Printable silicone release paper

Abstract

The present invention relates to a printable silicone release paper, and belongs to the technical field of release paper. The present invention discloses that the structure of the printable silicone release paper is a base paper-release agent coating layer, and the steps of preparing the printable silicone release paper are as follows: one side or both sides of the base paper are coated with a silicone release agent on the surface of the coated adhesive, dried, and then coated again, and the printable silicone release paper is obtained after drying. The modified silicone contained in the release agent has defoaming and anti-sticking properties; in addition, it also contains fluorinated polysiloxane and wax powder, and the two work together to reduce the surface energy of the release paper. The present invention can prepare silicone release paper with a smooth surface, low surface energy, clear printing, writable, and printed matter that does not adhere to the paper.

Description

Technical Field

[0001] The invention belongs to the technical field of release paper and relates to printable silicone release paper. Background Art

[0002] Release paper is a special paper with a low surface energy coating and a non-adhesive surface, suitable for electronics, automotive foam, printing and other industries. According to different uses, release paper can be divided into ordinary release paper, glassine silicone oil paper, polyvinyl chloride wallpaper and artificial leather release paper. The low surface energy coating of release paper is usually called paper release agent, which mainly includes non-silicone release agent, silicone release agent and fluorine-containing release agent.

[0003] Silicone release agent is a cross-linked polymer with a silicon-oxygen chain as its skeleton. It has low polarity, small intermolecular force, low surface energy, excellent weather resistance and aging resistance. It is currently the mainstream type of paper release agent. Summary of the invention

[0004] The present invention relates to a printable silicone release paper, and belongs to the technical field of release paper. The present invention discloses that the structure of the printable silicone release paper is a base paper-release agent coating layer, and the steps of preparing the printable silicone release paper are as follows: one side or both sides of the base paper are coated with a silicone release agent on the surface of the coated adhesive, dried, and then coated again, and the printable silicone release paper is obtained after drying. The modified silicone contained in the release agent has defoaming and anti-sticking properties; in addition, it also contains fluorinated polysiloxane and wax powder, and the two work together to reduce the surface energy of the release paper. The present invention can prepare silicone release paper with a smooth surface, low surface energy, clear printing, writable, and printed matter that does not adhere to the paper.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A printable organosilicon release paper has a structure of base paper-release agent coating layer. The printable organosilicon release paper is prepared by the following steps: coating one or both sides of the base paper with an organosilicon release agent on a surface coated with an adhesive, drying, and then coating again to obtain the printable organosilicon release paper after drying.

[0007] Furthermore, the specific preparation method of the release agent is: heating and stirring the solvent, adding all the raw materials to mix, then adding the leveling agent and stirring, aging for 20-24 hours, stirring and cooling to obtain the silicone release agent.

[0008] Furthermore, the solvent is toluene, heating refers to heating to 50-55° C., the mass ratio of the solvent, the raw material and the leveling agent is 60-80:40-50:1-3, and cooling refers to cooling to room temperature.

[0009] Furthermore, the raw materials are as follows: 10-20 parts of water-based acrylic resin, 2-3 parts of polyester resin, 2-3 parts of wax powder, 8-10 parts of modified silicone, and 3-5 parts of fluorine-containing polysiloxane.

[0010] Furthermore, the preparation method of the modified silicone comprises the following steps: preparing a catalyst by mixing chloroplatinic acid and isopropanol in a mass ratio of 1:90, adding olefins, heating to activate, adding hydrogenated silicone oil and stirring, heating to 100-110° C. and keeping the temperature, and removing excess olefins by reduced pressure distillation after the reaction to obtain the modified silicone.

[0011] Furthermore, the mass ratio of the catalyst, olefin and hydrogen-containing silicone oil is 1:10:10, the olefin is composed of 1-tridecene and 1-pentadecene in a mass ratio of 1:1, and the heating temperature is 70-80°C.

[0012] Furthermore, the preparation method of the fluorine-containing polyoxysilane comprises the following steps:

[0013] A1: trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane are mixed, nitrogen is introduced, and then heated and stirred to obtain a mixture;

[0014] A2: Add trifluoromethanesulfonic acid as a catalyst to the mixture for reaction, then add n-heptane, filter, and perform vacuum distillation to obtain fluorine-containing polyoxysilane.

[0015] Furthermore, in the step A1, the mass ratio of trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane is 12:8:0.1, the heating temperature is 75-80° C., and the stirring time is 0.5-1 h.

