CN113509034A - Texture paper frame strip - Google Patents

Texture paper frame strip Download PDF

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Publication number
CN113509034A
CN113509034A CN202110711626.3A CN202110711626A CN113509034A CN 113509034 A CN113509034 A CN 113509034A CN 202110711626 A CN202110711626 A CN 202110711626A CN 113509034 A CN113509034 A CN 113509034A
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poss
paper
modified
frame strip
texture
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CN113509034B (en
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龚品忠
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Huahonghua Home Furnishing Co ltd
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Huahonghua Home Furnishing Co ltd
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    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G1/00—Mirrors; Picture frames or the like, e.g. provided with heating, lighting or ventilating means
    • A47G1/06—Picture frames
    • A47G1/0616—Ornamental frames, e.g. with illumination, speakers or decorative features
    • A47G1/0627—Ornamental frames, e.g. with illumination, speakers or decorative features with decorative strips or layers on the frame members
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G1/00—Mirrors; Picture frames or the like, e.g. provided with heating, lighting or ventilating means
    • A47G1/02—Mirrors used as equipment
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G1/00—Mirrors; Picture frames or the like, e.g. provided with heating, lighting or ventilating means
    • A47G1/14—Photograph stands
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G1/00—Mirrors; Picture frames or the like, e.g. provided with heating, lighting or ventilating means
    • A47G1/16—Devices for hanging or supporting pictures, mirrors, or the like
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • 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

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

Abstract

The invention discloses a texture paper frame strip, which comprises a frame strip and texture paper coated outside the frame strip, and the preparation method comprises the following steps: (1) embossing the base paper; (2) printing a pattern layer on the embossed paper; (3) coating a protective coating on one side printed with the pattern layer to obtain texture paper; (4) and cutting texture paper, then coating the frame strips, cutting nails, and assembling to obtain the texture paper frame strips. According to the invention, the paper has a natural plant texture effect by embossing the base paper and printing patterns; and then the surface of the paper is coated with a protective coating, so that the paper has good weather resistance and mechanical properties, and the decorative effect and the service life of the finally obtained texture paper frame strip are improved.

Description

Texture paper frame strip
Technical Field
The invention relates to the technical field of decorative frame strips, in particular to a texture paper frame strip.
Background
The paper material is an environment-friendly green material, and has the advantages of being recyclable, sustainable and reusable when being used for manufacturing frame strip materials of frame products such as picture frames, photo frames, picture frames, wall supports and the like. However, the conventional decorative paper has a smooth surface, and has poor decorative effect when used for manufacturing frame strip materials; and some special decorative papers with textures are not suitable for batch production due to complex manufacturing process.
For example, the texture dry stained paper obtained by adding natural flowers and leaves into paper has good decorative effect, and the preparation method generally comprises the step of adding the natural flowers and leaves which are air-dried in advance into the paper, so that the air-dried flowers and leaves are mixed in the paper layer to generate a hidden and obvious texture effect. For example, a method for preparing natural dried flowers and dried leaf wallpaper disclosed in chinese patent document, application No. CN200610106709.5, the process flow thereof is: 1. placing: according to the design pattern, dry flowers, dry leaves or flower leaves are mixed and placed on the wallpaper substrate with the glue; 2. hot pressing: feeding the wallpaper substrate with the dry flowers and the dry leaves into a hot press for hot press molding; 3. dyeing: after hot press molding, dyeing the surface layer (except the natural color); 4. gluing or paper feeding: according to the requirement, gluing or adhering a transparent paper protective surface layer; 5. cutting: and cutting the finished product according to the required size.
However, the addition of natural plants causes the traditional texture dry stained paper to be expensive in cost, generally needs manual production and is not suitable for batch production; and when the composite material is used for manufacturing frame strip materials of frame products, because the paper has poor weather resistance and mechanical property and is easy to damage under the action of external force, the service life of the manufactured frame strip is short, and the application of texture paper in the frame products is influenced.
Disclosure of Invention
The invention aims to overcome the defects that the traditional texture dry stained paper is expensive in cost, generally needs manual production and is not suitable for batch production due to the addition of natural plants; the texture paper frame strip is provided, and the paper has the natural plant texture effect by embossing the base paper and printing patterns; and then the surface of the paper is coated with a protective coating, so that the paper has good weather resistance and mechanical properties, and the decorative effect and the service life of the finally obtained texture paper frame strip are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a texture paper frame strip comprises a frame strip and texture paper coated outside the frame strip, and the preparation method comprises the following steps:
(1) embossing the base paper;
(2) printing a pattern layer on the embossed paper;
(3) coating a protective coating on one side printed with the pattern layer to obtain texture paper;
(4) and cutting texture paper, then coating the frame strips, cutting nails, and assembling to obtain the texture paper frame strips.
According to the invention, the raw paper is embossed, and then patterns simulating the effect of real plants are printed on the embossed paper by means of spray painting or printing and the like, so that the obtained texture paper can achieve the same texture effect as the texture dry stained paper obtained by traditional manual production and as if the plants are mixed in the paper layer to generate a hidden texture effect; the cladding makes the texture paper frame strip outside the frame strip of wooden or other materials, can satisfy the customer to its decorative effect's demand, can improve production efficiency again simultaneously, realizes the mass production.
Meanwhile, in order to prolong the service life of the texture paper frame strip, the protective coating is coated on the paper after the pattern layer is printed, so that the texture paper has good weather resistance and mechanical property under the protection action of the protective coating, is not easy to be polluted and damaged in the using process, and the service life of the finally obtained texture paper frame strip is prolonged.
Preferably, the gram weight of the base paper in the step (1) is 160-180 g/m2。
Preferably, the thickness of the protective coating in the step (3) is 5-10 μm; the coating method of the protective coating comprises the following steps: coating the POSS modified UV cured hyperbranched polyurethane acrylate coating on one side of paper printed with a pattern layer, and then coating the POSS modified UV cured hyperbranched polyurethane acrylate coating on the side of the paper printed with the pattern layer at a light intensity of 100-300 mW/cm2Irradiating for 8-10 s under the ultraviolet light to obtain the protective coating.
