CN1772820A - Ultraviolet cured paint for plastics and its production process - Google Patents
Ultraviolet cured paint for plastics and its production process Download PDFInfo
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- CN1772820A CN1772820A CN 200410090634 CN200410090634A CN1772820A CN 1772820 A CN1772820 A CN 1772820A CN 200410090634 CN200410090634 CN 200410090634 CN 200410090634 A CN200410090634 A CN 200410090634A CN 1772820 A CN1772820 A CN 1772820A
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Abstract
The present invention relates to one kind of ultraviolet cured paint for plastics and its production process. The paint includes matrix resin, active diluent, light initiator and solvent and features its antiwear hardness additive accounting for 0.1-8.0 wt% of the paint. The paint has high hardness, high antiwear performance, forms smooth paint coating through spraying, high toughness, high adhesion and high chemical corrosion resistance.
Description
Technical field
The invention belongs to technical field of coatings, relate to a kind of ultraviolet-curing paint and manufacture method thereof that is used for plastics, particularly relate to a kind of ultraviolet-curing paint that is used for plastics with high rigidity and wear resisting property.
Background technology
It is efficient, energy-conservation, pollution-free that ultraviolet-curing paint has, and paint film layer is wear-resisting, hardness is high, strong adhesion, characteristics such as corrosion-resistant, has been widely used in furniture application, house decoration and printing ink etc.Since the These characteristics of ultraviolet-curing paint, the present finish paint that just is being applied to the plastic fittings of portable device, as the handset shell surface, portable computer external, toiletry bag casing etc.Spray this kind plastic component with ultraviolet-curing paint, can make its tough and hard wear resistant, the corrosion of sweat proof water or other chemical, the glossiness height, advantages such as usage period overlength, therefore, application in this regard is the focus that this kind coating promotes the use at present.
Traditional ultraviolet-curing paint that is used for woodenware, leather, metal etc., two or more that mostly adopt aliphatic urethane acrylate, polyester acrylate or epoxy acrylate are as main film forming substance, with 1 to 3 functional group reactions Acrylic Acid Monomer as diluting monomer, add a spot of auxiliary agent again and form, promptly adopt this kind method as CN1277232A, CN1297973A etc.Because the limitation of its composition and proportioning, when this kind coating was used for the finish paint of often frayed plastic device, its hardness and wear resistance were then inadequate.CN1436825A speaks of and add the anti-wear additive that accounts for gross weight 0.5～3% in coating system, this kind anti-wear additive model is BYK920, it is a kind of reactive auxiliary agent, can promote the cross-linking effect of resin or diluting monomer, therefore can increase the wear resistance of solidifying the back paint film to a certain extent, but be difficult to increase simultaneously largely the hardness and the wear resistance of paint film, therefore can not reach the service requirements of portable plastic device coating.
Summary of the invention
Technical problem to be solved by this invention is the defective that does not reach service requirements at the hardness of the portable plastic device coating of existing in prior technology paint film and wear resistance, a kind of ultraviolet-curing paint and manufacture method thereof that is used for plastics is provided, by in coating, increasing a kind of high-intensity hardness and anti-wear additive powder, can improve the fastness to rubbing and the hardness of ultraviolet-curing paint simultaneously, make it reach of the requirement of high-grade plastic device paint film coating.After being sprayed at frosting, use UV-irradiation, its solidifying film layer is the wear resisting property excellence not only, and the hardness height, ability sweat and the corrosion of general chemical, and the surface quality of coating is fabulous, is well positioned to meet the requirement of the coating of portable plastic device.
According to the present invention, the ultraviolet-curing paint that is used for plastics that is provided comprises matrix resin, reactive thinner, light trigger and solvent, it is characterized in that also comprising wear-resisting-hardness additive, this wear-resisting-hardness additive weight percent content in this coating is 0.1～8.0%, preferred 0.2～5.0%.Described wear-resisting-the hardness additive is that microhardness is at 500kgf/mm
2Above pressed powder.
In general the use, the hardness and the wear resisting property of portable plastic device paint film there is higher requirement than other coated.With respect to performances such as adhesive force of coatings, solvent resistances, the hardness of raising coating and the difficulty of wear resisting property are often bigger.
