CN109679488A - A kind of high-temperature resistant, cracking resistance ultraviolet cured paint composition and preparation method thereof - Google Patents
A kind of high-temperature resistant, cracking resistance ultraviolet cured paint composition and preparation method thereof Download PDFInfo
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- CN109679488A CN109679488A CN201811630129.5A CN201811630129A CN109679488A CN 109679488 A CN109679488 A CN 109679488A CN 201811630129 A CN201811630129 A CN 201811630129A CN 109679488 A CN109679488 A CN 109679488A
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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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides a kind of high-temperature resistants, cracking resistance ultraviolet cured paint composition and preparation method thereof；The composition includes each component of following parts by weight: 30~60 parts of high functionality acrylate's resin, 15~30 parts of low degree of functionality acrylate, 10~20 parts of acrylate monomer, 5~15 parts of nanometer particle colloid, 5~9 parts of photoinitiator, 0.05~2 part of auxiliary agent.High functionality acrylate's resin, low degree of functionality acrylate, acrylate monomer and nanometer particle colloid are placed in reaction kettle, stirring is uniformly mixed；Photoinitiator is added, stirring is to being completely dissolved；Add auxiliary agent, stirring is to being uniformly dispersed to get the coating.Compared with prior art, coating composition temperature tolerance of the invention is good, and splitting resistance is excellent, coating transparent；Certain hardness, wear-resisting, excellent combination property are had both, applicability is wider.
Description
Technical field
The present invention relates to ultraviolet-curing paint fields, and in particular to a kind of high-temperature resistant, cracking resistance ultraviolet-curing paint
Composition and preparation method thereof.
Background technique
Ultraviolet-curing paint is a kind of new coating of the rapid crosslinking curing film forming under ultraviolet light, is had with it
" 5E " feature having, i.e., efficiently, wide adaptability are economical, energy saving and environmental-friendly, have developed pole since becoming the sixties in 20th century
For a kind of rapid novel green technology.Since the 1990s, ultraviolet light solidification industry development is swift and violent, special for the country
It is not photocureable coating, it has also become the third-largest radiation-curable products place of production in the whole world.Ultraviolet-curing paint is quickly grown, due to solid
Coating after change has many advantages, such as that excellent scratch resistance, high rigidity, richness are good, logical in building, sports goods, electronics at present
It is widely used in news, packaging material and automobile component.Conventional ultraviolet curable coating is anti-scratch etc. with high rigidity, height
Performance, but in use exist not heatproof, xanthochromia, cracking, even be broken the case where, this has seriously affected making for product
With and product the correlated performances such as beauty, protection, reduce the use feeling of consumer.
In recent years, ultraviolet light is solidificated in building, packaging, automobile etc. industry and is widely used, and product is answered
With field also from the closed environment such as interior, gradually toward outdoor bound.Outdoor environment is complicated and changeable, wherein more influencing coating
Performance, mainly there are high temperature and the big factor of ultraviolet light two, the requirement to light solidifying coating performance proposes further requirement；
Not only want the performances such as hardness with higher, bloom, scratch resistance, wear-resisting, but also to have heatproof, it is resistance to it is ultraviolet, the function such as do not crack
Energy property, and then the demand of relevant ultraviolet-curing paint product just becomes extremely urgent.
The Chinese patent of Publication No. CN 101787238 discloses a kind of high stain-resistant and thermal-insulating type UV curing fluorine coating, the Shen
Please in based on UV solidification fluororesin, is blended with nano powder slurry it is obtained can UV photocuring fluoro coatings, prepared painting
Material has the performances such as higher visible light transmittance rate, film are transparent, hardness is strong, ultraviolet aging resistance.But the fluorine prepared in the patent applies
Expect that the coating light transmittance after solidifying only 80% or so, fails to reach 90% or more, in demands such as packaging, household electrical appliances, telecommunications
The field of high transparency coating needs can not apply.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of high-temperature resistants, cracking resistance UV light
Change coating composition and preparation method thereof.The performances such as coating composition of the invention hardness with higher, bloom also have resistance to
Temperature does not crack, the functionality such as non yellowing；Suitable for the adverse circumstances such as open air, excellent combination property, applicability is wider.
The purpose of the present invention is achieved through the following technical solutions:
The present invention provides a kind of high-temperature resistant, cracking resistance ultraviolet cured paint composition, including each of following parts by weight
Component:
Preferably, high functionality acrylate's resin is urethane acrylate.More preferable degree of functionality is 6~15.
Such as 6145,6150,6161,6194,6195, the 6196 of Changxing company；CN8000NS, CN8011NS of Sartomer,
CN9013,CN975.High functionality acrylic resin can provide the property such as hardness, scratch-resistant of coating as main body film forming matter
Energy.