The protective coating is prepared by using the POSS modified UV cured hyperbranched polyurethane acrylate coating, has the comprehensive characteristics of photocuring and hyperbranched polyurethane, and has high curing speed and high production efficiency; the urethane bond is used as the main structure of the hyperbranched polyurethane branching unit, so that the protective coating has good flexibility, excellent chemical resistance, weather resistance and good adhesive force; however, the hyperbranched polyurethane acrylate has poor mechanical strength and can influence the service life of the texture paper frame strip, so that the hyperbranched polyurethane acrylate is modified by POSS (polyhedral oligomeric silsesquioxane), the POSS has a nano cage-shaped structure taking Si-O-Si bonds as a core, and the inorganic core of the hyperbranched polyurethane acrylate can greatly improve the hardness, heat resistance, wear resistance and the like of the protective coating; in addition, POSS's addition can also improve protective coating's self-cleaning ability to effectively improved the resistant dirt nature and the life of texture paper frame strip.
Preferably, the POSS modified UV-cured hyperbranched polyurethane acrylate coating comprises the following components: 75-85 parts of POSS modified hyperbranched polyurethane acrylate, 10-20 parts of 1, 6-hexanediol diacrylate, 5-6 parts of photoinitiator and 0.1-1 part of flatting agent.
Preferably, the preparation method of the POSS modified hyperbranched polyurethane acrylate comprises the following steps:
A) mixing heptaisobutyl trisilanol and vinyl trichlorosilane, adding into tetrahydrofuran, adding triethylamine, reacting for 40-60 min at-10 to-5 ℃ under the protection of nitrogen, reacting for 12-18 h at normal temperature, filtering, concentrating the filtrate, adding deionized water for precipitation, and filtering the precipitated product to obtain vinyl modified POSS; adding vinyl modified POSS and mercaptosuccinic acid into tetrahydrofuran, stirring and dissolving under the protection of nitrogen, adding azobisisobutyronitrile, heating to 75-85 ℃, reacting for 12-24 hours, concentrating the reaction liquid, adding deionized water for precipitation, filtering and drying the precipitation product to obtain carboxyl modified POSS;
the preparation method comprises the steps of firstly, preparing vinyl modified POSS with one corner provided with vinyl and the other seven corners provided with isobutyl by using heptaisobutyl trisilanol and vinyl trichlorosilane as raw materials, and then reacting the vinyl with sulfydryl in mercaptosuccinic acid to obtain carboxyl modified POSS with one corner provided with dicarboxyl;
B) adding isophorone diisocyanate into a solvent under the protection of nitrogen, then dropwise adding a DMF (dimethyl formamide) solution of polyethylene glycol, and reacting at 35-45 ℃ until the NCO value is unchanged; cooling to 0-4 ℃, then dropwise adding a DMF (dimethyl formamide) solution of diethanolamine, and carrying out heat preservation reaction until the NCO value is unchanged to obtain a polymerized monomer;
C) mixing a part of polymerization monomer with a catalyst, heating to 35-45 ℃, stopping reaction until the NCO value reaches 1.5-2.0%, cooling to room temperature, washing the product with water, and drying to obtain pre-branched polyurethane; adding carboxyl modified POSS and pre-branched polyurethane into DMF (dimethyl formamide) for dissolving, adding concentrated sulfuric acid, reacting for 4-6 h at 100-120 ℃, washing and drying a product to obtain POSS modified pre-branched polyurethane; mixing the POSS modified pre-branched polyurethane with the rest of polymerization monomers, adding the mixture into a solvent, adding a catalyst, heating to 35-45 ℃, and stopping reaction until the NCO value reaches 0.3-1.0% to obtain POSS modified hyperbranched polyurethane;
D) under the protection of nitrogen, mixing isophorone diisocyanate, DMF (dimethyl formamide), a catalyst and a polymerization inhibitor, then dropwise adding a DMF (dimethyl formamide) solution of hydroxyethyl acrylate, and reacting at 35-45 ℃ until the NCO value is unchanged to obtain an isocyanate-terminated prepolymer;
E) and mixing the POSS modified hyperbranched polyurethane with the isocyanate-terminated prepolymer, adding a catalyst, and reacting at 35-45 ℃ until the NCO value is less than 0.3% to obtain the POSS modified hyperbranched polyurethane acrylate.
In the preparation process of the POSS modified hyperbranched polyurethane acrylate, firstly, the carboxyl modified POSS with double carboxyl is prepared through the step A); then preparing a polymerization monomer of the hyperbranched polyurethane by using isophorone diisocyanate, polyethylene glycol and diethanol amine as raw materials in the step B); then in the step C), the NCO value of the product is controlled, so that the polymerized monomer is automatically polycondensed to the second generation product to obtain the pre-branched polyurethane; then modifying POSS on the prefabricated polyurethane through esterification reaction of carboxyl in the carboxyl modified POSS and partial hydroxyl in the pre-branched polyurethane; then, the POSS modified hyperbranched polyurethane and the rest of the polymerized monomers are continuously subjected to self-polycondensation reaction, and the reaction is stopped when the product of the fourth generation is obtained, so that the POSS modified hyperbranched polyurethane is obtained; and finally, reacting the POSS modified hyperbranched polyurethane with the isocyanate-terminated prepolymer to obtain the POSS modified hyperbranched polyurethane acrylate through the steps D) and E).
In the POSS modified hyperbranched polyurethane acrylate, double bonds in acrylate groups enable the POSS modified hyperbranched polyurethane acrylate to have UV curing performance; the polyethylene glycol flexible chain segment introduced into the hyperbranched polyurethane can improve the adhesive force and the impact strength of the protective coating; according to the invention, the POSS is connected in the hyperbranched polyurethane acrylate structure, so that the compatibility of the POSS and the hyperbranched polyurethane acrylate can be effectively improved, and the POSS with high hardness is uniformly distributed among the flexible chain segments by controlling the adding time of the carboxyl modified POSS, so that the flexible chain segments are separated, and thus, the protective coating can have good flexibility and hardness and has strong resistance to external forces such as impact force, friction, scratch and the like, and the service life of the texture paper frame strip is prolonged.
