A pyrograph transfer film and a method for manufacturing the same

Abstract

The application discloses a kind of iron picture transfer film and preparation method thereof, belong to transfer film technical field, including PET release film, printing protective layer, printing layer and modified adhesive layer;The printing protective layer is formed by printing protective agent, and printing protective agent is formed by component A and component B according to mass ratio 105~223:100, A component includes: hyaluronic acid, dopamine hydrochloride, nano organic zirconium;B component includes: ionic liquid, anti-aging agent;The modified adhesive layer is formed by modified adhesive, and modified adhesive is prepared by mixing butadiene-styrene latex, starch-based microgel microspheres, ultraviolet absorber according to mass ratio 80~100:8~15:1~3.It is high between the printing protective layer and printing layer Adhesion, the iron picture transfer film prepared has the advantages that adhesion is strong, resistant to scratch, resistant to moisture, resistant to high temperature and, weather resistance is good, printing layer is not prone to aging, fading, deformation, blistering, wrinkling and other problems, guarantee the transfer decoration effect of iron picture transfer film.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of transfer film, in particular to a pyrography transfer film and a preparation method thereof. BACKGROUND

[0002] The pyrography transfer film is a material for pyrography of patterns, characters and the like on the surface of fabrics, plastics and the like. It is generally composed of a base layer, a release layer, a printing layer and an adhesive layer.

[0003] For example, the invention patent CN111016488A discloses a transfer film for the surface of fitness equipment and a preparation method thereof. The transfer film is composed of a base layer, a polyvinyl alcohol adhesive layer, a release layer, an ink absorption layer, a printing layer and an adhesive layer from bottom to top. The cured transfer film has the advantages of good scratch resistance, good moisture resistance and no cracks on the surface.

[0004] However, due to its six-layer structure, the number of layers is relatively large. Since each additional layer of structure increases the coating, drying, curing and other process steps of one coating layer, the production efficiency is reduced. At the same time, the ink absorption layer is prepared by using hollow plastic pigments and nano-sized silicon dioxide. The adhesion between the ink absorption layer and the printing layer is low, and the weather resistance needs to be further improved. The printing layer may have problems such as aging, discoloration and deformation, which reduces the transfer decoration effect.

[0005] Based on this, the present application designs a pyrography transfer film and a preparation method thereof to solve the above problems. SUMMARY

[0006] In view of the above-mentioned shortcomings of the prior art, the present application provides a pyrography transfer film and a preparation method thereof.

[0007] To achieve the above purpose, the present application is realized by the following technical scheme:

[0008] A pyrography transfer film, comprising a PET release film, a printing protection layer, a printing layer and a modified adhesive layer; the printing protection layer is formed by a printing protection agent, and the printing protection agent is composed of component A and component B in a mass ratio of 105-223:100, the A component comprising: hyaluronic acid, dopamine hydrochloride and nano organic zirconium; the B component comprising: ionic liquid and anti-aging agent; the modified adhesive layer is formed by a modified adhesive, and the modified adhesive is prepared by mixing butadiene-styrene latex, starch-based microgel microspheres and ultraviolet absorber in a mass ratio of 80-100:8-15:1-3.

[0009] Further, the PET release film comprises a PET base layer and a release layer coated on the PET base layer.

[0010] Further, the anti-aging agent is an antioxidant, which can be antioxidant 1010 or antioxidant 246.

[0011] Further, the nano-organic zirconium is tetra-n-propyl zirconate.

[0012] Further, the ionic liquid is 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide or N-ethylimidazolium bis(trifluoromethylsulfonyl) imide.

[0013] Further, in the A component, the mass ratio of hyaluronic acid, dopamine hydrochloride and nano-organic zirconium is 3.1-5.4: 1.5-2.2: 5.7-6.6.

[0014] Further, in the B component, the mass ratio of ionic liquid and anti-aging agent is 8.2-10.4: 1.3-2.2.

