CN110205048A - A kind of preparation method of thermostable transparent adhesive protecting film - Google Patents
A kind of preparation method of thermostable transparent adhesive protecting film Download PDFInfo
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- CN110205048A CN110205048A CN201910462438.4A CN201910462438A CN110205048A CN 110205048 A CN110205048 A CN 110205048A CN 201910462438 A CN201910462438 A CN 201910462438A CN 110205048 A CN110205048 A CN 110205048A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/12—Polypropene
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- 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
- C09J7/29—Laminated material
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
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- 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
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
Abstract
The invention discloses a kind of preparation methods of thermostable transparent adhesive protecting film, belong to protection technical field of membrane.Adhesive protecting film of the invention is using silica and antimony-doped tin oxide nano powder as backing layer altered contents; improve the high temperature resistance and transparent performance of protective film; silica freeze-drying glue and antimony-doped tin oxide nano powder silicon dioxide gel hydrolytic condensation under high speed shear environment form inorganic reticular structure in the present invention, and metal oxide and silica improve the high temperature resistance of adhesive protecting film；Self-adhesive layer is that random polypropylene and low density polyethylene (LDPE) raw material are blended in the present invention, both low density polyethylene (LDPE) and random polypropylene viscoplasticity are good, antimony-doped tin oxide powder used in the present invention is nano-powder, agglomeration is few, glue particle surface hydroxyl rich in is lyophilized in this silica, the stability that anti-reflection high temperature resistant glue can be improved after compound with antimony-doped tin oxide powder, increases the transmitance of sunlight, has a extensive future.
Description
Technical field
The invention discloses a kind of preparation methods of thermostable transparent adhesive protecting film, belong to protection technical field of membrane.
Background technique
Protective film can be divided into coating glue film and self-adhesive film by property point, and self-adhesive film is the abbreviation of self-adhesive protective film, for protecting
Protect the delicate plastic film in surface, for coating glue film, self-adhesive film have the advantages that it is more, such as without residue glue, adhesion strength stabilization, at
This low and profit is high, and self-adhesive film becomes the mainstream in market in recent years.
There are many products, require to be protected from small mobile phone screen to big car external decoration paint film, to prevent
Salt fog in storage and transportational process middle-ultraviolet lamp, the acid rain in atmosphere, birds droppings, small insect, microorganism and seawater etc. is to these
Erosion caused by product.Protective film is exactly to be born to adapt to this market demand.Another function of protective film is anti-
Only protected object body surface face is contaminated in storage and transportational process makes, scratches or causes scratch dirty.Many household electrical appliance, it is high-grade
Furniture, ornament materials are also all protected with this protective film.
Self-adhesive film is usually to be produced in a manner of co-extrusion, in one-time formed co-extrusion self-adhesive film field, due to technique and is matched
The difficulty of side is all larger, can only make the co-extrusion product of low viscosity at present.Gluing (coating) type protective film is due to using
With the material compared with lower glass transition temperatures and lower molecular weight, the often bonding tree on protective film after tearing protective film
Rouge can remain in protected object body surface face, and production process has used organic solvent, and not environmentally, pollution is big, and safety coefficient is low, and
The production technology of co-extrusion protective film is then comparatively environmentally friendly, and process contamination is small, and it is few that protective film tears rear remaining binding resin.
As previously mentioned, high temperature resistant, cleaning and viscosity are that surface protection membrane material institute is prerequisite using feature well, although existing
The production technology of some co-extrusion protective films is more environmentally friendly and has been used widely, but still comes with some shortcomings, for example, existing
Three-layer co-extruded blown film, high temperature resistance is poor, and adhesive strength changes, firm pasting when high temperature with temperature height,
But it is difficult to remove when excessively secured serious sometimes, influences these deficiencies of protected object body surface face and affect protective film, especially
The development of self-adhering protective film.
