A kind of water-based touch resin emulsion and preparation method

Abstract

The present invention relates to an aqueous touch resin emulsion and a preparation method, comprising an aqueous polyurethane resin dispersion, an aqueous polyacrylate emulsion, a wax emulsion, a silicone additive and a curing agent; the aqueous polyurethane resin dispersion comprises deionized water, a polyglycol mixture, dimethylol propionic acid, a diisocyanate mixture, ethylenediamine and 2,2-dimethylol butyric acid; the polyglycol mixture comprises polyester diol, polyether diol and polycaprolactone diol; the diisocyanate mixture comprises hexamethylene diisocyanate, MDI-100 and MDI-50. The prepared aqueous touch resin emulsion is added with an aqueous polyacrylate emulsion, which provides a skin-feeling tactile effect for paper. The aqueous polyacrylate emulsion added to the formula realizes that the coating has adjustable debonding force and hardness, and the designable and adjustable nature of the formula enables the adhesion and hardness of the touch coating to be designed in advance, solving the common problems in the industry such as scratch resistance, wear resistance and anti-adhesion.

Description

Technical Field

[0001] The invention relates to an aqueous touch resin emulsion and a preparation method thereof, belonging to the technical field of resins for art papers. Background Art

[0002] Tactile paper is a kind of artistic paper that is coated with a layer of water-based tactile resin emulsion on the surface of paper through gravure, flexographic printing or air knife coating processes. After dehydration and drying, it can present a special skin or touch feeling on the surface of the paper. Tactile paper is widely used in printing and high-end packaging fields such as tobacco and alcohol gift boxes, gift boxes, jewelry and cosmetics boxes and other artwork decorations due to its unique suede feel, rich colors and texture diversity and selectivity.

[0003] The tactile water-based resin emulsions currently on the market are mainly used in leather and paper coatings. Due to differences in processing technology levels, the tactile paper produced accordingly currently has several major problems and defects:

[0004] 1. Poor adhesion; the surface of the tactile paper has poor color fixation and is easy to fade, and the printing is blurry and weak.

[0005] 2. The surface is easily scratched and dirty; the surface of the tactile paper is easily dirty, and it is easy to leave scratches when rubbed or slightly scratched.

[0006] 3. The hand feel is not strong; the surface of the paper is not delicate and smooth enough, and the suede feel is not good.

[0007] 4. Double-sided adhesion is easy; the surface of the tactile paper is easy to stick and tear after stacking.

[0008] 5. Poor anti-hand sweat effect; easily corroded by hand sweat.

[0009] How to prepare a water-based tactile resin for tactile art paper to enhance the tactile effect and improve the anti-hand sweat effect. Summary of the invention

[0010] In order to improve and solve the above defects, the present invention relates to an aqueous touch resin emulsion, which improves the touch effect and the anti-hand sweat effect.

[0011] To solve the above technical problems, the purpose of the present invention is achieved as follows:

[0012] The present invention relates to an aqueous touch resin emulsion, comprising an aqueous polyurethane resin dispersion, an aqueous polyacrylate emulsion, a wax emulsion, an organosilicon additive and a curing agent;

[0013] The aqueous polyurethane resin dispersion comprises deionized water, a polyglycol mixture, dimethylol propionic acid, a diisocyanate mixture, ethylenediamine and 2,2-dimethylol butyric acid;

[0014] The polyglycol mixture includes polyester diol, polyether diol and polycaprolactone diol;

[0015] The diisocyanate mixture includes hexamethylene diisocyanate, MDI-100 and MDI-50.

[0016] On the basis of the above scheme and as a preferred scheme of the above scheme: in the aqueous polyurethane resin dispersion, the content of deionized water is 8% to 20%, the content of the polyglycol mixture is 45% to 60%, the content of the dihydroxymethylpropionic acid is 3% to 5%, the content of the diisocyanate mixture is 10% to 15%, the content of ethylenediamine is 15% to 30%, and the content of 2,2-dihydroxymethylbutyric acid is 3% to 5%.

[0017] On the basis of the above scheme and as a preferred scheme of the above scheme: the polyglycol mixture comprises polyester diol, polyether diol and polycaprolactone diol in a molar ratio of 8:1:1;

[0018] The hydroxyl value of the polyester diol is 32; the hydroxyl value of the polyether diol is 56.1; and the hydroxyl value of the polycaprolactone diol is 39.

[0019] On the basis of the above scheme and as a preferred scheme of the above scheme: the diisocyanate mixture includes hexamethylene diisocyanate, MDI-100 and MDI-50 in a molar ratio of 6:3:1.

[0020] The present invention also relates to a method for preparing an aqueous touch resin emulsion, including the preparation of an aqueous polyurethane resin dispersion and the preparation of an aqueous touch resin emulsion;

[0021] The preparation of the aqueous polyurethane resin dispersion comprises the following steps:

[0022] 1) Dehydrate the polyglycol mixture under vacuum at 130±5°C for 2-3h, cool it down, fill it with nitrogen and set it aside for later use;

[0023] 2) mixing the dehydrated polyglycol mixture with dimethylolpropionic acid previously dehydrated by molecular sieves until the mixture is clear and transparent;

[0024] 3) slowly adding the diisocyanate mixture to the mixture in step 2) in batches to carry out polymerization reaction to generate a -NCO terminated first prepolymer. During the reaction, the reaction temperature is controlled not to exceed 130° C., the reaction time is set for 3 hours, and the temperature is lowered to 80° C. for standby use after the time is up;

[0025] 4) After the prepolymer is cooled, 10% of the weight is taken out and filled with N2 for standby use. Ethylenediamine is slowly added dropwise to the remaining 90% of the prepolymer for reaction at a rate of 2 drops per second. After the addition is completed, the reaction temperature is controlled to 125°C and the reaction is continued for 2 hours to form a second prepolymer terminated with -NCO;

