CN108219715B - Adhesive for polarizer, preparation method of polarizer and display - Google Patents

Adhesive for polarizer, preparation method of polarizer and display Download PDF

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Publication number
CN108219715B
CN108219715B CN201611198735.5A CN201611198735A CN108219715B CN 108219715 B CN108219715 B CN 108219715B CN 201611198735 A CN201611198735 A CN 201611198735A CN 108219715 B CN108219715 B CN 108219715B
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main material
polarizer
mass
adhesive
polyvinyl alcohol
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CN108219715A (en
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钟伟宏
孙海如
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SHENZHEN SAPO PHOTOELECTRIC CO Ltd
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SHENZHEN SAPO PHOTOELECTRIC 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
    • C09J129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)

Abstract

The invention relates to an adhesive for a polarizer, the polarizer, a preparation method thereof and a display. The adhesive for the polaroid comprises a first main material, a second main material, a cross-linking agent and water, wherein the first main material is polyvinyl alcohol with the average polymerization degree of 1700-4000, the second main material is polyvinyl alcohol with the average polymerization degree of 300-600, the mass of the second main material is 10% -50% of the sum of the mass of the first main material and the mass of the second main material, the viscosity of the adhesive for the polaroid is 15-200 cPs, and the mass percentage content of a solid phase is 2% -8%. The adhesive for the polaroid has good thermal stability and adhesiveness.

Description

Adhesive for polarizer, preparation method of polarizer and display
Technical Field
The invention relates to an adhesive for a polarizer, the polarizer, a preparation method thereof and a display.
Background
As a polarizer for LCD (liquid crystal panel display), a polyvinyl alcohol film (PVA film) is usually made by adsorbing a dichroic substance (commonly used iodine and dichroic dye), stretching and drying the adsorbed material to form a PVA film having a polarizing function, and then attaching (at least one side) an inner protective film (commonly used cellulose triacetate film TAC film) to the PVA film with an adhesive (glue). The polarizer made of the dichroic substance using iodine is generally called "iodine-based polarizer", and the polarizer made of the dichroic substance using a dye is generally called "dye-based polarizer".
Iodine-based polarizers have significant advantages in transmittance, polarization degree, contrast, etc., compared to dye-based polarizers, and thus are widely used. Currently, mainstream LCD display devices, such as televisions, notebook computers, monitors, industrial displays, mobile phones, etc., all use iodine-based polarizers. With the increase of the application range of LCD devices, the polarizer is used for a long time under severe environment (such as high temperature, low temperature, high humidity, strong light irradiation, etc.), so it is an urgent need in the market to develop a polarizer with excellent thermal stability, and in order to improve the high temperature resistance of the iodine-based polarizer, it is an effective method to improve the thermal stability and the adhesive property of the adhesive (glue) for bonding the polarizer film and the TAC film.
Disclosure of Invention
Accordingly, there is a need for an adhesive for a polarizer that has both good thermal stability and good adhesion.
In addition, the invention also relates to a preparation method of the adhesive for the polarizer, the polarizer and a display.
The adhesive for the polarizer comprises a first main material, a second main material, a cross-linking agent and water, wherein the first main material is polyvinyl alcohol with the average polymerization degree of 1700-4000, the second main material is polyvinyl alcohol with the average polymerization degree of 300-600, the mass of the second main material is 10-50% of the sum of the mass of the first main material and the second main material, the viscosity of the adhesive for the polarizer is 15-200 cPs, and the mass percentage content of a solid phase is 2-8%.
To obtain a good bonding effect, the adhesive must be in sufficient contact with the bonding material, and microscopically, the adhesive molecules must penetrate into the fine structure of the bonding surface as much as possible, which requires sufficient stretching of the adhesive molecules, while the polyvinyl alcohol molecules have a relatively regular molecular structure, strong hydrogen bonds between molecular chains, and are easily entangled, and microscopically, the polyvinyl alcohol molecules are in the form of non-stretched clusters in an aqueous solution. In order to ensure good moisture resistance of the polarizer, polyvinyl alcohol resin with high degree of hydrolysis (not less than 92%) is usually selected as a main component of an adhesive, and the higher the degree of alcoholysis, the more prominent the phenomenon is, so that the conventional polyvinyl alcohol adhesive cannot be in full contact with an adhesive surface, and the adhesion force is not high, the adhesive for the polarizer takes polyvinyl alcohol with the average degree of polymerization of 1700-4000 as a first main material, takes polyvinyl alcohol with the average degree of polymerization of 300-600 as a second main material, and the mass of the second main material is 10-50% of the sum of the mass of the first main material and the second main material, wherein the first main material plays a role of a main material 'skeleton', is a main part of the adhesive, so that the adhesive has high temperature and high humidity resistance, and the mechanical property of a colloid layer formed by the adhesive is ensured; the second main material plays a role in internal plasticization so as to play a role in permeating a bonding surface fine structure and increasing the flexibility of a colloid layer, and polyvinyl alcohol molecular chains with high and low average polymerization degrees are mutually interpenetrated under the proportion, so that the microstructure formed by the adhesive is changed, the hydrogen bond effect among the polyvinyl alcohol molecules can be obviously reduced, the molecular chains can be favorably stretched, and the bonding performance of the polyvinyl alcohol is improved; meanwhile, the crystallization rate of the polyvinyl alcohol with high and low average polymerization degrees after being blended in the proportion is faster than that of a pure component system, the size of formed spherulites is smaller, but the crystallinity is not greatly changed, and the structure is more compact and complete in microcosmic view, so that the high temperature resistance of the whole adhesive for the polaroid is improved, and therefore, the adhesive for the polaroid has better thermal stability and adhesiveness.
In one embodiment, the first main material is a mixture of polyvinyl alcohol with the average polymerization degree of 1700-2400 and polyvinyl alcohol with the average polymerization degree of 2500-4000; or the average polymerization degree of the first main material is 1700-3000.
In one embodiment, the average polymerization degree of the second main material is 400-550.
In one embodiment, the cross-linking agent is selected from one of dialdehyde, organic metal chelate and hydroxy melamine; the ratio of the mass of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 2-1: 200.
In one embodiment, the catalyst is selected from one of zinc chloride, zinc acetate, zinc sulfate and cobalt acetate, and the mass ratio of the catalyst to the sum of the mass of the first main material and the mass of the second main material is 1: 5-1: 1000.
A method for preparing an adhesive for a polarizer, comprising the steps of:
mixing a first main material and a second main material to obtain a mixture, wherein the first main material is polyvinyl alcohol with the average polymerization degree of 1700-4000, the second main material is polyvinyl alcohol with the average polymerization degree of 300-600, and the mass of the second main material is 10-50% of the sum of the mass of the first main material and the mass of the second main material;
fully swelling the mixture in water at a temperature of below 35 ℃ under continuous stirring to obtain a swollen matter;
under the condition of continuous stirring, preserving the temperature of the swelling substance at 95-98 ℃ for 50-70 minutes, and cooling to obtain a pre-prepared solution;
and mixing the pre-prepared solution and a cross-linking agent under the conditions of continuous stirring and room temperature to obtain the adhesive for the polarizer, wherein the viscosity of the adhesive is 15 to 200cPs, and the mass percentage content of a solid phase is 2 to 8 percent.
