CN111907165A - Wear-resistant scratch-resistant antibacterial BOPET film and preparation method thereof - Google Patents

Wear-resistant scratch-resistant antibacterial BOPET film and preparation method thereof Download PDF

Info

Publication number
CN111907165A
CN111907165A CN202010825433.6A CN202010825433A CN111907165A CN 111907165 A CN111907165 A CN 111907165A CN 202010825433 A CN202010825433 A CN 202010825433A CN 111907165 A CN111907165 A CN 111907165A
Authority
CN
China
Prior art keywords
layer
resistant
weight
antibacterial
parts
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.)
Pending
Application number
CN202010825433.6A
Other languages
Chinese (zh)
Inventor
李法雷
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to CN202010825433.6A priority Critical patent/CN111907165A/en
Publication of CN111907165A publication Critical patent/CN111907165A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/10—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to inorganic materials
    • 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
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/329—Phosphorus containing 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a wear-resistant scratch-resistant antibacterial BOPET film which consists of a surface layer A, a core layer B and a bottom layer C, wherein the thickness ratio of the surface layer A to the core layer B to the bottom layer C is 2-5:20-40:2-5, the surface layer A and the bottom layer C are positioned on two sides of the core layer B, the surface layer A is an antibacterial layer, the core layer B is a filling layer, and the bottom layer C is a wear-resistant scratch-resistant layer; the surface layer A comprises the following raw materials: PET slices, a composite antibacterial agent, a catalyst and a stabilizer; the core layer B is a PCTG copolyester slice; the bottom layer C comprises the following raw materials: the invention also discloses a preparation method of the wear-resistant scratch-resistant antibacterial BOPET film, and the prepared BOPET film has the performances of wear resistance, scratch resistance and lasting antibiosis, and has the advantages of simple production process, wide raw material source and low production cost.

