TW201319186A - Coating composition for heat transfer printing and coating - Google Patents

Abstract

A coating composition for heat transfer printing comprises a double bond-containing resin, a reactive UV absorbing agent represented by formula (I) or (II), and a hardening agent, in which the formula (I) and (II) is set forth as defined in the specification. The coating composition for heat transfer printing of this invention is used to coat surfaces of any articles to form a coat, and transfer print the ink to said coat through heat transfer printing, thereby said ink have an excellent property of weathering resistance.

Description

Coating composition and coating film for heat transfer printing

The present invention relates to a coating composition and a coating film formed therefrom, and more particularly to a coating composition for heat transfer printing and a coating film therefor.

The thermal transfer technology is a treatment method which is often used for aesthetically modifying the surface of ceramics or inorganic materials. The treatment process is to transfer the sublimation dye ink to the surface of the ceramic or inorganic material by heating, and form a surface on the surface of the ceramic or inorganic material. Pattern layer. However, since the sublimation dye ink is poorly resistant to ultraviolet rays (for example, the ink may be discolored or peeled off due to long-term ultraviolet irradiation), the pattern layer formed on the surface of the ceramic or inorganic material has poor weather resistance.

No. 5,336,660 provides an image receiving sheet for use in combination with a heat transfer sheet comprising a base sheet and a receiving layer formed on the surface of the substrate. The substrate has a porous structure or a foamed structure, and the receiving layer is composed of a resin that can be dyed (for example, saturated polyester, polyurethane, polystyrene, polyamine, etc.). Although the above-mentioned pattern receiving sheet can be successfully combined with the ink, it cannot prevent the ink from being discolored, discolored or peeled off after the ultraviolet irradiation.

US 5,397,763 discloses a thermal transfer sheet comprising a substrate, a pattern receiving layer releasably formed on the substrate, an adhesive layer formed on a surface of the pattern receiving layer, and a formation formed on the pattern receiving layer. a thermally moving dye layer on the plane, and an insulating layer formed on a plane different from the plane in which the pattern receiving layer and the thermally transitioning dye layer are formed. The thermal transfer sheet further comprises a protective layer releasably formed on a plane formed by the pattern receiving layer, the protective layer comprising a resin (selected from polyester, polyvinyl acetate or acrylic resin), ultraviolet absorption Agent or antioxidant. The protective layer of this patent is not disposed on the pattern receiving layer, and thus the transfer pattern cannot be effectively protected.

It can be seen from the above that how to make the transfer pattern firmly bond with the surface of the ceramic or inorganic material, and at the same time protect the transfer pattern from the fading, discoloration or peeling caused by long-term ultraviolet irradiation, etc., for the current industry, there is still There is a great demand.

Accordingly, it is an object of the present invention to provide a coating composition for heat transfer.

Therefore, the coating composition for heat transfer printing of the present invention comprises: a double bond-containing resin, a reactive ultraviolet absorber having a structure represented by the following formula (I) or (II), and a curing agent:

Wherein R ¹ and R ² represent respectively ,

Another object of the present invention is to provide a coating film formed from the above coating composition.

The coating film of the present invention is formed by curing the above coating composition.

The coating composition for heat transfer printing of the present invention can be cross-linked with a resin containing a double bond by using a reactive ultraviolet absorber having a double bond structure at the end, thereby making it difficult for the ultraviolet absorber to migrate. At the same time, the amount of the ultraviolet absorber added can be increased, and the coating film formed by the subsequent curing of the coating composition has a good ultraviolet protection effect. Therefore, when the thermal sublimation dye ink is thermally transferred onto the coating film of the present invention and a pattern layer is formed, the coating film of the present invention can protect the pattern layer from ultraviolet light to be discolored, discolored or peeled off, thereby allowing the pattern layer to have Good weatherability.

The coating composition for heat transfer printing of the present invention comprises: a resin containing a double bond, a reactive ultraviolet absorber having a structure represented by the above formula (I) or the above formula (II), and a curing agent.

Preferably, the reactive ultraviolet absorber has a structure represented by the formula (I). In one embodiment of the invention, the reactive ultraviolet absorber has the following structure of formula (III):

Preferably, the double bond-containing resin is selected from the group consisting of polyurethane ester diacrylate, bisphenol A epoxy resin acrylate, double bond-containing chlorinated polyester resin, acrylic acid oligomer, or a combination thereof.

Preferably, the reactive ultraviolet absorber is used in an amount ranging from 1 to 14% by weight based on the total weight of the coating composition for heat transfer printing, and the amount of the double bond-containing resin is in the range of 100 wt%. 76~98 wt%, and the curing agent is used in an amount ranging from 1 to 10 wt%.

The curing agent in the coating composition of the present invention may be selected from any curing agent suitable for the coating. Preferably, the curing agent is selected from the group consisting of benzoyl peroxide, cumene hydroperoxide, silicone or a combination thereof.

