CN106939084B - Plastic plate or film with super steel wool resistance and weather resistance and preparation method thereof - Google Patents
Plastic plate or film with super steel wool resistance and weather resistance and preparation method thereof Download PDFInfo
- Publication number
- CN106939084B CN106939084B CN201710181297.XA CN201710181297A CN106939084B CN 106939084 B CN106939084 B CN 106939084B CN 201710181297 A CN201710181297 A CN 201710181297A CN 106939084 B CN106939084 B CN 106939084B
- Authority
- CN
- China
- Prior art keywords
- coating
- resistance
- weather resistance
- film
- reactant
- 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
Links
Classifications
-
- 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
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- 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
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
Abstract
The invention discloses a plastic plate or film with both super steel wool resistance and weather resistance, which comprises a substrate, a first film layer with weather resistance on the surface of the substrate, and a second film layer with both super steel wool resistance and weather resistance on the surface of the first film layer. The plastic plate or film with the super steel wool resistance and the weather resistance has improved hardening, hydrophobic, oleophobic, anti-fouling and weather resistance, and can replace the traditional glass product to be applied to different industries (windows of automobiles, high-speed rails and subways in the traffic industry), thereby replacing the traditional glass product and being capable of reducing cost, weight, emission and energy consumption.
Description
Technical Field
The invention relates to the technical field of plate processing, in particular to a plastic plate or film with super steel wool resistance and weather resistance and a preparation method thereof.
Background
Glass products applied to the building industry, the transportation industry and the 3C industry are gradually banned by plastic plates or films such as PC, PMMA, PET and the like. However, these plastic plates or films such as PC, PMMA, and PET are required to have a certain hardness, abrasion resistance, water resistance, and stain resistance. And products applied outdoors need weather resistance. The improvement of the performance is generally realized by adding a hard coating film on the coating so as to endow special functions and meet the application requirements.
The coating has good effects of hydrophobicity, oleophobicity, stain resistance, wear resistance and hardening after being coated with a film, and the solution to date is realized by adding a fluorine auxiliary agent into the coating. However, after the fluorine assistant is added into the coating, although the coating can have a high water contact angle (100-108 ℃) and good wear resistance (the number of times of a steel wool wear-resistant test is 50-200 rounds) after film formation, the fluorine assistant has high cost, poor compatibility with a system and poor stability, and various limitations in the coating preparation or application process are easily caused, so that the optimal ideal effect is often not achieved.
The improvement of weather resistance is generally realized by adding some ultraviolet absorbers which can absorb ultraviolet parts in sunlight and fluorescent light sources and do not change per se, so that the long-term exposure to the sunlight is avoided, but the degradation of polymers is caused by the automatic oxidation reaction caused by the absorption of ultraviolet energy, so that the product performance and the appearance are easily seriously damaged.
With the development of science and technology and the pursuit of high quality of people, a plastic plate or film such as PC, PMMA, PET and the like, which can meet the requirements of excellent steel wool resistance and weather resistance after film coating, and simultaneously has the performances of hydrophobicity, oleophobicity, stain resistance, wear resistance, hardening and weather resistance, is applied to a plurality of industries (such as vehicle windows of automobiles, high-speed rails and subways in the traffic industry), thereby replacing the traditional glass product, and being capable of reducing the cost, the weight, the emission and the energy consumption.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a plastic plate or film which has super steel wool resistance and weather resistance at the same time, and the plastic plate or film has improved hardening, hydrophobic, oleophobic and anti-fouling effects at the same time.
The invention also aims to provide a preparation method of the plastic plate or the film with both the super steel wool resistance and the weather resistance.
The invention is realized by the following technical scheme:
the plastic plate or film simultaneously has super steel wool resistance and weather resistance, comprises a substrate, a first layer of weather-resistant film layer on the surface of the substrate, and a second layer of the weather-resistant film layer on the surface of the first layer of weather-resistant film layer, wherein the second layer of the weather-resistant film layer simultaneously has the super steel wool resistance and the weather resistance.
The first film layer with weather resistance is obtained by coating the coating with weather resistance on the surface of a base material in a curtain coating, spraying, dip coating or roll coating mode on two sides and then coating the coating with low-temperature flash drying.
The coating with the weather resistance comprises the following components in parts by weight:
wherein, the plastic in the plastic master batch is selected from PC and/or PMMA.
Wherein, the multifunctional polyurethane acrylic resin is selected from one or more of two to nine functional polyurethane acrylic resins; but not limited to, one or more of aliphatic urethane acrylate CN996, urethane acrylate CN989, aliphatic urethane acrylate CN9010 and aliphatic urethane acrylate CN9013 of sartomer.
The inorganic ultraviolet absorbent can be one or more of BYK-3812, BYK-3821 and liquid nano cerium dioxide ultraviolet absorbent of Chinese patent CN201310362095.7, preferably liquid nano cerium dioxide ultraviolet absorbent of Chinese patent CN 201310362095.7.
The solvent may be one or more selected from, but not limited to, isopropyl alcohol, n-butanol, ethylene glycol monobutyl ether, propylene glycol methyl ether, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and butyl acetate. The viscosity is adjusted by selecting and using the solvent, and the coating can be suitable for different coating processes such as spraying, curtain coating, dip coating or roll coating.
