CN110734711B - Pressure-sensitive adhesive for polarizer protective film and preparation method thereof - Google Patents
Pressure-sensitive adhesive for polarizer protective film and preparation method thereof Download PDFInfo
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- CN110734711B CN110734711B CN201910881930.5A CN201910881930A CN110734711B CN 110734711 B CN110734711 B CN 110734711B CN 201910881930 A CN201910881930 A CN 201910881930A CN 110734711 B CN110734711 B CN 110734711B
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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
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
Abstract
The invention discloses a pressure-sensitive adhesive for a polarizer protective film, which belongs to the technical field of pressure-sensitive adhesives and is prepared from the following raw materials in parts by weight: 31-35 parts of soft monomer, 6-8 parts of functional monomer, 0.15-0.35 part of initiator, 57-63 parts of solvent and 2-4 parts of curing agent. The pressure-sensitive adhesive for the polarizer protective film has excellent antistatic property, can not generate a large amount of static charges during peeling to cause dust adsorption and potential safety hazard, has strong heat resistance and small peeling force, has no residual adhesive after being subjected to cold tearing after being baked at a high temperature of 180 ℃, has no precipitation, no yellowing, easy peeling and good humidity and heat resistance, and the prepared polarizer protective film is highly transparent, has extremely low surface energy influence on the surface of a polarizer, has excellent chemical stability and good fitting performance, can realize automatic bubble discharge during operation, and has wide market prospect and high economic value.
Description
Technical Field
The invention belongs to the technical field of pressure-sensitive adhesives, and particularly relates to a pressure-sensitive adhesive for a polarizer protective film and a preparation method thereof.
Background
Polarizers are widely used in consumer and industrial electronic display panels, such as mobile phones, computers, liquid crystal televisions, automotive electronics, medical instruments, instruments and meters, and other application scenarios including sunglasses, anti-glare goggles, filters for photographic equipment, and light controllers. With the double drive of the continuous increase of market demand and the continuous expansion of screen area of consumer electronic terminals (televisions, tablet computers, smart phones and the like), the global display panel industry is continuously and stably developed, and is expected to reach 5 hundred million square meters in 2019, wherein a large-size TFT-LCD contributes to the demand of more than 80%. Polarizers are indispensable components for TFT-LCD imaging. The worldwide polarizer production capacity in 2019 is expected to reach 7.28 hundred million square meters. Therefore, the dosage of the special shipment protective film for the polaroid is not less than 7.3 billion square meters per year, and the economic value is 30 to 40 billion yuan per year.
The polaroid is subjected to surface treatment, so that the liquid crystal panel is endowed with higher definition, and the functions of reflection resistance, pollution resistance, scratch resistance and the like are achieved. Before the surface treatment process, the surface of the polaroid cannot be polluted by any chemical pollution, the change of the surface energy of the polaroid can seriously influence the treatment effect, and great material waste is caused.
As a protective film for a polarizer, it is necessary to have excellent chemical stability and to ensure that its influence on the surface energy of the polarizer is within 2 dynes. In addition, the protective film has good fitting performance, and automatic bubble discharge can be realized during operation; the protective film is also highly transparent, which facilitates optical inspection of the quality of the polarizer, and the protective film needs to have antistatic properties to prevent dust contamination.
The invention aims to develop the pressure-sensitive adhesive for the shipment protective film of the polaroid, which has extremely low surface energy influence on the surface of the polaroid, and has wide market prospect and high economic value.
Disclosure of Invention
The invention mainly aims to overcome the defects that the existing acrylate pressure-sensitive adhesive is easy to remain adhesive, is easy to precipitate, cannot resist high temperature and the like, and develops the pressure-sensitive adhesive for the shipment protective film of the polaroid.
In order to solve the problems, the adopted technical scheme is as follows:
a pressure-sensitive adhesive for a polarizer protective film is prepared from the following raw materials in parts by weight: 31-35 parts of soft monomer, 6-8 parts of functional monomer, 0.15-0.35 part of initiator, 57-63 parts of solvent and 2-4 parts of curing agent.
Preferably, the soft monomer is butyl acrylate and/or isooctyl acrylate.
Further preferably, the soft monomer consists of 80 to 90 wt% of butyl acrylate and 10 to 20 wt% of isooctyl acrylate.
