CN105400410B - It is a kind of applied to waterborne UV coating of artificial leather and preparation method thereof - Google Patents
It is a kind of applied to waterborne UV coating of artificial leather and preparation method thereof Download PDFInfo
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- CN105400410B CN105400410B CN201510954031.5A CN201510954031A CN105400410B CN 105400410 B CN105400410 B CN 105400410B CN 201510954031 A CN201510954031 A CN 201510954031A CN 105400410 B CN105400410 B CN 105400410B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a kind of waterborne UV coating applied to artificial leather, the component of the coating includes waterborne polyurethane resin, aqueous fluorine-containing polyurethane acrylic resin, water, photoinitiator, dumb light powder, levelling agent, defoamer and dispersant.The preferred roller coat of waterborne UV coating in the present invention is in the application decoration coating that on artificial leather, can be adornd as automobile interior exterior, and not only crosslink density high adhesion force is good for the paint film formed, and environmental protection and energy saving, smell are small, acid-proof alkaline is good.
Description
Technical field
The present invention relates to a kind of waterborne UV coating, and in particular to a kind of waterborne UV coating and its preparation applied to artificial leather
Method.
Background technology
UV coating is ultraviolet-curing paint, earliest applied to furniture, Floor Industry, with curing rate is fast, low energy consumption,
The advantages of low stain.As coating science and technology is growing, UV coating is applied to plastics, paper, timber, metal, leather etc. gradually
On material, the important selection as decorative paint in many industries.Gradually go deep into the theory of energy-saving and emission-reduction and Environmental Safety
The UV coating of the popular feeling, waterborne UV coating and high solid part gradually shows the trend of the oiliness UV coating of substitution organic solvent class.
On automobile interior exterior decorations, many producers have not used corium decoration, but use more environmentally friendly inexpensive people
Fabricate-leather, such as PVC artificial leather.It is much using UV coating progress decoration on artificial leather, utilize organic of the prior art
Often there is following key issue in UV coating：First, odor problem, most oil paint is due to dissolvent residual or reaction
Not exclusively often there is penetrating odor；2nd, environmental issue, the preparation process of oil paint and all has VOC's using process
Discharge, is even more that can come out solvent during solidification heating；3rd, crosslink density, the crosslink density of oil paint is lower slightly.Compare
Under, waterborne UV coating odorlessness problem, without environmentally friendly risk, as long as lifting its crosslink density, waterborne UV coating is with regard to that can reach biography
The effect and performance of system oil paint.
The content of the invention
For the shortcomings of the prior art, the invention provides a kind of crosslink density height, environmental protection and energy saving, smell
The good waterborne UV coating applied to artificial leather of small, acid-proof alkaline.
The technical problems to be solved by the invention are achieved by the following technical programs：
The component and weight/mass percentage composition of the heretofore described waterborne UV coating applied to artificial leather are as follows：
Waterborne polyurethane resin 40-60%
Aqueous fluorine-containing polyurethane-acrylic resin 10-30%
Water 10-20%
Photoinitiator 5-10%
Dumb light powder 3-5%
Levelling agent 1-2%
Defoamer 1-2%
Dispersant 1-2%
The photoinitiator is polyethylene oxygen ethyl cinnamate or polyparaphenylene diacrylate.
The levelling agent is to commonly use commercially available aqueous levelling agent.The defoamer is polysorbas20, polysorbate40, polysorbate60, tween
One kind in 80.The dispersant is triethanolamine.
The dumb light powder uses commercially available dumb light powder, can not only adjust the viscosity and face of UV coating in the present invention
Color, while may also function as supporting role.
Waterborne polyurethane resin in the present invention is used as aqueous UV formulation for coating material in the present invention using commercially available matured product
Basic resin, constitutes the basic framework of cured article.While the basic performance in order to further lift product film layer after solidification, such as
A kind of poly- ammonia of homemade aqueous fluorine-containing is added in hardness, pliability, adhesive force, light fastness, acid-proof alkaline etc., the present invention
Ester-acrylic resin, the water-base resin has hydrophilic radical so good water solubility, both the high intensity containing polyurethane resin, resistance to
Mill, tear resistance, the pliability but also with acrylic resin, excellent ageing resistance.Meanwhile, aqueous fluorine-containing polyurethane-the third
Fluoro-containing group in olefin(e) acid resin can be enriched on the interface of polymer and air, and main chain and interior molecules formation protection are made
With the emulsion for forming the resin is more stable, while yet further enhances the pliability and adhesive force of paint film.
