CN108931833A - Polarization plates - Google Patents

Polarization plates Download PDF

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Publication number
CN108931833A
CN108931833A CN201810505008.1A CN201810505008A CN108931833A CN 108931833 A CN108931833 A CN 108931833A CN 201810505008 A CN201810505008 A CN 201810505008A CN 108931833 A CN108931833 A CN 108931833A
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CN
China
Prior art keywords
methyl
film
resin film
polarization plates
adhesive
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Granted
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CN201810505008.1A
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Chinese (zh)
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CN108931833B (en
Inventor
永安智
李正银
藤田政大
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • C09J139/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A kind of polarization plates are provided, it is the polarization plates comprising polarizing film He (methyl) acrylic resin film, after being placed under hygrothermal environment (hot and humid environment), the adhesion between polarizing film and (methyl) acrylic resin film is good.A kind of polarization plates are provided, successively include polarizing film, the 1st adhesive layer and (methyl) acrylic resin film, the 1st adhesive layer is the layer formed by the adhesive composite containing the compound containing oxazolinyl.

Description

Polarization plates
Technical field
The present invention relates to polarization plates.
Background technique
Usually have by widely used polarization plates in image display device of representative etc. of liquid crystal display device inclined The one or two sides stacking of vibration piece is fitted with the composition of the thermoplastic resin film of protective film etc.In polarizing film and thermoplastic resin In the fitting of film, usually using bonding agent.As the bonding agent, it is known that active energy ray-curable bonding agent, water system bonding Agent.(for example, Japanese Unexamined Patent Publication 2009-008860 bulletin (patent document 1)).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2009-008860 bulletin
Summary of the invention
Problems to be solved by the invention
The object of the present invention is to provide a kind of polarization plates, to include polarizing film and (methyl) acrylic resin film Polarization plates, after being placed under hygrothermal environment (hot and humid environment), polarizing film and (methyl) acrylic resin film it Between adhesion it is good.
The means used to solve the problem
The present invention provides polarization plates as shown below.
[1] a kind of polarization plates, successively include polarizing film, the 1st adhesive layer and (methyl) acrylic resin film, aforementioned 1st adhesive layer is the layer formed by the adhesive composite containing the compound containing oxazolinyl.
[2] polarization plates according to [1], wherein aforementioned adhesive composite also contains acetoacetyl modified poly- second Enol polymer.
[3] polarization plates according to [1] or [2], wherein successively comprising thermoplastic resin film, the 2nd adhesive layer, preceding State polarizing film, aforementioned 1st adhesive layer and aforementioned (methyl) acrylic resin film.
[4] polarization plates according to any one of [1]~[3], wherein aforementioned 1st adhesive layer and aforementioned (methyl) Acrylic resin film contact.
[5] polarization plates according to [4], wherein aforementioned (methyl) acrylic resin film with aforementioned 1st bonding agent The water contact angle in the face of layer contact is 80 ° or less.
[6] polarization plates according to any one of [1]~[5], wherein aforementioned polarizing film and aforementioned 1st adhesive layer Contact.
[7] a kind of adhesive composite, for the bonding for keeping polarizing film Nian Jie with (methyl) acrylic resin film Agent composition, aforementioned adhesive composite contain Han oxazolinyl compound.
[8] adhesive composite according to [7], also contains acetoacetyl modified polyvinyl alcohol polymer.
[9] adhesive composite according to [7] or [8], also contains water.
Invention effect
It may be provided in after being placed under hygrothermal environment (hot and humid environment), polarizing film and (methyl) acrylic resin The good polarization plates of adhesion between film.
Detailed description of the invention
Fig. 1 is the schematic sectional view of an example for indicating that the layer of polarization plates of the invention is constituted.
Fig. 2 is another schematic sectional view for indicating the layer of polarization plates of the invention and constituting.
Specific embodiment
<Polarization plates>
Polarization plates of the invention successively include polarizing film, the 1st adhesive layer and (methyl) acrylic resin film, and the 1st is viscous Connecing oxidant layer is the adhesive layer formed by the adhesive composite containing the compound containing oxazolinyl.
Polarization plates of the invention are after being placed under hygrothermal environment (hot and humid environment), polarizing film and (methyl) propylene Adhesion between sour resin film is good.
In the present specification, " (methyl) acrylic acid " indicates at least one kind of in acrylic acid and methacrylic acid." (first Base) acryloyl group " and the statements such as " (methyl) acrylate " it is also the same.
(1) composition of polarization plates
The example that the layer of polarization plates of the invention is constituted is shown in Fig. 1 and Fig. 2.
As shown in Figure 1, polarization plates of the invention may include：Polarizing film 30；Its one side across the 1st adhesive layer 15 and layer (methyl) acrylic resin film 10 of folded fitting.
It is preferred that the 1st adhesive layer 15 is directly contacted with (methyl) acrylic resin film 10.
It is preferred that polarizing film 30 is directly contacted with the 1st adhesive layer 15.
In addition, as shown in Fig. 2, polarization plates of the invention also may include：Polarizing film 30；In its one side across the 1st bonding Oxidant layer 15 and be laminated fitting (methyl) acrylic resin film 10；With the another side in polarizing film 30 across the 2nd adhesive layer 25 and be laminated fitting thermoplastic resin film 20.That is, polarization plates of the invention can successively include：Thermoplastic resin film the 20, the 2nd Adhesive layer 25, polarizing film 30, the 1st adhesive layer 15 and (methyl) acrylic resin film 10.
It is preferred that the 2nd adhesive layer 25 is directly contacted with thermoplastic resin film 20.
It is preferred that polarizing film 30 is directly contacted with the 2nd adhesive layer 25.
Polarization plates of the invention preferably successively include thermoplastic resin film 20, the 2nd adhesive layer 25, polarizing film the 30, the 1st The polarization plates of adhesive layer 15 and (methyl) acrylic resin film 10.
It is not limited to the example of Fig. 1 and Fig. 2, polarization plates of the invention may include other layers (or film) other than the above. As other layers, it can be mentioned, for example：It is laminated in (methyl) acrylic resin film 10, thermoplastic resin film 20 and/or polarization The adhesive phase of the outer surface of piece 30；It is laminated in the isolation film (also referred to as " stripping film " of the outer surface of the adhesive phase.)；Stacking In (methyl) acrylic resin film 10, the outer surface of thermoplastic resin film 20 and/or polarizing film 30 protecting film (also referred to as " surface protection film ".)；The outer surface of (methyl) acrylic resin film 10, thermoplastic resin film 20 and/or polarizing film 30 every Adhesive layer, adhesive phase and optical functional film (or layer) for being laminated etc..
(2) the 1st adhesive layers
1st adhesive layer 15 is the layer formed by the adhesive composite (S) containing compound containing oxazolinyl (A).
Han oxazolinyl compound (A) is preferably Han oxazolinyl polymer.
Han oxazolinyl polymer is the polymer of intramolecular Ju You oxazolinyl, preferably side chain Ju You oxazolinyl Polymer.The main chain of polymer is not particularly limited, for example, may include selected from (methyl) acrylic compounds skeleton, styrene bone The skeleton of one or more of frame etc..
Han oxazolinyl polymer can be in the side chain Ju You oxazolinyl of above-mentioned main chain.
Preferred an example of Han oxazolinyl polymer is comprising the main chain containing (methyl) acrylic compounds skeleton and in the master Side chain Ju You oxazolinyl Han oxazolinyl (methyl) acrylic acid series polymeric compounds of chain.
Dang Han oxazolinyl polymer in side chain Ju You oxazolinyl, the company of can have between main chain He oxazolinyl Connect group, but the polymer of preferably main chain He oxazolinyl Direct Bonding.
Zuo Wei oxazolinyl, it can be mentioned, for example：2- oxazolinyl, 3- oxazolinyl, 4- oxazolinyl etc..Oxazolinyl is excellent It is selected as 2- oxazolinyl etc..
The number-average molecular weight of Han oxazolinyl polymer is preferably 5000 or more, and more preferably 10000 or more.If number is divided equally Son amount then has the tendency that being easy to show good adhesion in above range.The number-average molecular weight of Han oxazolinyl polymer Usually 100000 or less.
The number-average molecular weight of Han oxazolinyl polymer can be with the standard polyphenyl second based on gel permeation chromatography (GPC) The form of alkene scaled value is measured.
Oxazoline base unit weight (the oxazolinyl of the solid component of every 1g polymer containing oxazolinyl of the polymer containing oxazolinyl Molal quantity) be preferably 0.4mmol/gsolid or more and 10mmol/gsolid or less.If oxazoline base unit weight is excessively high, It is difficult to obtain good adhesion, if oxazoline base unit weight is less than above range, there is the water resistance of the 1st adhesive layer 15 to decline it Anxiety.From such a viewpoint, the oxazoline base unit weight of the polymer containing oxazolinyl be more preferably 3mmol/gsolid or more and 9mmol/gsolid or less.
It is that (bonding agent ingredient is to be dissolved in water or be scattered in water to water system adhesive composite in adhesive composite (S) Bonding agent) when , Han oxazolinyl polymer be preferably water system, i.e., water-soluble polymer or water dispersible polymer.From viscous , Han oxazolinyl polymer is preferably water-soluble polymer from the perspective of connecing the optical characteristics of oxidant layer.