A method for preparing an adhesive for a polarizer, comprising the steps of:
fully swelling a first main material in water to obtain a first swelling material and fully swelling a second main material in water to obtain a second swelling material under the conditions of being lower than 35 ℃ and continuously stirring, wherein the first main material is polyvinyl alcohol with the average polymerization degree of 1700-4000, the second main material is polyvinyl alcohol with the average polymerization degree of 300-600, and the mass of the second main material is 10% -50% of the sum of the mass of the first main material and the mass of the second main material;
under the condition of continuous stirring, preserving the heat of the first swelling substance at 95-98 ℃ for 50-70 minutes, cooling to obtain a first pre-prepared liquid, preserving the heat of the second swelling substance at 95-98 ℃ for 50-70 minutes, and cooling to obtain a second pre-prepared liquid;
mixing the first pre-prepared liquid and the second pre-prepared liquid under the conditions of continuous stirring and room temperature to obtain a mixed liquid;
and mixing the mixed solution with a cross-linking agent under the conditions of continuous stirring and room temperature to obtain the adhesive for the polarizer, wherein the viscosity of the adhesive is 15 to 200cPs, and the mass percentage content of a solid phase is 2 to 8 percent.
A preparation method of a polarizer comprises the following steps:
the adhesive for a polarizer was used to form an adhesive layer between a polyvinyl alcohol resin film and an inner protective film, thereby obtaining the polarizer.
The polaroid prepared by the preparation method of the polaroid.
A display comprises the polarizer.
Drawings
FIG. 1 is a flowchart illustrating a method for manufacturing a polarizer according to an embodiment;
FIG. 2 is a flowchart illustrating a method of preparing an adhesive for a polarizer in the method of preparing a polarizer shown in FIG. 1;
fig. 3 is a flowchart of a method for preparing an adhesive for a polarizer in a method for preparing a polarizer according to another embodiment.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The display of an embodiment may be a planar or non-planar display. Among them, the flat type display may be a Liquid Crystal Display (LCD) or an organic electroluminescent device; the non-planar display may be a curved display, a flexible display, or glasses (e.g., 3D glasses or sunglasses). The display comprises a polaroid, wherein the polaroid comprises a polyvinyl alcohol resin film, an inner protective film and an adhesive layer.
The polyvinyl alcohol resin film may be a polyvinyl alcohol resin film that is conventional in the art, and in the present embodiment, the polyvinyl alcohol resin film is a polyvinyl alcohol resin film having a polarizing function.
The inner protective film is an optical film. Specifically, the inner protective film is one of a cellulose triacetate film (TAC), a polyethylene terephthalate film (PET), a polymethyl methacrylate film (PMMA), a polycarbonate film (PC), a polycycloolefin film (COP), and the like. These optical films have excellent transparency, mechanical strength, thermal stability and water resistance.
The adhesive layer is fixedly connected with a polyvinyl alcohol resin film and an inner protective film and is prepared from an adhesive for a polarizer. The adhesive for the polarizer comprises a first main material, a second main material, a cross-linking agent and water.
The first main material is polyvinyl alcohol with the average polymerization degree (if not specifically indicated, the average polymerization degree is represented by weight-average polymerization degree) of 1700-4000. The first main material plays a role of a skeleton, is the main part of the adhesive, can enable the adhesive to have high temperature and high humidity resistance, and simultaneously ensures the mechanical property of a colloid layer formed by the adhesive. If the average degree of polymerization of the first major material is too low, the high temperature resistance of the adhesive is reduced, and if the average degree of polymerization of the first major material is too high, the dissolution is difficult, and the stability is poor.
Further, the average polymerization degree of the first main material is 1700-3000. Furthermore, the average polymerization degree of the first main material is 2000-2600. The first main material may be, for example: PVA-117, 124 and the like available from Coly corporation, Z-200, Z-320, Z-410 and the like available from Nippon synthetic chemical Co., Ltd, and PVA-1799, 2099, 2699, 3099 available from Sichuan vinylon.
It is understood that the first main material is not limited to the above selection, and in another embodiment, the first main material is a mixture including polyvinyl alcohol having an average degree of polymerization of 1700 to 2400 and polyvinyl alcohol having an average degree of polymerization of 2500 to 4000. Or, the first main material may also include more than three kinds of polyvinyl alcohol with an average polymerization degree of 1700-3000, as long as the average polymerization degree difference of several selected substances of the first main material is ensured to be large.
The second main material is polyvinyl alcohol with the average polymerization degree of 300-600. The second main material plays a role in internal plasticization so as to play a role in permeating a bonding surface fine structure and increasing the flexibility of a colloid layer. If the average polymerization degree of the second main material is too low, the overall mechanical property of the adhesive is affected due to poor mechanical property; if the average degree of polymerization of the second main material is too high, the second main material cannot play a role of internal plasticization, and the infiltration capability to the bonding surface is obviously reduced.
Further, the average polymerization degree of the second main material is 400-550. The second main material may be, for example, PVA-105 from Cola and PVA-0599 from Sichuan vinylon.
Wherein the mass of the second main material is 10-50% of the sum of the mass of the first main material and the mass of the second main material. The second main material with the proportion not only can play a role in internal plasticization and permeability improvement, but also can enable the adhesive to form colloid with better mechanical property and high temperature resistance; if the content of the second main material is too low, the effects of internal plasticization and permeability improvement cannot be realized, and if the content is too much, the improvement of the mechanical property and high temperature resistance of the whole colloid is influenced.
In order to ensure good moisture resistance of the polarizer, a polyvinyl alcohol resin with a higher degree of hydrolysis is usually selected as a main component of the adhesive, in this embodiment, the alcoholysis degree of the first main material is greater than or equal to 92%, and the alcoholysis degree of the second main material is greater than or equal to 92%, so that the adhesive has good moisture resistance. Furthermore, the alcoholysis degree of the first main material is greater than or equal to 99%, and the alcoholysis degree of the second main material is greater than or equal to 99%.
Wherein the cross-linking agent is selected from one of dialdehyde, organic metal chelate and hydroxy melamine. Wherein the dialdehyde is one of glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, etc.; the organic metal chelate is one of organic titanium chelate, organic zirconium chelate and the like; the organic chelate compound may be, for example, TYZOR TE manufactured by Dupont; the organozirconium chelate compound may be, for example, organozirconium boron chelate OBZ-1; the hydroxy melamine is one of trimethylol melamine, hexamethylol melamine, etc. The crosslinking agent enables the adhesive for a polarizer to undergo a crosslinking reaction during use.
Specifically, the ratio of the mass of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 2-1: 200. Further, the ratio of the mass of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 5-1: 100.
