CN111073424B - High-adhesion-resistant coating material and high-heat-resistance adhesion-resistant PVC product - Google Patents

High-adhesion-resistant coating material and high-heat-resistance adhesion-resistant PVC product Download PDF

Info

Publication number
CN111073424B
CN111073424B CN201911382194.5A CN201911382194A CN111073424B CN 111073424 B CN111073424 B CN 111073424B CN 201911382194 A CN201911382194 A CN 201911382194A CN 111073424 B CN111073424 B CN 111073424B
Authority
CN
China
Prior art keywords
parts
coating material
pvc
adhesion
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911382194.5A
Other languages
Chinese (zh)
Other versions
CN111073424A (en
Inventor
吴志光
许琳琼
熊瑞斌
王立献
刘涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Jingmei Science And Technology Co ltd
Original Assignee
Ningbo Shuaitelong Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Shuaitelong Group Co Ltd filed Critical Ningbo Shuaitelong Group Co Ltd
Priority to CN201911382194.5A priority Critical patent/CN111073424B/en
Publication of CN111073424A publication Critical patent/CN111073424A/en
Application granted granted Critical
Publication of CN111073424B publication Critical patent/CN111073424B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C08J2327/00—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 at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • 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
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • 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
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention relates to a high-adhesion-resistant coating material and a high-heat-resistant adhesion-resistant PVC product, belonging to the technical field of high polymer materials. The high anti-adhesion coating material for PVC comprises the following components in parts by weight: 0.3-0.6 part of acrylate copolymer, 0.2-0.3 part of water-soluble polyurethane, 0.05-0.2 part of wax emulsion, 0.2-0.4 part of fluorine-silicon modified nano particles, 0.2-0.4 part of polyacrylamide, 0.15-0.3 part of polyethylene glycol and 0.4-1 part of solvent; the high anti-adhesion coating material can effectively inhibit the migration of the plasticizer when being applied to the soft PVC product, and the coated PVC product does not foam or peel.