Commercially available product can be used in Han oxazolinyl polymer.Specifically, can enumerate：Nippon Shokubai Co., Ltd's system EPOCROS WS-300, EPOCROS WS-500, EPOCROS WS-700 (are trade name) Deng Han oxazolinyl acrylic compounds Polymer；Nippon Shokubai Co., Ltd EPOCROS K-1000 series, EPOCROS K-2000 series, EPOCROS RPS system Column (are trade name) Deng Han oxazolinyl acrylic compounds/styrene polymer.
Han oxazolinyl polymer can be used in combination of two or more and use.
From the viewpoint of adhesion, optical characteristics, water resistance, preferably EPOCROS WS-300, EPOCROS WS-700 Deng Han oxazolinyl acrylic polymer.
When the total amount of adhesive composite (S) is set as 100 mass %, the content of , Han oxazolinyl polymer is preferably 0.1 mass % or more and 30 mass % are hereinafter, more preferably 0.5 mass % or more and 20 mass % are hereinafter, further preferably 1 Quality % or more and 15 mass % or less.After being placed under hygrothermal environment (hot and humid environment), polarizing film 30 and (first Base) from the perspective of adhesion between acrylic resin film 10, the content of Shi Han oxazolinyl polymer is in above range Within be preferred.
Adhesive composite (S) can also contain acetoacetyl modified polyvinyl alcohol polymer (B).Also contain acetyl second Acyl modified polyvinyl alcohol polymer (B) can be conducive to improve between polarizing film 30 and (methyl) acrylic resin film 10 Adhesion.
Acetoacetyl modified vinol series polymer (B) refers to：Changed and importing acetoacetyl to side chain The vinol series polymer of property.
The vinol series polymer of the main chain of acetoacetyl modified polyvinyl alcohol polymer (B) is constituted, either Polyvinyl acetate as the homopolymer of vinyl acetate is subjected to alcotex (complete soap obtained from saponification process Change polyvinyl alcohol or partly-hydrolysed polyvinyl alcohol), be also possible to by vinyl acetate with can be with other monomers of its copolymerization Copolymer carries out polyvinyl alcohol based copolymer obtained from saponification process.
As can be enumerated with other monomers of vinyl acetate copolymerization：Unsaturated carboxylic acid class, olefines, vinyl Ethers, unsaturated sulfonic acid class and (methyl) acrylic amide with ammonium etc..
The saponification degree of acetoacetyl modified polyvinyl alcohol polymer (B) is usually 80 moles of % or more and 100 mole of % Hereinafter, preferably 85 moles of % or more.
The saponification degree of acetoacetyl modified polyvinyl alcohol polymer (B) can be based on JIS K 6726：1994 measure.
From the viewpoint of adhesion, acetoacetyl modified polyvinyl alcohol polymer (B) based on acetoacetyl Modification degree (modified amount) is usually 0.1 mole of % or more and 40 mole of % hereinafter, preferably 0.5 mole of % or more and 40 mole of % Hereinafter, more preferably 1 mole of % or more and 20 mole of % or less.Modification degree is for example available1H-NMR is measured.
From the viewpoint of adhesion, the average degree of polymerization of acetoacetyl modified polyvinyl alcohol polymer (B) is preferably 100 or more and 3000 hereinafter, more preferably 500 or more and 3000 or less.
The average degree of polymerization of acetoacetyl modified polyvinyl alcohol polymer (B) can be based on JIS K6726：1994 survey It is fixed.
The content of acetoacetyl modified polyvinyl alcohol polymer (B) is relative to 100 mass of Han oxazolinyl compound (A) It part is usually 1 mass parts or more and 300 below the mass, more than preferably 5 mass parts and 250 below the mass, more preferably More than 10 mass parts and 200 below the mass.If the content of acetoacetyl modified polyvinyl alcohol polymer (B) in the range, Then have the tendency that being easy to show to improve the effect of adhesion.
Adhesive composite (S) can also contain aziridine cpd (C).Aziridine cpd (C) refers to：Intramolecular tool There is the compound of 1 or more aziridine ring.Aziridine cpd (C) is preferably the change that intramolecular has 2 or 3 aziridine rings Close object.
Aziridine cpd (C) is preferably monomer, and the molecular weight of aziridine cpd (C) can be 150 or more and 1000 Below.
Aziridine cpd (C) can be commercially available product, specifically, can enumerate：Nippon Shokubai Co., Ltd's system CHEMITITE PZ-33, CHEMITITE DZ-22E (being trade name)；MENADIONA corporation CROSSLINKER CL- 422, the aziridine based compound such as CROSSLINKER CL-427, CROSSLINKER CL-467 (being trade name).From contiguity From the perspective of property, particularly preferred CROSSLINKER CL-427.
The content of aziridine cpd (C) is usually 0.1 mass relative to 100 mass parts of Han oxazolinyl compound (A) Part or more and 50 below the mass, more than preferably 0.2 mass parts and 30 below the mass, more than more preferably 0.5 mass parts And 20 below the mass.
Adhesive composite (S) preferably comprises solvent.As solvent, can enumerate：Water, organic solvent or their mixing Object.Solvent preferably comprises water, water and water-soluble organic solvent can also be used in combination.As organic solvent, can enumerate：Ethyl alcohol, The alcoholic solvents such as 1- methoxy-2-propanol.
The principal component of preferred solvent is water.Principal component refers to：Account for the 50 mass % or more of whole solvents.
The solid component concentration of adhesive composite (S) is usually 0.5 mass % or more and 20 mass % hereinafter, preferably 1 mass % or more and 15 mass % or less.
Solid component concentration refers to：Total concentration of ingredient contained by adhesive composite (S) in addition to solvent.
Adhesive composite (S) can be poly- containing Chu Han oxazolinyl compound (A), acetoacetyl modified polyvinyl alcohol Close other ingredients other than object (B) and solvent.
As other ingredients, can enumerate：Polyaldehyde, melamine based compound, zirconia compound, zinc compound, second The curability compositions such as dialdehyde, glyoxal derivative, water-soluble epoxy resin or crosslinking agent；Coupling agent, tackifier, antioxidant, The additives such as ultraviolet absorbing agent, heat stabilizer, hydrolysis preventing agent.
Adhesive composite (S) is preferably water system bonding agent.That is, adhesive composite (S) preferably keeps gradation composition molten The solution of Xie Yu aqueous solvent makes gradation composition be scattered in the dispersion (such as lotion) of aqueous solvent.
Viscosity at 25 DEG C of adhesive composite (S) be preferably 50mPasec hereinafter, more preferably 2mPasec with Upper and 30mPasec is hereinafter, further preferably 4mPasec or more and 20mPasec or less.If viscosity at 25 DEG C is super 50mPasec is crossed, then becomes difficult to equably be applied, it is possible to produce coating is uneven.Furthermore, it is possible to which pipeline occurs A problem that blocking.
Viscosity at 25 DEG C of adhesive composite (S) can be measured by E type viscosimeter.
PH at 25 DEG C of adhesive composite (S) is preferably 3 or more and 10 hereinafter, more preferably 4 or more and 9 or less. When the pH of adhesive composite (S) is less than 3, it is possible to be unable to fully show the water resistance of the 1st adhesive layer 15, be bonded When the pH of agent composition (S) is more than 10, the validity period of adhesive composite (S) is possible to shorten.
Portable pH meter (such as HORIBA system " D-51 ") can be used to measure for the pH of adhesive composite (S).
(3) polarizing film
Polarizing film 30 is the film with following function：Selectively transmit the linear polarization of a direction from natural light Light.It can be mentioned, for example：The iodine system polarizing film for making the iodine absorption as dichroism pigment, being oriented in polyvinyl alcohol resin film；Make Dichroic dye as dichroism pigment adsorbs, is oriented in the dyestuff system polarizing film of polyvinyl alcohol resin film；And coating The dichroic dye of lysotropic liquid crystal state is simultaneously orientated, the application type polarizing film of immobilization etc..These polarizing films are selectively It transmits the rectilinearly polarized light of a direction from natural light, absorb the rectilinearly polarized light of other direction, thus be referred to as and absorb Type polarizing film.
Polarizing film 30 is not limited to absorption-type polarizing film, or selectively transmits a direction from natural light Rectilinearly polarized light, reflect other direction rectilinearly polarized light reflection type polarizer or scatter other direction rectilinearly polarized light Scatter-type polarizing disc, from the viewpoint of visibility is excellent, preferred absorption-type polarizing film.Wherein, more preferably by poly- second The polyethenol series polarizing film that enol system resin is constituted further preferably makes the absorption of the dichroism pigments such as iodine, dichroic dye, takes To in the polyethenol series polarizing film of polyvinyl alcohol resin film, particularly preferably makes iodine absorption, is oriented in polyvinyl alcohol resin The polyethenol series polarizing film of film.
As the polyvinyl alcohol resin for constituting polyethenol series polarizing film, can be used polyvinyl acetate system resin soap Polyvinyl alcohol resin after change.As polyvinyl acetate system resin, in addition to the poly- second of the homopolymer as vinyl acetate Other than vinyl acetate, the copolymer etc. of vinyl acetate with the other monomers that can be copolymerized with it can be also enumerated.As can be with Other monomers of vinyl acetate copolymerization, can enumerate：Unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class and (methyl) acrylic amide with ammonium etc..