The base material is selected from a PC plate, a PMMA plate, a PC and PMMA composite plate or a PET film.
The coating with the super steel wool resistance and the weather resistance comprises the following components in parts by weight:
wherein the polyurethane acrylate copolymer containing the fluorosilicone block has a structural formula shown as formula i:
or
Wherein formula i is obtained from reactant A, B, C by an addition reaction;
wherein R is oligomeric fluorosilicone derived from a reactant A,
r' is a diisocyanate derived from reactant B,
r' is an alkyl acrylate derived from reactant C;
the value range of m is 1-100, preferably 10-50.
Wherein the reactant A has a structural formula shown as a formula ii:
wherein, the value range of n is 1-100, preferably 5-50;
when the value range of m is more than 100, the polymerization degree is high, so that the viscosity is high and the operation is difficult.
Wherein the reactant A has a structural formula shown as a formula ii:
wherein, the value range of n is 1-100, preferably 5-50.
When the value range of n is more than 100, the polymerization degree is high, so that the viscosity is high, the operation is difficult, and the reaction is not facilitated.
Wherein the polyurethane acrylate copolymer containing the polysiloxane block is 20-50 parts based on the total weight of the super steel wool resistant coating, and the expected steel wool resistant performance cannot be achieved; when the weight part of the polyurethane acrylate copolymer containing the fluorosilicone block is too much and exceeds 50 parts by weight, the steel wool resistance is weakly improved.
Wherein the viscosity of the reactant A is 0.005 to 100 Pa.s. The viscosity is measured by adopting a Bohler Fei viscometer after the temperature is kept at 25 ℃ for more than 2 hours.
The reactant B is diisocyanate and is selected from one or more of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), 4' -dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI) and Toluene Diisocyanate (TDI).
Wherein, the reactant C is selected from one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
The invention also discloses a preparation method of the polyurethane acrylate copolymer containing the polyfluorosiloxane block, which comprises the following steps:
1) preparation of a reactant A: reacting trifluoropropyl methyl cyclotrisiloxane at 50-90 ℃ under the catalysis of acid, and obtaining a reactant A after lowering;
2) preparation of NCO group-terminated
Or
Blocking a precursor: the reactant A is vacuumized for 1 to 2 hours at the temperature of 110-120 ℃ and then is reduced to 15 to 35 ℃, and reacts with the reactant B for 2 to 4 hours at the temperature of 50 to 70 ℃ to obtain the NCO group end-capped
Or
Blocking a precursor;
3) the reactant C is vacuumized for 1 to 2 hours at the temperature of 110-120 ℃ and then is reduced to 15 to 35 ℃, and is blocked with NCO groups
Or
And reacting the block precursor at 70-90 ℃ for 3-6 hours to obtain the block precursor.
In the step 1), the acid catalysis refers to the use of cationic resin as an acid catalyst; the low-boiling point material is extracted by negative pressure.
Wherein, in the step 2), the molar ratio of the reactant A to the reactant B is 1: 1-2.
Wherein, in step 3), the reactant C is blocked with NCO groups
Or
The molar ratio of the block precursors is 1-2: 1.
Wherein, the multifunctional polyurethane acrylic resin is selected from one or more of two to nine functional polyurethane acrylic resins; but not limited to, one or more of aliphatic urethane acrylate CN996, urethane acrylate CN989, aliphatic urethane acrylate CN9010 and aliphatic urethane acrylate CN9013 of sartomer.
The organic uv absorber may be, but not limited to, Tinuvin384, Tinuvin400, Tinuvin 928, Tinuvin1130, or one or more of the solid organic uv absorbers of chinese patent CN201310362094.2, and preferably the solid organic uv absorber of chinese patent CN 201310362094.2.
Wherein, the photoinitiator can be one or more of Irgacure 184, Irgacure 819, Lucirin TPO, Irgacure 907 and Irgacure 651;
the leveling agent can be one or more of BYK-302, BYK-346, BYK-354, Tego Rad2100 and Tego Rad 2300;
the solvent may be one or more selected from, but not limited to, isopropyl alcohol, n-butanol, ethylene glycol monobutyl ether, propylene glycol methyl ether, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and butyl acetate. The viscosity is adjusted by selecting and using the solvent, and the coating can be suitable for different coating processes such as spraying, curtain coating, dip coating or roll coating.
The paint with both super steel wool resistance and weather resistance can be prepared by the following steps: dispersing the above components at high speed, and filtering with 0.45 μm filter core.
Wherein the device for sufficiently dispersing at high speed is a high-speed dispersing machine with the rotating speed of 300-1500rpm and the dispersing time of 30-120 min.
