CN116333617A - Polypropylene decorative film for floor surface facing and preparation method thereof - Google Patents

Polypropylene decorative film for floor surface facing and preparation method thereof Download PDF

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Publication number
CN116333617A
CN116333617A CN202310346030.7A CN202310346030A CN116333617A CN 116333617 A CN116333617 A CN 116333617A CN 202310346030 A CN202310346030 A CN 202310346030A CN 116333617 A CN116333617 A CN 116333617A
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parts
layer
polypropylene
wear
base film
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陈福德
周小冬
陈良栋
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Dazheng New Material Zhaoqing Co ltd
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Dazheng New Material Zhaoqing Co ltd
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Priority to CN202310346030.7A priority Critical patent/CN116333617A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • 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
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene
    • 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
    • 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
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2471/00—Presence of polyether

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  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a polypropylene decorative film for floor surface facing and a preparation method thereof, wherein the polypropylene decorative film consists of a polypropylene base film layer, a printing layer, a breathable wear-resistant layer and a back adhesive layer, the breathable wear-resistant layer comprises 30-40 parts of polyether-ether-ketone resin, 15-25 parts of polyether-block amide elastomer, 15-25 parts of polyhedral oligomeric silsesquioxane, 15-25 parts of wear-resistant filler, 4-5 parts of photoinitiator, 0.1-8 parts of matting agent, 1-3 parts of flatting agent and 0.1-0.5 part of defoaming agent, and the wear-resistant filler is the wear-resistant filler treated by adopting a coupling agent. The polypropylene decorative film for the floor surface facing adopts polyether-ether-ketone resin to be matched with polyhedral oligomeric silsesquioxane, polyether block amide elastomer, wear-resistant filler and the like, and has the effects of polymerization, crosslinking and the like under the action of a photoinitiator, so that the polypropylene decorative film has better air permeability, better wear resistance, scratch resistance and impact toughness.

Description

Polypropylene decorative film for floor surface facing and preparation method thereof
Technical Field
The invention relates to the technical field of decorative films, in particular to a polypropylene decorative film for floor surface facing and a preparation method thereof.
Background
The decorative film is a novel decorative material which is prepared by taking high molecular Polymer (PVC) as a raw material, adding various auxiliary agents, calendaring and compounding, can be compounded with base materials such as wood, plastic plates, aluminum plates, iron plates and the like to prepare a multipurpose decorative material, and can be widely applied to household appliances, acoustic surface decoration, interior decoration of indoor decoration, airplanes, ships and trains, and can also be used for billboards and the like. The bonding mode of the decorative film and the substrate plate is mainly formed by bonding glue at a certain temperature and pressure, and the process is complex. The decorative film is used as a facing material, and when the decorative film is attached to a base material, the decorative film can be attached to the base material only by tearing off the back release paper, so that the operation is convenient and simple, at present, the self-adhesive decorative film on the market mainly uses PVC, but the PVC material has the problems of chlorine, plasticizer, difficult degradation, dioxin release and other heavy environmental protection due to the fact that the PVC material contains chlorine, plasticizer, flame retardant and the like, and some countries have sequentially proposed a plastic limiting command to limit the use of the PVC.
The polypropylene (PP) is a polymer with high temperature resistance, good toughness and strong chemical corrosion resistance, the material does not contain chlorine elements, formaldehyde, heavy metals and other harmful substances, has excellent comprehensive performance, is a thermoplastic polymer material with the most development prospect at present, but is a nonpolar polymer, and has good wear resistance, but is easy to scratch, so that the product is not durable, and is especially applied to the decorative surface of the floor. The decorative board in the existing market can generate the phenomenon of bulge after long-term use due to poor air permeability, and is difficult to repair.
In the prior art, CN112940635a discloses a polypropylene decorative film for floor surface finishing, which consists of a polypropylene base film layer, a printing layer, a polypropylene breathable wear-resistant layer and a backing layer, wherein the polypropylene breathable wear-resistant layer consists of the following components: 93-97% of polypropylene resin, 3-8% of nano calcium carbonate, 2-10% of POE (polyethylene-octene co-elastomer), 0.2-1% of nucleating transparent agent, 0.2-0.5% of polyurethane and 0.5-2% of polyethylene wax. In the above technology, the polypropylene air permeability wear-resistant layer is added on the polypropylene base film layer, and the wear resistance and impact toughness of the decorative film are improved by utilizing the actions of materials such as polypropylene resin, nano calcium carbonate, POE and polyurethane, but the air permeability problem still exists, and the surface of the floor is hydrophobic, so that air bubbles are easily generated on the surface of the base material in the pasting process, and the pasting performance between the base material and the decorative film is affected.