[0026] 5) adding the first prepolymer set aside in step 4) to the second prepolymer for stirring and dispersion, and adding deionized water to form a prepolymer dispersion;

[0027] 6) adding 2,2-dimethylolbutyric acid (DMBA) dropwise to the prepolymer dispersion, and performing a chain extension reaction at a speed of 200-2000 rpm for 1-3 hours to finally obtain a solvent-free waterborne polyurethane dispersion having a solid content of 30%;

[0028] The preparation of the aqueous touch resin emulsion comprises the following steps:

[0029] A. First add deionized water into the stirring and dispersing kettle, start the motor, set the speed to 200-500rpm, add the waterborne polyurethane resin dispersion in sequence under stirring, and stir and disperse for 20 minutes;

[0030] B. When the time is up, slowly add the polyacrylate emulsion in order while stirring. After adding the materials, adjust the speed to 500-1000rpm and stir and disperse for 20 minutes;

[0031] C. When the time is up, add 1040 wax emulsion, silicone additive, and togo825 leveling agent in sequence under stirring. After adding the materials, adjust the speed to 200-500rpm and stir and disperse for 20 minutes;

[0032] D. After the time is up, filter the material using a 100-mesh stainless steel mesh to obtain a water-based touch resin emulsion;

[0033] E. The obtained water-based touch resin emulsion is mixed and added with curing agent on site before being used on the machine. The mixing process is to stir and disperse at a speed of 200-500 rpm for 20 minutes.

[0034] On the basis of the above scheme and as a preferred scheme of the above scheme: the aqueous polyacrylate emulsion is obtained by the following method:

[0035] 10% to 20% (meth)acrylate, 10% to 20% vinyl monomer, 5% to 10% active functional monomer, 1% to 3% emulsifier and the balance of tap water are added to the reaction kettle in order, the speed is set to 1000-1500rpm, the time is 30-40 minutes, and the dispersion and emulsification are carried out;

[0036] After the time is up, 0.1% to 0.5% buffer is added to the reactor, and the temperature is slowly raised to 65±5°C under stirring, and 0.1% to 0.5% initiator is slowly added dropwise. After the addition is completed, the temperature is controlled not to exceed 80°C, and the reaction is kept warm for 2-3 hours, and the temperature is lowered and discharged to obtain a polyacrylate emulsion;

[0037] The initiator can be prepared in advance as an aqueous solution, with a drop adding rate of 3-5 drops per minute, and the addition should be completed within 1-2 hours.

[0038] On the basis of the above scheme and as a preferred scheme of the above scheme: the (meth) acrylic acid ester is one or a mixture of butyl acrylate, methyl methacrylate, ethyl acrylate, butyl methacrylate and isooctyl acrylate;

[0039] The vinyl monomer is one or a mixture of styrene, methyl styrene and vinyl hexanoate;

[0040] The active functional monomer is one or a mixture of hydroxyethyl methacrylate, hydroxypropyl acrylate and glycidyl acrylate.

[0041] On the basis of the above scheme and as a preferred scheme of the above scheme: the emulsifier is preferably a non-ionic emulsifier polyoxyethylene alkyl ether; the buffer is preferably ammonia water or ammonium bicarbonate or a mixture of the two; the initiator is preferably benzoyl peroxide or cumene hydroperoxide or a mixture of the two.

[0042] On the basis of the above scheme and as a preferred scheme of the above scheme: the curing agent includes one or more of aziridine, modified isocyanate emulsion and modified amine curing agent.

[0043] On the basis of the above scheme and as a preferred scheme of the above scheme: the 1040 wax emulsion is a commercially available product of Shanghai Dingming Chemical;

[0044] The organosilicon additive is a water-based feel agent produced by Guangzhou Silok Polymer, and the selected models are 3200, 3300 and 9155;

[0045] The 825 leveling agent is a conventional product sold on the market by Togo Company.

[0046] The beneficial effects of the present invention are as follows: the aqueous touch resin emulsion and the preparation method thereof involved in the present invention, the prepared aqueous touch resin emulsion adds a homemade aqueous polyacrylate emulsion, provides a specific skin-feeling tactile effect for paper, and the differentiation of the skin-feeling tactile effect can also be adjusted. The homemade aqueous polyacrylate emulsion added to the formula realizes that the coating's adhesion and hardness can be adjusted, and the designable and adjustable nature of the formula enables the adhesion and hardness of the touch coating to be designed in advance, perfectly solving the industry common problems such as scratch resistance, wear resistance, and anti-adhesion. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 is a process flow chart of the method for preparing the tactile art paper involved in Example 5;

[0048] Figure 2 is a process flow chart of the method for preparing the tactile art paper involved in Example 6;

[0049] Figure 3 is a process flow chart of the method for preparing the tactile art paper involved in Example 7;

[0050] Figure 4 Here is a photo of the anti-scratch test results for comparison;

[0051] Figure 5 is a photo of the anti-scratch test result of the tactile art paper prepared in Example 5;

[0052] Figure 6 yes Figure 4 A magnified image of

[0053] Figure 7 yes Figure 5 A magnified image of

[0054] Figure 8 Here is a comparative photo of the alcohol wipe test results;

[0055] Fig. 9 is a photograph of the alcohol-wipe resistance test result of the tactile art paper prepared in Example 5;

[0056] Fig.10 Here are the photos of the anti-manipulation test results for comparison;

[0057] Fig.11 This is a photograph of the anti-tactic test results of the tactile art paper prepared in Example 5. DETAILED DESCRIPTION

[0058] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments.

[0059] The present invention relates to an aqueous touch resin emulsion, comprising an aqueous polyurethane resin dispersion, an aqueous polyacrylate emulsion, a wax emulsion, an organosilicon additive and a curing agent; the aqueous polyurethane resin dispersion comprises deionized water, a polyglycol mixture, dimethylol propionic acid, a diisocyanate mixture, ethylenediamine and 2,2-dimethylol butyric acid; the polyglycol mixture comprises polyester diol, polyether diol and polycaprolactone diol; the diisocyanate mixture comprises hexamethylene diisocyanate, MDI-100 and MDI-50.