Preferably, the low degree of functionality acrylate is polyester acrylate, aliphatic urethane acrylate, virtue
It is one or more of in fragrant adoption urethane acrylate, epoxy acrylate.More preferable degree of functionality is 2~4.Such as Changxing company
6106,6118,6165,6168,6215；CN8003NS, CN8881NS, CN1963NS, CN2003 of Sartomer.Low function
The addition for spending acrylic resin, can be improved the flexility of coating.
Preferably, the weight ratio of high functionality acrylate's resin and low degree of functionality acrylate be (1.5~
2): 1.It is prepared when the weight ratio of high functionality acrylate's resin and low degree of functionality acrylate is lower than 1.5:1
Composition coating is partially soft, lower hardness, is unfavorable for protecting coated substrate, can not play a protective role；When high functionality third
When the weight ratio of alkene acid ester resin and low degree of functionality acrylate is higher than 2:1, prepared composition coating is partially crisp, partially
Firmly, easy to crack.
Preferably, the acrylate monomer is the compound of bifunctional acrylate, trifunctional acrylate.Difunctionality
It is small to spend shrinking percentage of the acrylate monomer after photocuring, while having certain corrosivity to substrate, is conducive to improve attachment；Three
Crosslink density can be improved in degree of functionality acrylate monomer after photocuring, while keeping certain flexibility, advantageously ensures that
The toughness of coating.Using difunctionality and trifunctional acrylic ester compound, it is ensured that the adhesive force and toughness of coating.It is more excellent
Choosing, the acrylate monomer is that weight ratio is 1:(2~3) bifunctional acrylate, trifunctional acrylate compound.
Under the proportion, the adhesive force and toughness of the coating of system of the present invention are best.
Preferably, the bifunctional acrylate is selected from 1,6- hexanediyl ester, the double acrylic acid of two contracting propylene glycol
Ester, tripropylene glycol double methacrylate, ethoxylated bisphenol A diacrylate；The trifunctional acrylate is selected from trihydroxy methyl
Propane triacrylate, ethoxyquin trimethylolpropane trimethacrylate, the third oxidation trimethylolpropane trimethacrylate, season penta
Tetrol triacrylate.
Preferably, the nanometer particle colloid be selected from nano silica, nano-titanium dioxide, nano-aluminium oxide,
One or more of nanometer chromium dioxide is dispersed in the colloidal solution formed in acrylate monomer.Nanometer particle colloid adds
Enter can be improved the damage resistant and wear-resisting property of coating.Inventors be surprised to learn that nanoparticle is added in system of the invention
The anti-cracking performance of coating can be improved in colloidal solution, this may be because nanoparticle has high intensity, in high temperature or stress
In the case of, it can be used as stress concentration point, absorb big energy, to significantly improve the splitting resistance of coating.
Preferably, the photoinitiator is selected from benzophenone, 1- hydroxy-cyclohexyl-phenyl ketone (1- hydroxy phenyl hexamethylene
Ketone), -1 acetone of 2- hydroxy-2-methyl -1- phenyl, 2,4,6- trimethylbenzoy-dipheny phosphorous oxides, isopropyl thioxanthone anthracene
One or more of ketone.
Preferably, the photoinitiator is that one or two kinds of crack type photoinitiators and a kind of hydrogen-capture-type light initiator form
Composite photoinitiator system, wherein the crack type photoinitiator be selected from 1- hydroxy-cyclohexyl-phenyl ketone, 2- hydroxyl-
One or more of 2- methyl-1-- 1 acetone of phenyl, 2,4,6- trimethylbenzoy-dipheny phosphorous oxides, it is described to take hydrogen by force
Type photoinitiator is selected from one or more of benzophenone, styrax methyl phenyl ethers anisole.Oxygen can be reduced using composite photoinitiator
Polymerization inhibitor, keeps paint solidification more complete.
Preferably, the auxiliary agent is the combination of one or more of levelling agent, defoaming agent, wetting agent, polymerization inhibitor.It is more excellent
Choosing, the auxiliary agent include that dimethyl silicone polymer, organic silicon modified by polyether, polyester resin change properties of organic silicon, reactive organosilicon, fluorine change
One or more of property acrylate, polyacrylate analog assistant.
The present invention also provides the preparation method of a kind of high-temperature resistant, cracking resistance ultraviolet cured paint composition, including it is as follows
Step:
A, it by high functionality acrylate's resin, low degree of functionality acrylate, acrylate monomer and receives
Rice corpuscles colloid is placed in reaction kettle, and stirring is uniformly mixed；
B, it is added the photoinitiator, stirring is to being completely dissolved；
C, it is added the auxiliary agent, stirring is to being uniformly dispersed to get the high-temperature resistant, cracking resistance ultraviolet-curing paint group
Close object.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, solvent-free, baking link, solvent-free volatilization, environmental-friendly, energy consumption is few.