The preparation method of the aqueous fluorine-containing polyurethane-acrylic resin is：
（1）By methyl methacrylate, lauryl methacrylate, Hexafluorobutyl mathacrylate, methacrylic acid ten
Difluoro heptyl ester is with mass ratio 1:1:0.2:0.4 mixing, it is 5 times of mix monomer gross mass that above-mentioned mix monomer is dissolved in into quality
In butyl acetate, then mixed liquor is placed in reactor to the peroxidating for being warming up to and mix monomer gross mass 6% being added dropwise after 120 DEG C
Continued mechanical is stirred in benzoyl, course of reaction, is reacted 3-5 hours, is produced fluoroacrylic resin.
（2）Will（1）In obtained fluoroacrylic resin, dibutyl tin laurate, absolute ethyl alcohol with mass ratio 50:2:
8 are mixed in reaction vessel, and reaction vessel is warming up into 80-85 DEG C after stirring, and then add fluoroacrylic resin matter
The IPDI of amount 5%, reaction cools the temperature to 55 DEG C after 0.5-1 hours, add fluoroacrylic resin quality
10% dimethylolpropionic acid, reaction is warming up to 80 after 1 hour
DEG C, the hydroxy-ethyl acrylate of fluoroacrylic resin quality 20% is added, 4 hours are incubated, that is, is made containing hydrophilic
Group-COOH fluorochemical urethane-acrylic resin.
（3）To（2）In the obtained fluoroacrylic resin for having hydrophilic group to add ammoniacal liquor to resin system pH value be 7-
7.5, with 3500-4500r/min's in high speed dispersor after then the deionized water of addition resin system phase homogenous quantities is mixed
Rate of dispersion is scattered 1.5-2 hours, produces aqueous fluorine-containing polyurethane-acrylic resin emulsion.
Methyl methacrylate and both different monomers of lauryl methacrylate and methyl-prop are used in the present invention
Olefin(e) acid hexafluoro butyl ester, both fluorochemical monomers of dodecafluoroheptyl methacrylate react under the effect of initiator benzoyl peroxide
Generate fluoroacrylic resin.Then on the basis of fluoroacrylic resin, isocyanates and dihydroxymethyl fourth are passed through first
Acid grafting, prepares intermediate, and then carrying out end-blocking by hydroxy-ethyl acrylate prepares aqueous fluorochemical urethane-acrylic acid
Resin, pH value is adjusted finally by ammoniacal liquor, then emulsion is made in the resin by obtained by as dispersion steps.
The preparation method of the waterborne UV coating applied to artificial leather in the present invention is as follows：
All raw materials are mixed according to formula and are placed in high speed dispersor, with 2000-3000r/min scattered speed
Degree is scattered 1-2 hours.
The method that the waterborne UV coating applied to artificial leather in invention preferably uses roller coat carries out application.
The present invention has the advantages that：
1st, the waterborne UV coating in the present invention can be applied to artificial leather external coating decoration, and the crosslinking coatings density is high, attached
Put forth effort that strong, environmental protection and energy saving, smell be small, acid-proof alkaline is good.
2nd, the waterborne UV coating preparation technology and coating process in the present invention are simple, are adapted to industrialized production.
Embodiment
Present disclosure is further described below by embodiment.
1st, the preparation of aqueous fluorine-containing polyurethane-acrylic resin
Step 1：By methyl methacrylate, lauryl methacrylate, Hexafluorobutyl mathacrylate, methacrylic acid
Ten difluoro heptyl esters are with mass ratio 1:1:0.2:0.4 mixing, quality is dissolved in for 5 times of mix monomer gross mass by above-mentioned mix monomer
Butyl acetate in, then mixed liquor is placed in reactor to the peroxide for being warming up to and mix monomer gross mass 6% being added dropwise after 120 DEG C
Change continued mechanical in benzoyl, course of reaction to stir, react 4 hours, produce fluoroacrylic resin.
Step 2：By obtained fluoroacrylic resin, dibutyl tin laurate, absolute ethyl alcohol in step 1 with mass ratio
50:2:8 are mixed in reaction vessel, and reaction vessel is warming up into 80 DEG C after stirring, fluoroacrylic resin is then added
The IPDI of quality 5%, reaction cools the temperature to 55 DEG C after 0.5 hour, add fluoroacrylic resin quality
10% dimethylolpropionic acid, reaction is warming up to 80 after 1 hour
DEG C, the hydroxy-ethyl acrylate of fluoroacrylic resin quality 20% is added, 4 hours are incubated, that is, is made containing hydrophilic
Group-COOH fluorochemical urethane-acrylic resin.
