CN101967255A - Waterborne resin for plastic film coating and preparation method thereof - Google Patents
Waterborne resin for plastic film coating and preparation method thereof Download PDFInfo
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- CN101967255A CN101967255A CN 201010291366 CN201010291366A CN101967255A CN 101967255 A CN101967255 A CN 101967255A CN 201010291366 CN201010291366 CN 201010291366 CN 201010291366 A CN201010291366 A CN 201010291366A CN 101967255 A CN101967255 A CN 101967255A
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Abstract
The invention discloses waterborne resin for plastic film coating and a preparation method thereof. The method comprises the following steps: adding 60 to 70% of waterborne polyacrylate latex, 10 to 20% of waterborne aliphatic polyurethane resin latex, 5 to 15% of waterborne polyester resin latex, 3 to 5% of active group-containing compound, waterborne propionic resin latex and polyurethane latex into a reactor, heating to 40+/-1 DEG C and reacting for 2 h to obtain latex homogeneous body with blue fluorescence; adding the linear polyester resin latex and the active group-containing compound into the reactor, heating with stirring to 40+/-1 DEG C, reacting with mixing for 2 h to obtain latex homogeneous body with blue fluorescence; performing ternary blending; and blending and winding the active group-containing compound through linear polymer to obtain a latex interpenetrating polymer network (LIPN) with reaction activity. The waterborne resin has relatively high attachment fastness on the surface of a plastic film and is favorable for releasing water in a polymer system so as to increase drying speed.
Description
Technical field
The present invention relates to a kind of water-base resin, be specifically related to a kind of water-base resin that the plastics film coating uses and preparation method thereof that is used for.
Background technology
In recent years, along with the raising of plastics film production technology, it is increasing in the shared ratio of packaging industry, and the resin demand that is used for the plastics film coating also constantly increases thereupon.Because aspects such as environmental protection, safety, health, the consumption of water-base resin is in continuous expansion.Because a little less than the solvation very of water for plastics film, and the resin solidification film-forming temperature is subjected to the restriction of plastics film easy deformation under comparatively high temps, Zhi Bei water-base resin is as the plastics film coating resin according to a conventional method, the more conventional solvent type resin of attachment fastness is low, influences its widespread use at packaging industry.
The water-base resin that is used for the plastics film coating is to use as the base resin of the low-melting ink vehicle of water color ink and aqueous binders greatly, and the two is normally coated on the plastics film with printing press and sizing applicator.Different with the water-base resin that general plastics coating is used, in order to guarantee the production efficiency of machine, not to be only required in good attachment fastness is arranged on the plastics film, and require resin system that good water release property is arranged, have rate of drying faster.
Because the singularity of plastics film itself, single resinous type is difficult to satisfy this requirement, now mostly adopts resin modified method to realize this purpose.In the patent CN1155638C (patent No.: adopt epoxy-modified acrylic acid-polyurethane to obtain Resins, epoxy, acrylic resin and urethane resin interpenetrating polymer networks ZL01115056.4), this emulsion has three resinoid advantages separately, minimum film-forming temperature is low, water-resistant coating, hardness, sticking power solvent resistance high abrasion resistance can be used for water color ink; In the patent CN100400590C (patent No.: ZL200510029694.2), adopt nano-oxide to obtain the high-solid lower-viscosity resin with the hydroxyl acrylic resin blending technology, because nanoparticle is evenly distributed in the acrylic resin coating with the primary particle state, interaction between particle and acrylate copolymer is strong, as plastic coating higher sticking power is arranged, show that rub resistance and scoring resistance improve more than 30%; In the patent CN100540623C (patent No.: adopt water nano composite polyester resin and watersoluble closed polyisocyanates under room temperature or heating condition, to carry out the two-pack cross-linking and curing reaction ZL200610026686.7), the plastic coating wear resistance that obtains can improve 20-70%, shows that sticking power improves a lot.