The invention also discloses a preparation method of the plastic plate or the film with the super steel wool resistance and the weather resistance, which comprises the following steps:
1) construction environment: temperature 20-35 ℃, relative humidity 20-50% r.h.;
2) the coating method comprises the following steps: double-sided coating, spray coating, curtain coating, dip coating and roller coating; the first layer and the second layer are in a wet-on-wet mode;
3) viscosity of the coating: spraying, namely 7-20s in a No. 2 cup in a rock field; flow coating, wherein the Coriolis viscometer is 3-20 mPa.s; dip-coating, with a viscometer of 3-20mPa · s; roller coating, a Tanshi viscometer is 3-20 mPa.s;
4) treating a base material: cleaning a PC, PMMA, PET or composite plastic substrate by using ethanol or isopropanol to remove pollutants, and performing electrostatic dust removal;
5) leveling time: room temperature for 1-5 min;
6) and (3) low-temperature flash drying: 50-80 deg.C for 2-5 min;
7) ultraviolet light curing: fusion H lamp, curing energy 200-2；
8) The thickness of the cured film is as follows: 3-20 μm.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention prepares the coating with both super steel wool resistance and weather resistance by adding the polyurethane acrylate copolymer containing the polyfluorosiloxane block with specific content and specific structure, coats the coating with both super steel wool resistance and weather resistance on the surface of a first layer of film layer with weather resistance through double-sided coating, and obtains a second layer with both super steel wool resistance and weather resistance through ultraviolet irradiation curing film coating, wherein the second layer has the improved hardening, hydrophobic, oleophobic, anti-fouling and weather resistance performances, particularly has the super steel wool resistance and is far beyond the steel wool resistance standard on the market.
2) The plastic plate or film with the super steel wool resistance and the weather resistance has improved hardening, hydrophobic, oleophobic, anti-fouling and weather resistance, and can replace the traditional glass product to be applied to different industries (such as vehicle windows of automobiles, high-speed rails and subways in the traffic industry), thereby replacing the traditional glass product and being capable of reducing cost, weight, emission reduction and energy consumption.
3) According to the invention, the inorganic ultraviolet absorbent is introduced into the coating with the weather-resistant film layer on the first layer, and the organic ultraviolet absorbent is introduced into the coating with the super steel wool resistance and the weather-resistant film layer on the second layer, so that the weather resistance of the prepared plastic plate or film can be enhanced, and the service life of the plastic plate or film can be prolonged.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
The raw materials used in the examples and comparative examples are now described below, but are not limited to these materials:
polyfunctional polyurethane acrylic resin: aliphatic urethane acrylate CN9013, sartomer;
aliphatic urethane acrylate CN996, sartomer;
aliphatic urethane acrylate CN9010, sartomer;
urethane acrylate CN989, sartomer;
photoinitiator (2): irgacure 184, Ciba;
irgacure 651, Ciba;
lucirin TPO, basf;
irgacure 907, Ciba;
irgacure 819, Ciba;
leveling agent: BYK-346, bike;
tego Rad2300, Digao;
BYK-354, bike;
BYK-302, bike;
tego Rad2100, Digao;
solvent: isopropanol, n-butanol, propylene glycol methyl ether, ethyl acetate and butanone are all commercially available;
test criteria or methods for each property:
viscosity: the temperature is kept constant for more than 2 hours at 25 ℃ by adopting a Bohler viscometer, and then the test is carried out to obtain the product;
appearance: visual inspection;
pencil hardness: ASTM D3363;
adhesion force: cross-hatch method, mitsubishi pencil, 750g, ASTM D3002, D3359;
light transmittance and haze: ASTM D1003;
water contact angle: ASTM D5964;
boiling water resistance: after boiling in distilled water for 4hrs, the adhesion was tested;
steel wool resistance: linear abrasion tester, steel wool is U.S. HOMAX #0000, pressure 1000g/cm23.3cm of stroke, 40cycles/min of speed, wearing for a certain number of times (observing once every 200 cycles), and observing whether scratches exist on the surface appearance by using a magnifier;
taber abrasion resistance: taber 5135, CS-10F, Gen. IV, Load: 500g, 60rpm, 1000cycles attrition, haze change observed.
Weather resistance: ASTM G154, observed once every 400hrs, tested for appearance (crazing, paint-off, yellowing, etc.), light transmission/haze (change in haze value less than 7%), yellowness index (change value less than 4).