The coating composition for heat transfer printing of the present invention optionally further comprises a diluent solvent. Preferably, the diluent solvent is selected from the group consisting of n-butyl acetate, toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, isopropanol or a combination thereof.

Preferably, the total weight of the coating composition for the heat transfer transfer is 100 parts by weight, and the diluent solvent is used in an amount ranging from 50 to 150 parts by weight. In a specific example of the present invention, the dilution solvent is composed of n-butyl acetate and toluene, and the weight ratio of n-butyl acetate:toluene ranges from 1:1 to 5:1.

The coating composition of the present invention may optionally be added with a functional auxiliary agent depending on the subsequent application, such as an agent for increasing the adhesion strength, an antifoaming agent or a leveling agent, and the like. Examples of the agent for increasing the adhesion strength include, but are not limited to, 2-hydroxyethyl methacrylate phosphate (commercially available as DM-9166 sold by Shuangjian Chemical Co., Ltd.) and 3- 3-methacryloxypropyl trimethoxysilane (available from Degussa Corporation). Examples of defoamers include, but are not limited to, Deform 5300 sold by Hemings Deqian. Examples of leveling agents include, but are not limited to, L-066 sold by Qinglin Trading Company.

Preferably, the functional additive is used in an amount ranging from 0.1 to 10 parts by weight based on 100 parts by weight of the total weight of the coating composition for heat transfer.

The coating composition for heat transfer printing of the present invention is used, for example, by coating the coating composition on the surface of a substrate to be transferred, and then curing the coating composition on the surface of the substrate. Forming a coating film thereon; then, transferring a transfer paper containing a pattern composed of the dye-sublimation dye ink to the coating film, and applying a hot pressing on the transfer paper to transfer the pattern on the transfer paper to On the coating film.

The material of the above substrate is not limited in any way, that is, the coating composition for heat transfer printing of the present invention can be coated on the surface of any substrate.

The invention is further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

<Example> [Chemicals]

The following examples use the following chemicals:

1. Resin with double bond:

Examples 1 and 4: Polyurethane diacrylate (available from Double Bond Chemical Co., Ltd., DM-541, molecular weight 1800, hereinafter referred to as "DM-541") and bisphenol A epoxy resin acrylate (purchased) Since Double Bond Chemical Co., Ltd., the product name is DM-127-TP20, the molecular weight is 400-600, hereinafter referred to as "DM-127-TP20"); Example 2 uses a chlorinated polyester resin containing double bonds (purchased from double Key Chemical Co., Ltd., DM-236, molecular weight 7000-8000, hereinafter referred to as "DM-236") and acrylic oligomer (purchased from Double Bond Chemical Co., Ltd., DM-3710, molecular weight 36000 ~38000, hereinafter referred to as "DM-3710") Example 3 uses polyurethane diacrylate (available from Double Bond Chemical Co., Ltd., DM-584, molecular weight 1200, hereinafter referred to as "DM-584") and polyurethane II. Acrylate (purchased from Double Bond Chemical Co., Ltd., DM-541, molecular weight 1800, hereinafter referred to as "DM-541").

2. Reactive ultraviolet absorber: In Examples 1 to 4, the ultraviolet absorber represented by the following formula (III) is used:

3. Curing agent: Examples 1 and 3 used benzoic acid benzoquinone (purchased from Alchemy Co., Ltd., hereinafter referred to as "BPO"); Example 2 used cumene hydroperoxide (purchased from Alima Co., Ltd.) , hereinafter referred to as "Cumene hydroperoxide"); and Example 4 using an anthrone resin (available from Dow Corning Corporation under the trade name Sylgard 184, hereinafter referred to as "184").

4. Dilution solvent: Examples 1 to 3 used a mixture of n-butyl acetate (purchased from China National Petroleum Corporation) and toluene (purchased from China National Petroleum Corporation).

5. Functional additives:

(1) Reagents for increasing adhesion strength: 2-hydroxyethyl methacrylate phosphate (purchased from Double Bond Chemical Co., Ltd., DM-9166, hereinafter referred to as "DM-9166") and 3-methacryl oxime Oxypropyl trimethoxy decane ("MEMO", available from Degussa).

(2) Defoamer: Deform 5300 sold by Hemings Deqian Company, hereinafter referred to as "Deform 5300".

(3) Leveling agent: L-066 sold by Qinglin Trading Company, hereinafter referred to as "L-066".

[Examples 1 to 4] Coating compositions for heat transfer printing

The materials were weighed according to the chemicals and weight ratios in Table 1 below, and mixed at room temperature to obtain the coating compositions for heat transfer of Examples 1 to 4, respectively.

a. Calculated based on the total weight of the double bond-containing resin, the reactive ultraviolet absorber, and the curing agent of 100 wt%.

b. Calculated based on 100 parts by weight of the total weight of the double bond-containing resin, the reactive ultraviolet absorber, and the curing agent.

