CN106957597B - UV curing coating and preparation method and application thereof - Google Patents
UV curing coating and preparation method and application thereof Download PDFInfo
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- CN106957597B CN106957597B CN201710248703.XA CN201710248703A CN106957597B CN 106957597 B CN106957597 B CN 106957597B CN 201710248703 A CN201710248703 A CN 201710248703A CN 106957597 B CN106957597 B CN 106957597B
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a UV curing coating and a preparation method and application thereof, wherein the UV curing coating comprises the following components in percentage by weight: 30-40% of high-functional polyurethane acrylate; 10-20% of trifunctional polyurethane acrylic resin; 10-20% of difunctional polyurethane acrylic resin; 3-5% of trimethylolpropane triacrylate; 2-4% of a photosensitizer; 10-15% of a solvent. The UV curing coating is sprayed on the surface of the single-liquid type colored paint and is used for finishing the surface of the single-liquid type colored paint, a tough coating film can be formed on the surface of the single-liquid type colored paint, the single-liquid type colored paint has good adhesive force, good flexibility and good bending resistance, the product is not easy to bend and burst in the using process, and the single-liquid type colored paint cannot be influenced.
Description
Technical Field
The invention relates to the field of coatings, in particular to a UV (ultraviolet) curing coating and a preparation method and application thereof, and particularly relates to a high-flexibility bending-resistant UV curing coating for a single-liquid colored paint surface and a preparation method and application thereof.
Background
At present, the single-liquid colored paint and the UV curing finish paint have become a common effect in the mobile phone manufacturing industry. The processing technology of the mobile phone shell is as follows: raw materials → injection molding → cleaning → spraying of single-liquid type color paint → spraying of UV curing finish → packaging. The main purpose of spraying is to make a delicate appearance effect on the surface of the material, make up for the surface defects of the material, play a certain role in protection and enhance the aesthetic practicability of the mobile phone. However, not all coatings can play a good role in protection, for example, the existing mobile phone tends to be ultra-thin, so that the battery cover of the mobile phone is thinner and thinner, the middle frame is narrower and narrower, the narrow edge of some middle frames is only 1-2 mm, the traditional UV curing coating is generally high in hardness, and the coating is easy to bend and break in the production process.
The basic requirements for such protective coatings are: the coating not only maintains the basic characteristics of the current market circulation products, but also has the characteristics of ultrahigh flexibility, bending resistance and the like, so that unnecessary material and production waste caused by hard coating in the spraying production process are reduced; the process has strong operability.
At the same time, with the increasing awareness of global environmental protection, the coating industry is beginning to move along sustainability. The UV coating has the advantages of environmental protection, convenience, economy and the like, is widely used in modern society, particularly has incomparable advantages in the aspect of 3C products, and particularly has the following advantages compared with the traditional volatile drying type coating: the curing is rapid, and the production efficiency is high; excellent cured film properties (abrasion resistance, chemical resistance, etc.); low temperature cure, suitable for heat sensitive substrates (e.g., plastics); the solvent content is low or no solvent is contained, so that the environmental hazard is small; saving field and low energy consumption.
However, the disadvantages of the existing UV coating, such as high hardness and easy breaking during bending, are not compatible with the characteristics of the existing ultrathin product, such as thinness and narrow edge of the middle frame, so the prior art needs to be perfected and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a UV curing coating, a preparation method and application thereof, in particular to a UV curing coating with good flexibility and bending resistance, and aims to solve the problems that the existing UV curing coating has high hardness and is easy to break when bent, and the disadvantages are not in accordance with the characteristics of the existing ultrathin product material and the narrow edge of the middle frame.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a UV-curable coating, which comprises the following components in percentage by weight:
30-40% of high-functional polyurethane acrylate; 10-20% of trifunctional polyurethane acrylic resin; 10-20% of difunctional polyurethane acrylic resin; 3-5% of trimethylolpropane triacrylate; 2-4% of a photosensitizer; 10-25% of a solvent.
According to the invention, the components are combined according to a certain proportion, and the components have a synergistic interaction effect, so that the prepared UV curing coating greatly improves the adhesive force, flexibility and bending resistance of the original UV curing coating while ensuring the basic characteristics of the original UV curing coating.