Preferably, the molar ratio of the heptaisobutyl trisilanol, the vinyl trichlorosilane and the triethylamine in the step A) is 1-1.2: 1: 2.8-3; the mol ratio of the vinyl modified POSS to the mercaptosuccinic acid is 1: 1-1.2; the addition amount of the azodiisobutyronitrile is 1-2% of the total mass of reactants.
Preferably, the mass ratio of the isophorone diisocyanate, the polyethylene glycol and the diethanol amine added in the step B) is 1.1-1.2: 1: 0.26-0.27.
Preferably, the mass ratio of the polymerized monomers added twice in the step C) is 1: 1-1.2; the catalyst is dibutyltin dilaurate, and the adding amount of the catalyst in each time is 0.08-0.12% of the total mass of reactants; when the POSS modified pre-branched polyurethane is prepared, the mass ratio of the carboxyl modified POSS to the pre-branched polyurethane is 4-5: 25, and the addition amount of concentrated sulfuric acid is 5-10% of the total mass of reactants. The carboxyl modified POSS with two carboxyl groups is adopted to modify the pre-branched polyurethane, the carboxyl groups of the POSS can be utilized to react with the hydroxyl groups in the pre-branched polyurethane, the POSS can be modified on the pre-branched polyurethane, and the subsequent branching degree of the pre-branched polyurethane cannot be influenced by excessive reactive carboxyl groups.
Preferably, the mole ratio of the isophorone diisocyanate and the hydroxyethyl acrylate added in the step D) is 1: 1-1.2; the catalyst is dibutyltin dilaurate, and the adding amount of the catalyst is 0.08-0.12% of the total mass of reactants; the polymerization inhibitor is p-hydroxyanisole, and the addition amount of the polymerization inhibitor is 0.05-0.1% of the total mass of the reactants.
Preferably, the mass ratio of the POSS modified hyperbranched polyurethane to the isocyanate-terminated prepolymer in the step E) is 1.2-1.4: 1; the catalyst is dibutyltin dilaurate, and the adding amount of the catalyst is 0.08-0.12% of the total mass of reactants.
Therefore, the invention has the following beneficial effects:
(1) embossing the base paper, and then printing patterns simulating the real plant effect on the embossed paper in a spray painting or printing mode and the like, so that the obtained texture paper can achieve a natural texture effect, not only can the requirement of a customer on the decorative effect be met, but also the production efficiency can be improved, and batch production can be realized;
(2) after the pattern layer is printed, the paper is coated with the protective coating, so that the texture paper has good weather resistance and mechanical property under the protection of the protective coating, is not easy to be polluted and damaged in the using process, and the service life of the finally obtained texture paper frame strip is prolonged;
(3) the protective coating is prepared by using the POSS modified UV cured hyperbranched polyurethane acrylate coating, so that the curing speed is high, and the production efficiency is high; the protective coating has good flexibility, excellent chemical resistance, weather resistance and good adhesive force; after the hyperbranched polyurethane acrylate is modified by POSS, the hardness, heat resistance and wear resistance of the protective coating can be greatly improved; in addition, POSS's addition can also improve protective coating's self-cleaning ability to effectively improved the resistant dirt nature and the life of texture paper frame strip.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is a diagram of a texture paper frame strip manufactured in embodiment 1 of the present invention.
Detailed Description
The invention is further described with reference to specific embodiments.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
a texture paper frame strip comprises a wooden frame strip and texture paper coated outside the wooden frame strip, as shown in figure 1, and the preparation method comprises the following steps:
(1) the gram weight is 170g/m2Embossing the base paper;
(2) spray-painting a designed pattern layer simulating the effect of real plants on the embossed paper;
(3) coating a protective coating with the thickness of 8 mu m on one side printed with the pattern layer to obtain texture paper; the coating method of the protective coating comprises the following steps: coating the POSS modified UV cured hyperbranched polyurethane acrylate coating on one side of paper printed with a pattern layer, and then coating the POSS modified UV cured hyperbranched polyurethane acrylate coating on the side of the paper printed with the pattern layer at a light intensity of 200mW/cm2Irradiating for 9s under ultraviolet light to obtain a protective coating;
(4) the texture paper is cut and then the wooden frame strip is coated, and the texture paper frame strip shown in figure 2 is obtained after nail cutting and assembling.
The POSS modified UV-cured hyperbranched polyurethane acrylate coating comprises the following components in parts by weight: 80 parts of POSS modified hyperbranched polyurethane acrylate, 15 parts of 1, 6-hexanediol diacrylate, 5.5 parts of 2, 2-dimethoxy-2-phenylacetophenone photoinitiator and 0.5 part of BYK3560 leveling agent.