The saponification degree of polyvinyl alcohol resin is usually 85 moles of % or more and 100 mole of % hereinafter, preferably 98 rub You are % or more.Polyvinyl alcohol resin can be modified, for example, it is also possible to using through the modified polyvinyl formal of aldehydes or Polyvinyl acetal etc..The average degree of polymerization of polyvinyl alcohol resin is usually 1000 or more and 10000 hereinafter, preferably 1500 or more and 5000 or less.The average degree of polymerization of polyvinyl alcohol resin can be based on JIS K 6726：1994 find out.
By the product after such polyvinyl alcohol resin film, the reel film that can be used as polarizing film 30 is used.By poly- second The method of enol system resin film is not particularly limited, and well known method can be used.The thickness of polyethenol series reel film is for example It for 150 μm hereinafter, preferably 100 μm or less (such as 50 μm or less), and is 5 μm or more.
Polarizing film 30 can be manufactured by the inclusion of the method for following processes：Polyvinyl alcohol resin film is carried out uniaxial The process of stretching；Polyvinyl alcohol resin film is dyed with dichroism pigment, it is thus made to adsorb the work of dichroism pigment Sequence；The process that (crosslinking Treatment) is handled to the polyvinyl alcohol resin film for being adsorbed with dichroism pigment with boric acid aqueous solution； And the process washed after the processing using boric acid aqueous solution.
Polyvinyl alcohol resin film be uniaxially stretched can before the dyeing of dichroism pigment, with dyeing simultaneously or It is carried out after dyeing.In the case where being uniaxially stretched after dyeing, this be uniaxially stretched can boric acid processing before or boric acid It is carried out in processing.Alternatively, it is also possible to be uniaxially stretched in above-mentioned multiple stages.
When being uniaxially stretched, it can be stretched uniaxially between the different roller of peripheral speed, hot-rolling list also can be used Stretched to axis.It can be the dry type stretching stretched in an atmosphere in addition, being uniaxially stretched, be also possible to using water etc. Solvent makes the wet tensile stretched in the state of polyvinyl alcohol resin membrane swelling.Stretching ratio is usually 3 times or more and 8 Times or less.
As the method dyed with dichroism pigment to polyvinyl alcohol resin film, it can be mentioned, for example by the film immersion In the method etc. of the aqueous solution containing dichroism pigment.As dichroism pigment, iodine, dichroic organic dye can be used.It needs Illustrate, polyvinyl alcohol resin film preferably implements impregnation in water in advance before dyeing processing.
As the dyeing treatment using iodine, can enumerate polyvinyl alcohol resin film immersion in containing iodine and potassium iodide Aqueous solution method etc..The water that the content of iodine of the aqueous solution can be every 100 mass parts is 0.01 mass parts or more and 1 mass Part or less.The water that the content of potassium iodide can be every 100 mass parts is 0.5 mass parts or more and 20 below the mass.In addition, should The temperature of aqueous solution can be 20 DEG C or more and 40 DEG C or less.
On the other hand, it as the dyeing treatment using dichroic organic dye, can enumerate polyvinyl alcohol resin Film immersion is in the method etc. of the aqueous solution containing dichroic organic dye.Aqueous solution containing dichroic organic dye can contain sulphur The inorganic salts such as sour sodium are as dyeing assistant.The content of the dichroic organic dye of the aqueous solution can be the water of every 100 mass parts It is 1 × 10-4More than mass parts and 10 below the mass.The temperature of the aqueous solution can be 20 DEG C or more and 80 DEG C or less.
As using the boric acid processing method after the dyeing of dichroism pigment, can enumerate the polyethenol series tree after dyeing The method etc. that adipose membrane is impregnated in boracic aqueous acid.In the case where using iodine as dichroism pigment, the preferred boracic sour water Solution contains potassium iodide.The water that the amount of the boric acid of boracic aqueous acid can be every 100 mass parts is 2 mass parts or more and 15 matter Measure part or less.The amount of the potassium iodide of the aqueous solution can be every 100 mass parts water be 0.1 mass parts more than and 20 mass parts with Under.The temperature of the aqueous solution can be 50 DEG C or more, such as 50 DEG C or more and 85 DEG C or less.
Treated that polyvinyl alcohol resin film usually carries out washing process for boric acid.Washing process for example can be by by boric acid Treated, and polyvinyl alcohol resin film immersion carries out in water.The temperature of the water of washing process is usually 5 DEG C or more and 40 DEG C or less.Implement to be dried after washing, obtains polarizing film 30.
It is dried and air drier, far infra-red heater can be used to carry out.By making in the single side of the polarizing film 30 Adhesive composite (S) is used to be bonded (methyl) acrylic resin film 10 as protective film etc., so that polarization plates can be obtained. Thermoplastic resin film 20 can be bonded using adhesive composite in the another side of polarizing film 30.
In addition, other examples of the manufacturing method as polarizing film 30, it can be mentioned, for example Japanese Unexamined Patent Publication 2000-338329 The method recorded in bulletin, Japanese Unexamined Patent Publication 2012-159778 bulletin.In the method, on the surface of base material film, coating contains Resin layer is arranged in the solution of polyvinyl alcohol resin, then stretches to the stacked film formed by base material film and resin layer, Then implement dyeing processing, crosslinking Treatment etc., polarizer layer (polarizer layer) is formed by resin layer.About by base material film and polarization The polarizability stacked film that lamella is formed is bonded (methyl) acrylic resin film as protective film etc. on polarizer layer surface After 10, substrate film stripping is removed, can be made into the polarization plates constituted shown in Fig. 1.If exposed by the removing of base material film Polarizer layer surface be further bonded thermoplastic resin film, then become composition shown in Fig. 2 polarization plates.
The thickness of polarizing film 30 can be set as 40 μm, and (such as 20 μm hereinafter, be further 15 μm hereinafter, preferably 30 μm or less Hereinafter, being further 10 μm or less or 8 μm or less).According to Japanese Unexamined Patent Publication 2000-338329 bulletin, Japanese Unexamined Patent Publication 2012- The method recorded in No. 159778 bulletins can more easily manufacture the polarizing film 30 of film, it is easier to by the thickness of polarizing film 30 Be set as such as 20 μm or less, be further 15 μm or less, it is further be 10 μm or less or 8 μm or less.The thickness of polarizing film 30 Usually 2 μm or more.The thickness for reducing polarizing film 30 is advantageous to the slimming of polarization plates and then image display device.
(4) (methyl) acrylic resin film
(methyl) acrylic resin film 10 can be in unstretched film or film through uniaxial or biaxial stretching It is any.It is biaxial stretch-formed either along 2 draw directions simultaneously stretched while it is biaxial stretch-formed, be also possible to along 1st direction is stretched gradually biaxial stretch-formed further along the 2nd direction unlike this after stretching.
(methyl) acrylic resin film 10 either undertake protection polarizing film 30 effect protective film, be also possible to Phase difference film etc. has both the protective film of optical function.
(methyl) acrylic resin for constituting (methyl) acrylic resin film 10 is containing from (methyl) acrylic acid It is the polymer of the Component units of monomer, as (methyl) acrylic monomer, methacrylate and acrylate can be enumerated.
As methacrylate, can enumerate：Methyl methacrylate, ethyl methacrylate, methacrylic acid just, it is different Or the tert-butyl ester, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-Ethylhexyl Methacrylate, 2-Hydroxyethyl methacrylate etc..
As acrylate, can enumerate：Ethyl acrylate, acrylic acid just, the exclusive or tert-butyl ester, cyclohexyl acrylate, propylene Acid phenenyl ester, benzyl acrylate, 2-EHA, acrylic acid 2- hydroxyl ethyl ester etc..
(methyl) acrylic resin the Component units from (methyl) acrylic monomer either be only made of Polymer can also contain other Component units.
In 1 preferred embodiment, (methyl) acrylic resin contains methyl methacrylate or contains first Base methyl acrylate and methyl acrylate are as copolymer composition.
In 1 preferred embodiment, (methyl) acrylic resin can be for using methacrylate as mainly Monomer (containing 50 mass % or more) polymer, preferably methacrylate and other copolymer compositions copolymerization after being total to Polymers.
As other copolymer compositions other than above-mentioned acrylate, it can be mentioned, for example：
2- (hydroxymethyl) methyl acrylate, 2- (1- hydroxyethyl) methyl acrylate, 2- (hydroxymethyl) acrylic acid second Ester, 2- (hydroxymethyl) acrylic acid just, the acrylic acid hydroxy alkyl esters class such as the exclusive or tert-butyl ester；
The unsaturation acids such as methacrylic acid, acrylic acid；
The halogenated styrenes class such as chlorostyrene, bromstyrol；
The substituted phenylethylenes class such as vinyltoluene, α-methylstyrene；
The unsaturated nitriles such as acrylonitrile, methacrylonitrile；
The unsaturated acids anhydride such as maleic anhydride, citraconic anhydride；
The unsaturated acyls imines such as phenyl maleimide, N-cyclohexylmaleimide；
Equal monofunctional monomers.