Summary of the invention
The object of the present invention is to provide that a kind of technology is easy, practical, the plastics film coating use resin of excellent performance and plastics film coating use process for preparing resins.
The present invention adopts aqueous polyacrylamide acid resin emulsion, aqueous polyurethane resin emulsion and three kinds of dissimilar resin emulsions of aqueous polyester resin emulsion to carry out tertiary blending, mutual winding between linear resin in the blend process, formed emulsion and interted polymer network (LIPN), and be wrapped in the compound that grafting in the network contains active group by blend.
Water-base resin system provided by the present invention, outside having kept the high advantage of aqueous polyacrylamide acid resin emulsion attachment fastness and physical strength, the also modification by aqueous polyurethane resin emulsion and aqueous polyester resin emulsion, overcome the shortcoming that film forming is more crisp, water-fast and resistance to acids and bases is relatively poor, rate of drying is slow, possessed simultaneously anti-ly rub, damage resistant, water-fast and acid and alkali-resistance, the fast characteristics of ridity, and, further improve attachment fastness by the plastics film surface active groups generation chemical reaction of active group compound after with corona.
Technical scheme provided by the invention is: prepare a kind of water-base resin that the plastics film coating is used that is used for, it consists of: water polyacrylic acid emulsion 60～70%, water-based aliphatic polyurethane resin emulsion 10～20%, aqueous polyester resin emulsion 5～15%, contain active group compound 3～5%, composite assistant 2～3%.Used composite assistant comprises compositions such as flow agent, defoamer, wetting agent, rheology modifier.Aqueous polyacrylamide acid resin emulsion molecular weight is 150000～200000, and solid content is 39～48%, and viscosity is 100～300mPaS, PH=7.5～8.5; The aqueous polyurethane resin emulsion molecular weight is 15000～25000, and solid content is 31～38%, and viscosity is 50～100mPaS, PH=7.5～8.5; Aqueous polyester resin emulsion molecular weight is 10000～20000, and solid content is 25～32%, and viscosity is 60～100mPaS, PH=7.5～8.5; The active group compound is a polyether amine compound, molecular weight 500～2000, the total amine of primary amine value＞95%.Above-mentioned said composite assistant preferably includes compositions such as emulsifying agent, wetting agent, flow agent, defoamer, rheology modifier.
Plastics film coating use process for preparing resins of the present invention, it is composition by the plastics film coating use resin of the invention described above, by aqueous polyacrylamide acid resin emulsion, aqueous polyester resin emulsion and aqueous polyurethane resin emulsion tertiary blending, and twine to insert the compound that contains active group by blend, it consists of (weight percent):
Aqueous polyacrylamide acid resin emulsion 60～70%
Aqueous polyurethane resin emulsion 10～20%
Aqueous polyester resin emulsion 5～15%
Contain active group compound 3～5%
Composite assistant 2～3%;
At first water-based propionic acid resin emulsion and polyaminoester emulsion are joined in the reactor, under agitation composite assistant is slowly added, be warming up to 40 ± 1 ℃, hybrid reaction is 2 hours under this temperature, forms the emulsion homogeneous body that has blue-fluorescence; Add linear polyester resin emulsion and the compound that contains active group again in reactor, under agitation be warming up to 40 ± 1 ℃, hybrid reaction is 2 hours under this temperature, forms the emulsion homogeneous body that has blue-fluorescence.
Technical essential of the present invention is: three kinds of polymer emulsions are carried out blend in two steps, after the formation binary IPN of two kinds of polymer emulsions through twining inserted polymer network, carry out next step blend again and twine grafting, the method of this progressively blend makes polymer molecular structure clear, molecular weight distribution is narrower, product performance are stable, show that minimum film-forming temperature (MFFT:4-8 ℃) and second-order transition temperature (Tg:6-10 ℃) scope are narrower, and 20min is not stratified in the 3000rmp centrifugation.