The preparation method of the POSS modified hyperbranched polyurethane acrylate comprises the following steps:
A) mixing heptaisobutyl trisilanol and vinyl trichlorosilane, adding tetrahydrofuran, and adding triethylamine, wherein the molar ratio of the heptaisobutyl trisilanol to the vinyl trichlorosilane to the triethylamine is 1:1: 3; reacting for 50min at-8 ℃ under the protection of nitrogen, then reacting for 16h at normal temperature, filtering, concentrating the filtrate, adding excessive deionized water for precipitation, and filtering the precipitated product to obtain vinyl modified POSS; adding vinyl modified POSS and mercaptosuccinic acid with the molar ratio of 1:1.1 into tetrahydrofuran, stirring and dissolving under the protection of nitrogen, then adding azobisisobutyronitrile with the total mass of 1.5% of reactants, heating to 80 ℃ to react for 18 hours, concentrating the reaction liquid, then adding excessive deionized water to precipitate, filtering and drying the precipitated product to obtain carboxyl modified POSS;
B) adding isophorone diisocyanate into DMF (dimethyl formamide) with equal mass under the protection of nitrogen, then dropwise adding 50 wt% of DMF solution of polyethylene glycol, and reacting at 40 ℃ until the NCO value is unchanged; cooling to 2 ℃, then dropwise adding 50 wt% of DMF solution of diethanolamine, and carrying out heat preservation reaction until the NCO value is unchanged to obtain a polymerized monomer; wherein the mass ratio of the added isophorone diisocyanate to the added polyethylene glycol to the added diethanol amine is 1.1:1: 0.26;
C) taking half mass of polymerization monomer, mixing with dibutyltin dilaurate, wherein the addition amount of the dibutyltin dilaurate is 0.1% of the total mass of reactants; heating to 40 ℃, stopping the reaction until the NCO value reaches 1.63 percent, cooling to room temperature, washing the product with water, and drying to obtain pre-branched polyurethane; adding carboxyl modified POSS and pre-branched polyurethane with the mass ratio of 4.5:25 into DMF (dimethyl formamide) for dissolving, adding concentrated sulfuric acid accounting for 8% of the total mass of reactants, reacting for 5 hours at 110 ℃, washing and drying a product to obtain POSS modified pre-branched polyurethane; then mixing the POSS modified pre-branched polyurethane with the other half of the polymerized monomer, adding the mixture into DMF with equal mass, and adding dibutyltin dilaurate accounting for 0.1 percent of the total mass of reactants; heating to 40 ℃, and stopping the reaction until the NCO value reaches 0.54 percent to obtain POSS modified hyperbranched polyurethane;
D) adding isophorone diisocyanate into DMF (dimethyl formamide) with equal mass under the protection of nitrogen, adding dibutyltin dilaurate accounting for 0.1% of the total mass of reactants and p-hydroxyanisole accounting for 0.08% of the total mass of the reactants, and then dropwise adding a DMF (dimethyl formamide) solution of hydroxyethyl acrylate with the weight of 50% to ensure that the molar ratio of isophorone diisocyanate to hydroxyethyl acrylate is 1: 1.1; reacting at 40 ℃ until the NCO value is unchanged to obtain an isocyanate-terminated prepolymer;
E) and (2) mixing the POSS modified hyperbranched polyurethane with the isocyanate-terminated prepolymer in a mass ratio of 1.3:1, adding dibutyltin dilaurate accounting for 0.1% of the total mass of reactants, and reacting at 40 ℃ until the NCO value is less than 0.3% to obtain the POSS modified hyperbranched polyurethane acrylate.
Example 2:
a texture paper frame strip comprises a wooden frame strip and texture paper coated outside the wooden frame strip, and the preparation method comprises the following steps:
(1) the gram weight is 160g/m2Embossing the base paper;
(2) spray-painting a pattern layer simulating the effect of real plants on the embossed paper;
(3) coating a protective coating with the thickness of 5 mu m on one side printed with the pattern layer to obtain texture paper; the coating method of the protective coating comprises the following steps: coating the POSS modified UV cured hyperbranched polyurethane acrylate coating on one side of paper printed with a pattern layer, and then coating the POSS modified UV cured hyperbranched polyurethane acrylate coating on the side of the paper printed with the pattern layer at a light intensity of 100mW/cm2Irradiating for 10s under ultraviolet light to obtain a protective coating;
(4) and cutting texture paper, then coating the wood frame strip, cutting nails, and assembling to obtain the texture paper frame strip.
The POSS modified UV-cured hyperbranched polyurethane acrylate coating comprises the following components in parts by weight: 75 parts of POSS modified hyperbranched polyurethane acrylate, 10 parts of 1, 6-hexanediol diacrylate, 5 parts of 2, 2-dimethoxy-2-phenylacetophenone photoinitiator and 0.1 part of BYK3560 leveling agent.
The preparation method of the POSS modified hyperbranched polyurethane acrylate comprises the following steps:
A) mixing heptaisobutyl trisilanol and vinyl trichlorosilane, adding tetrahydrofuran, and adding triethylamine, wherein the molar ratio of the heptaisobutyl trisilanol to the vinyl trichlorosilane to the triethylamine is 1.1:1: 2.9; reacting for 60min at-5 ℃ under the protection of nitrogen, then reacting for 12h at normal temperature, filtering, concentrating the filtrate, adding excessive deionized water for precipitation, and filtering the precipitated product to obtain vinyl modified POSS; adding vinyl modified POSS and mercaptosuccinic acid with the molar ratio of 1:1 into tetrahydrofuran, stirring and dissolving under the protection of nitrogen, then adding azobisisobutyronitrile with the total mass of 1% of the reactants, heating to 75 ℃ for reaction for 24 hours, concentrating the reaction liquid, then adding excessive deionized water for precipitation, filtering and drying the precipitated product to obtain carboxyl modified POSS;
B) adding isophorone diisocyanate into DMF (dimethyl formamide) with the same mass under the protection of nitrogen, then dropwise adding 50 wt% of DMF solution of polyethylene glycol, and reacting at 45 ℃ until the NCO value is unchanged; cooling to 0 ℃, then dropwise adding 50 wt% of DMF solution of diethanolamine, and carrying out heat preservation reaction until the NCO value is unchanged to obtain a polymerized monomer; wherein the mass ratio of the added isophorone diisocyanate to the added polyethylene glycol to the added diethanol amine is 1.2:1: 0.27;
C) taking half mass of polymerization monomer, mixing with dibutyltin dilaurate, wherein the addition amount of the dibutyltin dilaurate is 0.08 percent of the total mass of reactants; heating to 45 ℃, stopping the reaction until the NCO value reaches 1.52%, cooling to room temperature, washing the product with water, and drying to obtain pre-branched polyurethane; adding carboxyl modified POSS and pre-branched polyurethane with the mass ratio of 4:25 into DMF (dimethyl formamide) for dissolving, adding concentrated sulfuric acid accounting for 5% of the total mass of reactants, reacting for 6 hours at 120 ℃, washing and drying a product to obtain POSS modified pre-branched polyurethane; then mixing the POSS modified pre-branched polyurethane with the other half of the polymerized monomer, adding the mixture into DMF with equal mass, and adding dibutyltin dilaurate accounting for 0.08 percent of the total mass of reactants; heating to 45 ℃, and stopping the reaction until the NCO value reaches 0.36 percent to obtain POSS modified hyperbranched polyurethane;
D) adding isophorone diisocyanate into DMF (dimethyl formamide) with equal mass under the protection of nitrogen, adding dibutyltin dilaurate accounting for 0.08 percent of the total mass of reactants and p-hydroxyanisole accounting for 0.05 percent of the total mass of the reactants, and then dropwise adding a DMF solution of hydroxyethyl acrylate with 50 percent by weight to ensure that the molar ratio of isophorone diisocyanate to hydroxyethyl acrylate is 1: 1; reacting at 45 ℃ until the NCO value is unchanged to obtain an isocyanate-terminated prepolymer;
E) and (2) mixing the POSS modified hyperbranched polyurethane with the isocyanate-terminated prepolymer in a mass ratio of 1.2:1, adding dibutyltin dilaurate accounting for 0.08 percent of the total mass of reactants, and reacting at 45 ℃ until the NCO value is less than 0.3 percent to obtain the POSS modified hyperbranched polyurethane acrylate.