Preferably, the functional monomer is one or more of acrylic acid, hydroxyethyl acrylate and methacryloyloxyethyl trimethyl ammonium chloride.
Further preferably, the functional monomer is prepared from acrylic acid, hydroxyethyl acrylate and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1: (5.8-6.2): (5-5.5).
Preferably, the solvent is one or more of ethyl acetate, methyl acetate, acetone and toluene.
Preferably, the curing agent is an isocyanate curing agent or an epoxy curing agent.
Further preferably, the isocyanate curing agent is one or more of hexamethylene polyisocyanate, isophorone diisocyanate, toluene diisocyanate and triglycidyl isocyanurate.
More preferably, the epoxy curing agent is an m-xylylenediamine type epoxy resin.
Preferably, the initiator is at least one selected from a peroxy initiator and an azo initiator.
More preferably, the peroxy initiator is at least one of ammonium persulfate, potassium persulfate, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dibenzoyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.
More preferably, the azo initiator is at least one of Azobisisoheptonitrile (ABVN), Azobisisobutyronitrile (AIBN), and 2, 2' -azo-bis- (2-methylbutyronitrile).
The invention also provides a preparation method of the pressure-sensitive adhesive for the polarizer protective film, which comprises the following steps:
A. weighing soft monomers, functional monomers and initiator with two thirds of the material amount according to the weight parts, adding the soft monomers, the functional monomers and the initiator into a head tank, and uniformly stirring to obtain a mixed material;
B. weighing a solvent with a feeding amount of 40-60%, and putting the solvent into a reaction kettle to be heated to a reflux state;
C. quickly adding one third of the mixed material into a reaction kettle, and keeping reflux reaction for 1-1.5 h;
D. dropwise adding the rest mixed materials into the reaction kettle at a constant speed, controlling the mixture to be completely dripped within 3-3.5h, and carrying out reflux and heat preservation for 0.5-1.5h after the dripping is completed;
E. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 5-15% of the feeding amount, and carrying out reflux and heat preservation for 0.5-1.5 h;
F. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 5-15% of the feeding amount, and carrying out reflux and heat preservation for 1.5-2.5 h;
G. cooling the temperature of the reaction kettle to below 50 ℃, adding the rest solvent, uniformly stirring, and discharging to obtain a polymer;
H. and uniformly stirring the polymer and the curing agent to obtain the pressure-sensitive adhesive for the polarizer protective film.
The invention also provides a protective film, which is prepared by uniformly coating the pressure-sensitive adhesive for the polarizer protective film on a base material, preserving the heat for 1-3min at the temperature of 110-130 ℃, and curing for 45-50h at the temperature of 45-50 ℃.
The substrate includes, but is not limited to, a PET substrate having a thickness of 40-60 μm.
The thickness of the dry glue on the protective film is 8-12 mu m.
The invention also provides application of the protective film to polarizer surface protection.
Compared with the prior art, the invention has the beneficial effects that:
the pressure-sensitive adhesive for the polarizer protective film has excellent antistatic property, can not generate a large amount of static charges during peeling to cause dust adsorption and potential safety hazard, has strong heat resistance and small peeling force, has no residual adhesive after being subjected to cold tearing after being baked at a high temperature of 180 ℃, has no precipitation, no yellowing, easy peeling and good humidity and heat resistance, and the prepared polarizer protective film is highly transparent, has extremely low surface energy influence on the surface of a polarizer, has excellent chemical stability and good fitting performance, can realize automatic bubble discharge during operation, and has wide market prospect and high economic value.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "further preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
The invention provides a pressure-sensitive adhesive for a polarizer protective film, which is prepared from the following raw materials in parts by weight: 31-35 parts of soft monomer, 6-8 parts of functional monomer, 0.15-0.35 part of initiator, 57-63 parts of solvent and 2-4 parts of curing agent.
In one embodiment, the pressure-sensitive adhesive for the polarizer protective film is prepared from the following raw materials in parts by weight: 33 parts of soft monomer, 7 parts of functional monomer, 0.25 part of initiator, 60 parts of solvent and 3 parts of curing agent.
In one embodiment, the soft monomer is butyl acrylate and/or isooctyl acrylate.