Further, the adhesive for the polarizer further comprises a catalyst, wherein the catalyst is selected from one of zinc chloride, zinc acetate, zinc sulfate and cobalt acetate. The catalyst is used to accelerate a crosslinking reaction of the adhesive for a polarizer during use. Wherein the ratio of the mass of the catalyst to the sum of the mass of the first main material and the mass of the second main material is 1: 5-1: 1000; further, the ratio of the mass of the catalyst to the sum of the mass of the first main material and the mass of the second main material is 1: 10-1: 100.
Wherein, the viscosity of the adhesive for the polaroid is 15 to 200cPs, and the mass percentage of the solid phase is 2 to 8 percent. Wherein, the viscosity of the adhesive for the polarizer can be determined by a rotational viscometer according to the determination of the viscosity of the adhesive in GB/T2794-1995; the determination of the solid content of the adhesive for a polarizer may be performed according to "determination of nonvolatile matter content of adhesive in GB/T2793-.
Further, the viscosity of the adhesive for the polarizer is 25 to 100 cPs; further, the adhesive for a polarizer has a viscosity of 25 to 50 cPs.
Further, the solid phase of the adhesive for the polarizer is 3-6% by mass.
In order to obtain a good bonding effect, the adhesive must be in sufficient contact with the bonding material, and from a microscopic viewpoint, the adhesive molecules must penetrate into the interior of the microstructure of the bonding surface as much as possible, which requires sufficient stretching of the adhesive molecules, while the polyvinyl alcohol molecules have a relatively regular molecular structure, and strong hydrogen bonds between molecular chains, and are easily entangled, and in an aqueous solution, the polyvinyl alcohol molecules are microscopically in the form of non-stretched clusters. In order to ensure good moisture resistance of the polarizer, polyvinyl alcohol resin with high degree of hydrolysis (not less than 92%) is usually selected as a main component of the adhesive, and the higher the degree of alcoholysis, the more prominent the phenomenon is, so that the conventional polyvinyl alcohol-based water adhesive cannot be in full contact with the bonding surface, and the bonding force is not high, the adhesive for the polarizer takes the polyvinyl alcohol with the average degree of polymerization of 1700-4000 as a first main material, takes the polyvinyl alcohol with the average degree of polymerization of 300-600 as a second main material, and makes the mass of the second main material 10-50% of the sum of the mass of the first main material and the second main material, wherein the first main material plays a role of a skeleton, is a main part of the adhesive, so that the adhesive has high-temperature and high-humidity resistance, and simultaneously ensures the mechanical property of a colloid layer formed by the adhesive; the second main material plays a role in internal plasticization so as to play a role in permeating a bonding surface fine structure and increasing the flexibility of a colloid layer, and polyvinyl alcohol molecular chains with high and low average polymerization degrees are mutually interpenetrated under the proportion, so that the microstructure formed by the adhesive for the polaroid is changed, the hydrogen bond effect among the polyvinyl alcohol molecules can be obviously reduced, the molecular chains can be favorably stretched, and the adhesive has better bonding performance; meanwhile, the crystallization rate of the polyvinyl alcohol with high and low average polymerization degrees after being blended in the proportion is faster than that of a pure component system, the size of formed spherulites is smaller, but the crystallinity is not greatly changed, and the structure is more compact and complete in microcosmic view, so that the high temperature resistance of the whole adhesive for the polaroid is improved, and therefore, the adhesive for the polaroid has better thermal stability and adhesiveness.
And because the adhesive for the polarizer uses polyvinyl alcohols with different average polymerization degrees, belongs to homologues, fully conforms to the principle of 'similar and compatible', does not have the condition of phase separation, does not have the problems of delamination, foreign matter precipitation and the like which damage a glue layer formed by the adhesive for the polarizer, and has good stability in engineering application.
The adhesive for the polarizer can fully replace the current polyvinyl alcohol adhesive application.
As shown in fig. 1, a method for manufacturing a polarizer according to an embodiment includes the steps of:
step S110: an adhesive for a polarizer was prepared.
Referring to fig. 2, the adhesive for polarizer is prepared by the following steps:
step S112: and mixing the first main material and the second main material to obtain a mixture.
The first main material is polyvinyl alcohol with the average polymerization degree of 1700-4000. Further, the average polymerization degree of the first main material is 1700-3000. Furthermore, the average polymerization degree of the first main material is 2000-2600. The first main material may be, for example: PVA-117, 124 and the like available from Coly corporation, Z-200, Z-320, Z-410 and the like available from Nippon synthetic chemical Co., Ltd, and PVA-1799, 2099, 2699, 3099 available from Sichuan vinylon.
It is understood that the first main material is not limited to the above selection, and in another embodiment, the first main material is a mixture including polyvinyl alcohol having an average degree of polymerization of 1700 to 2400 and polyvinyl alcohol having an average degree of polymerization of 2500 to 4000. Or, the first main material may also include more than three kinds of polyvinyl alcohol with an average polymerization degree of 1700-3000, as long as the average polymerization degree difference of several selected substances of the first main material is ensured to be large.
The second main material is polyvinyl alcohol with the average polymerization degree of 300-600. Further, the average polymerization degree of the second main material is 400-550. The second main material may be, for example, PVA-105 from Cola and PVA-0599 from Sichuan vinylon.
Wherein the mass of the second main material is 10-50% of the sum of the mass of the first main material and the mass of the second main material.
The alcoholysis degree of the first main material is greater than or equal to 92%, and the alcoholysis degree of the second main material is greater than or equal to 92%. Furthermore, the alcoholysis degree of the first main material is greater than or equal to 99%, and the alcoholysis degree of the second main material is greater than or equal to 99%.
The first main material and the second main material are mixed in a dry mixing mode.
Step S114: the mixture was fully swollen in water at below 35 ℃ with constant stirring to give a swollen mass.
Specifically, the step of swelling the mixture in water is specifically as follows: the mixture is sequentially soaked and washed for a plurality of times by deionized water, and the soaking time is not less than 1 hour in accumulated time, so that the mixture can be fully soaked and swelled by water, the effect of cleaning polyvinyl alcohol can be achieved, alkali (sodium hydroxide, potassium hydroxide and the like) in the polyvinyl alcohol can be removed, the subsequent cross-linking reaction of the adhesive for the polaroid is prevented from being influenced by the existence of the alkali, and the color tone of the polaroid is prevented from being influenced by the yellowing of the adhesive for the polaroid caused by the existence of the alkali. Specifically, the number of washing is not less than 5.
Further, the step of swelling the mixture in water is carried out at a temperature of 25 ℃ to 35 ℃.
Step S116: and under the condition of continuous stirring, preserving the temperature of the swelling material at 95-98 ℃ for 50-70 minutes, and cooling to obtain a pre-prepared solution.
Wherein the swelling material is kept at 95-98 ℃ for 50-70 minutes under the condition of continuous stirring so as to dissolve the swelling material.