Above-mentioned resin aqueous emulsion is applied in the plastics film coating, as prepare water color ink and aqueous binder, make the T type stripping strength of water-based compound oil ink on the BOPP film from conventional water-base resin≤1.5N/15mm brings up to 〉=2.5N/15mm, make stripping strength that water-based plastic film laminated adhesive is used for BOPP/PET film compound tense bring up to 3.5N/15mm from the 2.0N/15mm of conventional resin, attachment fastness is significantly improved, and has reached the attachment fastness requirement of solvent type ink and tackiness agent.Major technique and performance index:
Outward appearance: white is to little yellow band blue-fluorescence emulsion
Solid content: 45% ± 5%
PH value: 7.7-8.5
Viscosity: 100-300mPa.s
Acid number: 40-60mg KOH/g
Sticking power (plastics film behind the corona, surface tension＞38dyn/cm):
Water-based composite ink (BOPP film): T type stripping strength 〉=2.5N/15mm
Aqueous laminating adhesive (BOPP/PET): T type stripping strength 〉=3.5N/15mm
Embodiment:
The present invention is further elaborated below by embodiment:
Embodiment 1:
In the present embodiment, propionic acid resin emulsion specification is a molecular weight 150000 ± 10%, solid content 48 ± 1%, viscosity 300 ± 20mPa.s, PH=7.5-8.5; The specification of polyaminoester emulsion is a molecular weight 20000 ± 10%, solid content 31 ± 1%, viscosity 50 ± 10mPa.s, PH=7.5-8.5; The specification of polyester emulsion is a molecular weight 10000 ± 10%, solid content 32 ± 1%, viscosity 100 ± 10mPa.s, PH=7.5-8.5; Polyetheramine molecular weight 500 ± 10%.
Water-based propionic acid resin emulsion 60g and polyaminoester emulsion 20g are joined in the reactor, under agitation slowly add composite assistant 3g, be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence; Add linear polyester resin 12g and polyetheramine 5g again, under agitation be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence.
The gained water-base resin mixed obtaining water color ink with aqueous color paste, gained used for water color ink color development rod is coated in through corona rear surface tension force reaches on the BOPP film of 38 dyne/cm, it is 2.1N/15mm that its stripping strength is surveyed in dry back.
With gained water-base resin and tackifier, strengthening agent uniform mixing, obtain water-based plastic film laminated adhesive, it is pressed 3g/m
2(butt tackiness agent) is coated on BOPP and the PET film, and it is compound to carry out dry type after the drying, in 50～55 ℃ of kilns, place 48h after, its stripping strength is 3.4N/15mm.
Embodiment 2
In the present embodiment, propionic acid resin emulsion specification is a molecular weight 200000 ± 10%, solid content 39 ± 1%, viscosity 100 ± 20mPa.s, PH=7.5-8.5; The specification of polyaminoester emulsion is a molecular weight 15000 ± 10%, solid content 38 ± 1%, viscosity 100 ± 10mPa.s, PH=7.5-8.5; The specification of polyester emulsion is a molecular weight 20000 ± 10%, solid content 25 ± 1%, viscosity 60 ± 10mPa.s, PH=7.5-8.5; Polyetheramine molecular weight 900 ± 10%.
Water-based propionic acid resin emulsion 70g and polyaminoester emulsion 15g are joined in the reactor, under agitation slowly add composite assistant 2g, be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence; Add linear polyester resin 10g and polyetheramine 3g again, under agitation be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence.
The gained water-base resin mixed obtaining water color ink with aqueous color paste, gained used for water color ink color development rod is coated in through corona rear surface tension force reaches on the BOPP film of 38 dyne/cm, it is 2.4N/15mm that its stripping strength is surveyed in dry back.
With gained water-base resin and tackifier, strengthening agent uniform mixing, obtain water-based plastic film laminated adhesive, it is pressed 3g/m
2(butt tackiness agent) is coated on BOPP and the PET film, and it is compound to carry out dry type after the drying, in 50～55 ℃ of kilns, place 48h after, its stripping strength is 3.2N/15mm.