According to the invention, the high-functional polyurethane acrylate accounts for 30-40% by weight, such as 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40%; the weight percentage of the trifunctional polyurethane acrylic resin is 10-20%, such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%; the weight percentage of the difunctional polyurethane acrylic resin is 10-20%, such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%; the trimethylolpropane triacrylate accounts for 3-5 wt%, such as 3%, 3.2%, 3.5%, 3.6%, 3.8%, 4%, 4.1%, 4.3%, 4.5%, 4.8% or 5%; the photosensitizer accounts for 2-4% by weight, such as 2%, 2.2%, 2.5%, 2.6%, 2.8%, 3%, 3.1%, 3.3%, 3.5%, 3.8% or 4%; the solvent is 10-25% by weight, for example 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%.
Preferably, the high functional urethane acrylate has a TG point of 69, a molecular weight of 1000, a viscosity of 2000mpa.s/60 ℃, and an elongation of 2%.
Preferably, the trifunctional urethane acrylate resin has a viscosity of 4500mpa.s/60 ℃ and an elongation of 37%, and thus, the trifunctional urethane acrylate resin having such special properties is preferably used because it can be combined with a difunctional urethane acrylate resin, which have a synergistic effect, thereby providing excellent flexibility and bending resistance to the UV-curable coating.
Preferably, the viscosity of the difunctional polyurethane acrylic resin is 9000mpa.s/60 ℃, the molecular weight of the difunctional polyurethane acrylic resin is 1000, and the difunctional polyurethane acrylic resin can be better matched with the trifunctional polyurethane acrylic resin to realize the effects of improving the high flexibility and bending resistance of the UV-cured coating.
Preferably, the trimethylolpropane triacrylate has an acid value (KOH/g) of 0.2mg, a refractive index of 1.47nD, and a surface tension of 35 dyne/cm.
Preferably, the photosensitizer is 1-hydroxy-cyclohexylbenzophenone.
According to the invention, the UV curing coating can also comprise the following components in percentage by weight: 5.0-8.0% of an auxiliary agent; the weight percentage of the auxiliary agent in the UV curable coating material may be, for example, 5.0%, 5.2%, 5.3%, 5.5%, 5.8%, 6.0%, 6.5%, 6.8%, 7.0%, 7.5%, 7.8%, or 8.0%, where the weight percentage refers to the weight percentage of the auxiliary agent in the UV curable coating material.
Preferably, the adjuvant comprises a silicone adjuvant.
Preferably, the UV-curable coating comprises the following components in percentage by weight: 35-40% of high-functional polyurethane acrylate; 10-15% of trifunctional polyurethane acrylic resin; 15-20% of difunctional polyurethane acrylic resin; 3-4% of trimethylolpropane triacrylate; 3.5-4% of a photosensitizer; 6.5-7% of an organic silicon assistant; 20-22% of a solvent.
In the invention, the auxiliary agent can comprise a leveling agent and a defoaming agent besides the organic silicon auxiliary agent.
Preferably, the auxiliary agent in the UV curing coating comprises the following components in percentage by weight: 5.0-7.0% (e.g., 5.0%, 5.2%, 5.3%, 5.5%, 5.8%, 6.0%, 6.5%, 6.8%, or 7.0%) of an organosilicon adjuvant; 0.3-0.5% (e.g., 0.3%, 0.35%, 0.4%, 0.45%, or 0.5%) of a leveling agent; 0.3-0.5% (such as 0.3%, 0.35%, 0.4%, 0.45% or 0.5%) of defoaming agent, wherein the weight percentage refers to the weight percentage of the auxiliary agent in the UV curing coating.
Preferably, the silicone additive color number is ≦ 1max (Gardner); viscosity of 2500 + -1000 (25 deg.C, cps); the solids content was 70. + -. 2% (105 ℃ C./2 hr).
Preferably, the leveling agent is silicone.
Preferably, the defoamer is a silicone.
In a second aspect, the present invention further provides a method for preparing the UV curable coating according to the first aspect, which specifically includes: adding the components into a container according to the weight percentage, and uniformly mixing under the stirring condition to obtain the UV curing coating.
In a third aspect, the invention also provides the application of the UV-cured coating in the first aspect, wherein the UV-cured coating is used for a UV top coat sprayed on the surface of the single-liquid type colored paint.