Disclosure of Invention
In order to overcome the defects in the prior art, one of the purposes of the invention is to provide a polypropylene decorative film for floor surface finishing, which solves the problems of the prior art, and has better air permeability, better wear resistance, scratch resistance and impact toughness.
The second object of the invention is to provide a method for preparing the polypropylene decorative film for floor surface finishing.
One of the purposes of the invention is realized by adopting the following technical scheme:
the utility model provides a polypropylene decorating film for floor surface facing comprises polypropylene base film layer, printing layer, gas permeability wearing layer, gum layer, the gum layer laminating in one side of polypropylene base film layer, the printing layer is printed the opposite side of polypropylene base film layer, gas permeability wearing layer coating is in the surface of printing layer, wherein, gas permeability wearing layer includes the following component of parts by weight: 30-40 parts of polyether-ether-ketone resin, 15-25 parts of polyether-block-amide elastomer, 15-25 parts of polyhedral oligomeric silsesquioxane, 15-25 parts of wear-resistant filler, 4-5 parts of photoinitiator, 0.1-8 parts of matting powder, 1-3 parts of leveling agent, 0.1-0.5 part of defoamer and the wear-resistant filler treated by adopting 3- (trimethoxysilyl) propyl methacrylate coupling agent.
The polypropylene decorative film for the floor surface facing adopts polyether-ether-ketone resin to be matched with polyhedral oligomeric silsesquioxane, polyether block amide elastomer, wear-resistant filler and the like, and has the effects of polymerization, crosslinking and the like under the action of a photoinitiator, so that the polypropylene decorative film has better air permeability, better wear resistance, scratch resistance and impact toughness.
Wherein, polyether ether ketone (PEEK) is an aromatic crystallization type thermoplastic polymer material and has high mechanical strength, high temperature resistance, impact resistance, flame retardance, acid and alkali resistance, hydrolysis resistance, wear resistance, fatigue resistance, irradiation resistance and good electrical property.
The polyhedral oligomeric silsesquioxane is divinyl hexamethyl octameric cage type silsesquioxane which is synthesized by taking absolute ethyl alcohol as a solvent and performing cohydrolysis copolycondensation reaction on vinyl trimethoxy silane and methyl trimethoxy silane under an acidic condition. The multi-ring organic monomer consists of a silicon frame and oxygen atoms of embedded bonds thereof, forms a gear-like structure of a plurality of silicon rings, and forms better air permeability in a system.
Further, the mass ratio of polyamide block amine to polyether block in the polyether block amide elastomer is 1:0.2, the melting finger is 50g/10min-60g/10min. The main frame of the elastomer has better rebound resilience by controlling the proportion of polyamide segment amine and polyether segment in the elastomer and controlling the melt finger. It is formed by polycondensation of carboxylic polyamide and alcohol terminated polyether (polyethylene glycol PTMG, PEG).
Further, the wear-resistant filler is one or more than two of aluminum oxide, titanium dioxide and barium sulfate.
Further, the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone, the extinction powder is silicon dioxide, the leveling agent is polyester modified polydimethylsiloxane, and the defoaming agent is polysiloxane.
Further, the mass ratio of the polyether-ether-ketone resin to the polyether block amide elastomer to the wear-resistant filler is 1: (0.5-0.6): (0.5-0.6).
Further, groove-type embossing is arranged on the surface of the gum layer, and the gum layer comprises the following components in parts by weight:
acrylic amide monomer SW 94120-30 parts, poly (ethylene glycol) methacrylate 5-10 parts, 2-hydroxyethyl methacrylate phosphate 5-10 parts, acrylic amide monomer SW 9250.5-2 parts, nano Al 2 O 3 0.01 to 0.1 part of particles, 1 to 5 parts of potassium persulfate-sodium thiosulfate-copper sulfate initiator and 30 to 50 parts of deionized water.
