Polyurethane type UV visbreaking protective film and preparation method thereof

Abstract

The invention discloses a preparation method of a polyurethane type UV (ultraviolet) visbreaking protective film, which comprises the following steps: (1) mixing hydroxyl-terminated polybutadiene, ethyl acetate, 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, ethidene diamine, dibutyltin dilaurate and hydroquinone in a reaction kettle in a nitrogen protection atmosphere, heating, adding isophorone diisocyanate, stirring at a constant temperature, adding a catalyst, stirring at a constant temperature, and reacting for 2-4 hours; adding 1, 4-butanediol to obtain an adhesive; (2) uniformly mixing hydroxyethyl acrylate, methyl tetrahydrophthalic anhydride and maleic anhydride, heating, adding triethylamine, stirring at a constant temperature, and adding epoxidized soybean oil to obtain a modified acrylate monomer; and (3) stirring the adhesive, then adding the modified acrylate monomer, 1-ethyl-3-methylimidazolium tetrafluoroborate, sodium octane sulfonate and the photoinitiator into the adhesive in a stirring state, stirring to obtain a UV viscosity-reducing adhesive, and coating to obtain the UV viscosity-reducing protective film. The UV viscosity-reducing glue prepared by the method provided by the invention has a good viscosity-reducing effect, is easy to peel after viscosity reduction, and is convenient to operate.

Description

Technical Field

[0001] The invention relates to the technical field of anti-viscosity protective films, and in particular to a polyurethane type UV anti-viscosity protective film and a preparation method thereof. Background Art

[0002] With the continuous development of information technology and the semiconductor industry, the demand for various wafer-based devices is increasing. Anti-viscosity film is one of the key materials for wafer processing. Anti-viscosity film, also known as anti-viscosity tape, is made by coating anti-viscosity adhesive on substrates such as polyester film (PET) and polyolefin film (PO). In addition to the processing of semiconductor wafer materials, anti-viscosity film is also required for the cutting of ultra-thin glass and the acid treatment of glass such as mobile phone screens. Anti-viscosity film plays a fixing and protective role when processing easily damaged materials to prevent splashing fragments and breakage; after the processing is completed, in order to facilitate the picking up of the workpiece, the curing and anti-viscosity effect greatly reduces the adhesion of the anti-viscosity film, and the workpiece is separated from the substrate, and then the next step of processing is carried out. Summary of the invention

[0003] To this end, the present invention provides a method for preparing a polyurethane type UV viscosity-reducing protective film, the preparation steps comprising:

[0004] (1) In a nitrogen atmosphere, hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate and hydroquinone are mixed in a reaction kettle, and the mixture is heated to 60±3° C. in a water bath, and stirred at the temperature after reaching the temperature. During the stirring process, isophorone diisocyanate is added to the mixture, and after the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. in a nitrogen atmosphere for more than 2 hours, and then 1,4-butanediol is added. After the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. in a nitrogen atmosphere for more than 3 hours to obtain an adhesive;

[0005] (2) Mix hydroxyethyl acrylate, methyltetrahydrophthalic anhydride and maleic anhydride uniformly, then heat to 90±2°C and keep warm, stir for more than 10 minutes after reaching the temperature, then add triethylamine under stirring, continue to stir at 90±2°C for more than 30 minutes after the addition is completed, then add epoxy soybean oil, continue to stir at 90±2°C for 50-60 minutes after the addition is completed, and obtain a modified acrylic ester monomer;

[0006] (3) stirring the adhesive, and then adding the modified acrylic ester monomer, 1-ethyl-3-methylimidazole tetrafluoroboric acid, sodium octane sulfonate and photoinitiator to the adhesive under stirring, and continuing to stir for more than 30 minutes after the addition is completed to obtain a UV viscosity-reducing adhesive, and coating the UV viscosity-reducing adhesive on the surface of the polyolefin film after corona pretreatment, and after the solvent is completely evaporated, the UV viscosity-reducing protective film is obtained.