Embodiment 3
In the present embodiment, propionic acid resin emulsion specification is a molecular weight 200000 ± 10%, solid content 42 ± 1%, viscosity 360 ± 20mPa.s, PH=7.5-8.5; The specification of polyaminoester emulsion is a molecular weight 20000 ± 10%, solid content 34 ± 1%, viscosity 50 ± 10mPa.s, PH=7.5-8.5; The specification of polyester emulsion is a molecular weight 10000 ± 10%, solid content 25 ± 1%, viscosity 80 ± 10mPa.s, PH=7.5-8.5; Polyetheramine molecular weight 1500 ± 10%.
Water-based propionic acid resin emulsion 65g and polyaminoester emulsion 20g are joined in the reactor, under agitation slowly add composite assistant 3g, be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence; Add linear polyester resin 8g and polyetheramine 4g again, under agitation be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence.
The gained water-base resin mixed obtaining water color ink with aqueous color paste, gained used for water color ink color development rod is coated in through corona rear surface tension force reaches on the BOPP film of 38 dyne/cm, it is 2.6N/15mm that its stripping strength is surveyed in dry back.
With gained water-base resin and tackifier, strengthening agent uniform mixing, obtain water-based plastic film laminated adhesive, it is pressed 3g/m
2(butt tackiness agent) is coated on BOPP and the PET film, and it is compound to carry out dry type after the drying, in 50～55 ℃ of kilns, place 48h after, its stripping strength is 3.5N/15mm.
Embodiment 4
In the present embodiment, propionic acid resin emulsion specification is a molecular weight 150000 ± 10%, solid content 45 ± 1%, viscosity 240 ± 20mPa.s, PH=7.5-8.5; The specification of polyaminoester emulsion is a molecular weight 15000 ± 10%, solid content 36 ± 1%, viscosity 70 ± 10mPa.s, PH=7.5-8.5; The specification of polyester emulsion is a molecular weight 18000 ± 10%, solid content 30 ± 1%, viscosity 80 ± 10mPa.s, PH=7.5-8.5; Polyetheramine molecular weight 2000 ± 10%.
Water-based propionic acid resin emulsion 70g and polyaminoester emulsion 10g are joined in the reactor, under agitation slowly add composite assistant 2g, be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence; Add linear polyester resin 15g and polyetheramine 3g again, under agitation be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence.
The gained water-base resin mixed obtaining water color ink with aqueous color paste, gained used for water color ink color development rod is coated in through corona rear surface tension force reaches on the BOPP film of 38 dyne/cm, it is 2.2N/15mm that its stripping strength is surveyed in dry back.
With gained water-base resin and tackifier, strengthening agent uniform mixing, obtain water-based plastic film laminated adhesive, it is pressed 3g/m
2(butt tackiness agent) is coated on BOPP and the PET film, and it is compound to carry out dry type after the drying, in 50～55 ℃ of kilns, place 48h after, its stripping strength is 3.1N/15mm.
Comparative example 1
In the present embodiment, propionic acid resin emulsion specification is a molecular weight 200000 ± 10%, solid content 42 ± 1%, viscosity 360 ± 20mPa.s, PH=7.5-8.5; The specification of polyaminoester emulsion is a molecular weight 20000 ± 10%, solid content 34 ± 1%, viscosity 50 ± 10mPa.s, PH=7.5-8.5; The specification of polyester emulsion is a molecular weight 10000 ± 10%, solid content 25 ± 1%, viscosity 80 ± 10mPa.s, PH=7.5-8.5.
Water-based propionic acid resin emulsion 70g and polyaminoester emulsion 15g are joined in the reactor, under agitation slowly add composite assistant 2g, be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence; Add linear polyester resin emulsion 10g again, under agitation be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence.
The gained water-base resin mixed obtaining water color ink with aqueous color paste, gained used for water color ink color development rod is coated in through corona rear surface tension force reaches on the BOPP film of 38 dyne/cm, it is 1.8N/15mm that its stripping strength is surveyed in dry back.