In the present invention, employing adds a certain amount of wear-resisting-hardness additive that is used to improve hardness and wear resistance in the total system of coating, described wear-resisting-material of hardness additive is the pressed powder with higher mechanical strength, when matrix resin and reactive thinner behind photocuring, wear-resisting-hardness additive powder is just sneaked into and is coated with in the rete, because this wear-resisting-hardness additive is the material with higher hardness and intensity, so just improve the whole physical and mechanical properties that is coated with rete greatly, greatly improved the hardness and the wear resistance of paint film.
In the outer photo-cured coating of purple of the present invention, so long as its microhardness satisfies the pressed powder of above-mentioned requirements, can as described wear-resisting-the hardness additive, for example, this wear-resisting-hardness additive can be for being selected from least a in carbide, nitride, oxide compound or the organic polymer.Preferably, described carbide is to be selected from least a in silicon carbide, zirconium carbide, norbide, aluminium carbide, iron carbide, the chromium carbide; Described nitride is to be selected from least a in titanium nitride, zirconium nitride, gan, aluminium nitride, the CaCl2; Described oxide compound is to be selected from least a in titanium dioxide, aluminum oxide, chromic oxide, stannic oxide, the silicon-dioxide; Described organic polymer is to be selected from least a in nylon, polyethylene wax, Poly Propylene Wax, polyvinyl chloride wax, the polycarbonate.
Described wear-resisting-mean particle size of hardness additive solids powder is preferably less than 10 μ m, 3 μ m～8 μ m more preferably.Can increase the difficulty of sneaking into matrix resin when its particle diameter is too big, and make the coating surface flow leveling bad, particle diameter is too little might to be reduced the hardness of raising paint film layer and the ability of wear resistance.
Described wear-resisting-addition of hardness additive must strict control, adds very few be not enough to increase solidify after the hardness and the wear resisting property of rete, too many then can influence the sticking power of paint film to ground, make paint film layer bad to the sticking power of ground.
In ultraviolet-curing paint of the present invention, the weight percent content of each component preferably:
Matrix resin 15-70%
Reactive thinner 10～55%
Wear-resisting-hardness additive 0.1～8.0%
Light trigger 2.0～10.0%
Solvent 2～50%
In ultraviolet-curing paint of the present invention, described matrix resin can adopt the matrix resin that is used for ultraviolet-curing paint traditional in the prior art, the present invention has no particular limits it, but preferably second-order transition temperature (Tg) is at the matrix resin more than 60 ℃, for example, this matrix resin can be for being selected from least a in aliphatic urethane acrylate resin, epoxy (methyl) acrylate resin and the polyester acrylate resin.Particularly preferably be, the hybrid resin of described matrix resin for being formed by aliphatic urethane acrylate resin, epoxy (methyl) interior olefin(e) acid ester resin and polyester acrylate resin, this moment, the weight percent content of each composition was in the described hybrid resin with respect to the gross weight of described coating:
Aliphatic urethane acrylate resin 5～20%;
Epoxy (methyl) acrylate resin 5～30%;
Polyester acrylate resin 5～20%.
Matrix resin in the ultraviolet-curing paint of the present invention can adopt the product of Basfu (BASF) or galstaff part models such as (lid Si Tafu).
In ultraviolet-curing paint of the present invention, described reactive thinner can adopt the reactive thinner that is used for ultraviolet-curing paint traditional in the prior art, and for example reactive acrylate monomer that the employing official can the number of degrees from 1 to 3 is at least a simple function group acrylate monomer, bifunctional acrylate's monomer, the trifunctional group acrylate's monomer.The single functionality acrylate monomer has Hydroxyethyl acrylate (HEA), isobornyl acrylate, Isooctyl acrylate monomer, ethoxyquin hydroxyethyl meth acrylate etc.The difunctionality acrylate monomer has tri (propylene glycol) diacrylate (TPGDA), 1 usually, 6 hexanediyl esters (HDDA), polyethyleneglycol diacrylate etc., the three-functionality-degree acrylate monomer has Viscoat 295 (TMPTA), pentaerythritol triacrylate etc.Usually, functional group is low more, and its dilution effect to matrix resin is good, but its activity is little, and cross-linking density is little, and the paint film wear resistance and the hardness of therefore solidifying back formation often do not reach higher requirement.High monomer belongs to the hyperergy monomer, has very high cross-linking density, and helpful to improving the wear resistance and the hardness of solidifying the back paint film, the solvent resistance of the rete of formation might as well.But can increase the dilution difficulty of matrix resin, and may more seriously cause paint film loss of adhesion to ground.In the present invention, described reactive thinner particularly preferably is and adopts simple function group acrylate monomer, bifunctional acrylate's monomer and the monomeric mixture of trifunctional group acrylate, this moment, preferably each monomeric weight percent content was as follows with respect to the gross weight of described coating:
Simple function group acrylate monomer 2～15%;
Bifunctional acrylate's monomer 4～20%;
Trifunctional group acrylate's monomer 4～20%.
