CN117586702B - Self-adhesive protective film for PP decorative plate and preparation method thereof - Google Patents

Self-adhesive protective film for PP decorative plate and preparation method thereof Download PDF

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CN117586702B
CN117586702B CN202410079788.3A CN202410079788A CN117586702B CN 117586702 B CN117586702 B CN 117586702B CN 202410079788 A CN202410079788 A CN 202410079788A CN 117586702 B CN117586702 B CN 117586702B
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polyvinyl chloride
protective film
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CN117586702A (en
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孙强云
邓迎春
高晓梅
姜嘉林
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Haiyang Linghui Packaging Co ltd
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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
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • C—CHEMISTRY; METALLURGY
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    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
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    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
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    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/22—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers modified by chemical after-treatment
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    • C08J2497/00—Characterised by the use of lignin-containing materials
    • C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
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    • 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
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    • C08K3/38—Boron-containing compounds
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    • C08K5/00—Use of organic ingredients
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Abstract

The invention relates to the technical field of polymer protective films, in particular to a self-adhesive protective film for a PP decorative plate and a preparation method thereof, wherein an ultraviolet light absorber of phenyl o-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone and resorcinol monobenzoate are dispersed and adsorbed in a pore diameter structure on the surface of nano titanium dioxide, and then a silane coupling agent is grafted on the surface of nano titanium dioxide, so that the prepared modified titanium dioxide has stable ultraviolet resistance, and the modified titanium dioxide and modified bamboo powder fiber are added into polyvinyl chloride for blending, so that the prepared polyvinyl chloride has good mechanical property and ultraviolet resistance, thereby improving the durability of the prepared self-adhesive protective film; and secondly, the self-made organic silicon pressure-sensitive adhesive prepared by the invention has lower stripping force on the basis of better high temperature resistance, so that the prepared self-adhesive protective film can be stripped more easily, and the market application prospect of the prepared self-adhesive protective film is improved to a certain extent.

Description

Self-adhesive protective film for PP decorative plate and preparation method thereof
Technical Field
The invention relates to the technical field of polymer protective films, in particular to a self-adhesive protective film for a PP decorative plate and a preparation method thereof.
Background
The protective film is widely applied to various fields, such as electronic products, glass, aluminum alloy profiles and the like, and is mainly used for preventing the surface from being damaged by scratch, pollution, corrosion and the like. The surface of the PP decorative plate is also adhered with a layer of protective film to protect the PP decorative plate, and the protective film with self-adhesive performance is more applied to the protection of the PP decorative plate. The self-adhesive protecting film is mainly used for temporary protection of the surface of articles, and is composed of a base material and a pressure-sensitive adhesive, and has the characteristics of easy adhesion, easy uncovering and no pollution to the protected surface.
At present, most of the self-adhesive protective films on the market are made of polyvinyl chloride, and a lot of products for improving the performance of the protective films by modifying the polyvinyl chloride are produced, but the products are improved for a certain specific performance, and the optimal state is not achieved in practical use, for example, the protective films with good wear resistance can be easily mildewed in practical use or become yellow under the condition of being irradiated by ultraviolet, so how to improve the technical defects is a technical problem to be solved urgently by the technicians in the field.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the self-adhesive protective film for the PP decorative plate and the preparation method thereof, which can effectively solve the problem of poor performance of the self-adhesive protective film in the prior art.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a preparation method of a self-adhesive protective film for a PP decorative plate, which comprises the following steps:
step1, performing antibacterial modification on polyvinyl chloride to prepare self-made antibacterial polyvinyl chloride, then performing modification on hexagonal boron nitride to prepare surface-modified hexagonal boron nitride, and finally performing surface treatment on bamboo powder fibers to prepare modified bamboo powder fibers;
step2, weighing 10-15 parts by weight of nano titanium dioxide, dispersing in 100 parts by weight of absolute ethyl alcohol, adding 4-5 parts by weight of phenyl o-hydroxybenzoate, 3-4 parts by weight of 2-hydroxy-4-methoxybenzophenone and 5-6 parts by weight of resorcinol monobenzoate, uniformly mixing, performing ultrasonic dispersion, adding 11-12 parts by weight of silane coupling agent KH-570, stirring for 5-6min at the original stirring speed, filtering to remove filtrate, and drying to obtain the modified titanium dioxide;
step 3, weighing 100 parts by weight of self-made antibacterial polyvinyl chloride, 4-5 parts by weight of surface modified hexagonal boron nitride, 3-5 parts by weight of modified bamboo powder fiber and 8-10 parts by weight of modified titanium dioxide, pouring the materials into a torque rheometer, and banburying the materials at 180 ℃ for 10-12min at a rotating speed of 30r/min to obtain a mixed system;
and 4, rolling the mixed system into a film through a calender, and rolling one side of the film by using a self-made organosilicon pressure-sensitive adhesive to obtain the self-adhesive protective film for the PP decorative plate.
Further, the preparation method of the self-made antibacterial polyvinyl chloride in the step1 comprises the following steps:
s1, cleaning polyvinyl chloride, placing the cleaned polyvinyl chloride at a position 30mm away from an outlet of an atmospheric pressure plasma jet glass tube, and treating the cleaned polyvinyl chloride for 5min under the conditions that the flow rates of oxygen and helium are respectively 6L/min and the discharge voltage is 6kV in oxygen and helium mixed working gas with the oxygen volume fraction of 0.75%, so that the obtained polyvinyl chloride is marked as pre-modified polyvinyl chloride;
s2, according to 1:1:2:1, weighing dodecyl dimethyl benzyl ammonium chloride, dioctyl dimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride and octadecyl dimethyl benzyl ammonium chloride according to the weight ratio, mixing, and marking the mixture as an antibacterial component;
s3, dispersing the antibacterial component in deionized water to prepare a mixed component with the mass fraction of 15-18%, then soaking the pre-modified polyvinyl chloride in the mixed component for 4-5 hours, filtering to remove filtrate, and drying the product in an oven at 45-48 ℃ for 3-5 hours to obtain the self-made antibacterial polyvinyl chloride.