To solve the above problem existing for common protective film, adhesive protecting film is developed to be formed.The adhesion of adhesive protecting film
Layer choosing tack material, therefore do not need additionally to use sticker, it is not needed using organic solvent in manufacturing process yet, and
Adhesion coating has good stripping performance, is not easy to form residue glue in product surface when removing with product or dirt is hurt, therefore this self-adhesive film
Be of wide application.Such as a kind of adhesive protecting film of patent and preparation method thereof, by outer membrane, mesopelagic layer and inner layer film structure
It is metallocene PE, low density polyethylene (LDPE) or linear low density polyethylene at, the primary raw material of outer membrane and mesopelagic layer, it is interior
The main component of tunic is DOW Chemical elastomer, but it needs to guarantee that in the preparation different material is intracavitary with different temperature
Degree, it is cumbersome, be not suitable for industrialization large-scale application.
Therefore, invent that a kind of heat-resisting quantity is good and the adhesive protecting film that easily removes is to protection technical field of membrane has actively meaning
Justice.
Summary of the invention
Present invention mainly solves the technical issues of, poor for the high temperature resistance of current adhesive protecting film, viscosity is strong
Degree change, firm pasting when high temperature with temperature height, but sometimes excessively securely seriously when be difficult to remove, influence to be protected
Body surface provides a kind of thermostable transparent self-adhesion guarantor applied to the defect that electronic field optical clarity does not reach requirement
The preparation method of cuticula.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of thermostable transparent adhesive protecting film the preparation method comprises the following steps:
Self-adhesive layer raw material, middle layer raw material and backing layer raw material are mixed, three-layer co-extruded blown film unit is subsequently sent to and squeezes out blown film,
The extruder temperature for controlling extruder is 210~220 DEG C, and blow-up ratio is 3 ︰ 1 when blown film, and extruded film is air-cooled with a thickness of 45~50 μm
Thermostable transparent adhesive protecting film is obtained after being cooled to room temperature；
Backing layer method for preparing raw material are as follows:
It takes on the ethylene-vinyl acetate copolymer, 20~25 parts of white carbon blacks, 10~15 parts that molecular weight is 20000~22000D
State anti-reflection high temperature resistant glue, 8~10 parts of SEBS rubber powders are put into reaction kettle, wherein acetic acid in ethylene-vinyl acetate copolymer
Ethylene mass content 30~35% is heated to 230~250 DEG C, is kneaded 3~5h, obtains backing layer raw material；
Middle layer method for preparing raw material are as follows:
It measures 100~120mLDMF to be placed in the water-bath with magnetic stirring apparatus, starts magnetic stirring apparatus, with 500~550r/
The revolving speed of min stirs, and 5~7g4 is added into water-bath, and 4 '-diaminodiphenyl ethers stir 10~15min, add 6~8g
Pyromellitic dianhydride is stirred to react 3~4h, obtains vitreosol as middle layer raw material.
Self-adhesive layer raw material raw material is that 2 ︰ 1 are mixed to get by random polypropylene and low density polyethylene (LDPE) in mass ratio.
Self-adhesive layer raw material described in the specific preparation process of thermostable transparent adhesive protecting film, middle layer raw material and backing layer
Raw material mixing mass ratio is 1 ︰, 3 ︰ 1.
In the specific preparation method of backing layer raw material each raw material according to parts by weight, including molecular weight be 20000~22000D
60~70 parts of ethylene-vinyl acetate copolymer, 20~25 parts of white carbon black, 10~15 parts of anti-reflection high temperature resistant glue, SEBS glue
8~10 parts of powder.
Needing to control water bath temperature in the specific preparation method of middle layer raw material in reaction process is 35~40 DEG C.
Anti-reflection high-temperature plastic liquid and preparation method thereof in backing layer method for preparing raw material are as follows:
(1) 10~15mL ethyl orthosilicate and 100~110mL tert-butyl alcohol are mixed in beaker, 50 is heated to beaker
~55 DEG C, the dilute hydrochloric acid catalyzing hydrolysis that 3~5mL mass fraction is 5% is added into beaker, stirs 1~2h, obtains silica
The ammonium hydroxide that 5~7mL mass fraction is 20% is added dropwise into silicon dioxide gel and pours into culture dish after stirring 2~3min for colloidal sol
Sealing stands 3~4h at room temperature, obtains gel；
(2) above-mentioned gel is washed 3~5 times with the tert-butyl alcohol, at room temperature after 12~14h of aging, is put into freeze drier, very
2~3h of vacuum freecing-dry obtains silica freeze-drying glue, glue is lyophilized in silica and antimony-doped tin oxide nano powder presses quality
Than being mixed to get mixing rubber powder for 1 ︰ 3；
(3) mixing rubber powder is placed in ethyl acetate, obtains mixing suspension, after tristerin is added into suspension,
10~12h is stirred with the revolving speed of 1500~2000r/min with shear mixer, obtains anti-reflection high temperature resistant with 200 mesh filtered through gauze
Glue.
