CN108727557B - Waterborne hyperbranched structure anti-dazzle polyurethane acrylate UV (ultraviolet) curing resin composition and preparation method thereof - Google Patents

Waterborne hyperbranched structure anti-dazzle polyurethane acrylate UV (ultraviolet) curing resin composition and preparation method thereof Download PDF

Info

Publication number
CN108727557B
CN108727557B CN201810274989.3A CN201810274989A CN108727557B CN 108727557 B CN108727557 B CN 108727557B CN 201810274989 A CN201810274989 A CN 201810274989A CN 108727557 B CN108727557 B CN 108727557B
Authority
CN
China
Prior art keywords
hours
acrylate
catalyst
octoate
reaction kettle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810274989.3A
Other languages
Chinese (zh)
Other versions
CN108727557A (en
Inventor
刘国强
岳利培
李卫东
白永平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuxi Bojia electronic new material Co.,Ltd.
Wuxi Haite New Material Research Institute Co Ltd
Original Assignee
Wuxi Boqiang Polymer Materials Science And Technology Co ltd
Wuxi Haite New Material Research Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuxi Boqiang Polymer Materials Science And Technology Co ltd, Wuxi Haite New Material Research Institute Co Ltd filed Critical Wuxi Boqiang Polymer Materials Science And Technology Co ltd
Priority to CN201810274989.3A priority Critical patent/CN108727557B/en
Publication of CN108727557A publication Critical patent/CN108727557A/en
Application granted granted Critical
Publication of CN108727557B publication Critical patent/CN108727557B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4283—Hydroxycarboxylic acid or ester
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses an aqueous hyperbranched structure anti-dazzle polyurethane acrylate UV (ultraviolet) curing resin composition and a preparation method thereof, wherein the aqueous hyperbranched structure anti-dazzle polyurethane acrylate UV curing resin composition contains 20-50% of solid components in percentage by weight, and the balance is deionized water; the solid components comprise the following components in percentage by weight: 10-80% of polyurethane acrylate with hyperbranched polyester as a core and 20-90% of polyurethane acrylate with hyperbranched polyether as a core. The waterborne hyperbranched structure anti-dazzle polyurethane acrylate UV curing resin composition has good diffusion performance and transparency, and has both hardness and flexibility.