[0007] Furthermore, in the step (1), the hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate, hydroquinone, isophorone diisocyanate and 1,4-butanediol are calculated in parts by weight as follows: 10 parts of hydroxy-terminated polybutadiene, 25-30 parts of ethyl acetate, 2-3 parts of 2-chloro-4,6-diphenyl-1,3,5-triazine, 0.4-0.8 parts of ethylenediamine; 0.006-0.008 parts of dibutyltin dilaurate, 0.07-0.09 parts of hydroquinone, 2-4 parts of isophorone diisocyanate, and 1-2 parts of 1,4-butanediol.

[0008] Furthermore, in the step (2), the hydroxyethyl acrylate, methyltetrahydrophthalic anhydride, maleic anhydride, triethylamine and epoxidized soybean oil are calculated in parts by weight as follows: 100 parts of hydroxyethyl acrylate, 35-40 parts of methyltetrahydrophthalic anhydride, 46-48 parts of maleic anhydride, 2-3 parts of triethylamine and 100-110 parts of epoxidized soybean oil.

[0009] Furthermore, in the step (3), the mass ratio of the modified acrylic ester monomer, 1-ethyl-3-methylimidazole tetrafluoroborate, sodium octane sulfonate and photoinitiator added to the adhesive is adhesive: modified acrylic ester monomer: 1-ethyl-3-methylimidazole tetrafluoroborate: sodium octane sulfonate: photoinitiator = 100:15-18:6-7:0.8-1:2-4.

[0010] Furthermore, in step (3), the photoinitiator is (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

[0011] Furthermore, in the step (3), the coating wet film thickness is 50 to 60 μm.

[0012] The beneficial effects of the present invention are as follows: the UV viscosity-reducing adhesive prepared by the method of the present invention has a good viscosity-reducing effect, is easy to peel off after viscosity reduction, and is convenient to operate. And the adhesion performance before UV irradiation is good, the wafer can be well fixed, and the use effect is excellent. The present invention modifies the terminal hydroxyl polybutadiene by 2-chloro-4,6-diphenyl-1,3,5-triazine, so that it is easier to undergo a cross-linking reaction under the action of a photoinitiator (2,4,6-trimethylbenzoyl) diphenylphosphine oxide during UV irradiation, thereby increasing the degree of cross-linking, causing the volume of the adhesive layer to shrink, and greatly reducing the bonding points. Then, by treating the acrylate monomer, an epoxy soybean oil group is introduced into the acrylate monomer, the functionality of the monomer is increased, and the number of unsaturated C=C contained in the monomer is increased, further increasing the degree of cross-linking of the viscosity-reducing adhesive under UV irradiation, increasing the cross-linking density, and significantly reducing the peeling strength after irradiation. Finally, by introducing 1-ethyl-3-methylimidazole tetrafluoroboric acid, the cross-linking of the monomer under UV irradiation can be promoted to a certain extent, so that the viscosity-reducing effect is further improved. DETAILED DESCRIPTION

[0013] The present invention will be further described below in conjunction with the embodiments.

[0014] Example 1

[0015] A method for preparing a polyurethane type UV viscosity-reducing protective film, the preparation steps comprising:

[0016] (1) In a nitrogen atmosphere, hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate and hydroquinone are mixed in a reaction kettle, and the mixture is heated to 60±3° C. in a water bath, and stirred after reaching the temperature. During the stirring process, isophorone diisocyanate is added to the mixture, and after the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 2 h in a nitrogen atmosphere, and then 1,4-butanediol is added. After the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 3 h in a nitrogen atmosphere to obtain an adhesive. Agent; wherein the hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate, hydroquinone, isophorone diisocyanate and 1,4-butanediol are calculated in parts by weight: 10 parts of hydroxy-terminated polybutadiene, 25 parts of ethyl acetate, 2 parts of 2-chloro-4,6-diphenyl-1,3,5-triazine, 0.4 parts of ethylenediamine; 0.006 parts of dibutyltin dilaurate, 0.07 parts of hydroquinone, 2 parts of isophorone diisocyanate, and 1 part of 1,4-butanediol;