In a preferred embodiment, the soft monomer consists of 80 to 90 wt% butyl acrylate and 10 to 20 wt% isooctyl acrylate.
In a more preferred embodiment, the soft monomer consists of 85wt% butyl acrylate and 15wt% isooctyl acrylate.
In one embodiment, the functional monomer is one or more of acrylic acid, hydroxyethyl acrylate, methacryloyloxyethyl trimethyl ammonium chloride.
In a preferred embodiment, the functional monomer is prepared from acrylic acid, hydroxyethyl acrylate and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1: (5.8-6.2): (5-5.5).
In a more preferred embodiment, the functional monomer is prepared from acrylic acid, hydroxyethyl acrylate and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1: 6: 5.2.
In one embodiment, the solvent is one or more of ethyl acetate, methyl acetate, acetone, toluene.
In one embodiment, the curing agent is an isocyanate-based curing agent or an epoxy curing agent.
In a preferred embodiment, the isocyanate curing agent is one or more of hexamethylene polyisocyanate, isophorone diisocyanate, toluene diisocyanate, and triglycidyl isocyanurate.
In a preferred embodiment, the epoxy curing agent is an m-xylylene type epoxy resin.
In one embodiment, the initiator is selected from at least one of peroxy initiators and azo initiators.
In a preferred embodiment, the peroxy initiator is at least one of ammonium persulfate, potassium persulfate, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dibenzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.
In a preferred embodiment, the azo initiator is at least one of Azobisisoheptonitrile (ABVN), Azobisisobutyronitrile (AIBN), 2' -azo-bis- (2-methylbutyronitrile).
The second aspect of the present invention provides a preparation method of the pressure-sensitive adhesive for polarizer protective films, comprising the following steps:
A. weighing soft monomers, functional monomers and initiator with two thirds of the material amount according to the weight parts, adding the soft monomers, the functional monomers and the initiator into a head tank, and uniformly stirring to obtain a mixed material;
B. weighing a solvent with a feeding amount of 40-60%, and putting the solvent into a reaction kettle to be heated to a reflux state;
C. quickly adding one third of the mixed material into a reaction kettle, and keeping reflux reaction for 1-1.5 h;
D. dropwise adding the rest mixed materials into the reaction kettle at a constant speed, controlling the mixture to be completely dripped within 3-3.5h, and carrying out reflux and heat preservation for 0.5-1.5h after the dripping is completed;
E. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 5-15% of the feeding amount, and carrying out reflux and heat preservation for 0.5-1.5 h;
F. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 5-15% of the feeding amount, and carrying out reflux and heat preservation for 1.5-2.5 h;
G. cooling the temperature of the reaction kettle to below 50 ℃, adding the rest solvent, uniformly stirring, and discharging to obtain a polymer;
H. and uniformly stirring the polymer and the curing agent to obtain the pressure-sensitive adhesive for the polarizer protective film.
The third aspect of the invention provides a protective film, wherein the pressure-sensitive adhesive for the polarizer protective film is uniformly coated on a base material, is subjected to heat preservation at the temperature of 110-130 ℃ for 1-3min, and is cured at the temperature of 45-50 ℃ for 45-50h to obtain the protective film.
In one embodiment, the substrate includes, but is not limited to, a PET substrate having a thickness of 40 to 60 μm.
In one embodiment, the dry glue thickness on the protective film is 8-12 μm.
The fourth aspect of the present invention provides the use of the above protective film for protecting a surface of a polarizer.
The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.
Examples
Example 1
The pressure-sensitive adhesive for the polarizer protective film is prepared from the following raw materials in parts by weight: 33 parts of soft monomer, 7 parts of functional monomer, 0.25 part of initiator, 60 parts of solvent and 3 parts of curing agent.
The soft monomer consists of 85wt% of butyl acrylate and 15wt% of isooctyl acrylate.
The functional monomer is prepared from acrylic acid, hydroxyethyl acrylate and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1: 6: 5.2.
The solvent is ethyl acetate.
The curing agent is hexamethylene polyisocyanate (Bayer N3390, Germany).
The initiator is dibenzoyl peroxide.