Description

Wear-resistant scratch-resistant antibacterial BOPET film and preparation method thereof
Technical Field
The invention belongs to the technical field of plastic film manufacturing, and particularly relates to a wear-resistant scratch-resistant antibacterial BOPET film and a preparation method thereof.
Background
The BOPET film is a packaging film with relatively comprehensive performance. The transparency is good and the gloss is good; has good air tightness and fragrance retention. The BOPET film has excellent mechanical performance, high toughness, high tensile strength, high impact strength, high stiffness and stable size, and is suitable for secondary processing of printing, paper bag and other plastic. The BOPET film has excellent cold resistance and good chemical resistance and oil resistance.
In recent years, the BOPET film industry is rapidly developed, the application field of the industry market is continuously expanded, the professional degree of the product is higher and higher, and the step of import substitution is accelerated. The existing PET base material used in film coating and coating is low in hardness and generally lingers between 2H and 3H, so that the poor scratching of two sides of the PET film is easily caused, the rear-end working procedure is greatly influenced, the antibacterial property is poor, the product quality is greatly reduced, the cost is increased, the BOPET film is low in hardness, and the defects of no abrasion resistance and scratch resistance are caused, so that the BOPET film is not suitable for flexible cover plates which are increasingly popular or is suitable for being used as a screen explosion-proof film.
Disclosure of Invention
The invention aims to provide a wear-resistant scratch-resistant antibacterial BOPET film and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
in the prior art, the BOPET film has low hardness, poor antibacterial property, easy abrasion and scratch and does not utilize the normal production and life of people.
The purpose of the invention can be realized by the following technical scheme:
a wear-resistant scratch-resistant antibacterial BOPET film comprises a surface layer A, a core layer B and a bottom layer C, wherein the surface layer A and the bottom layer C are positioned on two sides of the core layer B, the surface layer A is an antibacterial layer, the core layer B is a filling layer, and the bottom layer C is a wear-resistant scratch-resistant layer;
the surface layer A comprises the following raw materials: according to the mass percentage, 95.5 to 98 percent of PET slice, 1.5 to 4.0 percent of composite antibacterial agent, 0.001 to 0.002 percent of catalyst and 0.003 to 0.03 percent of stabilizer;
the core layer B is a PCTG copolyester slice;
the bottom layer C comprises the following raw materials: 94.5-98.5% of PET slice, 1.0-4.0% of toughening agent, 0.5-1.5% of KH550 silane coupling agent, 0.1-1.5% of functional additive, 0.001-0.02% of catalyst and 0.003-0.03% of stabilizing agent.
The thickness of the wear-resistant scratch-resistant antibacterial BOPET film is 20-50 mu m, and the thickness ratio of the surface layer A, the core layer B and the bottom layer C is 2-5:20-40: 2-5.
The functional additive is one or a mixture of more of silicon carbide whisker, zinc oxide whisker, potassium titanate whisker and calcium carbonate whisker which are mixed in any proportion.
The catalyst is a mixture of one or more of antimony, titanium compounds and organic complexes of antimony and titanium mixed in any proportion.
The stabilizer is one or a mixture of more of phosphoric acid, phosphorous acid, polyphosphoric acid, trimethyl phosphate, triphenyl phosphate and triethyl phosphate which are mixed in any proportion.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 20-30 parts by weight of fulvic acid into 80-120 parts by weight of deionized water, stirring for 30-60min at the temperature of 25-30 ℃ and the rotation speed of 300-;
s2, ball-milling the slurry D in the S1 for 30-50min by using a ball mill, carrying out spray granulation on the ball-milled slurry, and collecting and granulating to obtain powder E;
s3, adding the powder E into 500 parts by weight of deionized water 200-;
s4, adding 0.1-0.5 part by weight of silane into the slurry F under the conditions of 70-80 ℃ and 100-0 r/min of rotation speed, stirring for 30min, then carrying out suction filtration, washing a filter cake with 2000 parts by weight of deionized water, and drying the washed filter residue for 12-36h under the conditions of 2-6 ℃ and 0.005-0.03MPa of absolute pressure to obtain the composite antibacterial agent.
The toughening agent is prepared by the following steps:
s11, putting 1 part by weight of graphene into 20-30 parts by weight of nitric acid solution with mass fraction of 30%, performing reflux reaction at 80-100 ℃ for 4-6h, then filtering, and collecting filter residues for later use;
s12, placing the filter residue in S11 in 30-40 parts by weight of 40% ethanol water solution with mass fraction, adding 3-6 parts by weight of gamma-hydrophobic propyl trimethoxy silane, stirring at the normal temperature at the speed of 150r/min for 3-6h, then performing suction filtration, and washing the filter residue with toluene for 3-5 times to obtain pre-modified graphene;
s13, placing the pre-modified graphene in a DMF solvent dissolved with 30-40 parts by weight of vinyl acetate in advance, adding 1.5 parts by weight of a photoinitiator 1173, irradiating for 1-3h by using ultraviolet light, then filtering, washing filter residues for 5-10 times by using ethyl acetate, and then drying for 4-6h at the temperature of 100-110 ℃ to obtain the toughening agent.
The preparation method of the wear-resistant scratch-resistant antibacterial BOPET film comprises the following steps:
respectively melting and extruding a raw material of a surface layer A, a raw material of a core layer B and a raw material of a bottom layer C to obtain a surface layer melt A, a core layer melt B and a bottom layer melt C, converging and extruding the surface layer melt A, the core layer melt B and the bottom layer melt C in a three-layer structure film head to obtain a film, wherein the converging and extruding temperature is 265-275 ℃;
secondly, cooling the diaphragm in the first step into a cast sheet by a cold roll, wherein the cooling temperature is 25-30 ℃;
step three, preheating the casting sheet in the step two, and then longitudinally stretching, wherein the preheating temperature is 60-95 ℃, the stretching temperature is 100-;