[0017] (2) Mix hydroxyethyl acrylate, methyltetrahydrophthalic anhydride and maleic anhydride uniformly, then heat to 90±2° C. and keep warm, stir for 10 min after reaching temperature, then add triethylamine under stirring, continue stirring at 90±2° C. for 30 min after adding, then add epoxidized soybean oil, continue stirring at 90±2° C. for 50 min after adding, to obtain a modified acrylic ester monomer; wherein the hydroxyethyl acrylate, methyltetrahydrophthalic anhydride, maleic anhydride, triethylamine and epoxidized soybean oil are calculated by weight as follows: 100 parts of hydroxyethyl acrylate, 35 parts of methyltetrahydrophthalic anhydride, 46 parts of maleic anhydride, 2 parts of triethylamine and 100 parts of epoxidized soybean oil;

[0018] (3) Stirring the adhesive, and then adding the modified acrylate monomer, 1-ethyl-3-methylimidazole tetrafluoroboric acid, sodium octane sulfonate and photoinitiator to the adhesive under stirring, the mass ratio of the modified acrylate monomer, 1-ethyl-3-methylimidazole tetrafluoroboric acid, sodium octane sulfonate and photoinitiator added to the adhesive is adhesive: modified acrylate monomer: 1-ethyl-3-methylimidazole tetrafluoroboric acid: sodium octane sulfonate: photoinitiator = 100:15:6:0.8:2; the photoinitiator is (2,4,6-trimethylbenzoyl) diphenylphosphine oxide; after the addition is completed, stirring is continued for 30 minutes to obtain a UV viscosity-reducing adhesive, and the UV viscosity-reducing adhesive is coated on the surface of the polyolefin film after corona pretreatment, and the coating wet film thickness is 50 μm; after the solvent is completely evaporated, the UV viscosity-reducing protective film is obtained.

[0019] Example 2

[0020] A method for preparing a polyurethane type UV viscosity-reducing protective film, the preparation steps comprising:

[0021] (1) In a nitrogen atmosphere, hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate and hydroquinone are mixed in a reaction kettle, and the mixture is heated to 60±3° C. in a water bath, and stirred after reaching the temperature. During the stirring process, isophorone diisocyanate is added to the mixture, and after the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 2 h in a nitrogen atmosphere, and then 1,4-butanediol is added. After the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 3 h in a nitrogen atmosphere to obtain an adhesive. Agent; wherein the terminal hydroxyl polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate, hydroquinone, isophorone diisocyanate and 1,4-butanediol are calculated in parts by weight: 10 parts of terminal hydroxyl polybutadiene, 27 parts of ethyl acetate, 2 parts of 2-chloro-4,6-diphenyl-1,3,5-triazine, 0.6 parts of ethylenediamine; 0.007 parts of dibutyltin dilaurate, 0.08 parts of hydroquinone, 3 parts of isophorone diisocyanate, and 1 part of 1,4-butanediol;

[0022] (2) Mix hydroxyethyl acrylate, methyltetrahydrophthalic anhydride and maleic anhydride uniformly, then heat to 90±2° C. and keep warm, stir for 10 min after reaching temperature, then add triethylamine under stirring, continue stirring at 90±2° C. for 30 min after adding, then add epoxidized soybean oil, continue stirring at 90±2° C. for 50 min after adding, to obtain a modified acrylic ester monomer; wherein the hydroxyethyl acrylate, methyltetrahydrophthalic anhydride, maleic anhydride, triethylamine and epoxidized soybean oil are calculated by weight as follows: 100 parts of hydroxyethyl acrylate, 38 parts of methyltetrahydrophthalic anhydride, 47 parts of maleic anhydride, 2 parts of triethylamine and 100 parts of epoxidized soybean oil;

[0023] (3) Stirring the adhesive, and then adding the modified acrylate monomer, 1-ethyl-3-methylimidazole tetrafluoroboric acid, sodium octane sulfonate and photoinitiator to the adhesive under stirring, the mass ratio of the modified acrylate monomer, 1-ethyl-3-methylimidazole tetrafluoroboric acid, sodium octane sulfonate and photoinitiator added to the adhesive is adhesive: modified acrylate monomer: 1-ethyl-3-methylimidazole tetrafluoroboric acid: sodium octane sulfonate: photoinitiator = 100:16:6:0.9:3; the photoinitiator is (2,4,6-trimethylbenzoyl) diphenylphosphine oxide; after the addition is completed, stirring is continued for 30 minutes to obtain a UV viscosity-reducing adhesive, and the UV viscosity-reducing adhesive is coated on the surface of the polyolefin film after corona pretreatment, and the coating wet film thickness is 50 μm; after the solvent is completely evaporated, the UV viscosity-reducing protective film is obtained.