With gained water-base resin and tackifier, strengthening agent uniform mixing, obtain water-based plastic film laminated adhesive, it is pressed 3g/m
2(butt tackiness agent) is coated on BOPP and the PET film, and it is compound to carry out dry type after the drying, in 50～55 ℃ of kilns, place 48h after, its stripping strength is 2.1N/15mm.
Comparative example 2
In the present embodiment, propionic acid resin emulsion specification is a molecular weight 200000 ± 10%, solid content 42 ± 1%, viscosity 360 ± 20mPa.s, PH=7.5-8.5; The specification of polyaminoester emulsion is a molecular weight 20000 ± 10%, solid content 34 ± 1%, viscosity 50 ± 10mPa.s, PH=7.5-8.5; Polyetheramine molecular weight 1500 ± 10%.
Water-based propionic acid resin emulsion 70g and polyaminoester emulsion 15 are joined in the reactor, under agitation slowly add composite assistant 2g, be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence; Add polyetheramine 5g again, under agitation be warming up to 40 ± 1 ℃, under this temperature, mixed 2 hours, form the emulsion homogeneous body that has blue-fluorescence.
The gained water-base resin mixed obtaining water color ink with aqueous color paste, gained used for water color ink color development rod is coated in through corona rear surface tension force reaches on the BOPP film of 38 dyne/cm, it is 1.6N/15mm that its stripping strength is surveyed in dry back.
With gained water-base resin and tackifier, strengthening agent uniform mixing, obtain water-based plastic film laminated adhesive, it is pressed 3g/m
2(butt tackiness agent) is coated on BOPP and the PET film, and it is compound to carry out dry type after the drying, in 50～55 ℃ of kilns, place 48h after, its stripping strength is 2.4N/15mm.
Claims (3)
1. one kind is used for the water-base resin that the plastics film coating is used, by aqueous polyacrylamide acid resin emulsion, aqueous polyester resin emulsion and aqueous polyurethane resin emulsion tertiary blending, and twine to insert the compound that contains active group by blend, it is formed weight percent and is:
Aqueous polyacrylamide acid resin emulsion 60～70%
Aqueous polyurethane resin emulsion 10～20%
Aqueous polyester resin emulsion 5～15%
Contain active group compound 3～5%
Composite assistant 2～3%;
Aqueous polyacrylamide acid resin emulsion molecular weight is 150000～200000, and solid content is 39～48%, and viscosity is 100～300mPaS, PH=7.5～8.5; Aqueous polyurethane resin emulsion is at molecular weight 15000～25000, and solid content is 31～38%, and viscosity is 50～100mPaS, PH=7.5～8.5; Aqueous polyester resin emulsion molecular weight is 10000～20000, and solid content is 25～32%, and viscosity is 60～100mPaS, PH=7.5～8.5; The active group compound is a polyether amine compound, molecular weight 500～2000, the total amine of primary amine value＞95%.
2. the composite assistant in the claim 1 comprises compositions such as emulsifying agent, wetting agent, flow agent, defoamer, rheology modifier.