Still further, the cleaning operation in S1 is: firstly, soaking polyvinyl chloride in acetone for 30min in ultrasonic dispersion at the frequency of 22-23kHz, then soaking polyvinyl chloride in deionized water for 30min in ultrasonic dispersion at the frequency of 22-23kHz, and finally drying in an oven at 40 ℃ for 2h.
Further, the preparation method of the surface modified hexagonal boron nitride in the step1 comprises the following steps:
step1, weighing 8-10 parts by weight of hexagonal boron nitride, dispersing into 100 parts by weight of sodium hydroxide solution with the mass concentration of 20%, performing ultrasonic dispersion for 1h at the frequency of 26-27kHz, heating to 100 ℃, preserving heat for 15-18h, performing centrifugal washing for 3 times after the heat preservation is finished, and drying and marking as activated hexagonal boron nitride;
step2, weighing 9-10 parts by weight of isopropyl tri (dioctyl pyrophosphoryloxy) titanate, dispersing in 100 parts by weight of isopropanol, adding 2-3 parts by weight of activated hexagonal boron nitride, performing ultrasonic dispersion at a frequency of 28-29kHz for 10min, then placing the mixture in a temperature condition of 68 ℃ for reaction for 1h, performing centrifugal washing for 3 times after the reaction is completed, and drying to obtain the surface modified hexagonal boron nitride.
Furthermore, the specific operation of centrifugal washing in Step1 and Step2 is to centrifuge three times with deionized water at a rotational speed of 8000r/min, wherein the centrifugation time is 10min each time, the drying temperature in Step1 and Step2 is 65 ℃, and the drying time is 5-6h.
Further, the preparation method of the modified bamboo powder fiber in the step1 comprises the following steps: soaking bamboo powder fiber in 20% sodium hydroxide solution for 48 hr, washing with deionized water for 3-5 times, drying in 85 deg.c oven for 12 hr, soaking the treated bamboo powder fiber in silane coupling agent dispersion for 5-6 hr, filtering to eliminate filtrate, and drying in 85 deg.c oven for 12 hr to obtain the modified bamboo powder fiber.
Further, the preparation method of the silane coupling agent dispersion liquid in the preparation method of the modified bamboo powder fiber comprises the following steps: weighing 5-6 parts by weight of silane coupling agent KH-560, dispersing in 50 parts by weight of deionized water, and stirring at a stirring speed of 500-600r/min for 20min to obtain silane coupling agent dispersion.
Further, the stirring speed of the uniform mixing in the step2 is 300-500r/min, the stirring time is 10min, the ultrasonic dispersing frequency in the step2 is 26-27kHz, the ultrasonic dispersing time is 30min, the drying temperature in the step2 is 65 ℃, and the drying time is 5-6h.
Further, the preparation method of the self-made organic silicon pressure-sensitive adhesive in the step 4 comprises the following steps:
1) Weighing 45-50 parts by weight of methyl vinyl MQ resin and 50 parts by weight of dimethylbenzene, mixing, stirring at a stirring speed of 400-500r/min for 10min, adding 1-2 parts by weight of octamethyl cyclotetrasiloxane, 0.5-0.6 part by weight of alpha, omega-dihydroxypolysiloxane, 1-2 parts by weight of heptane and 2-3 parts by weight of petroleum ether, and continuously stirring at the original stirring speed for 5-6min to obtain a premix component;
2) And dissolving dibutyl tin dilaurate into toluene to prepare a mixed solution with the mass concentration of 2%, heating the premixed component to 100-120 ℃, dripping the mixed solution at the dripping speed of 1 drop/s, preserving heat for 4-5h, and cooling to normal temperature to obtain the self-made organosilicon pressure-sensitive adhesive.
The utility model provides a PP is self-adhesion protection film for decorative board, the raw materials constitution of self-adhesion protection film for the decorative board of PP includes: polyvinyl chloride, dodecyl dimethyl benzyl ammonium chloride, dioctyl dimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, hexagonal boron nitride, sodium hydroxide solution with the mass concentration of 20%, isopropyl tri (dioctyl pyrophosphoyloxy) titanate, isopropyl alcohol, bamboo powder fiber, silane coupling agent KH-560, nano titanium dioxide, absolute ethyl alcohol, phenyl o-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone, resorcinol monobenzoate, silane coupling agent KH-570, methyl vinyl MQ resin, xylene, octamethyl cyclotetrasiloxane, alpha, omega-dihydroxypolysiloxane, heptane, petroleum ether, dibutyl tin dilaurate and toluene.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, different types of quaternary ammonium salt antibacterial agents are grafted on the surface of the polyvinyl chloride, so that the polyvinyl chloride has stable antibacterial performance, and the mildew resistance of the polyvinyl chloride is improved; secondly, the surface modification of the hexagonal boron nitride can improve the dispersibility of the hexagonal boron nitride in the polyvinyl chloride, the surface modified hexagonal boron nitride can be uniformly dispersed in the polyvinyl chloride in the blending process, and the alkali corrosion resistance of the polyvinyl chloride can be improved through the blending modification of the surface modified hexagonal boron nitride, so that the corrosion resistance of the prepared self-adhesive protective film is improved to a certain extent.