When the UV curing coating is used for the UV finishing coat sprayed on the surface of the single-liquid type colored paint, the specific operation is as follows:
(1) diluting the coating: mixing and diluting the UV curing coating with butyl acetate and ethyl acetate according to the weight ratio of 100:65: 35;
(2) spraying: spraying the diluent of the UV curing coating on the surface of the single-liquid type colored paint;
(3) and (3) drying: drying after spraying, wherein the drying conditions are as follows: leveling for 2-5 min at normal temperature; and (3) IR baking: baking for 5-8 min at the temperature of 60-65 ℃; UV curing: 1000 to 1200mj/cm2。
Wherein the coating film thickness of the UV curing coating is 18-24 mu m (Mitutoyo); the temperature of the IR (infrared ray) in the IR baking process is 60-65 ℃, and the time is 5-8 min; in the UV curing process, the accumulated UV energy is 1000-1200 mj/cm2(EIT UV Power Puck II), the spectral range is 180-420 nm, and the Power of the UV lamp tube is 80-120W/cm.
And (3) applying the UV curing coating to a sample obtained by spraying UV finishing coat on the surface of the single-liquid colored paint, and performing bending test (180-degree bending), wherein the bending test specifically comprises the following steps:
and (3) spraying the sample to face outwards, bending the sample on a cylindrical shaft with the diameter of 40mm at the same position for 180 degrees on the cylindrical shaft, and finishing the bending within 1-2 seconds, wherein the test result shows that all bent materials cannot be broken.
Compared with the prior art, the invention has at least the following beneficial effects:
the UV curing coating provided by the invention is sprayed on the single-liquid type colored paint, and after the UV curing coating is cured by a UV photocuring machine, a tough paint film can be formed on the surface of the single-liquid type colored paint, so that the basic characteristics of the original UV curing coating can be effectively ensured, the flexibility and the bending resistance of the original UV curing coating can be greatly improved, and the UV curing coating has the advantages of low odor, no toluene, no halogen, no heavy metal and the like, meets the RoHS standard, and is low in environmental hazard.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific implementation ratios described herein are merely to illustrate the invention and are not intended to limit the invention.
Example 1
The UV curing coating comprises the following components in percentage by weight:
35% of high-functional urethane acrylate; 10% of trifunctional polyurethane acrylic resin; 20% of difunctional polyurethane acrylic resin; trimethylolpropane triacrylate 3%; 3.5% of photosensitizer; 6.5 percent of organic silicon additive; and 22% of a solvent.
The TG point of the high-functional polyurethane acrylate is 69, the molecular weight is 1000, the viscosity is 2000mpa.s/60 ℃, and the elongation is 2%; the viscosity of the trifunctional polyurethane acrylic resin is 4500mpa.s/60 ℃, and the elongation is 37%; the viscosity of the difunctional polyurethane acrylic resin is 9000mpa.s/60 ℃, and the molecular weight is 1000; the trimethylolpropane triacrylate acid value (KOH/g) is 0.2mg, the refractive index is 1.47nD, and the surface tension is 35 dyne/cm; the photosensitizer is 1-hydroxy-cyclohexyl benzophenone.
Adding the components into a container according to the weight percentage, and uniformly mixing under the stirring condition to obtain the UV curing coating.
Example 2
The UV curing coating comprises the following components in percentage by weight:
35% of high-functional urethane acrylate; 20% of trifunctional polyurethane acrylic resin; 10% of difunctional polyurethane acrylic resin; trimethylolpropane triacrylate 3%; 3.5% of photosensitizer; 6.5 percent of organic silicon additive; and 22% of a solvent.
The specific selection of the components was the same as in example 1.
Adding the components into a container according to the weight percentage, and uniformly mixing under the stirring condition to obtain the UV curing coating.
Example 3
The UV curing coating comprises the following components in percentage by weight:
40% of high-functional polyurethane acrylate; 10% of trifunctional polyurethane acrylic resin; 20% of difunctional polyurethane acrylic resin; 5% of trimethylolpropane triacrylate; 3.5% of photosensitizer; 6.5 percent of organic silicon additive; 15% of a solvent.
The specific selection of the components was the same as in example 1.
Adding the components into a container according to the weight percentage, and uniformly mixing under the stirring condition to obtain the UV curing coating.