Above-mentioned other monofunctional monomers both can only be used alone a kind, also may be two kinds or more.
As above-mentioned other copolymer compositions, polyfunctional monomer also can be used.
As polyfunctional monomer, it can be mentioned, for example：Ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) propylene Acid esters, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, nine ethylene glycol two (methyl) acrylic acid Ester, ten tetraethylene glycol two (methyl) acrylate etc. by two terminal hydroxyls of ethylene glycol or its oligomer (methyl) acrylic acid Monomer after esterification；
By the monomer after two terminal hydroxyls of propylene glycol or its oligomer (methyl) acroleic acid esterification；
Neopentyl glycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, butanediol two (methyl) acrylic acid Monomer after (methyl) acroleic acid esterification of the hydroxyl by dihydric alcohol of ester etc.；
By two terminal hydroxyls (methyl) acrylic acid of bisphenol-A, the alkylene oxide addition product of bisphenol-A or their halides Monomer after esterification；
By the monomer after the polyalcohols such as trimethylolpropane, pentaerythrite (methyl) acroleic acid esterification, and make (first Base) glycidyl acrylate monomer of the epoxy ring-opening addition after these terminal hydroxyls；
Make the epoxy ring-opening addition of (methyl) glycidyl acrylate in succinic acid, adipic acid, terephthalic acid (TPA), neighbour Monomer after phthalic acid, their binary acid or their alkylene oxide addition product etc. such as halides；
(methyl) aryl acrylate；The divinyl aromatic compounds such as divinylbenzene；Deng.
Wherein, it is preferable to use ethylene glycol dimethacrylate, tetraethylene glycol dimethylacrylate, neopentyl glycol diformazan Base acrylate.
(methyl) acrylic resin can be to be modified by the reaction between functional group possessed by copolymer (methyl) acrylic resin.As the reaction, it can be mentioned, for example：The carbomethoxy and 2- (hydroxyl first of (methyl) methyl acrylate Base) methyl acrylate hydroxyl macromolecular chain in separating methanol condensation reaction, the carboxyl of (methyl) acrylic acid and 2- (hydroxyl first Base) methyl acrylate hydroxyl macromolecular chain in dehydration condensation etc..
The glass transition temperature of (methyl) acrylic resin is preferably 80 DEG C or more and 160 DEG C or less.Vitrifying turns Temperature can be by adjusting the polymerization ratio of methacrylate ester monomer and acrylate monomer, the carbon chain length of respective ester group The type and polyfunctional monomer of degree and functional group possessed by them are controlled relative to the polymerization ratio of whole monomers.
As the means of the glass transition temperature for improving (methyl) acrylic resin, in high molecular main chain It is also effective for importing ring structure.Ring structure is preferably the heterocycles such as cyclic acid anhydride structure, cyclic imide structure and lactone structure Structure.Specifically, can enumerate：The cyclic acid anhydrides structures such as glutaric anhydride structure, succinic anhydride structure；Glutarimide structure, The cyclic imides structure such as succinimide structure；The lactones ring structure such as butyrolactone, valerolactone.
There is following tendency：The content for increasing the ring structure in main chain, then more can be improved (methyl) acrylic acid series tree The glass transition temperature of rouge.
Cyclic acid anhydride structure, cyclic imide structure can be imported by following methods：By making maleic anhydride, Malaysia acyl Imines etc. has the monomer copolymerization of cyclic structure and the method for importing；It is imported by dehydration separating methanol condensation reaction after polymerization The method of cyclic acid anhydride structure；The method etc. for making amino-compound reaction import cyclic imide structure.
Resin (polymer) with lactone ring structure can obtain by the following method：Preparation has hydroxyl on macromolecular chain After the polymer of base and ester group, by heating, as needed in the presence of the catalyst such as organic phosphorus compound, make obtained poly- The hydroxyl and ester group cyclizative condensation in object are closed, to form lactone ring structure.
(methyl) acrylic resin and (methyl) acrylic resin film 10 formed by it can according to need containing Additive.As additive, it can be mentioned, for example：Lubricant, antiblocking agent, heat stabilizer, antioxidant, ultraviolet absorbing agent, Antistatic agent, photostabilizer, impact modifier, surfactant etc..
As ultraviolet absorbing agent, can enumerate：Salicylate based compound, benzophenone based compound, enumerate BTA system Compound, cyanoacrylate based compound, nickel complex salt based compound etc.
From viewpoints such as the film formation property of film, the impact resistances of film, (methyl) acrylic resin can be containing as anti- The acrylic rubber particle of impact modifier.Acrylic rubber particle is to make the elastomeric polymer based on acrylate For the particle of neccessary composition, the rubber particles of the single layer structure substantially only formed by the elastomeric polymer can be enumerated, by the bullet The rubber particles of the multilayered structure of a layer are made in property polymer.
As the example of above-mentioned elastomeric polymer, can enumerate has and can be copolymerized with it by principal component, copolymerization of acrylate Other vinyl monomers and cross-linkable monomer crosslinking elastocopolymer.
As become elastomeric polymer principal component acrylate, it can be mentioned, for example：Methyl acrylate, acrylic acid second The carbon number of the alkyl such as ester, butyl acrylate, 2-EHA is the acrylate of 1 or more and 8 degree below, preferably The alkyl acrylate of alkyl with 4 or more carbon number.
As above-mentioned intramolecular can be enumerated with 1 polymerization with other vinyl monomers of acrylic ester copolymer More specifically the compound of property carbon-to-carbon double bond can be enumerated：The methacrylates such as methyl methacrylate；The virtues such as styrene Fragrant race's vinyl compound；Vinyl cyanide compounds such as acrylonitrile etc..
As cross-linkable monomer, the chemical combination of bridging property of the intramolecular at least two polymerism carbon-to-carbon double bond can be enumerated More specifically object can be enumerated：The polyalcohols such as ethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate (methyl) esters of acrylic acid；The alkenyl esters of (methyl) allyl acrylate etc. (methyl) acrylic acid；Divinylbenzene etc..
The average diameter of acrylic rubber particle is usually 50nm or more and 400nm or less.
The content of acrylic rubber particle is usually 5 mass parts relative to 100 mass parts of (methyl) acrylic resin Above and 50 below the mass.
(methyl) acrylic resin for being mixed with acrylic rubber particle can be commercially available product, can enumerate " HT55X " (trade name Sumitomo Chemical (strain)) etc..
(methyl) acrylic resin film 10 can be comprising without rubber particles (methyl) acrylic resin layer, With the laminated body of the layer formed by (methyl) acrylic resin containing rubber particles.
The thickness of (methyl) acrylic resin film 10 be usually 5 μm or more and 200 μm hereinafter, preferably 10 μm or more and 120 μm hereinafter, more preferably 10 μm or more and 85 μm hereinafter, further preferably 15 μm or more and 65 μm or less.
It should be noted that preferably its integral thickness exists in the case where (methyl) acrylic resin film 10 is multilayer In above range.
(methyl) acrylic resin film 10 can have in its outer surface (surface with 15 opposite side of the 1st adhesive layer) The surface-treated layers (overlay) such as standby hard conating, antiglare layer, anti-reflection layer, light diffusion layer, antistatic layer, stain-proofing layer, conductive layer.
From the viewpoint of improving adhesion, the binding face of (methyl) acrylic resin film 10 can be carried out at saponification The surface modification treatments such as reason, corona treatment, sided corona treatment, primary coat processing.About surface modification treatment, (first can replace Base) acrylic resin film 10 binding face or together with the binding face, and the binding face of polarizing film 30 is carried out.,
In the case where (methyl) acrylic resin film and the 1st adhesive layer contact, (methyl) acrylic resin film The face contacted with the 1st adhesive layer water contact angle be preferably 80 ° hereinafter, more preferably 70 ° hereinafter, further preferably 65 ° or less.The lower limit of the water contact angle in the face contacted with the 1st adhesive layer of (methyl) acrylic resin film does not limit especially System, usually 20 ° or more.
If the face contacted with the 1st adhesive layer of (methyl) acrylic resin film water contact angle be 80 ° hereinafter, if partially The adhesion shaken between piece and (methyl) acrylic resin film is not only good under hygrothermal environment (hot and humid environment), in room Also become good under warm (such as 23 DEG C, relative humidity 55%).
For the water contact angle in the face contacted with the 1st adhesive layer of (methyl) acrylic resin film, for example, can lead to It crosses and implements above-mentioned surface modification treatment and obtain desired water contact angle.
(5) thermoplastic resin film
Thermoplastic resin film 20 is preferably the thermoplastic resin film with translucency.As thermoplastic resin film, for example, can To be poly- by chain polyolefin-based resins (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system resin (norbornene resin etc.) etc. Olefin-based resin；The cellulose esters such as triacetyl cellulose, diacetyl cellulose system resin；Polyethylene terephthalate gathers The polyester based resin of (ethylene naphthalate), polybutylene terephthalate (PBT) etc.；Polycarbonate-based resin；(methyl) propylene Acid system resin；Or the film of the formation such as their mixture, copolymer.
In the case where thermoplastic resin film 20 is (methyl) acrylic resin film, can quote about (methyl) acrylic acid The above-mentioned record of resin film 10.