[0060] The water-based touch resin emulsion involved in the present invention is mainly composed of water-based polyurethane resin dispersion, and water-based polyacrylate emulsion is used to improve adhesion and anti-adhesion, and silicone additives are used to improve the touch effect and improve the anti-hand sweat performance, and then a curing agent is used to have a better color fixing effect, and the color will not fade when wiped with alcohol. The water-based touch resin emulsion for tactile paper prepared in this way is suitable for tactile paper gravure, flexographic printing and air knife coating processes.

[0061] Furthermore, in the aqueous polyurethane resin dispersion, the content of deionized water is 8% to 20%, the content of the polyglycol mixture is 45% to 60%, the content of dihydroxymethylpropionic acid is 3% to 5%, the content of the diisocyanate mixture is 10% to 15%, the content of ethylenediamine is 15% to 30%, and the content of 2,2-dihydroxymethylbutyric acid is 3% to 5%.

[0062] Furthermore, the polyglycol mixture comprises polyester diol, polyether diol and polycaprolactone diol in a molar ratio of 8:1:1; the hydroxyl value of the polyester diol is 32; the hydroxyl value of the polyether diol is 56.1, and the hydroxyl value of the polycaprolactone diol is 39. The diisocyanate mixture comprises hexamethylene diisocyanate, MDI-100 and MDI-50 in a molar ratio of 6:3:1.

[0063] The preparation method of the aqueous touch resin emulsion comprises the following steps:

[0064] A. First add deionized water into the stirring and dispersing kettle, start the motor, set the speed to 200-500rpm, add the aqueous polyurethane resin dispersion in sequence under stirring, and stir and disperse for 20 minutes.

[0065] B. When the time is up, slowly add the polyacrylate emulsion in sequence while stirring. After adding the materials, adjust the speed to 500-1000rpm and stir and disperse for 20 minutes.

[0066] C. When the time is up, add 1040 wax emulsion, silicone additive and togo825 leveling agent in sequence under stirring. After adding the materials, adjust the speed to 200-500rpm and stir and disperse for 20 minutes.

[0067] D. After the time is up, use a 100-mesh stainless steel mesh to filter the material to obtain a water-based touch resin emulsion.

[0068] E. The obtained water-based touch resin emulsion is mixed and added with a curing agent on site before being used on the machine. The mixing process is to stir and disperse at a rotation speed of 200 to 500 rpm for 20 minutes.

[0069] In the preparation process of the water-based touch resin emulsion, the curing agent includes one or more of aziridine, modified isocyanate emulsion and modified amine curing agent, which is used to play a curing and cross-linking role to improve the gloss and uniformity of the touch paper surface, and at the same time give the touch paper excellent tensile strength and folding resistance.

[0070] Furthermore, the 1040 wax emulsion is a commercial product of Shanghai Dingming Chemical, which is used to adjust the smoothness of the resin coating. The silicone additive is a water-based hand feel agent produced by Guangzhou Siluoke Polymer, and the selected models are 3200, 3300 and 9155. It has good compatibility with the system, can adjust the touch paper skin effect, and can cross-link with the system latex at high temperature during the paper coating and drying process, improve the high temperature resistance of the ink, and improve the subsequent printing and anti-hot stamping oxidation ability of the super-sensitive paper. The 825 leveling agent is a conventional product sold by Togo Company.

[0071] The preparation of the aqueous polyurethane resin dispersion comprises the following steps:

[0072] 1) Dehydrate the polyglycol mixture under vacuum at 130±5°C for 2-3h, cool it down, fill it with nitrogen and set it aside for later use.

[0073] 2) Mixing the dehydrated polyglycol mixture with dimethylolpropionic acid previously dehydrated by molecular sieves until the mixture is clear and transparent.

[0074] 3) The diisocyanate mixture is slowly added to the mixture in step 2) in batches to carry out polymerization reaction to generate a -NCO-terminated first prepolymer. During the reaction, the reaction temperature is controlled not to exceed 130° C. The reaction is timed for 3 hours. After the time is up, the temperature is lowered to 80° C. for use.

[0075] 4) After the prepolymer is cooled, 10% of the weight is taken out and filled with N2 for standby use; ethylenediamine is slowly added dropwise to the remaining 90% of the prepolymer for reaction at a rate of 2 drops per second. After the addition is completed, the reaction temperature is controlled to 125°C and the reaction is continued for 2 hours to form a second prepolymer terminated with ~NCO.

[0076] 5) The first prepolymer set aside in step 4) is added to the second prepolymer for stirring and dispersion, and deionized water is added to form a prepolymer dispersion.

[0077] 6) adding 2,2-dihydroxymethylbutyric acid (DMBA) dropwise to the prepolymer dispersion, and performing a chain extension reaction at a rotation speed of 200-2000 rpm for 1-3 hours, and finally obtaining a solvent-free waterborne polyurethane dispersion with a solid content of 30%.

[0078] The aqueous polyacrylate emulsion is obtained by the following method:

[0079] 10% to 20% (meth)acrylate, 10% to 20% vinyl monomer, 5% to 10% active functional monomer, 1% to 3% emulsifier and the balance of tap water are added to the reaction kettle in order, the speed is set to 1000 to 1500 rpm, the time is 30 to 40 minutes, and the dispersion and emulsification are carried out;

[0080] After the time is up, 0.1% to 0.5% buffer is added to the reactor, and the temperature is slowly raised to 65±5°C under stirring, and 0.1% to 0.5% initiator is slowly added dropwise. After the addition is completed, the temperature is controlled not to exceed 80°C, and the reaction is kept warm for 2 to 3 hours, and the temperature is lowered and the material is discharged to obtain a polyacrylate emulsion;

[0081] The initiator can be prepared in advance as an aqueous solution, with the dripping speed being 3 to 5 drops per minute, and the addition should be completed within 1 to 2 hours.