Example 3:
a texture paper frame strip comprises a wooden frame strip and texture paper coated outside the wooden frame strip, and the preparation method comprises the following steps:
(1) the gram weight is 180g/m2Embossing the base paper;
(2) spray-painting a pattern layer simulating the effect of real plants on the embossed paper;
(3) coating a protective coating with the thickness of 10 mu m on one side printed with the pattern layer to obtain texture paper; the coating method of the protective coating comprises the following steps: coating the POSS modified UV cured hyperbranched polyurethane acrylate coating on one side of paper printed with a pattern layer, and then coating the POSS modified UV cured hyperbranched polyurethane acrylate coating on the side of the paper printed with the pattern layer at a light intensity of 300mW/cm2Irradiating for 8s under ultraviolet light to obtain a protective coating;
(4) and cutting texture paper, then coating the wood frame strip, cutting nails, and assembling to obtain the texture paper frame strip.
The POSS modified UV-cured hyperbranched polyurethane acrylate coating comprises the following components in parts by weight: 85 parts of POSS modified hyperbranched polyurethane acrylate, 20 parts of 1, 6-hexanediol diacrylate, 6 parts of 2, 2-dimethoxy-2-phenylacetophenone photoinitiator and 1 part of BYK3560 leveling agent.
The preparation method of the POSS modified hyperbranched polyurethane acrylate comprises the following steps:
A) mixing heptaisobutyl trisilanol and vinyl trichlorosilane, adding tetrahydrofuran, and adding triethylamine, wherein the molar ratio of the heptaisobutyl trisilanol to the vinyl trichlorosilane to the triethylamine is 1.2:1: 2.8; reacting at-10 ℃ for 40min under the protection of nitrogen, then reacting at normal temperature for 18h, filtering, concentrating the filtrate, adding excessive deionized water for precipitation, and filtering the precipitated product to obtain vinyl modified POSS; adding vinyl modified POSS and mercaptosuccinic acid with the molar ratio of 1:1.2 into tetrahydrofuran, stirring and dissolving under the protection of nitrogen, then adding azobisisobutyronitrile with the mass of 2% of the total mass of reactants, heating to 85 ℃ for reaction for 12 hours, concentrating the reaction liquid, then adding excessive deionized water for precipitation, filtering and drying the precipitated product to obtain carboxyl modified POSS;
B) adding isophorone diisocyanate into DMF (dimethyl formamide) with the same mass under the protection of nitrogen, then dropwise adding 50 wt% of DMF solution of polyethylene glycol, and reacting at 35 ℃ until the NCO value is unchanged; cooling to 4 ℃, then dropwise adding 50 wt% of DMF solution of diethanolamine, and carrying out heat preservation reaction until the NCO value is unchanged to obtain a polymerized monomer; wherein the mass ratio of the added isophorone diisocyanate to the added polyethylene glycol to the added diethanol amine is 1.2:1: 0.27;
C) taking half mass of polymerization monomer, mixing with dibutyltin dilaurate, wherein the addition amount of the dibutyltin dilaurate is 0.12% of the total mass of reactants; heating to 35 ℃, stopping the reaction until the NCO value reaches 1.97%, cooling to room temperature, washing the product with water, and drying to obtain pre-branched polyurethane; adding carboxyl modified POSS and pre-branched polyurethane with the mass ratio of 5:25 into DMF (dimethyl formamide) for dissolving, adding concentrated sulfuric acid accounting for 10% of the total mass of reactants, reacting for 4 hours at 100 ℃, washing and drying a product to obtain POSS modified pre-branched polyurethane; then mixing the POSS modified pre-branched polyurethane with the other half of the polymerized monomer, adding the mixture into DMF with equal mass, and adding dibutyltin dilaurate accounting for 0.12 percent of the total mass of reactants; heating to 35 ℃, and stopping the reaction until the NCO value reaches 0.92% to obtain POSS modified hyperbranched polyurethane;
D) adding isophorone diisocyanate into DMF (dimethyl formamide) with equal mass under the protection of nitrogen, adding dibutyltin dilaurate accounting for 0.12% of the total mass of reactants and p-hydroxyanisole accounting for 0.1% of the total mass of the reactants, and then dropwise adding a DMF solution of hydroxyethyl acrylate with the weight of 50% to ensure that the molar ratio of isophorone diisocyanate to hydroxyethyl acrylate is 1: 1.2; reacting at 35 ℃ until the NCO value is unchanged to obtain an isocyanate-terminated prepolymer;
E) and (2) mixing the POSS modified hyperbranched polyurethane with the isocyanate-terminated prepolymer in a mass ratio of 1.4:1, adding dibutyltin dilaurate accounting for 0.12% of the total mass of reactants, and reacting at 35 ℃ until the NCO value is less than 0.3% to obtain the POSS modified hyperbranched polyurethane acrylate.
Comparative example 1 (hyperbranched urethane acrylate not modified with POSS):
in comparative example 1, a UV-curable hyperbranched urethane acrylate coating was used for applying the protective coating, and the composition thereof in parts by weight included: 80 parts of hyperbranched polyurethane acrylate, 15 parts of 1, 6-hexanediol diacrylate, 5.5 parts of 2, 2-dimethoxy-2-phenylacetophenone photoinitiator and 0.5 part of BYK3560 leveling agent.