Namely, the adhesive backing layer of the invention can be better compatible with the polypropylene base film layer by adopting the monomers such as the acrylamide monomers SW941, the acrylamide monomers SW925 and the like and combining the components such as poly (ethylene glycol) methacrylate, 2-hydroxyethyl methacrylate phosphate, potassium persulfate-sodium thiosulfate-copper sulfate initiator and the like, thereby enhancing the adhesiveness between the adhesive backing layer and the polypropylene base film layer, and can be better adhered on the base material by the self-crosslinking reaction of the monomers, and the structure of the groove embossing of the adhesive backing layer and the nano Al are utilized 2 O 3 The particles can exhaust the gas, so that no bubbles are generated on the surface of the film, and the attaching effect is better.
The acrylamide monomer SW941 is a normal-temperature self-crosslinking monomer, and can be copolymerized with monomers such as acrylic ester monomers, methacrylic ester phosphate monomers and the like, and the obtained copolymer has good initial viscosity, strong cohesive force and can strengthen the adhesiveness between a back adhesive layer and a base material.
The poly (ethylene glycol) methacrylate has hydrophobic and hydrophilic amphoteric monomers, and after the amphoteric monomers are added, the compatibility of the back adhesive layer and the polypropylene base film layer can be enhanced, and meanwhile, the polymerization degree of the system can also be enhanced, so that stronger cross-linking network is formed.
The 2-hydroxyethyl methacrylate phosphate has a plurality of functional groups such as hydroxyl, double bond, phosphate and the like, so that the adhesive force and the adhesiveness of the system to surface finishes such as furniture, wall surfaces, wall panels and the like can be enhanced.
Compared with the acrylamide monomer SW941, the acrylamide monomer SW925 is a high-temperature self-crosslinking monomer, and can be combined with external heat by utilizing heat generated by polymerization of the acrylamide monomer SW941 and other monomers, so that the acrylamide monomer SW925 can perform anti-graft polymerization reaction with unreacted monomers in the system, and can also perform self-crosslinking reaction after moisture is volatilized, so that the adhesiveness between the system and a substrate is further enhanced.
Nano Al 2 O 3 The particle size of the particles is 30-60nm, and nanometer Al is utilized 2 O 3 The effect of the particles, in the process of constructing the film, is combined with groove embossing, and the gas is discharged, so that no bubbles are generated on the surface of the film, and the film attaching effect is better.
Further, the mass ratio of the acrylamide monomer SW941 to the poly (ethylene glycol) methacrylate to the 2-hydroxyethyl methacrylate phosphate is 1: (0.2-0.5): (0.3-0.4).
Preferably, the mass ratio of the acrylamide monomer SW941 to the poly (ethylene glycol) methacrylate to the 2-hydroxyethyl methacrylate phosphate is 1:0.4:0.3.
further, the mass ratio of the acrylamide monomer SW925 to the deionized water is (0.05-0.07): 1. by controlling the water content, the self-crosslinking reaction of the later acrylamide monomer SW925 is enhanced, so that the overall adhesive force is stronger.
Preferably, the mass ratio of the acrylamide monomer SW925 to the deionized water is (0.05-0.07): 1.
further, both acrylamide monomer SW941 and acrylamide monomer SW925 were purchased from Sanwang chemical materials, inc.
Further, nanometer Al 2 The O3 particles are nano Al treated by 3- (trimethoxysilyl) propyl methacrylate coupling agent (MPS) 2 O3 particles, research shows that nano Al treated by MPS coupling agent 2 The O3 particles can increase the surface lipophilicity and inhibit the escape phenomenon from the oil phase to the water phase.
Further, the grooved embossing is of a semicircular structure, and the diameter of the grooved embossing is 0.2-0.4mm. By controlling the size of the groove embossing, the adhesive performance is improved.