Example 4
The UV curing coating comprises the following components in percentage by weight:
30% of high-functional polyurethane acrylate; 20% of trifunctional polyurethane acrylic resin; 15% of difunctional polyurethane acrylic resin; trimethylolpropane triacrylate 3%; 3.5% of photosensitizer; 6.5 percent of organic silicon additive; and 22% of a solvent.
The specific selection of the components was the same as in example 1.
Adding the components into a container according to the weight percentage, and uniformly mixing under the stirring condition to obtain the UV curing coating.
Example 5
The UV curing coating comprises the following components in percentage by weight:
35% of high-functional urethane acrylate; 20% of trifunctional polyurethane acrylic resin; 10% of difunctional polyurethane acrylic resin; trimethylolpropane triacrylate 3%; 3.5% of photosensitizer; 5.5 percent of organic silicon additive; 0.5 percent of leveling agent; 0.5 percent of defoaming agent; and 22% of a solvent.
The specific selection of the components was the same as in example 1.
Adding the components into a container according to the weight percentage, and uniformly mixing under the stirring condition to obtain the UV curing coating.
Comparative example 1
The same as example 1 was repeated except that the trifunctional urethane acrylic resin was removed, that is, the UV curable coating material did not contain this component, as compared with example 1.
Comparative example 2
The same as example 1 was repeated except that the difunctional urethane acrylic resin was removed, that is, the UV curable coating material did not contain this component, as compared with example 1.
The specific composition of each example is shown in table 1, and the content of each component in the table is in percent by weight (%).
TABLE 1
The UV curing coating obtained in the above examples 1-5 and comparative examples 1-2 is subjected to the following processes:
the process sequence is as follows: substrate cleaning → coating dilution → spraying → IR baking → UV curing, the specific process parameters are as follows:
the paint dilution ratio is as follows: coating, wherein the weight ratio of butyl acetate to ethyl acetate is 100:65: 35;
film thickness: 18-24 μm (Mitutoyo);
cumulative UV energy: 1000 to 1200mj/cm2(EIT UV Power Puck II)；
Spectral range: 180-420 nm;
UV lamp tube power: 80-120W/cm;
IR temperature: 60-65 ℃ for 5-8 min.
The properties of the coating layers obtained in examples 1 to 5 and comparative examples 1 to 2 on the metal surface are shown in Table 2.
TABLE 2
As can be seen from the table 2, the trifunctional polyurethane acrylic resin and the difunctional polyurethane acrylic resin in the UV curing coating have a synergistic effect, so that the UV curing coating has the characteristics of good adhesive force, good flexibility and good bending resistance.
In conclusion, the UV curing coating is sprayed on the single-liquid type colored paint, and after the UV curing coating is cured by the UV curing machine, a tough paint film can be formed on the surface of the single-liquid type colored paint, so that the UV curing coating has good adhesive force, good flexibility and good bending resistance on the single-liquid type colored paint, and can effectively ensure that the product is not easy to bend and crack in the using process. Moreover, the single-liquid type colored paint itself is not affected at all. Therefore, the flexible bending-resistant UV photocureable coating can be effectively applied to the surface of the single-liquid colored paint. Moreover, the UV curing coating has the advantages of low odor, no toluene, no halogen, no heavy metal and the like, meets the RoHS standard, and has small harm to the environment.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (12)
1. The application of the UV curing coating for spraying the surface of the single-liquid colored paint is characterized in that the UV curing coating comprises the following components in percentage by weight:
30-40% of high-functional polyurethane acrylate; 10-20% of trifunctional polyurethane acrylic resin; 10-20% of difunctional polyurethane acrylic resin; 3-5% of trimethylolpropane triacrylate; 2-4% of a photosensitizer; 10-25% of a solvent;
the TG point of the high-functional polyurethane acrylate is 69, the molecular weight is 1000, the viscosity is 2000mpa.s/60 ℃, and the elongation is 2%;
the viscosity of the trifunctional polyurethane acrylic resin is 4500mpa.s/60 ℃, and the elongation is 37%;
the viscosity of the difunctional polyurethane acrylic resin is 9000mpa.s/60 ℃, and the molecular weight is 1000;
the operation of applying the UV curing coating to the UV finishing coat sprayed on the surface of the single-liquid type colored paint is as follows:
(1) diluting the coating: mixing and diluting the UV curing coating with butyl acetate and ethyl acetate according to the weight ratio of 100:65: 35;
(2) spraying: spraying the diluent of the UV curing coating on the surface of the single-liquid type colored paint;
(3) and (3) drying: drying after spraying, wherein the drying conditions are as follows: leveling for 2-5 min at normal temperature; and (3) IR baking: baking for 5-8 min at the temperature of 60-65 ℃; UV curing: 1000 to 1200mj/cm2。
2. Use according to claim 1, wherein the trimethylolpropane triacrylate has an acid value (KOH/g) of 0.2mg, a refractive index of 1.47nD and a surface tension of 35 dyne/cm.