2. According to the invention, the ultraviolet light absorber of phenyl o-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone and resorcinol monobenzoate are dispersed and adsorbed in the pore diameter structure on the surface of nano titanium dioxide, then the silane coupling agent is grafted on the surface of nano titanium dioxide, so that the prepared modified titanium dioxide has stable ultraviolet resistance, and the modified titanium dioxide and modified bamboo powder fiber are added into polyvinyl chloride for blending, so that the prepared polyvinyl chloride has good mechanical property and ultraviolet resistance, and the durability of the prepared self-adhesive protective film is improved; and secondly, the self-made organic silicon pressure-sensitive adhesive prepared by the invention has lower stripping force on the basis of better high temperature resistance, so that the prepared self-adhesive protective film can be stripped more easily, and the market application prospect of the prepared self-adhesive protective film is improved to a certain extent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further described below with reference to examples.
Example 1
The preparation method of the self-adhesive protective film for the PP decorative plate comprises the following steps of:
step1, performing antibacterial modification on polyvinyl chloride to prepare self-made antibacterial polyvinyl chloride, then performing modification on hexagonal boron nitride to prepare surface-modified hexagonal boron nitride, and finally performing surface treatment on bamboo powder fibers to prepare modified bamboo powder fibers;
the preparation method of the self-made antibacterial polyvinyl chloride in the step1 comprises the following steps:
s1, cleaning polyvinyl chloride, placing the cleaned polyvinyl chloride at a position 30mm away from an outlet of an atmospheric pressure plasma jet glass tube, and treating the cleaned polyvinyl chloride for 5min under the conditions that the flow rates of oxygen and helium are respectively 6L/min and the discharge voltage is 6kV in oxygen and helium mixed working gas with the oxygen volume fraction of 0.75%, so that the obtained polyvinyl chloride is marked as pre-modified polyvinyl chloride;
s2, according to 1:1:2:1, weighing dodecyl dimethyl benzyl ammonium chloride, dioctyl dimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride and octadecyl dimethyl benzyl ammonium chloride according to the weight ratio, mixing, and marking the mixture as an antibacterial component;
s3, dispersing the antibacterial component in deionized water to prepare a mixed component with the mass fraction of 15%, then soaking the pre-modified polyvinyl chloride in the mixed component for 4 hours, filtering to remove filtrate, and drying the product in an oven at 45 ℃ for 3 hours to obtain the self-made antibacterial polyvinyl chloride.
The cleaning operation in S1 is: firstly, polyvinyl chloride is soaked in acetone for 30min in ultrasonic dispersion at the frequency of 22kHz, then, polyvinyl chloride is soaked in deionized water for 30min in ultrasonic dispersion at the frequency of 22kHz, and finally, the polyvinyl chloride is placed in an oven at the temperature of 40 ℃ for drying for 2h.
The preparation method of the surface modified hexagonal boron nitride in the step1 comprises the following steps:
step1, weighing 8 parts by weight of hexagonal boron nitride, dispersing into 100 parts by weight of sodium hydroxide solution with the mass concentration of 20%, performing ultrasonic dispersion for 1h at the frequency of 26kHz, heating to 100 ℃, preserving heat for 15h, performing centrifugal washing for 3 times after the heat preservation is finished, and drying and marking as activated hexagonal boron nitride;
step2, weighing 9 parts by weight of isopropyl tri (dioctyl pyrophosphoryl oxy) titanate, dispersing in 100 parts by weight of isopropanol, adding 2 parts by weight of activated hexagonal boron nitride, performing ultrasonic dispersion at a frequency of 28kHz for 10min, then placing the mixture in a temperature condition of 68 ℃ for reaction for 1h, performing centrifugal washing for 3 times after the reaction is finished, and drying to obtain the surface modified hexagonal boron nitride.
The specific operation of centrifugal washing in Step1 and Step2 is to centrifuge three times with deionized water at 8000r/min, wherein the centrifugation time is 10min each time, the drying temperature in Step1 and Step2 is 65 ℃, and the drying time is 5h.
The preparation method of the modified bamboo powder fiber in the step1 comprises the following steps: soaking bamboo powder fiber in sodium hydroxide solution with the mass concentration of 20% for 48 hours, washing 3 times by using deionized water after soaking, drying in an oven at 85 ℃ for 12 hours, soaking the treated bamboo powder fiber in silane coupling agent dispersion liquid for 5 hours, filtering to remove filtrate, and drying in the oven at 85 ℃ for 12 hours to obtain modified bamboo powder fiber; the preparation method of the silane coupling agent dispersion liquid comprises the following steps: 5 parts by weight of silane coupling agent KH-560 is weighed and dispersed in 50 parts by weight of deionized water, and the mixture is stirred for 20min at a stirring speed of 500r/min, so that the silane coupling agent dispersion is obtained.
Step2, weighing 10 parts by weight of nano titanium dioxide, dispersing in 100 parts by weight of absolute ethyl alcohol, adding 4 parts by weight of phenyl o-hydroxybenzoate, 3 parts by weight of 2-hydroxy-4-methoxybenzophenone and 5 parts by weight of resorcinol monobenzoate, uniformly mixing, performing ultrasonic dispersion, adding 11 parts by weight of silane coupling agent KH-570, stirring for 5min at the original stirring speed, filtering to remove filtrate, and drying to obtain the modified titanium dioxide;
wherein, the stirring speed of the uniform mixing in the step2 is 300r/min, the stirring time is 10min, the ultrasonic dispersion frequency in the step2 is 26kHz, the ultrasonic dispersion time is 30min, the drying temperature in the step2 is 65 ℃, and the drying time is 5h.