[0015] Further, the preparation method of the printing protection agent is:

[0016] Step (1): mixing the ionic liquid and the anti-aging agent to obtain the B component;

[0017] Step (2): adding the hyaluronic acid into the deionized water to prepare a 0.5-1.3%wt hyaluronic acid aqueous solution, then slowly adding the nano-organic zirconium into the hyaluronic acid aqueous solution, the dropping speed is controlled at 20-40 drops / min, stirring while dropping, finally adjusting the pH of the solution to 5.5-6.5 with hydrochloric acid solution; adding the dopamine hydrochloride into the mixed solution obtained in the previous step, and darkly reacting for 5-10h under the condition of nitrogen protection to obtain the A component;

[0018] Step (3): mixing the A component and the B component, and irradiating the solution with γ-rays, the radiation dose rate is controlled at 20-40 Gy / h to obtain the printing protection agent.

[0019] Further, the preparation method of the starch-based microgel microspheres is: adding 8-10 parts of starch into deionized water to obtain a starch dispersion liquid; adding 120-150 parts of liquid paraffin as an oil phase into a reaction container, adding 5-8 parts of Span-80 emulsifier into the oil phase, stirring uniformly to make the emulsifier fully dissolved in the oil phase, slowly adding the prepared starch dispersion liquid into the oil phase containing the emulsifier, and stirring at the same time to form a stable emulsion; adding 10-15%wt of sodium hydroxide solution into the emulsion to adjust the pH to 9.5-10.5; then slowly adding 3-5 parts of epoxy chloropropane crosslinking agent, continuing to stir at 40-60℃ for 2-3h after the addition is completed; then separating and washing the starch-based microgel microspheres for multiple times.

[0020] In order to better achieve the purpose of the present application, the present application also provides a preparation method of the iron-on picture transfer film, comprising the following steps: coating a printing protective agent on a PET release film, drying to form a printing protective layer; printing an ink of the printing layer on the printing protective layer by a printing machine, and drying to form a printing layer; and coating a modified adhesive on the printing layer, and drying to form a modified adhesive layer; the thickness of the PET release film is 20-25 microns; and the thickness of the printing protective layer is 0.3-0.7 microns.

[0021] Compared with the prior art, the present application has the following beneficial effects: 1. The iron-on picture transfer film of the present application only adds a printing protective layer on the basis of a four-layer basic structure, and the preparation process is simpler than that of a six-layer structure transfer film, which is beneficial to improving the production efficiency.

[0022] 2. The adhesion between the printing protective layer and the printing layer of the present application is high, and the prepared iron-on picture transfer film has the advantages of strong adhesion, scratch resistance, moisture resistance, high temperature resistance, and good weather resistance, and the printing layer is not prone to aging, fading, deformation, blistering, wrinkling and other problems, which ensures the transfer decoration effect of the iron-on picture transfer film. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0024] Embodiment 1: In some embodiments, the preparation method of the iron-on picture transfer film comprises the following steps:

[0025] Step 1: Raw material preparation:

[0026] The PET release film comprises a PET base layer and a release layer coated on the PET base layer; the release layer is formed by a silicone release agent; preferably, a silicone release agent containing no solvent silicone oil is used.

[0027] Printing protective agent: 8.2 parts of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide salt was mixed with 1.3 parts of antioxidant 1010 to obtain component B; 3.1 parts of hyaluronic acid was added to deionized water to prepare a 0.5%wt hyaluronic acid aqueous solution, then 5.7 parts of tetra-n-propyl zirconate was slowly added dropwise to the hyaluronic acid aqueous solution, the dropwise speed was controlled at 20 drops / min, and stirring was carried out during the dropwise addition; finally, the pH of the solution was adjusted to 5.5 with a hydrochloric acid solution to obtain a mixed solution; 1.5 parts of dopamine hydrochloride was added to the mixed solution, and the solution was dark reacted for 5h under the condition of nitrogen protection to obtain component A; components A and B were mixed in a mass ratio of 105:100, and the solution was irradiated with γ-rays, and the radiation dose rate was controlled at 20 Gy / h to obtain the printing protective agent.

[0028] Modified adhesive: 8 parts of starch was added to deionized water to obtain a starch dispersion; 120 parts of liquid paraffin was added to a reaction container as an oil phase, 5 parts of Span-80 emulsifier was added to the oil phase, and stirring was carried out to dissolve the emulsifier in the oil phase, the prepared starch dispersion was slowly added to the oil phase containing the emulsifier, and stirring (500 r / min) was carried out at the same time to form a stable oil-in-water (O / W) emulsion; 10%wt sodium hydroxide solution was added to the emulsion to adjust the pH to 9.5; then 3 parts of epoxy chloropropane crosslinking agent was slowly added, and the reaction was continued to stir at 40℃ for 2h; then the starch-based microgel microspheres were separated and washed multiple times. The butadiene-styrene latex, starch-based microgel microspheres, and ultraviolet absorber were mixed in a mass ratio of 80:8:1 to obtain the modified adhesive.