Wherein, under the condition of continuous stirring, the step of keeping the temperature of the swelling material at 95-98 ℃ for 50-70 minutes is as follows: under the condition of continuous stirring, the temperature of the swelling material is raised to 95-98 ℃ within 60 minutes, and the temperature is kept at 95-98 ℃ for 50-70 minutes. Further, the temperature of the swelling material is raised for 40-60 minutes to 95-98 ℃.
Wherein the cooling step after the swelling material is kept at the temperature of 95-98 ℃ for 50-70 minutes is as follows: and (3) preserving the heat of the swelling material at 95-98 ℃ for 50-70 minutes, and cooling to room temperature within 45 minutes to ensure that molecular chains of the polyvinyl alcohol are not entangled for the second time.
Step S118: and mixing the pre-prepared solution and a cross-linking agent under the conditions of continuous stirring and room temperature to obtain the adhesive for the polarizer, wherein the viscosity of the adhesive is 15 to 200cPs, and the mass percentage content of a solid phase is 2 to 8 percent.
The cross-linking agent is selected from one of dialdehyde, organic metal chelate and hydroxyl melamine. Wherein the dialdehyde is one of glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, etc.; the organic metal chelate is one of organic titanium chelate, organic zirconium chelate and the like; the organic chelate compound may be, for example, TYZOR TE manufactured by Dupont; the organozirconium chelate compound may be, for example, organozirconium boron chelate OBZ-1; the hydroxy melamine is one of trimethylol melamine, hexamethylol melamine, etc.
Specifically, the ratio of the mass of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 2-1: 200. Further, the ratio of the mass of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 5-1: 100.
Further, in the step of mixing the pre-prepared liquid and the cross-linking agent, a catalyst is also added, and the catalyst is selected from one of zinc chloride, zinc acetate, zinc sulfate and cobalt acetate. Specifically, the ratio of the mass of the catalyst to the sum of the mass of the first main material and the mass of the second main material is 1: 5-1: 1000; further, the ratio of the mass of the catalyst to the sum of the mass of the first main material and the mass of the second main material is 1: 10-1: 100.
Further, the viscosity of the adhesive for the polarizer is 25 to 100 cPs; further, the adhesive for a polarizer has a viscosity of 25 to 50 cPs.
Further, the solid phase of the adhesive for the polarizer is 3-6% by mass.
Specifically, the method further comprises the step of sequentially filtering and defoaming the mixed solution obtained by mixing the pre-prepared solution and the cross-linking agent after the step of mixing the pre-prepared solution and the cross-linking agent.
Wherein, the filtration can adopt the gravity filtration, the pressure filtration and other modes which are common in engineering, and the defoaming can adopt the standing defoaming, the ultrasonic defoaming and other modes which are common in engineering. The selection can be carried out according to actual requirements.
Step S120: the adhesive for a polarizer was used to form an adhesive layer between a polyvinyl alcohol resin film and an inner protective film, thereby obtaining a polarizer.
Wherein the inner protective film is selected from one of cellulose triacetate film (TAC), polyethylene terephthalate film (PET), polymethyl methacrylate film (PMMA), polycarbonate film (PC), polycycloolefin film (COP), etc.
The method for forming the bonding layer between the polyvinyl alcohol resin film and the inner protective film by using the adhesive for the polarizer specifically comprises the following steps: arranging the polyvinyl alcohol resin film and the inner protective film at intervals and oppositely, dripping an adhesive for the polarizer between the polyvinyl alcohol resin film and the inner protective film, rolling by using a laminating roller to spread the adhesive for the polarizer, and drying to form a bonding layer; or coating the polarizer on one of the polyvinyl alcohol resin film and the inner protective film by using an adhesive, then attaching, and drying to form the bonding layer.
Wherein, before the step of forming the adhesive layer between the polyvinyl alcohol resin film and the inner protective film by using the adhesive for the polarizer, the method further comprises the step of carrying out surface modification treatment on the inner protective film. Among them, the surface modification treatment may be, for example, saponification treatment, hydrophilic coating treatment, corona treatment, or the like.
Wherein, before the step of forming the adhesive layer between the polyvinyl alcohol resin film and the inner protective film by using the adhesive for the polarizer, the method further comprises the step of modifying the polyvinyl alcohol resin film to obtain the polyvinyl alcohol resin film with the polarizing function: swelling polyvinyl alcohol resin film in deionized water at 30 ℃ for 2 minutes, soaking in mixed aqueous solution of I2/KI (I2 is 0.1% and KI is 5%) at 32 ℃ for 1 minute to adsorb iodine as a dichromatic substance, soaking in mixed aqueous solution of boric acid/KI (boric acid is 4% and KI is 5%) at 50 ℃ while extending to 5.5 times of the original film, washing with deionized water at room temperature, and hot-air drying at 55 ℃ for 10 minutes to obtain polyvinyl alcohol resin film (i.e., polarizer film, also called as polarizer) having a polarization function. At this time, an adhesive layer is formed between the polarizing polyvinyl alcohol resin film and the inner protective film using the above adhesive for a polarizer.
The preparation method of the adhesive for the polaroid is simple to operate and easy for industrial production; the preparation method of the polaroid is simple to operate and easy for industrial production.
The method for manufacturing a polarizer according to another embodiment is substantially the same as the method for manufacturing a polarizer shown in fig. 1, except that the method for manufacturing an adhesive for a polarizer according to the present embodiment is different, and the method for manufacturing an adhesive for a polarizer according to the present embodiment is as follows, as shown in fig. 3:
step S210: fully swelling the first main material in water to obtain a first swelling substance and fully swelling the second main material in water to obtain a second swelling substance under the conditions of lower than 35 ℃ and continuous stirring.
Step S220: under the condition of continuous stirring, the first swelling material is kept at the temperature of 95-98 ℃ for 50-70 minutes, and is cooled to obtain a first pre-prepared liquid, and the second swelling material is kept at the temperature of 95-98 ℃ for 50-70 minutes and is cooled to obtain a second pre-prepared liquid.
Step S230: and mixing the first pre-prepared liquid and the second pre-prepared liquid under the conditions of continuous stirring and room temperature to obtain a mixed liquid.
Namely, under the condition of continuous stirring, the first pre-prepared liquid and the second pre-prepared liquid are mixed at room temperature to obtain a mixed liquid.
Step S240: and mixing the mixed solution with a cross-linking agent under the conditions of continuous stirring and room temperature to obtain the adhesive for the polarizer, wherein the viscosity of the adhesive is 15 to 200cPs, and the mass percentage content of a solid phase is 2 to 8 percent.
The preparation method of the adhesive for the polarizer of the embodiment is simple to operate and easy for industrial production.