and fourthly, preheating the film obtained by the longitudinal stretching in the third step, then transversely stretching the film, wherein the preheating temperature is 80-90 ℃, the stretching temperature is 100-.
The invention has the beneficial effects that:
the wear-resistant scratch-resistant antibacterial BOPET film prepared by the invention consists of an antibacterial layer, a filling layer and a wear-resistant scratch-resistant layer, wherein whisker additives are added into the antibacterial layer and the wear-resistant scratch-resistant layer in the preparation process, and the whiskers are subjected to surface active treatment by using a silane coupling agent, so that macromolecular particles are grafted on whisker fibers, and the whiskers with longer molecular chains have good reinforcing and toughening effects on resin, can improve the appearance of the film, reduce the shrinkage deformation rate, improve the dimensional stability, and improve the thermal deformation temperature, the chemical resistance, the corrosion resistance and the mechanical property; the composite antibacterial agent is added into the antibacterial layer, the surface of montmorillonite loaded with zinc is firstly modified with a layer of silicon oxide with hydroxyl groups, and then silane is grafted through hydroxyl reaction to obtain the composite antibacterial agent, the composite antibacterial agent has good dispersibility in master batches, has strong bonding effect with resin, and enables the BOPET film to keep high-efficiency and lasting antibacterial ability Scratch resistance, lasting antibacterial property, simple production process, wide raw material source and low production cost.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A wear-resistant scratch-resistant antibacterial BOPET film comprises a surface layer A, a core layer B and a bottom layer C, wherein the surface layer A and the bottom layer C are positioned on two sides of the core layer B, the surface layer A is an antibacterial layer, the core layer B is a filling layer, and the bottom layer C is a wear-resistant scratch-resistant layer;
the surface layer A comprises the following raw materials: by mass percentage, 96 percent of PET slices, 4.0 percent of composite antibacterial agent, 0.001 percent of catalyst and 0.003 percent of stabilizer;
the core layer B is a PCTG copolyester slice;
the bottom layer C comprises the following raw materials: by mass percent, 96 percent of PET slice, 1.5 percent of toughening agent, 1.0 percent of KH550 silane coupling agent, 1.5 percent of functional additive, 0.001 percent of catalyst and 0.003 percent of stabilizing agent.
The thickness of the wear-resistant scratch-resistant antibacterial BOPET film is 20 micrometers, and the thickness ratio of the surface layer A, the core layer B and the bottom layer C is 2:20: 2.
The functional additive is a mixture of silicon carbide whiskers and zinc oxide whiskers mixed in any proportion.
The catalyst is ethylene glycol antimony catalyst.
The stabilizer is a mixture of phosphoric acid, phosphorous acid and polyphosphoric acid mixed in any proportion.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 20 parts by weight of fulvic acid into 80 parts by weight of deionized water, stirring for 30min at the temperature of 25 ℃ and the rotation speed of 300r/min, then adding 1.5 parts by weight of zinc oxide at the speed of 0.05g/min in the stirring process, stirring for 20min at the temperature of 25 ℃ and the rotation speed of 300r/min after the addition is finished, then performing microwave treatment for 20min at the microwave frequency of 2400MHz and the microwave power of 300W, adding 50 parts by weight of montmorillonite, and stirring for 40min at the rotation speed of 200r/min to obtain slurry D;
s2, ball-milling the slurry D in the S1 for 30min by using a ball mill, carrying out spray granulation on the ball-milled slurry, and collecting and granulating to obtain powder E;
s3, adding the powder E into 200 parts by weight of deionized water, carrying out microwave treatment for 20min under the conditions that the microwave frequency is 2400MHz and the microwave power is 300W, adding 0.1 part by weight of sodium hexametaphosphate, dispersing for 30min at the rotating speed of 1000r/min, then heating to 70 ℃, adjusting the pH value to 7.0 by using sodium hydroxide, adding 2 parts by weight of sodium metasilicate nonahydrate and 1 part by weight of sulfuric acid aqueous solution with the mass fraction of 5%, and adjusting the pH value to 6.5 to obtain slurry F;
s4, adding 0.1 part by weight of silane into the slurry F under the conditions of 70 ℃ and 100r/min of rotation speed, stirring for 30min, then carrying out suction filtration, washing a filter cake with 1000 parts by weight of deionized water, and drying the washed filter residue for 12h under the conditions of 2 ℃ and 0.005MPa of absolute pressure to obtain the composite antibacterial agent.
The toughening agent is prepared by the following steps:
s11, putting 1 part by weight of graphene into 20 parts by weight of nitric acid solution with the mass fraction of 30%, performing reflux reaction at 80 ℃ for 4 hours, then filtering, and collecting filter residues for later use;
s12, placing the filter residue in the S11 into 30 parts by weight of 40% ethanol water solution with mass fraction, adding 3 parts by weight of gamma-hydrophobic propyl trimethoxy silane, stirring at the normal temperature at the speed of 150r/min for 3 hours, then carrying out suction filtration, and washing the filter residue with toluene for 3 times to obtain pre-modified graphene;
s13, placing the pre-modified graphene in a DMF solvent dissolved with 30 parts by weight of vinyl acetate in advance, adding 1.5 parts by weight of a photoinitiator 1173, irradiating for 1 hour by using ultraviolet light, then filtering, washing filter residues for 5 times by using ethyl acetate, and then drying for 4 hours at the temperature of 100 ℃ to obtain the toughening agent.
The preparation method of the wear-resistant scratch-resistant antibacterial BOPET film comprises the following steps:
respectively melting and extruding a raw material of a surface layer A, a raw material of a core layer B and a raw material of a bottom layer C to obtain a surface layer melt A, a core layer melt B and a bottom layer melt C, converging and extruding the surface layer melt A, the core layer melt B and the bottom layer melt C in a three-layer structure film head to obtain a membrane, wherein the converging and extruding temperature is 265 ℃;
secondly, cooling the diaphragm in the first step into a cast sheet by a cold roll, wherein the cooling temperature is 25 ℃;