It is -40~-20 DEG C that temperature control is freeze-dried in anti-reflection high-temperature plastic liquid and preparation method thereof, and glue and antimony is lyophilized in silica
Doped tin oxide nano powder mixing mass ratio is 1 ︰ 3.
In anti-reflection high-temperature plastic liquid and preparation method thereof each raw material according to parts by weight, including mixing 10~15 parts of rubber powder, acetic acid
40~45 parts of ethyl ester, 4~5 parts of tristerin.
The beneficial effects of the present invention are:
(1) adhesive protecting film of the invention is using silica and antimony-doped tin oxide nano powder as backing layer altered contents,
The high temperature resistance and transparent performance for improving protective film, are obtained with 4,4 '-diaminodiphenyl ethers and pyromellitic dianhydride raw material
Bright colloidal sol is as middle layer, and silica freeze-drying glue and antimony-doped tin oxide nano powder are two under high speed shear environment in the present invention
Silica sol hydrolytic condensation forms inorganic reticular structure, is finally divided between organic polymer by hydrogen bond, crosslinked action
Sub horizontal hybridized film, forms the hybridized film of nano-scale, due to the scattering process of nano-silicon dioxide particle, and has ultraviolet
Screen effect, hybrid film is improved in the transmitance of visible region after doping, and during blown film, the internal stress of antimony and tin oxide increases
Add, to inhibit the growth of tin oxide grain, reduces the impurity scattering center formed in film, impurity scattering declines,
The visible light transmittance of film increases, and furthermore nucleation rate improves when generated tin oxide grain, tin oxide grain degree of refinement
It is higher, while metal oxide and silica improve the high temperature resistance of adhesive protecting film；
(2) self-adhesive layer is that random polypropylene and low density polyethylene (LDPE) raw material are blended in the present invention, low density polyethylene (LDPE) and nothing
Both isotactic polypropylenes viscoplasticity is good, and random polypropylene is heat-resist, and anti-corrosion capability is strong, simultaneously because its is random equal
Phase structure is not easy to crystallize, and transparency compares other thermo-elastic plastics more advantage, and antimony-doped tin oxide powder used in the present invention is
Nano-powder, agglomeration is few, and glue particle surface hydroxyl rich in is lyophilized in this silica, helps to disperse the anchor of agent
It is fixed, the stability of anti-reflection high temperature resistant glue can be improved after compound with antimony-doped tin oxide powder, improve inorganic particle in backing
The dispersibility of layer can increase the transmitance of sunlight to make in backing layer hybrid film nano particle diameter distribution narrower,
It has a extensive future.