The following is a section of specific examples in which cellulose triacetate film (TAC) is used as an inner protective film in the following examples:
example 1
The adhesive for a polarizer of this example was prepared as follows:
(1) and (3) dry-mixing the first main material and the second main material uniformly according to the mass ratio of 8:2 to obtain a mixture. Wherein the first main material is polyvinyl alcohol with average polymerization degree of 2400, and the alcoholysis degree is 99%; the second main material is polyvinyl alcohol with the average polymerization degree of 500, and the alcoholysis degree is 99%.
(2) The mixture was sequentially soaked and washed with deionized water at 28 ℃ with constant stirring, and repeated 5 times, the cumulative time of soaking being 1.2 hours to fully swell the mixture to obtain a swollen material.
(3) Adding deionized water into the swelling material, heating the swelling material to 96 ℃ within 60 minutes under the condition of continuous stirring, preserving the temperature for 60 minutes at 96 ℃ to dissolve the swelling material, and cooling to room temperature within 45 minutes to obtain a pre-prepared solution.
(4) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent and a catalyst into the pre-prepared liquid, adjusting the viscosity of the pre-prepared liquid to 42cPs by using deionized water, wherein the mass percentage of a solid phase is 3.4%, and filtering, standing and defoaming to obtain the adhesive for the polarizer. Wherein the cross-linking agent is glyoxal, and the mass ratio of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 10; the catalyst is zinc chloride, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the second main material is 0.3: 10.
Preparation of polyvinyl alcohol resin film (polarizer element film) having polarizing function: a polyvinyl alcohol resin film having an average polymerization degree of 2400, an alcoholysis degree of 99.9% or more, and a thickness of 75 μm was swollen in deionized water at 30 ℃ for 2 minutes, and then immersed in an I2/KI mixed aqueous solution (I2% 0.1% and KI 5%) at 32 ℃ for 1 minute to adsorb iodine as a dichroic material, and then immersed in a boric acid/KI mixed aqueous solution (boric acid 4% and KI 5%) at 50 ℃ while extending 5.5 times as much as the original film, followed by washing with deionized water at room temperature and hot air drying at 55 ℃ for 10 minutes to obtain a polyvinyl alcohol resin film having a polarization function. The adhesive for polarizer of this example was dropped on the opposite surfaces of the polyvinyl alcohol resin film having polarizing function, and then a saponified cellulose triacetate film (TAC, fuji film corporation, thickness 80 μm) was attached thereto, and dried at 75 ℃ for 10 minutes to form an adhesive layer between the polyvinyl alcohol resin film having polarizing function and the cellulose triacetate film, thereby obtaining a polarizer sample.
The polarizer samples of the present example were tested for adhesion of the adhesive layer using the following method: the polarizer sample of this example was prepared into a test specimen having a length of 200mm and a width of 25. + -. 0.5mm (extending in a direction parallel to the long side). The peel force that the adhesive layer of the polarizer sample could withstand was measured by using an AGS-X tensile machine of Shimadzu corporation, Japan, with reference to GB/T2791-1995, wherein the peel force that the adhesive layer of the polarizer sample of this example could withstand is shown in Table 1.
The polarizer sample of this example was judged for delamination and foreign matter precipitation by the following methods: the polarizer sample of this example was cut into 120 × 120mm size, and observed on the backlight of the LCD panel to determine whether or not there was delamination or foreign matter precipitation, and the delamination and foreign matter precipitation results of the polarizer sample of this example are shown in table 1.
The high temperature resistance of the polarizer sample of this example was tested by the following method: the polarizer samples of this example were placed at 100 ℃ and kept warm for 12 hours for dry heat testing, and the optical properties of the polarizer samples before and after heat treatment were measured using a "REST-100" spectrophotometer from tsuka electronics (suzhou) ltd, and the high temperature resistance of the polarizer samples before and after dry heat testing was evaluated using the change in the cross-color hue b (Δ b), with the smaller the change, the better the high temperature resistance, and the Δ b of the polarizer samples of this example being shown in table 1.
Example 2
The adhesive for a polarizer of this example was prepared as follows:
(1) and (3) dry-mixing the first main material and the second main material uniformly according to the mass ratio of 7:3 to obtain a mixture. Wherein the first main material is polyvinyl alcohol with the average polymerization degree of 1700, and the alcoholysis degree is 99%; the second main material is polyvinyl alcohol with the average polymerization degree of 300, and the alcoholysis degree is 92%.
(2) The mixture was sequentially soaked and washed with deionized water at 35 c with constant stirring, and repeated 6 times, the cumulative time of soaking being 1 hour to fully swell the mixture to obtain a swollen material.
(3) Adding deionized water into the swelling material, heating the swelling material to 95 ℃ within 50 minutes under the condition of continuous stirring, preserving the temperature at 95 ℃ for 70 minutes to dissolve the swelling material, and cooling to room temperature within 45 minutes to obtain a pre-prepared solution.
(4) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent and a catalyst into the pre-prepared liquid, adjusting the viscosity of the pre-prepared liquid to 44cPs by using deionized water, wherein the mass percentage of a solid phase is 3.2%, and filtering, standing and defoaming to obtain the adhesive for the polarizer. Wherein the cross-linking agent is malondialdehyde, and the mass ratio of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 5; the catalyst is zinc acetate, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the mass of the second main material is 1: 10.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Example 3
The adhesive for a polarizer of this example was prepared as follows:
(1) and (3) dry-mixing the first main material and the second main material uniformly according to the mass ratio of 9:1 to obtain a mixture. Wherein the first main material is polyvinyl alcohol with the average polymerization degree of 4000, and the alcoholysis degree is 99%; the second main material is selected from polyvinyl alcohol with the average polymerization degree of 550, and the alcoholysis degree is 99%.
(2) Sequentially soaking the mixture in deionized water at 30 deg.C and washing, repeating for 5 times, and soaking for 1.5 hr to swell the mixture sufficiently to obtain a swollen matter.
(3) Adding deionized water into the swelling material, heating the swelling material to 98 ℃ within 60 minutes under the condition of continuous stirring, preserving the temperature for 60 minutes at 98 ℃ to dissolve the swelling material, and cooling to room temperature within 30 minutes to obtain a pre-prepared solution.
(4) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent and a catalyst into the pre-prepared liquid, adjusting the viscosity of the pre-prepared liquid to 45cPs by using deionized water, wherein the mass percentage of a solid phase is 3.8%, and filtering, standing and defoaming to obtain the adhesive for the polarizer. The cross-linking agent is succinaldehyde, and the mass ratio of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 2; the catalyst is zinc sulfate, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the mass of the second main material is 1: 5.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Example 4
The adhesive for a polarizer of this example was prepared as follows:
(1) and (3) dry-mixing the first main material and the second main material uniformly according to the mass ratio of 5:5 to obtain a mixture. Wherein the first main material is polyvinyl alcohol with the average polymerization degree of 2000, and the alcoholysis degree is 98%; the second main material is polyvinyl alcohol with the average polymerization degree of 400, and the alcoholysis degree is 98%.
(2) Sequentially soaking the mixture in deionized water at 25 deg.C and washing for 6 times, wherein the soaking time is 1 hr to swell the mixture sufficiently to obtain a swollen matter.