Step 3：Into step 2 it is obtained have hydrophilic group fluoroacrylic resin addition ammoniacal liquor to resin system pH value be
7-7.5, with the scattered of 4500r/min in high speed dispersor after then the deionized water of addition resin system phase homogenous quantities is mixed
Rate Dispersion 2 hours, produces aqueous fluorine-containing polyurethane-acrylic resin emulsion.
2nd, the preparation of waterborne UV coating
The component and weight/mass percentage composition of coating are as shown in the table in embodiment, and correspondence numerical value is the quality hundred of correspondence component
Divide content.
The photoinitiator used in embodiment is polyethylene oxygen ethyl cinnamate, and levelling agent is aqueous levelling agent
BYK333, defoamer is polysorbate40, and dispersant is triethanolamine.The dumb light powder used uses commercially available prod, powder size choosing
With more fine and smooth product, solid particle granularity is less than 5 μm.
The preparation method of waterborne UV coating is as follows in embodiment：
All raw materials are mixed according to formula and are placed in high speed dispersor, with 2500r/min rate of dispersion point
Dissipate 2 hours, required coating is produced after cooling.
Test comparison is carried out using the coating in the commercially available oiliness UV coating available for PVC artificial leather and the present embodiment.Will
Surveyed coating roll is applied on PVC artificial leather sample, and it is resistance to carry out RCA paper tapes after uviol lamp effect 5-10min photocurings after coating
The test of mill property, resistance to acids and bases test and smell test.
The method of resistance to acids and bases test be will be coated and cured after artificial leather sample to be soaked in concentration respectively be 2.5wt%
Hydrochloric acid and sodium hydrate aqueous solution in 24 hours, observe paint film state.
The method of smell test is with reference to Volkswagen《Car room component Odor Examination》Method of testing：By 3 × 3mm
Artificial leather sample be placed in 1 liter of beaker, be put into 200g deionized waters and submerged, the water in beaker is then heated to 80
DEG C insulation 4 hours, closes beaker mouthful in insulating process.Select 5 people carry out news beaker in smell, oder levels be divided into have taste and
It is tasteless, wherein there is taste to be subdivided into：B grades refer to and have pleasant smell, and C grades are bad smell, and D grade difficult by smell, and E grades are disliked
Motive taste.It is tasteless：A grades.Experimental result judges standard：As a result 4 more than A are obtained and then meet requirement of the automotive trim to smell.
Oder levels objective effectively can be judged by the training that 5 people for carrying out smell test need to test by smell before testing.
Test result is as follows：
When being applied to from the waterborne UV coating in the test result of embodiment, the present invention on the decoration of artificial leather, no
Only without smell, and resistance to acids and bases, wearability are good.
It is last it should be noted that above example is only entered to the technical scheme that illustrates the embodiment of the present invention rather than to it
Row limitation, although the embodiment of the present invention is described in detail with reference to preferred embodiment, one of ordinary skill in the art
It should be understood that the technical scheme of the embodiment of the present invention can still be modified or equivalent substitution, and these are changed or waited
It can not also make the scope of amended technical scheme disengaging technical scheme of the embodiment of the present invention with replacing.