3. plastics film coating use process for preparing resins, by aqueous polyacrylamide acid resin emulsion, aqueous polyester resin emulsion and aqueous polyurethane resin emulsion tertiary blending, and twine to insert the compound that contains active group by blend, it is formed weight percent and is:
Aqueous polyacrylamide acid resin emulsion 60～70%
Aqueous polyurethane resin emulsion 10～20%
Aqueous polyester resin emulsion 5～15%
Contain active group compound 3～5%
Composite assistant 2～3%;
At first water-based propionic acid resin emulsion and polyaminoester emulsion are joined in the reactor, under agitation composite assistant is slowly added, be warming up to 40 ± 1 ℃, hybrid reaction is 2 hours under this temperature, forms the emulsion homogeneous body that has blue-fluorescence; Add linear polyester resin emulsion and the compound that contains active group again in reactor, under agitation be warming up to 40 ± 1 ℃, hybrid reaction is 2 hours under this temperature, forms the emulsion homogeneous body that has blue-fluorescence.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102134466A (en) * | 2011-04-25 | 2011-07-27 | 大连市轻化工研究所 | Reactive water-borne adhesive and preparation method thereof |
| CN102153930A (en) * | 2011-04-22 | 2011-08-17 | 大连市轻化工研究所 | Chelate type flashing erosion-resistant water-based metal anticorrosion coating and preparation method thereof |
| CN103254685A (en) * | 2013-04-25 | 2013-08-21 | 深圳市美丽华油墨涂料有限公司 | Ink for surface of finish paint and preparation method thereof |
| CN103275334A (en) * | 2013-06-07 | 2013-09-04 | 安徽大学 | Preparation method of waterborne polyurethane containing fluorescent dye |
| CN105801776A (en) * | 2016-05-12 | 2016-07-27 | 武汉赫斯特涂层材料股份有限公司 | Aqueous polysiloxane resin and preparation method thereof |
| CN111471424A (en) * | 2020-04-17 | 2020-07-31 | 上海抚佳精细化工有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
| CN113956771A (en) * | 2021-12-06 | 2022-01-21 | 鑫鸿宝(广州)科技有限公司 | Plastic-absorbable water-based touch paint and preparation method thereof |
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| CN101343525A (en) * | 2008-08-15 | 2009-01-14 | 百利合化工（中山）有限公司 | Watersoluble adhesive agent used in imitation leather electrostatic real leather embedding product and preparation thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101033322A (en) * | 2006-03-08 | 2007-09-12 | 北京化工大学 | Room temperature crosslinking curing polyurethane-polyacrylic ester composite aqueous emulsion and preparing method thereof |
| CN101343525A (en) * | 2008-08-15 | 2009-01-14 | 百利合化工（中山）有限公司 | Watersoluble adhesive agent used in imitation leather electrostatic real leather embedding product and preparation thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153930A (en) * | 2011-04-22 | 2011-08-17 | 大连市轻化工研究所 | Chelate type flashing erosion-resistant water-based metal anticorrosion coating and preparation method thereof |
| CN102153930B (en) * | 2011-04-22 | 2014-09-03 | 大连市轻化工研究所 | Chelate type flashing erosion-resistant water-based metal anticorrosion coating and preparation method thereof |
| CN102134466A (en) * | 2011-04-25 | 2011-07-27 | 大连市轻化工研究所 | Reactive water-borne adhesive and preparation method thereof |
| CN103254685A (en) * | 2013-04-25 | 2013-08-21 | 深圳市美丽华油墨涂料有限公司 | Ink for surface of finish paint and preparation method thereof |
| CN103254685B (en) * | 2013-04-25 | 2015-06-17 | 深圳市美丽华油墨涂料有限公司 | Ink for surface of finish paint and preparation method thereof |
| CN103275334A (en) * | 2013-06-07 | 2013-09-04 | 安徽大学 | Preparation method of waterborne polyurethane containing fluorescent dye |
| CN105801776A (en) * | 2016-05-12 | 2016-07-27 | 武汉赫斯特涂层材料股份有限公司 | Aqueous polysiloxane resin and preparation method thereof |
| CN105801776B (en) * | 2016-05-12 | 2019-01-11 | 武汉赫斯特涂层材料股份有限公司 | A kind of water based silicone resin and preparation method thereof |
| CN111471424A (en) * | 2020-04-17 | 2020-07-31 | 上海抚佳精细化工有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
| CN111471424B (en) * | 2020-04-17 | 2022-08-12 | 上海抚佳精细化工有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
| CN113956771A (en) * | 2021-12-06 | 2022-01-21 | 鑫鸿宝(广州)科技有限公司 | Plastic-absorbable water-based touch paint and preparation method thereof |
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Application publication date: 20110209 |