 ~ 5.0.0 parts of color paste;
(3) manufacturing of UV curing synthetic leather:
a) directly coating the UV curing slurry in the step (2) on the surface of a synthetic leather base material, controlling the thickness of a coating film to be 0.8 ~ 1.2.2 mm, placing the synthetic leather base material under a UV curing machine, and curing the coating film for 20 ~ 40 s to obtain a solvent-free polyurethane-organic silicon synthetic leather semi-finished product, wherein the curing machine adopts 3 British Primarc 9.7KW 1387 mm mercury lamps, and the position angle and the height of each lamp tube in the UV furnace can be adjusted, so that the solvent-free polyurethane-organic silicon synthetic leather semi-finished product is suitable for ultraviolet light curing of various synthetic leather products;
b) and (3) coating line absorption, namely performing line absorption treatment on the surface of the coating by using a vacuum line absorption machine to endow the surface of the synthetic leather with lines, wherein the line absorption temperature is 60 ~ 80 ℃, the time is 3 ~ 10 s, and cooling to obtain the finished leather.
The UV-curing solvent-free polyurethane-organic silicon synthetic leather and the manufacturing method thereof are characterized in that the liquid polyester or polyether diol is at least one of poly adipic acid-1, 3-butanediol glycol with the number average molecular weight of 1000 ~ 3000, polypropylene carbonate glycol and polypropylene glycol with the number average molecular weight of 1000 ~ 4000.
The solvent-free polyurethane-organic silicon synthetic leather based on UV curing and the manufacturing method thereof are characterized in that the liquid diisocyanate is at least one of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and diphenylmethane diisocyanate (MDI-50).
The solvent-free polyurethane-organic silicon synthetic leather based on UV curing and the manufacturing method thereof are characterized in that the compound containing photosensitive groups is one of acrylic acid-beta-hydroxyethyl ester, acrylic acid-beta-hydroxypropyl ester, methacrylic acid-beta-hydroxyethyl ester, methacrylic acid-beta-hydroxypropyl ester, allyl hydroxyethyl ether and 4-hydroxybutyl vinyl ether.
The solvent-free polyurethane-organic silicon synthetic leather based on UV curing and the manufacturing method thereof are characterized in that the photosensitive polysiloxane is vinyl-terminated silicone oil (vinyl content: 0.05 ~ 0.5%, structural general formula: CH)2=CH(CH3)2-Si-O-[(CH3)2SiO]nSi(CH3)2CH=CH2N =200 ~ 3000, tetramethyltetravinylcyclotetrasiloxane (vinyl content: 30%, structural formula: CH)3(CH2=CH)SiO]4) And at least one of polyvinyl silicone oil (vinyl content: 10 ~ 12%, vinyl group being mainly branched).
The UV-curing-based solvent-free polyurethane-organic silicon synthetic leather and the manufacturing method thereof are characterized in that the photoinitiator is one of 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-isopropyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl acetone or isopropyl thioxanthone.
The solvent-free polyurethane-organic silicon synthetic leather based on UV curing and the manufacturing method thereof are characterized in that the synthetic leather base material is one of woven fabric, non-woven fabric and microfiber fabric.
The solvent-free polyurethane-organic silicon synthetic leather comprises sofa leather, home decoration leather, automobile decoration leather, clothing leather or vamp leather and the like.
Compared with the prior art, the invention has the following positive effects:
(1) by adopting the UV curing technology, the used raw materials do not contain organic solvents, compared with the traditional solvent type polyurethane, the pollution of the organic solvents is eliminated from the source, the product does not contain VOCs, and the ecological grade and the product quality of the synthetic leather are improved;
(2) the photo-curing crosslinking technology is adopted to replace the traditional chemical curing crosslinking technology, the chemical problem is solved by a physical method, the energy consumption is lower, the efficiency is higher, and the environment is protected;
(3) the polysiloxane is connected with the polyurethane through a covalent bond, so that the complementary advantages of the polyurethane and the organosilicon in performance are realized, the cost of the organosilicon synthetic leather is reduced, the wear-resistant, scratch-resistant, cold-resistant, heat-resistant, hydrophobic and antifouling properties of the polyurethane synthetic leather are improved, the synthetic leather is endowed with excellent comprehensive performance, and the quality and the international market competitiveness of the synthetic leather are improved.