Description

Waterborne hyperbranched structure anti-dazzle polyurethane acrylate UV (ultraviolet) curing resin composition and preparation method thereof
Technical Field
The invention relates to the field of polyurethane acrylate coatings, in particular to an aqueous hyperbranched structure anti-dazzle polyurethane acrylate UV (ultraviolet) curing resin composition and a preparation method thereof.
Background
With the upgrading of the social industry level and the people consumption level, the requirements of consumers on the appearance, the touch and the experience comfort of daily supplies and industrial supplies are more and more strict. Many high-end products are beginning to attract the attention of the public with beautiful and comfortable appearance and touch. The use of anti-glare coatings has also come into play. The novel automobile interior decoration film has attractive appearance and comfortable physiological touch of human body, gradually occupies a place in industries such as automobile interior decoration, electronic products and the like, and is gradually favored more and more. The UV light curing technology has the advantages of environmental protection, no VOC emission, low energy consumption, rapid curing and the like, and becomes a new green coating material technology with great development potential in the future.
The glare is caused by the fact that the unreasonable and uneven light distribution causes the reduction of contrast to affect the observation of human eyes, and the glare can be divided into direct glare and indirect glare according to the difference of light sources. Direct glare refers to the sensation of vertigo caused by high intensity light directly striking the human eye; indirect glare, also known as reflected glare, refers to glare caused by light reflecting through a smooth surface to form intense reflected light. Glare is a serious light pollution, and common sources of glare hazards are architectural lighting, road traffic lighting, electronic display screens and the like. In addition, traffic accidents caused by sudden blindness of drivers due to glare frequently occur, and people are affected by the glare for a long time, so that ophthalmic diseases are more easily caused. Although the problem of glare has brought serious influence for people's daily life, no clear regulation and control standard has been provided for the treatment of the problem of glare in China, so in order to protect people's visual health and improve life weight, a series of measures must be taken to prevent and treat glare. The prevention and control of glare can be performed from the light propagation process, in addition to the aspects of improving the light source, controlling the distance of the light source and the like. The anti-glare material is an effective method, and a layer of anti-glare coating, such as an electronic screen protective film, a lampshade coating film and the like, is added between a light source and human eyes, so that the mutual interference of light rays can be weakened, the function of a polaroid is equivalent to that of a polaroid, and the formation of glare can be reduced.
Anti-glare materials can be divided into two types: a particle diffusion type and a surface relief type. The particle diffusion type anti-glare material includes a light diffusion layer composed of a binder resin and Light Diffusion Particles (LDP), and light is refracted when passing through an interface between the resin and the particles. The surface relief type anti-glare material relies on a significantly uneven surface to accomplish light scattering. CN101235244A describes a method for preparing silica particles by inorganic-organic composite method, which is then used together with multifunctional acrylate and initiator to prepare an anti-glare coating, which is then coated to obtain a hard coating layer, and the coating layer has good wear resistance, aging resistance and dirt resistance. In addition, the anti-glare material is required to have high light transmittance and light diffusion property, but the light diffusion effect is increased and is accompanied by the decrease of light transmittance, which is a great challenge for preparing a film having both high light transmittance and light diffusion property.
The polyurethane has good light transmission and weather resistance, and the polyurethane synthesized by using the aliphatic diisocyanate has excellent yellowing resistance and ensures high light transmission, thus being an ideal optical coating. The Chinese patent application 2014105797477 discloses a method for synthesizing an anti-glare polyurethane coating, which is simple and low in cost, and the synthesized polyurethane coating has good stability and excellent anti-glare performance, but has poor transparency. Chinese patent application 201710037727.0 discloses a self-repairing anti-glare waterborne polyurethane coating which has good transparency, but because the coating is linear polyurethane prepared from dihydric alcohol and diisocyanate, a compact space network structure cannot be formed, and the coating has good flexibility but insufficient hardness.
In addition, the ultraviolet light curing coating material has high polymer molecular weight and high system viscosity, so that the coating processing process difficulty is increased, and the viscosity of the aqueous ultraviolet light curing coating material system can be adjusted, so that the coating processing process difficulty is greatly reduced.
Therefore, how to prepare the ultraviolet curing anti-glare water-based coating with good transparency, hardness and flexibility becomes a great challenge.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a waterborne hyperbranched structure anti-dazzle polyurethane acrylate UV-cured resin composition and a preparation method thereof. The aqueous hyperbranched structure anti-dazzle polyurethane acrylate UV curing resin composition has good diffusion performance and transparency, and has both hardness and flexibility.
The aqueous hyperbranched structure anti-dazzle polyurethane acrylate UV curing resin composition is characterized by comprising 20-50% of solid components and the balance of deionized water in percentage by weight;
the solid components comprise the following components in percentage by weight:
10-80% of polyurethane acrylate with hyperbranched polyester as core
20-90% of polyurethane acrylate with hyperbranched polyether as a core.
The polyurethane acrylate with the hyperbranched polyester as the core is prepared by the following method:
(1) placing pentaerythritol and dimethylolpropionic acid into a reaction kettle, adding a catalyst p-toluenesulfonic acid with the solid weight fraction of 0.01-1%, introducing nitrogen, heating to 70-120 ℃, stopping introducing nitrogen after 0.5-1 hour, and performing reduced pressure vacuum pumping for 2-4 hours to prepare hydroxyl-terminated hyperbranched polyester;
(2) weighing a certain amount of aliphatic diisocyanate monomer, wherein the weighed amount is 4 times of the molar amount of pentaerythritol, weighing a catalyst accounting for 0.001-0.5% of the weight of the aliphatic diisocyanate, slowly adding the catalyst into a reaction kettle for 2-6 hours, carrying out heat preservation reaction for 2-5 hours, weighing a certain amount of hydrophilic chain extender, wherein the weighed amount is 4 times of the molar amount of pentaerythritol, slowly adding the hydrophilic chain extender into the reaction kettle for 2-6 hours, and carrying out heat preservation reaction for 2-5 hours;
(3) weighing a certain amount of aliphatic diisocyanate monomer, placing the aliphatic diisocyanate monomer in a reaction kettle, adding a catalyst accounting for 0.01-0.5% of the weight of the aliphatic diisocyanate monomer, heating to 35-90 ℃, and introducing nitrogen; adding hydroxyl acrylate monomer with the same molar weight as the aliphatic diisocyanate monomer for 2-6 hours, and reacting for 2-5 hours under heat preservation to prepare isocyanate-terminated acrylate dimer;
(4) blending the prepared isocyanate-terminated acrylate dimer and hyperbranched polyester subjected to chain extension by a hydrophilic chain extender, placing the mixture in a reaction kettle, adding a catalyst with the solid weight fraction of 0.01-1%, introducing nitrogen, heating to 60-120 ℃, reacting for 2-5 hours, cooling to normal temperature, weighing a certain amount of neutralizing agent, wherein the weighed amount is the same as the molar weight of the hydrophilic chain extender, adding the mixture into the reaction kettle at one time, and stirring for 0.5-1 hour to prepare the polyurethane acrylate taking the hyperbranched polyester as a core.