2, have that heatproof, the functionality such as do not crack；The performances such as certain hardness, bloom are had both, it is severe to be suitable for open air etc.
Environment, excellent combination property, applicability are wider.
3, middle compared with the existing technology that UV is used to solidify fluoro coatings prepared by fluororesin and nano powder slurry, it is of the invention
Photocureable coating light transmittance is higher, adhesive force is good, heatproof cracking resistance, non yellowing.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
Examples 1 to 6
Examples 1 to 7 each provides a kind of high-temperature resistant, cracking resistance ultraviolet cured paint composition, component and contains
Amount is as shown in table 1；Each component is taken in parts by weight, and each component is uniformly mixed later, can be prepared by coating composition.
Comparative example 1~4
Comparative example 1~4 each provides a kind of high-temperature resistant, cracking resistance ultraviolet cured paint composition, component and contains
Amount is as shown in table 1；Each component is taken in parts by weight, and each component is uniformly mixed later, can be prepared by coating composition.
Table 1
Note 1: the aliphatic urethane acrylate purchased from Changxing company；
Note 2: the aliphatic urethane acrylate purchased from Sartomer；
Note 3: the nanometer titanium dioxide colloidal silica purchased from Digao；Note 4: purchased from the nano silica powder for winning wound；
Note 5: the tego410 purchased from Digao；Note 6: the BYK 333 purchased from Bi Ke chemistry.
Performance detection
In order to which the present invention is compared with the coating of the prior art, coating obtained above is coated on No. 6 bars
In PET film, through 200~400mJ/cm2Energy-curable, measure the adhesive force, pencil hardness, temperature tolerance of coating, cracking resistance
Property, light transmittance and mist degree.
One, adhesive force
By hundred lattice test knife in cutting hundred lattice on template, glutinous grid spaces are pasted with 3M-610 adhesive tape, with close to 180 rapidly to
Pull-up afterwards.
Two, pencil hardness
Using Mitsubishi UNI hardness pencil, Yu Hechong 750g, the pencil hardness of testing coating.
Three, temperature tolerance and splitting resistance
Specimen page after solidification is placed under 120 DEG C of environment, after 10 days, observes the apparent of coating.
Four, light transmittance and mist degree are low
By the light transmittance-mist degree tester of the specimen page after solidification, its light transmittance and mist degree are tested.
Performance test results are as shown in table 2:
Table 2
By upper table 2 it is found that comparative example 1 is compared with embodiment 1, the composition of preparation applies after high temperature of 120 DEG C is placed 10 days
There is apparent cracking phenomena in layer.6145 resins used in comparative example 1 are the light-cured resins of 6 degrees of functionality, and the degree of cross linking is high, firmly
Degree is high, but in the case where no addition low official's resin, coating is partially hard and crisp, and flexibility is poor, and coating goes out under high temperature environment
Cracking is showed.
Comparative example 2 is compared with embodiment 2, and coating is complete at high temperature for the composition of preparation, does not crack, but hardness only has
2B, coating are too soft.The CN9178 resin used in comparative example 2 is the light-cured resin of 2 degrees of functionality, and flexibility is fine, but hardness
It is very low, effectively substrate can not be protected at all, coating does not play a role.
Comparative example 3 is compared with embodiment 4, and the adhesive force of the composition of preparation only has 3B, and coating portion separates at high temperature
It splits.Six acrylate of pentaerythrite used in comparative example 3 is the acrylic monomers of 6 degrees of functionality, and the degree of cross linking is very high, but brittleness
Greatly, in the case where two officials of no addition and three official's acrylic monomers, adhesive force is slightly poor；Thus coating itself is partially hard crisp, in height
Under temperature, there is part and cracks in coating.
There is the case where cracking at high temperature in the composition that comparative example 4 compares preparation with embodiment 6, and coating is saturating
Light rate<85%, mist degree>10, coating is opaque, shows certain matte effect.Use nanoparticle for powder in comparative example 4
Body, disperses inhomogenous in the composition, occurs diffusing reflection under the irradiation of light, coating is opaque in this case；And
The C140 used in embodiment 6 is the uniform system of nanoparticle, improves the splitting resistance of coating after addition, and light transmittance >
92%, belong to clear coat, can be applied to the field in the demands high transparency coating needs such as packaging, household electrical appliances, telecommunications.