Drawings
FIG. 1 is a UV curable solvent-free polyurethane structure;
in the figure, 1 is a photosensitive group, 2 is a polyurethane macromolecular chain soft segment, and 3 is a polyurethane macromolecular chain hard segment.
Detailed Description
The present invention is described in detail by the following embodiments, it should be noted that the following embodiments are only used for further illustration of the present invention, and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations based on the above disclosure, and still fall within the scope of the present invention.
Example 1:
preparation of solvent-free polyurethane-organic silicon synthetic leather for clothing
(1) Preparation of UV curable solvent-free polyurethane:
adding 40 parts of poly (1, 3-butylene glycol) glycol with the number average molecular weight of 2000, 15 parts of poly (propylene carbonate) glycol with the number average molecular weight of 1000, 20 parts of polypropylene glycol with the number average molecular weight of 4000 and 1.5 parts of 1, 4-butanediol into a reaction kettle after vacuum dehydration, sequentially adding 10 parts of isophorone diisocyanate, 10 parts of hexamethylene diisocyanate and 0.1 part of organic bismuth catalyst, heating to 85 ℃, stirring for reaction for 1h, adding 1.0 part of trimethylolpropane, continuing stirring for reaction for 1.5 h at 85 ℃, cooling, adding beta-hydroxyethyl acrylate, carrying out end capping at 60 ℃, determining-NCO groups by a di-n-butylamine method, completely reacting to obtain a UV-curable solvent-free polyurethane prepolymer with a terminal group and a side chain containing a photosensitive group, and sealing and packaging for later use;
(2) preparation of UV curing slurry: fully and uniformly mixing 12 parts of UV-curable solvent-free polyurethane, 88 parts of vinyl-terminated silicone oil with the vinyl content of 0.4%, 5.0 parts of 1-hydroxycyclohexyl phenyl ketone, 3.0 parts of surfactant, 5.0 parts of filler and 3.0 parts of color paste;
(3) manufacturing of UV curing synthetic leather:
a) directly coating the UV curing slurry obtained in the step (2) on the surface of the microfiber cloth, controlling the thickness of a coating film to be 0.8 mm, placing the microfiber cloth under a UV curing machine, and curing the microfiber cloth for 20 seconds to form a film, thus obtaining a solvent-free polyurethane-organic silicon synthetic leather semi-finished product; the curing machine adopts 3 mercury lamps with the thickness of 1387 mm in British Primarc 9.7KW, the position angle and the height of the lamp tube in the UV furnace can be adjusted, and the curing machine is suitable for ultraviolet light curing of various synthetic leather products;
b) coating and absorbing lines: and (3) carrying out grain absorption treatment on the surface of the coating by using a vacuum grain absorption machine, endowing grains on the surface of the synthetic leather with the temperature of 60 ℃ for 3 s, and cooling to obtain the finished leather.
Compared with the common polyurethane synthetic leather, the synthetic leather for the clothes prepared by the patent technology has the advantages that the cold resistance is obviously improved, and the low-temperature (-25 ℃) flexing resistance fastness of the finished leather is improved from 120000 times to 150000 times.
