CN105807357A - Manufacturing method of polarizing plate - Google Patents

Manufacturing method of polarizing plate Download PDF

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Publication number
CN105807357A
CN105807357A CN201610243979.4A CN201610243979A CN105807357A CN 105807357 A CN105807357 A CN 105807357A CN 201610243979 A CN201610243979 A CN 201610243979A CN 105807357 A CN105807357 A CN 105807357A
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Prior art keywords
cyclic olefine
protecting film
olefine resin
resin
adhesive
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CN201610243979.4A
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CN105807357B (en
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藤长将司
藤田政大
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00634—Production of filters
    • B29D11/00644—Production of filters polarizing
    • 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
    • B32B27/08—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 of synthetic resin
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • Ophthalmology & Optometry (AREA)
  • Manufacturing & Machinery (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Liquid Crystal (AREA)
  • Laminated Bodies (AREA)

Abstract

In making a polarizing plate, wherein a protective film composed of cycloolefin resin is laminated through adhesives to a polarizing film on which dichroic dye has been adsorbed and aligned in the polyvinyl alcohol-based resin, given the thin film haze value is not more than 0.5%, the protective film is, after contacting a mixed organic solvent including a good solvent and a weak solvent and essentially containing no solute, wherein the good solvent refers to the organic solvent that would result in changing the resin due to the contact, and the weak solvent refers to the organic solvent that would not make substantial changes to the resin due to the contact, adhesively laminated to the polarizing film. The mixed organic solvent can be substituted by alicyclic hydrocarbon alone, but the alicyclic hydrocarbon is favorably mixed with the weak solvent.