[0082] Furthermore, in the preparation process of the aqueous polyacrylate emulsion, the (meth)acrylate is one or a mixture of butyl acrylate, methyl methacrylate, ethyl acrylate, butyl methacrylate and isooctyl acrylate.

[0083] The vinyl monomer is one or a mixture of styrene, methyl styrene and vinyl hexanoate.

[0084] The active functional monomer is one or a mixture of hydroxyethyl methacrylate, hydroxypropyl acrylate and glycidyl acrylate.

[0085] The emulsifier is preferably a nonionic emulsifier polyoxyethylene alkyl ether (commercially available brand OP-10); the buffer is preferably ammonia water or ammonium bicarbonate or a mixture of the two; the initiator is preferably benzoyl peroxide or cumene hydroperoxide or a mixture of the two.

[0086] Example 1

[0087] The aqueous touch resin emulsion involved in this embodiment includes 20 parts by mass of deionized water, 60 parts by mass of aqueous polyurethane resin dispersion, 14 parts by mass of aqueous polyacrylate emulsion, 2 parts by mass of wax emulsion, 2 parts by mass of silicone additive, and 2 parts by mass of leveling agent. After the emulsion is prepared according to the preparation process, 0.5 parts by mass of curing agent is added before use on the machine and stirred evenly.

[0088] In the aqueous polyurethane resin dispersion used in this embodiment, the content of the polyglycol mixture is 50%, the content of dimethylol propionic acid is 5%, the content of the diisocyanate mixture is 10%, the content of ethylenediamine is 20%, the content of 2,2-dimethylolbutyric acid is 5%, and the content of deionized water is 10%.

[0089] In this embodiment, the aqueous polyacrylate emulsion is obtained by the following method:

[0090] 10% (meth)acrylate, 20% vinyl monomer, 10% active functional monomer, 3% emulsifier and the rest of tap water are added to a reactor in sequence, and the speed is set to 1000rpm for 40 minutes to disperse and emulsify; after the time is up, 0.5% buffer is added to the reactor, and the temperature is slowly raised to 65±5°C under stirring, and 0.1% initiator is slowly added dropwise. After the addition is completed, the temperature is controlled not to exceed 80°C, and the reaction is kept warm for 2 hours, and the temperature is lowered and discharged to obtain a polyacrylate emulsion; the initiator can be prepared in advance as an aqueous solution, and the addition speed is 3 to 5 drops per minute, and the addition is completed within 1 to 2 hours.

[0091] Furthermore, the (meth)acrylate is a mixture of butyl acrylate and methyl methacrylate in a molar ratio of 1:1; the vinyl monomer is methyl styrene; the active functional monomer is a mixture of hydroxyethyl methacrylate, hydroxypropyl acrylate and glycidyl acrylate in a molar ratio of 1:1:1. The emulsifier is preferably a nonionic emulsifier polyoxyethylene alkyl ether; the buffer is preferably ammonia water; the initiator is a mixture of benzoyl peroxide or cumene hydroperoxide in a molar ratio of 1:1.

[0092] The preparation of the aqueous touch resin emulsion comprises the following steps:

[0093] A. First add deionized water into the stirring and dispersing kettle, start the motor, set the speed to 200rpm, add the waterborne polyurethane resin dispersion in sequence under stirring, and stir and disperse for 20 minutes;

[0094] B. When the time is up, slowly add the polyacrylate emulsion in order while stirring. After adding the materials, adjust the speed to 500 rpm and stir and disperse for 20 minutes;

[0095] C. When the time is up, add 1040 wax emulsion, silicone additive, and togo825 leveling agent in sequence under stirring. After adding the materials, adjust the speed to 500 rpm and stir and disperse for 20 minutes;

[0096] D. After the time is up, filter the material using a 100-mesh stainless steel mesh to obtain a water-based touch resin emulsion;

[0097] E. The obtained water-based touch resin emulsion is mixed and added with a curing agent on site before being used on the machine. The mixing process is a rotation speed of 200 rpm and stirring and dispersing for 20 minutes.

[0098] Furthermore, the curing agent includes aziridine. The 1040 wax emulsion is a commercial product of Shanghai Dingming Chemical; the silicone additive is a water-based hand feel agent produced by Guangzhou Siluoke High Molecular Polymer, and the selected models are 3200, 3300 and 9155. The model selected in this embodiment is 3200; the 825 leveling agent is a conventional product commercially available from Togo Company.

[0099] Example 2

[0100] The aqueous touch resin emulsion involved in this embodiment includes 10 parts by mass of deionized water, 70 parts by mass of aqueous polyurethane resin dispersion, 10 parts by mass of aqueous polyacrylate emulsion, 3 parts by mass of wax emulsion, 3 parts by mass of silicone additive, and 4 parts by mass of leveling agent. After the emulsion is prepared according to the preparation process, 1.0 part by mass of curing agent is added before use on the machine and stirred evenly.

[0101] In the aqueous polyurethane resin dispersion used in this embodiment, the content of deionized water is 10%, the content of the polyglycol mixture is 50%, the content of dimethylol propionic acid is 3%, the content of the diisocyanate mixture is 10%, the content of ethylenediamine is 24%, and the content of 2,2-dimethylolbutyric acid is 3%.

[0102] The aqueous polyacrylate emulsion involved in this embodiment is obtained by the following method:

[0103] 15% (meth)acrylate, 15% vinyl monomer, 8% active functional monomer, 2% emulsifier and the rest of tap water are added to a reactor in sequence, and the rotation speed is set to 1200rpm for 35 minutes to disperse and emulsify; after the time is up, 0.3% buffer is added to the reactor, and the temperature is slowly raised to 65±5°C under stirring, and 0.3% initiator is slowly added dropwise. After the addition is completed, the temperature is controlled not to exceed 80°C, and the reaction is kept warm for 2.5 hours, and the temperature is lowered and discharged to obtain a polyacrylate emulsion; the initiator can be prepared in advance in an aqueous solution, and the addition speed is 3 to 5 drops per minute, and the addition is completed within 1 to 2 hours.