[0016] Furthermore, in step A2, the mass ratio of the mixture, the catalyst and n-heptane is 10:0.5:5-6, and the distillation time and temperature are 15-30 min and 150-170° C., respectively.

[0017] Furthermore, the base paper is one of kraft paper, masking paper and glassine paper, the thickness of one side of each coating is 0.25-0.5 μm, and the drying temperature and time are 30-50° C. and 20-30 min, respectively.

[0018] Beneficial effects of the present invention:

[0019] 1. The present invention uses two release agent coating processes. Since the release agent is penetrated and the surface is uneven during the first coating, the second coating can effectively improve the flatness of the release paper surface and improve the printing clarity.

[0020] 2. The present invention uses 1-tridecene and 1-pentadecene to modify the silicone oil, and replaces part of the methyl groups in the silicone oil copolymer molecules with long-chain alkyl groups, so that the silicone oil has lubricity, defoaming properties, and anti-stickiness, effectively preventing the adhesion of printed matter to the surface of release paper, ensuring that the pattern or text formed by the remaining printed matter will not leave other residues, and at the same time ensuring the clarity of the printing.

[0021] 3. The presence of CF3 in fluorinated polysiloxane provides lower surface energy, and the wax powder has micro-powder particles with good lubricity and anti-stickiness. The two work together to reduce the surface energy of the release agent, thereby effectively preventing the adhesion of the printed matter to the surface of the release paper and ensuring the clarity of the printing. DETAILED DESCRIPTION

[0022] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with embodiments.

[0023] Example 1

[0024] A printable organosilicon release paper has a structure of base paper-release agent coating layer. The printable organosilicon release paper is prepared by the following steps: coating one or both sides of the base paper with an organosilicon release agent on a surface coated with an adhesive, drying, and then coating again to obtain the printable organosilicon release paper after drying.

[0025] The specific preparation method of the release agent is: heating and stirring the solvent, adding all raw materials to mix, then adding the leveling agent and stirring, aging for 20 hours, stirring and cooling to obtain the silicone release agent.

[0026] The solvent is toluene, the heating refers to heating to 50° C., the mass ratio of the solvent, the raw material and the leveling agent is 60:40:1, and the cooling refers to cooling to room temperature.

[0027] The raw materials are as follows: 10 parts of water-based acrylic resin, 2 parts of polyester resin, 2 parts of wax powder, 8 parts of modified silicone, and 3 parts of fluorine-containing polysiloxane.

[0028] The preparation method of the modified organic silicon comprises the following steps: preparing a catalyst by mixing chloroplatinic acid and isopropanol in a mass ratio of 1:90, adding olefin, heating up for activation, adding hydrogen-containing silicone oil for stirring, heating up to 100° C. and keeping the temperature, and removing excess olefin by reduced pressure distillation after the reaction to obtain the modified organic silicon.

[0029] The mass ratio of the catalyst, olefin and hydrogen-containing silicone oil is 1:10:10, the olefin is composed of 1-tridecene and 1-pentadecene in a mass ratio of 1:1, and the heating temperature is 70°C.

[0030] The preparation method of the fluorine-containing polyoxysilane comprises the following steps:

[0031] A1: trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane are mixed, nitrogen is introduced, and then heated and stirred to obtain a mixture;

[0032] A2: Add trifluoromethanesulfonic acid as a catalyst to the mixture for reaction, then add n-heptane, filter, and perform vacuum distillation to obtain fluorine-containing polyoxysilane.

[0033] In the step A1, the mass ratio of trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane is 12:8:0.1, the heating temperature is 75° C., and the stirring time is 0.5 h.

[0034] The mass ratio of the mixture, the catalyst and n-heptane in step A2 is 10:0.5:5, and the distillation time and temperature are 15 min and 150° C. respectively.

[0035] The base paper is kraft paper, the thickness of one side of each coating is 0.25 μm, and the drying temperature and time are 30° C. and 20 min, respectively.

[0036] The water-based acrylic resin is purchased from: water-based acrylic resin / AC 3600-Obaodi; the polyester resin is purchased from: RS-970F polyester resin / Jinfengyuan Polymer; the leveling agent is purchased from: leveling agent / sunfor 435; the hydrogen-containing silicone oil is purchased from: silicone oil / Shengfeng; the adhesive in the adhesive coating layer is purchased from: Huawei / 6188.

[0037] Example 2

[0038] A printable organosilicon release paper has a structure of base paper-release agent coating layer. The printable organosilicon release paper is prepared by the following steps: coating one or both sides of the base paper with an organosilicon release agent on a surface coated with an adhesive, drying, and then coating again to obtain the printable organosilicon release paper after drying.