step three, preheating the cast sheet in the step two, and then longitudinally stretching, wherein the preheating temperature is 60 ℃, the stretching temperature is 100 ℃, and the stretching ratio is 3.5 times;
and fourthly, preheating the film obtained by longitudinal stretching in the third step, then transversely stretching the film, wherein the preheating temperature is 80 ℃, the stretching temperature is 100 ℃, then shaping the film at 180 ℃, and cooling the film at 23 ℃ to obtain the wear-resistant scratch-resistant antibacterial BOPET film.
Example 2
A wear-resistant scratch-resistant antibacterial BOPET film comprises a surface layer A, a core layer B and a bottom layer C, wherein the surface layer A and the bottom layer C are positioned on two sides of the core layer B, the surface layer A is an antibacterial layer, the core layer B is a filling layer, and the bottom layer C is a wear-resistant scratch-resistant layer;
the surface layer A comprises the following raw materials: by mass percentage, 96 percent of PET slices, 4.0 percent of composite antibacterial agent, 0.001 percent of catalyst and 0.003 percent of stabilizer;
the core layer B is a PCTG copolyester slice;
the bottom layer C comprises the following raw materials: by mass percent, 96 percent of PET slice, 1.5 percent of toughening agent, 1.0 percent of KH550 silane coupling agent, 1.5 percent of functional additive, 0.001 percent of catalyst and 0.003 percent of stabilizing agent.
The thickness of the wear-resistant scratch-resistant antibacterial BOPET film is 40 micrometers, and the thickness ratio of the surface layer A, the core layer B and the bottom layer C is 3:30: 4.
The functional additive is a mixture of silicon carbide whiskers and zinc oxide whiskers mixed in any proportion.
The catalyst is ethylene glycol antimony catalyst.
The stabilizer is a mixture of phosphoric acid, phosphorous acid and polyphosphoric acid mixed in any proportion.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 25 parts by weight of fulvic acid into 100 parts by weight of deionized water, stirring for 40min at the temperature of 28 ℃ and the rotation speed of 400r/min, then adding 2 parts by weight of zinc oxide at the speed of 0.08g/min in the stirring process, stirring for 30min at the temperature of 28 ℃ and the rotation speed of 400r/min after the addition is finished, then performing microwave treatment for 30min at the microwave frequency of 2400MHz and the microwave power of 500W, adding 80 parts by weight of montmorillonite, and stirring for 50min at the rotation speed of 300r/min to obtain slurry D;
s2, ball-milling the slurry D in the S1 for 40min by using a ball mill, carrying out spray granulation on the ball-milled slurry, and collecting and granulating to obtain powder E;
s3, adding the powder E into 300 parts by weight of deionized water, carrying out microwave treatment for 30min under the conditions that the microwave frequency is 2400MHz and the microwave power is 600W, adding 0.3 part by weight of sodium hexametaphosphate, dispersing for 40min at the rotating speed of 1200r/min, heating to 75 ℃, adjusting the pH value to 7.5 by using sodium hydroxide, adding 4 parts by weight of sodium metasilicate nonahydrate and 3 parts by weight of sulfuric acid aqueous solution with the mass fraction of 10%, and adjusting the pH value to 6.8 to obtain slurry F;
s4, adding 0.3 part by weight of silane into the slurry F under the conditions of the temperature of 75 ℃ and the rotation speed of 150r/min, stirring for 30min, then carrying out suction filtration, washing a filter cake with 1500 parts by weight of deionized water, and drying the washed filter residue for 24h under the conditions of 4 ℃ and the absolute pressure of 0.02MPa to obtain the composite antibacterial agent.
The toughening agent is prepared by the following steps:
s11, putting 1 part by weight of graphene into 20 parts by weight of nitric acid solution with the mass fraction of 30%, performing reflux reaction at 80 ℃ for 4 hours, then filtering, and collecting filter residues for later use;
s12, placing the filter residue in S11 in 35 parts by weight of 40% ethanol water solution with mass fraction, adding 4 parts by weight of gamma-hydrophobic propyl trimethoxy silane, stirring at a normal temperature at a rotating speed of 200r/min for 4 hours, then carrying out suction filtration, and washing the filter residue with toluene for 4 times to obtain pre-modified graphene;
s13, placing the pre-modified graphene in a DMF solvent dissolved with 35 parts by weight of vinyl acetate in advance, adding 1.5 parts by weight of a photoinitiator 1173, irradiating by ultraviolet light for 2 hours, then filtering, washing filter residues by ethyl acetate for 8 times, and then drying at the temperature of 105 ℃ for 5 hours to obtain the toughening agent.
The preparation method of the wear-resistant scratch-resistant antibacterial BOPET film comprises the following steps:
respectively melting and extruding a raw material of a surface layer A, a raw material of a core layer B and a raw material of a bottom layer C to obtain a surface layer melt A, a core layer melt B and a bottom layer melt C, converging and extruding the surface layer melt A, the core layer melt B and the bottom layer melt C in a three-layer structure film head to obtain a membrane, wherein the converging and extruding temperature is 270 ℃;
secondly, cooling the diaphragm in the first step into a cast sheet by a cold roll, wherein the cooling temperature is 28 ℃;
step three, preheating the cast sheet in the step two, and then longitudinally stretching, wherein the preheating temperature is 80 ℃, the stretching temperature is 105 ℃, and the stretching ratio is 3.8 times;
and fourthly, preheating the film obtained by longitudinal stretching in the third step, then transversely stretching the film, wherein the preheating temperature is 85 ℃, the stretching temperature is 105 ℃, then shaping the film at the temperature of 200 ℃, and cooling the film at the temperature of 25 ℃ to obtain the wear-resistant scratch-resistant antibacterial BOPET film.
Example 3
A wear-resistant scratch-resistant antibacterial BOPET film comprises a surface layer A, a core layer B and a bottom layer C, wherein the surface layer A and the bottom layer C are positioned on two sides of the core layer B, the surface layer A is an antibacterial layer, the core layer B is a filling layer, and the bottom layer C is a wear-resistant scratch-resistant layer;
the surface layer A comprises the following raw materials: by mass percentage, 96 percent of PET slices, 4.0 percent of composite antibacterial agent, 0.001 percent of catalyst and 0.003 percent of stabilizer;