[0029] Printing layer ink: color thermal transfer ink;

[0030] Step 2: The printing protective agent was coated on the PET release film, and after drying, a printing protective layer was formed; then the printing layer ink was printed on the printing protective layer by a printing machine, and after drying, a printing layer was formed; finally, the modified adhesive was coated on the printing layer, and after drying, a modified adhesive layer was formed; the thickness of the PET release film was 20μm; the thickness of the printing protective layer was 0.3μm.

[0031] Example 2: In some embodiments, the preparation method of the iron-on transfer film, the steps are as follows:

[0032] Step 1: Raw material preparation:

[0033] PET release film: including a PET base layer and a release layer coated on the PET base layer; the release layer is formed by a silicone release agent; preferably, a silicone release agent containing no solvent silicone oil is used.

[0034] Printing protective agent: 10.4 parts of N-ethyl imidazole bis(trifluoromethyl sulfone) imide salt was mixed with 2.2 parts of antioxidant 246 to obtain component B; 5.4 parts of hyaluronic acid was added to deionized water to prepare a 1.3%wt hyaluronic acid aqueous solution, then 6.6 parts of tetra-n-propyl zirconate was slowly added dropwise to the hyaluronic acid aqueous solution, the dropwise speed was controlled at 40 drops / min, and stirring was carried out during the dropwise addition; finally, the pH of the solution was adjusted to 6.5 with a hydrochloric acid solution to obtain a mixed solution; 2.2 parts of dopamine hydrochloride was added to the mixed solution, and dark reaction was carried out under the condition of nitrogen protection for 10h to obtain component A; component A and component B were mixed in a mass ratio of 223:100, and the solution was irradiated with γ-rays, and the irradiation dose rate was controlled at 40 Gy / h to obtain the printing protective agent.

[0035] Modified adhesive: 10 parts of starch was added to deionized water to obtain a starch dispersion; 150 parts of liquid paraffin was added to a reaction container as an oil phase, 8 parts of Span-80 emulsifier was added to the oil phase, and stirring was carried out until the emulsifier was fully dissolved in the oil phase, the prepared starch dispersion was slowly added to the oil phase containing the emulsifier, and stirring was carried out (800 r / min) at the same time to form a stable oil-in-water (O / W) emulsion; 15%wt sodium hydroxide solution was added to the emulsion to adjust the pH to 10.5; then 5 parts of epoxy chloropropane crosslinking agent was slowly added dropwise, and the reaction was continued at 60°C for 3h after the addition was completed; then the starch-based microgel microspheres were separated and washed multiple times. The butadiene-styrene latex, starch-based microgel microspheres, and ultraviolet absorber were mixed in a mass ratio of 100:15:3 to obtain the modified adhesive.

[0036] Printing layer ink: color thermal transfer ink;

[0037] Step 2: The printing protective agent was coated on the PET release film, and after drying, a printing protective layer was formed; then the printing layer ink was printed on the printing protective layer by a printing machine, and after drying, a printing layer was formed; finally, the modified adhesive was coated on the printing layer, and after drying, a modified adhesive layer was formed; the thickness of the PET release film was 25μm; the thickness of the printing protective layer was 0.7μm.

[0038] Example 3: In some embodiments, the preparation method of the iron-on transfer film, the steps are as follows:

[0039] Step 1: Raw material preparation:

[0040] PET release film: including a PET base layer and a release layer coated on the PET base layer; the release layer is formed by a silicone release agent; preferably, a silicone release agent containing no solvent silicone oil is used.

[0041] Printing protective agent: 9 parts of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide salt was mixed with 2 parts of antioxidant 246 to obtain component B; 4 parts of hyaluronic acid was added to deionized water to prepare a 1%wt hyaluronic acid aqueous solution, then 6 parts of tetra-n-propyl zirconate was slowly added dropwise to the hyaluronic acid aqueous solution, the dropwise speed was controlled at 30 drops / min, and the solution was stirred during the dropwise addition; finally, the pH of the solution was adjusted to 6 with a hydrochloric acid solution to obtain a mixed solution; 2 parts of dopamine hydrochloride was added to the mixed solution, and the solution was dark reacted for 7 h under the protection of nitrogen to obtain component A; components A and B were mixed in a mass ratio of 150:100, and the solution was irradiated with γ-rays, and the radiation dose rate was controlled at 30 Gy / h to obtain the printing protective agent.