The preparation method of the pressure-sensitive adhesive for the polarizer protective film comprises the following steps:
A. weighing soft monomers, functional monomers and initiator with two thirds of the material amount according to the weight parts, adding the soft monomers, the functional monomers and the initiator into a head tank, and uniformly stirring to obtain a mixed material;
B. weighing a solvent with 50% of the material feeding amount, putting the solvent into a reaction kettle, and heating to 80 ℃ for reflux;
C. quickly feeding one third of the mixed material into a reaction kettle, and keeping reflux reaction for 1.2 hours;
D. dropwise adding the rest mixed materials into the reaction kettle at a constant speed, controlling the dropping to be finished within 3.2 hours, and then carrying out reflux and heat preservation for 1 hour;
E. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 1 h;
F. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 2 hours;
G. reducing the temperature of the reaction kettle to 40 ℃, adding the rest solvent, uniformly stirring, and discharging to obtain a polymer;
H. and uniformly stirring the polymer and the curing agent to obtain the pressure-sensitive adhesive for the polarizer protective film.
A protective film is prepared by uniformly coating the pressure-sensitive adhesive for the polarizer protective film on a substrate, keeping the temperature at 120 ℃ for 2min, and curing at 48 ℃ for 48 h.
The base material is a PET base material, and the thickness of the base material is 50 mu m.
The thickness of the pressure-sensitive adhesive dry glue on the protective film is 10 mu m.
The protective film is applied to protecting the surface of the polaroid.
Example 2
The pressure-sensitive adhesive for the polarizer protective film is prepared from the following raw materials in parts by weight: 31 parts of soft monomer, 6 parts of functional monomer, 0.15 part of initiator, 57 parts of solvent and 2 parts of curing agent.
31-35 parts of soft monomer, 6-8 parts of functional monomer, 0.15-0.35 part of initiator, 57-63 parts of solvent and 2-4 parts of curing agent
The soft monomer consists of 80 wt% of butyl acrylate and 20 wt% of isooctyl acrylate.
The functional monomer is prepared from acrylic acid, hydroxyethyl acrylate and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1: 5.8: 5.
The solvent is ethyl acetate.
The curing agent is hexamethylene polyisocyanate (Bayer N3390, Germany).
The initiator is dibenzoyl peroxide.
The preparation method of the pressure-sensitive adhesive for the polarizer protective film comprises the following steps:
A. weighing soft monomers, functional monomers and initiator with two thirds of the material amount according to the weight parts, adding the soft monomers, the functional monomers and the initiator into a head tank, and uniformly stirring to obtain a mixed material;
B. weighing a solvent with 50% of the material feeding amount, putting the solvent into a reaction kettle, and heating to 80 ℃ for reflux;
C. quickly feeding one third of the mixed material into a reaction kettle, and keeping reflux reaction for 1.2 hours;
D. dropwise adding the rest mixed materials into the reaction kettle at a constant speed, controlling the dropping to be finished within 3.2 hours, and then carrying out reflux and heat preservation for 1 hour;
E. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 1 h;
F. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 2 hours;
G. reducing the temperature of the reaction kettle to 40 ℃, adding the rest solvent, uniformly stirring, and discharging to obtain a polymer;
H. and uniformly stirring the polymer and the curing agent to obtain the pressure-sensitive adhesive for the polarizer protective film.
A protective film is prepared by uniformly coating the pressure-sensitive adhesive for the polarizer protective film on a substrate, keeping the temperature at 120 ℃ for 2min, and curing at 48 ℃ for 48 h.
The base material is a PET base material, and the thickness of the base material is 50 mu m.
The thickness of the pressure-sensitive adhesive dry glue on the protective film is 10 mu m.
The protective film is applied to protecting the surface of the polaroid.
Example 3
The pressure-sensitive adhesive for the polarizer protective film is prepared from the following raw materials in parts by weight: 35 parts of soft monomer, 8 parts of functional monomer, 0.35 part of initiator, 63 parts of solvent and 4 parts of curing agent.
The soft monomer consists of 90 wt% of butyl acrylate and 10 wt% of isooctyl acrylate.
The functional monomer is prepared from acrylic acid, hydroxyethyl acrylate and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1: 6.2: 5.5.
The solvent is ethyl acetate.
The curing agent is hexamethylene polyisocyanate (Bayer N3390, Germany).
The initiator is dibenzoyl peroxide.