Description

High-adhesion-resistant coating material and high-heat-resistance adhesion-resistant PVC product
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a high-adhesion-resistant coating material and a high-heat-resistance adhesion-resistant PVC product.
Background
PVC is initiator of vinyl chloride monomer (VCM for short) in peroxide, azo compound, etc.; or a polymer polymerized by a free radical polymerization mechanism under the action of light and heat, has wide application, and has wide application in the aspects of building materials, industrial products, daily necessities, floor leathers, floor tiles, artificial leathers, pipes, electric wires and cables, packaging films, bottles, foaming materials, sealing materials, fibers and the like. The artificial polyvinyl chloride (PVC) leather is a leather-like plastic product obtained by laminating a mixture consisting of PVC resin, plasticizers and other additives to a base fabric in a calendering mode and the like. The PVC artificial leather has the appearance similar to natural leather, has the excellent characteristics of low cost, high strength, wear resistance, acid and alkali resistance and the like, and is widely applied to cases, furniture, automotive interiors and the like. However, PVC also has disadvantages in production and use, such as poor heat resistance and unstable plasticization. The Vicat softening point of the general PVC resin is only about 80 ℃, the thermal deformation temperature is about 70 ℃, the long-term use temperature cannot exceed 60 ℃, the minimum use temperature is only-15 ℃, and the poor deformation capability of the PVC under load also limits the PVC to be used as a structural material under the conditions of heating and stress, thereby hindering the engineering of the PVC so that the PVC cannot be applied to occasions with harsh working environments.
A large amount of plasticizer is needed in the soft PVC product, the content can reach 30-80% or more, and PVC chain-shaped molecules slide, so that the distance between macromolecular chains is enlarged, the attraction between the molecular chains is reduced, and the purposes of plasticizing and softening are achieved. However, the plasticizer is only physically mixed with the PVC resin, and the acting force between the plasticizer and the PVC resin is completely Van der Waals force, so that the precipitation is a necessary trend, and the precipitation has a strong temperature dependence. Generally, plasticizers are well compatible with PVC at normal temperatures and exude at elevated temperatures. PVC products usually adopt small molecule plasticizers, such as di-n-octyl phthalate, liquid paraffin, epoxy soybean oil and the like, and the small molecule plasticizers are easy to dissolve out, volatilize and migrate in the processing and long-term use processes of the products, so that the environment is polluted, the performance of the products is deteriorated, and the use value is lost. For example, when PVC leather is used for a sun screen of an SUV (sports utility vehicle), the PVC leather can be sticky under high-temperature insolation to generate abnormal sound, and the use is influenced.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a high-adhesion-resistance coating material for PVC products, which can inhibit the migration of a plasticizer when applied to soft PVC products, and the coated PVC products do not foam or peel off.
The purpose of the invention can be realized by the following technical scheme: the high anti-adhesion coating material for PVC comprises the following components in parts by weight:
0.3 to 0.6 part of acrylate copolymer,
0.2 to 0.3 part of water-soluble polyurethane,
0.05 to 0.2 part of wax emulsion,
0.2-0.4 part of fluorine-silicon modified nano particles
0.2 to 0.4 part of polyacrylamide,
0.15 to 0.3 portion of polyethylene glycol,
0.4-1 part of solvent.
The high anti-sticking coating material takes the acrylate copolymer, the water-soluble polyurethane and the wax emulsion as main raw materials, wherein the acrylate copolymer has stronger adhesive force with PVC and good film forming property, can form a transparent, flexible and elastic film coating, but has the defects of cold brittleness and hot sticking when the film is formed; the polyurethane also has good film forming property, and a thin film coating formed by the polyurethane has the advantages of high gloss, high wear resistance, high elasticity, water resistance, weather resistance, cold resistance, heat resistance, chemical resistance and the like; according to the invention, the water-soluble polyurethane and the acrylate copolymer are adopted for cooperation, so that the formed anti-adhesion material has good fluidity, the film-forming property of the high-adhesion-resistance coating material is further improved, and the problem of cold brittleness and hot adhesion caused by only using the acrylate copolymer is avoided; however, the addition of the water-soluble polyurethane can reduce the adhesive force between the anti-adhesion material and PVC, so that a coating formed by the anti-adhesion material is easy to separate from PVC in the long-term use process, and the peeling phenomenon is generated. The wax emulsion is added to fill the coating, improve the hand feeling of the film coating, resist wear and adhesion, increase the glossiness and the like.
The fluorine-silicon modified nano particles are added into the high anti-adhesion coating material, so that the migration of a plasticizer in PVC can be effectively inhibited, the surface energy of the nano particles is greatly reduced after the nano particles are modified by fluorine silicon, the agglomeration of the nano particles is effectively reduced, the dispersion performance of the nano particles in the anti-adhesion material is improved, meanwhile, the fluorine-silicon modified nano particles have amphiphobicity, have large contact angles (more than 150 degrees) with water, oil and other liquids, have a repulsive action on the plasticizer, and can maintain the plasticizer in the PVC without migrating to the surface of the PVC when the plasticizer exists in the surface coating of the PVC, so that the precipitation of the plasticizer is effectively inhibited.