Furthermore, in step (1), the molar ratio of dimethylolpropionic acid to pentaerythritol is 4:1, 12:1, 28: 1;
in the step (2), the catalyst is one or more of triethylamine, triethylenediamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the isocyanate monomer is one or more of hexamethylene diisocyanate, isophorone diisocyanate and the like; the hydrophilic chain extender is 2, 2-dimethylolpropionic acid and diaminebenzoic acid of which hydrophilic groups are carboxyl, the hydrophilic groups are ethylenediamine-ethyl sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and 1, 4-butanediol-2-sodium sulfonate of which the hydrophilic groups are sulfonic groups, and the hydrophilic groups are one or more of N-methyldiethanolamine (molecular formula HO-CH2CH2-N (-CH3) -CH2CH2-OH) of amines;
in the step (3), the aliphatic diisocyanate monomer is one or more of hexamethylene diisocyanate and isophorone diisocyanate; the catalyst is one or more of triethylamine, triethylene diamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the hydroxyl acrylic ester is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate;
in step (4), when the molar ratio of dimethylolpropionic acid to pentaerythritol in step (1) is 4:1, the molar ratio of the isocyanate-terminated acrylate dimer to pentaerythritol used in the hydroxyl-terminated hyperbranched polyester prepared in step (1) is 8: 1; when the molar ratio of dimethylolpropionic acid to pentaerythritol in step (1) is 12:1, the molar ratio of the isocyanate-terminated acrylate dimer to pentaerythritol used in the hydroxyl-terminated hyperbranched polyester prepared in step (1) is 16: 1; when the molar ratio of dimethylolpropionic acid to pentaerythritol in step (1) is 28:1, the molar ratio of the isocyanate-terminated acrylate dimer to pentaerythritol used in the hydroxyl-terminated hyperbranched polyester prepared in step (1) is 32: 1; the catalyst is one or more of triethylamine, triethylene diamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the neutralizing agent is one or more of triethanolamine, triethylamine, amino acid and terephthalic acid.
In addition, the polyurethane acrylate with the hyperbranched polyether as the core is prepared by the following method:
(1) 3-ethyl-3-hydroxymethyl butylene oxide (EHO) and diethyl ether (OEt)2) Placing the mixture in a reaction kettle, and adding EHO and OEt2Introducing nitrogen into a catalyst boron trifluoride with the total weight of 0.05-0.5%, and reacting at normal temperature for 6-12 hours to prepare hydroxyl-terminated hyperbranched polyether;
(2) weighing a certain amount of aliphatic diisocyanate monomer, weighing the aliphatic diisocyanate monomer in an amount which is 2 times of the molar weight of 3-ethyl-3-hydroxymethyl Epoxybutane (EHO), weighing a catalyst in an amount which is 0.001-0.5% of the weight of the aliphatic diisocyanate, slowly adding the catalyst into a reaction kettle, feeding for 2-6 hours, and carrying out heat preservation reaction for 2-5 hours; weighing a certain amount of hydrophilic chain extender, wherein the weighed amount is 2 times of the molar amount of 3-ethyl-3-hydroxymethyl Epoxybutane (EHO), slowly adding the chain extender into a reaction kettle for 2-6 hours, and carrying out heat preservation reaction for 2-5 hours;
(3) weighing a certain amount of aliphatic diisocyanate monomer, placing the aliphatic diisocyanate monomer in a reaction kettle, adding a catalyst accounting for 0.01-0.5% of the weight of the aliphatic diisocyanate monomer, heating to 35-90 ℃, and introducing nitrogen; adding hydroxyl acrylate monomer with the same molar weight as the aliphatic diisocyanate monomer for 2-6 hours, and reacting for 2-5 hours under heat preservation to prepare the isocyanate-terminated acrylate dimer.
(4) Blending the prepared isocyanate-terminated acrylate dimer and hyperbranched polyether after chain extension of the hydrophilic chain extender, placing the mixture in a reaction kettle, adding a catalyst with the solid weight fraction of 0.01-1%, introducing nitrogen, heating to 60-120 ℃, reacting for 2-5 hours, cooling to normal temperature, weighing a certain amount of neutralizing agent, wherein the weighed amount is the same as the molar weight of the hydrophilic chain extender, adding the mixture into the reaction kettle at one time, and stirring for 0.5-1 hour to prepare the polyurethane acrylic ether with the hyperbranched polyester as the core.
Wherein, in the step (1), the 3-ethyl-3-hydroxymethyl butylene oxide (EHO) and the diethyl ether (OEt)2) The molar ratio of (A) to (B) is 1: 1-1.5: 1;
in the step (2), the catalyst is one or more of triethylamine, triethylenediamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the isocyanate monomer is one or more of hexamethylene diisocyanate and isophorone diisocyanate; the hydrophilic chain extender is as follows: 2, 2-dimethylolpropionic acid and diaminebenzoic acid with hydrophilic group of carboxyl, ethylenediamine ethanesulfonic acid sodium salt, 1, 4-butanediol-2-sodium sulfonate and 1, 4-butanediol-2-sodium sulfonate with hydrophilic group of sulfonic group, and N-methyldiethanolamine with hydrophilic group of amine (molecular formula HO-CH)2CH2-N(-CH3)-CH2CH2-OH) or a plurality of the same;
in the step (3), the aliphatic diisocyanate monomer is one or more of hexamethylene diisocyanate and isophorone diisocyanate; the catalyst is one or more of triethylamine, triethylene diamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the hydroxyl acrylate monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate;
in step (4), the isocyanate-terminated acrylate dimer is 2 times the molar amount of 3-ethyl-3-hydroxymethyl butylene oxide (EHO) used in the preparation of the hydroxyl-terminated hyperbranched polyether in step (1); the catalyst is one or more of triethylamine, triethylene diamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the neutralizing agent is one or more of triethanolamine, triethylamine, amino acid and terephthalic acid.
The invention also provides a preparation method of the aqueous hyperbranched structure anti-dazzle polyurethane acrylate UV curing resin composition, which comprises the steps of adding solid components and deionized water according to the proportion that the solid components account for 20-50% in percentage by weight, and stirring for 2-5 hours; in the solid component, 10-80% of polyurethane acrylate with hyperbranched polyester as a core and 20-90% of polyurethane acrylate with hyperbranched polyether as a core.
The invention provides a hyperbranched structure polyurethane acrylate resin which has good diffusion performance, high transmission performance, self-repairing function and flexibility and hardness, and a preparation method thereof, and aims to overcome the defect of low light transmittance of a coating film under the condition of high light diffusion effect.
In general, when the diffusion property is higher, the transmission property is reduced because the hiding power of the coating film means that strong absorption, scattering and reflection are generated to the light entering into the film, and the hiding power is increased with the more scattered light, that is, the transmission of the light is reduced. In addition, the transmission performance is also related to the ratio of the refractive indices of the filler and the base material. When the UV curing resin structure contains polyester, polyether chain segment and polyurethane chain segment with different crystallization capacities, a certain light transmittance can be kept when the coating film obtains high diffusion performance when fillers are avoided.
The aqueous hyperbranched structure anti-dazzle urethane acrylate UV-cured resin composition is suitable for anti-dazzle aqueous UV-cured coatings with transparent surfaces and flexibility and hardness, and can achieve an excellent anti-dazzle effect without additional auxiliaries or surface treatment.
Compared with the prior art, the invention has the following advantages:
(1) the water-based ultraviolet curing coating is green and environment-friendly in process, free of pollution and VOC emission problem, and meets the low-carbon and environment-friendly concept. And the viscosity of the coating system can be adjusted, and the difficulty of the coating process is greatly reduced.
(2) The system has no addition of inorganic filler, is very uniform and stable in the processes of storage and use, and has no problems of layering, precipitation and phase separation.