Example 1
A plastic plate with both super steel wool resistance and weather resistance comprises a substrate, a first layer of weather-resistant film layer on the surface of the substrate, and a second layer of super steel wool resistance and weather-resistant film layer on the surface of the first layer of weather-resistant film layer, wherein the second layer of the super steel wool resistance and weather-resistant film layer is coated on the surface of the first layer of weather-resistant film layer on both sides in a spraying mode, and is obtained by curing a coated film after ultraviolet irradiation; the first film layer with weather resistance is obtained by coating the coating with weather resistance on the surface of a base material in a spraying mode on two sides and then carrying out low-temperature flash drying and film covering;
the base material is a 12.0mmPC and PMMA composite board of Sabic;
the first weatherable film layer having a weatherable coating therein, comprising:
35 parts by weight of plastic master batch: PMMA master batch;
35 parts by weight of a polyfunctional polyurethane acrylic resin: urethane acrylate CN 9013;
1.5 parts by weight of an inorganic ultraviolet absorber: chinese patent CN201310362095.7 example 1 liquid nano ceria ultraviolet absorber;
28.5 parts by weight of solvent: isopropyl alcohol;
flash drying the components according to parts by weight at low temperature (70 ℃, 2min), and coating a film to obtain the product; the viscosity of the coating with weather resistance is 15 mPas;
the second layer has the coating with the super steel wool resistance and the weather resistance in the film layer with the super steel wool resistance and the weather resistance at the same time, and the coating comprises:
22 parts by weight of a polyurethane acrylate copolymer containing a fluorosilicone block,
the molecular formula is as follows:
obtained from reaction A, B, C by addition reaction:
wherein R is derived from reactant A
R' is isophorone diisocyanate (IPDI) derived from reactant B,
r' is hydroxyethyl methacrylate and dipentaerythritol pentaacrylate derived from reactant C;
m takes the value of 27;
5 parts by weight of polyfunctional polyurethane acrylic resin: urethane acrylate CN 989;
1.5 parts by weight of an organic ultraviolet absorber: chinese patent CN201310362094.2, example 3, a solid organic ultraviolet resistant absorbent;
1.7 parts by weight of a photoinitiator: irgacure 819;
0.5 parts by weight of a leveling agent: 0.15 parts by weight of BYK-302 and 0.35 parts by weight of Tego Rad 2100;
69.3 parts by weight of solvent: n-butanol;
fully dispersing the components in parts by weight in a high-speed dispersion machine at high speed, and filtering by using a 0.45-micrometer filter element to obtain the high-performance nano-filtration membrane; the viscosity of the obtained coating with the super steel wool resistance and weather resistance is 3.5 mPas;
the preparation method of the plastic plate or the film with both the super steel wool resistance and the weather resistance comprises the following steps:
1) construction environment: temperature 23 ℃, relative humidity 35% r.h.;
2) the coating method comprises the following steps: coating on both sides, and spraying; the first layer and the second layer are in a wet-on-wet mode;
3) viscosity of the coating: spraying, namely 8s in a 2# cup in a rock field;
4) treating a base material: 12.0mm of PC and PMMA composite board is cleaned by ethanol or isopropanol to remove pollutants, and electrostatic dust removal is carried out;
5) leveling time: room temperature for 4 min;
6) and (3) low-temperature flash drying: the first layer, at 70 deg.C for 2 min; the second layer, at 80 ℃ for 4 min;
7) ultraviolet light curing: fusion H lamp, curing energy 3800mJ/cm2；
8) The thickness of the cured film is as follows: 16 μm.
Example 2
A plastic plate with both super steel wool resistance and weather resistance comprises a substrate, a first film layer with weather resistance on the surface of the substrate, and a second film layer with both super steel wool resistance and weather resistance on the surface of the first film layer, wherein the second film layer with both super steel wool resistance and weather resistance is obtained by coating a coating with both super steel wool resistance and weather resistance on the surface of the first film layer in a curtain coating manner on the surface of the first film layer with weather resistance on both sides, and curing a coated film after ultraviolet irradiation; the first film layer with weather resistance is obtained by coating the coating with weather resistance on the surface of a base material on two sides in a curtain coating mode and then carrying out low-temperature flash drying and film covering;
the base material is a Sabic 3.0mm PC plate;
the first weatherable film layer having a weatherable coating therein, comprising:
20 parts by weight of plastic master batch: PC master batch;
60 parts by weight of a polyfunctional polyurethane acrylic resin: aliphatic urethane acrylate CN 996;
1 part by weight of an inorganic ultraviolet absorber: chinese patent CN201310362095.7 example 3 liquid nano ceria ultraviolet absorber;
19 parts by weight of a solvent: methyl isobutyl ketone;
flash drying the components according to parts by weight at low temperature (60 ℃, 5min), and coating a film to obtain the product; the viscosity of the coating with weather resistance is 17 mPas;
the second layer has the coating with the super steel wool resistance and the weather resistance in the film layer with the super steel wool resistance and the weather resistance at the same time, and the coating comprises:
22 parts by weight of a polyurethane acrylate copolymer containing a fluorosilicone block,
the molecular formula is as follows:
obtained from reaction A, B, C by addition reaction:
wherein R is derived from reactant A
R' is isophorone diisocyanate (IPDI) derived from reactant B,
r' is hydroxyethyl methacrylate and dipentaerythritol pentaacrylate derived from reactant C;
m takes the value of 27;
7 parts by weight of polyfunctional polyurethane acrylic resin: aliphatic polyurethane acrylate CN 9010;
0.5 parts by weight of an organic ultraviolet absorber: chinese patent CN201310362094.2, example 1, a solid organic ultraviolet resistant absorbent;
0.5 parts by weight of a photoinitiator: lucirin TPO;
0.2 parts by weight of a leveling agent: BYK-354;
69.8 parts by weight of solvent: butanone;
fully dispersing the components in parts by weight in a high-speed dispersion machine at high speed, and filtering by using a 0.45-micrometer filter element to obtain the high-performance nano-filtration membrane; the viscosity of the obtained coating with the super steel wool resistance and weather resistance is 3.5 mPas;
the preparation method of the plastic plate or the film with both the super steel wool resistance and the weather resistance comprises the following steps:
1) construction environment: temperature 23 ℃, relative humidity 35% r.h.;
2) the coating method comprises the following steps: coating on both sides, and curtain coating; the first layer and the second layer are in a wet-on-wet mode;
3) viscosity of the coating: flow coating, the product viscosity is 3.5 mPa.s;
4) treating a base material: 3.0mm of PC board, cleaning with ethanol or isopropanol to remove pollutants, and performing electrostatic dust removal;
5) leveling time: room temperature for 2 min;
6) and (3) low-temperature flash drying: the first layer, 60 ℃, 5 min; the second layer, 75 ℃, 3 min;
7) ultraviolet light curing: fusion H lamp, curing energy 2800mJ/cm2；
8) The thickness of the cured film is as follows: 12 μm.