Specific embodiment
10~15mL ethyl orthosilicate and 100~110mL tert-butyl alcohol are mixed in beaker, 50 are heated to beaker
~55 DEG C, the dilute hydrochloric acid catalyzing hydrolysis that 3~5mL mass fraction is 5% is added into beaker, stirs 1~2h, obtains silica
The ammonium hydroxide that 5~7mL mass fraction is 20% is added dropwise into silicon dioxide gel and pours into culture dish after stirring 2~3min for colloidal sol
Sealing stands 3~4h at room temperature, obtains gel；Above-mentioned gel is washed 3~5 times with the tert-butyl alcohol, at room temperature aging 12~
It after 14h, is put into freeze drier, 2~3h of vacuum freeze drying at -40~-20 DEG C, obtains silica freeze-drying glue, it will
Glue is lyophilized in silica and antimony-doped tin oxide nano powder is that 1 ︰ 3 is mixed to get mixing rubber powder in mass ratio；According to parts by weight,
10~15 parts of mixing rubber powders are placed in 40~45 parts of ethyl acetate, mixing suspension is obtained, 4~5 parts are added into suspension
After tristerin, 10~12h is stirred with the revolving speed of 1500~2000r/min with shear mixer, with 200 mesh filtered through gauze
Obtain anti-reflection high temperature resistant glue；According to parts by weight, taking 60~70 parts of molecular weight is the ethyl vinyl acetate second of 20000~22000D
Enoate copolymer, 20~25 parts of white carbon blacks, 10~15 parts of above-mentioned anti-reflection high temperature resistant glues, 8~10 parts of SEBS rubber powders are put into reaction
In kettle, wherein vinyl acetate mass content 30~35% in ethylene-vinyl acetate copolymer, is heated to 230~250 DEG C,
It is kneaded 3~5h, obtains backing layer raw material；It measures 100~120mLDMF to be placed in the water-bath with magnetic stirring apparatus, controls water
Bath temperature is 35~40 DEG C, starts magnetic stirring apparatus, is stirred with the revolving speed of 500~550r/min, it is added 5 into water-bath~
7g4,4 '-diaminodiphenyl ethers stir 10~15min, add 6~8g pyromellitic dianhydride, be stirred to react 3~4h, obtain
Vitreosol is as middle layer raw material；In mass ratio it is 2 ︰ 1, random polypropylene and low density polyethylene (LDPE) is mixed and are used as self-adhesive layer
Raw material, then by self-adhesive layer raw material, middle layer raw material and backing layer raw material be in mass ratio that 1 ︰, 3 ︰ 1 is mixed, it is subsequently sent to three layers altogether
Extrusion film unit squeezes out blown film, and the extruder temperature for controlling extruder is 210~220 DEG C, and blow-up ratio is 3 ︰ 1, extruded film when blown film
With a thickness of 45~50 μm, it is air-cooled be cooled to room temperature after obtain thermostable transparent adhesive protecting film.
Example 1
The preparation of anti-reflection high temperature resistant glue:
10mL ethyl orthosilicate and the 100mL tert-butyl alcohol are mixed in beaker, 50 DEG C are heated to beaker, is added into beaker
Enter the dilute hydrochloric acid catalyzing hydrolysis that 3mL mass fraction is 5%, stirs 1h, obtain silicon dioxide gel, dripped into silicon dioxide gel
Adding 5mL mass fraction is that 20% ammonium hydroxide pours into culture dish and seals, stand 3h at room temperature, obtain gel after stirring 2min；
Above-mentioned gel is washed 3 times with the tert-butyl alcohol, at room temperature after aging 12h, is put into freeze drier, it is true at -40 DEG C
Vacuum freecing-dry 2h obtains silica freeze-drying glue, glue and antimony-doped tin oxide nano powder is lyophilized in mass ratio in silica
Mixing rubber powder is mixed to get for 1 ︰ 3；
According to parts by weight, 10 parts of mixing rubber powders are placed in 40 parts of ethyl acetate, obtain mixing suspension, added into suspension
After entering 4 parts of tristerins, 10h is stirred with the revolving speed of 1500r/min with shear mixer, is obtained with 200 mesh filtered through gauze
Anti-reflection high temperature resistant glue；
The preparation of backing layer raw material:
According to parts by weight, taking 60 parts of molecular weight is ethylene-vinyl acetate copolymer, the 20 parts of white carbon blacks, 10 parts of 20000D
Above-mentioned anti-reflection high temperature resistant glue, 8 parts of SEBS rubber powders are put into reaction kettle, wherein acetic acid second in ethylene-vinyl acetate copolymer
Alkene mass content 30% is heated to 230 DEG C, is kneaded 3h, obtains backing layer raw material；
The preparation of middle layer raw material:
It measures 100mLDMF to be placed in the water-bath with magnetic stirring apparatus, control water bath temperature is 35 DEG C, and starting magnetic force stirs
Device is mixed, is stirred with the revolving speed of 500r/min, 5g4 is added into water-bath, 4 '-diaminodiphenyl ethers stir 10min, add
6g pyromellitic dianhydride, is stirred to react 3h, obtains vitreosol as middle layer raw material；
The preparation of thermostable transparent adhesive protecting film:
In mass ratio it is 2 ︰ 1, random polypropylene and low density polyethylene (LDPE) is mixed and are used as self-adhesive layer raw material, then self-adhesive layer is former
Material, middle layer raw material and backing layer raw material are 1 ︰, 3 ︰ 1 mixing in mass ratio, are subsequently sent to three-layer co-extruded blown film unit extrusion and blow
Film, the extruder temperature for controlling extruder is 210 DEG C, and blow-up ratio is 3 ︰ 1 when blown film, and extruded film is air-cooled to be cooled to a thickness of 45 μm
Thermostable transparent adhesive protecting film is obtained after room temperature.