the core layer B is a PCTG copolyester slice;
the bottom layer C comprises the following raw materials: by mass percent, 96 percent of PET slice, 1.5 percent of toughening agent, 1.0 percent of KH550 silane coupling agent, 1.5 percent of functional additive, 0.001 percent of catalyst and 0.003 percent of stabilizing agent.
The thickness of the wear-resistant scratch-resistant antibacterial BOPET film is 40 micrometers, and the thickness ratio of the surface layer A, the core layer B and the bottom layer C is 3:30: 4.
The functional additive is a mixture of silicon carbide whiskers and zinc oxide whiskers mixed in any proportion.
The catalyst is ethylene glycol antimony catalyst.
The stabilizer is a mixture of phosphoric acid, phosphorous acid and polyphosphoric acid mixed in any proportion.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 30 parts by weight of fulvic acid into 120 parts by weight of deionized water, stirring for 60min at the temperature of 30 ℃ and the rotation speed of 500r/min, then adding 3 parts by weight of zinc oxide at the speed of 0.1g/min in the stirring process, stirring for 50min at the temperature of 30 ℃ and the rotation speed of 500r/min after the addition is finished, then performing microwave treatment for 40min at the microwave frequency of 2500MHz and the microwave power of 800W, adding 100 parts by weight of montmorillonite, and stirring for 60min at the rotation speed of 500r/min to obtain slurry D;
s2, ball-milling the slurry D in the S1 for 50min by using a ball mill, carrying out spray granulation on the ball-milled slurry, and collecting and granulating to obtain powder E;
s3, adding the powder E into 500 parts by weight of deionized water, carrying out microwave treatment for 40min under the conditions that the microwave frequency is 2500MHz and the microwave power is 800W, adding 0.5 part by weight of sodium hexametaphosphate, dispersing at the rotating speed of 1500r/min for 60min, then heating to 80 ℃, adjusting the pH value to 8.0 by using sodium hydroxide, adding 6 parts by weight of sodium metasilicate nonahydrate and 7 parts by weight of sulfuric acid aqueous solution with the mass fraction of 20%, and adjusting the pH value to 7.0 to obtain slurry F;
s4, adding 0.5 part by weight of silane into the slurry F under the conditions of 80 ℃ and 300r/min of rotation speed, stirring for 30min, then carrying out suction filtration, washing a filter cake with 2000 parts by weight of deionized water, and drying the washed filter residue for 36h under the conditions of 6 ℃ and 0.03MPa of absolute pressure to obtain the composite antibacterial agent.
The toughening agent is prepared by the following steps:
s11, putting 1 part by weight of graphene into 30 parts by weight of nitric acid solution with the mass fraction of 30%, performing reflux reaction at 100 ℃ for 6 hours, then filtering, and collecting filter residues for later use;
s12, placing the filter residue in the S11 into 40 parts by weight of 40% ethanol water solution with mass fraction, adding 6 parts by weight of gamma-hydrophobic propyl trimethoxy silane, stirring at the normal temperature at the rotating speed of 300r/min for 6 hours, then carrying out suction filtration, and washing the filter residue with toluene for 5 times to obtain pre-modified graphene;
s13, placing the pre-modified graphene in a DMF solvent dissolved with 40 parts by weight of vinyl acetate in advance, adding 1.5 parts by weight of a photoinitiator 1173, irradiating for 3 hours by using ultraviolet light, then filtering, washing filter residues by using ethyl acetate for 10 times, and then drying for 6 hours at the temperature of 110 ℃ to obtain the toughening agent.
The preparation method of the wear-resistant scratch-resistant antibacterial BOPET film comprises the following steps:
respectively melting and extruding a raw material of a surface layer A, a raw material of a core layer B and a raw material of a bottom layer C to obtain a surface layer melt A, a core layer melt B and a bottom layer melt C, converging and extruding the surface layer melt A, the core layer melt B and the bottom layer melt C in a three-layer structure film head to obtain a membrane, wherein the converging and extruding temperature is 275 ℃;
secondly, cooling the diaphragm in the first step into a cast sheet by a cold roll, wherein the cooling temperature is 30 ℃;
step three, preheating the cast sheet in the step two, and then longitudinally stretching, wherein the preheating temperature is 95 ℃, the stretching temperature is 110 ℃, and the stretching ratio is 4.0 times;
and fourthly, preheating the film obtained by longitudinal stretching in the third step, then transversely stretching the film, wherein the preheating temperature is 90 ℃, the stretching temperature is 110 ℃, then shaping the film at 230 ℃, and cooling the film at 27 ℃ to obtain the wear-resistant scratch-resistant antibacterial BOPET film.
Comparative example 1
The composite antibacterial agent in the surface layer raw material A in the embodiment 1 is removed, and the rest preparation processes are not changed.
Comparative example 2
And (3) removing the toughening agent from the bottom layer raw material C in the embodiment 2, and keeping the rest preparation processes unchanged.
Comparative example 3
The comparative example is a BOPET film which is common in the market.
The BOPET films obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to the following performance tests, and the test results are shown in Table 1.
Firstly, transmittance: the test was performed according to GB/T2410-2008.
II, testing tensile strength: the tensile rate was 50mm/min, as measured in accordance with GB/T1040-2006.
And thirdly, antibacterial property test: soaking in 55 deg.C water for 16h according to QB/T2591-2003 sticking method, and determining antibacterial rate of the BOPET film after water treatment on Staphylococcus aureus ATCC NO.6538 according to QB/T2591-2003 sticking method.
TABLE 1 results of Performance test of examples 1-3 and comparative examples 1-3
Figure BDA0002636032270000121
As can be seen from the above table, the transmittance, the longitudinal tensile strength, the transverse tensile strength, the original antibacterial rate and the antibacterial rate after water treatment of the BOPET films of the embodiments 1 to 3 are all superior to those of the comparative examples 1 to 3, which shows that the BOPET film prepared by the invention has higher wear resistance, scratch resistance and antibacterial performance and higher application value than the common BOPET film in the market.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (7)