[0104] Furthermore, the (meth)acrylate is methyl methacrylate; the vinyl monomer is a mixture of styrene, methyl styrene and vinyl hexanoate in a molar ratio of 1:1:1; the active functional monomer is hydroxyethyl methacrylate. The emulsifier is preferably a nonionic emulsifier polyoxyethylene alkyl ether; the buffer is ammonium bicarbonate; and the initiator is preferably benzoyl peroxide.

[0105] The preparation of the aqueous touch resin emulsion described in this embodiment includes the following steps:

[0106] A. First add deionized water into the stirring and dispersing kettle, start the motor, set the speed to 300rpm, add the waterborne polyurethane resin dispersion in sequence under stirring, and stir and disperse for 20 minutes;

[0107] B. When the time is up, slowly add the polyacrylate emulsion in order while stirring. After adding the materials, adjust the speed to 800 rpm and stir and disperse for 20 minutes;

[0108] C. When the time is up, add 1040 wax emulsion, silicone additive, and togo825 leveling agent in sequence under stirring. After adding the materials, adjust the speed to 400 rpm and stir and disperse for 20 minutes;

[0109] D. After the time is up, filter the material using a 100-mesh stainless steel mesh to obtain a water-based touch resin emulsion;

[0110] E. The obtained water-based touch resin emulsion is mixed and added with a curing agent on site before being used on the machine. The mixing process is a rotation speed of 300 rpm and stirring and dispersing for 20 minutes.

[0111] Furthermore, the curing agent includes aziridine. The 1040 wax emulsion is a commercial product of Shanghai Dingming Chemical; the silicone additive is a water-based hand feel agent produced by Guangzhou Siluoke High Molecular Polymer, and the selected models are 3200, 3300 and 9155. In this embodiment, 3300 is selected; the 825 leveling agent is a conventional product commercially available from Togo Company.

[0112] Example 3

[0113] The aqueous touch resin emulsion involved in this embodiment includes 15 parts by mass of deionized water, 65 parts by mass of aqueous polyurethane resin dispersion, 15 parts by mass of aqueous polyacrylate emulsion, 2 parts by mass of wax emulsion, 1 part by mass of silicone additive, and 2 parts by mass of leveling agent. After the emulsion is prepared according to the preparation process, 2.0 parts by mass of curing agent is added before use on the machine and stirred evenly.

[0114] In the aqueous polyurethane resin dispersion used in this embodiment, the content of deionized water is 12%, the content of the polyglycol mixture is 55%, the content of dihydroxymethylpropionic acid is 3%, the content of the diisocyanate mixture is 11%, the content of ethylenediamine is 15%, and the content of 2,2-dihydroxymethylbutyric acid is 4%.

[0115] The aqueous polyacrylate emulsion involved in this embodiment is obtained by the following method:

[0116] 18% (meth)acrylate, 17% vinyl monomer, 9% active functional monomer, 2% emulsifier and the rest of tap water are added to a reactor in sequence, and the rotation speed is set to 1300 rpm for 38 minutes for dispersion and emulsification. After the time is up, 0.4% buffer is added to the reactor, and the temperature is slowly raised to 65±5° C. under stirring, and 0.2% initiator is slowly added dropwise. After the addition is completed, the temperature is controlled not to exceed 80° C., and the reaction is kept warm for 2.5 hours, and the temperature is lowered and discharged to obtain a polyacrylate emulsion. The initiator can be prepared in advance in an aqueous solution, and the addition speed is 3 to 5 drops per minute, and the addition is completed within 1 to 2 hours.

[0117] Furthermore, the (meth)acrylate is a mixture of ethyl acrylate, butyl methacrylate and isooctyl acrylate in a molar ratio of 1:1:1; the vinyl monomer is methyl styrene; the active functional monomer is hydroxypropyl acrylate. The emulsifier is preferably a nonionic emulsifier polyoxyethylene alkyl ether; the buffer is a mixture of ammonia water or ammonium bicarbonate in a mass ratio of 1:1; and the initiator is cumene hydroperoxide.

[0118] The preparation of the aqueous touch resin emulsion involved in this embodiment includes the following steps:

[0119] A. First add deionized water into the stirring and dispersing kettle, start the motor, set the speed to 400rpm, add the waterborne polyurethane resin dispersion in sequence under stirring, and stir and disperse for 20 minutes;

[0120] B. When the time is up, slowly add the polyacrylate emulsion in order while stirring. After adding the materials, adjust the speed to 900 rpm and stir and disperse for 20 minutes;

[0121] C. When the time is up, add 1040 wax emulsion, silicone additive, and togo825 leveling agent in sequence under stirring. After adding the materials, adjust the speed to 400 rpm and stir and disperse for 20 minutes;

[0122] D. After the time is up, filter the material using a 100-mesh stainless steel mesh to obtain a water-based touch resin emulsion;

[0123] E. The obtained water-based touch resin emulsion was mixed and added with curing agent on site before being used on the machine. The speed of the mixing process was 300 rpm and the stirring and dispersion was carried out for 20 minutes.

[0124] Furthermore, the curing agent includes aziridine, modified isocyanate emulsion and modified amine curing agent mixed in a mass ratio of 1:1:1. The 1040 wax emulsion is a commercially available product of Shanghai Dingming Chemical; the silicone additive is a water-based feel agent produced by Guangzhou Siluoke Polymer, the selected models are 3200, 3300 and 9155, and the naming is selected as 9155 in this implementation; the 825 leveling agent is a conventional commercially available product of Togo Company.