Example 3
A plastic plate with both super steel wool resistance and weather resistance comprises a substrate, a first film layer with weather resistance on the surface of the substrate, and a second film layer with both super steel wool resistance and weather resistance on the surface of the first film layer, wherein the second film layer with both super steel wool resistance and weather resistance is obtained by coating a coating with both super steel wool resistance and weather resistance on the surface of the first film layer in a curtain coating manner on the surface of the first film layer with weather resistance on both sides, and curing a coated film after ultraviolet irradiation; the first film layer with weather resistance is obtained by coating the coating with weather resistance on the surface of a base material on two sides in a curtain coating mode and then carrying out low-temperature flash drying and film covering;
the substrate is 188 mu mPE film of Dongli Japan;
the first weatherable film layer having a weatherable coating therein, comprising:
38 parts by weight of plastic master batch: PET master batch;
47 parts by weight of a polyfunctional polyurethane acrylic resin: aliphatic urethane acrylate CN 996;
4.5 parts by weight of an inorganic ultraviolet absorber: BYK-3812;
10.5 parts by weight of solvent: isopropyl alcohol;
flash drying the components according to parts by weight at low temperature (60 ℃, 2min), and coating a film to obtain the product; the viscosity of the coating with weather resistance is 20 mPas;
the second layer has the coating with the super steel wool resistance and the weather resistance in the film layer with the super steel wool resistance and the weather resistance at the same time, and the coating comprises:
22 parts by weight of a polyurethane acrylate copolymer containing a fluorosilicone block,
the molecular formula is as follows:
obtained from reaction A, B, C by addition reaction:
wherein R is derived from reactant A
R' is isophorone diisocyanate (IPDI) derived from reactant B,
r' is hydroxyethyl methacrylate and dipentaerythritol pentaacrylate derived from reactant C;
m takes the value of 27;
5 parts by weight of polyfunctional polyurethane acrylic resin: urethane acrylate CN 989;
3.5 parts by weight of an organic ultraviolet absorber: 1.5 parts by weight of Tinuvin400 and 2 parts by weight of Tinuvin 1130;
1.7 parts by weight of a photoinitiator: irgacure 819;
0.5 parts by weight of a leveling agent: 0.15 parts by weight of BYK-302, and 0.35 parts by weight of Tego Rad 2100;
67.3 parts by weight of solvent: isopropyl alcohol;
fully dispersing the components in parts by weight in a high-speed dispersion machine at high speed, and filtering by using a 0.45-micrometer filter element to obtain the high-performance nano-filtration membrane; the viscosity of the obtained coating with the super steel wool resistance and weather resistance is 3.5 mPas;
the preparation method of the plastic plate or the film with both the super steel wool resistance and the weather resistance comprises the following steps:
1) construction environment: temperature 23 ℃, relative humidity 35% r.h.;
2) the coating method comprises the following steps: coating on both sides, and curtain coating; the first layer and the second layer are in a wet-on-wet mode;
3) viscosity of the coating: flow coating, the product viscosity is 3.5 mPa.s;
4) treating a base material: 188 mu mPE film, cleaning with ethanol or isopropanol to remove pollutants, and performing electrostatic dust removal;
5) leveling time: 5min at room temperature;
6) and (3) low-temperature flash drying: the first layer, at 60 deg.C for 2 min; the second layer, 60 ℃, 5 min;
7) ultraviolet light curing: fusion H lamp, curing energy 1200mJ/cm2；
8) The thickness of the cured film is as follows: 7 μm.