In ultraviolet-curing paint of the present invention, described solvent can adopt the solvent that is used for ultraviolet-curing paint traditional in the prior art, but for reaching suitable solvency power and evaporation rate, the present invention preferably adopts two or more not mixed solvent of forming of organic solvent of the same race, for example, described solvent can be for being selected from toluene, ethyl acetate, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, pimelinketone, dimethylbenzene, hexone, acetone, methylethylketone, butyl glycol ether, the mixture of the solvent of two or more in the propylene glycol butyl ether.
In ultraviolet-curing paint of the present invention, described light trigger can adopt the light trigger that is used for ultraviolet-curing paint traditional in the prior art, the present invention has no particular limits it, for example, this light trigger can be selected IHT-PI185, IHT-PI907, Irgacure651, Irgacure184, Irgacure369, the Irgacure754 of vapour Bagong department for use, Irgacure2022, darocur1173, the mixture of one or more in the products such as Irgacure2959, darocurMBF.
In ultraviolet-curing paint of the present invention, except that said components, can also contain other auxiliary agents such as flow agent, defoamer, dispersion agent.
Described flow agent can adopt the flow agent that is used for ultraviolet-curing paint traditional in the prior art, the present invention has no particular limits it, for example can adopt one or more the mixture among EFKA3883, EFKA3886, EFKA3600, EFKA3035, BYK366, BYK333, BYK307, the DEGO410 etc., its content can be 0.1～1.0% of coating gross weight.
Described defoamer can adopt the defoamer that is used for ultraviolet-curing paint traditional in the prior art, the present invention has no particular limits it, for example can adopt one or more the mixture among EFKA2022, EFKA2527, EFKA2040, BYK352, BYK354, BYK357, the BYK052 etc., its content can be 0.1～1.5% of coating gross weight.
For make described wear-resisting-the hardness additive can be suspended in the described coating better, ultraviolet-curing paint of the present invention preferably also contains dispersion agent.Described dispersion agent can adopt dispersion agent traditional in the prior art, the present invention has no particular limits it, for example can adopt one or more the mixture among Kerper-602, Kerper-605, Kerper630, CFC-500HP, CFC-510, CFC-637, the CFC-604S etc.
May further comprise the steps according to the described method that is used for the ultraviolet-curing paint of plastics of manufacturing provided by the invention:
(1) matrix resin that will account for total system 15～70 weight % of coating is dissolved in the acrylate monomer reactive thinner that accounts for total system 10～55 weight %, stirs;
(2) light trigger that will account for total system 2～10 weight % of coating and the solvent that accounts for total system 2～50 weight % of coating are stirred to abundant dissolving;
(3) step (2) gained mixture and step (1) gained mixture are mixed;
(4) adding accounts for the microhardness of total system 0.1～8.0 weight % of coating at 500kgf/mm in step (3) gained mixture
2Above wear-resisting-hardness additive solids powder, high-speed stirring evenly suspends this pressed powder.
Wherein step (4) can also comprise adding foregoing flow agent, defoamer and dispersion agent in step (3) gained mixture.
Each component and consumption thereof are as previously described in the described method.
The ultraviolet-curing paint that obtains by above making and processing, its fastness to rubbing and hardness are greatly improved, can satisfy of the requirement of high-grade plastic device well to coating, good hardness and wear resisting property are arranged, spraying back paint film is smooth, snappiness good, strong adhesion, therefore can be used in the coating to the portable plastic device surface.And, the corrosion of this kind ultraviolet-curing paint ability sweat and general chemical, glossy degree height, advantages such as usage period overlength.