Preferably, the fluorine-silicon modified nano particles comprise the following raw material components in percentage by weight: 60-73% of ethanol,
15-28% of ammonia water,
1-2% of nano particles,
5-7% of tetraethyl orthosilicate,
0.8-2% of fluorosilane,
0.4-1% of silane.
Preferably, the fluorosilane is one or more of perfluorodecyltriethoxysilane and perfluorodecyltrichlorosilane.
Preferably, the silane is one or more of hexadecyl trimethoxy silane and hexadecyl triethoxy silane.
Preferably, the nano particles are one or more of nano silicon dioxide, nano calcium carbonate and nano montmorillonite.
Preferably, the preparation method of the fluorine-silicon modified nanoparticles comprises the following steps:
uniformly mixing ethanol and nano particles, slowly adding ammonia water, uniformly dispersing, slowly adding tetraethyl orthosilicate, 40-60% of fluorosilane and silane, stirring for 4-8 hours, then adding the remaining fluorosilane, and stirring for 4-8 hours; and then filtering and cleaning, and drying the collected solid particles for 2-4 h to obtain the fluorine-silicon modified nano particles.
The invention further reduces the surface energy of the nano particles through secondary fluorine-silicon modification, so that the oil-water contact angle of the modified nano particles is more than 150 degrees, thereby having stronger capability of inhibiting the migration of the plasticizer.
Preferably, the solvent is one or more of ethanol, ethylene glycol and isopropanol.
In the invention, one or more of ethanol, glycol and isopropanol are preferably used as a solvent, which is beneficial to the dissolution of polyacrylamide, and the polyacrylamide has better compatibility with other components and better coating performance.
The invention also aims to provide a high heat-resistant anti-sticking PVC product, which comprises the following raw material components in parts by weight:
100 portions of PVC resin,
30-70 parts of composite plasticizer,
1.5-3 parts of high anti-adhesion material,
And 5-30 parts of an auxiliary agent.
Preferably, the complex plasticizer comprises a plurality of didecyl phthalate, trioctyl trimellitate, undecyl phthalate, dodecyl phthalate, tridecyl phthalate and tetradecyl phthalate.
The high-heat-resistance anti-sticking PVC product adopts the high-molecular-weight plasticizer, has better compatibility with PVC, has the characteristics of low volatility, solvent extraction resistance, high temperature resistance, small migration and the like, and is favorable for improving the anti-sticking property and the heat resistance; however, compared with the small molecular plasticizer, the high molecular plasticizer generally has lower plasticizing efficiency, and the invention effectively improves the plasticizing effect by optimizing the specific components of the high molecular plasticizer and through the compound action of the plurality of high molecular plasticizers; meanwhile, the undecyl phthalate, the dodecyl phthalate, the tridecyl phthalate and the tetradecyl phthalate have lower mobility but lower acceleration efficiency compared with the didecyl phthalate and the trioctyl trimellitate, so the addition amount is not suitable to be too much.
Preferably, the auxiliary agent comprises the following components in parts by weight:
2-9 parts of heat stabilizer,
0.2 to 0.4 portion of antioxidant,
0.3 to 0.6 part of lubricant,
0.5 to 5 parts of flame retardant,
2-15 parts of a filler.
Preferably, the heat stabilizer comprises one or more of calcium-zinc composite stabilizer and organic tin stabilizer.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant 618.
Preferably, the flame retardant is a flame retardant of designation HT-103.
Preferably, the lubricant is one or more of solid paraffin, liquid paraffin, calcium stearate, zinc stearate, and stearic acid amide.
Preferably, the filler comprises one or more of nano barium sulfate, nano calcium carbonate, clay, alkaline alumina, magnesium oxide, white clay and white carbon black.
Still another object of the present invention is to provide a method for preparing a highly heat-resistant anti-stick PVC article, comprising the steps of:
(1) mixing materials: adding PVC resin, a composite plasticizer and an auxiliary agent into a high-speed dispersion mixer, and uniformly mixing to obtain a premix;
(2) and (3) calendering and forming: discharging the premix into an internal mixer for mixing, then discharging the premix into an open mill for plastication, then conveying the premix to a four-roll calender for calendering into a sheet, and attaching the sheet to base cloth to form a composite sheet;
(3) surface treatment: coating a high anti-sticking coating material on the surface of the composite sheet, and then drying to form a semi-finished product;
(4) thermoforming: and (4) conveying the semi-finished product into an embossing machine for heating and embossing, and then cooling and shaping.
Preferably, the stirring temperature of the high-speed dispersion mixer in the step (1) is 100-150 ℃, and the stirring time is 100-300 s;
preferably, the temperature for kneading in the step (2) is 130 to 160 ℃ and the kneading time is 200 to 300 seconds.
Preferably, the temperature of the plastication in the step (2) is 120-130 ℃, and the time of the plastication is 10-15 min.
Preferably, the thickness of the sheet rolled by the four-roll calender in the step (2) is 0.4-0.9 mm, and the rolling temperature is 165-170 ℃.
Preferably, the temperature of the embossing in the step (4) is 180-190 ℃.