[0024] Example 3

[0025] A method for preparing a polyurethane type UV viscosity-reducing protective film, the preparation steps comprising:

[0026] (1) In a nitrogen atmosphere, hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate and hydroquinone are mixed in a reaction kettle, and the mixture is heated to 60±3° C. in a water bath, and stirred after reaching the temperature. During the stirring process, isophorone diisocyanate is added to the mixture, and after the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 2 h in a nitrogen atmosphere, and then 1,4-butanediol is added. After the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 3 h in a nitrogen atmosphere to obtain an adhesive. Agent; wherein the hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate, hydroquinone, isophorone diisocyanate and 1,4-butanediol are calculated in parts by weight: 10 parts of hydroxy-terminated polybutadiene, 28 parts of ethyl acetate, 3 parts of 2-chloro-4,6-diphenyl-1,3,5-triazine, 0.6 parts of ethylenediamine; 0.007 parts of dibutyltin dilaurate, 0.08 parts of hydroquinone, 3 parts of isophorone diisocyanate, and 2 parts of 1,4-butanediol;

[0027] (2) Mix hydroxyethyl acrylate, methyltetrahydrophthalic anhydride and maleic anhydride uniformly, then heat to 90±2° C. and keep warm, stir for 10 min after reaching the temperature, then add triethylamine under stirring, continue to stir at 90±2° C. for 30 min after the addition is completed, then add epoxidized soybean oil, continue to stir at 90±2° C. for 50 min after the addition is completed, to obtain a modified acrylic ester monomer; wherein the hydroxyethyl acrylate, methyltetrahydrophthalic anhydride, maleic anhydride, triethylamine and epoxidized soybean oil are calculated in parts by weight: 100 parts of hydroxyethyl acrylate, 39 parts of methyltetrahydrophthalic anhydride, 47 parts of maleic anhydride, 3 parts of triethylamine, and 110 parts of epoxidized soybean oil;

[0028] (3) Stirring the adhesive, and then adding the modified acrylate monomer, 1-ethyl-3-methylimidazole tetrafluoroboric acid, sodium octane sulfonate and photoinitiator to the adhesive under stirring, the mass ratio of the modified acrylate monomer, 1-ethyl-3-methylimidazole tetrafluoroboric acid, sodium octane sulfonate and photoinitiator added to the adhesive is adhesive: modified acrylate monomer: 1-ethyl-3-methylimidazole tetrafluoroboric acid: sodium octane sulfonate: photoinitiator = 100:17:7:0.9:3; the photoinitiator is (2,4,6-trimethylbenzoyl) diphenylphosphine oxide; after the addition is completed, stirring is continued for 30 minutes to obtain a UV viscosity-reducing adhesive, and the UV viscosity-reducing adhesive is coated on the surface of the polyolefin film after corona pretreatment, and the coating wet film thickness is 50 μm; after the solvent is completely evaporated, the UV viscosity-reducing protective film is obtained.

[0029] Example 4

[0030] A method for preparing a polyurethane type UV viscosity-reducing protective film, the preparation steps comprising:

[0031] (1) In a nitrogen atmosphere, hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate and hydroquinone are mixed in a reaction kettle, and the mixture is heated to 60±3° C. in a water bath, and stirred after reaching the temperature. During the stirring process, isophorone diisocyanate is added to the mixture, and after the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 2 h in a nitrogen atmosphere, and then 1,4-butanediol is added. After the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 3 h in a nitrogen atmosphere to obtain an adhesive. Agent; wherein the terminal hydroxyl polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate, hydroquinone, isophorone diisocyanate and 1,4-butanediol are calculated in parts by weight: 10 parts of terminal hydroxyl polybutadiene, 30 parts of ethyl acetate, 3 parts of 2-chloro-4,6-diphenyl-1,3,5-triazine, 0.8 parts of ethylenediamine; 0.008 parts of dibutyltin dilaurate, 0.09 parts of hydroquinone, 4 parts of isophorone diisocyanate, and 2 parts of 1,4-butanediol;