Embodiment
According to step of manufacturing described in the invention, preparation has the ultraviolet-curing paint of the weight composition of following Comparative Examples and embodiment.
Comparative Examples 1
Aliphatic urethane acrylate resin (sartomer product, CN965) 10g, Epocryl (galstaff product, syncryl104) 20g, polyester acrylate resin (sartomer product, CNUVP225) 20g, simple function group acrylate monomer HEA 10g, bifunctional acrylate's monomer HDDA 10g, trifunctional group acrylate's monomer TMPTA 20g, light trigger Irgacure184 is 4g, and flow agent EFKA3035 is 0.3g, and defoamer BYK052 is 0.2g, dispersion agent Kerper-605 is 1.0g, acetone 10g, butylacetate 8g, propyl carbinol 8g.
Comparative Examples 2
Except that the BYK920 that adds 2.0g as the anti-wear agent, all the other are identical with Comparative Examples 1.
Embodiment 1
Except that the carborundum powder that adds 2.0g as according to of the present invention wear-resisting-the hardness additive, all the other are identical with Comparative Examples 1.
Embodiment 2
Except that the carborundum powder that adds 5.0g, all the other are identical with Comparative Examples 1.
Embodiment 3
Except that the carborundum powder that adds 8.0g, all the other are identical with Comparative Examples 1.
Embodiment 4
Except that the nitrogenize titanium valve that adds 5.0g, all the other are identical with Comparative Examples 1.
Embodiment 5
Except that the aluminum oxide powder that adds 5.0g, all the other are identical with Comparative Examples 1.
Embodiment 6
Except that nylon 66 powder that add 5.0g, all the other are identical with Comparative Examples 1.
Embodiment 7
(the sartomer product CN965) changes 5g into, Epocryl (galstaff product with the aliphatic urethane acrylate resin, syncryl104) change 10g into, do not add the polyester acrylate resin, but add the carborundum powder of 5.0g, all the other are identical with Comparative Examples 1.
Embodiment 8
With aliphatic urethane acrylate resin (sartomer product, CN965) change 40g into, Epocryl (galstaff product, syncryl104) change 50g into, polyester acrylate resin (sartomer product, CNUVP225) change 40g into, add the carborundum powder of 5.0g, all the other are identical with Comparative Examples 1.
Embodiment 9
Bifunctional Acrylic Acid Monomer HDDA changes 7g into, and trifunctional Acrylic Acid Monomer TMPTA changes 5g into, does not add the simple function group Acrylic Acid Monomer, but adds the carborundum powder of 5.0g, and all the other are identical with Comparative Examples 1.
Embodiment 10
HEA changes 20g into the simple function group Acrylic Acid Monomer, and bifunctional Acrylic Acid Monomer HDDA changes 25g into, and trifunctional Acrylic Acid Monomer TMPTA changes 25g into, adds the carborundum powder of 5.0g, and all the other are identical with Comparative Examples 1.
The former lacquer performance of above embodiment and made coating sees Table 1.
The performance of the paint film of coating behind ultraviolet light polymerization that each embodiment is made sees Table 2.
As can be seen from Table 2, do not add the abrasion resistance of the embodiment 1 of wear-resisting-hardness additive and have only 300 times, hardness is 2H, ethanol-tolerant test nondiscoloration.When adding the carborundum powder of 2.0g, its wear-resisting and hardness increases greatly, and the data results of embodiment 2 shows wear-resisting reaching 610 times, and hardness is 4H.The amount that continues the wear-resisting-hardness additive of increase reaches 8g, and this moment is wear-resisting and hardness amplification is little, but downtrending appears in sticking power, reaches 2B, and corrosion resistance nature also descends.Its reason is that wear-resisting and hardness additive has slackened the bonding force of body resin and ground.The inorganic additives of other kinds also reaches same effect, shown in embodiment 4,5.
Add a spot of organic additive and also can increase the wear-resisting and hardness that is coated with rete, shown in embodiment 6.