Example 2
The preparation of anti-reflection high temperature resistant glue:
12mL ethyl orthosilicate and the 105mL tert-butyl alcohol are mixed in beaker, 52 DEG C are heated to beaker, is added into beaker
Enter the dilute hydrochloric acid catalyzing hydrolysis that 4mL mass fraction is 5%, stirs 1.5h, silicon dioxide gel is obtained, into silicon dioxide gel
The ammonium hydroxide that 6mL mass fraction is 20% is added dropwise, after stirring 2min, pours into culture dish and seals, stand 3.5h at room temperature, obtain
Gel；
Above-mentioned gel is washed 4 times with the tert-butyl alcohol, at room temperature after aging 13h, is put into freeze drier, it is true at -30 DEG C
Vacuum freecing-dry 2.5h obtains silica freeze-drying glue, glue is lyophilized in silica and antimony-doped tin oxide nano powder presses quality
Than being mixed to get mixing rubber powder for 1 ︰ 3；
According to parts by weight, 12 parts of mixing rubber powders are placed in 42 parts of ethyl acetate, obtain mixing suspension, added into suspension
After entering 4 parts of tristerins, 11h is stirred with the revolving speed of 1700r/min with shear mixer, is obtained with 200 mesh filtered through gauze
Anti-reflection high temperature resistant glue；
The preparation of backing layer raw material:
According to parts by weight, taking 65 parts of molecular weight is ethylene-vinyl acetate copolymer, the 22 parts of white carbon blacks, 12 parts of 21000D
Above-mentioned anti-reflection high temperature resistant glue, 9 parts of SEBS rubber powders are put into reaction kettle, wherein acetic acid second in ethylene-vinyl acetate copolymer
Alkene mass content 32% is heated to 240 DEG C, is kneaded 4h, obtains backing layer raw material；
The preparation of middle layer raw material:
It measures 110mLDMF to be placed in the water-bath with magnetic stirring apparatus, control water bath temperature is 37 DEG C, and starting magnetic force stirs
Device is mixed, is stirred with the revolving speed of 520r/min, 6g4 is added into water-bath, 4 '-diaminodiphenyl ethers stir 12min, add
7g pyromellitic dianhydride, is stirred to react 3.5h, obtains vitreosol as middle layer raw material；
The preparation of thermostable transparent adhesive protecting film:
In mass ratio it is 2 ︰ 1, random polypropylene and low density polyethylene (LDPE) is mixed and are used as self-adhesive layer raw material, then self-adhesive layer is former
Material, middle layer raw material and backing layer raw material are 1 ︰, 3 ︰ 1 mixing in mass ratio, are subsequently sent to three-layer co-extruded blown film unit extrusion and blow
Film, the extruder temperature for controlling extruder is 215 DEG C, and blow-up ratio is 3 ︰ 1 when blown film, and extruded film is air-cooled to be cooled to a thickness of 47 μm
Thermostable transparent adhesive protecting film is obtained after room temperature.