Step 3, weighing 100 parts by weight of self-made antibacterial polyvinyl chloride, 4 parts by weight of surface modified hexagonal boron nitride, 3 parts by weight of modified bamboo powder fibers and 8 parts by weight of modified titanium dioxide, pouring the materials into a torque rheometer, and banburying the materials at 180 ℃ for 10min at a rotating speed of 30r/min to obtain a mixed system;
step 4, rolling the mixed system into a film through a calender, and rolling one side of the film by using a self-made organosilicon pressure-sensitive adhesive to obtain the self-adhesive protective film for the PP decorative plate;
the preparation method of the self-made organic silicon pressure-sensitive adhesive in the step 4 comprises the following steps:
1) Weighing 45 parts by weight of methyl vinyl MQ resin and 50 parts by weight of dimethylbenzene, mixing, stirring at a stirring speed of 400r/min for 10min, adding 1 part by weight of octamethyl cyclotetrasiloxane, 0.5 part by weight of alpha, omega-dihydroxypolysiloxane, 1 part by weight of heptane and 2 parts by weight of petroleum ether, and continuously stirring at the original stirring speed for 5min to obtain a premix component;
2) And dissolving dibutyl tin dilaurate into toluene to prepare a mixed solution with the mass concentration of 2%, heating the premixed component to 100 ℃, dripping the mixed solution at the dripping speed of 1 drop/s, preserving heat for 4 hours, and cooling to normal temperature to obtain the self-made organic silicon pressure-sensitive adhesive.
The utility model provides a PP is self-adhesion protection film for decorative board, the raw materials constitution of self-adhesion protection film for the decorative board of PP includes: polyvinyl chloride, dodecyl dimethyl benzyl ammonium chloride, dioctyl dimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, hexagonal boron nitride, sodium hydroxide solution with the mass concentration of 20%, isopropyl tri (dioctyl pyrophosphoyloxy) titanate, isopropyl alcohol, bamboo powder fiber, silane coupling agent KH-560, nano titanium dioxide, absolute ethyl alcohol, phenyl o-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone, resorcinol monobenzoate, silane coupling agent KH-570, methyl vinyl MQ resin, xylene, octamethyl cyclotetrasiloxane, alpha, omega-dihydroxypolysiloxane, heptane, petroleum ether, dibutyl tin dilaurate and toluene.
Example 2
The preparation method of the self-adhesive protective film for the PP decorative plate comprises the following steps of:
step1, performing antibacterial modification on polyvinyl chloride to prepare self-made antibacterial polyvinyl chloride, then performing modification on hexagonal boron nitride to prepare surface-modified hexagonal boron nitride, and finally performing surface treatment on bamboo powder fibers to prepare modified bamboo powder fibers;
the preparation method of the self-made antibacterial polyvinyl chloride in the step1 comprises the following steps:
s1, cleaning polyvinyl chloride, placing the cleaned polyvinyl chloride at a position 30mm away from an outlet of an atmospheric pressure plasma jet glass tube, and treating the cleaned polyvinyl chloride for 5min under the conditions that the flow rates of oxygen and helium are respectively 6L/min and the discharge voltage is 6kV in oxygen and helium mixed working gas with the oxygen volume fraction of 0.75%, so that the obtained polyvinyl chloride is marked as pre-modified polyvinyl chloride;
s2, according to 1:1:2:1, weighing dodecyl dimethyl benzyl ammonium chloride, dioctyl dimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride and octadecyl dimethyl benzyl ammonium chloride according to the weight ratio, mixing, and marking the mixture as an antibacterial component;
s3, dispersing the antibacterial component in deionized water to prepare a mixed component with the mass fraction of 18%, then soaking the pre-modified polyvinyl chloride in the mixed component for 5 hours, filtering to remove filtrate, and drying the product in an oven at 48 ℃ for 5 hours to obtain the self-made antibacterial polyvinyl chloride.
The cleaning operation in S1 is: firstly, polyvinyl chloride is soaked in acetone for 30min in ultrasonic dispersion at the frequency of 23kHz, then, polyvinyl chloride is soaked in deionized water for 30min in ultrasonic dispersion at the frequency of 23kHz, and finally, the polyvinyl chloride is placed in an oven at 40 ℃ for drying for 2h.
The preparation method of the surface modified hexagonal boron nitride in the step1 comprises the following steps:
step1, weighing 10 parts by weight of hexagonal boron nitride, dispersing into 100 parts by weight of sodium hydroxide solution with the mass concentration of 20%, performing ultrasonic dispersion for 1h at the frequency of 27kHz, heating to 100 ℃, preserving heat for 18h, performing centrifugal washing for 3 times after the heat preservation is finished, and drying and marking as activated hexagonal boron nitride;
step2, weighing 10 parts by weight of isopropyl tri (dioctyl pyrophosphoryl oxy) titanate, dispersing in 100 parts by weight of isopropanol, adding 3 parts by weight of activated hexagonal boron nitride, performing ultrasonic dispersion at a frequency of 29kHz for 10min, then placing the mixture in a temperature condition of 68 ℃ for reaction for 1h, performing centrifugal washing for 3 times after the reaction is finished, and drying to obtain the surface modified hexagonal boron nitride.
The specific operation of centrifugal washing in Step1 and Step2 is to centrifuge three times with deionized water at 8000r/min, wherein the centrifugation time is 10min each time, the drying temperature in Step1 and Step2 is 65 ℃, and the drying time is 6h.