(3) The anti-dazzle effect is realized by depending on the differences of crystallization properties and microscopic compatibility of polyester groups, polyether groups and polyurethane groups in a molecular chain, and is very stable in the using process and cannot be changed along with the prolonging of the using time.
(4) The curing agent contains a plurality of double-bond groups, is short in curing time, can be completely cured within 5-20S, is low in energy consumption, shortens the production period, and reduces the cost.
(5) The polyvinyl group contained in the molecular structure can ensure that the coating forms a compact three-dimensional network structure after being cured, and the pencil hardness of the coating is ensured to be more than 3H. Meanwhile, the special space three-dimensional network tree structure of the hyperbranched structure polymer ensures that molecular chains are not twisted, has good flexibility, and has no mark or damage after being folded for 180 degrees for many times. The coating can have both high hardness and flexibility.
The water-based hyperbranched structure anti-dazzle polyurethane acrylate UV curing coating can be widely applied to the decoration industries of automobile interior, automobile finish, electronic products and the like.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to the embodiments, but the descriptions in this section are only exemplary and explanatory, and should not be construed as limiting the scope of the present invention in any way.
In order to judge the anti-dazzle effect, the hardness and the flexibility of the prepared water-based hyperbranched structure anti-dazzle polyurethane acrylate UV curing coating, a certain amount of hyperbranched structure anti-dazzle polyurethane acrylate UV curing coating is weighed, and a cracking type photoinitiator with the solid weight of 1-2% is added, wherein the cracking type photoinitiator comprises but is not limited to 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and the like. Uniformly coating the coating on the surface of a polyester film subjected to corona treatment, drying the coating at the temperature of 80-120 ℃ until the dry thickness of the coating is 15-35 mu m, and curing the coating for 5-20s by using an ultraviolet curing machine with the power of 1000W to obtain the ultraviolet curing coating.
And (3) carrying out performance test on the prepared ultraviolet curing coating, and measuring the glossiness of the ultraviolet curing coating to be 60 degrees by using a gloss meter according to ISO/2813. The coating light transmittance is tested by adopting an ultraviolet visible light photometer model Carry60 of Agilent company, USA, a reference sample is a glass slide, the mode is T%, the scanning range is 300-700 nm, and the scanning speed is 600 nm/min. Anti-glare technical indexes: according to the anti-glare index of paper made by Bachuan of Japan K.K., when the 60-degree gloss is 20-50 and the light transmittance is more than or equal to 87%, the ideal anti-glare effect can be achieved.
The hardness of the ultraviolet curing coating is tested by pencil hardness, and the flexibility is doubled over 30 times at 180 degrees without impression and damage.
Example 1
177.84g (0.8mol) of isophorone diisocyanate were weighed into a reaction kettle, 0.02g of dibutyltin dilaurate as a catalyst was added, the mixture was heated to 50 ℃ and nitrogen was introduced. 92.50g (0.8mol) of hydroxyethyl acrylate was added for 4 hours, and the reaction was allowed to proceed under heat for 5 hours. An isocyanate terminated acrylate dimer was prepared.
13.62g (0.1mol) of pentaerythritol and 53.65g (0.4mol) of dimethylolpropionic acid were weighed out and placed in a reaction vessel, 0.06g of p-toluenesulfonic acid as a catalyst was added thereto, the mixture was heated to 80 ℃ and purged with nitrogen for 0.5 hour, and the reaction was carried out under reduced pressure and vacuum for 3 hours. Preparing 1 generation hydroxyl-terminated hyperbranched polyester. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 177.84g (0.8mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 107.30g (0.8mol) dimethylolpropionic acid is weighed out and slowly added into the reaction kettle for 3 hours, and the reaction is kept warm for 3 hours. 270.34g (0.8mol) of cyanate ester terminated acrylate dimer prepared above was added to the reaction kettle and the reaction was maintained for 4 hours. The temperature is reduced to normal temperature, 80.95g (0.8mol) of triethylamine is added, and the mixture is stirred for 0.5 hour. The polyurethane acrylate with the core of the hyperbranched polyester of the component A is prepared.
66.69g (0.3mol) of isophorone diisocyanate were weighed into a reaction kettle, 0.02g of dibutyltin dilaurate as a catalyst was added, the mixture was heated to 50 ℃ and nitrogen was introduced. 34.69g (0.3mol) of hydroxyethyl acrylate were added for 4 hours, and the reaction was incubated for 5 hours. An isocyanate terminated acrylate dimer was prepared. 17.4g (0.15mol) of 3-ethyl-3-hydroxymethylepoxybutane (EHO) and 7.4g (0.1mol) of diethyl ether (OEt)2) Putting the mixture into a reaction kettle, adding 0.08g of catalyst boron trifluoride, introducing nitrogen, and reacting for 9 hours at normal temperature. Preparing hydroxyl-terminated hyperbranched polyether. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 66.69g (0.3mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 40.24g (0.3mol) of dimethylolpropionic acid are weighed, slowly added into the reaction kettle for 3 hours, and the reaction is carried out for 3 hours under the condition of heat preservation. The temperature is raised to 80 ℃, 101.38g (0.3mol) of prepared isocyanate-terminated acrylate dimer is added into a reaction kettle, and the reaction is kept for 4 hours. The temperature is reduced to normal temperature, 30.36g (0.3mol) of triethylamine is added, and the mixture is stirred for 0.5 hour. The polyurethane acrylate with the hyperbranched polyether as the core of the component B is prepared.
And (2) mixing the component A and the component B according to the weight ratio of 1:1, weighing 20g of the component A and 20g of the component B, adding 60g of deionized water at normal temperature, and stirring for 1 hour to prepare the water-based hyperbranched structure anti-dazzle polyurethane acrylate coating. And (2) adding 0.3g of cracking type photoinitiator 1-hydroxycyclohexyl phenyl ketone into 20g of coating, uniformly coating the coating on the surface of the PET film subjected to corona treatment, heating the PET film at 100 ℃ for 30 seconds to dry the water, wherein the thickness of the coating is 25 mu m, and curing the coating for 10 seconds by using an ultraviolet curing machine with the power of 1000W to obtain the ultraviolet curing coating. The glossiness of the pencil is 50, the light transmittance is 95%, the pencil hardness is 3H, and no crease exists after 30 times of folding at 180 degrees.
Example 2
177.84g (0.8mol) of isophorone diisocyanate were weighed into a reaction kettle, 0.02g of dibutyltin dilaurate as a catalyst was added, the mixture was heated to 50 ℃ and nitrogen was introduced. 92.50g (0.8mol) of hydroxyethyl acrylate was added for 4 hours, and the reaction was allowed to proceed under heat for 5 hours. An isocyanate terminated acrylate dimer was prepared.
13.62g (0.1mol) of pentaerythritol and 53.65g (0.4mol) of dimethylolpropionic acid were weighed out and placed in a reaction vessel, 0.06g of p-toluenesulfonic acid as a catalyst was added thereto, the mixture was heated to 80 ℃ and purged with nitrogen for 0.5 hour, and the reaction was carried out under reduced pressure and vacuum for 3 hours. Preparing 1 generation hydroxyl-terminated hyperbranched polyester. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 177.84g (0.8mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 107.30g (0.8mol) dimethylolpropionic acid is weighed out and slowly added into the reaction kettle for 3 hours, and the reaction is kept warm for 3 hours. 270.34g (0.8mol) of cyanate ester terminated acrylate dimer prepared above was added to the reaction kettle and the reaction was maintained for 4 hours. The temperature is reduced to normal temperature, 80.95g (0.8mol) of triethylamine is added, and the mixture is stirred for 0.5 hour. The polyurethane acrylate with the core of the hyperbranched polyester of the component A is prepared.