It is the solvent-free volatilization of coating composition of the invention, environmental-friendly, have that heatproof, the functionality such as do not crack；Have both compared with
It is wider to be suitable for adverse circumstances, excellent combination property, the applicabilities such as open air for the performances such as high hardness, bloom.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.In the absence of conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (10)
1. a kind of high-temperature resistant, cracking resistance ultraviolet cured paint composition, which is characterized in that the composition includes following weight
The each component of number:
2. high-temperature resistant according to claim 1, cracking resistance ultraviolet cured paint composition, which is characterized in that the height
Degree of functionality acrylate is urethane acrylate；The degree of functionality of high functionality acrylate's resin is 6~15.
3. high-temperature resistant according to claim 1, cracking resistance ultraviolet cured paint composition, which is characterized in that described low
Degree of functionality acrylate be selected from polyester acrylate, aliphatic urethane acrylate, aromatic urethane acrylate,
It is one or more of in epoxy acrylate.
4. high-temperature resistant according to claim 1 or 3, cracking resistance ultraviolet cured paint composition, which is characterized in that described
The degree of functionality of low degree of functionality acrylate is 2~4.
5. high-temperature resistant according to claim 1, cracking resistance ultraviolet cured paint composition, which is characterized in that the height
The weight ratio of degree of functionality acrylate and low degree of functionality acrylate is (1.5~2): 1.
6. high-temperature resistant according to claim 1, cracking resistance ultraviolet cured paint composition, which is characterized in that described third
Olefin(e) acid ester monomer is the compound of bifunctional acrylate, trifunctional acrylate.
7. high-temperature resistant according to claim 6, cracking resistance ultraviolet cured paint composition, which is characterized in that described double
Functional acrylate is selected from the double acrylic acid of 1,6 hexanediol diacrylate, two contracting propylene glycol double methacrylates, tripropylene glycol
Ester, ethoxylated bisphenol A diacrylate；The trifunctional acrylate is selected from trimethylolpropane trimethacrylate, ethoxyquin
Trimethylolpropane trimethacrylate, the third oxidation trimethylolpropane trimethacrylate, pentaerythritol triacrylate.
8. high-temperature resistant according to claim 1, cracking resistance ultraviolet cured paint composition, which is characterized in that described to receive
Rice corpuscles colloid be selected from one of nano silica, nano-titanium dioxide, nano-aluminium oxide, nanometer chromium dioxide or
It is several to be dispersed in the colloid formed in acrylate monomer.
9. high-temperature resistant according to claim 1, cracking resistance ultraviolet cured paint composition, which is characterized in that the light
Initiator is selected from benzophenone, 1- hydroxy-cyclohexyl-phenyl ketone, -1 acetone of 2- hydroxy-2-methyl -1- phenyl, 2,4,6- tri-
One or more of methyl benzoyl-diphenyl phosphate oxidation, styrax methyl phenyl ethers anisole；The auxiliary agent be levelling agent, defoaming agent,
The combination of one or more of wetting agent, polymerization inhibitor.
10. the preparation method of a kind of high-temperature resistant according to claim 1, cracking resistance ultraviolet cured paint composition,
It is characterized in that, described method includes following steps:
A, by high functionality acrylate's resin, low degree of functionality acrylate, acrylate monomer and nanoparticle
Sub- colloid is placed in reaction kettle, and stirring is uniformly mixed；
B, it is added the photoinitiator, stirring is to being completely dissolved；
C, the auxiliary agent is added, stirring is combined to being uniformly dispersed to get the high-temperature resistant, cracking resistance ultraviolet-curing paint
Object.
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| CN111100545A (en) * | 2019-12-20 | 2020-05-05 | 上海维凯光电新材料有限公司 | High-wear-resistance anti-fingerprint ultraviolet curing coating composition and preparation method thereof |
| CN111944415A (en) * | 2020-07-09 | 2020-11-17 | 湖南松井新材料股份有限公司 | Ultraviolet curing coating and preparation method and application thereof |
| CN112063290A (en) * | 2020-08-03 | 2020-12-11 | 珠海展辰新材料股份有限公司 | Ultraviolet-curing matte clear-surface woodenware coating and preparation method thereof |
| CN112358751A (en) * | 2020-11-25 | 2021-02-12 | 山东益丰生化环保股份有限公司 | mercaptan/alkene-TiO for coating2Method for preparing composite material |
| CN112521856A (en) * | 2020-09-24 | 2021-03-19 | 湖南松井新材料股份有限公司 | UV (ultraviolet) silicon touch matte coating and preparation method and application thereof |
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| CN112063290A (en) * | 2020-08-03 | 2020-12-11 | 珠海展辰新材料股份有限公司 | Ultraviolet-curing matte clear-surface woodenware coating and preparation method thereof |
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Application publication date: 20190426 |