CN100419152C - Environment-friendly pigment printing adhesive and preparation method thereof - Google Patents

Abstract

The invention relates to an environment protecting resin-bonded pigment printing adhesive that is made up according the following steps: adding 0.5-1% polyacrylic acid salt into polyurethane acrylic ester emulsion, adjusting pH value to 7-8 to gain cream, and the viscosity is 30-60Pa.S. The preparation of polyurethane acrylic ester emulsion includes the following steps: gaining end ethenyl polyurethane performed polymer from polyether glycol, isocyanic ester and auxiliary agent, mixing the preformed polymer with acrylic ester monomer and water to make dispersing liquid, irradiating for 30-50 minutes at 1.5-2.5KGy radiation dose. The content of formaldehyde is below 5ppm and APEO below 5ppm in the adhesive. The product is environment protection.

Description

Environment-friendly pigment printing adhesive and preparation method thereof

technical field

The invention relates to an adhesive and a preparation method thereof, in particular to an environment-friendly pigment printing adhesive and a preparation method thereof.

Background technique

Pigment printing is a printing method that uses adhesives to fix pigments that have no affinity and reactivity to fabrics on fabrics. The process is simple, the color is bright, and it has the characteristics of washing resistance, friction resistance and strong fastness. At present, most pigment printing adhesives on the market contain a certain amount of N-hydroxyacrylamide cross-linking monomer, which will release formaldehyde during baking and storage, so that the free formaldehyde content on the fabric cannot meet the requirements of underwear and children's clothing, and the products are exported. restricted. At present, most of the high-quality, environmentally friendly pigment printing adhesives or printing pastes are imported from abroad to meet the domestic and foreign requirements for high-quality textiles and clothing.

In addition, the potential harm of alkylphenol polyoxyethylene ether (APEO) to the environment has been extensively studied and demonstrated, and some European countries have formulated regulations to restrict the production and use of APEO since 1976. The limit of APEO on imported textiles and clothing is now clearly defined: no more than 30ppm.

Therefore, it is a common subject in this field to prepare APEO-free and aldehyde-free environmentally friendly pigment printing adhesives.

Contents of the invention

The invention aims to provide a green and environment-friendly pigment printing adhesive, and the technical problem to be solved is to prepare the main component of the adhesive, polyurethane-acrylate emulsion, by radiation-induced radical emulsion polymerization.

The environmental-friendly pigment printing adhesive referred to in the present invention is a paste with a pH of 7-8 and a viscosity of 30-60 Pa·S composed of polyurethane-acrylate emulsion (PUA) prepared by radiation polymerization and thickener polyacrylate. thing, its parts by weight are as follows:

Polyurethane-acrylate emulsion 100 parts,

Polyacrylate 0.5-1 part.

The physical and chemical parameters of this adhesive are as follows:

Solid content (%) 40%

Tensile strength (MPa) 2.0-4.2MPa

Elongation at break (%) 900-1400%

Dry rubbing fastness (grade) 3-4

Wet rubbing fastness (grade) 3

Washing fastness (grade) 3

After testing, the formaldehyde content is less than 5ppm, and the APEO content is less than 5ppm, which is a green and environmental protection product.

The preparation method of this adhesive is to add 0.5-1% thickener to the polyurethane-acrylate emulsion prepared by radiation polymerization and adjust the pH to 7-8 with ammonia water to obtain a pigment printing adhesive with a viscosity of 30-60 Pa·S. mixture.

The thickener is polyacrylate. Polyacrylate is selected from PTF (Ciba), DM-5265 (Demei), NeopolPFL (Yuhui), HIT (BASF), FS-200A (Star) as a silk enhancer.

The polyurethane-acrylate emulsion (PUA) is prepared by nitrogen-passing and deoxidizing the aqueous dispersion of vinyl-terminated polyurethane (PU) and acrylate monomer, and then irradiating for 30-50 minutes under the radiation dose of 1.5-2.5KGy. of.