Change the amount of matrix resin or reactive monomer, add a spot of wear-resisting and hardness additive, can reach the effect that increases wear-resisting and hardness equally, but the minimizing of matrix resin or reactive thinner amount may cause the decline of paint film layer sticking power and corrosion resistance nature.Under equal conditions, the consequence that causes of the reduction of matrix resin amount can be more serious.Embodiment 7-10 has promptly shown this conclusion.
Testing method:
Wearability test: the 7-IBB type RCA abrasion instrument that uses U.S. Nuo Man Instrument and Equipment Company to produce, under the effect of 175g power, the paint film after the mill spraying, during the show-through material of paint film, the number of times that rubber wheel rotates.
Hardness test: adopt Chinese different H pencil, and surpass the 30mm indentation, put examination on the skin with rubber again, see to have or not indentation with 1kg power delineation length, as not having, H hardness for this reason then.
Sticking power test: draw 100 1 millimeter * 1 millimeter square lattice at sprayed surface with drawing the lattice device, the model of producing with Minnesota Mining and Manufacturing Company is 600 smooth being bonded on the grid of scotch tape, do not stay a space, vertically uncover with utmost dispatch then, observe cut edge and have or not depainting.Is 5B as the depainting amount between 0～5%, is 4B between 5～10%, is 3B between 10～20%, is 2B between 20～30%, is B between 30～50%, is being 0B more than 50%.
Ethanol-tolerant test: dip in clean gauze that to get concentration be 99% alcohol, put on the skin at the paint film same position with 0.5 kilogram power and wipe away, the observation finish paint has or not variable color.
Table 1
| State in the container | Stir the no lump in back, be uniform state |
| Viscosity (s) | 15～35 |
| Solid content (%) | 80～95 |
| Thickness (μ m) | 10～15 |
Table 2
| Wear resistance (inferior) | Hardness (H) | Sticking power (B) | Ethanol-tolerant | |
| Comparative Examples 1 | 300 | 2 | 3 | Nondiscoloration |
| Comparative Examples 2 | 460 | 2 | 3 | Nondiscoloration |
| Embodiment 1 | 610 | 4 | 5 | Nondiscoloration |
| Embodiment 2 | 650 | 5 | 4 | Nondiscoloration |
| Embodiment 3 | 700 | 5 | 2 | Variable color is arranged slightly |
| Embodiment 4 | 680 | 4 | 5 | Nondiscoloration |
| Embodiment 5 | 650 | 4 | 5 | Nondiscoloration |
| Embodiment 6 | 570 | 3 | 5 | Nondiscoloration |
| Embodiment 7 | 720 | 5 | 2 | Variable color is arranged slightly |
| Embodiment 8 | 520 | 4 | 5 | Nondiscoloration |
| Embodiment 9 | 650 | 5 | 3 | Nondiscoloration |
| Embodiment 10 | 550 | 4 | 4 | Nondiscoloration |
Claims (23)
1. ultraviolet-curing paint that is used for plastics, comprise matrix resin, reactive thinner, light trigger, solvent, it is characterized in that also comprising wear-resisting-hardness additive, this wear-resisting-hardness additive weight percent content in this coating is 0.1～8.0%.
2. the ultraviolet-curing paint that is used for plastics according to claim 1, it is characterized in that described wear-resisting-the hardness additive is that microhardness is at 500kgf/mm
2Above pressed powder.
3. the ultraviolet-curing paint that is used for plastics according to claim 2, it is characterized in that described wear-resisting-the hardness additive is to be selected from least a in carbide, nitride, oxide compound or the organic polymer.
4. the ultraviolet-curing paint that is used for plastics according to claim 3 is characterized in that described carbide is to be selected from least a in silicon carbide, zirconium carbide, norbide, aluminium carbide, iron carbide, the chromium carbide.
5. the ultraviolet-curing paint that is used for plastics according to claim 3 is characterized in that described nitride is to be selected from least a in titanium nitride, zirconium nitride, gan, aluminium nitride, the CaCl2.
6. the ultraviolet-curing paint that is used for plastics according to claim 3 is characterized in that described oxide compound is to be selected from least a in titanium dioxide, aluminum oxide, chromic oxide, stannic oxide, the silicon-dioxide.
7. the ultraviolet-curing paint that is used for plastics according to claim 3 is characterized in that described organic polymer is to be selected from least a in nylon, polyethylene wax, Poly Propylene Wax, polyvinyl chloride wax, the polycarbonate.