The premix is firstly mixed into a melt preliminarily through the mixing, and then plasticated by an open mill, so that the plastic effect can be effectively ensured.
Compared with the prior art, the invention has the following beneficial effects: through reasonable compatibility of the high anti-adhesion coating material, the PVC product using the high anti-adhesion coating material has excellent anti-adhesion and high temperature resistance, and the coating and the PVC product have good adhesion, so that the foaming and peeling phenomena can not be generated after long-time use.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1
The components of the high anti-stick coating material for PVC in this example were: 0.6 part of acrylate copolymer, 0.2 part of water-soluble polyurethane, 0.1 part of wax emulsion, 0.3 part of fluorine-silicon modified silicon dioxide, 0.2 part of polyacrylamide, 0.2 part of polyethylene glycol and 0.6 part of ethanol.
The preparation method of the fluorine-silicon modified nano particles comprises the following steps of: 67% of ethanol, 23% of ammonia water, 2% of nano silicon dioxide, 6% of tetraethyl orthosilicate, 1.3% of perfluorodecyl triethoxysilane, and 0.7% of hexadecyl trimethoxysilane; uniformly mixing ethanol and the nano particles, slowly adding ammonia water, uniformly dispersing, slowly adding tetraethyl orthosilicate, 50% of perfluorodecyl triethoxysilane and hexadecyl trimethoxysilane, stirring for 6 hours, adding the rest perfluorodecyl triethoxysilane, and continuously stirring for 6 hours; and then filtering and cleaning are carried out, and the collected solid particles are dried for 3 hours to obtain the fluorine-silicon modified nano particles.
Example 2
The components of the high anti-stick coating material for PVC in this example were: 0.4 part of acrylate copolymer, 0.3 part of water-soluble polyurethane, 0.2 part of wax emulsion, 0.2 part of fluorine-silicon modified calcium carbonate, 0.4 part of polyacrylamide, 0.3 part of polyethylene glycol and 0.5 part of ethylene glycol.
The preparation method of the fluorine-silicon modified nano particles comprises the following steps of: 70% of ethanol, 22% of ammonia water, 15% of nano calcium carbonate, 5% of tetraethyl orthosilicate, 1.3% of perfluorodecyl trichlorosilane and 0.7% of hexadecyl triethoxysilane;
uniformly mixing ethanol and nano calcium carbonate, slowly adding ammonia water, uniformly dispersing, slowly adding tetraethyl orthosilicate, 40% of perfluorodecyl trichlorosilane and hexadecyl triethoxysilane, stirring for 4 hours, adding the rest perfluorodecyl trichlorosilane, and continuously stirring for 4 hours; and then filtering and cleaning are carried out, and the collected solid particles are dried for 2 hours to obtain the fluorine-silicon modified nano particles.
Example 3
The components of the high anti-stick coating material for PVC in this example were: 0.5 part of acrylate copolymer, 0.2 part of water-soluble polyurethane, 0.2 part of wax emulsion, 0.4 part of fluorine-silicon modified montmorillonite, 0.3 part of polyacrylamide, 0.2 part of polyethylene glycol and 0.7 part of isopropanol.
The preparation method of the fluorine-silicon modified nano particles comprises the following steps of: 62% of ethanol, 28% of ammonia water, 2% of nano montmorillonite, 7% of tetraethyl orthosilicate, 2% of perfluorodecyl triethoxysilane, and 1% of hexadecyl trimethoxysilane; uniformly mixing ethanol and nano montmorillonite, slowly adding ammonia water, uniformly dispersing, slowly adding tetraethyl orthosilicate, 60% of perfluorodecyl triethoxysilane and hexadecyl trimethoxysilane, stirring for 7 hours, adding the rest perfluorodecyl triethoxysilane, and continuously stirring for 7 hours; and then filtering and cleaning are carried out, and the collected solid particles are dried for 4 hours to obtain the fluorine-silicon modified nano particles.
Example 4
The preparation of the high heat resistant anti-stick PVC article of this example is as follows:
(1) mixing materials: adding 100 parts by weight of PVC resin, 60 parts by weight of composite plasticizer (46 parts by weight of didecyl phthalate, 8 parts by weight of trioctyl trimellitate, 3.5 parts by weight of undecyl phthalate and 2.5 parts by weight of dodecyl phthalate) and auxiliary agent (3 parts by weight of calcium-zinc composite stabilizer, 0.3 part by weight of antioxidant 168, 0.4 part by weight of stearic acid amide, 1 part by weight of flame retardant HT-103, 3 parts by weight of alkaline alumina and 12 parts by weight of nano calcium carbonate) into a high-speed dispersion mixer, stirring at 130 ℃ for 240s, and uniformly mixing to obtain a premix;
(2) and (3) calendering and forming: discharging the premix into an internal mixer, mixing for 220s at 145 ℃, then discharging into an open mill, plastifying for 12min at 125 ℃, then conveying to a four-roll calender, calendering into a sheet with the thickness of 0.8mm at 165 ℃, and attaching the sheet to base cloth to form a composite sheet;
(3) surface treatment: mixing the components of the high anti-adhesion coating material in the embodiment 1 in proportion to form 2.2 parts of the high anti-adhesion coating material, coating the high anti-adhesion coating material on the surface of the composite sheet, and drying at 125 ℃ to form a semi-finished product;
(4) thermoforming: and (3) conveying the semi-finished product into an embossing machine, heating to 185 ℃ for embossing, and then cooling and shaping.
Example 5
The preparation of the high heat resistant anti-stick PVC article of this example is as follows:
(1) mixing materials: adding 100 parts by weight of PVC resin, 64.5 parts by weight of composite plasticizer (40 parts by weight of didecyl phthalate, 20 parts by weight of trioctyl trimellitate, 2 parts by weight of undecyl phthalate and 2.5 parts by weight of dodecyl phthalate) and auxiliary agent (3 parts by weight of methyl tin mercaptide DX-181, 0.3 part by weight of antioxidant 1010, 0.4 part by weight of zinc stearate, 1 part by weight of flame retardant HT-103, 3 parts by weight of alkaline alumina and 12 parts by weight of nano calcium carbonate) into a high-speed dispersion mixer, stirring for 240s at 130 ℃, and uniformly mixing to obtain a premix;
(2) and (3) calendering and forming: discharging the premix into an internal mixer, mixing for 220s at 145 ℃, then discharging into an open mill, plastifying for 12min at 125 ℃, then conveying to a four-roll calender, calendering into a sheet with the thickness of 0.8mm at 165 ℃, and attaching the sheet to base cloth to form a composite sheet;
(3) surface treatment: mixing the components of the high anti-adhesion coating material in the embodiment 2 in proportion to form 2.3 parts of the high anti-adhesion coating material, coating the high anti-adhesion coating material on the surface of the composite sheet, and drying at 125 ℃ to form a semi-finished product;
(4) thermoforming: and (3) conveying the semi-finished product into an embossing machine, heating to 185 ℃ for embossing, and then cooling and shaping.
Example 6
The preparation of the high heat resistant anti-stick PVC article of this example is as follows:
(1) mixing materials: adding 100 parts by weight of PVC resin, 60 parts by weight of composite plasticizer (46 parts by weight of didecyl phthalate, 8 parts by weight of trioctyl trimellitate, 3.5 parts by weight of undecyl phthalate and 2.5 parts by weight of dodecyl phthalate) and auxiliary agent (3 parts by weight of calcium-zinc composite stabilizer, 0.3 part by weight of antioxidant 168, 0.4 part by weight of calcium stearate, 1 part by weight of flame retardant HT-103, 3 parts by weight of carbon black and 12 parts by weight of nano calcium carbonate) into a high-speed dispersion mixer, stirring for 240s at 130 ℃, and uniformly mixing to obtain a premix;
(2) and (3) calendering and forming: discharging the premix into an internal mixer, mixing for 220s at 145 ℃, then discharging into an open mill, plastifying for 12min at 125 ℃, then conveying to a four-roll calender, calendering into a sheet with the thickness of 0.8mm at 165 ℃, and attaching the sheet to base cloth to form a composite sheet;
(3) surface treatment: mixing the components of the high anti-adhesion coating material in example 3 in proportion to form 2.5 parts of the high anti-adhesion coating material, coating the high anti-adhesion coating material on the surface of the composite sheet, and drying at 125 ℃ to form a semi-finished product;
(4) thermoforming: and (3) conveying the semi-finished product into an embossing machine, heating to 185 ℃ for embossing, and then cooling and shaping.
Comparative example 1
The PVC article was not coated with the high anti-stick coating material, and the other was the same as in example 4.
Comparative example 2
The high anti-adhesive coating material was the same as example 4 except that no fluorosilicone modified nanoparticles were added.
Comparative example 3
The high anti-adhesion coating material is added with conventional nano particles which are not modified by fluorine silicon to replace fluorine silicon modified nano particles, and the rest is the same as the embodiment 4.
Comparative example 4
The high anti-sticking coating material was not added with polyacrylamide and polyethylene glycol, and the rest was the same as example 4
Comparative example 5
The high anti-stick coating material was the same as example 4 except that polyacrylamide was not added.
Comparative example 6
The high anti-stick coating material was not added with polyethylene glycol, and the rest was the same as example 4.
Comparative example 7
The same procedure as in example 4 was repeated except that the composite plasticizer was replaced with di-n-octyl phthalate in equal parts by weight and the high anti-tack coating material was not coated.
Comparative example 8
The composite plasticizer did not include undecyl phthalate and dodecyl phthalate, and was not coated with the high anti-tack coating material, and the rest was the same as in example 4.
The PVC products prepared in the inventive examples 4-6 and the comparative examples 1-8 were subjected to a high temperature tack test, and the test conditions and results are shown in Table 1.
Table 1: comparison of high-temperature Properties of PVC products in examples 4 to 6 and comparative examples 1 to 7
Figure BDA0002342553230000101
In addition, when the PVC products prepared in the example 4 and the comparative examples 4-6 are soaked in a 5% sodium chloride salt aqueous solution, the PVC product of the example 4 has no abnormal phenomenon and no foaming on the surface, the PVC product of the comparative example 4 has a foaming phenomenon on the surface, and the PVC products of the comparative examples 5 and 6 have a slight foaming phenomenon on the surface when the test is carried out for 500 hours.
The technical scope of the invention claimed by the embodiments of the present application is not exhaustive, and new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the invention claimed by the present application; in all the embodiments of the present invention, which are listed or not listed, each parameter in the same embodiment only represents an example (i.e., a feasible embodiment) of the technical solution, and there is no strict matching and limiting relationship between the parameters, wherein the parameters may be replaced with each other without departing from the axiom and the requirements of the present invention, unless otherwise specified.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and the technical scheme also comprises the technical scheme formed by any combination of the technical characteristics. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.

