High-haze petg matt transfer film and preparation method thereof

Abstract

The application provides a high-haze PETG matt transfer film and a preparation method thereof, and relates to the technical field of matt transfer film preparation. The high-haze PETG matt transfer film comprises an upper surface layer, a core layer and a lower surface layer. The upper surface layer comprises the following raw materials in parts by mass: 40-60 parts of PETG, 1-3 parts of an antioxidant and 0.5-2 parts of an antistatic agent. The core layer comprises the following raw materials in parts by mass: 60-90 parts of PETG, 5-12 parts of a matt agent, 0.5-2 parts of a nucleating agent and 0.1-1 parts of an antioxidant. The lower surface layer comprises the following raw materials in parts by mass: 40-60 parts of PETG and 1-5 parts of an opening agent. The PETG matt transfer film prepared by the application has high haze.

Description

Technical Field

[0001] This invention relates to the field of matting transfer film preparation technology, and in particular to a high-haze PETG matting transfer film and its preparation method. Background Technology

[0002] PETG is a transparent, non-crystalline copolyester. The commonly used comonomer for PETG is 1,4-cyclohexanediethanol (CHDM), also known as polyethylene terephthalate-1,4-cyclohexanediethanol ester. It is a product of transesterification polymerization of terephthalic acid (PTA), ethylene glycol (EG), and 1,4-cyclohexanediethanol (CHDM). With the increasing market demand for haze reduction in PETG matting transfer films, the current market offerings cannot meet this requirement. Therefore, the development of a new PETG matting transfer film is urgently needed, which is of great significance for its widespread application. Summary of the Invention

[0003] Based on the technical problems existing in the background technology, the present invention proposes a high haze PETG matting transfer film and its preparation method.

[0004] The present invention proposes a high-haze PETG matting transfer film, comprising an upper surface layer, a core layer, and a lower surface layer.

[0005] The upper surface layer comprises the following raw materials in parts by weight: 40-60 parts PETG, 1-3 parts antioxidant, and 0.5-2 parts antistatic agent.

[0006] The core layer comprises the following raw materials in parts by weight: 60-90 parts PETG, 5-12 parts matting agent, 0.5-2 parts nucleating agent, and 0.1-1 parts antioxidant.

[0007] Preferably, the method for preparing the matting agent includes the following steps:

[0008] Pretreated silica is obtained by immersing it in a titanium tetrachloride solution and drying it. Tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water are mixed evenly to obtain a mixed solution. Pretreated silica is added to the mixed solution and mixed evenly. The mixture is then calcined in stages to obtain a mixed material. The mixed material is then mixed evenly with a silane coupling agent and dried to obtain a matting agent.

[0009] More preferably, the concentration of the titanium tetrachloride solution is 0.05-2M.

[0010] More preferably, the mass ratio of the silicon dioxide to the titanium tetrachloride solution is 1:(1-2).

[0011] More preferably, the drying temperature is 80-105°C.

[0012] More preferably, the mass ratio of tetrabutyl titanate, tetrahydrofuran, hydrochloric acid and water is (0.5-1):(2-5):(10-20):(10-20).

[0013] More preferably, the mass ratio of the mixed solution to the pretreated silica is 10:(0.5-3).

[0014] More preferably, the silicon dioxide is nano-silica with a particle size of 5-80 nm.

[0015] More preferably, the segmented calcination includes: reacting at temperature T1 for 1-2 hours, then heating to temperature T2 for 4-8 hours, and reacting the mixture at temperature T3 under an inert atmosphere for 6-12 hours.

[0016] More preferably, the T1 temperature is 30-50℃; the T2 temperature is 70-100℃; and the T3 temperature is 150-200℃.

[0017] More preferably, the silane coupling agent is KH550.

[0018] The lower surface layer comprises the following raw materials in parts by weight: 40-60 parts PETG and 1-5 parts opening agent.

[0019] Preferably, the opening agent is selected from one or more of silica, calcium carbonate, and artificial talc.