[0039] The specific preparation method of the release agent is: heating and stirring the solvent, adding all the raw materials to mix, then adding the leveling agent and stirring, aging for 22 hours, stirring and cooling to obtain the silicone release agent.

[0040] The solvent is toluene, the heating refers to heating to 53° C., the mass ratio of the solvent, the raw material and the leveling agent is 70:45:2, and the cooling refers to cooling to room temperature.

[0041] The raw materials are as follows: 15 parts of water-based acrylic resin, 2.5 parts of polyester resin, 2.5 parts of wax powder, 9 parts of modified silicone, and 4 parts of fluorine-containing polysiloxane.

[0042] The preparation method of the modified organic silicon comprises the following steps: preparing a catalyst by mixing chloroplatinic acid and isopropanol in a mass ratio of 1:90, adding olefin, heating up for activation, adding hydrogen-containing silicone oil for stirring, heating up to 105° C. and keeping the temperature, and removing excess olefin by reduced pressure distillation after the reaction to obtain the modified organic silicon.

[0043] The mass ratio of the catalyst, olefin and hydrogen-containing silicone oil is 1:10:10, the olefin is composed of 1-tridecene and 1-pentadecene in a mass ratio of 1:1, and the heating temperature is 75°C.

[0044] The preparation method of the fluorine-containing polyoxysilane comprises the following steps:

[0045] A1: trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane are mixed, nitrogen is introduced, and then heated and stirred to obtain a mixture;

[0046] A2: Add trifluoromethanesulfonic acid as a catalyst to the mixture for reaction, then add n-heptane, filter, and perform vacuum distillation to obtain fluorine-containing polyoxysilane.

[0047] In the step A1, the mass ratio of trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane is 12:8:0.1, the heating temperature is 75° C., and the stirring time is 0.5 h.

[0048] In the step A2, the mass ratio of the mixture, the catalyst and n-heptane is 10:0.5:5.5, and the distillation time and temperature are 20 min and 160° C. respectively.

[0049] The base paper is kraft paper, the thickness of one side of each coating is 0.35 μm, and the drying temperature and time are 40° C. and 25 min, respectively.

[0050] The water-based acrylic resin is purchased from: water-based acrylic resin / AC 3600-Obaodi; the polyester resin is purchased from: RS-970F polyester resin / Jinfengyuan Polymer; the leveling agent is purchased from: leveling agent / sunfor 435; the hydrogen-containing silicone oil is purchased from: silicone oil / Shengfeng; the adhesive in the adhesive coating layer is purchased from: Huawei / 6188.

[0051] Example 3

[0052] A printable silicone release paper has a structure of base paper-release agent coating layer. The printable silicone release paper is prepared by the following steps: coating one or both sides of the base paper with a silicone release agent on a surface coated with an adhesive, drying, and then coating again to obtain the printable silicone release paper after drying.

[0053] The specific preparation method of the release agent is: heating and stirring the solvent, adding all the raw materials to mix, then adding the leveling agent and stirring, aging for 24 hours, stirring and cooling to obtain the silicone release agent.

[0054] The solvent is toluene, the heating refers to heating to 55° C., the mass ratio of the solvent, the raw material and the leveling agent is 80:50:3, and the cooling refers to cooling to room temperature.

[0055] The raw materials are as follows: 20 parts of water-based acrylic resin, 3 parts of polyester resin, 3 parts of wax powder, 10 parts of modified silicone, and 5 parts of fluorine-containing polysiloxane.

[0056] The preparation method of the modified organic silicon comprises the following steps: preparing a catalyst by mixing chloroplatinic acid and isopropanol in a mass ratio of 1:90, adding olefin, heating to activate, adding hydrogen-containing silicone oil and stirring, heating to 110° C. and keeping the temperature, and removing excess olefin by reduced pressure distillation after the reaction to obtain the modified organic silicon.

[0057] The mass ratio of the catalyst, olefin and hydrogen-containing silicone oil is 1:10:10, the olefin is composed of 1-tridecene and 1-pentadecene in a mass ratio of 1:1, and the heating temperature is 80°C.

[0058] The preparation method of the fluorine-containing polyoxysilane comprises the following steps:

[0059] A1: trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane are mixed, nitrogen is introduced, and then heated and stirred to obtain a mixture;

[0060] A2: Add trifluoromethanesulfonic acid as a catalyst to the mixture for reaction, then add n-heptane, filter, and perform vacuum distillation to obtain fluorine-containing polyoxysilane.