[0125] Example 4

[0126] The aqueous touch resin emulsion involved in this embodiment includes 12 parts of deionized water, 68 parts of aqueous polyurethane resin dispersion, 14 parts of aqueous polyacrylate emulsion, 3 parts of wax emulsion, 1 part of silicone additive, and 2 parts of leveling agent. After the emulsion is prepared according to the preparation process, 1.5 parts of curing agent is added before use on the machine and stirred evenly.

[0127] In the aqueous polyurethane resin dispersion used in this embodiment, the content of deionized water is 11%, the content of the polyglycol mixture is 55%, the content of dimethylol propionic acid is 3%, the content of the diisocyanate mixture is 10%, the content of ethylenediamine is 18%, and the content of 2,2-dimethylolbutyric acid is 3%.

[0128] The aqueous polyacrylate emulsion involved in this embodiment is obtained by the following method:

[0129] 20% (meth)acrylate, 10% vinyl monomer, 5% active functional monomer, 1% emulsifier and the rest of tap water are added to a reactor in sequence, and the rotation speed is set to 1500rpm for 30 minutes to disperse and emulsify; after the time is up, 0.1% buffer is added to the reactor, and the temperature is slowly raised to 65±5°C under stirring, and 0.5% initiator is slowly added dropwise. After the addition is completed, the temperature is controlled not to exceed 80°C, and the reaction is kept warm for 3 hours, and the temperature is lowered and discharged to obtain a polyacrylate emulsion; the initiator can be prepared in advance in an aqueous solution, and the addition speed is 3 to 5 drops per minute, and the addition is completed within 1 to 2 hours.

[0130] Furthermore, the (meth)acrylate is a mixture of butyl acrylate, methyl methacrylate, ethyl acrylate, butyl methacrylate and isooctyl acrylate in a molar ratio of 1:1:1:1:1; the vinyl monomer is vinyl hexanoate; the active functional monomer is a mixture of hydroxyethyl methacrylate, hydroxypropyl acrylate and glycidyl acrylate in a molar ratio of 1:1:1. The emulsifier is preferably a nonionic emulsifier polyoxyethylene alkyl ether; the buffer is ammonium bicarbonate; the initiator is preferably a mixture of benzoyl peroxide and cumene hydroperoxide in a molar ratio of 1:2.

[0131] The preparation of the aqueous touch resin emulsion comprises the following steps:

[0132] A. Add deionized water into the stirring and dispersing kettle, start the motor, set the speed to 500 rpm, add the waterborne polyurethane resin dispersion in sequence under stirring, and stir and disperse for 20 minutes;

[0133] B. When the time is up, slowly add the polyacrylate emulsion in order while stirring. After adding the materials, adjust the speed to 1000 rpm and stir and disperse for 20 minutes;

[0134] C. When the time is up, add 1040 wax emulsion, silicone additive, and togo825 leveling agent in sequence under stirring. After adding the materials, adjust the speed to 500 rpm and stir and disperse for 20 minutes;

[0135] D. After the time is up, filter the material using a 100-mesh stainless steel mesh to obtain a water-based touch resin emulsion;

[0136] E. The obtained water-based touch resin emulsion is mixed and added with curing agent on site before being used on the machine. The speed of the mixing process is 00rpm, and the stirring and dispersion is carried out for 20 minutes.

[0137] Furthermore, the curing agent includes aziridine. The 1040 wax emulsion is a commercial product of Shanghai Dingming Chemical; the silicone additive is a water-based feel agent produced by Guangzhou Siluoke High Molecular Polymer, and the selected models are 3200, 3300 and 9155. In this embodiment, 3200 is selected; the 825 leveling agent is a conventional commercial product of Togo Company.

[0138] The present invention relates to a method for preparing tactile art paper, comprising the following steps:

[0139] S1. Selection of base paper: The base paper has a smoothness greater than 10s, a wax stick value greater than 15, and an ash content less than 25%.

[0140] S2. Preparation of water-based touch resin emulsion.

[0141] S3. Coating: coating the water-based touch resin emulsion on the surface of the base paper by gravure, flexographic printing and air knife coating process, and drying and curing at 100° C. to 150° C. for 5 to 10 minutes to obtain the tactile art paper.

[0142] In step S1, because the production process of base paper of different colors is different in paper mills, this technical solution divides the base paper into three categories of white, black and other colored papers to illustrate the technical index requirements for base paper selection when processing tactile paper. See Table 1, Table 2 and Table 3 for details.

[0143] Key indicators for selecting backing paper:

[0144] 1. Smoothness

[0145] The base paper with smoothness>10s is preferred. The surface of the base paper with high smoothness is smoother, which makes the bonding adhesion between the base color coating and the surface touch coating better, thereby improving the bonding strength. After processing with the touch oil topcoat, a better suede touch can be obtained, and the hand feel is more delicate and smooth.

[0146] 2. Wax stick value (surface strength)

[0147] The base paper with wax stick value>15 is preferred. The paper with surface strength meeting the standard is selected to help avoid the situation that the surface of the tactile paper is not printed with true gold stamping or is blurred and hollow during the subsequent processing.

[0148] 3. Paper ash content

[0149] The base paper with ash content less than 25% is preferred. Ash content refers to the content of inorganic impurities in the pulp raw material during papermaking. The ash content index of the paper will affect its whiteness, glossiness, smoothness, surface strength, folding times, and transverse tearing. The base paper with lower ash content has fewer impurities, which means better paper quality. It can have better ink absorption effect when printing ink and color correction, and the printing effect and feel of the produced tactile paper can be guaranteed.

[0150] Table 1 Technical standards for white base paper

[0151]

[0152]

[0153] Table 2 Technical standards for black base paper

[0154]

[0155]

[0156] Table 3 Technical standards for colored base paper

[0157]

[0158]

[0159] The different choices of base paper and the demand for tactile paper products affect the process flow of tactile paper. For this reason, this technical solution lists the following three process flows according to the different base paper and the demand for tactile paper products. The specific process parameters are: rubber roller printing pressure: 50 pounds per square inch, vehicle speed 40m-50m, oven temperature 70℃-100℃.