(3) Adding deionized water into the swelling material, heating the swelling material to 97 ℃ within 30 minutes under the condition of continuous stirring, preserving the temperature for 55 minutes at 97 ℃ to dissolve the swelling material, and cooling to room temperature within 10 minutes to obtain a pre-prepared solution.
(4) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent and a catalyst into the pre-prepared liquid, adjusting the viscosity of the pre-prepared liquid to 25cPs by using deionized water, wherein the mass percentage of a solid phase is 3%, and filtering, standing and defoaming to obtain the adhesive for the polarizer. Wherein the cross-linking agent is glutaraldehyde, and the ratio of the mass of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 200; the catalyst is zinc acetate, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the mass of the second main material is 1: 1000.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Example 5
The adhesive for a polarizer of this example was prepared as follows:
(1) and (3) dry-mixing the first main material and the second main material uniformly according to the mass ratio of 6:4 to obtain a mixture. Wherein the first main material is polyvinyl alcohol with average polymerization degree of 2600, and alcoholysis degree is 99%; the second main material is polyvinyl alcohol with the average polymerization degree of 500, and the alcoholysis degree is 99%.
(2) The mixture was sequentially soaked and washed with deionized water at 30 ℃ for 5 times, and the cumulative soaking time was 1.1 hours to fully swell the mixture, to obtain a swollen material.
(3) Adding deionized water into the swelling material, heating the swelling material to 95 ℃ within 45 minutes under the condition of continuous stirring, preserving the temperature at 95 ℃ for 65 minutes to dissolve the swelling material, and cooling to room temperature within 15 minutes to obtain a pre-prepared solution.
(4) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent and a catalyst into the pre-prepared liquid, adjusting the viscosity of the pre-prepared liquid to 50cPs by using deionized water, wherein the mass percentage of a solid phase is 4.4%, and filtering, standing and defoaming to obtain the adhesive for the polarizer. Wherein the cross-linking agent is trimethylolmelamine, and the mass ratio of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 100; the catalyst is cobalt acetate, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the second main material is 1: 100.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Example 6
The adhesive for a polarizer of this example was prepared as follows:
(1) and (3) dry-mixing the first main material and the second main material uniformly according to the mass ratio of 7.5:2.5 to obtain a mixture. Wherein the first main material is polyvinyl alcohol with the average polymerization degree of 1700, and the alcoholysis degree is 99%; the second main material is polyvinyl alcohol with the average polymerization degree of 600, and the alcoholysis degree is 99%.
(2) The mixture was sequentially soaked and washed with deionized water at 30 ℃ for 5 times, and the cumulative soaking time was 1.1 hours to fully swell the mixture, to obtain a swollen material.
(3) Adding deionized water into the swelling material, heating the swelling material to 95 ℃ within 40 minutes under the condition of continuous stirring, preserving the temperature at 95 ℃ for 65 minutes to dissolve the swelling material, and cooling to room temperature within 20 minutes to obtain a pre-prepared solution.
(4) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent and a catalyst into the pre-prepared liquid, adjusting the viscosity of the pre-prepared liquid to 190cPs by using deionized water, wherein the mass percentage of a solid phase is 8%, and filtering, standing and defoaming to obtain the adhesive for the polarizer. Wherein the cross-linking agent is hexamethylol melamine, and the mass ratio of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 50; the catalyst is zinc chloride, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the mass of the second main material is 1: 50.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Example 7
The adhesive for a polarizer of this example was prepared as follows:
(1) and (3) dry-mixing the first main material and the second main material uniformly according to the mass ratio of 7.5:2.5 to obtain a mixture. The first main material is polyvinyl alcohol with the average polymerization degree of 1700 and polyvinyl alcohol with the average polymerization degree of 2600, the alcoholysis degree of the polyvinyl alcohol with the average polymerization degree of 1700 is 98%, the polyvinyl alcohol with the average polymerization degree of 2600 is 98%, and the mass ratio of the polyvinyl alcohol with the average polymerization degree of 1700 to the polyvinyl alcohol with the average polymerization degree of 2600 is 1: 1; the second main material is polyvinyl alcohol with the average polymerization degree of 600, and the alcoholysis degree is 98%.
(2) The mixture was sequentially soaked and washed with deionized water at 30 ℃ for 5 times, and the cumulative soaking time was 1.1 hours to fully swell the mixture, to obtain a swollen material.
(3) Adding deionized water into the swelling material, heating the swelling material to 95 ℃ within 40 minutes under the condition of continuous stirring, preserving the temperature at 95 ℃ for 65 minutes to dissolve the swelling material, and cooling to room temperature within 15 minutes to obtain a pre-prepared solution.
(4) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent into the pre-prepared liquid, adjusting the viscosity of the pre-prepared liquid to 200cPs by using deionized water, wherein the mass percentage of a solid phase is 6.2%, and filtering, standing and defoaming the mixture to obtain the adhesive for the polarizer. Wherein the cross-linking agent is organic titanium chelate (TYZOR TE produced by Dupont company), and the ratio of the mass of the cross-linking agent to the sum of the mass of the first main material and the second main material is 1: 20.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Example 8
The adhesive for a polarizer of this example was prepared as follows:
(1) and (3) dry-mixing the first main material and the second main material uniformly according to the mass ratio of 8.5:1.5 to obtain a mixture. The first main material is polyvinyl alcohol with the average polymerization degree of 2200 and polyvinyl alcohol with the average polymerization degree of 4000, the alcoholysis degree of the polyvinyl alcohol with the average polymerization degree of 2200 is 99 percent, the polyvinyl alcohol with the average polymerization degree of 4000 is 99 percent, and the mass ratio of the polyvinyl alcohol with the average polymerization degree of 2200 to the polyvinyl alcohol with the average polymerization degree of 4000 is 2: 1; the second main material is polyvinyl alcohol with the average polymerization degree of 350, and the alcoholysis degree is 99%.
(2) The mixture was sequentially soaked and washed with deionized water at 30 ℃ for 5 times, and the cumulative soaking time was 1.1 hours to fully swell the mixture, to obtain a swollen material.
(3) Adding deionized water into the swelling material, heating the swelling material to 95 ℃ within 40 minutes under the condition of continuous stirring, preserving the temperature at 95 ℃ for 65 minutes to dissolve the swelling material, and cooling to room temperature within 20 minutes to obtain a pre-prepared solution.