[0032] (2) Mix hydroxyethyl acrylate, methyltetrahydrophthalic anhydride and maleic anhydride uniformly, then heat to 90±2° C. and keep warm, stir for 10 min after reaching temperature, then add triethylamine under stirring, continue stirring at 90±2° C. for 30 min after adding, then add epoxidized soybean oil, continue stirring at 90±2° C. for 50 min after adding, to obtain a modified acrylic ester monomer; wherein the hydroxyethyl acrylate, methyltetrahydrophthalic anhydride, maleic anhydride, triethylamine and epoxidized soybean oil are calculated in parts by weight as follows: 100 parts of hydroxyethyl acrylate, 40 parts of methyltetrahydrophthalic anhydride, 48 parts of maleic anhydride, 3 parts of triethylamine and 110 parts of epoxidized soybean oil;

[0033] (3) Stirring the adhesive, and then adding the modified acrylate monomer, 1-ethyl-3-methylimidazolium tetrafluoroboric acid, sodium octane sulfonate and photoinitiator to the adhesive under stirring, wherein the mass ratio of the modified acrylate monomer, 1-ethyl-3-methylimidazolium tetrafluoroboric acid, sodium octane sulfonate and photoinitiator added to the adhesive is adhesive: modified acrylate monomer: 1-ethyl-3-methylimidazolium tetrafluoroboric acid: sodium octane sulfonate: photoinitiator = 100:18:7:1:4; the photoinitiator is (2,4,6-trimethylbenzoyl) diphenylphosphine oxide; after the addition is completed, stirring is continued for 30 minutes to obtain a UV viscosity-reducing adhesive, and the UV viscosity-reducing adhesive is coated on the surface of the polyolefin film after corona pretreatment, and the coating wet film thickness is 50 μm; after the solvent is completely evaporated, the UV viscosity-reducing protective film is obtained.

[0034] Comparative Example 1

[0035] A method for preparing a polyurethane type UV viscosity-reducing protective film as a comparison, the preparation steps comprising:

[0036] (1) In a nitrogen atmosphere, hydroxy-terminated polybutadiene, ethyl acetate, ethylenediamine, dibutyltin dilaurate and hydroquinone are mixed in a reaction kettle, and the mixture is heated to 60±3°C in a water bath, and then kept warm and stirred. During the stirring process, isophorone diisocyanate is added to the mixture. After the addition is completed, the mixture is kept at a constant temperature of 60±3°C in a nitrogen atmosphere and stirred for 2 hours. Then, 1,4-butanediol is added. After the addition is completed, the mixture is kept at a constant temperature of 60±3°C in a nitrogen atmosphere and stirred for 2 hours. ℃ constant temperature stirring for 3h to obtain an adhesive; wherein the terminal hydroxyl polybutadiene, ethyl acetate, ethylenediamine, dibutyltin dilaurate, hydroquinone, isophorone diisocyanate and 1,4-butanediol are calculated in parts by weight: 10 parts of terminal hydroxyl polybutadiene, 28 parts of ethyl acetate, 0.6 parts of ethylenediamine; 0.007 parts of dibutyltin dilaurate, 0.08 parts of hydroquinone, 3 parts of isophorone diisocyanate, and 2 parts of 1,4-butanediol;

[0037] (2) Mix hydroxyethyl acrylate, methyltetrahydrophthalic anhydride and maleic anhydride uniformly, then heat to 90±2° C. and keep warm, stir for 10 min after reaching the temperature, then add triethylamine under stirring, continue to stir at 90±2° C. for 30 min after the addition is completed, then add epoxidized soybean oil, continue to stir at 90±2° C. for 50 min after the addition is completed, to obtain a modified acrylic ester monomer; wherein the hydroxyethyl acrylate, methyltetrahydrophthalic anhydride, maleic anhydride, triethylamine and epoxidized soybean oil are calculated in parts by weight: 100 parts of hydroxyethyl acrylate, 39 parts of methyltetrahydrophthalic anhydride, 47 parts of maleic anhydride, 3 parts of triethylamine, and 110 parts of epoxidized soybean oil;