[0160] Example 5

[0161] The method for preparing a tactile art paper involved in this embodiment is to select a white base paper, a single-sided tactile paper, and a surface with textures. The production process is as follows Figure 1 As shown, the specific process is as follows: flexographic printing of water-based ink twice (the first group uses a 145-mesh screen, and the second group uses a 175-mesh screen) - surface polishing - printing of primer once (150-mesh screen) - printing of water-based touch resin emulsion once (150-mesh screen) - sizing on the reverse side (150-mesh) - embossing - cutting according to the size required by the customer. The water-based touch resin emulsion used is the water-based touch resin emulsion involved in Example 1.

[0162] Example 6

[0163] The method for preparing a tactile art paper involved in this embodiment uses a black base paper, and the double-sided tactile paper has no texture. Figure 2 As shown, the specific process is as follows: flexographic printing twice with water ink (the first group of 145 mesh screens, the second group of 175 mesh screens) - printing once with water ink (150 mesh screens) - polishing on both sides - printing twice with water-based touch resin emulsion (150 mesh) - gluing on both sides - cutting according to the size required by the customer. And the process of double-sided touch, front and back is the same. The water-based touch resin emulsion used is the water-based touch resin emulsion involved in Example 2.

[0164] Example 7

[0165] The method for preparing a tactile art paper involved in this embodiment is to select a colored base paper with a printed tactile feel on the surface. Figure 3 As shown, the specific process is as follows: base paper polishing - printing ink once (150 mesh screen) - flexographic printing ink twice (145 mesh screen, 175 mesh screen) - surface printing (using 150 mesh screen) - surface polishing - printing water-based touch resin emulsion once (using 150 mesh screen) - reverse sizing (using 150 mesh screen) - cutting according to customer requirements. The water-based touch resin emulsion used is the water-based touch resin emulsion involved in Example 3.

[0166] Example 8

[0167] The method for preparing a tactile art paper involved in this embodiment is to select a white base paper, a single-sided tactile paper, and a surface with textures. The production process is as follows Figure 1 As shown, the specific process is as follows: flexographic printing of water-based ink twice (the first group uses a 145-mesh screen, and the second group uses a 175-mesh screen) - surface polishing - printing of primer once (150-mesh screen) - printing of water-based touch resin emulsion once (150-mesh screen) - sizing on the reverse side (150-mesh) - embossing - cutting according to the size required by the customer. The water-based touch resin emulsion used is the water-based touch resin emulsion involved in Example 4.

[0168] Example 9

[0169] The method for preparing a tactile art paper involved in this embodiment uses a black base paper, and the double-sided tactile paper has no texture. Figure 2 As shown, the specific process is as follows: flexographic printing twice with water ink (the first group of 145 mesh screens, the second group of 175 mesh screens) - printing once with water ink (150 mesh screens) - polishing on both sides - printing twice with water-based touch resin emulsion (150 mesh) - gluing on both sides - cutting according to the size required by the customer. And the process of double-sided touch, front and back is the same. The water-based touch resin emulsion used is the water-based touch resin emulsion involved in Example 4.

[0170] Flexo ink: refers to the use of 145 mesh screen and 175 mesh screen to apply the bottom color ink to the base paper. It has controllable color matching and can meet the customized needs of customers. In addition, the surface of the paper is supported by the bottom ink, providing reliable support for the subsequent color restoration of printing.

[0171] Surface polishing: refers to using a steel roller to apply a certain amount of pressure to the paper surface, which can make the original high-thickness surface of the base paper more flat and compact, which is beneficial to improve the surface smoothness, ensure the uniformity of the primer ink on the paper surface, and provide better adhesion for the surface of the paper.

[0172] Printing water-based touch resin emulsion: refers to the process of coating the bottom ink layer with a water-based touch resin emulsion coating on the surface of the paper. The water-based touch resin emulsion is a self-blended technical solution that can have different tactile effects. The coating not only has good wear and scratch resistance, but also prevents alcohol from wiping and does not fade.

[0173] Embossing / printing: Leaving corresponding textures or patterns on the paper surface by applying pressure to the pattern roller or pattern plate.

[0174] Back side sizing: Since the paper is processed on one side, starch latex needs to be applied to the back side of the paper to make the weight of both sides of the paper consistent.

[0175] The tactile art papers prepared in Examples 5, 6 and 7 were compared with commercially available conventional tactile papers, as shown in Table 4.

[0176] Table 4 Test results of the embodiments and comparison ratios

[0177]

[0178] See the specific test photos for comparison. Figures 4 to 11 , wherein the invention examples in the picture are all tactile art papers prepared in Example 5. Figure 4 and Figure 5 , Figure 6 and Figure 7 It can be seen from the comparative results that the tactile art paper prepared in Example 5 has no traces on the surface. Figure 8 and Fig. 9 The comparison results show that the tactile art paper prepared in Example 5 has no traces on the surface. Fig.10 and Fig.11 It can be seen from the comparison results that the tactile art paper prepared in Example 5 has no traces on the surface.

[0179] The preferred specific embodiments of the present invention are described in detail above. It should be understood that a person skilled in the art can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solution that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A water-based touch resin emulsion, characterized in that: Including water-based polyurethane resin dispersion, water-based polyacrylate emulsion, wax emulsion, silicone additive and curing agent; The aqueous polyurethane resin dispersion comprises deionized water, a polyglycol mixture, dimethylol propionic acid, a diisocyanate mixture, ethylenediamine and 2,2-dimethylol butyric acid; The polyglycol mixture includes polyester diol, polyether diol and polycaprolactone diol; The diisocyanate mixture includes hexamethylene diisocyanate, MDI-100 and MDI-50.