The preparation method of the modified bamboo powder fiber in the step1 comprises the following steps: soaking bamboo powder fiber in sodium hydroxide solution with the mass concentration of 20% for 48 hours, washing 5 times by using deionized water after soaking, drying in an oven at 85 ℃ for 12 hours, soaking the treated bamboo powder fiber in silane coupling agent dispersion liquid for 6 hours, filtering to remove filtrate, and drying in the oven at 85 ℃ for 12 hours to obtain modified bamboo powder fiber; the preparation method of the silane coupling agent dispersion liquid comprises the following steps: 6 parts by weight of silane coupling agent KH-560 is weighed and dispersed in 50 parts by weight of deionized water, and the mixture is stirred for 20min at a stirring speed of 600r/min, so that the silane coupling agent dispersion liquid is obtained.
Step2, weighing 15 parts by weight of nano titanium dioxide, dispersing in 100 parts by weight of absolute ethyl alcohol, adding 5 parts by weight of phenyl o-hydroxybenzoate, 4 parts by weight of 2-hydroxy-4-methoxybenzophenone and 6 parts by weight of resorcinol monobenzoate, uniformly mixing, performing ultrasonic dispersion, adding 12 parts by weight of silane coupling agent KH-570, stirring for 6min at the original stirring speed, filtering to remove filtrate, and drying to obtain the modified titanium dioxide;
wherein, the stirring speed of the uniform mixing in the step2 is 500r/min, the stirring time is 10min, the ultrasonic dispersion frequency in the step2 is 27kHz, the ultrasonic dispersion time is 30min, the drying temperature in the step2 is 65 ℃, and the drying time is 6h.
Step 3, weighing 100 parts by weight of self-made antibacterial polyvinyl chloride, 5 parts by weight of surface modified hexagonal boron nitride, 5 parts by weight of modified bamboo powder fibers and 10 parts by weight of modified titanium dioxide, pouring the materials into a torque rheometer, and banburying the materials at 180 ℃ for 12min at a rotating speed of 30r/min to obtain a mixed system;
step 4, rolling the mixed system into a film through a calender, and rolling one side of the film by using a self-made organosilicon pressure-sensitive adhesive to obtain the self-adhesive protective film for the PP decorative plate;
the preparation method of the self-made organic silicon pressure-sensitive adhesive in the step 4 comprises the following steps:
1) Weighing 50 parts by weight of methyl vinyl MQ resin and 50 parts by weight of dimethylbenzene, mixing, stirring at a stirring speed of 500r/min for 10min, adding 2 parts by weight of octamethyl cyclotetrasiloxane, 0.6 part by weight of alpha, omega-dihydroxypolysiloxane, 2 parts by weight of heptane and 3 parts by weight of petroleum ether, and continuously stirring at the original stirring speed for 6min to obtain a premix component;
2) And dissolving dibutyl tin dilaurate into toluene to prepare a mixed solution with the mass concentration of 2%, heating the premixed component to 120 ℃, dripping the mixed solution at the dripping speed of 1 drop/s, preserving heat for 5 hours, and cooling to normal temperature to obtain the self-made organic silicon pressure-sensitive adhesive.
The utility model provides a PP is self-adhesion protection film for decorative board, the raw materials constitution of self-adhesion protection film for the decorative board of PP includes: polyvinyl chloride, dodecyl dimethyl benzyl ammonium chloride, dioctyl dimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, hexagonal boron nitride, sodium hydroxide solution with the mass concentration of 20%, isopropyl tri (dioctyl pyrophosphoyloxy) titanate, isopropyl alcohol, bamboo powder fiber, silane coupling agent KH-560, nano titanium dioxide, absolute ethyl alcohol, phenyl o-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone, resorcinol monobenzoate, silane coupling agent KH-570, methyl vinyl MQ resin, xylene, octamethyl cyclotetrasiloxane, alpha, omega-dihydroxypolysiloxane, heptane, petroleum ether, dibutyl tin dilaurate and toluene.
Example 3
The preparation method of the self-adhesive protective film for the PP decorative plate comprises the following steps of:
step1, performing antibacterial modification on polyvinyl chloride to prepare self-made antibacterial polyvinyl chloride, then performing modification on hexagonal boron nitride to prepare surface-modified hexagonal boron nitride, and finally performing surface treatment on bamboo powder fibers to prepare modified bamboo powder fibers;
the preparation method of the self-made antibacterial polyvinyl chloride in the step1 comprises the following steps:
s1, cleaning polyvinyl chloride, placing the cleaned polyvinyl chloride at a position 30mm away from an outlet of an atmospheric pressure plasma jet glass tube, and treating the cleaned polyvinyl chloride for 5min under the conditions that the flow rates of oxygen and helium are respectively 6L/min and the discharge voltage is 6kV in oxygen and helium mixed working gas with the oxygen volume fraction of 0.75%, so that the obtained polyvinyl chloride is marked as pre-modified polyvinyl chloride;
s2, according to 1:1:2:1, weighing dodecyl dimethyl benzyl ammonium chloride, dioctyl dimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride and octadecyl dimethyl benzyl ammonium chloride according to the weight ratio, mixing, and marking the mixture as an antibacterial component;
s3, dispersing the antibacterial component in deionized water to prepare a mixed component with the mass fraction of 17%, then soaking the pre-modified polyvinyl chloride in the mixed component for 5 hours, filtering to remove filtrate, and drying the product in an oven at 47 ℃ for 4 hours to obtain the self-made antibacterial polyvinyl chloride.
The cleaning operation in S1 is: firstly, polyvinyl chloride is soaked in acetone for 30min in ultrasonic dispersion at the frequency of 22kHz, then is soaked in deionized water for 30min in ultrasonic dispersion at the frequency of 23kHz, and finally is dried in an oven at 40 ℃ for 2h.