The preparation method of the pressure-sensitive adhesive for the polarizer protective film comprises the following steps:
A. weighing soft monomers, functional monomers and initiator with two thirds of the material amount according to the weight parts, adding the soft monomers, the functional monomers and the initiator into a head tank, and uniformly stirring to obtain a mixed material;
B. weighing a solvent with 50% of the material feeding amount, putting the solvent into a reaction kettle, and heating to 80 ℃ for reflux;
C. quickly feeding one third of the mixed material into a reaction kettle, and keeping reflux reaction for 1.2 hours;
D. dropwise adding the rest mixed materials into the reaction kettle at a constant speed, controlling the dropping to be finished within 3.2 hours, and then carrying out reflux and heat preservation for 1 hour;
E. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 1 h;
F. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 2 hours;
G. reducing the temperature of the reaction kettle to 40 ℃, adding the rest solvent, uniformly stirring, and discharging to obtain a polymer;
H. and uniformly stirring the polymer and the curing agent to obtain the pressure-sensitive adhesive for the polarizer protective film.
A protective film is prepared by uniformly coating the pressure-sensitive adhesive for the polarizer protective film on a substrate, keeping the temperature at 120 ℃ for 2min, and curing at 48 ℃ for 48 h.
The base material is a PET base material, and the thickness of the base material is 50 mu m.
The thickness of the pressure-sensitive adhesive dry glue on the protective film is 10 mu m.
The protective film is applied to protecting the surface of the polaroid.
Example 4
The pressure-sensitive adhesive for the polarizer protective film is prepared from the following raw materials in parts by weight: 33 parts of soft monomer, 7 parts of functional monomer, 0.25 part of initiator, 60 parts of solvent and 3 parts of curing agent.
The soft monomer consists of 85wt% of butyl acrylate and 15wt% of isooctyl acrylate.
The functional monomer is prepared from acrylic acid and hydroxyethyl acrylate according to a mass ratio of 1: 6.
The solvent is ethyl acetate.
The curing agent is hexamethylene polyisocyanate (Bayer N3390, Germany).
The initiator is dibenzoyl peroxide.
The preparation method of the pressure-sensitive adhesive for the polarizer protective film comprises the following steps:
A. weighing soft monomers, functional monomers and initiator with two thirds of the material amount according to the weight parts, adding the soft monomers, the functional monomers and the initiator into a head tank, and uniformly stirring to obtain a mixed material;
B. weighing a solvent with 50% of the material feeding amount, putting the solvent into a reaction kettle, and heating to 80 ℃ for reflux;
C. quickly feeding one third of the mixed material into a reaction kettle, and keeping reflux reaction for 1.2 hours;
D. dropwise adding the rest mixed materials into the reaction kettle at a constant speed, controlling the dropping to be finished within 3.2 hours, and then carrying out reflux and heat preservation for 1 hour;
E. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 1 h;
F. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 2 hours;
G. reducing the temperature of the reaction kettle to 40 ℃, adding the rest solvent, uniformly stirring, and discharging to obtain a polymer;
H. and uniformly stirring the polymer and the curing agent to obtain the pressure-sensitive adhesive for the polarizer protective film.
A protective film is prepared by uniformly coating the pressure-sensitive adhesive for the polarizer protective film on a substrate, keeping the temperature at 120 ℃ for 2min, and curing at 48 ℃ for 48 h.
The base material is a PET base material, and the thickness of the base material is 50 mu m.
The thickness of the pressure-sensitive adhesive dry glue on the protective film is 10 mu m.
The protective film is applied to protecting the surface of the polaroid.
Example 5
The pressure-sensitive adhesive for the polarizer protective film is prepared from the following raw materials in parts by weight: 33 parts of soft monomer, 7 parts of functional monomer, 0.25 part of initiator, 60 parts of solvent and 3 parts of curing agent.
The soft monomer consists of 85wt% of butyl acrylate and 15wt% of isooctyl acrylate.
The functional monomer is prepared from acrylic acid, hydroxyethyl acrylate and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1: 6: 2.
The solvent is ethyl acetate.
The curing agent is hexamethylene polyisocyanate (Bayer N3390, Germany).
The initiator is dibenzoyl peroxide.