[0042] Modified adhesive: 9 parts of starch was added to deionized water to obtain a starch dispersion; 130 parts of liquid paraffin was added to a reaction container as an oil phase, 6 parts of Span-80 emulsifier was added to the oil phase, and the emulsifier was fully dissolved in the oil phase after stirring uniformly, the prepared starch dispersion was slowly added to the oil phase containing the emulsifier while stirring (700 r / min) to form a stable oil-in-water (O / W) emulsion; 12%wt sodium hydroxide solution was added to the emulsion to adjust the pH to 10; then 4 parts of epoxy chloropropane crosslinking agent was slowly added, and the reaction was continued at 50°C for 2.5 h after the addition was completed; then the starch-based microgel microspheres were separated and washed repeatedly. The butadiene-styrene latex, starch-based microgel microspheres, and ultraviolet absorber were mixed in a mass ratio of 90:11:2 to obtain the modified adhesive.

[0043] Printing layer ink: color thermal transfer ink;

[0044] Step 2: The printing protective agent was coated on the PET release film, and after drying, a printing protective layer was formed; then the printing layer ink was printed on the printing protective layer by a printing machine, and after drying, a printing layer was formed; finally, the modified adhesive was coated on the printing layer, and after drying, a modified adhesive layer was formed; the thickness of the PET release film was 22 μm; the thickness of the printing protective layer was 0.4 μm.

[0045] Comparative Example 1: Different from Example 3, no printing protective layer was contained.

[0046] Comparative Example 2: Different from Example 3, no γ-rays were used to irradiate the solution during the preparation process of the printing protective layer.

[0047] The preparation method of the printing protective agent is as follows: 9 parts of 1-ethyl-3-methyl imidazole bis(trifluoromethyl sulfonate) imidate salt is mixed with 2 parts of antioxidant 246 to obtain component B; 4 parts of hyaluronic acid is added to deionized water to prepare a 1 wt% hyaluronic acid aqueous solution, then 6 parts of tetra-n-propyl zirconate is slowly added dropwise to the hyaluronic acid aqueous solution, the dropwise speed is controlled at 30 drops / min, and stirring is performed during dropwise addition; finally, hydrochloric acid solution is used to adjust the pH of the solution to 6 to obtain a mixed solution; 2 parts of dopamine hydrochloride is added to the mixed solution, and dark reaction is performed under nitrogen protection conditions for 7 h to obtain component A; component A and component B are mixed according to a mass ratio of 150:100 to obtain the printing protective agent.

[0048] Experimental example: after the transfer printing films prepared from example 1 to example 3 and comparative example 1 to comparative example 2 are transferred to plastic parts and completely cured, the adhesion, scratch resistance, moisture resistance, high temperature resistance and weather resistance tests are carried out, and the results are shown in table 1.

[0049] Adhesion test: GB / T 9286-2021.

[0050] Scratch resistance test: ASTM D4060, 500g load, 1200 cycles. There are four grades of excellent, good, general and poor.

[0051] Moisture resistance test: the plastic part is placed in a 38℃x100%RH environment for 144h, and the appearance change is observed.

[0052] High temperature resistance test: the plastic part is placed in a 95℃ environment for 168h, and the appearance change is observed.

[0053] Weather resistance test: ISO 105-B06, using a xenon lamp accelerated aging oven, the total irradiation amount is 1240.8KJ / m 2 .

[0054] Table 1 performance test results

[0055] Item adhesion resistance to scratching resistance to moisture resistance to high temperature resistance to weather Example 1 0 level excellent no change no change no change Example 2 0 level excellent no change no change no change Example 3 0 level excellent no change no change no change Comparative Example 1 1 level poor wrinkling, discoloration blistering, discoloration fading, deformation Comparative Example 2 0 level general wrinkling blistering deformation

[0056] The transfer printing film of the present application is based on a four-layer basic structure, only one printing protective layer is added, compared with the six-layer structure transfer printing film, the preparation process is simpler, which is conducive to improving the production efficiency.