The preparation method of the surface modified hexagonal boron nitride in the step1 comprises the following steps:
step1, weighing 9 parts by weight of hexagonal boron nitride, dispersing into 100 parts by weight of sodium hydroxide solution with the mass concentration of 20%, performing ultrasonic dispersion for 1h at the frequency of 27kHz, heating to 100 ℃, preserving heat for 17h, performing centrifugal washing for 3 times after the heat preservation is finished, and drying and marking as activated hexagonal boron nitride;
step2, weighing 10 parts by weight of isopropyl tri (dioctyl pyrophosphoryl oxy) titanate, dispersing in 100 parts by weight of isopropanol, adding 2 parts by weight of activated hexagonal boron nitride, performing ultrasonic dispersion at a frequency of 29kHz for 10min, then placing the mixture in a temperature condition of 68 ℃ for reaction for 1h, performing centrifugal washing for 3 times after the reaction is finished, and drying to obtain the surface modified hexagonal boron nitride.
The specific operation of centrifugal washing in Step1 and Step2 is to centrifuge three times with deionized water at 8000r/min, wherein the centrifugation time is 10min each time, the drying temperature in Step1 and Step2 is 65 ℃, and the drying time is 6h.
The preparation method of the modified bamboo powder fiber in the step1 comprises the following steps: soaking bamboo powder fiber in sodium hydroxide solution with the mass concentration of 20% for 48 hours, washing for 4 times by using deionized water after soaking, drying for 12 hours in an oven with the temperature of 85 ℃, soaking the treated bamboo powder fiber in silane coupling agent dispersion liquid for 6 hours, filtering to remove filtrate, and drying for 12 hours in the oven with the temperature of 85 ℃ to obtain modified bamboo powder fiber; the preparation method of the silane coupling agent dispersion liquid comprises the following steps: 6 parts by weight of silane coupling agent KH-560 is weighed and dispersed in 50 parts by weight of deionized water, and the mixture is stirred for 20min at a stirring speed of 600r/min, so that the silane coupling agent dispersion liquid is obtained.
Step2, weighing 13 parts by weight of nano titanium dioxide, dispersing in 100 parts by weight of absolute ethyl alcohol, adding 5 parts by weight of phenyl o-hydroxybenzoate, 4 parts by weight of 2-hydroxy-4-methoxybenzophenone and 5 parts by weight of resorcinol monobenzoate, uniformly mixing, performing ultrasonic dispersion, adding 12 parts by weight of silane coupling agent KH-570, stirring for 6min at the original stirring speed, filtering to remove filtrate, and drying to obtain the modified titanium dioxide;
wherein, the stirring speed of the uniform mixing in the step2 is 400r/min, the stirring time is 10min, the ultrasonic dispersion frequency in the step2 is 27kHz, the ultrasonic dispersion time is 30min, the drying temperature in the step2 is 65 ℃, and the drying time is 6h.
Step 3, weighing 100 parts by weight of self-made antibacterial polyvinyl chloride, 5 parts by weight of surface modified hexagonal boron nitride, 4 parts by weight of modified bamboo powder fibers and 9 parts by weight of modified titanium dioxide, pouring the materials into a torque rheometer, and banburying the materials at 180 ℃ for 11min at a rotating speed of 30r/min to obtain a mixed system;
step 4, rolling the mixed system into a film through a calender, and rolling one side of the film by using a self-made organosilicon pressure-sensitive adhesive to obtain the self-adhesive protective film for the PP decorative plate;
the preparation method of the self-made organic silicon pressure-sensitive adhesive in the step 4 comprises the following steps:
1) Weighing 48 parts by weight of methyl vinyl MQ resin and 50 parts by weight of dimethylbenzene, mixing, stirring at a stirring speed of 500r/min for 10min, adding 2 parts by weight of octamethyl cyclotetrasiloxane, 0.6 part by weight of alpha, omega-dihydroxypolysiloxane, 1 part by weight of heptane and 2 parts by weight of petroleum ether, and continuously stirring at the original stirring speed for 6min to obtain a premix component;
2) And dissolving dibutyl tin dilaurate into toluene to prepare a mixed solution with the mass concentration of 2%, heating the premixed component to 110 ℃, dripping the mixed solution at the dripping speed of 1 drop/s, preserving heat for 5 hours, and cooling to normal temperature to obtain the self-made organic silicon pressure-sensitive adhesive.
The utility model provides a PP is self-adhesion protection film for decorative board, the raw materials constitution of self-adhesion protection film for the decorative board of PP includes: polyvinyl chloride, dodecyl dimethyl benzyl ammonium chloride, dioctyl dimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, hexagonal boron nitride, sodium hydroxide solution with the mass concentration of 20%, isopropyl tri (dioctyl pyrophosphoyloxy) titanate, isopropyl alcohol, bamboo powder fiber, silane coupling agent KH-560, nano titanium dioxide, absolute ethyl alcohol, phenyl o-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone, resorcinol monobenzoate, silane coupling agent KH-570, methyl vinyl MQ resin, xylene, octamethyl cyclotetrasiloxane, alpha, omega-dihydroxypolysiloxane, heptane, petroleum ether, dibutyl tin dilaurate and toluene.
Comparative example 1
The self-adhesive protective film for PP decorative sheets and the preparation method thereof are substantially the same as those of example 1, and the main differences are that: this comparative example 1 replaces the homemade antimicrobial polyvinyl chloride of example 1 with unmodified polyvinyl chloride.
Comparative example 2
The self-adhesive protective film for PP decorative sheets and the preparation method thereof are substantially the same as those of example 1, and the main differences are that: this comparative example 2 replaces the modified hexagonal boron nitride in example 1 with unmodified hexagonal boron nitride.