Described terminal vinyl polyurethane (PU) and acrylate monomer aqueous dispersion are prepared like this:

Mix PU and acrylate monomer, add 1-5% emulsifier Pingping O, then add 1-2% (weight percentage, based on the mixture, the same below) triethylamine, stir for 2-5 minutes, and then Add 2 to 4 times the amount of water under stirring (1400 rpm to 2500 rpm) to obtain an aqueous dispersion of vinyl-terminated urethane acrylate monomer (abbreviated as aqueous dispersion). The ratio (mass ratio) of PU to acrylate monomer is 1:9-4:6.

If there is acetone in the PU, the water dispersion can be obtained after vacuum removal of the acetone.

The acrylate monomer is selected from one or more mixtures of methyl methacrylate (MMA), butyl acrylate (BA), ethyl acrylate (EA), acrylonitrile (AN), and acrylic acid (AA). monomer.

Described vinyl-terminated polyurethane (PU) is prepared like this:

After vacuum dehydration of polyether polyol, add 40-50% (weight percent, in terms of polyol, the same below) of isocyanate and react at 85-90°C for 1.5-2.5 hours, then add 4-8% dihydroxypropyl The acid, 2-10% functional monomer and 3-6% chain extender are reacted at 70-80°C for 2.5-3.5 hours to obtain PU. If the viscosity is high during the reaction, acetone can be added to dilute to facilitate stirring.

The polyether polyol is a polyether polyol selected from polyoxypropylene glycol, polyoxyethylene glycol, polyoxypropylene-oxyethylene polyol, and polytetrahydrofuran ether polyol.

The isocyanate is selected from toluene diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexane diisocyanate and isophorone diisocyanate.

The functional monomer is selected from one or more monomers selected from -β-hydroxypropyl methacrylate, -β-hydroxyethyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate.

The chain extender is selected from one or more chain extenders in ethylene glycol (EG), diethylene glycol (DEG), butanediol (BDO).

The present invention prepares hydrophilic polyurethane prepolymer (PU) through solution polymerization, and disperses the hydrophilic polyurethane prepolymer/acrylate monomer mixture in water, and utilizes cobalt 60-γ radiation to carry out the original production of vinyl monomers. Free radical emulsion polymerization to prepare water-based polyurethane-acrylate emulsion. In the process of free radical polymerization, PU molecular chains and growing PA molecular chains interpenetrate, cross and entangle, and grafting or crosslinking further increases the compatibility between PU and PA, through the "synergistic effect of IPN " and "forced mutual solubility" are easy to prepare composite PUA emulsions with uniform size and regular shape, thereby improving the performance of pigment printing adhesives such as water resistance, antifouling, moisture permeability, wash fastness and good hand feeling.

Detailed ways

The present invention will be described in detail below by way of examples.

The used main raw material of embodiment is as follows:

Polyether polyol compounds, namely polyoxypropylene diol, polyoxyethylene binary alcohol, polyoxypropylene-oxyethylene polyol, polytetrahydrofuran ether polyol, industrial product, produced by Tianjin Petrochemical No. 3 Plant;

The isocyanate is selected from toluene diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, industrial products, produced by German Bayer company;

Dimethylol propionic acid (DMPA), industrial product, produced in Perstorp, Sweden;

Chain extender: ethylene glycol (EG), diethylene glycol (DEG), butanediol (BDO), chemically pure, produced by Beijing Yili Fine Chemicals Company;

Acetone (AT), industrial products; triethylamine (TEA), chemically pure, produced by Beijing Yili Fine Chemicals Company;

Methyl methacrylate (MMA), butyl acrylate (BA), ethyl acrylate (EA), acrylonitrile (AN), acrylic acid (AA), all of the above are industrial products, produced by Shanghai Gaoqiao Petrochemical No. 3 Plant; β-hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, β-hydroxyethyl methacrylate, are all industrial products, produced by Beijing Dongfang Chemical Factory;

Emulsifier Pingping plus O: industrial grade, produced by Hangzhou Changhe Auxiliary Factory; thickener is anionic polyacrylate, industrial product, provided by Dandong Xingxing Fine Chemical Co., Ltd.; deionized water, self-made.

Cobalt source ( ⁶⁰ Co γ-ray radiation source), about 20,000 Curies, Anhui Bingyan Radiation Chemical Co., Ltd.