The preparation method of the hyperbranched polyurethane acrylate comprises the following steps:
A) adding isophorone diisocyanate into DMF (dimethyl formamide) with equal mass under the protection of nitrogen, then dropwise adding 50 wt% of DMF solution of polyethylene glycol, and reacting at 40 ℃ until the NCO value is unchanged; cooling to 2 ℃, then dropwise adding 50 wt% of DMF solution of diethanolamine, and carrying out heat preservation reaction until the NCO value is unchanged to obtain a polymerized monomer; wherein the mass ratio of the added isophorone diisocyanate to the added polyethylene glycol to the added diethanol amine is 1.1:1: 0.26;
B) mixing a polymerization monomer with dibutyltin dilaurate, wherein the addition amount of the dibutyltin dilaurate is 0.1 percent of the total mass of reactants; heating to 40 ℃, and stopping the reaction until the NCO value reaches 0.54 percent to obtain hyperbranched polyurethane;
C) adding isophorone diisocyanate into DMF (dimethyl formamide) with equal mass under the protection of nitrogen, adding dibutyltin dilaurate accounting for 0.1% of the total mass of reactants and p-hydroxyanisole accounting for 0.08% of the total mass of the reactants, and then dropwise adding a DMF (dimethyl formamide) solution of hydroxyethyl acrylate with the weight of 50% to ensure that the molar ratio of isophorone diisocyanate to hydroxyethyl acrylate is 1: 1.1; reacting at 40 ℃ until the NCO value is unchanged to obtain an isocyanate-terminated prepolymer;
D) mixing hyperbranched polyurethane with a mass ratio of 1.3:1 with the isocyanate-terminated prepolymer, adding dibutyltin dilaurate accounting for 0.1% of the total mass of reactants, and reacting at 40 ℃ until the NCO value is less than 0.3% to obtain the hyperbranched polyurethane acrylate.
The rest is the same as in example 1.
Comparative example 2 (hyperbranched urethane acrylate directly blended with POSS):
the POSS modified UV cured hyperbranched urethane acrylate coating used in the protective coating application of comparative example 2 comprises the following components in parts by weight: 80 parts of hyperbranched polyurethane acrylate, 7 parts of carboxyl modified POSS, 15 parts of 1, 6-hexanediol diacrylate, 5.5 parts of 2, 2-dimethoxy-2-phenylacetophenone photoinitiator and 0.5 part of BYK3560 leveling agent.
The preparation method of the carboxyl modified POSS comprises the following steps: mixing heptaisobutyl trisilanol and vinyl trichlorosilane, adding tetrahydrofuran, and adding triethylamine, wherein the molar ratio of the heptaisobutyl trisilanol to the vinyl trichlorosilane to the triethylamine is 1:1: 3; reacting for 50min at-8 ℃ under the protection of nitrogen, then reacting for 16h at normal temperature, filtering, concentrating the filtrate, adding excessive deionized water for precipitation, and filtering the precipitated product to obtain vinyl modified POSS; adding vinyl modified POSS and mercaptosuccinic acid with the molar ratio of 1:1.1 into tetrahydrofuran, stirring and dissolving under the protection of nitrogen, then adding azobisisobutyronitrile with the total mass of 1.5% of reactants, heating to 80 ℃ to react for 18 hours, concentrating the reaction liquid, then adding excessive deionized water to precipitate, filtering and drying the precipitated product to obtain carboxyl modified POSS;
the preparation method of the hyperbranched polyurethane acrylate is the same as that of comparative example 1;
the rest is the same as in example 1.
Comparative example 3 (varying the time of addition of the carboxyl modified POSS):
the preparation method of the POSS modified hyperbranched urethane acrylate in the comparative example 3 is as follows:
A) mixing heptaisobutyl trisilanol and vinyl trichlorosilane, adding tetrahydrofuran, and adding triethylamine, wherein the molar ratio of the heptaisobutyl trisilanol to the vinyl trichlorosilane to the triethylamine is 1:1: 3; reacting for 50min at-8 ℃ under the protection of nitrogen, then reacting for 16h at normal temperature, filtering, concentrating the filtrate, adding excessive deionized water for precipitation, and filtering the precipitated product to obtain vinyl modified POSS; adding vinyl modified POSS and mercaptosuccinic acid with the molar ratio of 1:1.1 into tetrahydrofuran, stirring and dissolving under the protection of nitrogen, then adding azobisisobutyronitrile with the total mass of 1.5% of reactants, heating to 80 ℃ to react for 18 hours, concentrating the reaction liquid, then adding excessive deionized water to precipitate, filtering and drying the precipitated product to obtain carboxyl modified POSS;
B) adding isophorone diisocyanate into DMF (dimethyl formamide) with equal mass under the protection of nitrogen, then dropwise adding 50 wt% of DMF solution of polyethylene glycol, and reacting at 40 ℃ until the NCO value is unchanged; cooling to 2 ℃, then dropwise adding 50 wt% of DMF solution of diethanolamine, and carrying out heat preservation reaction until the NCO value is unchanged to obtain a polymerized monomer; wherein the mass ratio of the added isophorone diisocyanate to the added polyethylene glycol to the added diethanol amine is 1.1:1: 0.26;
C) mixing a polymerization monomer with dibutyltin dilaurate, wherein the addition amount of the dibutyltin dilaurate is 0.1 percent of the total mass of reactants; heating to 40 ℃, stopping the reaction until the NCO value reaches 0.54%, cooling to room temperature, washing the product with water, and drying to obtain hyperbranched polyurethane; adding carboxyl modified POSS and hyperbranched polyurethane with the mass ratio of 4.5:25 into DMF (dimethyl formamide) for dissolving, adding concentrated sulfuric acid accounting for 8% of the total mass of reactants, reacting for 5 hours at 110 ℃, washing and drying a product to obtain POSS modified hyperbranched polyurethane;
D) adding isophorone diisocyanate into DMF (dimethyl formamide) with equal mass under the protection of nitrogen, adding dibutyltin dilaurate accounting for 0.1% of the total mass of reactants and p-hydroxyanisole accounting for 0.08% of the total mass of the reactants, and then dropwise adding a DMF (dimethyl formamide) solution of hydroxyethyl acrylate with the weight of 50% to ensure that the molar ratio of isophorone diisocyanate to hydroxyethyl acrylate is 1: 1.1; reacting at 40 ℃ until the NCO value is unchanged to obtain an isocyanate-terminated prepolymer;
E) the POSS modified hyperbranched polyurethane and the isocyanate-terminated prepolymer in the mass ratio of 1.3:1 are mixed, added into DMF (dimethyl formamide) with the same mass as the POSS modified hyperbranched polyurethane, added with dibutyltin dilaurate accounting for 0.1% of the total mass of reactants, and reacted at 40 ℃ until the NCO value is less than 0.3%, so as to obtain the POSS modified hyperbranched polyurethane acrylate.