Example 4
A plastic plate with both super steel wool resistance and weather resistance comprises a substrate, a first film layer with weather resistance on the surface of the substrate, and a second film layer with both super steel wool resistance and weather resistance on the surface of the first film layer, wherein the second film layer with both super steel wool resistance and weather resistance is obtained by coating a coating with both super steel wool resistance and weather resistance on the surface of the first film layer in a curtain coating manner on the surface of the first film layer with weather resistance on both sides, and curing a coated film after ultraviolet irradiation; the first film layer with weather resistance is obtained by coating the coating with weather resistance on the surface of a base material on two sides in a curtain coating mode and then carrying out low-temperature flash drying and film covering;
the substrate is 188 mu mPE film of Dongli Japan;
the first weatherable film layer having a weatherable coating therein, comprising:
48 parts by weight of plastic master batch: PMMA master batch;
30 parts by weight of a polyfunctional polyurethane acrylic resin: aliphatic urethane acrylate CN 989;
0.5 parts by weight of an inorganic ultraviolet absorber: chinese patent CN201310362095.7 example 3 liquid nano ceria ultraviolet absorber;
21.5 parts by weight of solvent: acetic acid ethyl ester;
flash drying the components according to parts by weight at low temperature (65 ℃, 2min), and coating a film to obtain the composition; the viscosity of the coating with weather resistance is 17 mPas;
the second layer has the coating with the super steel wool resistance and the weather resistance in the film layer with the super steel wool resistance and the weather resistance at the same time, and the coating comprises:
42 parts by weight of a polyurethane acrylate copolymer containing a fluorosilicone block,
the molecular formula is as follows:
obtained from reaction A, B, C by addition reaction:
wherein R is derived from reactant A
R' is isophorone diisocyanate (IPDI) derived from reactant B,
r' is hydroxyethyl methacrylate and dipentaerythritol pentaacrylate derived from reactant C;
m takes the value of 48;
10 parts by weight of a polyfunctional polyurethane acrylic resin: aliphatic polyurethane acrylate CN 9010;
5 parts by weight of an organic ultraviolet absorber: tinuvin 928;
0.5 parts by weight of a photoinitiator: irgacure 907;
0.1 parts by weight of leveling agent: BYK-354;
42.4 parts by weight of solvent: acetic acid ethyl ester;
fully dispersing the components in parts by weight in a high-speed dispersion machine at high speed, and filtering by using a 0.45-micrometer filter element to obtain the high-performance nano-filtration membrane; the viscosity of the obtained coating with the super steel wool resistance and weather resistance is 7 mPas;
the preparation method of the plastic plate or the film with both the super steel wool resistance and the weather resistance comprises the following steps:
1) construction environment: temperature 23 ℃, relative humidity 35% r.h.;
2) the coating method comprises the following steps: double-sided coating and roll coating; the first layer and the second layer are in a wet-on-wet mode;
3) viscosity of the coating: roller coating, a Tanshi viscometer of 7mPa & s;
4) treating a base material: 188 mu mPE film, cleaning with ethanol or isopropanol to remove pollutants, and performing electrostatic dust removal;
5) leveling time: 5min at room temperature;
6) and (3) low-temperature flash drying: the first layer, at 65 ℃ for 2 min; the second layer, at 70 deg.C for 2 min;
7) ultraviolet light curing: fusion H lamp, curing energy 200mJ/cm2；
8) The thickness of the cured film is as follows: 5 μm.
Example 5
20 parts by weight of a polyurethane acrylate copolymer containing a fluorosilicone block, the viscosity of which is 3 mPas; the rest is the same as example 3.
Example 6
50 parts by weight of a polyurethane acrylate copolymer containing a fluorosilicone block, having a viscosity of 7 mPas; the rest is the same as example 3.
Comparative example 1
10 parts by weight of a polyurethane acrylate copolymer containing a fluorosilicone block, having a viscosity of 2.5 mPas; the rest is the same as example 3.
Comparative example 2
60 parts by weight of a polyurethane acrylate copolymer containing a fluorosilicone block, having a viscosity of 8 mPas; the rest is the same as example 3.
Comparative example 3
A film comprises a substrate, a first film layer with weather resistance on the surface of the substrate and a second ultraviolet light curing film layer on the surface of the first film layer with weather resistance, wherein the ultraviolet light curing film layer is obtained by coating the UV light curing coating for IMF in the embodiment 1 of Chinese patent CN 103333603B on the surface of the first film layer with weather resistance on two sides in a curtain coating mode, and curing and laminating the coating after ultraviolet light irradiation;
the substrate is 188 mu mPE film of Dongli Japan;
the UV photocureable coating for IMF is the UV photocureable coating for IMF in the embodiment 1 in Chinese patent CN 103333603B, and the preparation steps are as follows:
(1) uniformly mixing 15g of aliphatic polyurethane acrylate (Cytec-EB9260), 4g of nanoparticle graft modified polyether acrylate (Basf-PO9026), 4g of hyperbranched polyester acrylate (Eternal-6361-one 100) and 70g of organic solvent (35g of ethyl acetate and 35g of methyl isobutyl ketone) to obtain a resin mixture;
(2) adding 5g of reactive diluent (Eternal-EM70), 0.1g of flatting agent (BYK-UV3500), 1g of silicon dioxide dispersion (NANOBYK-3650) and 1g of photoinitiator (Darocur MBF) into the mixture obtained in the step (1), stirring and filtering to obtain a UV photocuring coating for IMF; the viscosity of the obtained UV light curable coating for IMF was 3 mPas;
the rest is the same as example 3.
Comparative example 4
A film comprises a substrate, a first film layer with weather resistance on the surface of the substrate and a second ultraviolet light curing film layer on the surface of the first film layer with weather resistance, wherein the ultraviolet light curing film layer is obtained by coating the UV light curing coating for IMF in the embodiment 2 of Chinese patent CN 103333603B on the surface of the first film layer with weather resistance on two sides in a curtain coating mode, and curing and laminating the coating after ultraviolet light irradiation;
the substrate is 188 mu mPE film of Dongli Japan;
the UV photocureable coating for IMF is the UV photocureable coating for IMF in the embodiment 2 in Chinese patent CN 103333603B, and the preparation steps are as follows:
(1) uniformly mixing 30g of aliphatic polyurethane acrylate (Eternal-6130B-80), 2g of nanoparticle graft modified polyether acrylate (Basf-PO9026), 5g of hyperbranched polyester acrylate (Sartomer-CN2302) and 50g of organic solvent (34g of ethyl acetate and 16g of cyclohexanone) to obtain a resin mixture;
(2) adding 10g of reactive diluent (Eternal-EM90), 0.5g of flatting agent (BYK-UV3530), 0.5g of alumina dispersion (NANOBYK-3610) and 2g of photoinitiator (Darocur 1173) into the mixture obtained in the step (1), stirring and filtering to obtain a UV photocuring coating for IMF; the viscosity of the resulting UV light curable coating for IMF was 7 mPas;
the rest is the same as example 3.