Example 3
The preparation of anti-reflection high temperature resistant glue:
15mL ethyl orthosilicate and the 110mL tert-butyl alcohol are mixed in beaker, 55 DEG C are heated to beaker, is added into beaker
Enter the dilute hydrochloric acid catalyzing hydrolysis that 5mL mass fraction is 5%, stirs 2h, obtain silicon dioxide gel, dripped into silicon dioxide gel
Adding 7mL mass fraction is that 20% ammonium hydroxide pours into culture dish and seals, stand 4h at room temperature, obtain gel after stirring 3min；
Above-mentioned gel is washed 5 times with the tert-butyl alcohol, at room temperature after aging 14h, is put into freeze drier, it is true at -20 DEG C
Vacuum freecing-dry 3h obtains silica freeze-drying glue, glue and antimony-doped tin oxide nano powder is lyophilized in mass ratio in silica
Mixing rubber powder is mixed to get for 1 ︰ 3；
According to parts by weight, 15 parts of mixing rubber powders are placed in 45 parts of ethyl acetate, obtain mixing suspension, added into suspension
After entering 5 parts of tristerins, 12h is stirred with the revolving speed of 2000r/min with shear mixer, is obtained with 200 mesh filtered through gauze
Anti-reflection high temperature resistant glue；
The preparation of backing layer raw material:
According to parts by weight, taking 70 parts of molecular weight is ethylene-vinyl acetate copolymer, the 25 parts of white carbon blacks, 15 parts of 22000D
Above-mentioned anti-reflection high temperature resistant glue, 10 parts of SEBS rubber powders are put into reaction kettle, wherein acetic acid second in ethylene-vinyl acetate copolymer
Alkene mass content 35% is heated to 250 DEG C, is kneaded 5h, obtains backing layer raw material；
The preparation of middle layer raw material:
It measures 120mLDMF to be placed in the water-bath with magnetic stirring apparatus, control water bath temperature is 40 DEG C, and starting magnetic force stirs
Device is mixed, is stirred with the revolving speed of 550r/min, 7g4 is added into water-bath, 4 '-diaminodiphenyl ethers stir 15min, add
8g pyromellitic dianhydride, is stirred to react 4h, obtains vitreosol as middle layer raw material；
The preparation of thermostable transparent adhesive protecting film:
In mass ratio it is 2 ︰ 1, random polypropylene and low density polyethylene (LDPE) is mixed and are used as self-adhesive layer raw material, then self-adhesive layer is former
Material, middle layer raw material and backing layer raw material are 1 ︰, 3 ︰ 1 mixing in mass ratio, are subsequently sent to three-layer co-extruded blown film unit extrusion and blow
Film, the extruder temperature for controlling extruder is 220 DEG C, and blow-up ratio is 3 ︰ 1 when blown film, and extruded film is air-cooled to be cooled to a thickness of 50 μm
Thermostable transparent adhesive protecting film is obtained after room temperature.
Comparative example 1: it is essentially identical with the preparation method of example 2, it has only the difference is that lacking anti-reflection high temperature resistant glue.
Comparative example 2: it is essentially identical with the preparation method of example 2, it has only the difference is that lacking backing layer raw material.
Comparative example 3: the thermostable transparent adhesive protecting film of Zhejiang company production.
Adhesion strength test is detected using adherence force tester.
Peel strength test is detected by GB/T7122 standard.
Light transmittance test is detected by GBT2410-2008 standard.
1 adhesive protecting film performance measurement result of table
| Test item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Adhesion strength (N/cm) | 4.0 | 4.1 | 4.2 | 2.5 | 2.7 | 2.8 |
| 70 DEG C of adhesion strengths (N/cm) | 3.6 | 3.7 | 3.8 | 1.5 | 2.0 | 2.2 |
| 70 DEG C of peel strengths (N/25mm) | 1.6 | 1.4 | 1.2 | 5.6 | 4.3 | 4.0 |
| Light transmittance (%) | 93 | 93 | 94 | 82 | 75 | 83 |
According to above-mentioned detection data, thermostable transparent adhesive protecting film heat-resisting quantity of the invention is good, adhesion strength under high temperature
Height, adhesion strength will not change with temperature height, and high temperature peel strength is low, easily removes under high temperature, and light transmittance is high, cleanliness
Up to optical grade, have broad application prospects.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of thermostable transparent adhesive protecting film, it is characterised in that specific preparation step are as follows:
Self-adhesive layer raw material, middle layer raw material and backing layer raw material are mixed, three-layer co-extruded blown film unit is subsequently sent to and squeezes out blown film,
The extruder temperature for controlling extruder is 210~220 DEG C, and blow-up ratio is 3 ︰ 1 when blown film, and extruded film is air-cooled with a thickness of 45~50 μm
Thermostable transparent adhesive protecting film is obtained after being cooled to room temperature；
The specific preparation step of backing layer raw material are as follows:
It takes on the ethylene-vinyl acetate copolymer, 20~25 parts of white carbon blacks, 10~15 parts that molecular weight is 20000~22000D
State anti-reflection high temperature resistant glue, 8~10 parts of SEBS rubber powders are put into reaction kettle, wherein acetic acid in ethylene-vinyl acetate copolymer
Ethylene mass content 30~35% is heated to 230~250 DEG C, is kneaded 3~5h, obtains backing layer raw material；
The specific preparation step of middle layer raw material are as follows:
It measures 100~120mLDMF to be placed in the water-bath with magnetic stirring apparatus, starts magnetic stirring apparatus, with 500~550r/
The revolving speed of min stirs, and 5~7g4 is added into water-bath, and 4 '-diaminodiphenyl ethers stir 10~15min, add 6~8g
Pyromellitic dianhydride is stirred to react 3~4h, obtains vitreosol as middle layer raw material.