1. The wear-resistant scratch-resistant antibacterial BOPET film is characterized by consisting of a surface layer A, a core layer B and a bottom layer C, wherein the thickness ratio of the surface layer A to the core layer B to the bottom layer C is 2-5:20-40:2-5, the surface layer A and the bottom layer C are positioned on two sides of the core layer B, the surface layer A is an antibacterial layer, the core layer B is a filling layer, and the bottom layer C is a wear-resistant scratch-resistant layer;
the surface layer A comprises the following raw materials: according to the mass percentage, 95.5 to 98 percent of PET slice, 1.5 to 4.0 percent of composite antibacterial agent, 0.001 to 0.002 percent of catalyst and 0.003 to 0.03 percent of stabilizer;
the core layer B is a PCTG copolyester slice;
the bottom layer C comprises the following raw materials: 94.5-98.5% of PET slice, 1.0-4.0% of toughening agent, 0.5-1.5% of KH550 silane coupling agent, 0.1-1.5% of functional additive, 0.001-0.02% of catalyst and 0.003-0.03% of stabilizing agent.
2. The film of claim 1, wherein the functional additive is a mixture of one or more of silicon carbide whiskers, zinc oxide whiskers, potassium titanate whiskers, and calcium carbonate whiskers mixed in any proportion.
3. The abrasion-resistant scratch-resistant antibacterial BOPET film according to claim 1, wherein the catalyst is a mixture of one or more of antimony, titanium compounds and organic complexes of antimony and titanium in any proportion.
4. The abrasion-resistant scratch-resistant antibacterial BOPET film according to claim 1, wherein the stabilizer is one or more of phosphoric acid, phosphorous acid, polyphosphoric acid, trimethyl phosphate, triphenyl phosphate and triethyl phosphate mixed in any proportion.
5. The abrasion-resistant scratch-resistant antibacterial BOPET film according to claim 1, wherein the preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 20-30 parts by weight of fulvic acid into 80-120 parts by weight of deionized water, stirring for 30-60min at the temperature of 25-30 ℃ and the rotation speed of 300-;
s2, ball-milling the slurry D in the S1 for 30-50min by using a ball mill, carrying out spray granulation on the ball-milled slurry, and collecting and granulating to obtain powder E;
s3, adding the powder E into 500 parts by weight of deionized water 200-;
s4, adding 0.1-0.5 part by weight of silane into the slurry F under the conditions of 70-80 ℃ and 100-0 r/min of rotation speed, stirring for 30min, then carrying out suction filtration, washing a filter cake with 2000 parts by weight of deionized water, and drying the washed filter residue for 12-36h under the conditions of 2-6 ℃ and 0.005-0.03MPa of absolute pressure to obtain the composite antibacterial agent.
6. The abrasion-resistant scratch-resistant antibacterial BOPET film according to claim 1, wherein the toughening agent is prepared by the following steps:
s11, putting 1 part by weight of graphene into 20-30 parts by weight of nitric acid solution with mass fraction of 30%, performing reflux reaction at 80-100 ℃ for 4-6h, then filtering, and collecting filter residues for later use;
s12, placing the filter residue in S11 in 30-40 parts by weight of 40% ethanol water solution with mass fraction, adding 3-6 parts by weight of gamma-hydrophobic propyl trimethoxy silane, stirring at the normal temperature at the speed of 150r/min for 3-6h, then performing suction filtration, and washing the filter residue with toluene for 3-5 times to obtain pre-modified graphene;
s13, placing the pre-modified graphene in a DMF solvent dissolved with 30-40 parts by weight of vinyl acetate in advance, adding 1.5 parts by weight of a photoinitiator 1173, irradiating for 1-3h by using ultraviolet light, then filtering, washing filter residues for 5-10 times by using ethyl acetate, and then drying for 4-6h at the temperature of 100-110 ℃ to obtain the toughening agent.
7. The preparation method of the wear-resistant scratch-resistant antibacterial BOPET film according to claim 1, which comprises the following steps:
respectively melting and extruding a raw material of a surface layer A, a raw material of a core layer B and a raw material of a bottom layer C to obtain a surface layer melt A, a core layer melt B and a bottom layer melt C, converging and extruding the surface layer melt A, the core layer melt B and the bottom layer melt C in a three-layer structure film head to obtain a film, wherein the converging and extruding temperature is 265-275 ℃;
secondly, cooling the diaphragm in the first step into a cast sheet by a cold roll, wherein the cooling temperature is 25-30 ℃;
step three, preheating the casting sheet in the step two, and then longitudinally stretching, wherein the preheating temperature is 60-95 ℃, the stretching temperature is 100-;
and fourthly, preheating the film obtained by the longitudinal stretching in the third step, then transversely stretching the film, wherein the preheating temperature is 80-90 ℃, the stretching temperature is 100-.
CN202010825433.6A 2020-08-17 2020-08-17 Wear-resistant scratch-resistant antibacterial BOPET film and preparation method thereof Pending CN111907165A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010825433.6A CN111907165A (en) 2020-08-17 2020-08-17 Wear-resistant scratch-resistant antibacterial BOPET film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010825433.6A CN111907165A (en) 2020-08-17 2020-08-17 Wear-resistant scratch-resistant antibacterial BOPET film and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111907165A true CN111907165A (en) 2020-11-10