Thermoplastic resin film 20 can be unstretched any one of film or the film through uniaxial or biaxial stretching. It is biaxial stretch-formed either along 2 draw directions simultaneously stretched while it is biaxial stretch-formed, be also possible to along the 1st direction It is stretched after stretching further along the 2nd direction unlike this gradually biaxial stretch-formed.
Thermoplastic resin film 20 either undertake protection polarizing film 30 effect protective film, be also possible to phase difference film Etc. the protective film for having both optical function.
As chain polyolefin-based resins, other than the homopolymer of the chain olefins such as polyvinyl resin, acrylic resin, The copolymer formed by chain olefin of more than two kinds can also be enumerated.
Cyclic polyolefin hydrocarbon system resin is to contain general name of the cyclic olefin as the resin of polymerized unit, the cyclic olefin with Norbornene, tetracyclododecane (alias：Dimethano octahydro naphthalene) or they derivative be typical example.As cyclic polyolefin It is resin, can enumerates：The open loop (co) polymer and its hydride of cyclic olefin, the addition polymers of cyclic olefin, cyclic olefin with The copolymer of the chain olefins such as ethylene, propylene or the aromatic compound with vinyl and with unsaturated carboxylic acid or its spread out The modification (co) polymer etc. that biology is modified them.
Wherein, it is preferable to use using the orbornene-baseds monomers such as norbornene, polycyclic orbornene-based monomer as ring The norbornene resin of shape alkene.
Cellulose esters system resin is at least part of the hydroxyl in cellulose by the resin of acid esterification, or one Part is by acid esterification, a part by other Esterification mixed esters.Cellulose esters system resin is preferably acetyl fibre prime system tree Rouge.
As acetyl fibre prime system resin, can enumerate：Triacetyl cellulose, diacetyl cellulose, cellulose-acetate propionate, Cellulose acetate-butyrate etc..
Polyester based resin be with resin ester bond, other than above-mentioned cellulose esters system resin, usually by polybasic carboxylic acid or The condensation polymer of its derivative and polyalcohol is formed.
As polyester based resin, can enumerate：Polyethylene terephthalate, polybutylene terephthalate (PBT), poly- naphthalene Naphthalate, polypropylene terephthalate, polytrimethylene naphthalate, gathers at polybutylene naphthalate Terephthalic acid (TPA) cyclohexanedimethanoester ester, poly- naphthalenedicarboxylic acid cyclohexane dicarboxylates alcohol etc..
Wherein, from viewpoints such as engineering properties, solvent resistance, scratch resistance, costs, it is preferable to use poly terephthalic acid Glycol ester.Polyethylene terephthalate refers to 80 moles of % or more of repetitive unit by ethylene glycol terephthalate structure At resin, also may include the Component units from other copolymer compositions.
As other copolymer compositions, can enumerate：Dicarboxylic acid component, diol component.
As dicarboxylic acid component, can enumerate：M-phthalic acid, 4,4 '-dicarboxylate biphenyls, 4,4 '-benzophenonedicarboxylic acids, Bis- (4- carboxyl phenyl) ethane, adipic acid, decanedioic acid, 5-sodium sulfo isophthalate, Isosorbide-5-Nitrae-dicarboxyl butylcyclohexane etc..
As diol component, can enumerate：Propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, bisphenol-A Ethylene oxide adduct, polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc..
Dicarboxylic acid component, diol component also can according to need and be respectively combined two or more use.
Alternatively, it is also possible to together with above-mentioned dicarboxylic acid component, diol component and and with P-hydroxybenzoic acid, to '-hydroxyethoxy The hydroxycarboxylic acids such as yl benzoic acid, beta-hydroxy ethoxybenzoic acid.
It, can also be on a small quantity using with amido bond, urethane bond, ehter bond, carbonic acid ester bond as other copolymer compositions Deng dicarboxylic acid component and/or diol component.
Polycarbonate-based resin is the polyester formed by carbonic acid and glycol or bis-phenol.Wherein, from heat resistance, weatherability and resistance to From the perspective of acidity, it is preferable to use with the aromatic copolycarbonate of diphenyl alkane in strand.
As polycarbonate, can enumerate by bis- (4- hydroxy phenyl) propane (alias bisphenol-A) of 2,2-, bis- (the 4- hydroxyls of 2,2- Phenyl) butane, 1,1- bis(4-hydroxyphenyl)cyclohexane, bis- (4- hydroxy phenyl) iso-butanes of 1,1-, bis- (the 4- hydroxy benzenes of 1,1- Base) polycarbonate derived from the bis-phenols such as ethane.
Thermoplastic resin film 20 is preferably cellulose esters resin film or cyclic polyolefin resin film.
Thermoplastic resin film 20 can contain additive as needed.As additive, it can be mentioned, for example：It is lubricant, anti-stick Even agent, heat stabilizer, antioxidant, ultraviolet absorbing agent, antistatic agent, photostabilizer, impact modifier, surfactant etc..
As ultraviolet absorbing agent, can enumerate：Salicylate based compound, benzophenone based compound, enumerate BTA system Compound, cyanoacrylate based compound, nickel complex salt based compound etc..
In the case where polarization plates are applied to the image display devices such as liquid crystal display device, inhaled by the way that ultraviolet light will be contained It receives the thermoplastic resin film 20 of agent or (methyl) acrylic resin film 10 containing ultraviolet absorbing agent is configured at image and shows The visuognosis side of element (such as liquid crystal cells), so as to inhibit the deterioration caused by ultraviolet light of image-displaying member.
The thickness of thermoplastic resin film 20 be usually 5 μm or more and 200 μm hereinafter, preferably 10 μm or more and 120 μm with Under, more preferably 10 μm or more and 85 μm or less, be more preferably 15 μm or more and 60 μm or less.Thermoplastic resin film 20 Thickness can be 50 μm or less, or 40 μm or less.Reduce the thickness of thermoplastic resin film 20 to polarization plates and then image The slimming of display device is advantageous.
Thermoplastic resin film 20 can have hard painting in its outer surface (surface with 25 opposite side of the 2nd adhesive layer) The surface-treated layers such as layer, antiglare layer, anti-reflection layer, light diffusion layer, antistatic layer, stain-proofing layer, conductive layer (overlay).
From the viewpoint of improving adhesion, can to the binding face of thermoplastic resin film 20 carry out saponification process, etc. from The surface modification treatments such as daughter processing, sided corona treatment, primary coat processing.About surface modification treatment, thermoplastic resin can replace The binding face of film 20 or together with the binding face, and the binding face of polarizing film 30 is carried out.
In the case where thermoplastic resin film 20 is cellulose acetate resin film, from the viewpoint of improving adhesion, It is preferred that carrying out saponification process.As saponification process, the side for being impregnated in the aqueous alkali of sodium hydroxide, potassium hydroxide etc can be enumerated Method.
(6) the 2nd adhesive layers
The bonding agent for forming the 2nd adhesive layer 25 can be above-mentioned adhesive composite (S), be also possible to unlike this Other adhesive composites.2nd adhesive layer 25 is preferably the adhesive layer formed by adhesive composite (S).
2nd adhesive layer 25 can be the solidified material layer of adhesive composite.
In the case where the 1st adhesive layer 15 and the 2nd adhesive layer 25 are formed by adhesive composite (S), these bondings Agent composition both can be same composition, or difference composition.
As other adhesive composites, can enumerate：The well known water system for making bonding agent ingredient be dissolved or dispersed in water is viscous Connect agent and the well known active energy ray-curable bonding agent containing active energy ray-curable compound etc..
As water system adhesive composite, can enumerate：By the bonding agents such as polyvinyl alcohol resin, carbamate resins at Divide the water system adhesive composite for being dissolved or dispersed in water.
To improve cementability, the water system bonding agent containing polyvinyl alcohol resin can contain polyaldehyde, melamine series The curability compositions such as compound, zirconia compound, zinc compound, glyoxal, glyoxal derivative, water-soluble epoxy resin, Crosslinking agent.
As the water system bonding agent containing carbamate resins, can enumerate containing Polyester ionomer type carbamate The water system bonding agent of resin and the compound with glycidoxypropyl.Polyester ionomer type carbamate resins refer to： Belong to the carbamate resins with polyester backbone and in the ammonia for being wherein imported with a small amount of ionic ingredient (hydrophilic component) Carbamate resin.
Active energy ray-curable bonding agent is by irradiating ultraviolet light, visible light, electron beam, X-ray isoreactivity energy Ray is measured to carry out cured bonding agent.When using active energy ray-curable bonding agent, the 2nd adhesive layer 25 is viscous for this Connect the solidified material layer of agent.
Active energy ray-curable bonding agent can be for containing carrying out cured epoxy by cationic polymerization Bonding agent of the object as curability composition is closed, the ultraviolet light for preferably containing the epoxy compound as curability composition is solid The property changed bonding agent.Epoxy compound refers to compound of the intramolecular with averagely 1 or more, preferably 2 or more epoxy groups. Epoxy compound can both be used only a kind, and also two or more kinds may be used.