Comparative example 3
The self-adhesive protective film for PP decorative sheets and the preparation method thereof are substantially the same as those of example 1, and the main differences are that: this comparative example 3 replaces the modified bamboo powder fiber in example 1 with an unmodified bamboo powder fiber.
Comparative example 4
The self-adhesive protective film for PP decorative sheets and the preparation method thereof are substantially the same as those of example 1, and the main differences are that: this comparative example 4 replaces the modified titanium dioxide in example 1 with unmodified nano titanium dioxide.
Performance testing
The self-adhesive protective films for PP decorative sheets prepared in examples 1 to 3 and comparative examples 1 to 4 were labeled as example 1, example 2, example 3, comparative example 1, comparative example 2, comparative example 3 and comparative example 4, respectively, and then the properties of examples 1 to 3 and comparative examples 1 to 4 were examined, and specific examination methods and examination items were as follows:
1. examples 1 to 3 and comparative examples 1 to 4 were examined for tensile strength, retention of tensile strain after alkali corrosion, impact strength and comprehensive antibacterial rate with reference to the standards of GB/T1049-92, GB/T11547-2008, GB/T1043-93 and QB/T2591-2003, respectively, and the obtained data are recorded in Table 1;
2. examples 1-3 and comparative examples 1-4 were subjected to ultraviolet light irradiation for 12 hours, 24 hours and 36 hours, and the yellowing degree after irradiation was recorded, and the obtained data are recorded in Table 2;
TABLE 1
TABLE 2
As is clear from the data in table 1, the self-adhesive protective films for PP decorative plates in examples 1 to 3 are superior to comparative examples 1 to 4 in mechanical properties, corrosion resistance and antibacterial properties, demonstrating that the surface-modified hexagonal boron nitride and modified bamboo powder fibers added in the preparation of the self-adhesive protective films for PP decorative plates can play a role in improving the properties; next, as is evident from the data in table 2, the discoloration degree of the self-adhesive protective film for PP decorative sheets in examples 1 to 3 under uv irradiation is not obvious, indicating that the modified titanium dioxide added in the preparation of the self-adhesive protective film for PP decorative sheets can improve the uv resistance of the self-adhesive protective film for PP decorative sheets.
To sum up, the self-adhesive protective film for the PP decorative plate and the preparation method thereof provided by the invention have excellent market application value and excellent market application prospect.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (6)

1. The preparation method of the self-adhesive protective film for the PP decorative plate is characterized by comprising the following steps of:
step1, performing antibacterial modification on polyvinyl chloride to prepare self-made antibacterial polyvinyl chloride, then performing modification on hexagonal boron nitride to prepare surface-modified hexagonal boron nitride, and finally performing surface treatment on bamboo powder fibers to prepare modified bamboo powder fibers;
step2, weighing 10-15 parts by weight of nano titanium dioxide, dispersing in 100 parts by weight of absolute ethyl alcohol, adding 4-5 parts by weight of phenyl o-hydroxybenzoate, 3-4 parts by weight of 2-hydroxy-4-methoxybenzophenone and 5-6 parts by weight of resorcinol monobenzoate, uniformly mixing, performing ultrasonic dispersion, adding 11-12 parts by weight of silane coupling agent KH-570, stirring for 5-6min at the original stirring speed, filtering to remove filtrate, and drying to obtain the modified titanium dioxide;
step 3, weighing 100 parts by weight of self-made antibacterial polyvinyl chloride, 4-5 parts by weight of surface modified hexagonal boron nitride, 3-5 parts by weight of modified bamboo powder fiber and 8-10 parts by weight of modified titanium dioxide, pouring the materials into a torque rheometer, and banburying the materials at 180 ℃ for 10-12min at a rotating speed of 30r/min to obtain a mixed system;
step 4, rolling the mixed system into a film through a calender, and rolling one side of the film by using a self-made organosilicon pressure-sensitive adhesive to obtain the self-adhesive protective film for the PP decorative plate;
the preparation method of the self-made antibacterial polyvinyl chloride in the step1 comprises the following steps:
s1, cleaning polyvinyl chloride, placing the cleaned polyvinyl chloride at a position 30mm away from an outlet of an atmospheric pressure plasma jet glass tube, and treating the cleaned polyvinyl chloride for 5min under the conditions that the flow rates of oxygen and helium are respectively 6L/min and the discharge voltage is 6kV in oxygen and helium mixed working gas with the oxygen volume fraction of 0.75%, so that the obtained polyvinyl chloride is marked as pre-modified polyvinyl chloride;
s2, according to 1:1:2:1, weighing dodecyl dimethyl benzyl ammonium chloride, dioctyl dimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride and octadecyl dimethyl benzyl ammonium chloride according to the weight ratio, mixing, and marking the mixture as an antibacterial component;
s3, dispersing the antibacterial component in deionized water to prepare a mixed component with the mass fraction of 15-18%, then soaking the pre-modified polyvinyl chloride in the mixed component for 4-5 hours, filtering to remove filtrate, and drying the product in an oven at 45-48 ℃ for 3-5 hours to obtain the self-made antibacterial polyvinyl chloride;
the preparation method of the surface modified hexagonal boron nitride in the step1 comprises the following steps:
step1, weighing 8-10 parts by weight of hexagonal boron nitride, dispersing into 100 parts by weight of sodium hydroxide solution with the mass concentration of 20%, performing ultrasonic dispersion for 1h at the frequency of 26-27kHz, heating to 100 ℃, preserving heat for 15-18h, performing centrifugal washing for 3 times after the heat preservation is finished, and drying and marking as activated hexagonal boron nitride;
step2, weighing 9-10 parts by weight of isopropyl tri (dioctyl pyrophosphoryloxy) titanate, dispersing in 100 parts by weight of isopropanol, adding 2-3 parts by weight of activated hexagonal boron nitride, performing ultrasonic dispersion at a frequency of 28-29kHz for 10min, then placing the mixture in a temperature condition of 68 ℃ for reaction for 1h, performing centrifugal washing for 3 times after the reaction is completed, and drying to obtain the surface modified hexagonal boron nitride;
the preparation method of the modified bamboo powder fiber in the step1 comprises the following steps: soaking bamboo powder fiber in sodium hydroxide solution with the mass concentration of 20% for 48 hours, washing 3-5 times by using deionized water after soaking, drying in an oven at 85 ℃ for 12 hours, soaking the treated bamboo powder fiber in silane coupling agent dispersion liquid for 5-6 hours, filtering to remove filtrate, and drying in the oven at 85 ℃ for 12 hours to obtain modified bamboo powder fiber;
the preparation method of the self-made organic silicon pressure-sensitive adhesive in the step 4 comprises the following steps:
1) Weighing 45-50 parts by weight of methyl vinyl MQ resin and 50 parts by weight of dimethylbenzene, mixing, stirring at a stirring speed of 400-500r/min for 10min, adding 1-2 parts by weight of octamethyl cyclotetrasiloxane, 0.5-0.6 part by weight of alpha, omega-dihydroxypolysiloxane, 1-2 parts by weight of heptane and 2-3 parts by weight of petroleum ether, and continuously stirring at the original stirring speed for 5-6min to obtain a premix component;
2) And dissolving dibutyl tin dilaurate into toluene to prepare a mixed solution with the mass concentration of 2%, heating the premixed component to 100-120 ℃, dripping the mixed solution at the dripping speed of 1 drop/s, preserving heat for 4-5h, and cooling to normal temperature to obtain the self-made organosilicon pressure-sensitive adhesive.
2. The method for preparing a self-adhesive protective film for PP decorative sheets according to claim 1, wherein the cleaning operation in S1 is: firstly, soaking polyvinyl chloride in acetone for 30min in ultrasonic dispersion at the frequency of 22-23kHz, then soaking polyvinyl chloride in deionized water for 30min in ultrasonic dispersion at the frequency of 22-23kHz, and finally drying in an oven at 40 ℃ for 2h.
3. The method for preparing the self-adhesive protective film for the PP decorative plate according to claim 1, wherein the specific operation of centrifugal washing in Step1 and Step2 is that deionized water is used for three times at a rotating speed of 8000r/min, the centrifugal time is 10min each time, the drying temperature in Step1 and Step2 is 65 ℃, and the drying time is 5-6h.
4. The method for preparing the self-adhesive protective film for the PP decorative plate according to claim 1, wherein the preparation method of the silane coupling agent dispersion liquid in the preparation method of the modified bamboo powder fiber is as follows: weighing 5-6 parts by weight of silane coupling agent KH-560, dispersing in 50 parts by weight of deionized water, and stirring at a stirring speed of 500-600r/min for 20min to obtain silane coupling agent dispersion.
5. The method for preparing the self-adhesive protective film for the PP decorative plate according to claim 1, wherein the stirring speed of the uniform mixing in the step2 is 300-500r/min, the stirring time is 10min, the ultrasonic dispersion frequency in the step2 is 26-27kHz, the ultrasonic dispersion time is 30min, the drying temperature in the step2 is 65 ℃, and the drying time is 5-6h.
6. A self-adhesive protective film for PP decorative sheets, characterized by being produced by a method for producing a self-adhesive protective film for PP decorative sheets as claimed in any one of claims 1 to 5.
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CN111978660A (en) * 2020-08-31 2020-11-24 潘晶 Antibiotic mould proof bamboo wood fibre integrated wallboard
CN113861584A (en) * 2021-09-14 2021-12-31 浙江亚厦装饰股份有限公司 PVC (polyvinyl chloride) plate and manufacturing method thereof
CN114716627A (en) * 2022-03-14 2022-07-08 东莞市迪彩塑胶五金有限公司 High-molecular UV absorbent for outdoor non-woven fabric and preparation method thereof
CN115011048A (en) * 2022-07-20 2022-09-06 广东亮丰达实业有限公司 Preparation method and application of polyvinyl chloride antibacterial composite material
CN116102673A (en) * 2022-12-09 2023-05-12 北京化工大学 Antibacterial additive based on crosslinked antibacterial polymer particles, method for producing same, vinyl chloride resin composition, and molded article
CN116728924A (en) * 2023-06-14 2023-09-12 广东瀚泰装饰材料有限公司 PVC decorative film containing thermal transfer printing gold and silver patterns

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JPH09137020A (en) * 1995-11-17 1997-05-27 Sintokogio Ltd Antimicrobial flexible polyvinyl chloride resin composition
KR20000020690A (en) * 1998-09-23 2000-04-15 조민호 Antibacterial resin including quaternary ammonium phosphate
CN111978660A (en) * 2020-08-31 2020-11-24 潘晶 Antibiotic mould proof bamboo wood fibre integrated wallboard
CN113861584A (en) * 2021-09-14 2021-12-31 浙江亚厦装饰股份有限公司 PVC (polyvinyl chloride) plate and manufacturing method thereof
CN114716627A (en) * 2022-03-14 2022-07-08 东莞市迪彩塑胶五金有限公司 High-molecular UV absorbent for outdoor non-woven fabric and preparation method thereof
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