66.69g (0.3mol) of isophorone diisocyanate were weighed into a reaction kettle, 0.02g of dibutyltin dilaurate as a catalyst was added, the mixture was heated to 50 ℃ and nitrogen was introduced. 34.69g (0.3mol) of hydroxyethyl acrylate were added for 4 hours, and the reaction was incubated for 5 hours. An isocyanate terminated acrylate dimer was prepared. 17.4g (0.15mol) of 3-ethyl-3-hydroxymethylepoxybutane (EHO) and 7.4g (0.1mol) of diethyl ether (OEt)2) Putting the mixture into a reaction kettle, adding 0.08g of catalyst boron trifluoride, introducing nitrogen, and reacting for 9 hours at normal temperature. Preparing hydroxyl-terminated hyperbranched polyether. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 66.69g (0.3mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 40.24g (0.3mol) of dimethylolpropionic acid are weighed, slowly added into the reaction kettle for 3 hours, and the reaction is carried out for 3 hours under the condition of heat preservation. The temperature is raised to 80 ℃, 101.38g (0.3mol) of prepared isocyanate-terminated acrylate dimer is added into a reaction kettle, and the reaction is kept for 4 hours. The temperature is reduced to normal temperature, 30.36g (0.3mol) of triethylamine is added, and the mixture is stirred for 0.5 hour. The polyurethane acrylate with the hyperbranched polyether as the core of the component B is prepared.
And (2) mixing the component A and the component B according to the weight ratio of 3:1, weighing 30g of the component A and 10g of the component B, adding 60g of deionized water at normal temperature, and stirring for 1 hour to prepare the water-based hyperbranched structure anti-dazzle polyurethane acrylate coating. And (2) adding 0.3g of cracking type photoinitiator 1-hydroxycyclohexyl phenyl ketone into 20g of coating, uniformly coating the coating on the surface of the PET film subjected to corona treatment, heating the PET film at 100 ℃ for 30 seconds to dry the water, wherein the thickness of the coating is 25 mu m, and curing the coating for 10 seconds by using an ultraviolet curing machine with the power of 1000W to obtain the ultraviolet curing coating. The glossiness of the pencil is 45, the light transmittance is 95%, the pencil hardness is 3H, and no crease exists after the pencil is folded for 30 times at 180 degrees.
Example 3
355.68g (1.6mol) of isophorone diisocyanate were weighed into a reaction kettle, 0.02g of dibutyltin dilaurate as a catalyst was added, the mixture was heated to 50 ℃ and nitrogen was introduced. 185.00g (1.6mol) of hydroxyethyl acrylate were added for 4 hours, and the reaction was allowed to proceed under reduced pressure for 5 hours. An isocyanate terminated acrylate dimer was prepared.
13.62g (0.1mol) of pentaerythritol and 160.95g (1.2mol) of dimethylolpropionic acid were weighed out and placed in a reaction vessel, 0.06g of p-toluenesulfonic acid as a catalyst was added thereto, the mixture was heated to 80 ℃ and purged with nitrogen for 0.5 hour, and the reaction was carried out under reduced pressure and vacuum for 3 hours. Preparing 2-generation hydroxyl-terminated hyperbranched polyester. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 355.68g (1.6mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 214.60g (1.6mol) dimethylolpropionic acid is weighed out and slowly added into the reaction kettle for 3 hours, and the reaction is kept warm for 3 hours. 540.68g (1.6mol) of cyanate ester terminated acrylate dimer prepared above was added to the reaction kettle and the reaction was maintained for 4 hours. The temperature was reduced to normal temperature, 161.90g (1.6mol) of triethylamine was added, and the mixture was stirred for 0.5 hour. The polyurethane acrylate with the core of the hyperbranched polyester of the component A is prepared.
66.69g (0.3mol) of isophorone diisocyanate were weighed into a reaction kettle, 0.02g of dibutyltin dilaurate as a catalyst was added, the mixture was heated to 50 ℃ and nitrogen was introduced. 34.69g (0.3mol) of hydroxyethyl acrylate were added for 4 hours, and the reaction was incubated for 5 hours. An isocyanate terminated acrylate dimer was prepared. 17.4g (0.15mol) of 3-ethyl-3-hydroxymethyl epoxybutane(EHO), 7.4g (0.1mol) diethyl ether (OEt)2) Putting the mixture into a reaction kettle, adding 0.08g of catalyst boron trifluoride, introducing nitrogen, and reacting for 9 hours at normal temperature. Preparing hydroxyl-terminated hyperbranched polyether. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 66.69g (0.3mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 40.24g (0.3mol) of dimethylolpropionic acid are weighed, slowly added into the reaction kettle for 3 hours, and the reaction is carried out for 3 hours under the condition of heat preservation. The temperature is raised to 80 ℃, 101.38g (0.3mol) of prepared isocyanate-terminated acrylate dimer is added into a reaction kettle, and the reaction is kept for 4 hours. The temperature is reduced to normal temperature, 30.36g (0.3mol) of triethylamine is added, and the mixture is stirred for 0.5 hour. The polyurethane acrylate with the hyperbranched polyether as the core of the component B is prepared.
Mixing the component A and the component B according to the weight ratio of 1:9, weighing 2g of the component A and 18g of the component B, adding 80g of deionized water at normal temperature, and stirring for 1 hour to prepare the aqueous hyperbranched structure anti-dazzle polyurethane acrylate coating. And (2) adding 0.3g of cracking type photoinitiator 1-hydroxycyclohexyl phenyl ketone into 20g of coating, uniformly coating the coating on the surface of the PET film subjected to corona treatment, heating the PET film at 100 ℃ for 30 seconds to dry the water, wherein the thickness of the coating is 25 mu m, and curing the coating for 10 seconds by using an ultraviolet curing machine with the power of 1000W to obtain the ultraviolet curing coating. The glossiness of the pencil is 40, the light transmittance is 92%, the pencil hardness is 3H, and no crease exists after 30 times of folding at 180 degrees.
Example 4
355.68g (1.6mol) of isophorone diisocyanate were weighed into a reaction kettle, 0.02g of dibutyltin dilaurate as a catalyst was added, the mixture was heated to 50 ℃ and nitrogen was introduced. 185.00g (1.6mol) of hydroxyethyl acrylate were added for 4 hours, and the reaction was allowed to proceed under reduced pressure for 5 hours. An isocyanate terminated acrylate dimer was prepared.
13.62g (0.1mol) of pentaerythritol and 160.95g (1.2mol) of dimethylolpropionic acid were weighed out and placed in a reaction vessel, 0.06g of p-toluenesulfonic acid as a catalyst was added thereto, the mixture was heated to 80 ℃ and purged with nitrogen for 0.5 hour, and the reaction was carried out under reduced pressure and vacuum for 3 hours. Preparing 2-generation hydroxyl-terminated hyperbranched polyester. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 355.68g (1.6mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 214.60g (1.6mol) dimethylolpropionic acid is weighed out and slowly added into the reaction kettle for 3 hours, and the reaction is kept warm for 3 hours. 540.68g (1.6mol) of cyanate ester terminated acrylate dimer prepared above was added to the reaction kettle and the reaction was maintained for 4 hours. The temperature was reduced to normal temperature, 161.90g (1.6mol) of triethylamine was added, and the mixture was stirred for 0.5 hour. The polyurethane acrylate with the core of the hyperbranched polyester of the component A is prepared.
66.69g (0.3mol) of isophorone diisocyanate were weighed into a reaction kettle, 0.02g of dibutyltin dilaurate as a catalyst was added, the mixture was heated to 50 ℃ and nitrogen was introduced. 34.69g (0.3mol) of hydroxyethyl acrylate were added for 4 hours, and the reaction was incubated for 5 hours. An isocyanate terminated acrylate dimer was prepared. 17.4g (0.15mol) of 3-ethyl-3-hydroxymethylepoxybutane (EHO) and 7.4g (0.1mol) of diethyl ether (OEt)2) Putting the mixture into a reaction kettle, adding 0.08g of catalyst boron trifluoride, introducing nitrogen, and reacting for 9 hours at normal temperature. Preparing hydroxyl-terminated hyperbranched polyether. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 66.69g (0.3mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 40.24g (0.3mol) of dimethylolpropionic acid are weighed, slowly added into the reaction kettle for 3 hours, and the reaction is carried out for 3 hours under the condition of heat preservation. The temperature is raised to 80 ℃, 101.38g (0.3mol) of prepared isocyanate-terminated acrylate dimer is added into a reaction kettle, and the reaction is kept for 4 hours. The temperature is reduced to normal temperature, 30.36g (0.3mol) of triethylamine is added, and the mixture is stirred for 0.5 hour. The polyurethane acrylate with the hyperbranched polyether as the core of the component B is prepared.