As epoxy compound, can enumerate：Make hydrogenated epoxy system obtained from epichlorohydrin and ester ring type polyol reaction Compound (glycidyl ether of the polyalcohol with ester ring), wherein the ester ring type polyalcohol is by fragrance The aromatic rings of race's polyalcohol carries out obtained from hydrogenation；More shrinks of aliphatic polyol or its alkylene oxide adducts are sweet The aliphatic epoxies based compound such as oily ether；Ring as the epoxy group being bonded with ester ring in the molecule with 1 or more Ester ring type epoxy compound of oxygen based compound etc..
For active energy ray-curable bonding agent, as curability composition, it can contain free-radical polymerised (methyl) acrylic compounds include to replace above-mentioned epoxy compound or come together with above-mentioned epoxy compound. As (methyl) acrylic compounds, can enumerate：(methyl) third of the intramolecular with 1 or more (methyl) acryloxy Olefin(e) acid ester monomer；As make it is of more than two kinds containing functional compounds reaction obtained from, intramolecular have at least two (methyl) (methyl) acrylate oligomer of acryloxy etc. contains (methyl) acryloyl-oxy based compound.
Contain in active energy ray-curable bonding agent through cationic polymerization and carries out cured epoxy compound In the case where as curability composition, light cationic polymerization initiator is preferably comprised.As light cationic polymerization initiator, can arrange Citing is such as：Aromatic diazonium salt；The salt such as aromatic iodonium salts, aromatic series sulfonium salt；Iron-allene complex object etc..
Contain the free-radical polymerised ingredients such as (methyl) acrylic compounds in active energy ray-curable bonding agent In the case where, preferably comprise optical free radical polymerization initiator.As optical free radical polymerization initiator, it can be mentioned, for example：Acetophenone Series initiators, benzophenone series initiators, benzoin ether series initiators, thioxanthones series initiators, xanthone, Fluorenone, camphorquinone, Benzaldehyde, anthraquinone etc..
Polarization plates may include adhesive phase to replace the 2nd adhesive layer 25.I.e., it is possible to across adhesive phase by thermoplasticity Resin film 20 fits in polarizing film 30.About the adhesive phase, the aftermentioned record about adhesive phase can be quoted.
(7) manufacture of polarization plates
By the one side in polarizing film 30 across 15 lamination adhesive of the 1st adhesive layer (methyl) acrylic resin film 10, The polarization plates that composition shown in FIG. 1 can be obtained, by the another side in polarizing film 30 across the 2nd further stacking of adhesive layer 25 It is bonded thermoplastic resin film 20, the polarization plates of composition shown in Fig. 2 can be obtained.
In the case where manufacture has the polarization plates of both (methyl) acrylic resin film 10 and thermoplastic resin film 20, These films both can also can carry out lamination adhesive by the film to two sides simultaneously in each single side by lamination adhesive by stages.
1st adhesive layer 15 and/or the 2nd adhesive layer 25 can be the solidified material layer of adhesive composite.
As the method for being bonded polarizing film 30 and (methyl) acrylic resin film 10, method can be listed below：It will glue Agent composition (S) is met coated on any one or this two in binding face of polarizing film 30 and (methyl) acrylic resin film 10 Another binding face is laminated in person on it, is bonded with such as doubling roller etc. from upper and lower pressing.
It can use such as scraper, bar, die coating machine, comma coating machine, intaglio plate in the coating of adhesive composite (S) to apply The various application patterns such as cloth machine.Alternatively, it is also possible to being such as under type：On one side by polarizing film 30 and (methyl) acrylic resin film 10 by the binding face of the two become inside in the way of continuously supplied, make on one side adhesive composite (S) the two it Between be cast.
After being bonded polarizing film 30 and (methyl) acrylic resin film 10, preferably to viscous comprising polarizing film the 30, the 1st The laminated body for connecing oxidant layer 15 and (methyl) acrylic resin film 10 implements heat treatment.The temperature of heat treatment is such as 40 DEG C Above and 100 DEG C hereinafter, preferably 50 DEG C or more and 90 DEG C or less.By heat treatment, adhesive composite layer can remove Contained solvent.In addition, in the case where adhesive composite is the adhesive composite of curability, by the heat treatment, Curing cross-linking reaction can be made to carry out.
It is bonding with thermoplastic resin film 20 that above adhering method also can be applied to polarizing film 30.
Using active energy ray-curable bonding agent, adhesive composite layer is being carried out as needed After drying, active energy beam is irradiated, solidifies adhesive composite layer.
As long as the light source for irradiating active energy beam can generate ultraviolet light, electron beam, X-ray etc..Especially It is suitable for using such as low pressure mercury lamp, the medium pressure mercury lamp, high-pressure sodium lamp, ultra high pressure mercury below wavelength 400nm with the distribution that shines Lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp etc..
The 1st adhesive layer 15 formed by adhesive composite (S) with a thickness of for example, 10nm or more and 10 μm hereinafter, Preferably 20nm or more and 5 μm hereinafter, more preferably 30nm or more and 1 μm hereinafter, further preferably 40nm or more and 500nm Below.It also can have the thickness with this with degree by the adhesive layer that above-mentioned well known water system bonding agent is formed.
The adhesive layer formed by active energy ray-curable bonding agent with a thickness of for example, 10nm or more and 20 μm Hereinafter, preferably 100nm or more and 10 μm hereinafter, more preferably 500nm or more and 5 μm or less.
The thickness of 1st adhesive layer 15 and the 2nd adhesive layer 25 both can be the same or different.
(8) other constituent elements of polarization plates
(8-1) optical functional film
Polarization plates can have for assigning desired optical function, other optical functionals in addition to polarizing film 30 Film, suitable an example are phase difference film.
As described above, (methyl) acrylic resin film 10 and/or thermoplastic resin film 20 can also be used as phase simultaneously Poor film, but can also except these films separately laminated phase-difference film.In the latter case, phase difference film can be across bonding Oxidant layer, adhesive layer and the outer surface for being laminated in (methyl) acrylic resin film 10 and/or thermoplastic resin film 20.
As phase difference film, can enumerate：The birefringence film being made of the stretched film of the thermoplastic resin with translucency； Dish-like liquid crystal or nematic crystal are oriented fixed film；The film etc. of above-mentioned liquid crystal layer is formed on base material film.
Base material film is usually the film formed by thermoplastic resin, and an example of thermoplastic resin is the fibers such as triacetyl cellulose Plain ester system resin.
The example for the other optical functional films (optical component) that may include in polarization plates is light collecting plate, brightness enhancement film, anti- Penetrate layer (reflectance coating), Transflective layer (Transflective film), light diffusion layer (optical diffusion film) etc..They are usually in polarization plates It is set in the case where polarization plates to be configured at the back side (backlight side) of liquid crystal cells.
The purpose of light collecting plate is for light path control and used, can be set up for prism array piece, lens array sheet, dot matrix Piece (Japanese：De Star ト Fu Let シ ー ト) etc..
Brightness enhancement film is used to improve the brightness for the liquid crystal display device for applying polarization plates.Specifically, can arrange It lifts：So that reflectivity is generated anisotropic mode according to the film stacking different from each other of the anisotropy by multiple refractive index and set The alignment films of cholesteryl liquid crystal polymer or its aligned liquid-crystal layer are supported on base material film by the reflective polarizing light separate sheet of meter Circularly polarizing separation sheet etc..
Reflecting layer, Transflective layer, light diffusion layer are in order to which reflection-type, Semitransmissive, expansion is made in polarization plates respectively It dissipates the optical component of type and is arranged.The polarization plates of reflection-type be used to make the reflection of generation incident light from visuognosis side and carry out The liquid crystal display device of the type of display, it is convenient to omit the light sources such as backlight, therefore easily it is thinned liquid crystal display device.Half transmitting The liquid crystal display for the type that the polarization plates of type be used to be shown at bright place as reflection-type, in the dark with light from a backlight Device.In addition, the polarization plates of diffused such as be used to assign light diffusing and inhibit ripple undesirable liquid crystal display device at the display. Reflecting layer, Transflective layer and light diffusion layer can be formed using well known method.
(8-2) adhesive phase
Polarization plates of the invention can contain adhesive phase.As adhesive phase, can enumerate for polarization plates to be fitted in liquid The adhesive phase of the image-displaying members such as brilliant unit or other optical components.For the adhesive phase, composition shown in Fig. 1 Polarization plates in can be laminated in the outer surface of polarizing film 30, (methyl) third can be laminated in the polarization plates of composition shown in Fig. 2 The outer surface of olefin(e) acid resin film 10 or thermoplastic resin film 20.
As adhesive used in adhesive phase, it can be used with (methyl) acrylic resin, organic silicon-type resin, gather Ester system resin, polyurethane series resin, polyether system resin etc. are the adhesive of basic polymer.Wherein, from the transparency, bonding force, The viewpoints such as reliability, weatherability, heat resistance, secondary workability are set out, preferably (methyl) acrylic adhesive.
In (methyl) acrylic adhesive, 25 DEG C or less are preferably reached according to glass transition temperature, is more preferably up to To 0 DEG C of mode below, cooperate have methyl, ethyl, just, (methyl) propylene of the alkyl below of carbon numbers 20 such as exclusive or tert-butyl (methyl) acrylic monomer containing functional group such as acid alkyl ester and (methyl) acrylic acid, (methyl) hydroxy-ethyl acrylate and (methyl) acrylic resin that obtain, weight average molecular weight is 100,000 or more, is useful as basic polymer.