One of the purposes of the invention is realized by adopting the following technical scheme:
the polypropylene decorative film for the floor surface facing consists of a polypropylene base film layer, a printing layer, a breathable wear-resistant layer and a back adhesive layer, wherein the back adhesive layer is attached to one side of the polypropylene base film layer, the printing layer is printed on the other side of the polypropylene base film layer, and the breathable wear-resistant layer is coated on the surface of the printing layer;
the polypropylene base film layer comprises the following components in parts by weight:
85-92 parts of copolymerized polypropylene (PP-R), 20-30 parts of polyhedral oligomeric silsesquioxane, 5-10 parts of light calcium carbonate, 4-15 parts of color master batch, 1-3 parts of nano titanium dioxide, 0.2-0.5 part of polyurethane antistatic agent and 0.5-1.5 parts of dispersing agent polyethylene wax; wherein the polypropylene base film layer is formed by mixing and melting the components and extruding a sheet-shaped base film, and the thickness of the base film is 0.10mm-0.20mm;
the base film has high strength, good heat resistance, good dimensional stability and excellent low-temperature toughness (good flexibility). The propylene is obtained by copolymerizing propylene monomer and a small amount of ethylene (1-4%) monomer under the actions of heating, pressurizing and catalyst, and the ethylene monomer is randomly distributed in long chains of propylene. The random addition of ethylene reduces the crystallinity and melting point of the polymer, improves the impact, long-term thermal-oxidative aging resistance, processing and forming properties of the material, and the like. The light calcium carbonate has great effect on the overall stability of the product, and can also improve the hardness and the surface smoothness of the product. The white loose nano titanium dioxide powder can enhance the coverage rate of products, has ultraviolet resistance due to high light refraction and high light activity, and can improve the ageing resistance of the products. Its ultraviolet resistance and its mechanism are related to its particle size: when the particle size is large, the blocking of ultraviolet rays is mainly reflected and scattered, and the ultraviolet rays in a medium wave area and a long wave area are effective. The anti-aging mechanism is simple covering, belongs to a common physical effect, and has weak anti-aging capability; with the reduction of the particle size, light can penetrate through the particle surface of the nano titanium dioxide, the reflection and scattering properties of the ultraviolet rays in a long wave region are not obvious, and the absorption properties of the ultraviolet rays in a medium wave region are obviously enhanced. The anti-aging mechanism is that ultraviolet rays are absorbed, and ultraviolet rays in a medium wave area are mainly absorbed; meanwhile, polyhedral oligomeric silsesquioxane is added, so that the polyhedral oligomeric silsesquioxane has better air permeability.
Therefore, the nano titanium dioxide has different anti-aging mechanisms on ultraviolet rays with different wavelengths, mainly blocks ultraviolet rays in a long-wave region, mainly blocks ultraviolet rays in a medium-wave region, and mainly absorbs the ultraviolet rays in the medium-wave region. The nano titanium dioxide has excellent absorption performance in different wavelength regions, and compared with other ultraviolet resistant agents, the nano titanium dioxide has the characteristics of no toxicity, stable performance, good effect and the like. The polyurethane antistatic agent is a high-molecular permanent antistatic agent, and the electrostatic charge generated by conduction and release of ionic conduction is achieved by reducing the volume resistivity of the material, and the antistatic effect is achieved without completely relying on surface water absorption, so that the influence of environmental humidity is relatively small, and the antistatic effect is durable and efficient.
The printing layer comprises the following components in parts by weight:
55-60 parts of water-soluble acrylic resin, 15-20 parts of pigment, 15-20 parts of main solvent water, 5-8 parts of auxiliary solvent ethanol, 1-3 parts of dispersing agent sodium oleate and 1-3 parts of ultraviolet resistant nano titanium dioxide; wherein, the printing layer is prepared into printing ink by the process technologies of dispersing and mixing uniformly, filtering and the like, and the printing ink is printed on the polypropylene base film layer by a gravure printing machine. The pigment is one or more of benzidine yellow, permanent magenta, carbon black and phthalocyanine blue. The printing ink is environment-friendly and safe, has good adhesive force, full and vivid color and light fastness reaching the level 6 blue wool.
The breathable wear-resistant layer comprises the following components in parts by weight: 30-40 parts of polyether-ether-ketone resin, 15-25 parts of polyether-block-amide elastomer, 15-25 parts of polyhedral oligomeric silsesquioxane, 15-25 parts of wear-resistant filler, 4-5 parts of photoinitiator, 0.1-8 parts of matting powder, 1-3 parts of leveling agent, 0.1-0.5 part of defoamer and the wear-resistant filler treated by adopting 3- (trimethoxysilyl) propyl methacrylate coupling agent; the breathable wear-resistant layer is formed by coating the photo-curing coating on a printing layer by a coating machine, wherein the thickness of the coating is 10-30 mu m.