[0057] The adhesion between the printing protective layer and the printing layer of the present application is high, the prepared transfer printing film has the advantages of strong adhesion, scratch resistance, moisture resistance, high temperature resistance and good weather resistance, and the printing layer is not prone to aging, fading, deformation, blistering, wrinkling and other problems, which ensures the transfer decoration effect of the transfer printing film.

[0058] The above examples are only used to illustrate the technical solutions of the present application, and are not intended to limit the present application; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can be modified, or some technical features can be replaced by equivalent features; and these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A heat transfer film, characterized in that, The product includes a PET release film, a printed protective layer, a printed layer, and a modified adhesive layer. The printed protective layer is formed by a printing protective agent, which is prepared by mixing component A and component B in a mass ratio of 105–223:100 and simultaneously irradiating the solution with gamma rays. Component A includes hyaluronic acid, dopamine hydrochloride, and nano-organic zirconium; component B includes ionic liquid and anti-aging agent. The modified adhesive layer is formed by a modified adhesive, which is prepared by mixing styrene-butadiene latex, starch-based microgel microspheres, and ultraviolet absorbers in a mass ratio of 80-100:8-15:1-3.

2. The heat transfer film according to claim 1, characterized in that, PET release film consists of a PET base layer and a release layer coated on the PET base layer.

3. The heat transfer film according to claim 1, characterized in that, The anti-aging agent is an antioxidant, selected from antioxidant 1010 or antioxidant 246.

4. The heat transfer film according to claim 1, characterized in that, The nano-organic zirconium is tetra-n-propyl zirconate.

5. The heat transfer film according to claim 1, characterized in that, The ionic liquid is 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt or N-ethylimidazolium bis(trifluoromethanesulfonyl)imide salt.

6. The heat transfer film according to claim 1, characterized in that, In component A, the mass ratio of hyaluronic acid, dopamine hydrochloride, and nano-organic zirconium is 3.1–5.4: 1.5–2.2: 5.7–6.

6.

7. The heat transfer film according to claim 1, characterized in that, In component B, the mass ratio of ionic liquid to anti-aging agent is 8.2–10.4:1.3–2.

2.

8. The heat transfer film according to claim 1, characterized in that, The preparation method of the printing protectant is as follows: Step (1): Mix the ionic liquid with the anti-aging agent to obtain component B; Step (2): Hyaluronic acid is added to deionized water to prepare a 0.5-1.3 wt% hyaluronic acid aqueous solution. Then, nano-organic zirconium is slowly added dropwise to the hyaluronic acid aqueous solution at a rate of 20-40 drops / min while stirring. Finally, the pH of the solution is adjusted to 5.5-6.5 with hydrochloric acid solution. Dopamine hydrochloride is added to the mixed solution obtained in the previous step and reacted in the dark for 5-10 hours under nitrogen protection to obtain component A. Step (3): Mix component A with component B, and simultaneously irradiate the solution with γ rays, controlling the radiation dose rate at 20-40 Gy / h to obtain the printing protectant.

9. The heat transfer film according to claim 1, characterized in that, The method for preparing starch-based microgel microspheres is as follows: 8-10 parts of starch are added to deionized water to obtain a starch dispersion; 120-150 parts of liquid paraffin are added to a reaction vessel as the oil phase, and 5-8 parts of Span-80 emulsifier are added to the oil phase. The mixture is stirred until the emulsifier is fully dissolved in the oil phase. The prepared starch dispersion is slowly added dropwise to the oil phase containing the emulsifier while stirring to form a stable emulsion; 10-15 wt% sodium hydroxide solution is added to the emulsion to adjust the pH to 9.5-10.5; then 3-5 parts of epichlorohydrin crosslinking agent are slowly added dropwise. After the addition is complete, the mixture is stirred and reacted at 40-60℃ for 2-3 hours; the starch-based microgel microspheres are then separated and washed multiple times.

10. A method for preparing a heat transfer film according to any one of claims 1 to 9, characterized in that, The steps are as follows: a printing protectant is applied to a PET release film and dried to form a printing protectant layer; then, printing ink is applied to the printing protectant layer using a printing press and dried to form a printing layer; finally, a modified adhesive is applied to the printing layer and dried to form a modified adhesive layer; the thickness of the PET release film is 20–25 μm; and the thickness of the printing protectant layer is 0.3–0.7 μm.