[0061] In the step A1, the mass ratio of trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane is 12:8:0.1, the heating temperature is 80° C., and the stirring time is 1 hour.

[0062] In the step A2, the mass ratio of the mixture, the catalyst and n-heptane is 10:0.5:6, and the distillation time and temperature are 30 min and 170° C. respectively.

[0063] The base paper is kraft paper, the thickness of one side of each coating is 0.5 μm, and the drying temperature and time are 50° C. and 30 minutes respectively.

[0064] The water-based acrylic resin is purchased from: water-based acrylic resin / AC 3600-Obaodi; the polyester resin is purchased from: RS-970F polyester resin / Jinfengyuan Polymer; the leveling agent is purchased from: leveling agent / sunfor 435; the hydrogen-containing silicone oil is purchased from: silicone oil / Shengfeng; the adhesive in the adhesive coating layer is purchased from: Huawei / 6188.

[0065] Comparative Example 1

[0066] On the basis of Example 2, a printable silicone release paper is provided, wherein the structure of the printable silicone release paper is base paper-release agent coating layer, and the printable silicone release paper is prepared by the following steps: a silicone release agent is applied to one or both sides of the base paper on the surface of the adhesive film, and the printable silicone release paper is obtained after drying.

[0067] The specific preparation method of the release agent is: heating and stirring the solvent, adding all the raw materials to mix, then adding the leveling agent and stirring, aging for 22 hours, stirring and cooling to obtain the silicone release agent.

[0068] The solvent is toluene, the heating refers to heating to 53° C., the mass ratio of the solvent, the raw material and the leveling agent is 70:45:2, and the cooling refers to cooling to room temperature.

[0069] The raw materials are as follows: 15 parts of water-based acrylic resin, 2.5 parts of polyester resin, 2.5 parts of wax powder, 9 parts of modified silicone, and 4 parts of fluorine-containing polysiloxane.

[0070] The preparation method of the modified organic silicon comprises the following steps: preparing a catalyst by mixing chloroplatinic acid and isopropanol in a mass ratio of 1:90, adding olefin, heating up for activation, adding hydrogen-containing silicone oil for stirring, heating up to 105° C. and keeping the temperature, and removing excess olefin by reduced pressure distillation after the reaction to obtain the modified organic silicon.

[0071] The mass ratio of the catalyst, olefin and hydrogen-containing silicone oil is 1:10:10, the olefin is composed of 1-tridecene and 1-pentadecene in a mass ratio of 1:1, and the heating temperature is 75°C.

[0072] The preparation method of the fluorine-containing polyoxysilane comprises the following steps:

[0073] A1: trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane are mixed, nitrogen is introduced, and then heated and stirred to obtain a mixture;

[0074] A2: Add trifluoromethanesulfonic acid as a catalyst to the mixture for reaction, then add n-heptane, filter, and perform vacuum distillation to obtain fluorine-containing polyoxysilane.

[0075] In the step A1, the mass ratio of trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane is 12:8:0.1, the heating temperature is 75° C., and the stirring time is 0.5 h.

[0076] In the step A2, the mass ratio of the mixture, the catalyst and n-heptane is 10:0.5:5.5, and the distillation time and temperature are 20 min and 160° C. respectively.

[0077] The base paper is kraft paper, the thickness of the coated side is 0.35 μm, and the drying temperature and time are 40° C. and 25 min, respectively.

[0078] The water-based acrylic resin is purchased from: water-based acrylic resin / AC 3600-Obaodi; the polyester resin is purchased from: RS-970F polyester resin / Jinfengyuan Polymer; the leveling agent is purchased from: leveling agent / sunfor 435; the hydrogen-containing silicone oil is purchased from: silicone oil / Shengfeng; the adhesive in the adhesive coating layer is purchased from: Huawei / 6188.

[0079] Comparative Example 2

[0080] On the basis of Example 2, 1-tridecene was used to modify the organosilicon during the preparation of the modified organosilicon, and other conditions were consistent with those in Example 2.

[0081] Comparative Example 3

[0082] On the basis of Example 2, the modified silicone was replaced by hydrogen-containing silicone oil, and other conditions were consistent with Example 2.

[0083] Comparative Example 4

[0084] On the basis of Example 2, the fluorinated polysiloxane was removed and replaced with wax powder of equal weight, and other conditions were the same as those in Example 2.