The rest is the same as in example 1.
Comparative example 4 (varying the number of carboxyl groups in the carboxyl-modified POSS):
comparative example 4 the preparation of the carboxy modified POSS in step a) was as follows: mixing vinyl trimethoxy silane, acetone, concentrated hydrochloric acid and deionized water in a volume ratio of 26.7:270:45:52, reacting at 40 ℃ for 48 hours, filtering the product, and cleaning with absolute ethyl alcohol to obtain octavinyl POSS; adding octavinyl POSS and mercaptosuccinic acid with the molar ratio of 1:8 into tetrahydrofuran, stirring and dissolving under the protection of nitrogen, then adding azobisisobutyronitrile with the total mass of 1.5% of reactants, heating to 80 ℃ for reaction for 18 hours, concentrating the reaction liquid, then adding excessive deionized water for precipitation, filtering and drying the precipitated product to obtain the carboxyl modified POSS.
The rest is the same as in example 1.
Comparative example 5 (too much carboxyl modified POSS addition):
comparative example 5 the mass ratio of carboxy modified POSS to pre-branched polyurethane in step C) was 6:25, all the remainder being the same as in example 1.
The performance of the protective coatings on the surfaces of the textured paper frame strips prepared in the above examples and comparative examples was tested, and the results are shown in table 1.
Wherein, the test of the wear resistance refers to the method in GB/T1768-2006;
the adhesion test is carried out according to the method in GB/T9286-1998;
the flexibility is tested according to the method in GB/T1731-93;
the acid and alkali resistance test method comprises the following steps: 2mL of 5 wt% dilute sulfuric acid and 5 wt% sodium hydroxide solution were dropped on the surface of the protective coating, respectively, and left at room temperature for 24 hours, and then wiped with absorbent cotton dipped with ethanol, and it was observed whether the coating was damaged or not.
Table 1: and (5) testing the performance of the protective coating.
Figure BDA0003134003900000111
As can be seen from table 1, the protective coatings prepared by using the POSS modified UV cured hyperbranched urethane acrylate coating of the present invention in embodiments 1 to 3 have good hardness and flexibility, and have good adhesion, wear resistance, acid and alkali resistance, and hydrophobicity, and can effectively improve the service life and stain resistance of the textured paper frame strip.
In contrast, in comparative example 1, the UV-curable hyperbranched urethane acrylate was not modified with POSS, and the hardness, abrasion resistance, and hydrophobicity of the protective coating were significantly reduced as compared to example 1.
In comparative example 2, POSS is not modified on a hyperbranched polyurethane acrylate molecular chain, but hyperbranched polyurethane acrylate is directly blended with POSS, and as the compatibility of POSS and hyperbranched polyurethane acrylate is reduced and agglomeration is easy to occur, the hardness, flexibility, adhesive force, wear resistance and other properties of the protective coating are reduced.
In comparative example 3, after the polymerized monomers are condensed to the fourth generation product, the carboxyl modified POSS is added to modify the polymerized monomers, so that the hardness and the wear resistance of the obtained protective coating are reduced, the use of the texture paper frame strip is not facilitated, but the flexibility of the protective coating is improved compared with that of the protective coating in example 1; probably, in the embodiment 1, when the polymerized monomers are condensed to the second generation product, POSS is firstly modified, and then the polycondensation is continued to the fourth generation product, so that POSS with higher rigidity can be uniformly distributed among the flexible chain segments; and in the comparative example 3, POSS is directly modified by polycondensation to the fourth generation product, the length of the flexible chain segment is longer, so that the hardness of the coating can not meet the requirement.
In the comparative example 4, the carboxyl-modified POSS having two carboxyl groups at eight corners is adopted, and the branching degree and the molecular structure of the obtained hyperbranched polyurethane-polyacrylate are affected after excessive carboxyl groups react with the pre-branched polyurethane, so that the adhesive force, flexibility and other properties of the obtained protective coating are obviously reduced.
In comparative example 5, the carboxyl modified POSS is added too much, and although the hardness of the protective coating is higher, the adhesion and the flexibility are reduced, and the service life of the texture paper frame strip is also influenced.

Claims (10)

1. A texture paper frame strip is characterized by comprising a frame strip and texture paper coated outside the frame strip, and the preparation method comprises the following steps:
(1) embossing the base paper;
(2) printing a pattern layer on the embossed paper;
(3) coating a protective coating on one side printed with the pattern layer to obtain texture paper;
(4) and cutting texture paper, then coating the frame strips, cutting nails, and assembling to obtain the texture paper frame strips.
2. A textured paper frame strip according to claim 1, which is characterized in thatCharacterized in that the gram weight of the base paper in the step (1) is 160-180 g/m2。
3. The texture paper frame strip according to claim 1, wherein the thickness of the protective coating in step (3) is 5-10 μm; the coating method of the protective coating comprises the following steps: coating the POSS modified UV cured hyperbranched polyurethane acrylate coating on one side of paper printed with a pattern layer, and then coating the POSS modified UV cured hyperbranched polyurethane acrylate coating on the side of the paper printed with the pattern layer at a light intensity of 100-300 mW/cm2Irradiating for 8-10 s under the ultraviolet light to obtain the protective coating.