The appearance, hardness, adhesion, light transmittance, haze, water contact angle, boiling water boiling resistance, and steel wool resistance of the plastic sheets or films obtained in examples 1 to 6 and comparative examples 1 to 4 were measured as shown in table 1.
TABLE 1 test results of the component ratios and performance indexes of examples 1 to 6 and comparative examples 1 to 4
(example 5 haze "0.00", please confirm or modify).
Claims (6)
1. A plastic plate or film with both super steel wool resistance and weather resistance comprises a substrate, a first film layer with weather resistance on the surface of the substrate, and a second film layer with both super steel wool resistance and weather resistance on the surface of the first film layer, wherein the second film layer with both super steel wool resistance and weather resistance is prepared by coating a coating with both super steel wool resistance and weather resistance on the surface of the first film layer in a curtain coating, spraying, dip coating or roller coating manner, and curing a coated film after ultraviolet irradiation;
the coating with the super steel wool resistance and the weather resistance simultaneously comprises the following components in parts by weight:
wherein the polyurethane acrylate copolymer containing the fluorosilicone block has a structural formula shown as formula i:
or
Formula i is obtained by addition reaction of reactant A, B, C, wherein R is oligomeric fluorosilicone derived from reactant A, R 'is diisocyanate derived from reactant B, R' is alkyl acrylate derived from reactant C, and m ranges from 1 to 100;
wherein the reactant A has a structural formula shown as a formula ii:
in formula ii, n ranges from 1 to 100;
the viscosity of the reactant A is 0.005-100 Pa.s.
2. The plastic panel or film with both ultra steel wool resistance and weather resistance as claimed in claim 1, wherein the substrate is selected from PC board, PMMA board, PC and PMMA composite board or PET film.
3. The plastic plate or film with both ultra steel wool resistance and weather resistance as claimed in claim 1, wherein the reactant B is selected from one or more of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), 4' -dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), and Toluene Diisocyanate (TDI);
the reactant C is selected from one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
4. The plastic panel or film having both super steel wool resistance and weather resistance according to any one of claims 1 to 3, wherein the preparation method of the polyurethane acrylate copolymer containing the fluorosilicone block comprises the steps of:
1) preparation of a reactant A: reacting trifluoropropyl methyl cyclotrisiloxane at 50-90 ℃ under the catalysis of acid, and extracting to obtain a reactant A, wherein the extraction is to extract a low-boiling-point material under negative pressure;
2) preparation of NCO group-terminated
Or
Blocking a precursor: the reactant A is vacuumized for 1 to 2 hours at the temperature of 110-120 ℃ and then is reduced to 15 to 35 ℃, and reacts with the reactant B for 2 to 4 hours at the temperature of 50 to 70 ℃ to obtain the NCO group end-capped
Or
Blocking a precursor;
3) the reactant C is vacuumized for 1 to 2 hours at the temperature of 110-120 ℃ and then is reduced to 15 to 35 ℃, and is blocked with NCO groups
Or
The block precursor reacts for 3 to 6 hours at the temperature of between 70 and 90 ℃ to obtain the block precursor;
wherein, in the step 2), the molar ratio of the reactant A to the reactant B is 1: 1-2;
in step 3), the reactant C is blocked with NCO groups
Or
The molar ratio of the block precursors is 1-2: 1.
5. The plastic plate or film with both super steel wool resistance and weather resistance as claimed in claim 1, wherein the multifunctional urethane acrylic resin is one or more selected from two to nine functional polyurethane acrylic resins.