[0038] (3) Stirring the adhesive, and then adding the modified acrylate monomer, 1-ethyl-3-methylimidazolium tetrafluoroboric acid, sodium octane sulfonate and photoinitiator to the adhesive under stirring, the mass ratio of the modified acrylate monomer, 1-ethyl-3-methylimidazolium tetrafluoroboric acid, sodium octane sulfonate and photoinitiator added to the adhesive is adhesive: modified acrylate monomer: 1-ethyl-3-methylimidazolium tetrafluoroboric acid: sodium octane sulfonate: photoinitiator = 100:17:7:0.9:3; the photoinitiator is (2,4,6-trimethylbenzoyl) diphenylphosphine oxide; after the addition is completed, stirring is continued for 30 minutes to obtain a UV viscosity-reducing adhesive, and the UV viscosity-reducing adhesive is coated on the surface of the polyolefin film after corona pretreatment, and the coating wet film thickness is 50 μm; after the solvent is completely evaporated, the UV viscosity-reducing protective film of this comparative example is obtained.

[0039] Comparative Example 2

[0040] A method for preparing a polyurethane type UV viscosity-reducing protective film as a comparison, the preparation steps comprising:

[0041] (1) In a nitrogen atmosphere, hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate and hydroquinone are mixed in a reaction kettle, and the mixture is heated to 60±3° C. in a water bath, and stirred after reaching the temperature. During the stirring process, isophorone diisocyanate is added to the mixture, and after the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 2 h in a nitrogen atmosphere, and then 1,4-butanediol is added. After the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 3 h in a nitrogen atmosphere to obtain an adhesive. Agent; wherein the hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate, hydroquinone, isophorone diisocyanate and 1,4-butanediol are calculated in parts by weight: 10 parts of hydroxy-terminated polybutadiene, 28 parts of ethyl acetate, 3 parts of 2-chloro-4,6-diphenyl-1,3,5-triazine, 0.6 parts of ethylenediamine; 0.007 parts of dibutyltin dilaurate, 0.08 parts of hydroquinone, 3 parts of isophorone diisocyanate, and 2 parts of 1,4-butanediol;

[0042] (2) Mix hydroxyethyl acrylate, methyltetrahydrophthalic anhydride and maleic anhydride uniformly, then heat to 90±2° C. and keep warm, stir for 10 min after reaching the temperature, then add triethylamine under stirring, and continue stirring at 90±2° C. for 80 min after the addition is completed, to obtain the modified acrylic ester monomer described in this comparative example; wherein the hydroxyethyl acrylate, methyltetrahydrophthalic anhydride, maleic anhydride and triethylamine are calculated in parts by weight: 100 parts of hydroxyethyl acrylate, 39 parts of methyltetrahydrophthalic anhydride, 47 parts of maleic anhydride, and 3 parts of triethylamine;

[0043] (3) Stirring the adhesive, and then adding the modified acrylate monomer, 1-ethyl-3-methylimidazolium tetrafluoroboric acid, sodium octane sulfonate and photoinitiator to the adhesive under stirring, the mass ratio of the modified acrylate monomer, 1-ethyl-3-methylimidazolium tetrafluoroboric acid, sodium octane sulfonate and photoinitiator added to the adhesive is adhesive: modified acrylate monomer: 1-ethyl-3-methylimidazolium tetrafluoroboric acid: sodium octane sulfonate: photoinitiator = 100:17:7:0.9:3; the photoinitiator is (2,4,6-trimethylbenzoyl) diphenylphosphine oxide; after the addition is completed, stirring is continued for 30 minutes to obtain a UV viscosity-reducing adhesive, and the UV viscosity-reducing adhesive is coated on the surface of the polyolefin film after corona pretreatment, and the coating wet film thickness is 50 μm; after the solvent is completely evaporated, the UV viscosity-reducing protective film of this comparative example is obtained.