Claims (8)

1. The high anti-adhesion coating material for PVC is characterized by comprising the following components in parts by weight:
0.3 to 0.6 part of acrylate copolymer,
0.2 to 0.3 part of water-soluble polyurethane,
0.05 to 0.2 part of wax emulsion,
0.2-0.4 part of fluorine-silicon modified nano particles,
0.2 to 0.4 part of polyacrylamide,
0.15 to 0.3 portion of polyethylene glycol,
0.4-1 part of a solvent;
the fluorine-silicon modified nano particles comprise the following raw material components in percentage by weight:
60-73% of ethanol,
15-28% of ammonia water,
1-2% of nano particles,
5-7% of tetraethyl orthosilicate,
0.8-2% of fluorosilane,
0.4-1% of silane;
the preparation method of the fluorine-silicon modified nano particles comprises the following steps:
uniformly mixing ethanol and nano particles, slowly adding ammonia water, uniformly dispersing, slowly adding tetraethyl orthosilicate, 40-60% of fluorosilane and silane, stirring for 4-8 hours, then adding the remaining fluorosilane, and stirring for 4-8 hours; and then filtering and cleaning, and drying the collected solid particles for 2-4 h to obtain the fluorine-silicon modified nano particles.
2. The high anti-adhesion coating material of claim 1, wherein said fluorosilane is one or more of perfluorodecyltriethoxysilane, perfluorodecyltrichlorosilane.
3. The high anti-adhesion coating material of claim 1, wherein the silane is one or more of hexadecyltrimethoxysilane and hexadecyltriethoxysilane.
4. The high anti-adhesion coating material of claim 1, wherein the nanoparticles are one or more of nano silica, nano calcium carbonate and nano montmorillonite.
5. The high anti-stick coating material of claim 1, wherein the solvent is one or more of ethanol, ethylene glycol, isopropanol.
6. The high heat-resistant anti-sticking PVC product is characterized by comprising the following raw material components in parts by weight:
100 portions of PVC resin,
30-70 parts of composite plasticizer,
The high anti-adhesion coating material for PVC according to claim 1, 1.5-3 parts,
And 5-30 parts of an auxiliary agent.
7. The PVC article of claim 6, wherein the complex plasticizer comprises a plurality of didecyl phthalate, trioctyl trimellitate, undecyl phthalate, dodecyl phthalate, tridecyl phthalate, and tetradecyl phthalate.
8. The PVC product according to claim 6, wherein the auxiliary comprises the following components in parts by weight:
2-9 parts of heat stabilizer,
0.2 to 0.4 portion of antioxidant,
0.3 to 0.6 part of lubricant,
0.5 to 5 parts of flame retardant,
2-15 parts of a filler.
CN201911382194.5A 2019-12-27 2019-12-27 High-adhesion-resistant coating material and high-heat-resistance adhesion-resistant PVC product Active CN111073424B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911382194.5A CN111073424B (en) 2019-12-27 2019-12-27 High-adhesion-resistant coating material and high-heat-resistance adhesion-resistant PVC product