The preparation method of the pressure-sensitive adhesive for the polarizer protective film comprises the following steps:
A. weighing soft monomers, functional monomers and initiator with two thirds of the material amount according to the weight parts, adding the soft monomers, the functional monomers and the initiator into a head tank, and uniformly stirring to obtain a mixed material;
B. weighing a solvent with 50% of the material feeding amount, putting the solvent into a reaction kettle, and heating to 80 ℃ for reflux;
C. quickly feeding one third of the mixed material into a reaction kettle, and keeping reflux reaction for 1.2 hours;
D. dropwise adding the rest mixed materials into the reaction kettle at a constant speed, controlling the dropping to be finished within 3.2 hours, and then carrying out reflux and heat preservation for 1 hour;
E. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 1 h;
F. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 2 hours;
G. reducing the temperature of the reaction kettle to 40 ℃, adding the rest solvent, uniformly stirring, and discharging to obtain a polymer;
H. and uniformly stirring the polymer and the curing agent to obtain the pressure-sensitive adhesive for the polarizer protective film.
A protective film is prepared by uniformly coating the pressure-sensitive adhesive for the polarizer protective film on a substrate, keeping the temperature at 120 ℃ for 2min, and curing at 48 ℃ for 48 h.
The base material is a PET base material, and the thickness of the base material is 50 mu m.
The thickness of the pressure-sensitive adhesive dry glue on the protective film is 10 mu m.
The protective film is applied to protecting the surface of the polaroid.
Example 6
The pressure-sensitive adhesive for the polarizer protective film is prepared from the following raw materials in parts by weight: 33 parts of soft monomer, 7 parts of functional monomer, 0.25 part of initiator, 60 parts of solvent and 3 parts of curing agent.
The soft monomer consists of 85wt% of butyl acrylate and 15wt% of isooctyl acrylate.
The functional monomer is prepared from acrylic acid, hydroxyethyl acrylate and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1: 6: 10.
The solvent is ethyl acetate.
The curing agent is hexamethylene polyisocyanate (Bayer N3390, Germany).
The initiator is dibenzoyl peroxide.
The preparation method of the pressure-sensitive adhesive for the polarizer protective film comprises the following steps:
A. weighing soft monomers, functional monomers and initiator with two thirds of the material amount according to the weight parts, adding the soft monomers, the functional monomers and the initiator into a head tank, and uniformly stirring to obtain a mixed material;
B. weighing a solvent with 50% of the material feeding amount, putting the solvent into a reaction kettle, and heating to 80 ℃ for reflux;
C. quickly feeding one third of the mixed material into a reaction kettle, and keeping reflux reaction for 1.2 hours;
D. dropwise adding the rest mixed materials into the reaction kettle at a constant speed, controlling the dropping to be finished within 3.2 hours, and then carrying out reflux and heat preservation for 1 hour;
E. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 1 h;
F. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 2 hours;
G. reducing the temperature of the reaction kettle to 40 ℃, adding the rest solvent, uniformly stirring, and discharging to obtain a polymer;
H. and uniformly stirring the polymer and the curing agent to obtain the pressure-sensitive adhesive for the polarizer protective film.
A protective film is prepared by uniformly coating the pressure-sensitive adhesive for the polarizer protective film on a substrate, keeping the temperature at 120 ℃ for 2min, and curing at 48 ℃ for 48 h.
The base material is a PET base material, and the thickness of the base material is 50 mu m.
The thickness of the pressure-sensitive adhesive dry glue on the protective film is 10 mu m.
The protective film is applied to protecting the surface of the polaroid.
Example 7
The pressure-sensitive adhesive for the polarizer protective film is prepared from the following raw materials in parts by weight: 33 parts of soft monomer, 7 parts of functional monomer, 0.25 part of initiator, 60 parts of solvent and 3 parts of curing agent.
The soft monomer consists of 85wt% of butyl acrylate and 15wt% of isooctyl acrylate.
The functional monomer is prepared from acrylic acid and methacryloyloxyethyl trimethyl ammonium chloride according to the mass ratio of 1: 5.2.
The solvent is ethyl acetate.
The curing agent is hexamethylene polyisocyanate (Bayer N3390, Germany).
The initiator is dibenzoyl peroxide.