The back adhesive layer is provided with groove-type embossing on the surface of the release paper, and comprises the following components in parts by weight:
acrylic amide monomer SW 94120-30 parts, poly (ethylene glycol) methacrylate 5-10 parts, 2-hydroxyethyl methacrylate phosphate 5-10 parts, acrylic amide monomer SW 9250.5-2 parts, nano Al 2 O 3 0.01 to 0.1 part of particles, 1 to 5 parts of potassium persulfate-sodium thiosulfate-copper sulfate initiator and 30 to 50 parts of deionized water;
the groove type embossing is of a semicircular structure, and the diameter of the groove type embossing is 0.2-0.4mm.
The back adhesive layer is formed by coating back adhesive by a coating machine, has good compatibility with polypropylene, is nontoxic, does not absorb water, has good viscosity, can be attached to a substrate plate at room temperature, and has good water resistance, acid and alkali resistance and weather resistance. The process is favorable for removing gas during construction of the film, does not generate bubbles, and has smoother attaching effect.
The second purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the polypropylene decorative film for the floor surface finish comprises the following preparation steps:
s1: uniformly mixing raw materials of the polypropylene base film layer according to the formula, then putting the raw materials into a film backing machine, heating, mixing and melting, extruding a sheet-shaped base film, and simultaneously carrying out corona to obtain the polypropylene base film layer;
s2: uniformly mixing the printing ink of the printing layer, pouring the mixture into an ink tank of a printer, adjusting the temperature of an oven to 100-110 ℃, rolling up, adjusting the printing speed, and beginning to print on the surface of the polypropylene base film layer to form a printing layer;
s3: uniformly mixing the coating of the breathable wear-resistant layer, homogenizing under ultrasonic vibration, pouring into a coating groove of a coating machine, adjusting the temperature of the coating machine to 60-120 ℃, adjusting each parameter of an expert-UV system, winding a printing film, adjusting the coating speed, and starting coating on the printing layer to form the breathable wear-resistant layer;
s4: uniformly mixing the raw materials of the back adhesive layer, homogenizing under ultrasonic vibration, pouring into a coating machine adhesive tank, regulating the temperature of the coating machine to 110-125 ℃, coating at a coating speed of 20-25m/min and a coating weight of 30-60g/m 2 Coating on the other side of the polypropylene base film layer, and forming groove embossing with diameter of 0.2-0.4mm on the surface by using a groove pressing machine.
When in use, two processes of flat pasting and cladding can be adopted, and the specific process is as follows:
and (3) flat paste:
the device comprises: the glue applying amount of the flat paste machine is 50-60g/m 2 The bonding pressure is 0.4MPa, and the bonding speed is 20-25 m/min.
Coating:
the device comprises: coating machine, sizing temperature is about 120 ℃, sizing amount is 30-40g/m 2 The pressure is 0.4-0.5 MPa, and the pasting speed is 20-25 m/min.
Compared with the prior art, the invention has the beneficial effects that:
1. the polypropylene decorative film for the floor surface facing adopts polyether-ether-ketone resin to be matched with polyhedral oligomeric silsesquioxane, polyether block amide elastomer, wear-resistant filler and the like, and has the effects of polymerization, crosslinking and the like under the action of a photoinitiator, so that the polypropylene decorative film has better air permeability, better wear resistance, scratch resistance and impact toughness.