(4) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent into the pre-prepared liquid, adjusting the viscosity of the pre-prepared liquid to 15cPs by using deionized water, wherein the mass percentage of a solid phase is 2.6%, and filtering, standing and defoaming the mixture to obtain the adhesive for the polarizer. The cross-linking agent is an organic boron zirconium chelating agent OBZ-1, and the ratio of the mass of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 10.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Example 9
The adhesive for a polarizer of this example was prepared as follows:
(1) and (3) dry-mixing the first main material and the second main material uniformly according to the mass ratio of 7:3 to obtain a mixture. The first main material is polyvinyl alcohol with the average polymerization degree of 2000 and polyvinyl alcohol with the average polymerization degree of 3400, the alcoholysis degree of the polyvinyl alcohol with the average polymerization degree of 2000 is 99%, the polyvinyl alcohol with the average polymerization degree of 3400 is 99%, and the mass ratio of the polyvinyl alcohol with the average polymerization degree of 2000 to the polyvinyl alcohol with the average polymerization degree of 3400 is 1: 2; the second main material is polyvinyl alcohol with the average polymerization degree of 450, and the alcoholysis degree is 99%.
(2) The mixture was sequentially soaked and washed with deionized water at 30 ℃ for 5 times, and the cumulative soaking time was 1.1 hours to fully swell the mixture, to obtain a swollen material.
(3) Adding deionized water into the swelling material, heating the swelling material to 95 ℃ within 40 minutes under the condition of continuous stirring, preserving the temperature at 95 ℃ for 65 minutes to dissolve the swelling material, and cooling to room temperature within 30 minutes to obtain a pre-prepared solution.
(4) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent and a catalyst into the pre-prepared liquid, adjusting the viscosity of the pre-prepared liquid to 40cPs by using deionized water, wherein the mass percentage of a solid phase is 3.1%, and filtering, standing and defoaming to obtain the adhesive for the polarizer. Wherein the cross-linking agent is glyoxal, and the mass ratio of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 10; the catalyst is zinc chloride, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the second main material is 0.3: 10.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Example 10
The adhesive for a polarizer of this example was prepared as follows:
(1) and (3) dry-mixing the first main material and the second main material uniformly according to the mass ratio of 9:1 to obtain a mixture. The first main material is polyvinyl alcohol with the average polymerization degree of 1700, polyvinyl alcohol with the average polymerization degree of 2400 and polyvinyl alcohol with the average polymerization degree of 4000, the alcoholysis degree of the polyvinyl alcohol with the average polymerization degree of 1700 is 99%, the alcoholysis degree of the polyvinyl alcohol with the average polymerization degree of 2400 is 99%, the alcoholysis degree of the polyvinyl alcohol with the average polymerization degree of 4000 is 99%, and the mass ratio of the polyvinyl alcohol with the average polymerization degree of 1700, the polyvinyl alcohol with the average polymerization degree of 2400 and the polyvinyl alcohol with the average polymerization degree of 4000 is 1:2: 1; the second main material is polyvinyl alcohol with the average polymerization degree of 450, and the alcoholysis degree is 99%.
(2) The mixture was sequentially soaked and washed with deionized water at 30 ℃ for 5 times, and the cumulative soaking time was 1.1 hours to fully swell the mixture, to obtain a swollen material.
(3) Adding deionized water into the swelling material, heating the swelling material to 95 ℃ within 40 minutes under the condition of continuous stirring, preserving the temperature at 95 ℃ for 65 minutes to dissolve the swelling material, and cooling to room temperature within 25 minutes to obtain a pre-prepared solution.
(4) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent and a catalyst into the pre-prepared liquid, adjusting the viscosity of the pre-prepared liquid to 50cPs by using deionized water, wherein the mass percentage of a solid phase is 3.8%, and filtering, standing and defoaming to obtain the adhesive for the polarizer. Wherein the cross-linking agent is glyoxal, and the mass ratio of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 10; the catalyst is zinc chloride, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the second main material is 0.3: 10.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Example 11
The adhesive for a polarizer of this example was prepared as follows:
(1) sequentially soaking the first main material in deionized water at 28 ℃ and continuously stirring, washing, and repeating for 5 times, wherein the cumulative soaking time is 1.2 hours so as to fully swell the mixture, thereby obtaining a first swelling substance; adding deionized water into the first swelling material, heating the first swelling material to 96 ℃ within 60 minutes under the condition of continuous stirring, preserving the heat at 96 ℃ for 60 minutes to dissolve the first swelling material, and cooling to room temperature within 45 minutes to obtain a first pre-prepared liquid. Wherein, the first main material is polyvinyl alcohol with average polymerization degree of 2400, and the alcoholysis degree is 99%.
(2) And sequentially soaking the second main material in deionized water and washing at 28 ℃ under the condition of continuous stirring, repeating for 5 times, wherein the cumulative soaking time is 1.2 hours to fully swell the mixture to obtain a second swelling material, adding deionized water into the second swelling material, heating the second swelling material to 96 ℃ within 60 minutes under the condition of continuous stirring, preserving the temperature at 96 ℃ for 60 minutes to dissolve the second swelling material, and cooling to room temperature within 45 minutes to obtain a second pre-prepared solution. Wherein, the second main material is polyvinyl alcohol with the average polymerization degree of 500, and the alcoholysis degree is 99%.
(3) And mixing the first pre-prepared solution and the second pre-prepared solution at room temperature under the condition of continuous stirring to obtain a mixed solution. Wherein in the mixed solution, the mass ratio of the first main material to the second main material is 8: 2.
(4) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent and a catalyst into the mixed solution, adjusting the viscosity of the pre-prepared solution to 42cPs by using deionized water, wherein the mass percentage of a solid phase is 3.4%, and filtering, standing and defoaming the mixture to obtain the adhesive for the polarizer. Wherein the cross-linking agent is glyoxal, and the mass ratio of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 10; the catalyst is zinc chloride, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the second main material is 0.3: 10.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Example 12
The adhesive for a polarizer of this example was prepared as follows:
(1) sequentially soaking and washing polyvinyl alcohol with average polymerization degree of 2400 and alcoholysis degree of 99% by using deionized water at 28 ℃, repeating for 5 times, wherein the cumulative soaking time is 1.2 hours so as to fully swell the mixture, and thus obtaining a swelling substance.
(2) Adding deionized water into the swelling material, heating the swelling material to 96 ℃ within 60 minutes under the condition of continuous stirring, preserving the temperature for 60 minutes at 96 ℃ to dissolve the swelling material, and cooling to room temperature within 15 minutes to obtain a pre-prepared solution.
(3) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent and a catalyst into the pre-prepared liquid, adjusting the viscosity of the pre-prepared liquid to 42cPs by using deionized water, wherein the mass percentage of a solid phase is 3.4%, and filtering, standing and defoaming to obtain the adhesive for the polarizer. Wherein the cross-linking agent is glyoxal, and the mass ratio of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 10; the catalyst is zinc chloride, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the second main material is 0.3: 10.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Example 13
The adhesive for a polarizer of this example was prepared as follows:
(1) sequentially soaking and washing polyvinyl alcohol with average polymerization degree of 2400 and alcoholysis degree of 99% by using deionized water at 28 ℃, repeating for 5 times, wherein the cumulative soaking time is 1.2 hours so as to fully swell the mixture, and thus obtaining a swelling substance.