Adhesive phase is formed in polarization plates can for example be carried out by following manner：Adhesive composition is set to dissolve or divide It dissipates in organic solvents such as toluene, ethyl acetate, prepares adhesive liquid, it is viscous to be formed to be applied directly to the object surface of polarization plates The mode of mixture layer；Polarization is transferred them to sheet-shaped composite adhesives layer on the isolation film for implementing demoulding processing in advance The mode etc. of the object surface of plate.
The thickness of adhesive phase determines according to its bonding force etc., 1 μm or more and 50 μm of ranges below be it is suitable, it is excellent It is selected as 2 μm or more and 40 μm or less.
Polarization plates may include above-mentioned isolation film.Isolation film can be polyethylene-based resins, polypropylene such as polyethylene etc. poly- third Polyester based resins such as alkene system resin, polyethylene terephthalate etc. are formed by film.Wherein, preferred poly terephthalic acid second The stretched film of diol ester.
Adhesive phase can contain as needed glass fibre, bead, resin bead, by metal powder or other inorganic powder shapes At filler, pigment, colorant, antioxidant, ultraviolet absorbing agent, antistatic agent etc..
As antistatic agent, it can be mentioned, for example：Ionic compound, electrically conductive microparticle, electroconductive polymer etc., preferably make Use ionic compound.
The cation constituent for constituting ionic compound can be inorganic cation and be also possible to organic cation.
As organic cation, can enumerate：Pyridylium, glyoxaline cation, ammonium cation, sulfonium cation, Phosphonium Cation, piperidines cation, pyrrolidines cation etc., as inorganic cation, can enumerate lithium ion, potassium ion etc..
On the other hand, as the anion component for constituting ionic compound, it can be inorganic anion and be also possible to have Machine anion preferably comprises the anion of fluorine atom from providing antistatic property excellent ionic compound aspect Ingredient.As the anion component containing fluorine atom, can enumerate：Hexafluoro-phosphate radical anion [(PF6 -)], bis- (fluoroform sulphurs Acyl group) imide anion [(CF3SO2)2N-] anion, bis- (fluorosulfonyl) imide anion [(FSO2)2N-] anion Deng.
(8-3) protecting film
It (is in typical case (methyl) acrylic resin film that polarization plates of the invention, which may include for protecting its surface, 10 or thermoplastic resin film 20 surface) protecting film.Polarization plates are being fitted in into such as image-displaying member, other optics structures After part, protecting film is peeled off together into removing together with its adhesive phase.
Protecting film is for example made of the adhesive phase of base material film and stacking thereon.For adhesive phase, quote above-mentioned It describes.
The resin for constituting base material film can be for for example：Poly- the third of the polyethylene-based resin of polyethylene etc, polypropylene The polyester based resin of alkene system resin, polyethylene terephthalate, polyethylene naphthalate etc, polycarbonate-based tree The thermoplastic resins such as rouge.The preferably polyester based resins such as polyethylene terephthalate.
<Liquid crystal display panel and liquid crystal display device>
Polarization plates of the invention can be used for liquid crystal display panel and liquid crystal display device.Liquid crystal display panel includes liquid crystal cells and configuration Polarization plates in its two sides.Liquid crystal display device includes liquid crystal display panel and backlight.
Polarization plates of the invention are configured in the one or two sides of liquid crystal cells.The attaching of polarization plates and liquid crystal cells can make Use adhesive phase.
Liquid crystal cells can be arbitrary liquid crystal cells, for example, can be used using film transistor type as the active square of representative The driving liquid crystal cells of battle array, using various liquid crystal lists such as the super-twist nematic liquid crystal cells driving as the simple matrix of representative Member forms liquid crystal display panel and liquid crystal display device.Being set to the polarization plates on the two sides of liquid crystal cells both can be identical or not Together.
Embodiment
Embodiment described below is further elaborated with the present invention, but the present invention is not limited by these examples.In example, table % and the part for showing content or usage amount, are then quality criteria as long as no special declaration.
In table 1 , Han oxazolinyl polymer (A) and acetoacetyl modified polyvinyl alcohol (B) be simply denoted as respectively (A), (B)。
(Production Example 1：The production of (methyl) acrylic resin film)
As (methyl) acrylic resin, prepare methyl methacrylate/acrylic acid methyl esters=96%/4% (quality Than) copolymer.In addition, preparing the following elastomer particle for belonging to three-decker and to as intermediate as rubber particles The rubber particles that average grain diameter until the elastomer of layer is 240nm：Innermost layer is by using on a small quantity methyl methacrylate Allyl methacrylate and the polymer of hard being polymerize are formed；Middle layer by using butyl acrylate as principal component, The soft elastomer additionally being polymerize using styrene and a small amount of allyl methacrylate is formed；Outermost layer The polymer for the hard being polymerize by having used a small amount of ethyl acrylate to methyl methacrylate is formed.It needs Bright, in the rubber particles, total quality of innermost layer and middle layer is whole 70% of particle.
By above-mentioned 68.5 mass % of (methyl) acrylic resin, 29.6 mass % of above-mentioned rubber particles and Co., Ltd. Ultraviolet absorbing agent " ADEKA STAB LA31 " 1.9 mass % of ADEKA corporation are mixed with super mixer, use twin-screw Extruder melting mixing, is made particle.The particle is put intoIn single screw extrusion machine, it is by set temperature 275 DEG C of T-die is squeezed out, sandwich the two sides of film with two polishing rolls with mirror surface and is cooled down, obtain with a thickness of 60 μm (methyl) acrylic resin film.
(Production Example 2：The production of polarizing film)
It is about 2400 by average degree of polymerization, saponification degree is 99.9 moles of % or more and with a thickness of the leaching of 60 μm of polyvinyl alcohol film Then stain is impregnated in the aqueous solution that iodine/potassium iodide/water mass ratio is 0.02/2/100 in 30 DEG C of pure water at 30 DEG C In.Then, it is impregnated at 56.5 DEG C in the aqueous solution that potassium iodide/boric acid/water mass ratio is 12/5/100.Next, with 8 DEG C pure water, be then dried with 65 DEG C, obtain iodine gas absorption quantity in the polarizing film of polyvinyl alcohol.It stretches mainly in iodine Dyeing and boric acid processing process in carry out, total stretching ratio be 5.5 times, obtained polarizing film with a thickness of 23 μm.
<Embodiment 1>
(1) preparation of adhesive composite
Ingredient shown in table 1 is mixed together with the pure water as solvent using use level shown in table 1, to prepare Adhesive composite (bonding agent aqueous solution).The unit of the use level of each ingredient shown in table 1 is mass parts, the cooperation of each ingredient Amount is the amount to be converted with solid component.(solid component described herein is dense for the solid component concentration of obtained adhesive composite Degree refers to total concentration of the ingredient (A), (B) and (C) of adhesive composite.Also identical in other examples.) it is set as 2.0 matter Measure %.
(2) production of polarization plates
Sided corona treatment is implemented to the single side of (methyl) acrylic resin film made in above-mentioned Production Example 1, for (the first Base) acrylic resin film the face for implementing sided corona treatment and the triacetyl cellulose for implementing saponification process (TAC) film (trade name " KC2UAW " of Konica Minolta (strain) system, thickness：25 μm) single side, with rod coaters apply above-mentioned (1) in system Standby adhesive composite.In such a way that adhesive composite layer becomes polarizing film side, made in above-mentioned Production Example 2 inclined (methyl) acrylic resin film is laminated in the one side of vibration piece, and the TAC film after another side stacking saponification is had (methyl) third The laminated body that olefin(e) acid resin film/adhesive composite layer/polarizing film/adhesive composite layer/TAC film layer is constituted.Make this Laminated body passes through from air drier, thus carries out the heat treatment of 80 DEG C, 300 seconds, then cures 72 hours at 25 DEG C, To make polarization plates.
(3) evaluation of the adhesion after humid heat treatment
According to polarization plates, (methyl) obtained in following evaluations above-mentioned (2) between acrylic resin film and polarizing film Humid heat treatment after adhesion.
Corona discharge Treatment is implemented to the surface of (methyl) acrylic resin film of polarization plates, in the Corona discharge Treatment Face paste closes (methyl) acrylic adhesive piece, and the polarization plates with adhesive phase are made.From the obtained polarization with adhesive phase Plate determines the test film that width is 25mm, length is about 200mm, by its adhesive phase face paste together in soda-lime glass substrate.
The test film is taken care of 48 hours in the environment of 85 DEG C of temperature, relative humidity 85%, then in 23 DEG C of temperature, phase It is late to taking care of one in the environment of humidity 55%.
Then, the blade of cutter is made to enter (methyl) between acrylic resin film and polarizing film, alongst 30mm is removed from end, by released part universal tensile testing machine (trade name " AG-1 " of (strain) Shimadzu Seisakusho Ltd.) Clip portion is clamped.For the test film of the state, in the atmosphere of 23 DEG C of temperature and relative humidity 55%, it is based on JIS K 6854-2：1999 " bonding agents-removing adhesive strength test method-the 2：180 degree removing " is with clip movement speed 300mm/ Minute carries out 180 degree disbonded test, finds out the Average peel force of the 170mm length in addition to the 30mm in clip portion, as Touch power.Show the result in table 1.In table 1, " ※ " is indicated：Since contiguity power is high, when carrying out above-mentioned disbonded test, occurring Before the removing of the interface of (methyl) acrylic resin film and polarizing film, (methyl) acrylic resin film or polarizing film are Fracture.