2. The polypropylene decorative film for floor surface facing adopts monomers such as an acrylamide monomer SW941, an acrylamide monomer SW925 and the like, combines components such as poly (ethylene glycol) methacrylate, 2-hydroxyethyl methacrylate phosphate, potassium persulfate-sodium thiosulfate-copper sulfate initiator and the like, can be coated in one step to enhance the compatibility between a backing layer and a polypropylene base film layer, thereby enhancing the adhesiveness between the backing layer and the polypropylene base film layer, and can better adhere the backing layer on a substrate material through self-crosslinking reaction of the monomers, and adopts the grooved embossing structure of the backing layer and nano Al 2 O 3 The action of the particles, gasAnd the air bubbles are not generated on the surface of the film, so that the film has better attaching effect.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
Example 1
A polypropylene decorative film for floor surface facing is composed of a polypropylene base film layer, a printing layer, a breathable wear-resistant layer and a back adhesive layer, wherein the back adhesive layer is attached to one side of the polypropylene base film layer, the printing layer is printed on the other side of the polypropylene base film layer, the breathable wear-resistant layer is coated on the surface of the printing layer,
the polypropylene base film layer comprises the following components in parts by weight:
90 parts of copolymerized polypropylene, 20 parts of polyhedral oligomeric silsesquioxane, 6 parts of light calcium carbonate, 4 parts of color master batch, 1 part of nano titanium dioxide, 0.2 part of polyurethane antistatic agent and 0.5 part of dispersing agent polyethylene wax;
the printing layer comprises the following components in parts by weight:
55 parts of water-soluble acrylic resin, 15 parts of carbon black, 18 parts of main solvent water, 5 parts of auxiliary solvent ethanol, 2 parts of dispersing agent sodium oleate and 3 parts of ultraviolet resistant agent nano titanium dioxide;
the breathable wear-resistant layer comprises the following components in parts by weight:
33 parts of polyether-ether-ketone resin, 18 parts of polyether-block amide elastomer, 25 parts of polyhedral oligomeric silsesquioxane, 20 parts of wear-resistant filler, 4 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 0.1 part of silicon dioxide, 3 parts of polyester modified polydimethylsiloxane, 0.5 part of polysiloxane and barium sulfate treated by adopting a 3- (trimethoxysilyl) propyl methacrylate coupling agent;
the back adhesive layer is provided with groove-type embossing on the surface of the release paper, and comprises the following components in parts by weight:
acrylamide monomer SW94120 parts, and polymer5 parts of (ethylene glycol) methacrylate, 5 parts of 2-hydroxyethyl methacrylate phosphate, 9250.5 parts of acrylamide monomer SW and nano Al 2 O 3 0.01 part of particles, 1 part of potassium persulfate-sodium thiosulfate-copper sulfate initiator and 50 parts of deionized water;
the grooved embossing is of a semicircular structure, and the diameter of the grooved embossing is 0.3mm.
The preparation method of the polypropylene decorative film for the floor surface finish comprises the following preparation steps:
s1: uniformly mixing the raw materials of the polypropylene base film layer according to the formula, then putting the raw materials into a film backing machine, heating, mixing and melting, extruding a sheet-shaped base film, and simultaneously carrying out corona to obtain a polypropylene base film layer with the thickness of 0.10 mm;
s2: uniformly mixing the printing ink of the printing layer, pouring the mixture into an ink tank of a printer, adjusting the temperature of an oven to 110 ℃, winding, adjusting the printing speed, and beginning to print on the surface of the polypropylene base film layer to form the printing layer;
s3: uniformly mixing the coating of the breathable wear-resistant layer, homogenizing under ultrasonic vibration, pouring into a coating groove of a coating machine, adjusting the temperature of the coating machine to 100 ℃, adjusting each parameter of an Expimer-UV system, rolling a printing film, adjusting the coating speed, and starting coating on the printing layer to form the breathable wear-resistant layer with the thickness of 15 mu m;
s4: uniformly mixing the raw materials of the back adhesive layer, homogenizing under ultrasonic vibration, pouring into a coating machine adhesive tank, regulating the temperature of the coating machine to 120 ℃, adopting a coating machine at a coating speed of 25m/min and a coating weight of 40g/m 2 The pressure is 0.4MPa, the coating is coated on the other side of the polypropylene base film layer, then a groove embossing machine is used for forming groove embossing on the surface of the polypropylene base film layer, and when the polypropylene base film layer is used, the back adhesive layer is attached to the material.
Example 2
Unlike example 1, the breathable wear layer of the polypropylene decorative film for floor surface finish of example 2 comprises the following components in parts by weight: 40 parts of polyether-ether-ketone resin, 20 parts of polyether-block amide elastomer, 15 parts of polyhedral oligomeric silsesquioxane, 15 parts of wear-resistant filler, 5 parts of photoinitiator, 0.1 part of matting powder, 3 parts of flatting agent, 0.1 part of defoamer and alumina treated by adopting 3- (trimethoxysilyl) propyl methacrylate coupling agent.