(2) Adding deionized water into the swelling material, heating the swelling material to 96 ℃ within 60 minutes under the condition of continuous stirring, preserving the temperature for 60 minutes at 96 ℃ to dissolve the swelling material, and cooling to room temperature within 20 minutes to obtain a pre-prepared solution.
(3) Under the conditions of continuous stirring and room temperature, adding a cross-linking agent and a catalyst into the pre-prepared liquid, finally adding 25% of glycerol based on the total mass of polyvinyl alcohol, fully stirring, adjusting the viscosity of the pre-prepared liquid to 42cPs by using deionized water, wherein the mass percentage content of a solid phase is 3.4%, and filtering, standing and defoaming to obtain the adhesive for the polarizer. Wherein the cross-linking agent is glyoxal, and the mass ratio of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 10; the catalyst is zinc chloride, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the second main material is 0.3: 10.
The polarizer samples of this example were prepared in the same manner as in example 1, and the adhesive layer of the polarizer samples of this example were subjected to the peeling force, delamination and foreign matter precipitation results and Δ b values shown in table 1, using the same test methods as in example 1.
Table 1 shows the peeling force, delamination and foreign material deposition results and Δ b values that the adhesive layers of the polarizer samples of examples 1 to 13 can withstand.
TABLE 1
Figure BDA0001188570500000211
Figure BDA0001188570500000221
As can be seen from Table 1, the adhesive layers of the polarizer samples of examples 1 to 11 can withstand a peeling force of at least 765gf/25mm, while the adhesive layer of the polarizer sample of example 12 can withstand a peeling force of only 426gf/25mm, and it is clear that the adhesive layers of the polarizer samples of examples 1 to 11 can withstand a peeling force significantly improved compared to the polarizer sample of example 12 prepared by using a conventional polyvinyl alcohol adhesive. The polarizer samples of examples 1 to 11 have no delamination or foreign matter precipitation, which indicates that the adhesives for the polarizer of examples 1 to 11 also have significant advantages in terms of high temperature resistance, and the Δ b values of the polarizer samples of examples 1 to 11 are at most only 0.65, which is much lower than the Δ b values of the polarizer samples of example 12, which clearly indicates that the polarizer samples of examples 1 to 11 have better high temperature resistance.
Although the polarizer sample (example 13) prepared from the polyvinyl alcohol adhesive using glycerin as the plasticizer has a high peeling force, foreign matters (oily stains) distributed unevenly are precipitated, which seriously affects the optical performance of the polarizer and the display effect of the corresponding display; and the delta b value of the polarizer sample is far higher than that of the samples in the examples 1-11, and obviously, the high temperature resistance of the polarizer sample is different from that of the samples in the examples 1-11.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The adhesive for the polarizer is characterized by comprising a first main material, a second main material, a cross-linking agent and water, wherein the first main material is polyvinyl alcohol with the average polymerization degree of 1700-4000, the second main material is polyvinyl alcohol with the average polymerization degree of 300-600, the mass of the second main material is 10% -50% of the sum of the mass of the first main material and the mass of the second main material, the viscosity of the adhesive for the polarizer is 15-200 cPs, the mass percentage content of a solid phase is 2% -8%, the alcoholysis degree of the first main material is greater than or equal to 92%, and the alcoholysis degree of the second main material is greater than or equal to 92%.
2. The adhesive for a polarizer according to claim 1, wherein the first main material is a mixture comprising polyvinyl alcohol having an average degree of polymerization of 1700 to 2400 and polyvinyl alcohol having an average degree of polymerization of 2500 to 4000; or the average polymerization degree of the first main material is 1700-3000.
3. The adhesive for a polarizer according to claim 1, wherein the average degree of polymerization of the second main material is 400 to 550.
4. The adhesive for a polarizer according to claim 1, wherein the crosslinking agent is one selected from the group consisting of dialdehydes, organic metal chelates, and hydroxy-melamines; the ratio of the mass of the cross-linking agent to the sum of the mass of the first main material and the mass of the second main material is 1: 2-1: 200.
5. The adhesive for a polarizer according to claim 1, further comprising a catalyst, wherein the catalyst is one selected from zinc chloride, zinc acetate, zinc sulfate and cobalt acetate, and the ratio of the mass of the catalyst to the sum of the mass of the first main material and the mass of the second main material is 1:5 to 1: 1000.
6. A method for preparing an adhesive for a polarizer, comprising the steps of:
mixing a first main material and a second main material to obtain a mixture, wherein the first main material is polyvinyl alcohol with the average polymerization degree of 1700-4000, the second main material is polyvinyl alcohol with the average polymerization degree of 300-600, the mass of the second main material is 10% -50% of the sum of the mass of the first main material and the mass of the second main material, the alcoholysis degree of the first main material is greater than or equal to 92%, and the alcoholysis degree of the second main material is greater than or equal to 92%;
fully swelling the mixture in water at a temperature of below 35 ℃ under continuous stirring to obtain a swollen matter;
under the condition of continuous stirring, preserving the temperature of the swelling substance at 95-98 ℃ for 50-70 minutes, and cooling to obtain a pre-prepared solution;
and mixing the pre-prepared solution and a cross-linking agent under the conditions of continuous stirring and room temperature to obtain the adhesive for the polarizer, wherein the viscosity of the adhesive is 15 to 200cPs, and the mass percentage content of a solid phase is 2 to 8 percent.
7. A method for preparing an adhesive for a polarizer, comprising the steps of:
under the condition of being lower than 35 ℃ and continuously stirring, fully swelling a first main material in water to obtain a first swelling material, and fully swelling a second main material in water to obtain a second swelling material, wherein the first main material is polyvinyl alcohol with the average polymerization degree of 1700-4000, the second main material is polyvinyl alcohol with the average polymerization degree of 300-600, the mass of the second main material is 10-50% of the sum of the mass of the first main material and the mass of the second main material, the alcoholysis degree of the first main material is greater than or equal to 92%, and the alcoholysis degree of the second main material is greater than or equal to 92%;
under the condition of continuous stirring, preserving the heat of the first swelling substance at 95-98 ℃ for 50-70 minutes, cooling to obtain a first pre-prepared liquid, preserving the heat of the second swelling substance at 95-98 ℃ for 50-70 minutes, and cooling to obtain a second pre-prepared liquid;
mixing the first pre-prepared liquid and the second pre-prepared liquid under the conditions of continuous stirring and room temperature to obtain a mixed liquid;
and mixing the mixed solution with a cross-linking agent under the conditions of continuous stirring and room temperature to obtain the adhesive for the polarizer, wherein the viscosity of the adhesive is 15 to 200cPs, and the mass percentage content of a solid phase is 2 to 8 percent.
8. A preparation method of a polarizer is characterized by comprising the following steps:
the polarizer is obtained by forming an adhesive layer between a polyvinyl alcohol resin film and an inner protective film by using the adhesive for a polarizer according to any one of claims 1 to 5.
9. The polarizer prepared by the method of claim 8.
10. A display comprising the polarizer of claim 9.
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