In addition, the measured value based on obtained contiguity power, according to 3 Phase Evaluations (methyl) acrylic acid series tree below The adhesion after humid heat treatment between adipose membrane and polarizing film.Result is shown in table 1 together.
A：Touching power is more than 5N.
B：Touch power in the range of 1~5N
C：Touch power and is less than 1N.
<Embodiment 2~37, comparative example 1>
By gradation composition and their use level according to being changed like that shown in table 1, in addition to this, with embodiment 1 It is prepared as adhesive composite.
The solid component concentration of obtained adhesive composite is shown in table 1 together.
In addition, making polarization plates similarly to Example 1 other than using obtained adhesive composite, measure Contiguity power after the humid heat treatment of (methyl) between acrylic resin film and polarizing film simultaneously evaluates the adhesion after humid heat treatment. Show the result in table 1.
[table 1]
The details of each ingredient shown in table 1 is as follows.
a1：The trade name " EPOCROS WS-300 " of Nippon Shokubai Co., Ltd (has 2- oxazolinyl as side chain Aqueous solution, the solid component concentration of Han oxazolinyl acrylic acid series polymeric compounds：10 mass %, oxazoline values (theoretical value)： 130g solid/eq., oxazoline base unit weight (theoretical value)：7.7mmol/g, solid, number-average molecular weight：4×104, Weight-average molecular Amount：12×104)〕
a2：The trade name " EPOCROS WS-500 " of Nippon Shokubai Co., Ltd (has 2- oxazolinyl as side chain Solution (the solvent of Han oxazolinyl acrylic acid series polymeric compounds：Water and 1- methoxy-2-propanol), solid component concentration：39 matter It measures %, oxazoline value (theoretical value)：220g solid/eq., oxazoline base unit weight (theoretical value)：4.5mmol/g, solid, number are equal Molecular weight：2×104, weight average molecular weight：7×104)〕
a3：The trade name " EPOCROS WS-700 " of Nippon Shokubai Co., Ltd (has 2- oxazolinyl as side chain Aqueous solution, the solid component concentration of Han oxazolinyl acrylic acid series polymeric compounds：25 mass %, oxazoline values (theoretical value)： 220g solid/eq., oxazoline base unit weight (theoretical value)：4.5mmol/g, solid, number-average molecular weight：2×104, Weight-average molecular Amount：4×104)〕
b1：The trade name " GOHSENX Z-100 " of the Nippon Synthetic Chemical Industry Co., Ltd is (acetoacetyl modified poly- Vinyl alcohol, average degree of polymerization：500, saponification degree：98.5 moles of % or more)
b2：The trade name " GOHSENX Z-200 " of the Nippon Synthetic Chemical Industry Co., Ltd is (acetoacetyl modified poly- Vinyl alcohol, average degree of polymerization：1100, saponification degree：99.0 moles of % or more)
b3：The trade name " GOHSENX Z-300 " of the Nippon Synthetic Chemical Industry Co., Ltd is (acetoacetyl modified poly- Vinyl alcohol, average degree of polymerization：1700, saponification degree：98.0~99.0 moles of %)
c1：(intramolecular has 3 aziridine rings to the trade name " CROSSLINKER CL-427 " of MENADIONA corporation Following compounds)
d1：Trade name " Safelink SPM-01 " (friendship of glyoxylate system of the Nippon Synthetic Chemical Industry Co., Ltd Join agent, solid component concentration：10 mass %)
<Embodiment 38>
(1) measurement of water contact angle
Binding face for (methyl) acrylic resin film made in above-mentioned Production Example 1, with discharge capacity shown in table 2 (W·min/m2) implement sided corona treatment.8.0 μ of water is added dropwise to the face for implementing sided corona treatment of (methyl) acrylic resin film L, using the contact angle determination device " OCA35 " of Data Physics, the water after being stood 180 seconds by sessile drop method measurement is contacted Angle.
(2) production of polarization plates
In the face for implementing sided corona treatment of (methyl) acrylic resin film and saponification process is implemented with bar coater Triacetyl cellulose (TAC) film (trade name " KC2UAW " of Konica Minolta (strain) system, thickness：25 μm) single side painting apply State the adhesive composite prepared in embodiment 35.In the way of making adhesive composite layer become polarizing film side, above-mentioned One side stacking (methyl) acrylic resin film of the polarizing film made in Production Example 2 and the TAC after another side stacking saponification Film is had (methyl) acrylic resin film/adhesive composite layer/polarizing film/adhesive composite layer/TAC film The laminated body that layer is constituted.The laminated body is set, by carrying out the heat treatment of 80 DEG C, 300 seconds, then to exist from air drier 25 DEG C cure 72 hours, to make polarization plates.
(3) evaluation of initial stage contiguity power
According to polarization plates, (methyl) obtained in following evaluations above-mentioned (2) between acrylic resin film and polarizing film Initial stage adhesion.Initial stage adhesion refers to：In temperature after belonging to the polarization plates before implementing aftermentioned humid heat treatment and making The adhesion for the polarization plates taken care of in the environment of 23 DEG C and relative humidity 55%.
Corona discharge Treatment is implemented to the surface of (methyl) acrylic resin film of polarization plates, in its Corona discharge Treatment Face paste closes (methyl) acrylic adhesive piece, and the polarization plates with adhesive phase are made.From the obtained polarization with adhesive phase Plate determines the test film that width is 25mm, length is about 200mm, by its adhesive phase face paste together in soda-lime glass substrate.
Then, the blade of cutter is made to enter (methyl) between acrylic resin film and polarizing film, alongst 30mm is removed from end, by released part universal tensile testing machine (trade name " AG-1 " of (strain) Shimadzu Seisakusho Ltd.) Clip portion is clamped.For the test film of the state, in the atmosphere of 23 DEG C of temperature and relative humidity 55%, it is based on JIS K6854- 2：1999 " bonding agents-removing adhesive strength test method-the 2：180 degree removing " with clip movement speed 300mm/ minutes into Row 180 degree disbonded test finds out the Average peel force of the 170mm length in addition to the 30mm in clip portion, as contiguity power. Show the result in table 2.It should be noted that " cannot cut " in table 2 refers to：The blade of cutter cannot be introduced into (methyl) third Between olefin(e) acid resin film and polarizing film, indicate that contiguity power is very high.
(4) evaluation of the adhesion after humid heat treatment
Measurement and evaluation are carried out similarly with the method recorded among the above.In table 2, " ※ " is indicated：Since contiguity power is high, When carrying out above-mentioned disbonded test, (the first before the removing of generation (methyl) acrylic resin film and the interface of polarizing film Base) acrylic resin film or polarizing film be broken.
In addition, the measured value based on obtained contiguity power, according to 3 Phase Evaluations (methyl) acrylic resin below The adhesion after humid heat treatment between film and polarizing film.Result is shown in table 2 together.
A：Touching power is more than 5N.
B：Touch power in the range of 1~5N.
C：Touch power and is less than 1N.
<Embodiment 39 and embodiment 40>
Other than the discharge capacity in sided corona treatment is as shown in table 2, polarization plates are made in the same manner as embodiment 38.In addition, The initial stage for having carried out obtained polarization plates touches the evaluation of the adhesion after power, humid heat treatment.
[table 2]
Symbol description
10 (methyl) acrylic resin films, 15 the 1st adhesive layers, 20 thermoplastic resin films, 25 the 2nd adhesive layers, 30 Polarizing film.

Claims (9)

  1. It successively include polarizing film, the 1st adhesive layer and (methyl) acrylic resin film 1. a kind of polarization plates,
    1st adhesive layer is the layer formed by the adhesive composite containing the compound containing oxazolinyl.
  2. 2. polarization plates according to claim 1, wherein the adhesive composite also contains acetoacetyl modified poly- second Enol polymer.
  3. 3. polarization plates according to claim 1 or 2, wherein successively comprising thermoplastic resin film, the 2nd adhesive layer, described Polarizing film, the 1st adhesive layer and (methyl) acrylic resin film.
  4. 4. polarization plates described in any one of claim 1 to 3, wherein the 1st adhesive layer and (methyl) third The contact of olefin(e) acid resin film.
  5. 5. polarization plates according to claim 4, wherein (methyl) acrylic resin film it is Nian Jie with the described 1st The water contact angle in the face of oxidant layer contact is 80 ° or less.
  6. 6. polarization plates according to any one of claims 1 to 5, wherein the polarizing film connects with the 1st adhesive layer Touching.
  7. 7. a kind of adhesive composite combines for the bonding agent for being bonded polarizing film with (methyl) acrylic resin film Object,
    The adhesive composite contains Han oxazolinyl compound.
  8. 8. adhesive composite according to claim 7 also contains acetoacetyl modified polyvinyl alcohol polymer.
  9. 9. adhesive composite according to claim 7 or 8, also contains water.
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