Family

ID=73279330

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010825433.6A Pending CN111907165A (en) 2020-08-17 2020-08-17 Wear-resistant scratch-resistant antibacterial BOPET film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111907165A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116215031A (en) * 2022-12-16 2023-06-06 青岛振昌工贸有限公司 High-temperature-resistant steaming and boiling composite film, preparation method thereof and high-temperature-resistant steaming and boiling bag
CN116814120A (en) * 2023-06-09 2023-09-29 长三角(海盐)纳米镀膜技术与智能装备研究院 Composite coating applied to dental plate die and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103203934A (en) * 2013-03-26 2013-07-17 江苏双星彩塑新材料股份有限公司 Heat shrinkage copolyester film and preparation method thereof
CN104151577A (en) * 2014-08-19 2014-11-19 南通瑞隆新材料有限公司 Preparation method of enhanced PET modified engineering plastic
CN109251485A (en) * 2018-07-05 2019-01-22 安徽国风塑业股份有限公司 A kind of metal composite BOPET film and preparation method thereof
CN109576987A (en) * 2018-11-15 2019-04-05 南昌航空大学 A method of graphene oxide grafting carbon fiber is prepared based on mercapto alkene chemical reaction
CN109694498A (en) * 2018-12-28 2019-04-30 叶丹平 A kind of novel plastic montmorillonite carrier antibacterial agent and preparation method thereof
CN109912940A (en) * 2019-03-15 2019-06-21 广东格瑞纳思薄膜科技有限公司 A kind of transparent BOPET film and preparation method thereof of the low warpage of scratch resistance