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911382194.5A CN111073424B (en) 2019-12-27 2019-12-27 High-adhesion-resistant coating material and high-heat-resistance adhesion-resistant PVC product

Publications (2)

Publication Number Publication Date
CN111073424A CN111073424A (en) 2020-04-28
CN111073424B true CN111073424B (en) 2021-05-28

Family

ID=70318936

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911382194.5A Active CN111073424B (en) 2019-12-27 2019-12-27 High-adhesion-resistant coating material and high-heat-resistance adhesion-resistant PVC product

Country Status (1)

Country Link
CN (1) CN111073424B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002298A (en) * 2010-12-16 2011-04-06 广东嘉宝莉化工集团有限公司 Aqueous antifouling adhesive preventing coating and production method thereof
CN104327657A (en) * 2014-10-20 2015-02-04 芜湖县双宝建材有限公司 Special energy-saving heat-insulation water-resistant anticorrosive paint for architectural outer walls
CN106221068A (en) * 2016-08-19 2016-12-14 芜湖市天雄新材料科技有限公司 A kind of anti-ultraviolet plastic-steel section bar and production technology thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7615257B2 (en) * 2000-10-11 2009-11-10 Chemetall Gmbh Method for pretreating and/or coating metallic surfaces with a paint-like coating prior to forming and use of substrates coated in this way
DE10322182A1 (en) * 2003-05-16 2004-12-02 Blue Membranes Gmbh Process for the production of porous, carbon-based material
TWI581965B (en) * 2011-10-25 2017-05-11 Ｇｃｐ應用技術有限公司 Waterproofing membrane
CN102719125A (en) * 2012-06-12 2012-10-10 天长市巨龙车船涂料有限公司 Anti-sticking water-based coating
CN104448193B (en) * 2014-12-01 2017-06-23 泰兴市华盛银洋新材料科技有限公司 A kind of Aqueous Polyurethane Leather Finishing Agent and preparation method thereof
CN105128718B (en) * 2015-08-31 2018-10-02 宁波帅特龙集团有限公司 Touch automatic curtain saucer
CN107694868B (en) * 2017-09-28 2021-01-19 宁波帅特龙集团有限公司 Coating process of automotive interior trim part
CN107629673B (en) * 2017-09-28 2021-01-08 宁波帅特龙集团有限公司 High-strength coating material and coating process thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002298A (en) * 2010-12-16 2011-04-06 广东嘉宝莉化工集团有限公司 Aqueous antifouling adhesive preventing coating and production method thereof
CN104327657A (en) * 2014-10-20 2015-02-04 芜湖县双宝建材有限公司 Special energy-saving heat-insulation water-resistant anticorrosive paint for architectural outer walls
CN106221068A (en) * 2016-08-19 2016-12-14 芜湖市天雄新材料科技有限公司 A kind of anti-ultraviolet plastic-steel section bar and production technology thereof