[0044] Comparative Example 3

[0045] A method for preparing a polyurethane type UV viscosity-reducing protective film as a comparison, the preparation steps comprising:

[0046] (1) In a nitrogen atmosphere, hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate and hydroquinone are mixed in a reaction kettle, and the mixture is heated to 60±3° C. in a water bath, and stirred after reaching the temperature. During the stirring process, isophorone diisocyanate is added to the mixture, and after the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 2 h in a nitrogen atmosphere, and then 1,4-butanediol is added. After the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. for 3 h in a nitrogen atmosphere to obtain an adhesive. Agent; wherein the hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate, hydroquinone, isophorone diisocyanate and 1,4-butanediol are calculated in parts by weight: 10 parts of hydroxy-terminated polybutadiene, 28 parts of ethyl acetate, 3 parts of 2-chloro-4,6-diphenyl-1,3,5-triazine, 0.6 parts of ethylenediamine; 0.007 parts of dibutyltin dilaurate, 0.08 parts of hydroquinone, 3 parts of isophorone diisocyanate, and 2 parts of 1,4-butanediol;

[0047] (2) Mix hydroxyethyl acrylate, methyltetrahydrophthalic anhydride and maleic anhydride uniformly, then heat to 90±2° C. and keep warm, stir for 10 min after reaching the temperature, then add triethylamine under stirring, continue to stir at 90±2° C. for 30 min after the addition is completed, then add epoxidized soybean oil, continue to stir at 90±2° C. for 50 min after the addition is completed, to obtain a modified acrylic ester monomer; wherein the hydroxyethyl acrylate, methyltetrahydrophthalic anhydride, maleic anhydride, triethylamine and epoxidized soybean oil are calculated in parts by weight: 100 parts of hydroxyethyl acrylate, 39 parts of methyltetrahydrophthalic anhydride, 47 parts of maleic anhydride, 3 parts of triethylamine, and 110 parts of epoxidized soybean oil;

[0048] (3) Stirring the adhesive, and then adding the modified acrylate monomer, sodium octane sulfonate and photoinitiator to the adhesive under stirring, wherein the mass ratio of the modified acrylate monomer, sodium octane sulfonate and photoinitiator added to the adhesive is adhesive: modified acrylate monomer: sodium octane sulfonate: photoinitiator = 100:17:0.9:3; the photoinitiator is (2,4,6-trimethylbenzoyl) diphenylphosphine oxide; after the addition is completed, stirring is continued for 30 minutes to obtain a UV viscosity-reducing adhesive, and the UV viscosity-reducing adhesive is coated on the surface of the polyolefin film after corona pretreatment, and the coating wet film thickness is 50 μm; after the solvent is completely evaporated, the UV viscosity-reducing protective film of this comparative example is obtained.

[0049] Example 5

[0050] According to the requirements of standard GB / T 2792-2014, the 180° peel strength values ​​of the UV anti-viscosity protective films prepared by the methods described in the above embodiments and comparative examples before and after UV irradiation were tested respectively. The test sample width was 25 mm, the length was 200 mm, and the stretching rate was set to 300 mm / min. The results are shown in Table 1.

[0051] Table 1

[0052] Experimental Group 180° peel strength before UV irradiation (N / 25mm) 180° peel strength after UV irradiation (N / 25mm) Example 1 18.8 0.26 Example 2 19.1 0.23 Example 3 19.2 0.21 Example 4 19.0 0.23 Comparative Example 1 18.1 0.74 Comparative Example 2 18.3 1.08 Comparative Example 3 18.6 0.95

[0053] As can be seen from Table 1, the UV viscosity-reducing adhesive prepared by the method of the present invention has a good viscosity-reducing effect, is easy to peel off after viscosity reduction, and is convenient to operate. And the adhesion performance before UV irradiation is good, the wafer can be well fixed, and the use effect is excellent. The present invention modifies the terminal hydroxyl polybutadiene by 2-chloro-4,6-diphenyl-1,3,5-triazine, and makes it easier to undergo a cross-linking reaction under the action of the photoinitiator (2,4,6-trimethylbenzoyl) diphenylphosphine oxide during UV irradiation, thereby increasing the degree of cross-linking, causing the volume of the adhesive layer to shrink, and greatly reducing the bonding points. Then, by treating the acrylate monomer, an epoxy soybean oil group is introduced into the acrylate monomer, the functionality of the monomer is increased, and the number of unsaturated C=C contained in the monomer is increased, further increasing the degree of cross-linking of the viscosity-reducing adhesive under UV irradiation, increasing the cross-linking density, and significantly reducing the peeling strength after irradiation. Finally, by introducing 1-ethyl-3-methylimidazole tetrafluoroboric acid, the cross-linking of the monomer under UV irradiation can be promoted to a certain extent, so that the viscosity-reducing effect is further improved.