Example 2:
preparation of solvent-free polyurethane-organic silicon synthetic leather for automotive interior
(1) Preparation of UV curable solvent-free polyurethane:
adding 20 parts of polypropylene carbonate glycol with the number average molecular weight of 3000, 30 parts of polypropylene glycol with the number average molecular weight of 2000 and 1.0 part of 1, 4-butanediol into a reaction kettle after vacuum dehydration, sequentially adding 15 parts of diphenylmethane diisocyanate and 0 part of organic bismuth catalyst, heating to 75 ℃, stirring for reaction for 1.5 h, adding 1.0 part of trimethylolpropane, continuing stirring for reaction for 1h at 75 ℃, cooling, adding 4-hydroxybutyl vinyl ether for end capping at 55 ℃, determining-NCO groups by a di-n-butylamine method, completely reacting to obtain a UV-curable solvent-free polyurethane prepolymer with a terminal group and a side chain containing a photosensitive group, and sealing and packaging for later use;
(2) preparation of UV curing slurry: fully and uniformly mixing 50 parts of UV-curable solvent-free polyurethane, 4 parts of tetramethyl tetravinylcyclotetrasiloxane, 40 parts of vinyl-terminated silicone oil with the vinyl content of 0.5%, 3.0 parts of 2-hydroxy-2-methyl-1-phenyl acetone, 1.5 parts of surfactant, 11 parts of filler and 4.0 parts of color paste;
(3) manufacturing of UV curing synthetic leather:
a) directly coating the UV curing slurry obtained in the step (2) on the surface of a synthetic leather base material, controlling the thickness of a coating film to be 1.0 mm, placing the synthetic leather base material under a UV curing machine, and curing for 30 seconds to form a film, thus obtaining a solvent-free polyurethane-organic silicon synthetic leather semi-finished product; the curing machine adopts 3 mercury lamps with the thickness of 1387 mm in British Primarc 9.7KW, the position angle and the height of the lamp tube in the UV furnace can be adjusted, and the curing machine is suitable for ultraviolet light curing of various synthetic leather products;
b) coating and absorbing lines: and (3) carrying out grain absorption treatment on the surface of the coating by using a vacuum grain absorption machine, endowing grains on the surface of the synthetic leather with the temperature of 70 ℃ for 5 s, and cooling to obtain the finished leather.
Compared with the common polyurethane synthetic leather, the synthetic leather for the automotive interior prepared by the technology has the advantages that the waterproofness and the aging resistance are obviously improved, and the water contact angle of the surface of the synthetic leather is improved from 90 degrees to 120 degrees; the light aging property test shows that the yellowing index is reduced from 4.2 to 2.7.
Example 3:
preparation of solvent-free polyurethane-organic silicon synthetic leather for sofa
(1) Preparation of UV curable solvent-free polyurethane:
adding 45 parts of polypropylene glycol with the number average molecular weight of 2000 and 1.0 part of 1, 4-butanediol after vacuum dehydration into a reaction kettle, sequentially adding 12 parts of hexamethylene diisocyanate and 0.05 part of organic bismuth catalyst, heating to 85 ℃, stirring for reaction for 1 hour, adding 1.0 part of trimethylolpropane, continuing stirring for reaction for 1 hour at 85 ℃, cooling, adding beta-hydroxyethyl methacrylate for end capping at 60 ℃, completely reacting through determining-NCO groups by a di-n-butylamine method to obtain a UV-curable solvent-free polyurethane prepolymer with a terminal group and a side chain containing photosensitive groups, and sealing and packaging for later use;
(2) preparation of UV curing slurry: fully and uniformly mixing 80 parts of UV-curable solvent-free polyurethane, 20 parts of polyvinyl silicone oil with the vinyl content of 10%, 2.0 parts of 1-hydroxycyclohexyl phenyl ketone, 0.5 part of surfactant, 12 parts of filler and 5.0 parts of color paste;
(3) manufacturing of UV curing synthetic leather:
a) directly coating the UV curing slurry obtained in the step (2) on the surface of a synthetic leather base material, controlling the thickness of a coating film to be 1.2 mm, placing the coating film under a UV curing machine, and curing for 40 seconds to form a film, thus obtaining a solvent-free polyurethane-organic silicon synthetic leather semi-finished product; the curing machine adopts 3 mercury lamps with the thickness of 1387 mm in British Primarc 9.7KW, the position angle and the height of the lamp tube in the UV furnace can be adjusted, and the curing machine is suitable for ultraviolet light curing of various synthetic leather products;
b) coating and absorbing lines: and (3) carrying out grain absorption treatment on the surface of the coating by using a vacuum grain absorption machine, endowing grains on the surface of the synthetic leather with the temperature of 80 ℃ for 10 s, and cooling to obtain the finished leather.
Compared with the common polyurethane synthetic leather, the wear resistance of the synthetic leather for the sofa prepared by the technology is improved to 2.4 mg/r from 5.5 mg/r.