Also Published As

Publication number Publication date
CN111073424A (en) 2020-04-28

Similar Documents

Publication Publication Date Title
JPH10180185A (en) Plastisol composition
EP0544201B1 (en) An acrylic ester copolymer plastisol composition
CN106947187A (en) A kind of sunlight fabric is material modified and preparation method thereof with PVC
CN104109325A (en) Waterproof and environment-friendly PVC modified material and preparation method thereof
CN110816000A (en) Anticorrosive high-strength composite material and preparation method thereof
CN111088875B (en) PVC tile and preparation method thereof
CN101263166B (en) Method of preparing vinylchloride-based copolymer and vinylchloride plastisol composition including vinylchloride-based copolymer prepared using the method
CN111073424B (en) High-adhesion-resistant coating material and high-heat-resistance adhesion-resistant PVC product
CN112280219B (en) PVC high-wear-resistance edge sealing strip and preparation method thereof
KR101957854B1 (en) Acrylate based processing aid and vinyl chloride resin composition comprising thereof
KR101154457B1 (en) Process for the preparation of poly-vinylchloride resin with matte surface
CN115284703B (en) Wide low-temperature impact-resistant bending-resistant PVC (polyvinyl chloride) foaming co-extrusion plate and preparation method thereof
CN106084571A (en) A kind of embossing bronze printing polychlorovinyl sheet material and foaming method thereof
KR100871560B1 (en) Composition for pvc based foam products and pvc based foam products using the same
CN105968650A (en) Impact-resistant heat-resistant modified kaolin PVC (polyvinyl chloride) composite material and preparation method thereof
KR101997521B1 (en) Acrylic processing material, preparation method thereof and vinyl chloride resin composition comprising the same
CN111440398B (en) Special material for ion-crosslinked polyvinyl chloride protection tube
CN111534027A (en) Modified PVC material with impact resistance
CN106883532A (en) A kind of high temperature resistant shock resistance PVC floor and preparation method thereof
JPH06145454A (en) Plastisol composition of acrylic acid ester-based copolymer
CN112795064A (en) Foaming material with silica gel synthetic rubber Interpenetrating Polymer Network (IPN) structure and preparation method thereof
CN113462044B (en) Composite embossed flexible foam material and preparation method thereof
CN112123907A (en) Polytetrafluoroethylene/polypropylene film composite polyvinyl chloride plastic sheet
CN110951193A (en) Low-density UV special plate and preparation method thereof
CN117384442B (en) Corona master batch composition and preparation method and application thereof

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
EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20200428

Assignee: Ningbo yako vehicle parts Co.,Ltd.

Assignor: Ningbo Shuaitelong Group Co.,Ltd.

Contract record no.: X2021330000245

Denomination of invention: The invention relates to a high anti stick coating material and a high heat resistance and anti stick PVC product

Granted publication date: 20210528

License type: Common License

Record date: 20210904

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20221223

Address after: 238 Huiquan Road, Fenghua District, Ningbo, Zhejiang 315000

Patentee after: NINGBO JINGMEI SCIENCE AND TECHNOLOGY Co.,Ltd.

Address before: 315157 Shangshui village, Dongqiao Town, Haishu District, Ningbo City, Zhejiang Province

Patentee before: Ningbo Shuaitelong Group Co.,Ltd.