And mixing the component A and the component B according to a weight ratio of 4:1, weighing 40g of the component A and 10g of the component B, adding 50g of deionized water at normal temperature, and stirring for 1 hour to prepare the aqueous hyperbranched structure anti-dazzle polyurethane acrylate coating. And (2) adding 0.3g of cracking type photoinitiator 1-hydroxycyclohexyl phenyl ketone into 20g of coating, uniformly coating the coating on the surface of the PET film subjected to corona treatment, heating the PET film at 100 ℃ for 30 seconds to dry the water, wherein the thickness of the coating is 25 mu m, and curing the coating for 10 seconds by using an ultraviolet curing machine with the power of 1000W to obtain the ultraviolet curing coating. The glossiness of the pencil is 38, the light transmittance is 92%, the pencil hardness is 3H, and no crease exists after 30 times of folding at 180 degrees.
Example 5
711.36g (3.2mol) of isophorone diisocyanate were weighed into a reaction kettle, 0.02g of dibutyltin dilaurate as a catalyst was added, the mixture was heated to 50 ℃ and nitrogen was introduced. 370.00g (3.2mol) of hydroxyethyl acrylate was added for 4 hours, and the reaction was allowed to proceed under reduced pressure for 5 hours. An isocyanate terminated acrylate dimer was prepared.
13.62g (0.1mol) of pentaerythritol and 375.55g (2.8mol) of dimethylolpropionic acid were weighed out and placed in a reaction vessel, 0.06g of p-toluenesulfonic acid as a catalyst was added thereto, the mixture was heated to 80 ℃ and purged with nitrogen for 0.5 hour, and the reaction was carried out under reduced pressure and vacuum for 3 hours. Preparing 3-generation hydroxyl-terminated hyperbranched polyester. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 711.36g (3.2mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 429.20g (3.2mol) dimethylolpropionic acid is weighed out and slowly added into the reaction kettle for 3 hours, and the reaction is kept warm for 3 hours. 1081.36g (3.2mol) of the isocyanate terminated acrylate dimer prepared above was put into a reaction vessel and reacted for 4 hours while maintaining the temperature. The temperature was reduced to normal temperature, 233.80g (3.2mol) of triethylamine was added, and the mixture was stirred for 0.5 hour. The polyurethane acrylate with the core of the hyperbranched polyester of the component A is prepared.
66.69g (0.3mol) of isophorone diisocyanate were weighed into a reaction kettle, 0.02g of dibutyltin dilaurate as a catalyst was added, the mixture was heated to 50 ℃ and nitrogen was introduced. 34.69g (0.3mol) of hydroxyethyl acrylate were added for 4 hours, and the reaction was incubated for 5 hours. An isocyanate terminated acrylate dimer was prepared. 17.4g (0.15mol) of 3-ethyl-3-hydroxymethylepoxybutane (EHO) and 7.4g (0.1mol) of diethyl ether (OEt)2) Putting the mixture into a reaction kettle, adding 0.08g of catalyst boron trifluoride, introducing nitrogen, and reacting for 9 hours at normal temperature. Preparing hydroxyl-terminated hyperbranched polyether. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 66.69g (0.3mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 40.24g (0.3mol) of dimethylolpropionic acid are weighed, slowly added into the reaction kettle for 3 hours, and the reaction is carried out for 3 hours under the condition of heat preservation. Heating to1081.36g (3.2mol) of the isocyanate terminated acrylate dimer thus prepared was put into a reaction vessel at 80 ℃ and the reaction was carried out for 4 hours while maintaining the temperature. The temperature is reduced to normal temperature, 30.36g (0.3mol) of triethylamine is added, and the mixture is stirred for 0.5 hour. The polyurethane acrylate with the hyperbranched polyether as the core of the component B is prepared.
And mixing the component A and the component B according to the weight ratio of 1:3, weighing 10g of the component A and 30g of the component B, adding 60g of deionized water at normal temperature, and stirring for 1 hour to prepare the aqueous hyperbranched structure anti-dazzle polyurethane acrylate coating. And (2) adding 0.3g of cracking type photoinitiator 1-hydroxycyclohexyl phenyl ketone into 20g of coating, uniformly coating the coating on the surface of the PET film subjected to corona treatment, heating the PET film at 100 ℃ for 30 seconds to dry the water, wherein the thickness of the coating is 25 mu m, and curing the coating for 10 seconds by using an ultraviolet curing machine with the power of 1000W to obtain the ultraviolet curing coating. The glossiness of the pencil is 30, the light transmittance is 90%, the pencil hardness is 3H, and no crease exists after the pencil is folded at 180 degrees for 30 times.
Example 6
711.36g (3.2mol) of isophorone diisocyanate were weighed into a reaction kettle, 0.02g of dibutyltin dilaurate as a catalyst was added, the mixture was heated to 50 ℃ and nitrogen was introduced. 370.00g (3.2mol) of hydroxyethyl acrylate was added for 4 hours, and the reaction was allowed to proceed under reduced pressure for 5 hours. An isocyanate terminated acrylate dimer was prepared.
13.62g (0.1mol) of pentaerythritol and 375.55g (2.8mol) of dimethylolpropionic acid were weighed out and placed in a reaction vessel, 0.06g of p-toluenesulfonic acid as a catalyst was added thereto, the mixture was heated to 80 ℃ and purged with nitrogen for 0.5 hour, and the reaction was carried out under reduced pressure and vacuum for 3 hours. Preparing 3-generation hydroxyl-terminated hyperbranched polyester. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 711.36g (3.2mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 429.20g (3.2mol) dimethylolpropionic acid is weighed out and slowly added into the reaction kettle for 3 hours, and the reaction is kept warm for 3 hours. 1081.36g (3.2mol) of the isocyanate terminated acrylate dimer prepared above was put into a reaction vessel and reacted for 4 hours while maintaining the temperature. The temperature was reduced to normal temperature, 233.80g (3.2mol) of triethylamine was added, and the mixture was stirred for 0.5 hour. The polyurethane acrylate with the core of the hyperbranched polyester of the component A is prepared.
Weighing 66.69g (0.3mol) of isophorone diisocyanate were placed in a reaction vessel, 0.02g of dibutyltin dilaurate as a catalyst were added, the mixture was heated to 50 ℃ and nitrogen was introduced. 34.69g (0.3mol) of hydroxyethyl acrylate were added for 4 hours, and the reaction was incubated for 5 hours. An isocyanate terminated acrylate dimer was prepared. 17.4g (0.15mol) of 3-ethyl-3-hydroxymethylepoxybutane (EHO) and 7.4g (0.1mol) of diethyl ether (OEt)2) Putting the mixture into a reaction kettle, adding 0.08g of catalyst boron trifluoride, introducing nitrogen, and reacting for 9 hours at normal temperature. Preparing hydroxyl-terminated hyperbranched polyether. 0.02g of dibutyltin dilaurate serving as a catalyst is added, nitrogen is introduced, 66.69g (0.3mol) of isophorone diisocyanate is weighed and slowly added into a reaction kettle, the feeding time is 5 hours, and the heat preservation reaction is carried out for 3 hours. 40.24g (0.3mol) of dimethylolpropionic acid are weighed, slowly added into the reaction kettle for 3 hours, and the reaction is carried out for 3 hours under the condition of heat preservation. The temperature is raised to 80 ℃, 1081.36g (3.2mol) of prepared isocyanate-terminated acrylate dimer is added into a reaction kettle, and the reaction is kept for 4 hours. The temperature is reduced to normal temperature, 30.36g (0.3mol) of triethylamine is added, and the mixture is stirred for 0.5 hour. The polyurethane acrylate with the hyperbranched polyether as the core of the component B is prepared.
And (2) mixing the component A and the component B according to the weight ratio of 3:1, weighing 30g of the component A and 10g of the component B, adding 60g of deionized water at normal temperature, and stirring for 1 hour to prepare the water-based hyperbranched structure anti-dazzle polyurethane acrylate coating. And (2) adding 0.3g of cracking type photoinitiator 1-hydroxycyclohexyl phenyl ketone into 20g of coating, uniformly coating the coating on the surface of the PET film subjected to corona treatment, heating the PET film at 100 ℃ for 30 seconds to dry the water, wherein the thickness of the coating is 25 mu m, and curing the coating for 10 seconds by using an ultraviolet curing machine with the power of 1000W to obtain the ultraviolet curing coating. The glossiness of the pencil is 30, the light transmittance is 90%, the pencil hardness is 3H, and no crease exists after the pencil is folded at 180 degrees for 30 times.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention. .