Example 1:

The specific synthesis operation method is as follows:

(1) Preparation of aqueous dispersion of vinyl-terminated urethane acrylate monomer

Put ethylene oxide diol polyether diol into the stainless steel reaction kettle, vacuum dehydrate at 100-120°C for 2 hours; then cool down to 80°C, add toluene diisocyanate, keep warm at 85-90°C for 2 hours; cool down to 75°C , adding the hydrophilic monomer dimethylolpropionic acid, chain extender diethylene glycol, and methacrylate-β-hydroxypropyl methacrylate, and insulated for 3 hours. During the reaction, if the viscosity is high, acetone should be added. Then mix with acrylate mixed monomer (1:9), add emulsifier Pingping and O to prepare hydrophilic polyurethane prepolymer/vinyl monomer mixture, cool down to below 30°C, add neutralizing agent triethylamine, Stir and react for 2-5 minutes, add 2 to 4 times the amount of water under high-speed stirring (1400 rpm-2500 rpm) to disperse into an aqueous emulsion, and remove acetone in a vacuum to prepare vinyl-terminated polyurethane acrylate Monomer dispersion in water.

The consumption of each composition in the above-mentioned technological process is as follows:

Polyoxyethylene ether glycol 100g

Toluene diisocyanate 40-50g

Dimethylolpropionic acid 4-8g

Diethylene glycol 3-6g

β-hydroxypropyl methacrylate 2-10g

Acetone 30-60g

Triethylamine 2-4g

Pingpingjia O 1-5g

2-4 times the amount of water

(2), preparation of water-based polyurethane-acrylate (PUA) emulsion

Put the aqueous dispersion of vinyl-terminated urethane acrylate monomer in the irradiation tank and stir, put the irradiation tank in the irradiation field, blow nitrogen N ₂ for 5 minutes, remove the oxygen in the pre-emulsion, and irradiate with the cobalt source Initiation, the radiation dose is 2.0KGy, and the irradiation time is about 30min-50min;

(3), preparation of PUA pigment printing adhesive

Thickener is added to the polyurethane-acrylate emulsion under stirring, the amount added is 0.5-1% by weight, and the pH value is adjusted to 7-8 with ammonia water; the thickened emulsion is a paste with a viscosity of 30-60Pa· S, the water-based acrylate-polyurethane environment-friendly pigment printing adhesive.

Example 2:

The specific synthesis operation method is as follows:

(1) Preparation of aqueous dispersion of vinyl-terminated urethane acrylate monomer

Put polyoxypropylene-oxyethylene polyol in a stainless steel reaction kettle, dehydrate in vacuum at 100-120°C for 2 hours; then cool down to 80°C, add cyclohexane diisocyanate, keep warm at 85-90°C for 2 hours; cool down to 75°C , add hydrophilic monomer dimethylol propionic acid, chain extender diethylene glycol, hydroxypropyl acrylate, keep warm for 3 hours. During the reaction, if the viscosity is high, acetone should be added. Then mix with acrylate mixed monomer (2:8), add emulsifier Pingping and O to prepare hydrophilic polyurethane prepolymer/vinyl monomer mixture, cool down to below 30°C, add neutralizing agent triethylamine, stir React for 2-5 minutes, add 2 to 4 times the amount of water under high-speed stirring (1400 rpm-2500 rpm) to disperse into an aqueous emulsion, and remove acetone in a vacuum to prepare vinyl-terminated polyurethane acrylate Body water dispersion.

The consumption of each composition in the above-mentioned technological process is as follows:

Polyoxypropylene-oxyethylene polyol 100g

Cyclohexane diisocyanate 40-50g

Dimethylolpropionic acid 4-8g

Diethylene glycol 3-6g

Hydroxypropyl Acrylate 2-10g

Acetone 30-60g

Triethylamine 2-4g

Pingpingjia O 1-5g

2-4 times the amount of water

(2), preparation of water-based polyurethane-acrylate (PUA) emulsion

Put the aqueous dispersion of vinyl-terminated urethane acrylate monomer in the irradiation tank and stir, put the irradiation tank in the irradiation field, blow nitrogen N ₂ for 5 minutes, remove the oxygen in the pre-emulsion, and irradiate with the cobalt source Initiation, the radiation dose is 2.0KGy, and the irradiation time is about 30min-50min;

(3), preparation of PUA pigment printing adhesive

Thickener is added to the polyurethane-acrylate emulsion under stirring, the amount added is 0.5-1% by weight, and the pH value is adjusted to 7-8 with ammonia water; the thickened emulsion is a paste with a viscosity of 30-60Pa· S, the water-based acrylate-polyurethane environment-friendly pigment printing adhesive.