[0020] The present invention also proposes a method for preparing a high-haze PETG matting transfer film, comprising the following steps: mixing the raw materials of the upper surface layer, core layer and lower surface layer evenly and extruding them to obtain a melt; and subjecting the melt to composite, casting, longitudinal stretching, transverse stretching, winding and slitting to obtain a high-haze PETG matting transfer film.

[0021] Preferably, the preheating temperature during the transverse stretching is 75-85℃, the stretching temperature is 80-90℃, the setting temperature is 80-90℃, and the cooling temperature is 10-50℃.

[0022] Preferably, the stretching ratio of the horizontal stretch is 4-5, and the stretching angle is 3.5-4.5°.

[0023] The beneficial effects of this invention are as follows:

[0024] This invention provides a high-haze PETG matting transfer film comprising an upper surface layer, a core layer, and a lower surface layer. The invention adds a matting agent to the core layer, which helps to improve the haze of the PETG matting transfer film. The matting agent is compatible with PETG, resulting in uniform haze in the PETG matting transfer film prepared by this invention. This invention also provides a method for preparing high-haze PETG matting transfer film, which improves the haze of the PETG matting transfer film by reasonably adjusting the parameters of the transverse stretching process. Detailed Implementation

[0025] The technical solution of the present invention will be described in detail through specific embodiments.

[0026] Unless otherwise specified, all materials and reagents used in the following examples and comparative examples are commercially available.

[0027] Example 1

[0028] A high-haze PETG matting transfer film includes an upper surface layer, a core layer, and a lower surface layer. The upper surface layer comprises the following raw materials in parts by weight: 55 parts PETG, 1 part antioxidant, and 1 part antistatic agent. The core layer comprises the following raw materials in parts by weight: 85 parts PETG, 8 parts matting agent, 1 part nucleating agent, and 0.4 parts antioxidant. The lower surface layer comprises the following raw materials in parts by weight: 50 parts PETG and 2 parts synthetic talc.

[0029] The preparation method of the matting agent includes the following steps: immersing silica in a 0.1M titanium tetrachloride solution and drying at 85℃ to obtain pretreated silica; mixing tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water uniformly to obtain a mixed solution; adding the pretreated silica to the mixed solution and mixing uniformly, then performing segmented calcination to obtain a mixture; mixing the mixture uniformly with 1wt% silane coupling agent KH550 and drying to obtain the matting agent; wherein the mass ratio of silica to titanium tetrachloride solution is 1:2; the mass ratio of tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water is 0.5:2:15:15; the mass ratio of the mixed solution to pretreated silica is 10:2; the silica particle size is 30nm; the segmented calcination includes: reacting at 40℃ for 2h, then raising the temperature to 80℃ for 6h, and reacting the mixture at 180℃ for 10h under an argon atmosphere.

[0030] A method for preparing a high-haze PETG matte transfer film includes the following steps: mixing the raw materials of the upper surface layer, core layer, and lower surface layer evenly and extruding them to obtain a melt; subjecting the melt to composite, casting, longitudinal stretching, transverse stretching, winding, and slitting to obtain a high-haze PETG matte transfer film; wherein the preheating temperature during transverse stretching is 75℃, the stretching temperature is 80℃, the setting temperature is 80℃, and the cooling temperature is 30℃; the stretching ratio during transverse stretching is 5, the stretching angle is 4.5°, and the production speed of the matte transfer film is 75m / min.

[0031] Example 2

[0032] A high-haze PETG matting transfer film includes an upper surface layer, a core layer, and a lower surface layer. The upper surface layer comprises the following raw materials in parts by weight: 45 parts PETG, 1 part antioxidant, and 0.5 parts antistatic agent. The core layer comprises the following raw materials in parts by weight: 70 parts PETG, 6 parts matting agent, 1 part nucleating agent, and 0.5 parts antioxidant. The lower surface layer comprises the following raw materials in parts by weight: 50 parts PETG and 2 parts synthetic talc.