2. a kind of preparation method of thermostable transparent adhesive protecting film according to claim 1, it is characterised in that: described
Self-adhesive layer raw material raw material is that 2 ︰ 1 are mixed to get by random polypropylene and low density polyethylene (LDPE) in mass ratio.
3. a kind of preparation method of thermostable transparent adhesive protecting film according to claim 1, it is characterised in that: described
Self-adhesive layer raw material described in the specific preparation process of thermostable transparent adhesive protecting film, middle layer raw material and the mixing of backing layer raw material
Mass ratio is 1 ︰, 3 ︰ 1.
4. a kind of preparation method of thermostable transparent adhesive protecting film according to claim 1, it is characterised in that: described
Each raw material is ethylene-vinegar of 20000~22000D including molecular weight according to parts by weight in the specific preparation step of backing layer raw material
60~70 parts of vinyl acetate copolymer, 20~25 parts of white carbon black, 10~15 parts of anti-reflection high temperature resistant glue, 8~10 parts of SEBS rubber powder.
5. a kind of preparation method of thermostable transparent adhesive protecting film according to claim 1, it is characterised in that: described
Needing to control water bath temperature in the specific preparation step of middle layer raw material in reaction process is 35~40 DEG C.
6. a kind of preparation method of thermostable transparent adhesive protecting film according to claim 1, it is characterised in that: described
The anti-reflection specific preparation step of high temperature resistant glue in the specific preparation step of backing layer raw material are as follows:
(1) 10~15mL ethyl orthosilicate and 100~110mL tert-butyl alcohol are mixed in beaker, 50 is heated to beaker
~55 DEG C, the dilute hydrochloric acid catalyzing hydrolysis that 3~5mL mass fraction is 5% is added into beaker, stirs 1~2h, obtains silica
The ammonium hydroxide that 5~7mL mass fraction is 20% is added dropwise into silicon dioxide gel and pours into culture dish after stirring 2~3min for colloidal sol
Sealing stands 3~4h at room temperature, obtains gel；
(2) above-mentioned gel is washed 3~5 times with the tert-butyl alcohol, at room temperature after 12~14h of aging, is put into freeze drier, very
2~3h of vacuum freecing-dry obtains silica freeze-drying glue, glue is lyophilized in silica and antimony-doped tin oxide nano powder presses quality
Than being mixed to get mixing rubber powder for 1 ︰ 3；
(3) mixing rubber powder is placed in ethyl acetate, obtains mixing suspension, after tristerin is added into suspension,
10~12h is stirred with the revolving speed of 1500~2000r/min with shear mixer, obtains anti-reflection high temperature resistant with 200 mesh filtered through gauze
Glue.
7. a kind of preparation method of thermostable transparent adhesive protecting film according to claim 1, it is characterised in that: anti-reflection resistance to
The control of freeze-drying temperature is -40~-20 DEG C in the specific preparation step of high temperature glue (2), and glue and Sb doped oxygen is lyophilized in silica
Change sijna rice flour mixing mass ratio is 1 ︰ 3.
8. a kind of preparation method of thermostable transparent adhesive protecting film according to claim 1, it is characterised in that: anti-reflection resistance to
In the specific preparation step of high temperature glue (3) each raw material according to parts by weight, including mixing 10~15 parts of rubber powder, ethyl acetate 40~
45 parts, 4~5 parts of tristerin.
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