2. The aqueous touch resin emulsion according to claim 1, characterized in that: In the aqueous polyurethane resin dispersion, the content of deionized water is 8% to 20%, the content of the polyglycol mixture is 45% to 60%, the content of dihydroxymethylpropionic acid is 3% to 5%, the content of the diisocyanate mixture is 10% to 15%, the content of ethylenediamine is 15% to 30%, and the content of 2,2-dihydroxymethylbutyric acid is 3% to 5%.

3. The aqueous touch resin emulsion according to claim 1, characterized in that: The polyglycol mixture comprises polyester glycol, polyether glycol and polycaprolactone glycol in a molar ratio of 8:1:1; The hydroxyl value of the polyester diol is 32; the hydroxyl value of the polyether diol is 56.1; and the hydroxyl value of the polycaprolactone diol is 39.

4. The aqueous touch resin emulsion according to claim 1, characterized in that: The diisocyanate mixture includes hexamethylene diisocyanate, MDI-100 and MDI-50 in a molar ratio of 6:3:

1.

5. A method for preparing an aqueous touch resin emulsion, characterized in that: Including the preparation of waterborne polyurethane resin dispersion and waterborne touch resin emulsion; The preparation of the aqueous polyurethane resin dispersion comprises the following steps: 1) Dehydrate the polyglycol mixture under vacuum at 130±5°C for 2-3h, cool it down, fill it with nitrogen and set it aside for later use; 2) mixing the dehydrated polyglycol mixture with dimethylolpropionic acid previously dehydrated by molecular sieves until the mixture is clear and transparent; 3) slowly adding the diisocyanate mixture to the mixture in step 2) in batches to carry out polymerization reaction to generate a -NCO terminated first prepolymer. During the reaction, the reaction temperature is controlled not to exceed 130° C., the reaction time is set for 3 hours, and the temperature is lowered to 80° C. for standby use after the time is up; 4) After the prepolymer is cooled, 10% of the weight is taken out and filled with N2 for standby use. Ethylenediamine is slowly added dropwise to the remaining 90% of the prepolymer for reaction at a rate of 2 drops per second. After the addition is completed, the reaction temperature is controlled to 125°C and the reaction is continued for 2 hours to form a second prepolymer terminated with -NCO; 5) adding the first prepolymer set aside in step 4) to the second prepolymer for stirring and dispersion, and adding deionized water to form a prepolymer dispersion; 6) adding 2,2-dimethylolbutyric acid (DMBA) dropwise to the prepolymer dispersion, and performing a chain extension reaction at a speed of 200 to 2000 rpm for 1 to 3 hours, and finally obtaining a solvent-free waterborne polyurethane dispersion having a solid content of 30%; The preparation of the aqueous touch resin emulsion comprises the following steps: A. First add deionized water into the stirring and dispersing kettle, start the motor, set the speed to 200-500rpm, add the waterborne polyurethane resin dispersion in sequence under stirring, and stir and disperse for 20 minutes; B. When the time is up, slowly add the polyacrylate emulsion in order while stirring. After adding the materials, adjust the speed to 500-1000rpm and stir and disperse for 20 minutes; C. When the time is up, add 1040 wax emulsion, silicone additive, and togo825 leveling agent in sequence under stirring. After adding the materials, adjust the speed to 200-500rpm and stir and disperse for 20 minutes; D. After the time is up, filter the material using a 100-mesh stainless steel mesh to obtain a water-based touch resin emulsion; E. The obtained water-based touch resin emulsion is mixed and added with a curing agent on site before being used on the machine. The mixing process is to stir and disperse at a rotation speed of 200 to 500 rpm for 20 minutes.

6. The method for preparing an aqueous touch resin emulsion according to claim 5, characterized in that: The aqueous polyacrylate emulsion is obtained by the following method: 10% to 20% of (meth)acrylate, 10% to 20% of vinyl monomer, 5% to 10% of active functional monomer, 1% to 3% of emulsifier and the balance of tap water are added to the reaction kettle in order, the speed is set to 1000 to 1500 rpm, the time is 30 to 40 minutes, and dispersion and emulsification are performed; After the time is up, 0.1% to 0.5% buffer is added to the reactor, and the temperature is slowly raised to 65±5°C under stirring, and 0.1% to 0.5% initiator is slowly added dropwise. After the addition is completed, the temperature is controlled not to exceed 80°C, and the reaction is kept warm for 2 to 3 hours, and the temperature is lowered and the material is discharged to obtain a polyacrylate emulsion; The initiator can be prepared in advance as an aqueous solution, with the dripping speed being 3 to 5 drops per minute, and the addition should be completed within 1 to 2 hours.

7. The method for preparing an aqueous touch resin emulsion according to claim 6, characterized in that: The (meth)acrylate is one or a mixture of butyl acrylate, methyl methacrylate, ethyl acrylate, butyl methacrylate and isooctyl acrylate; The vinyl monomer is one or a mixture of styrene, methyl styrene and vinyl hexanoate; The active functional monomer is one or a mixture of hydroxyethyl methacrylate, hydroxypropyl acrylate and glycidyl acrylate.

8. The method for preparing an aqueous touch resin emulsion according to claim 6, characterized in that: The emulsifier is preferably a nonionic emulsifier polyoxyethylene alkyl ether; the buffer is preferably ammonia water or ammonium bicarbonate or a mixture of the two; the initiator is preferably benzoyl peroxide or cumene hydroperoxide or a mixture of the two.

9. The method for preparing an aqueous touch resin emulsion according to claim 5, characterized in that: The curing agent includes one or more of aziridine, modified isocyanate emulsion and modified amine curing agent.

10. The method for preparing a water-based touch resin emulsion according to claim 5, wherein the 1040 wax emulsion is a commercially available product of Shanghai Dingming Chemical; The organosilicon additive is a water-based feel agent produced by Guangzhou Silok Polymer, and the selected models are 3200, 3300 and 9155; The 825 leveling agent is a conventional product sold on the market by Togo Company.

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