[0033] The preparation method of the matting agent includes the following steps: immersing silica in a 0.15M titanium tetrachloride solution and drying at 90℃ to obtain pretreated silica; mixing tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water uniformly to obtain a mixed solution; adding the pretreated silica to the mixed solution and mixing uniformly, then performing segmented calcination to obtain a mixture; mixing the mixture uniformly with 1wt% silane coupling agent KH550 and drying to obtain the matting agent; wherein the mass ratio of silica to titanium tetrachloride solution is 1:2; the mass ratio of tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water is 0.5:2:15:15; the mass ratio of the mixed solution to pretreated silica is 10:1.5; the silica particle size is 30nm; the segmented calcination includes: reacting at 50℃ for 1 hour, then raising the temperature to 90℃ and reacting for 5 hours; and reacting the mixture at 160℃ for 12 hours under an argon atmosphere.

[0034] A method for preparing a high-haze PETG matting transfer film includes the following steps: mixing the raw materials of the upper surface layer, core layer, and lower surface layer evenly and extruding them to obtain a melt; subjecting the melt to composite, casting, longitudinal stretching, transverse stretching, winding, and slitting to obtain a high-haze PETG matting transfer film; wherein the preheating temperature during transverse stretching is 80℃, the stretching temperature is 85℃, the setting temperature is 85℃, and the cooling temperature is 30℃; the stretching ratio during transverse stretching is 5, the stretching angle is 4.5°, and the production speed of the matting transfer film is 75m / min.

[0035] Example 3

[0036] A high-haze PETG matting transfer film includes an upper surface layer, a core layer, and a lower surface layer. The upper surface layer comprises the following raw materials in parts by weight: 60 parts PETG, 1 part antioxidant, and 1 part antistatic agent. The core layer comprises the following raw materials in parts by weight: 88 parts PETG, 9 parts matting agent, 1 part nucleating agent, and 0.6 parts antioxidant. The lower surface layer comprises the following raw materials in parts by weight: 50 parts PETG and 2 parts synthetic talc.

[0037] The preparation method of the matting agent includes the following steps: immersing silica in a 0.2M titanium tetrachloride solution and drying at 85℃ to obtain pretreated silica; mixing tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water uniformly to obtain a mixed solution; adding the pretreated silica to the mixed solution and mixing uniformly, then performing segmented calcination to obtain a mixture; mixing the mixture uniformly with 1wt% silane coupling agent KH550 and drying to obtain the matting agent; wherein the mass ratio of silica to titanium tetrachloride solution is 1:2; the mass ratio of tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water is 0.5:2:15:15; the mass ratio of the mixed solution to pretreated silica is 10:2; the silica particle size is 30nm; the segmented calcination includes: reacting at 40℃ for 2h, then raising the temperature to 80℃ for 8h, and reacting the mixture at 160℃ for 10h under an argon atmosphere.

[0038] A method for preparing a high-haze PETG matting transfer film includes the following steps: mixing the raw materials of the upper surface layer, core layer, and lower surface layer evenly and extruding them to obtain a melt; subjecting the melt to composite, casting, longitudinal stretching, transverse stretching, winding, and slitting to obtain a high-haze PETG matting transfer film; wherein the preheating temperature during transverse stretching is 80℃, the stretching temperature is 85℃, the setting temperature is 85℃, and the cooling temperature is 30℃; the stretching ratio during transverse stretching is 5, the stretching angle is 3.5°, and the production speed of the matting transfer film is 80m / min.

[0039] Comparative Example 1

[0040] A PETG matting transfer film includes an upper surface layer, a core layer, and a lower surface layer. The upper surface layer comprises the following raw materials in parts by weight: 60 parts PETG, 1 part antioxidant, and 1 part antistatic agent. The core layer comprises the following raw materials in parts by weight: 88 parts PETG, 9 parts matting agent, 1 part nucleating agent, and 0.6 parts antioxidant. The lower surface layer comprises the following raw materials in parts by weight: 50 parts PETG and 2 parts synthetic talc.