Other components and preparation methods were the same as in example 1.
Example 3
Unlike example 1, the breathable wear layer of the polypropylene decorative film for floor surface finish of example 3 comprises the following components in parts by weight: 38 parts of polyether-ether-ketone resin, 22 parts of polyether-block amide elastomer, 20 parts of polyhedral oligomeric silsesquioxane, 15 parts of wear-resistant filler, 5 parts of photoinitiator, 0.1 part of matting powder, 3 parts of flatting agent, 0.1 part of defoamer and titanium dioxide treated by adopting a 3- (trimethoxysilyl) propyl methacrylate coupling agent. Other components and preparation methods were the same as in example 1.
Comparative example 1
Comparative example 1 is a polypropylene decorative film for floor surface finish of CN112940635 a.
Performance testing
The polypropylene decorative films for floor surface finishes of examples 1 to 3 and comparative example 1 were subjected to the following performance tests, and the test standards and test results are shown below.
1. Test standard
Surface hardness: GB/T17657-20134.57; surface scratch resistance: GB/T17657-20134.39; VOC measurement: HJT-400-2007; tensile strength: GB/T3830-2008; elongation at break: GB/T3830-2008; peel strength: ASTM D571-2011; light color fastness: CFFA-2C; gloss level: standard ISO2813; abrasion resistance: adopting a wear-resistant tool to rotate on the surface of a product, and observing the wear-resistant revolution of the surface of the product; impact resistance: at a height of 1.5 meters, the surface of the floor is reinforced by the impact of the sphere, the impact resistance is measured, and the diameter of a pit formed by the sphere falling on the surface of a test piece is measured by a vernier caliper; gas transmission rate: ASTM D1434-82.
2. Test results
Figure BDA0004159734520000121
Figure BDA0004159734520000131
Note that: MD represents a radial or longitudinal direction; CD means dimension or width direction.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.

Claims (10)

1. The utility model provides a polypropylene decorating film for floor surface facing comprises polypropylene base film layer, printing layer, gas permeability wearing layer, gum layer, the gum layer laminating in one side of polypropylene base film layer, the printing layer is printed the opposite side of polypropylene base film layer, gas permeability wearing layer coating is in the surface of printing layer, its characterized in that, gas permeability wearing layer includes the component of following parts by weight: 30-40 parts of polyether-ether-ketone resin, 15-25 parts of polyether-block-amide elastomer, 15-25 parts of polyhedral oligomeric silsesquioxane, 15-25 parts of wear-resistant filler, 4-5 parts of photoinitiator, 0.1-8 parts of matting powder, 1-3 parts of leveling agent, 0.1-0.5 part of defoamer and the wear-resistant filler treated by adopting 3- (trimethoxysilyl) propyl methacrylate coupling agent.
2. The polypropylene decorative film for floor surface finishing according to claim 1, wherein the mass ratio of polyamide-segment amine and polyether-segment in the polyether-segment amide elastomer is 1:0.2, the melting finger is 50g/10min-60g/10min.
3. The polypropylene decorative film for floor surface finishing according to claim 1, wherein the abrasion-resistant filler is one or two or more of alumina, titania and barium sulfate; the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone, the extinction powder is silicon dioxide, the leveling agent is polyester modified polydimethylsiloxane, and the defoaming agent is polysiloxane.
4. The polypropylene decorative film for floor surface finishing according to claim 1, wherein the mass ratio of the polyether-ether-ketone resin, the polyether-block-amide elastomer and the wear-resistant filler is 1: (0.5-0.6): (0.5-0.6).
5. The polypropylene decorative film for floor surface finishing according to claim 1, wherein the surface of the backing layer is provided with groove embossments, and the backing layer comprises the following components in parts by weight:
acrylic amide monomer SW 94120-30 parts, poly (ethylene glycol) methacrylate 5-10 parts, 2-hydroxyethyl methacrylate phosphate 5-10 parts, acrylic amide monomer SW 9250.5-2 parts, nano Al 2 O 3 0.01 to 0.1 part of particles, 1 to 5 parts of potassium persulfate-sodium thiosulfate-copper sulfate initiator and 30 to 50 parts of deionized water.