Example 3:

The specific synthesis operation method is as follows:

(1) Preparation of aqueous dispersion of vinyl-terminated urethane acrylate monomer

Put polyoxypropylene diol into the stainless steel reaction kettle, vacuum dehydrate at 100-120°C for 2 hours; then cool down to 80°C, add isophorone diisocyanate, keep warm at 85-90°C for 2 hours; cool down to 75°C, Add hydrophilic monomer dimethylolpropionic acid, chain extender butanediol, and hydroxyethyl acrylate, and keep warm for 3 hours. During the reaction, if the viscosity is high, acetone should be added. Then mix with acrylate mixed monomer (3:7), add emulsifier Pingping and O to prepare hydrophilic polyurethane prepolymer/vinyl monomer mixture, cool down to below 30°C, add neutralizing agent triethylamine, stir React for 2-5 minutes, add 2 to 4 times the amount of water under high-speed stirring (1400 rpm-2500 rpm) to disperse into an aqueous emulsion, and remove acetone in a vacuum to prepare vinyl-terminated polyurethane acrylate Body water dispersion.

The consumption of each composition in the above-mentioned technological process is as follows:

Polyoxypropylene diol 100g

Isophorone diisocyanate 40-50g

Dimethylolpropionic acid 4-8g

Butanediol 3-6g

Hydroxyethyl acrylate 2-10g

Acetone 30-60g

Triethylamine 2-4g

Pingpingjia O 1-5g

2-4 times the amount of water

(2), preparation of water-based polyurethane-acrylate (PUA) emulsion

Put the aqueous dispersion of vinyl-terminated urethane acrylate monomer in the irradiation tank and stir, put the irradiation tank in the irradiation field, blow nitrogen N ₂ for 5 minutes, remove the oxygen in the pre-emulsion, and irradiate with the cobalt source Initiation, the radiation dose is 2.0KGy, and the irradiation time is about 30min-50min;

(3), preparation of PUA pigment printing adhesive

Thickener is added to the polyurethane-acrylate emulsion under stirring, the amount added is 0.5-1% by weight, and the pH value is adjusted to 7-8 with ammonia water; the thickened emulsion is a paste with a viscosity of 30-60Pa· S, the water-based acrylate-polyurethane environment-friendly pigment printing adhesive.

Example 4:

The specific synthesis operation method is as follows:

(1) Preparation of aqueous dispersion of vinyl-terminated urethane acrylate monomer

Put polytetrahydrofuran ether polyols into a stainless steel reaction kettle, vacuum dehydrate at 100-120°C for 2 hours; then cool down to 80°C, add 1,6-hexamethylene diisocyanate, and keep warm at 85-90°C for 2 hours; cool down To 75°C, add hydrophilic monomer dimethylolpropionic acid, chain extender ethylene glycol, and β-hydroxyethyl methacrylate, and keep warm for 3 hours. During the reaction, if the viscosity is high, acetone should be added. Then mix with acrylate mixed monomer (4:6), add emulsifier Pingping and O to prepare hydrophilic polyurethane prepolymer/vinyl monomer mixture, cool down to below 30°C, add neutralizing agent triethylamine, stir React for 2-5 minutes, add 2 to 4 times the amount of water under high-speed stirring (1400 rpm-2500 rpm) to disperse into an aqueous emulsion, and remove acetone in a vacuum to prepare vinyl-terminated polyurethane acrylate Body water dispersion.