[0085] Comparative Example 5

[0086] On the basis of Example 2, the wax powder was removed and replaced with an equal weight portion of fluorine-containing polysiloxane, and other conditions were consistent with Example 2.

[0087] Performance Testing

[0088] 1. Ink dot property test: The printable silicone release papers prepared in Examples 1-3 and Comparative Examples 1-3 were used as samples. The samples were printed with ink dots, and each sample was divided into Group 1 and Group 2, with 20 ink dots selected from each group. The average value was taken according to the microscopic measurement instrument and the fidelity was obtained.

[0089] 2. Infection test: The printable silicone release papers prepared in Examples 1-3 and Comparative Examples 1-5 were used as samples to observe whether there were other residues besides the patterns formed by the printed material. The above test results are shown in Table 1.

[0090] Table 1 Test results

[0091]

[0092]

[0093] From the analysis of Table 1, it can be concluded that the difference in fidelity between Group 1 and Group 2 of Examples 1-3 is less than 0.01, and there is no residue; while the difference of Comparative Examples 1-3 is greater than 0.01, among which the difference of Comparative Example 1 is the largest, and residues exist in all the other comparative examples except Comparative Example 2. The smaller the difference in ink dot values, the better the stability and the clearer. When preparing release paper in Comparative Example 1, the release agent was only applied once, resulting in an uneven surface of the release paper and reducing the printing clarity. Comparative Example 2 only uses 1-13 olefins to modify the organosilicon, which affects its defoaming properties and reduces the printing clarity. Comparative Example 3 uses unmodified organosilicon to prepare the release agent, and the defoaming and anti-sticking properties are reduced, residues appear, and the printing clarity is affected. Comparative Example 4 and Comparative Example 5 remove one of the fluorinated polysiloxane and wax powder, and the surface energy of the release paper is increased, and residues appear.

[0094] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A printable silicone release paper, characterized in that: The printable silicone release paper has a structure of base paper-release agent coating layer, and the printable silicone release paper is prepared by the following steps: coating one or both sides of the base paper with a silicone release agent on the surface of the adhesive film, drying, and then coating again, and drying to obtain the printable silicone release paper; The specific preparation method of the release agent is: heating and stirring the solvent, adding all the raw materials to mix, then adding the leveling agent and stirring, aging for 20-24 hours, stirring and cooling to obtain the silicone release agent; The raw materials are as follows: 10-20 parts of water-based acrylic resin, 2-3 parts of polyester resin, 2-3 parts of wax powder, 8-10 parts of modified silicone, and 3-5 parts of fluorine-containing polysiloxane; The preparation method of the modified silicone comprises the following steps: Chloroplatinic acid and isopropanol are prepared into a catalyst in a mass ratio of 1:90, olefin is added, the temperature is raised for activation, hydrogen-containing silicone oil is added for stirring, the temperature is raised to 100-110° C. and the temperature is kept, and after the reaction, the excess olefin is removed by vacuum distillation to obtain modified organosilicon; The mass ratio of the catalyst, olefin and hydrogen-containing silicone oil is 1:10:10, the olefin is composed of 1-tridecene and 1-pentadecene in a mass ratio of 1:1, and the heating temperature is 70-80°C; The preparation method of the fluorine-containing polysiloxane comprises the following steps: A1: trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane are mixed, nitrogen is introduced, and then heated and stirred to obtain a mixture; A2: Add trifluoromethanesulfonic acid as a catalyst to the mixture for reaction, then add n-heptane, filter, and perform vacuum distillation to obtain fluorine-containing polysiloxane.

2. The printable silicone release paper according to claim 1, characterized in that: The solvent is toluene, the heating refers to heating to 50-55° C., the mass ratio of the solvent, the raw material and the leveling agent is 60-80:40-50:1-3, and the cooling refers to cooling to room temperature.

3. The printable silicone release paper according to claim 1, characterized in that: In the step A1, the mass ratio of trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyldihydrogendisiloxane is 12:8:0.1, the heating temperature is 75-80° C., and the stirring time is 0.5-1 h.

4. The printable silicone release paper according to claim 1, characterized in that: In the step A2, the mass ratio of the mixture, the catalyst and n-heptane is 10:0.5:5-6, and the distillation time and temperature are 15-30 min and 150-170° C., respectively.

5. The printable silicone release paper according to claim 1, characterized in that: The base paper is one of kraft paper, masking paper and glassine paper. The thickness of one side of each coating is 0.25-0.5 μm. The drying temperature and time are 30-50° C. and 20-30 min respectively.

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