6. A method for preparing a plastic sheet or film having both super steel wool resistance and weather resistance as claimed in any one of claims 1 to 5, comprising the steps of:
1) construction environment: temperature 20-35 ℃, relative humidity 20-50% r.h.;
2) the coating method comprises the following steps: double-sided coating, spray coating, curtain coating, dip coating and roller coating; the first layer and the second layer are in a wet-on-wet mode;
3) viscosity of the coating: spraying, namely 7-20s in a No. 2 cup in a rock field; flow coating, wherein the Coriolis viscometer is 3-20 mPa.s; dip-coating, with a viscometer of 3-20mPa · s; roller coating, a Tanshi viscometer is 3-20 mPa.s;
4) treating a base material: cleaning a PC, PMMA, PET or composite plastic substrate by using ethanol or isopropanol to remove pollutants, and performing electrostatic dust removal;
5) leveling time: room temperature for 1-5 min;
6) and (3) low-temperature flash drying: 50-80 deg.C for 2-5 min;
7) ultraviolet light curing: fusion H lamp, curing energy 200-2；
8) The thickness of the cured film is as follows: 3-20 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710181297.XA CN106939084B (en) | 2017-03-24 | 2017-03-24 | Plastic plate or film with super steel wool resistance and weather resistance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710181297.XA CN106939084B (en) | 2017-03-24 | 2017-03-24 | Plastic plate or film with super steel wool resistance and weather resistance and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106939084A CN106939084A (en) | 2017-07-11 |
| CN106939084B true CN106939084B (en) | 2019-12-20 |
Family
ID=59463570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710181297.XA Active CN106939084B (en) | 2017-03-24 | 2017-03-24 | Plastic plate or film with super steel wool resistance and weather resistance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106939084B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109570125A (en) * | 2018-12-17 | 2019-04-05 | 上海万明眼镜有限公司 | A kind of stiffened manufacturing process of PC optical mirror slip |
| CN111117471B (en) * | 2020-01-03 | 2021-09-07 | 湖南宏泰新材料有限公司 | Ultra-steel wool yellowing-resistant water-based UV finishing varnish and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585690A (en) * | 2011-12-30 | 2012-07-18 | 深圳市嘉卓成科技发展有限公司 | Steel wool-resistant high-hardness ultraviolet (UV) radiation cured coating, and preparation and using methods thereof |
| CN103642382A (en) * | 2013-11-25 | 2014-03-19 | 中国科学院长春应用化学研究所 | Ultraviolet light curing anti-fouling paint and preparation method thereof |
| CN104736611A (en) * | 2012-08-23 | 2015-06-24 | 株式会社Lg化学 | Hard coating film |
| CN105646828A (en) * | 2016-03-31 | 2016-06-08 | 青岛科技大学 | Organic fluorine-silicone-polyurethane block copolymer synthesizing method |
-
2017
- 2017-03-24 CN CN201710181297.XA patent/CN106939084B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585690A (en) * | 2011-12-30 | 2012-07-18 | 深圳市嘉卓成科技发展有限公司 | Steel wool-resistant high-hardness ultraviolet (UV) radiation cured coating, and preparation and using methods thereof |
| CN104736611A (en) * | 2012-08-23 | 2015-06-24 | 株式会社Lg化学 | Hard coating film |
| CN103642382A (en) * | 2013-11-25 | 2014-03-19 | 中国科学院长春应用化学研究所 | Ultraviolet light curing anti-fouling paint and preparation method thereof |
| CN105646828A (en) * | 2016-03-31 | 2016-06-08 | 青岛科技大学 | Organic fluorine-silicone-polyurethane block copolymer synthesizing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106939084A (en) | 2017-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101792639B (en) | Wear-resisting scratch-resisting weather-proof polyurethane coating and preparation method thereof | |
| EP1995260B1 (en) | High energy ray-curable composition | |
| RU2516736C2 (en) | Method of obtaining automobile lacquer with high resistance to abrasion, automobile lacquer and its application | |
| CN108192488B (en) | Solvent-based bi-component high-smoothness varnish composition, preparation method and application | |
| CN102498142B (en) | Actinic-radiation-curable resin composition, and cured products and films thereof | |
| CN104387945A (en) | Odorless staining-resistant anti-yellowing UV coated matt finish paint coating, and preparation method and construction technology thereof | |
| CN1844229A (en) | UV curable aqueous resin composition | |
| CN103031034A (en) | White finish coat photocurable UV (ultraviolet) paint and preparation method thereof | |
| US9243153B2 (en) | Polyisocyanate adducts as additives for radiation-curable coating material compositions | |
| CN101701059A (en) | Preparation method of cationic terpenyl epoxy resin polyalcohol water dispersoid and application thereof | |
| CN104263208A (en) | UV (Ultraviolet) laminated topcoat gloss coating with performances of smell removal, stain resistance and yellowing resistance as well as preparation method and construction process thereof | |
| CN101932626A (en) | Water dilutable uv-curable polyurethane | |
| CN106939084B (en) | Plastic plate or film with super steel wool resistance and weather resistance and preparation method thereof | |
| CN108884200B (en) | Polyurethane resin composition, coating agent, and article | |
| JP2017149985A (en) | Fluorinated water-oil repellency agent | |
| CN107936814A (en) | The net taste woodcare paint of high hardness polyurethane that a kind of POSS is modified | |
| CN104371086A (en) | Preparation method of ultraviolet-curing organosilane acrylic acid polyurethane | |
| US11267993B2 (en) | Polyurethane surfacing film | |
| CN111978506B (en) | Preparation method of aqueous hyperbranched polyurethane acrylate emulsion, UV (ultraviolet) curing coating and preparation method and application thereof | |
| CN1863745A (en) | Radiation-hardenable coating agent containing aliphatic urethane(meth)acrylate | |
| CN106947385B (en) | The super coating of resistance to steel wool of one kind and its application method | |
| CN1402755A (en) | Process for coating thermoplastic substrates with coating composition contg. non-aggressive solvent | |
| CN106957447B (en) | Plastic plate or film with super steel wool resistance and preparation method thereof | |
| KR20110080163A (en) | Scratch- and weather-resistant varnish curable by means of actinic radiation or curable by heat and by means of actinic radiation | |
| CN103865377A (en) | Water-based polyurethane acrylate organic silicon coating |
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 |