The preparation method of the pressure-sensitive adhesive for the polarizer protective film comprises the following steps:
A. weighing soft monomers, functional monomers and initiator with two thirds of the material amount according to the weight parts, adding the soft monomers, the functional monomers and the initiator into a head tank, and uniformly stirring to obtain a mixed material;
B. weighing a solvent with 50% of the material feeding amount, putting the solvent into a reaction kettle, and heating to 80 ℃ for reflux;
C. quickly feeding one third of the mixed material into a reaction kettle, and keeping reflux reaction for 1.2 hours;
D. dropwise adding the rest mixed materials into the reaction kettle at a constant speed, controlling the dropping to be finished within 3.2 hours, and then carrying out reflux and heat preservation for 1 hour;
E. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 1 h;
F. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 10 percent of the feeding amount, and carrying out reflux and heat preservation for 2 hours;
G. reducing the temperature of the reaction kettle to 40 ℃, adding the rest solvent, uniformly stirring, and discharging to obtain a polymer;
H. and uniformly stirring the polymer and the curing agent to obtain the pressure-sensitive adhesive for the polarizer protective film.
A protective film is prepared by uniformly coating the pressure-sensitive adhesive for the polarizer protective film on a substrate, keeping the temperature at 120 ℃ for 2min, and curing at 48 ℃ for 48 h.
The base material is a PET base material, and the thickness of the base material is 50 mu m.
The thickness of the pressure-sensitive adhesive dry glue on the protective film is 10 mu m.
The protective film is applied to protecting the surface of the polaroid.
Evaluation of Performance
1. Glue line resistance test
The protective film was cut to 12 × 12mm size, the release film was peeled off, and the sheet resistance was measured on a high resistance meter (model: SME-8310).
2. 180 degree peel strength
The measurement was carried out by an electronic universal tester (the adherend was a standard test steel plate, and the peel rate was 300mm/min) in accordance with GB/T2792-1995 "180 ℃ peel strength test method for pressure-sensitive adhesive tapes".
3. High temperature resistance
And uniformly coating the pressure-sensitive adhesive for the polarizer protective film on glass, storing for 2h in an environment with the temperature of 180 ℃, and then peeling off to observe the condition of adhesive residue.
4. High humidity and high temperature resistance
The pressure-sensitive adhesive for the polarizer protective film is uniformly coated on glass, stored for 48 hours in an environment with the temperature of 85 ℃ and the relative humidity of 85 percent, and then stripped to observe the condition of residual adhesive.
5. Light transmittance test
With reference to the standard GB/T2410-2008, the release film was peeled off using a haze meter (model: U3000), and the light transmittance was measured.
The pressure-sensitive adhesives for polarizer protective films prepared in examples 1 to 7 were tested, and the specific test results are shown in table 1.
Table 1: test result table
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (7)
1. The pressure-sensitive adhesive for the polarizer protective film is characterized by being prepared from the following raw materials in parts by weight: 31-35 parts of soft monomer, 6-8 parts of functional monomer, 0.15-0.35 part of initiator, 57-63 parts of solvent and 2-4 parts of curing agent;
the soft monomer consists of 85wt% of butyl acrylate and 15wt% of isooctyl acrylate;
the functional monomer is prepared from acrylic acid, hydroxyethyl acrylate and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1: 6: 5.2.
2. The pressure-sensitive adhesive for polarizer protective films according to claim 1, wherein the solvent is one or more of ethyl acetate, methyl acetate, acetone, and toluene.
3. The pressure-sensitive adhesive for polarizer protective films according to claim 1, wherein the curing agent is an isocyanate-based curing agent or an epoxy curing agent.
4. The pressure-sensitive adhesive for a polarizer protective film according to any one of claims 1 to 3, wherein the initiator is at least one selected from a peroxy initiator and an azo initiator.