[0041] The preparation method of the matting agent includes the following steps: immersing silica in a 0.2M titanium tetrachloride solution and drying at 85℃ to obtain pretreated silica; mixing tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water uniformly to obtain a mixed solution; adding the pretreated silica to the mixed solution and mixing uniformly, then performing segmented calcination to obtain a mixture; mixing the mixture uniformly with 1wt% silane coupling agent KH550 and drying to obtain the matting agent; wherein the mass ratio of silica to titanium tetrachloride solution is 1:2; the mass ratio of tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water is 0.5:2:15:15; the mass ratio of the mixed solution to pretreated silica is 10:2; the silica particle size is 30nm; the segmented calcination includes: reacting at 40℃ for 2h, then raising the temperature to 80℃ for 8h, and reacting the mixture at 160℃ for 10h under an argon atmosphere.

[0042] A method for preparing a PETG matte transfer film includes the following steps: mixing the raw materials of the upper surface layer, core layer, and lower surface layer evenly and extruding them to obtain a melt; subjecting the melt to composite, casting, longitudinal stretching, transverse stretching, winding, and slitting to obtain a PETG matte transfer film; wherein the preheating temperature during transverse stretching is 100℃, the stretching temperature is 120℃, the setting temperature is 120℃, and the cooling temperature is 30℃; the stretching ratio during transverse stretching is 5, the stretching angle is 3.5°, and the production speed of the matte transfer film is 30m / min.

[0043] Comparative Example 2

[0044] A PETG matting transfer film includes an upper surface layer, a core layer, and a lower surface layer. The upper surface layer comprises the following raw materials in parts by weight: 60 parts PETG, 1 part antioxidant, and 1 part antistatic agent. The core layer comprises the following raw materials in parts by weight: 88 parts PETG, 9 parts matting agent, 1 part nucleating agent, and 0.6 parts antioxidant. The lower surface layer comprises the following raw materials in parts by weight: 50 parts PETG and 2 parts synthetic talc.

[0045] The preparation method of the matting agent includes the following steps: immersing silica in a 0.2M titanium tetrachloride solution and drying at 85℃ to obtain pretreated silica; mixing tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water uniformly to obtain a mixed solution; adding the pretreated silica to the mixed solution and mixing uniformly, then performing segmented calcination to obtain a mixture; mixing the mixture uniformly with 1wt% silane coupling agent KH550 and drying to obtain the matting agent; wherein the mass ratio of silica to titanium tetrachloride solution is 1:2; the mass ratio of tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water is 0.5:2:15:15; the mass ratio of the mixed solution to pretreated silica is 10:2; the silica particle size is 30nm; the segmented calcination includes: reacting at 40℃ for 2h, then raising the temperature to 80℃ for 8h, and reacting the mixture at 160℃ for 10h under an argon atmosphere.

[0046] A method for preparing a PETG matte transfer film includes the following steps: mixing raw materials for the upper surface layer, core layer, and lower surface layer evenly and extruding them to obtain a melt; subjecting the melt to composite, casting, longitudinal stretching, transverse stretching, winding, and slitting to obtain a PETG matte transfer film; wherein the preheating temperature during transverse stretching is 80℃, the stretching temperature is 85℃, the setting temperature is 85℃, and the cooling temperature is 30℃; the stretching ratio during transverse stretching is 3, the stretching angle is 2°, and the production speed of the matte transfer film is 60m / min.

[0047] Comparative Example 3

[0048] A PETG matting transfer film includes an upper surface layer, a core layer, and a lower surface layer. The upper surface layer comprises the following raw materials in parts by weight: 60 parts PETG, 1 part antioxidant, and 1 part antistatic agent. The core layer comprises the following raw materials in parts by weight: 88 parts PETG, 9 parts matting agent, 1 part nucleating agent, and 0.6 parts antioxidant. The lower surface layer comprises the following raw materials in parts by weight: 50 parts PETG and 2 parts synthetic talc.

[0049] The preparation method of the matting agent includes the following steps: mixing silica, titanium dioxide and 1 wt% silane coupling agent KH550 evenly and drying to obtain the matting agent; wherein the mass ratio of silica and titanium dioxide is 1:1.