6. The polypropylene decorative film for floor surface finishing according to claim 5, wherein the mass ratio of the acrylamide monomer SW941, poly (ethylene glycol) methacrylate, 2-hydroxyethyl methacrylate phosphate is 1: (0.2-0.5): (0.3-0.4).
7. The polypropylene decorative film for floor surface finishing according to claim 5, wherein the mass ratio of the acrylamide-based monomer SW925 to deionized water is (0.05-0.07): 1.
8. the polypropylene decorative film for floor surface finishing according to claim 5, wherein the groove embossing has a semicircular structure, and the diameter of the groove embossing is 0.2 to 0.4mm.
9. The polypropylene decorative film for the floor surface facing is characterized by comprising a polypropylene base film layer, a printing layer, a breathable wear-resistant layer and a back adhesive layer, wherein the back adhesive layer is attached to one side of the polypropylene base film layer, the printing layer is printed on the other side of the polypropylene base film layer, and the breathable wear-resistant layer is coated on the surface of the printing layer;
the polypropylene base film layer comprises the following components in parts by weight:
85-92 parts of copolymerized polypropylene, 20-30 parts of polyhedral oligomeric silsesquioxane, 5-10 parts of light calcium carbonate, 4-15 parts of color master batch, 1-3 parts of nano titanium dioxide, 0.2-0.5 part of polyurethane antistatic agent and 0.5-1.5 parts of dispersing agent polyethylene wax;
the back adhesive layer is provided with groove-type embossing on the surface of the release paper, and comprises the following components in parts by weight:
acrylic amide monomer SW 94120-30 parts, poly (ethylene glycol) methacrylate 5-10 parts, 2-hydroxyethyl methacrylate phosphate 5-10 parts, acrylic amide monomer SW 9250.5-2 parts, nano Al 2 O 3 0.01 to 0.1 part of particles, 1 to 5 parts of potassium persulfate-sodium thiosulfate-copper sulfate initiator and 30 to 50 parts of deionized water;
the groove type embossing is of a semicircular structure, and the diameter of the groove type embossing is 0.2-0.4mm;
the breathable wear-resistant layer comprises the following components in parts by weight: 30-40 parts of polyether-ether-ketone resin, 15-25 parts of polyether-block-amide elastomer, 15-25 parts of polyhedral oligomeric silsesquioxane, 15-25 parts of wear-resistant filler, 4-5 parts of photoinitiator, 0.1-8 parts of matting powder, 1-3 parts of leveling agent, 0.1-0.5 part of defoamer and the wear-resistant filler treated by adopting 3- (trimethoxysilyl) propyl methacrylate coupling agent.
10. A method for producing a polypropylene decorative film for floor surface finishing according to any one of claims 1 to 9, comprising the steps of:
s1: uniformly mixing raw materials of the polypropylene base film layer according to the formula, then putting the raw materials into a film backing machine, heating, mixing and melting, extruding a sheet-shaped base film, and simultaneously carrying out corona to obtain the polypropylene base film layer;
s2: uniformly mixing the printing ink of the printing layer, pouring the mixture into an ink tank of a printer, adjusting the temperature of an oven to 100-110 ℃, rolling up, adjusting the printing speed, and beginning to print on the surface of the polypropylene base film layer to form a printing layer;
s3: uniformly mixing the coating of the breathable wear-resistant layer, homogenizing under ultrasonic vibration, pouring into a coating groove of a coating machine, adjusting the temperature of the coating machine to 60-120 ℃, adjusting each parameter of an expert-UV system, winding a printing film, adjusting the coating speed, and starting coating on the printing layer to form the breathable wear-resistant layer;
s4: uniformly mixing the raw materials of the back adhesive layer, homogenizing under ultrasonic vibration, pouring into a coating machine adhesive tank, regulating the temperature of the coating machine to 110-125 ℃, coating at a coating speed of 20-25m/min and a coating weight of 30-60g/m 2 Coating on the other side of the polypropylene base film layer, and forming groove embossing with diameter of 0.2-0.4mm on the surface by using a groove pressing machine.
CN202310346030.7A 2023-04-03 2023-04-03 Polypropylene decorative film for floor surface facing and preparation method thereof Pending CN116333617A (en)

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