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103203934A (en) * 2013-03-26 2013-07-17 江苏双星彩塑新材料股份有限公司 Heat shrinkage copolyester film and preparation method thereof
CN104151577A (en) * 2014-08-19 2014-11-19 南通瑞隆新材料有限公司 Preparation method of enhanced PET modified engineering plastic
CN109251485A (en) * 2018-07-05 2019-01-22 安徽国风塑业股份有限公司 A kind of metal composite BOPET film and preparation method thereof
CN109576987A (en) * 2018-11-15 2019-04-05 南昌航空大学 A method of graphene oxide grafting carbon fiber is prepared based on mercapto alkene chemical reaction
CN109694498A (en) * 2018-12-28 2019-04-30 叶丹平 A kind of novel plastic montmorillonite carrier antibacterial agent and preparation method thereof
CN109912940A (en) * 2019-03-15 2019-06-21 广东格瑞纳思薄膜科技有限公司 A kind of transparent BOPET film and preparation method thereof of the low warpage of scratch resistance

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116215031A (en) * 2022-12-16 2023-06-06 青岛振昌工贸有限公司 High-temperature-resistant steaming and boiling composite film, preparation method thereof and high-temperature-resistant steaming and boiling bag
CN116215031B (en) * 2022-12-16 2023-09-26 青岛振昌工贸有限公司 High-temperature-resistant steaming and boiling composite film, preparation method thereof and high-temperature-resistant steaming and boiling bag
CN116814120A (en) * 2023-06-09 2023-09-29 长三角(海盐)纳米镀膜技术与智能装备研究院 Composite coating applied to dental plate die and preparation method thereof
CN116814120B (en) * 2023-06-09 2023-12-12 长三角(海盐)纳米镀膜技术与智能装备研究院 Composite coating applied to dental plate die and preparation method thereof

Similar Documents

Publication Publication Date Title
CN111907165A (en) Wear-resistant scratch-resistant antibacterial BOPET film and preparation method thereof
CN110468614B (en) Preparation method and application of cellulose membrane
CN113801457B (en) Efficient antibacterial polycarbonate composite material and preparation method thereof
CN102304337B (en) Novel environmental-friendly modified glue for impregnated paper and preparation method thereof
CN110355855B (en) Shaving board capable of efficiently adsorbing formaldehyde and preparation process thereof
CN110696462A (en) High-strength bidirectional-stretching polylactic acid film and preparation method thereof
CN114213984A (en) BOPP pre-coating film and production process thereof
CN113045807A (en) Degradable butyronitrile latex for gloves and preparation method thereof
CN107652638A (en) A kind of plastic uptake film and preparation method thereof
CN107286547A (en) A kind of preparation method of chitin liquefaction products/polyvinyl alcohol blending film
CN116285852A (en) Adhesive and preparation method thereof
CN113912960B (en) Transparent PVC composite film and preparation method thereof
CN106220759A (en) A kind of film polyvinyl butyral resin and synthetic method thereof
CN113980421B (en) Environment-friendly melamine powder material and preparation method thereof
CN111393693B (en) Preparation method of nano silicon dioxide/polyvinyl alcohol/carapace liquefied product preservative film material
CN114773978A (en) Solar composite front plate prepared from anti-dazzle nano coating and processing method thereof
WO2018076578A1 (en) Preparation method for titanium dioxide based synthetic paper
CN112321194A (en) Preparation method of high-temperature-resistant additive for concrete
CN117362711B (en) Antibacterial environment-friendly plastic film and preparation method and application thereof
CN108441125B (en) High-strength water-resistant adhesive for processing multilayer plywood
CN107573718A (en) A kind of novel plastic for improving luminescent plastic mechanical property
CN115558273B (en) Front cladding production process of decorative plastic profile
CN117586716B (en) Self-adhesive protective film for color crystal glass and preparation method thereof
CN109733029B (en) Transparent light conversion composite film and preparation method thereof
CN112538335B (en) Bletilla striata wood glue powder and preparation method 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
RJ01 Rejection of invention patent application after publication

Application publication date: 20201110

RJ01 Rejection of invention patent application after publication