[0050] A method for preparing a PETG matte transfer film includes the following steps: mixing the raw materials of the upper surface layer, core layer, and lower surface layer evenly and extruding them to obtain a melt; subjecting the melt to composite, casting, longitudinal stretching, transverse stretching, winding, and slitting to obtain a PETG matte transfer film; wherein the preheating temperature during transverse stretching is 80℃, the stretching temperature is 85℃, the setting temperature is 85℃, and the cooling temperature is 30℃; the stretching ratio during transverse stretching is 5, the stretching angle is 3.5°, and the production speed of the matte transfer film is 80m / min.

[0051] The tensile strength and haze of the PETG matting transfer film prepared above were tested, and the test results are shown in Table 1.

[0052] Table 1

[0053] project Longitudinal tensile strength (MPa) Transverse tensile strength (MPa) Haze (%) Example 1 68 279 98 Example 2 67 283 92 Example 3 62 277 95 Comparative Example 1 59 272 85 Comparative Example 2 62 268 86 Comparative Example 3 63 280 79

[0054] As can be seen from the data in Table 1, the PETG matting transfer film prepared by this invention has high tensile strength and haze, indicating that the PETG matting transfer film of this invention has high haze. Comparative Examples 1-2 show that adjusting the transverse stretching parameters helps to improve haze; Comparative Example 3 shows that adding the matting agent prepared by this invention helps to achieve high haze in the PETG matting transfer film.

[0055] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A high-haze PETG matting transfer film, characterized in that, It includes an upper surface layer, a core layer, and a lower surface layer; the core layer includes the following raw materials in parts by weight: 60-90 parts PETG, 5-12 parts matting agent, 0.5-2 parts nucleating agent, and 0.1-1 parts antioxidant; The method for preparing the matting agent includes the following steps: immersing silica in a titanium tetrachloride solution and drying it to obtain pretreated silica; mixing tetrabutyl titanate, tetrahydrofuran, hydrochloric acid, and water to obtain a mixed solution; adding the pretreated silica to the mixed solution and mixing it evenly, then performing segmented calcination to obtain a mixture; mixing the mixture evenly with a silane coupling agent and drying it to obtain the matting agent.

2. The high-haze PETG matting transfer film according to claim 1, characterized in that, The concentration of the titanium tetrachloride solution is 0.05-2M; the mass ratio of silicon dioxide to titanium tetrachloride solution is 1:(1-2); and the drying temperature is 80-105℃.

3. The high-haze PETG matting transfer film according to claim 1, characterized in that, The mass ratio of tetrabutyl titanate, tetrahydrofuran, hydrochloric acid and water is (0.5-1):(2-5):(10-20):(10-20).

4. The high-haze PETG matting transfer film according to claim 1, characterized in that, The mass ratio of the mixed solution to the pretreated silica is 10:(0.5-3).

5. The high-haze PETG matting transfer film according to claim 1, characterized in that, The segmented calcination includes: reacting at temperature T1 for 1-2 hours, then raising the temperature to T2 and reacting for 4-8 hours, and then reacting the mixture at temperature T3 under an inert atmosphere for 6-12 hours; wherein the temperature T1 is 30-50℃; the temperature T2 is 70-100℃; and the temperature T3 is 150-200℃.

6. The high-haze PETG matting transfer film according to claim 1, characterized in that, The upper surface layer comprises the following raw materials in parts by weight: 40-60 parts PETG, 1-3 parts antioxidant, and 0.5-2 parts antistatic agent.

7. The high-haze PETG matting transfer film according to claim 1, characterized in that, The lower surface layer comprises the following raw materials in parts by weight: 40-60 parts PETG and 1-5 parts opening agent.

8. A method for preparing a high-haze PETG matting transfer film according to any one of claims 1-7, characterized in that, Includes the following steps: The raw materials for the upper surface layer, core layer, and lower surface layer are mixed evenly and extruded to obtain a melt; the melt is then compounded, cast, stretched longitudinally, stretched transversely, wound up, and slit to obtain a high-haze PETG matting transfer film.

9. The preparation method according to claim 8, characterized in that, The preheating temperature during the horizontal stretching is 75-85℃, the stretching temperature is 80-90℃, the setting temperature is 80-90℃, and the cooling temperature is 10-50℃; the stretching ratio during the horizontal stretching is 4-5, and the stretching angle is 3.5-4.5°.