5. A method for preparing a pressure-sensitive adhesive for polarizer protective films according to any one of claims 1 to 4, comprising the steps of:
A. weighing soft monomers, functional monomers and initiator with two thirds of the material amount according to the weight parts, adding the soft monomers, the functional monomers and the initiator into a head tank, and uniformly stirring to obtain a mixed material;
B. weighing a solvent with a feeding amount of 40-60%, and putting the solvent into a reaction kettle to be heated to a reflux state;
C. quickly adding one third of the mixed material into a reaction kettle, and keeping reflux reaction for 1-1.5 h;
D. dropwise adding the rest mixed materials into the reaction kettle at a constant speed, controlling the mixture to be completely dripped within 3-3.5h, and carrying out reflux and heat preservation for 0.5-1.5h after the dripping is completed;
E. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 5-15% of the feeding amount, and carrying out reflux and heat preservation for 0.5-1.5 h;
F. adding a mixed solution of an initiator with one sixth of the feeding amount and a solvent with 5-15% of the feeding amount, and carrying out reflux and heat preservation for 1.5-2.5 h;
G. cooling the temperature of the reaction kettle to below 50 ℃, adding the rest solvent, uniformly stirring, and discharging to obtain a polymer;
H. and uniformly stirring the polymer and the curing agent to obtain the pressure-sensitive adhesive for the polarizer protective film.
6. A protective film, characterized in that the pressure-sensitive adhesive for polarizer protective films as described in any one of claims 1-4 is uniformly coated on a substrate, heat-preserved at 110-130 ℃ for 1-3min, and then cured at 45-50 ℃ for 45-50h to obtain the protective film.
7. Use of the protective film according to claim 6 for protecting a surface of a polarizer.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705067A (en) * | 2009-11-23 | 2010-05-12 | 南亚塑胶工业股份有限公司 | Adhesive agent composition for attaching to polarizing plate |
| CN106520032A (en) * | 2016-10-18 | 2017-03-22 | 无锡海特新材料研究院有限公司 | High-temperature-resistant and low-peel-strength acrylate pressure-sensitive adhesive and preparation method thereof |
| CN106597596A (en) * | 2016-12-14 | 2017-04-26 | 合肥乐凯科技产业有限公司 | Pressure-sensitive adhesive for polaroid protection film and polaroid protection film |
| CN106632818A (en) * | 2016-12-07 | 2017-05-10 | 哈尔滨工业大学无锡新材料研究院 | High-permeability and high-temperature-resistant type acrylate pressure-sensitive adhesive and preparation method thereof |
| CN106749874A (en) * | 2016-12-27 | 2017-05-31 | 无锡海特新材料研究院有限公司 | Controllable pressure sensitive adhesive of a kind of peeling force and preparation method thereof |
| CN107556936A (en) * | 2017-09-08 | 2018-01-09 | 安徽明讯新材料科技股份有限公司 | A kind of environmentally friendly diaphragm for touch-control glass screen and preparation method thereof |
| CN110183981A (en) * | 2019-05-30 | 2019-08-30 | 惠州市科域新材料科技有限公司 | Glass plate processing procedure protective film after tearing without residue glue |
-
2019
- 2019-09-18 CN CN201910881930.5A patent/CN110734711B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705067A (en) * | 2009-11-23 | 2010-05-12 | 南亚塑胶工业股份有限公司 | Adhesive agent composition for attaching to polarizing plate |
| CN106520032A (en) * | 2016-10-18 | 2017-03-22 | 无锡海特新材料研究院有限公司 | High-temperature-resistant and low-peel-strength acrylate pressure-sensitive adhesive and preparation method thereof |
| CN106632818A (en) * | 2016-12-07 | 2017-05-10 | 哈尔滨工业大学无锡新材料研究院 | High-permeability and high-temperature-resistant type acrylate pressure-sensitive adhesive and preparation method thereof |
| CN106597596A (en) * | 2016-12-14 | 2017-04-26 | 合肥乐凯科技产业有限公司 | Pressure-sensitive adhesive for polaroid protection film and polaroid protection film |
| CN106749874A (en) * | 2016-12-27 | 2017-05-31 | 无锡海特新材料研究院有限公司 | Controllable pressure sensitive adhesive of a kind of peeling force and preparation method thereof |
| CN107556936A (en) * | 2017-09-08 | 2018-01-09 | 安徽明讯新材料科技股份有限公司 | A kind of environmentally friendly diaphragm for touch-control glass screen and preparation method thereof |
| CN110183981A (en) * | 2019-05-30 | 2019-08-30 | 惠州市科域新材料科技有限公司 | Glass plate processing procedure protective film after tearing without residue glue |
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