Claims (3)

1. The aqueous hyperbranched structure anti-dazzle polyurethane acrylate UV curing resin composition is characterized by comprising 20-50% of solid components and the balance of deionized water in percentage by weight;
the solid components comprise the following components in percentage by weight:
10-80% of polyurethane acrylate with hyperbranched polyester as core
20-90% of polyurethane acrylate with hyperbranched polyether as a core;
the polyurethane acrylate with the hyperbranched polyester as the core is prepared by the following method:
(1) placing pentaerythritol and dimethylolpropionic acid into a reaction kettle, adding a catalyst p-toluenesulfonic acid with the solid weight fraction of 0.01-1%, introducing nitrogen, heating to 70-120 ℃, stopping introducing nitrogen after 0.5-1 hour, and performing reduced pressure vacuum pumping for 2-4 hours to prepare hydroxyl-terminated hyperbranched polyester;
(2) weighing a certain amount of aliphatic diisocyanate monomer, wherein the weighed amount is 4 times of the molar amount of pentaerythritol, weighing a catalyst accounting for 0.001-0.5% of the weight of the aliphatic diisocyanate, slowly adding the catalyst into a reaction kettle for 2-6 hours, carrying out heat preservation reaction for 2-5 hours, weighing a certain amount of hydrophilic chain extender, wherein the weighed amount is 4 times of the molar amount of pentaerythritol, slowly adding the hydrophilic chain extender into the reaction kettle for 2-6 hours, and carrying out heat preservation reaction for 2-5 hours;
(3) weighing a certain amount of aliphatic diisocyanate monomer, placing the aliphatic diisocyanate monomer in a reaction kettle, adding a catalyst accounting for 0.01-0.5% of the weight of the aliphatic diisocyanate monomer, heating to 35-90 ℃, and introducing nitrogen; adding hydroxyl acrylate monomer with the same molar weight as the aliphatic diisocyanate monomer for 2-6 hours, and reacting for 2-5 hours under heat preservation to prepare isocyanate-terminated acrylate dimer;
(4) blending the prepared isocyanate-terminated acrylate dimer and hyperbranched polyester subjected to chain extension by a hydrophilic chain extender, placing the mixture in a reaction kettle, adding a catalyst with the solid weight fraction of 0.01-1%, introducing nitrogen, heating to 60-120 ℃, reacting for 2-5 hours, cooling to normal temperature, weighing a certain amount of neutralizing agent, wherein the weighed amount is the same as the molar weight of the hydrophilic chain extender, adding the mixture into the reaction kettle at one time, and stirring for 0.5-1 hour to prepare the polyurethane acrylate taking the hyperbranched polyester as a core;
in the preparation of the polyurethane acrylate taking the hyperbranched polyester as the core, in the step (1), the molar ratio of the dimethylol propionic acid to the pentaerythritol is 4:1, 12:1 and 28: 1;
in the step (2), the catalyst is one or more of triethylamine, triethylenediamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the isocyanate monomer is one or more of hexamethylene diisocyanate and isophorone diisocyanate; the hydrophilic chain extender is 2, 2-dimethylolpropionic acid and diaminebenzoic acid of which hydrophilic groups are carboxyl, the hydrophilic groups are ethylenediamine ethanesulfonic acid sodium salt and 1, 4-butanediol-2-sulfonic acid sodium salt of sulfonic acid groups, and the hydrophilic groups are one or more of N-methyldiethanolamine of amines; the molecular formula of the N-methyldiethanolamine is as follows: HO-CH2CH2-N (-CH3) -CH2CH 2-OH;
in the step (3), the aliphatic diisocyanate monomer is one or more of hexamethylene diisocyanate and isophorone diisocyanate; the catalyst is one or more of triethylamine, triethylene diamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the hydroxyl acrylic ester is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate;
in step (4), when the molar ratio of dimethylolpropionic acid to pentaerythritol in step (1) is 4:1, the molar ratio of the isocyanate-terminated acrylate dimer to pentaerythritol used in the hydroxyl-terminated hyperbranched polyester prepared in step (1) is 8: 1; when the molar ratio of dimethylolpropionic acid to pentaerythritol in step (1) is 12:1, the molar ratio of the isocyanate-terminated acrylate dimer to pentaerythritol used in the hydroxyl-terminated hyperbranched polyester prepared in step (1) is 16: 1; when the molar ratio of dimethylolpropionic acid to pentaerythritol in step (1) is 28:1, the molar ratio of the isocyanate-terminated acrylate dimer to pentaerythritol used in the hydroxyl-terminated hyperbranched polyester prepared in step (1) is 32: 1; the catalyst is one or more of triethylamine, triethylene diamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the neutralizing agent is one or more of triethanolamine, triethylamine, amino acid and terephthalic acid;
the polyurethane acrylate with the hyperbranched polyether as the core is prepared by the following method:
(1) 3-ethyl-3-hydroxymethyl butylene oxide EHO and diethyl ether OEt2Placing the mixture in a reaction kettle, and adding EHO and OEt2Introducing nitrogen into a catalyst boron trifluoride with the total weight of 0.05-0.5%, and reacting at normal temperature for 6-12 hours to prepare hydroxyl-terminated hyperbranched polyether;
(2) weighing a certain amount of aliphatic diisocyanate monomer, weighing the aliphatic diisocyanate monomer in an amount which is 2 times of the molar weight of 3-ethyl-3-hydroxymethyl epoxybutane EHO, weighing a catalyst in an amount which is 0.001-0.5% of the weight of the aliphatic diisocyanate, slowly adding the catalyst into a reaction kettle for 2-6 hours, and carrying out heat preservation reaction for 2-5 hours; weighing a certain amount of hydrophilic chain extender, wherein the weighed amount is 2 times of the molar amount of 3-ethyl-3-hydroxymethyl epoxybutane EHO, slowly adding the chain extender into a reaction kettle for 2-6 hours, and reacting for 2-5 hours in a heat preservation manner;
(3) weighing a certain amount of aliphatic diisocyanate monomer, placing the aliphatic diisocyanate monomer in a reaction kettle, adding a catalyst accounting for 0.01-0.5% of the weight of the aliphatic diisocyanate monomer, heating to 35-90 ℃, and introducing nitrogen; adding hydroxyl acrylate monomer with the same molar weight as the aliphatic diisocyanate monomer for 2-6 hours, and reacting for 2-5 hours under heat preservation to prepare isocyanate-terminated acrylate dimer;
(4) blending the prepared isocyanate-terminated acrylate dimer and hyperbranched polyether after chain extension of the hydrophilic chain extender, placing the mixture in a reaction kettle, adding a catalyst with the solid weight fraction of 0.01-1%, introducing nitrogen, heating to 60-120 ℃, reacting for 2-5 hours, cooling to normal temperature, weighing a certain amount of neutralizing agent, wherein the weighed amount is the same as the molar weight of the hydrophilic chain extender, adding the mixture into the reaction kettle at one time, and stirring for 0.5-1 hour to prepare the polyurethane acrylic ether with the hyperbranched polyester as the core.
2. The composition according to claim 1, wherein, in the preparation of the polyurethane acrylate with the core of the hyperbranched polyether,
in the step (1), the 3-ethyl-3-hydroxymethyl butylene oxide EHO and the diethyl ether OEt2The molar ratio of (A) to (B) is 1: 1-1.5: 1;
in the step (2), the catalyst is one or more of triethylamine, triethylenediamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the isocyanate monomer is one or more of hexamethylene diisocyanate and isophorone diisocyanate; the hydrophilic chain extender is as follows: hydrophilic groups are 2, 2-dimethylolpropionic acid and diaminebenzoic acid of carboxyl, the hydrophilic groups are ethylenediamine ethanesulfonic acid sodium salt and 1, 4-butanediol-2-sulfonic acid sodium salt of sulfonic acid group, and the hydrophilic groups are one or more of N-methyldiethanolamine of amine; the molecular formula of the N-methyldiethanolamine is as follows: HO-CH2CH2-N(-CH3)-CH2CH2-OH；
In the step (3), the aliphatic diisocyanate monomer is one or more of hexamethylene diisocyanate and isophorone diisocyanate; the catalyst is one or more of triethylamine, triethylene diamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the hydroxyl acrylate monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate;
in the step (4), the isocyanate-terminated acrylate dimer is 2 times of the molar amount of 3-ethyl-3-hydroxymethyl butylene oxide EHO used for preparing the hydroxyl-terminated hyperbranched polyether in the step (1); the catalyst is one or more of triethylamine, triethylene diamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate; the neutralizing agent is one or more of triethanolamine, triethylamine, amino acid and terephthalic acid.
3. The preparation method of the aqueous hyperbranched structure anti-glare urethane acrylate UV-curable resin composition according to claim 1 or 2, wherein the solid component and deionized water are added according to a proportion of 20-50% of the solid component by weight percentage, and the mixture is stirred for 2-5 hours;
in the solid component, 10-80% of polyurethane acrylate with hyperbranched polyester as a core and 20-90% of polyurethane acrylate with hyperbranched polyether as a core.
CN201810274989.3A 2018-03-29 2018-03-29 Waterborne hyperbranched structure anti-dazzle polyurethane acrylate UV (ultraviolet) curing resin composition and preparation method thereof Active CN108727557B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810274989.3A CN108727557B (en) 2018-03-29 2018-03-29 Waterborne hyperbranched structure anti-dazzle polyurethane acrylate UV (ultraviolet) curing resin composition and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810274989.3A CN108727557B (en) 2018-03-29 2018-03-29 Waterborne hyperbranched structure anti-dazzle polyurethane acrylate UV (ultraviolet) curing resin composition and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108727557A CN108727557A (en) 2018-11-02
CN108727557B true CN108727557B (en) 2021-02-26