4. The texture paper frame strip according to claim 3, wherein the POSS modified UV cured hyperbranched polyurethane acrylate coating comprises the following components in parts by weight: 75-85 parts of POSS modified hyperbranched polyurethane acrylate, 10-20 parts of 1, 6-hexanediol diacrylate, 5-6 parts of photoinitiator and 0.1-1 part of flatting agent.
5. The texture paper frame strip according to claim 4, wherein the POSS modified hyperbranched polyurethane acrylate is prepared by the following steps:
A) mixing heptaisobutyl trisilanol and vinyl trichlorosilane, adding into tetrahydrofuran, adding triethylamine, reacting for 40-60 min at-10 to-5 ℃ under the protection of nitrogen, reacting for 12-18 h at normal temperature, filtering, concentrating the filtrate, adding deionized water for precipitation, and filtering the precipitated product to obtain vinyl modified POSS; adding vinyl modified POSS and mercaptosuccinic acid into tetrahydrofuran, stirring and dissolving under the protection of nitrogen, adding azobisisobutyronitrile, heating to 75-85 ℃, reacting for 12-24 hours, concentrating the reaction liquid, adding deionized water for precipitation, filtering and drying the precipitation product to obtain carboxyl modified POSS;
B) adding isophorone diisocyanate into a solvent under the protection of nitrogen, then dropwise adding a DMF (dimethyl formamide) solution of polyethylene glycol, and reacting at 35-45 ℃ until the NCO value is unchanged; cooling to 0-4 ℃, then dropwise adding a DMF (dimethyl formamide) solution of diethanolamine, and carrying out heat preservation reaction until the NCO value is unchanged to obtain a polymerized monomer;
C) mixing a part of polymerization monomer with a catalyst, heating to 35-45 ℃, stopping reaction until the NCO value reaches 1.5-2.0%, cooling to room temperature, washing a product with water, and drying to obtain pre-branched polyurethane; adding carboxyl modified POSS and pre-branched polyurethane into DMF (dimethyl formamide) for dissolving, adding concentrated sulfuric acid, reacting for 4-6 h at 100-120 ℃, washing and drying a product to obtain POSS modified pre-branched polyurethane; mixing the POSS modified pre-branched polyurethane with the rest of polymerization monomers, adding the mixture into a solvent, adding a catalyst, heating to 35-45 ℃, and stopping reaction until the NCO value reaches 0.3-1.0% to obtain POSS modified hyperbranched polyurethane;
D) under the protection of nitrogen, mixing isophorone diisocyanate, DMF (dimethyl formamide), a catalyst and a polymerization inhibitor, then dropwise adding a DMF (dimethyl formamide) solution of hydroxyethyl acrylate, and reacting at 35-45 ℃ until the NCO value is unchanged to obtain an isocyanate-terminated prepolymer;
E) and mixing the POSS modified hyperbranched polyurethane with the isocyanate-terminated prepolymer, adding a catalyst, and reacting at 35-45 ℃ until the NCO value is less than 0.3% to obtain the POSS modified hyperbranched polyurethane acrylate.
6. The texture paper frame strip according to claim 5, wherein the molar ratio of the heptaisobutyltrisilanol, the vinyltrichlorosilane and the triethylamine in the step A) is 1-1.2: 1: 2.8-3; the mol ratio of the vinyl modified POSS to the mercaptosuccinic acid is 1: 1-1.2; the addition amount of the azodiisobutyronitrile is 1-2% of the total mass of reactants.
7. The texture paper frame strip according to claim 5, wherein the mass ratio of isophorone diisocyanate, polyethylene glycol and diethanolamine added in step B) is 1.1-1.2: 1: 0.26-0.27.
8. The texture paper frame strip according to claim 5, wherein the mass ratio of the two added polymerized monomers in the step C) is 1: 1-1.2; the catalyst is dibutyltin dilaurate, and the adding amount of the catalyst in each time is 0.08-0.12% of the total mass of reactants; when the POSS modified pre-branched polyurethane is prepared, the mass ratio of the carboxyl modified POSS to the pre-branched polyurethane is 4-5: 25, and the addition amount of concentrated sulfuric acid is 5-10% of the total mass of reactants.
9. The texture paper frame strip according to claim 5, wherein the molar ratio of isophorone diisocyanate and hydroxyethyl acrylate added in step D) is 1: 1-1.2; the catalyst is dibutyltin dilaurate, and the adding amount of the catalyst is 0.08-0.12% of the total mass of reactants; the polymerization inhibitor is p-hydroxyanisole, and the addition amount of the polymerization inhibitor is 0.05-0.1% of the total mass of the reactants.
10. The texture paper frame strip according to claim 5, wherein the mass ratio of POSS modified hyperbranched polyurethane to isocyanate-terminated prepolymer in the step E) is 1.2-1.4: 1; the catalyst is dibutyltin dilaurate, and the adding amount of the catalyst is 0.08-0.12% of the total mass of reactants.
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CN104533043A (en) * 2014-12-03 2015-04-22 珠海东诚光固化材料有限公司 Decoration board and preparation method thereof
CN104592473A (en) * 2013-10-31 2015-05-06 嘉兴禾欣化学工业有限公司 Preparation method of POSS modified polyurethane resin
WO2016095289A1 (en) * 2014-12-17 2016-06-23 杨磊 Preparation method for nanometer material capable of improving fire resistance of waterborne polyurethane coating and adhesive
CN111962334A (en) * 2020-08-28 2020-11-20 广东福美新材料科技有限公司 Wear-resistant wood-grain paper and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592473A (en) * 2013-10-31 2015-05-06 嘉兴禾欣化学工业有限公司 Preparation method of POSS modified polyurethane resin
CN104533043A (en) * 2014-12-03 2015-04-22 珠海东诚光固化材料有限公司 Decoration board and preparation method thereof
WO2016095289A1 (en) * 2014-12-17 2016-06-23 杨磊 Preparation method for nanometer material capable of improving fire resistance of waterborne polyurethane coating and adhesive
CN111962334A (en) * 2020-08-28 2020-11-20 广东福美新材料科技有限公司 Wear-resistant wood-grain paper and preparation method thereof

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