8. the ultraviolet-curing paint that is used for plastics according to claim 2, it is characterized in that described wear-resisting-mean particle size of hardness additive solids powder is for less than 10 μ m
9. the ultraviolet-curing paint that is used for plastics according to claim 8, it is characterized in that described wear-resisting-mean particle size of hardness additive solids powder is 3 μ m～8 μ m.
10. the ultraviolet-curing paint that is used for plastics according to claim 1 is characterized in that described coating contains the component with following weight percent content:
Matrix resin 15-70%
Reactive thinner 10～55%
Wear-resisting-hardness additive 0.1～8.0%
Light trigger 2.0～10.0%
Solvent 2～50%
11. the ultraviolet-curing paint that is used for plastics according to claim 1 is characterized in that described matrix resin is for being selected from least a in aliphatic urethane acrylate resin, epoxy (methyl) acrylate resin and the polyester acrylate resin.
12. the ultraviolet-curing paint that is used for plastics according to claim 11 is characterized in that, with respect to the gross weight of described coating, described coating contains component with following weight percent content as described matrix resin:
Aliphatic urethane acrylate resin 5～20%;
Epoxy (methyl) acrylate resin 5～30%;
Polyester acrylate resin 5～20%.
13. the ultraviolet-curing paint that is used for plastics according to claim 1 is characterized in that described reactive thinner is at least a among the reactive acrylate monomer who is selected from the group of being made up of simple function group acrylate monomer, bifunctional acrylate's monomer and trifunctional group acrylate's monomer.
14. the ultraviolet-curing paint that is used for plastics according to claim 13 is characterized in that, with respect to the gross weight of described coating, described coating contains component with following weight percent content as described reactive thinner:
Simple function group acrylate monomer 2～15%;
Bifunctional acrylate's monomer 4～20%;
Trifunctional group acrylate's monomer 4～20%.
15. the ultraviolet-curing paint that is used for plastics according to claim 1 is characterized in that described solvent is two or more mixed solvent of forming of organic solvent of the same race not.
16. the ultraviolet-curing paint that is used for plastics according to claim 15 is characterized in that described solvent is two or more the mixture of solvent that is selected from toluene, ethyl acetate, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, pimelinketone, dimethylbenzene, hexone, acetone, methylethylketone, butyl glycol ether, the propylene glycol butyl ether.
17. the ultraviolet-curing paint that is used for plastics according to claim 1 is characterized in that also containing the flow agent of 0.1～1.0 weight %.
18. the ultraviolet-curing paint that is used for plastics according to claim 1 is characterized in that also containing the defoamer of 0.1～1.5 weight %.
19. the ultraviolet-curing paint that is used for plastics according to claim 1 is characterized in that also containing the dispersion agent of 0.2～3.0 weight %.
20. a manufacturing may further comprise the steps according to the method for the ultraviolet-curing paint that is used for plastics of claim 1:
(1) matrix resin that will account for total system 15～70 weight % of coating is dissolved in the acrylate monomer reactive thinner that accounts for total system 10～55 weight %, stirs;
(2) light trigger that will account for total system 2～10 weight % of coating and the solvent that accounts for total system 2～50 weight % of coating are stirred to abundant dissolving;
(3) step (2) gained mixture and step (1) gained mixture are mixed;
(4) adding accounts for the microhardness of total system 0.1～8.0 weight % of coating at 500kgf/mm in step (3) gained mixture
2Above wear-resisting-hardness additive solids powder, high-speed stirring evenly suspends this pressed powder.
21, method according to claim 20, wherein step (4) also comprises in step (3) gained mixture and to add the flow agent that accounts for total system 0.1～1.0 weight % of coating.
22, method according to claim 20, wherein step (4) also comprises in step (3) gained mixture and to add the defoamer that accounts for total system 0.1～1.5 weight % of coating.
23, method according to claim 20, wherein step (4) also comprises in step (3) gained mixture and to add the dispersion agent that accounts for total system 0.2～3.0 weight % of coating.
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| CN 200410090634 CN1772820A (en) | 2004-11-10 | 2004-11-10 | Ultraviolet cured paint for plastics and its production process |
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