[Comparative Examples 1 to 3] Coating compositions in which no reactive ultraviolet absorber was added

The composition and ratio of the coating compositions of Comparative Examples 1 to 3 were the same as those of Examples 1 to 3, except that the reactive ultraviolet absorber was not added.

[Comparative Example 4]

The composition and ratio of the coating composition of Comparative Example 4 were substantially the same as those of Example 4, except that Comparative Example 4 used a non-reactive ultraviolet absorber. The coating composition of Comparative Example 4 was 75 wt% of DM-541, 10 wt% of DM-127-TP20, and 10 wt% of a non-reactive ultraviolet absorber (purchased from Double Bond Chemical Co., Ltd., under the name UV). -33) and 5 wt% of an anthrone resin curing agent (available from Dow Corning Corporation under the trade name Sylgard 184, hereinafter referred to as "184") were mixed at room temperature.

[Weathering test]

1. Sample production:

The coating composition for heat transfer and the coating compositions of Comparative Examples 1 to 3 prepared in Examples 1 to 3 were each subjected to test piece production according to the following procedures to obtain Examples 1 to 3 and Comparative Examples 1 to 3. The test piece: the coating composition is sprayed on a ceramic substrate, and then placed in a hot air oven (temperature 125 ° C), after 15 minutes, a cured coating film is formed on the ceramic substrate, the thickness is about 25-30 Mm.

The thermal sublimation dye ink (purchased from Furuide, the product name: disperse ink disperse series) was transferred to the surface of the cured coating film by a thermal transfer method (heating temperature: 215 ° C, transfer time: 210 seconds). A pattern layer is formed on the surface of the cured coating film, and a test piece (including the pattern layer, the cured coating film, and the ceramic substrate in this order) is obtained.

2. Weathering test:

The test pieces of Examples 1 to 3 and Comparative Examples 1 to 3 were placed in a QUV weathering test machine for artificial weathering test. The setting parameters of the QUV weathering test machine are as follows: lamp form QUV 313 nm; temperature 45 ° C; test time total 2500 hours, test and record the color change index (BRK meter) every 250 hours △ E). The results of the weathering test are recorded in Table 2 below.

[result]

From the results of Table 2, it was found that the color change indexes of the test pieces of Examples 1 to 3 were much lower than those of Comparative Examples 1 to 3, respectively, after the weathering test for 1500 hours, and it was confirmed that the test piece for the heat transfer of the present invention was used. The coating film formed by curing the coating composition does have excellent weather resistance.

[migration test]

1.25 g of the coating composition of Example 4 was taken and coated on a polyethylene terephthalate (PET) film with a wire bar to form a coating film on the PET film. Then, the coating film was irradiated with ultraviolet light and solidified to obtain a test sample. The test sample was immersed in an alcohol soaking solution, and after soaking for 24 hours and 72 hours, the infusion solution was taken out, and the dissolution concentration of the ultraviolet absorbent was measured by high performance liquid chromatography (HPLC), and the results were recorded in the following table. 3 in.

The coating composition of Comparative Example 4 was similarly repeated for the above-described procedure for the migration test, and the results are reported in Table 3 below.

Evaluation method: If the UV absorber is completely dissolved, the concentration of the UV absorber in the soaking solution is measured to be 2500 ppm; the dissolution rate is calculated using the above-mentioned measured concentration, the total dissolution concentration of 2500 ppm, and the following formula:

[result]

As is clear from the results in Table 3, the dissolution rate of Example 4 was 18% and 21%, and that of Comparative Example 4 was 74% and 78%, demonstrating that the reactive ultraviolet absorber used in the coating composition of Example 4 was long. Under the time of use, it is still not easy to change the movement, and the film has ultraviolet protection effect.

In summary, the coating composition for heat transfer printing of the present invention transmits a reactive ultraviolet absorber having a double bond structure at the end, in addition to allowing the ultraviolet absorber to be less likely to migrate, and at the same time allowing the amount of the ultraviolet absorber to be added. The addition, as well as the coating formed by the subsequent curing of the coating composition, has a good UV protection effect.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

Claims (4)

A coating composition for heat transfer printing comprising: a resin containing a double bond; and a reactive ultraviolet absorber having a structure represented by the following formula (I) or (II): Wherein R ¹ and R ² represent respectively , A curing agent. The coating composition for heat transfer according to claim 1, wherein the double bond-containing resin is selected from the group consisting of polyurethane diacrylate, bisphenol A epoxy acrylate, and double bond-containing A chlorinated polyester resin, an acrylic oligomer or a combination of these. The coating composition for heat transfer according to claim 1, wherein the amount of the reactive ultraviolet absorber is calculated based on a total weight of the coating composition for the heat transfer transfer of 100 wt%. The range is 1~14 wt%. A coating film for heat transfer printing, which is formed by curing a coating composition for heat transfer printing according to any one of claims 1 to 3.