Claims (7)
1. A solvent-free polyurethane-organic silicon synthetic leather based on UV curing and a manufacturing method thereof are characterized by comprising the following steps of:
(1) preparation of UV curable solvent-free polyurethane:
adding 45 ~ 75 parts of liquid polyester or polyether diol subjected to vacuum dehydration and 1.0 part of 1, 4-butanediol 1.0 ~ 1.5.5 parts into a reaction kettle, sequentially adding 10 ~ 20 parts of liquid diisocyanate and 0 ~ 0.1.1 parts of organic bismuth catalyst, heating to 75 ~ 85.85 ℃, stirring for reaction for 1 ~ 2 h, adding 0.5 ~ 1.0 part of trimethylolpropane, continuing stirring for reaction for 1 ~ 2 h at 75 ~ 85 ℃, cooling, adding a compound containing a photosensitive group, carrying out end capping at 50 ~ 60 ℃, determining-NCO group by a di-n-butylamine method, completely reacting to obtain a UV-curable solvent-free polyurethane prepolymer containing both a terminal group and a side chain containing the photosensitive group, and sealing and packaging for later use;
(2) preparing UV curing slurry, namely fully and uniformly mixing 12 ~ 80 parts of UV-curable solvent-free polyurethane, 20 ~ 88 parts of photosensitive polysiloxane, 2.0 ~ 5.0.0 parts of photoinitiator, 0.5 ~ 3.0.0 part of surfactant, 5.0 ~ 12 parts of filler and 3.0 ~ 5.0.0 parts of color paste;
(3) manufacturing of UV curing synthetic leather:
a) directly coating the UV curing slurry in the step (2) on the surface of a synthetic leather base material, controlling the thickness of a coating film to be 0.8 ~ 1.2.2 mm, placing the synthetic leather base material under a UV curing machine, and curing the coating film for 20 ~ 40 s to obtain a solvent-free polyurethane-organic silicon synthetic leather semi-finished product, wherein the curing machine adopts 3 British Primarc 9.7KW 1387 mm mercury lamps, and the position angle and the height of each lamp tube in the UV furnace can be adjusted, so that the solvent-free polyurethane-organic silicon synthetic leather semi-finished product is suitable for ultraviolet light curing of various synthetic leather products;
b) and (3) coating line absorption, namely performing line absorption treatment on the surface of the coating by using a vacuum line absorption machine to endow the surface of the synthetic leather with lines, wherein the line absorption temperature is 60 ~ 80 ℃, the time is 3 ~ 10 s, and cooling to obtain the finished leather.
2. A UV-curable solvent-free polyurethane-silicone synthetic leather and method for making the same according to claim 1, wherein the liquid polyester or polyether diol is at least one of poly (1, 3-butylene glycol) adipate with number average molecular weight of 1000 ~ 3000, poly (propylene carbonate) diol with number average molecular weight of 1000 ~ 4000.
3. The UV-curable solvent-free polyurethane-silicone synthetic leather and the manufacturing method thereof according to claim 1, wherein the liquid diisocyanate is at least one of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and diphenylmethane diisocyanate (MDI-50).
4. The UV-curable solventless polyurethane-silicone synthetic leather and the manufacturing method thereof according to claim 1, wherein the photosensitive group-containing compound is one of beta-hydroxyethyl acrylate, beta-hydroxypropyl acrylate, beta-hydroxyethyl methacrylate, beta-hydroxypropyl methacrylate, allyl hydroxyethyl ether, 4-hydroxybutyl vinyl ether.
5. The UV-curable solvent-free polyurethane-silicone synthetic leather and the manufacturing method thereof according to claim 1, wherein the photosensitive polysiloxane is vinyl terminated silicone oil (vinyl content: 0.05 ~ 0.5.5%, structural formula: CH)2=CH(CH3)2-Si-O-[(CH3)2SiO]nSi(CH3)2CH=CH2N =200 ~ 3000, tetramethyltetravinylcyclotetrasiloxane (vinyl content: 30%, structural formula: CH)3(CH2=CH)SiO]4) And at least one of polyvinyl silicone oil (vinyl content: 10 ~ 12%, vinyl group being mainly branched).
6. The UV-curable solvent-free polyurethane-silicone synthetic leather and the manufacturing method thereof according to claim 1, wherein the photoinitiator is one of 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-isopropyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl acetone or isopropyl thioxanthone.
7. The UV-curable solvent-free polyurethane-silicone synthetic leather and the manufacturing method thereof according to claim 1, wherein the synthetic leather base material is one of woven fabric, non-woven fabric and microfiber fabric.
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