The consumption of each composition in the above-mentioned technological process is as follows:

Polytetrahydrofuran ether polyol 100g

1,6-Hexamethylene diisocyanate 40-50g

Dimethylolpropionic acid 4-8g

Ethylene glycol 3-6g

β-Hydroxyethyl Methacrylate 2-10g

Acetone 30-60g

Triethylamine 2-4g

Pingpingjia O 1-5g

2-4 times the amount of water

(2), preparation of water-based polyurethane-acrylate (PUA) emulsion

Put the aqueous dispersion of vinyl-terminated urethane acrylate monomer in the irradiation tank and stir, put the irradiation tank in the irradiation field, blow nitrogen N ₂ for 5 minutes, remove the oxygen in the pre-emulsion, and irradiate with the cobalt source Initiation, the radiation dose is 2.0KGy, and the irradiation time is about 30min-50min;

(3), preparation of PUA pigment printing adhesive

Thickener is added to the polyurethane-acrylate emulsion under stirring, the amount added is 0.5-1% by weight, and the pH value is adjusted to 7-8 with ammonia water; the thickened emulsion is a paste with a viscosity of 30-60Pa· S, the water-based acrylate-polyurethane environment-friendly pigment printing adhesive.

Claims (8)

1. environment-protection coating printing adhesive, it is characterized in that: pH7～8, the viscosity be made up of the polyurethane-acrylic ester emulsion and the polyacrylate of radiation polymerization preparation are the paste of 30～60PaS, each composition weight umber is: 100 parts of polyurethane-acrylic ester emulsions, 0.5～1 part of polyacrylate.

2. by the preparation method of the described pigment printing binding agent of claim 1, it is characterized in that: transfer pH7～8 to obtain by the thickener polyacrylate that adds 0.5～1% (w/w) in the polyurethane-acrylic ester emulsion and with ammoniacal liquor.

3. preparation method according to claim 2 is characterized in that: described polyurethane-acrylic ester emulsion be by after the logical nitrogen deoxidation of end-vinyl polyurethane and acrylate monomer aqueous dispersions under 1.5～2.5KGy dosage of radiation condition irradiation 30～50 minutes and making.

4. preparation method according to claim 3, it is characterized in that: described end-vinyl urethane acrylate monomer aqueous dispersions is to mix the back with acrylate monomer by end-vinyl polyurethane to add 1～5% (w/w) emulsifying agent paregal O, the triethylamine that adds 1～2% (w/w) again, stirred 2～5 minutes, the water that adds 2～4 times of amounts then under high-speed stirred obtains, and the mass ratio of end-vinyl polyurethane and acrylate monomer is 1: 9～4: 6.

5. according to claim 3 or 4 described preparation methods, it is characterized in that: described acrylate monomer is selected from one or more mix monomers in methyl methacrylate, butyl acrylate, ethyl acrylate, acrylonitrile, the acrylic acid.

6. according to claim 3 or 4 described preparation methods, it is characterized in that: described end-vinyl polyurethane is to be reacted 1.5～2.5 hours under 85～90 ℃ of conditions by the isocyanates that adds 40～50% (w/w) after the polyether polyol vacuum dehydration, adds the dihydroxypropionic acid, 2～10% function monomer of 4～8% (w/w) and 3～6% chain extender then and reacts 2.5～3.5 hours under 70～80 ℃ of conditions and make;

Described function monomer is selected from a kind of in methacrylic acid-β-hydroxypropyl acrylate, methacrylic acid-beta-hydroxy ethyl ester, hydroxy-ethyl acrylate, the hydroxypropyl acrylate;

Described chain extender is selected from a kind of in ethylene glycol, diglycol, the butanediol.

7. preparation method according to claim 6 is characterized in that: described polyether polyol is selected from a kind of polyether polyol in polypropylene oxide dihydroxylic alcohols, polyethylene glycol oxide dihydroxylic alcohols, polypropylene oxide-ethylene oxide polyalcohol, the PolyTHF ethers polyalcohol.

8. preparation method according to claim 6 is characterized in that: described isocyanates is selected from toluene di-isocyanate(TDI), 1, a kind of isocyanates in 6-hexamethylene diisocyanate, cyclohexane diisocyanate, the isophorone diisocyanate.