Claims (7)
1. a kind of waterborne UV coating applied to artificial leather, it is characterised in that the component and weight/mass percentage composition of the coating are such as
Under：
Waterborne polyurethane resin 40-60%
Aqueous fluorine-containing polyurethane-acrylic resin 10-30%
Water 10-20%
Photoinitiator 5-10%
Dumb light powder 3-5%
Levelling agent 1-2%
Defoamer 1-2%
Dispersant 1-2%
The photoinitiator is polyethylene oxygen ethyl cinnamate or polyparaphenylene diacrylate；
The preparation method of the aqueous fluorine-containing polyurethane-acrylic resin is：
（1）By methyl methacrylate, lauryl methacrylate, Hexafluorobutyl mathacrylate, the difluoro of methacrylic acid ten
Heptyl ester is with mass ratio 1:1:0.2:0.4 mixing, the acetic acid that quality is 5 times of mix monomer gross mass is dissolved in by above-mentioned mix monomer
In butyl ester, then mixed liquor is placed in reactor to the benzoyl peroxide first for being warming up to and mix monomer gross mass 6% being added dropwise after 120 DEG C
Continued mechanical is stirred in acyl, course of reaction, is reacted 3-5 hours, is produced fluoroacrylic resin；
（2）Will（1）In obtained fluoroacrylic resin, dibutyl tin laurate, absolute ethyl alcohol with mass ratio 50:2:8
Mixed in reaction vessel, reaction vessel is warming up to 80-85 DEG C after stirring, then add fluoroacrylic resin quality 5%
IPDI, reaction cools the temperature to 55 DEG C after 0.5-1 hour, addition fluoroacrylic resin quality 10%
Dimethylolpropionic acid, reaction 1 hour after be warming up to 80 DEG C, add the acrylic acid hydroxyl second of fluoroacrylic resin quality 20%
Ester, is incubated 4 hours, that is, fluorochemical urethane-acrylic resin containing hydrophilic radical-COOH is made；
（3）To（2）In the obtained fluoroacrylic resin containing hydrophilic group to add ammoniacal liquor to resin system pH value be 7-7.5,
Then with the scattered of 3500-4500r/min in high speed dispersor after the deionized water of addition resin system phase homogenous quantities is mixed
Rate Dispersion 1.5-2 hours, produces aqueous fluorine-containing polyurethane-acrylic resin.
2. the waterborne UV coating of artificial leather is applied to as claimed in claim 1, it is characterised in that：The levelling agent is aqueous levelling
Agent.
3. the waterborne UV coating of artificial leather is applied to as claimed in claim 1, it is characterised in that：The defoamer be polysorbas20,
One kind in polysorbate40, polysorbate60, Tween 80.
4. the waterborne UV coating of artificial leather is applied to as claimed in claim 1, it is characterised in that：The dispersant is three ethanol
Amine.
5. the waterborne UV coating of artificial leather is applied to as claimed in claim 1, it is characterised in that：The water applied to artificial leather
Property UV coating carries out application with the method for roller coat.
6. the waterborne UV coating of artificial leather is applied to as claimed in claim 1, it is characterised in that：The water applied to artificial leather
Property UV coating be used for the preparation that automobile interior exterior is adornd.
7. a kind of method for preparing the waterborne UV coating that artificial leather is applied to as described in claim 1-4, it is characterised in that：By institute
There is raw material to mix according to formula to be placed in high speed dispersor, it is small to disperse 1-2 with 2000-3000r/min rate of dispersion
When.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510954031.5A CN105400410B (en) | 2015-12-18 | 2015-12-18 | It is a kind of applied to waterborne UV coating of artificial leather and preparation method thereof |
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| CN201510954031.5A CN105400410B (en) | 2015-12-18 | 2015-12-18 | It is a kind of applied to waterborne UV coating of artificial leather and preparation method thereof |
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| CN105400410B true CN105400410B (en) | 2017-11-07 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109651583A (en) * | 2018-11-28 | 2019-04-19 | 韶关市合众化工有限公司 | A kind of fluororesin modified ester-polyurethane resin emulsion of the acrylic acid that high rigidity is water-fast |
| CN112175162B (en) * | 2019-07-05 | 2022-04-19 | 万华化学（宁波）有限公司 | Modified waterborne polyurethane resin, preparation method and application thereof |
| CN113062125A (en) * | 2021-04-01 | 2021-07-02 | 昆山阿基里斯新材料科技有限公司 | Preparation method of hydrophobic artificial leather |
| CN115213072A (en) * | 2021-12-09 | 2022-10-21 | 广州汽车集团股份有限公司 | Stain-resistant light-color leather automobile seat fabric |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1436825A (en) * | 2002-02-08 | 2003-08-20 | 湖南亚大新材料科技股份有限公司 | Ultraviolet light cured paint for leather or leatherette |
| CN1696226A (en) * | 2004-05-14 | 2005-11-16 | 湖南亚大新材料科技股份有限公司 | Ultraviolet light solidified water born paint in use for leather or leatheroid |
| CN102432768B (en) * | 2011-10-10 | 2013-07-31 | 嘉兴禾欣化学工业有限公司 | Method for preparing fluorine-silicon containing polyurethane and acrylate emulsion |
| CN104152027A (en) * | 2014-07-30 | 2014-11-19 | 苏州聚康新材料科技有限公司 | Elastic coating for leather and preparation method of elastic coating |
| CN104312232B (en) * | 2014-09-28 | 2017-04-12 | 上海维凯光电新材料有限公司 | Anti-glare and anti-static light radiation curing coating composition |
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