Family

ID=63940526

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810274989.3A Active CN108727557B (en) 2018-03-29 2018-03-29 Waterborne hyperbranched structure anti-dazzle polyurethane acrylate UV (ultraviolet) curing resin composition and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108727557B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109721754A (en) * 2018-12-28 2019-05-07 邵敏芝 A kind of environment-friendly water-based oil resistant glue and the method using the hydrophobic high stretching PVC film of its preparation oil resistant
CN110105553B (en) * 2019-04-04 2020-05-26 湖南师范大学 Hyperbranched polyester modified itaconic acid-based waterborne light-cured resin and preparation method thereof
CN110305278B (en) * 2019-05-29 2021-04-13 华南农业大学 Application of cationic waterborne polyurethane in preparation of ultraviolet absorbing material
CN110294828B (en) * 2019-05-29 2021-04-13 华南农业大学 Waterborne polyurethane and preparation method and application thereof
CN114958180A (en) * 2022-06-30 2022-08-30 湖南松井新材料股份有限公司 Water-based paint for covering epoxy glass fiber screen prints and preparation method and application thereof
CN115521437B (en) * 2022-09-30 2024-05-31 中南民族大学 Preparation method of water-soluble ultraviolet light-cured hyperbranched polyurethane acrylic resin

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19715382C1 (en) * 1997-04-14 1998-11-19 Synthopol Chemie Dr Koch Water-dispersed, radiation-curable polyurethanes
US6436540B1 (en) * 2000-02-18 2002-08-20 Omnova Solutions Inc. Co-mingled polyurethane-polyvinyl ester polymer compositions and laminates
US7396875B2 (en) * 2003-06-20 2008-07-08 Bayer Materialscience Llc UV-curable waterborne polyurethane dispersions for soft touch coatings
DE102004011005A1 (en) * 2004-03-06 2005-09-22 Degussa Ag Low temperature curable uretdione group-containing polyurethane compositions
KR20100121502A (en) * 2008-03-06 2010-11-17 바이엘 머티리얼싸이언스 엘엘씨 Aqueous floor coatings based on uv-curable polyurethane dispersions
DE102008021151A1 (en) * 2008-04-28 2009-10-29 Bayer Materialscience Ag Block-resistant, radiation-curable coating systems based on high molecular weight, aqueous polyurethane dispersions
CN102030884B (en) * 2010-10-26 2012-08-08 华南理工大学 High-solid-content UV (Ultraviolet)-curing aqueous urethane acrylate dispersion liquid and preparation method thereof
CN102863829B (en) * 2012-09-26 2014-07-02 华南理工大学 Humidity and ultraviolet dual-cured polyurethane woodware coating and preparation method thereof
CN105694651B (en) * 2014-11-28 2018-06-15 合众（佛山）化工有限公司 A kind of preparation method of water-borne Self-Crosslinked Acrylic modified polyurethane dumb light resin
CN106867388B (en) * 2017-01-18 2019-08-20 华南理工大学 A kind of selfreparing anti-dazzle aqueous polyurethane coating and preparation method thereof
CN106866912A (en) * 2017-03-09 2017-06-20 广东昊辉新材料有限公司 A kind of ultraviolet light solidfication water polyurethane acrylate and preparation method thereof
CN107814902B (en) * 2017-11-06 2020-04-10 万华化学集团股份有限公司 Hydroxyl-containing polyurethane aqueous dispersion and preparation method and application thereof

Also Published As

Publication number Publication date
CN108727557A (en) 2018-11-02

Similar Documents

Publication Publication Date Title
CN108727557B (en) Waterborne hyperbranched structure anti-dazzle polyurethane acrylate UV (ultraviolet) curing resin composition and preparation method thereof
CN108752563B (en) Waterborne hyperbranched structure modified polyurethane polymer, preparation method thereof and self-repairing diffuse reflection coating composition
CN102762657B (en) Radiation curable resin composition, and fingerprint-resistant resin composition containing same
CN108659192B (en) Hyperbranched structure anti-dazzle polyurethane acrylate UV (ultraviolet) curing resin and preparation method thereof
CN102863829B (en) Humidity and ultraviolet dual-cured polyurethane woodware coating and preparation method thereof
CN102395637A (en) Primer composition for optical articles, and optical article
CN106750080A (en) It is a kind of from extinction type modified aqueous polyurethane coating and preparation method and application
CN101497749B (en) Surface modified nano silicon dioxide and acrylic resin coating containing the same
CN102585157B (en) Ultraviolet light polymerization polyfunctionality polyurethane acrylate vacuum coating surface coating resin
TWI439521B (en) Active energy line hardening composition and coated articles (1)
KR102404488B1 (en) Curable composition, cured product thereof, and optical member
CN1950472B (en) Coating composition
CN104877544A (en) UV photo-curing elastic self-repairing brightening paint composition
JP2022543368A (en) Method for producing a multi-layer coating containing a glitter coating layer and the multi-layer coating obtained by said method
CN109181516B (en) Water-based weather-resistant scratch-resistant self-cleaning inorganic nano ceramic automobile paint and preparation method thereof
CN115109474B (en) Water-based UV (ultraviolet) curing matte coating as well as preparation method and application thereof
EP0522454A1 (en) Method for flatting paint coating, coating and articles therefrom
CN110218288B (en) Silicon-modified zero-VOC (volatile organic compound) water-based polyester acrylic resin and preparation method thereof
CN113667393A (en) Anti-glare organic-inorganic hybrid antifogging coating and preparation thereof
CN111876070A (en) Leather finishing agent and preparation method thereof
JPH0433936A (en) Production of coated polycarbonate molded article
CN113576144B (en) Composition for nail sticker and preparation method thereof
JPH0418475A (en) Top-coating composition
KR102217428B1 (en) High gloss coating compoition and films made therefrom
CN107502172A (en) A kind of polyurethane glossy varnish

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: 214000 Luoshe Town Yangshi health care village, Huishan District, Wuxi City, Jiangsu Province

Patentee after: Wuxi Bojia electronic new material Co.,Ltd.

Patentee after: WUXI HAITE NEW MATERIAL INSTITUTE Co.,Ltd.

Address before: 214000 Luoshe Town Yangshi health care village, Huishan District, Wuxi City, Jiangsu Province

Patentee before: WUXI BOQIANG POLYMER MATERIALS SCIENCE AND TECHNOLOGY Co.,Ltd.

Patentee before: WUXI HAITE NEW MATERIAL INSTITUTE Co.,Ltd.