3. The use of claim 1, wherein the photosensitizer is 1-hydroxy-cyclohexylbenzophenone.
4. The use according to claim 1, wherein the UV-curable coating further comprises the following components in weight percent: 5.0-8.0% of an auxiliary agent.
5. The use of claim 4, wherein the adjuvant comprises a silicone adjuvant.
6. The use according to claim 1, wherein the UV-curable coating comprises, in weight percent: 35-40% of high-functional polyurethane acrylate; 10-15% of trifunctional polyurethane acrylic resin; 15-20% of difunctional polyurethane acrylic resin; 3-4% of trimethylolpropane triacrylate; 3.5-4% of a photosensitizer; 6.5-7% of an organic silicon assistant; 20-22% of a solvent.
7. The use according to claim 5, wherein the auxiliary agent further comprises a leveling agent and an antifoaming agent.
8. The use according to claim 4, wherein the auxiliary agent in the UV-curable coating consists of, in weight percent: 5.0-7.0% of an organic silicon assistant; 0.3-0.5% of a leveling agent; 0.3-0.5% of defoaming agent.
9. The use of claim 8, wherein the silicone adjuvant has a color number of 1max (Gardner); viscosity of 2500 + -1000 (25 deg.C, cps); the solids content was 70. + -. 2% (105 ℃ C./2 hr).
10. The use according to claim 8, wherein the levelling agent is a silicone.
11. Use according to claim 8, wherein the anti-foaming agent is a silicone.
12. Use according to one of claims 1 to 11, wherein the UV-curable coating is prepared by a process comprising: adding the components into a container according to the weight percentage, and uniformly mixing under the stirring condition to obtain the UV curing coating.
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| CN108501133A (en) * | 2017-12-30 | 2018-09-07 | 张梦琪 | A kind of PVC veneered plywoods and its manufacturing method |
| CN115074018A (en) * | 2021-12-31 | 2022-09-20 | 荣耀终端有限公司 | Finishing coat composition, composite material, electronic equipment middle frame, electronic equipment shell and electronic equipment |
| CN115193661A (en) * | 2022-08-18 | 2022-10-18 | 中广核达胜加速器技术有限公司 | Production method of PVC (polyvinyl chloride) floor |
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| CN101338088A (en) * | 2008-08-11 | 2009-01-07 | 深圳市美丽华油墨涂料有限公司 | Coating for UV cured plastic and use |
| CN102807814A (en) * | 2012-07-26 | 2012-12-05 | 惠州市至上化工有限公司 | Nano silica-modified recoatable ultraviolet (UV) varnish used on plastic and preparation method for varnish |
| CN103525220A (en) * | 2013-10-16 | 2014-01-22 | 惠州市凯辉化工有限公司 | Ultraviolet (UV) varnish series painting for spraying automotive interiors and preparation method of painting |
| CN106497393A (en) * | 2016-11-14 | 2017-03-15 | 惠州大亚湾浩德工贸有限公司 | A kind of automotive trim sprays UV gloss oil |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338088A (en) * | 2008-08-11 | 2009-01-07 | 深圳市美丽华油墨涂料有限公司 | Coating for UV cured plastic and use |
| CN102807814A (en) * | 2012-07-26 | 2012-12-05 | 惠州市至上化工有限公司 | Nano silica-modified recoatable ultraviolet (UV) varnish used on plastic and preparation method for varnish |
| CN103525220A (en) * | 2013-10-16 | 2014-01-22 | 惠州市凯辉化工有限公司 | Ultraviolet (UV) varnish series painting for spraying automotive interiors and preparation method of painting |
| CN106497393A (en) * | 2016-11-14 | 2017-03-15 | 惠州大亚湾浩德工贸有限公司 | A kind of automotive trim sprays UV gloss oil |
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