[0054] The technical solution provided by the present invention is introduced in detail above. For those skilled in the art, according to the concept of the embodiments of the present invention, there may be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as limiting the present invention.

Claims

1. A method for preparing a polyurethane type UV viscosity-reducing protective film, It is characterized in that The preparation steps include: (1) In a nitrogen atmosphere, hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate and hydroquinone are mixed in a reaction kettle, and the mixture is heated to 60±3° C. in a water bath, and stirred at the temperature after reaching the temperature. During the stirring process, isophorone diisocyanate is added to the mixture, and after the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. in a nitrogen atmosphere for more than 2 hours, and then 1,4-butanediol is added. After the addition is completed, the mixture is stirred at a constant temperature of 60±3° C. in a nitrogen atmosphere for more than 3 hours to obtain an adhesive; (2) Mix hydroxyethyl acrylate, methyltetrahydrophthalic anhydride and maleic anhydride uniformly, then heat to 90±2°C and keep warm, stir for more than 10 minutes after reaching the temperature, then add triethylamine under stirring, continue to stir at 90±2°C for more than 30 minutes after the addition is completed, then add epoxy soybean oil, continue to stir at 90±2°C for 50-60 minutes after the addition is completed, and obtain a modified acrylic ester monomer; (3) stirring the adhesive, and then adding the modified acrylic ester monomer, 1-ethyl-3-methylimidazole tetrafluoroboric acid, sodium octane sulfonate and photoinitiator to the adhesive under stirring, and continuing to stir for more than 30 minutes after the addition is completed to obtain a UV viscosity-reducing adhesive, and coating the UV viscosity-reducing adhesive on the surface of the polyolefin film after corona pretreatment, and after the solvent is completely evaporated, the UV viscosity-reducing protective film is obtained.

2. A method for preparing a polyurethane type UV viscosity-reducing protective film according to claim 1, It is characterized in that In the step (1), the hydroxy-terminated polybutadiene, ethyl acetate, 2-chloro-4,6-diphenyl-1,3,5-triazine, ethylenediamine, dibutyltin dilaurate, hydroquinone, isophorone diisocyanate and 1,4-butanediol are calculated in parts by weight as follows: 10 parts of hydroxy-terminated polybutadiene, 25-30 parts of ethyl acetate, 2-3 parts of 2-chloro-4,6-diphenyl-1,3,5-triazine, 0.4-0.8 parts of ethylenediamine; 0.006-0.008 parts of dibutyltin dilaurate, 0.07-0.09 parts of hydroquinone, 2-4 parts of isophorone diisocyanate, and 1-2 parts of 1,4-butanediol.

3. A method for preparing a polyurethane type UV viscosity-reducing protective film according to claim 1, It is characterized in that In the step (2), the hydroxyethyl acrylate, methyltetrahydrophthalic anhydride, maleic anhydride, triethylamine and epoxidized soybean oil are calculated in parts by weight as follows: 100 parts of hydroxyethyl acrylate, 35-40 parts of methyltetrahydrophthalic anhydride, 46-48 parts of maleic anhydride, 2-3 parts of triethylamine and 100-110 parts of epoxidized soybean oil.

4. The method for preparing a polyurethane type UV viscosity reducing protective film according to claim 1, It is characterized in that In the step (3), the mass ratio of the modified acrylic ester monomer, 1-ethyl-3-methylimidazole tetrafluoroborate, sodium octane sulfonate and photoinitiator added to the adhesive is adhesive: modified acrylic ester monomer: 1-ethyl-3-methylimidazole tetrafluoroborate: sodium octane sulfonate: photoinitiator = 100:15-18:6-7:0.8-1:2-4.

5. The method for preparing a polyurethane type UV viscosity reducing protective film according to claim 1, It is characterized in that In the step (3), the photoinitiator is (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

6. A method for preparing a polyurethane type UV viscosity reducing protective film according to claim 1, It is characterized in that In the step (3), the coating wet film thickness is 50 to 60 μm.