Description

The manufacture method of polarization plates
The divisional application of to be 201110378156.X, denomination of invention be " manufacture method of polarization plates " application for a patent for invention that the application is application number.
Technical field
The present invention relates to the protecting film being made up of cyclic olefine resin on the surface of the polarizing coating being made up of polyvinyl alcohol resin, the method manufacturing polarization plates by adhesive laminating.
Background technology
Polarization plates, usually by the one or two sides being adsorbed with dichromatic pigment the polarizing coating that makes the polyvinyl alcohol resin of its orientation constitute, by adhesive (Japanese: then) laminating transparent resin molding, such as, the film of the acetate fiber prime system being representative with triacetyl cellulose and constituted.By it across other the blooming such as optical compensation films as required, phase retardation film, utilize binding agent to fit on liquid crystal cell, become the component parts of liquid crystal indicator.
Liquid crystal indicator is as slim display pictures such as LCD TV, LCD monitor, PC, and purposes just sharply expands.The market expansion of LCD TV is especially notable, it addition, the requirement of cost degradation is also very strong.For the polarization plates of liquid crystal display television, in the past, the polarization plates utilizing water system adhesive stacking tri acetyl cellulose membrane on the two sides of the polarizing coating being made up of polyvinyl alcohol resin is main flow, is laminated with phase retardation film by adhesive phase on the one side of this polarization plates.It is laminated in the phase retardation film of polarization plates, use the stretch process product etc. of the stretch process product of Merlon resin film, cyclic olefine resin molding, when for LCD TV, the phase retardation film being made up of cyclic olefine resin molding that the phase contrasts used under high temperature uneven considerably less more.For the laminating product of polarization plates with the phase retardation film being made up of stretch ring olefin-based resin molding, for the reduction of the raising of productivity ratio and goods cost, carrying out reducing the component count constituted or simplifying the improvement of manufacturing process.Such as, in JPH08-43812-A, the stacking disclosing cyclic olefine (norborene system) resin molding/polarizing coating/tri acetyl cellulose membrane with phase difference function is constituted.
It addition, describe content polyethenol series polarizing coating and cyclic olefine resin molding engaged with the water system adhesive of carbamate system in JP2005-70140-A, JP2005-181817-A and JP2005-208456-A.On the other hand, describe in JP2004-245925-A, when polyethenol series polarizing coating being fitted with the low protecting film of moisture permeability that cyclic olefine resin molding is representative, use the content of the active energy ray-curable adhesive containing epoxide.
And then, in KR2010-92265-A, disclose the solution of at least one in the group that Ketohexamethylene, methyl iso-butyl ketone (MIBK), Anaesthetie Ether, oxirane, oxolane, Pentamethylene oxide., normal heptane, normal hexane, cresol, toluene, dimethylbenzene, dioctyl phthalate and dimethylformamide form, it is typical that the aqueous solution of the compound in above-mentioned group is applied to the surface treatment method of cyclic olefine resin molding.By adhesive, the cyclic olefine resin molding through above-mentioned surface treatment fitted in polyethenol series polarizing coating it addition, disclose, the method manufacturing polarization plates.
When using water system adhesive in the laminating of polyethenol series polarizing coating and cyclic olefine resin molding, both bonding forces may not be abundant, for instance, there is the situation peeling-off at the interface of polarizing coating and cyclic olefine resin molding.Therefore, after polarization plates configuration on liquid crystal cell, sometimes due to polarization plates is bad etc., need the operation (be called and do over again) again taken off, compared with the bonding force of the binding agent of bonding polarization plates and liquid crystal cells (Japanese: adhesion), bonding force in the stepped construction of polarization plates is (such as, bonding force between polarizing coating and cyclic olefine resin molding) relative little, occasionally there are on the glass unit taken off polarization plates, only remain cyclic olefine resin, the problem that liquid crystal cells becomes to recycle.
According to the method disclosed in above-mentioned KR2010-92265-A, although the cyclic olefine resin molding bonding force relative to polyethenol series polarizing coating can be improved, but when utilizing aqueous solution to carry out surface treatment, it is required to keep the drying oven of the temperature of transpiring moisture degree subsequently.On the other hand, with, in the organic compound disclosed particularly in document, the material (organic solvent) being liquid being directly applied to cyclic olefine resin molding, excessive erosion cyclic olefine resin molding sometimes under room temperature.
It is an object of the invention to, the polarizing coating being made up of polyvinyl alcohol resin is fitted with by adhesive in the polarization plates of the protecting film being made up of cyclic olefine resin, improve the bonding force between polarizing coating and cyclic olefine resin molding.Another object of the present invention is in that, when cyclic olefine resin molding not being carried out excessive erosion and process, by fitting in polyethenol series polarizing coating by adhesive, not only it is maintained as the high-performance of polarization plates, and improves the bonding force between polarizing coating and cyclic olefine resin molding.
Result of study finds, use the mixture of the organic solvent making this cyclic olefine resin change and the organic solvent not making this cyclic olefine resin generation substantial variations when being contacted with cyclic olefine resin molding when being contacted with cyclic olefine resin molding, in the way of the turbidity value of this cyclic olefine resin molding is less than 0.5%, it is effective for making the method that said mixture contacts with cyclic olefine resin molding.It has further been found that, make in the organic solvent that cyclic olefine resin changes by contacting, as long as ester ring type hydrocarbon, even if being used alone, contact process for cyclic olefine resin molding is also effective, also find, if with ester ring type hydrocarbon together and with the organic solvent not causing cyclic olefine resin generation substantial variations because contacting, then more efficient.
Summary of the invention
That is, the present invention includes following technology.
(1) manufacture method of a kind of polarization plates, it is to adsorb dichromatic pigment in polyvinyl alcohol resin and make the polarizing coating of this dichromatic pigment orientation, fits the protecting film being made up of cyclic olefine resin by adhesive, the method manufacturing polarization plates, wherein,
Make the described protecting film being made up of cyclic olefine resin; according to mode less than 0.5% of the turbidity value of this protecting film; contact with the essence mixed organic solvents without solute; then by the laminating of described adhesive and described polarizing coating, described mixed organic solvents be because of contact the organic solvent that makes this cyclic olefine resin change with will not because contacting the mixture of the organic solvent making this cyclic olefine resin generation substantial variations.
(2) manufacture method of a kind of polarization plates; it is to adsorb dichromatic pigment in polyvinyl alcohol resin and make the one side of polarizing coating of this dichromatic pigment orientation; by the first protecting film that adhesive laminating is made up of cyclic olefine resin; at the second protecting film that the another side of polarizing coating is made up of thermoplastic resin by adhesive laminating; the method manufacturing polarization plates; wherein
Make described the first protecting film being made up of cyclic olefine resin; according to mode less than 0.5% of the turbidity value of this first protecting film; contact with the essence mixed organic solvents without solute; then by the laminating of described adhesive and described polarizing coating, described mixed organic solvents be because of contact the organic solvent that makes this cyclic olefine resin change with will not because contacting the mixture of the organic solvent making this cyclic olefine resin generation substantial variations.
(3) manufacture method of a kind of polarization plates, it is to adsorb dichromatic pigment in polyvinyl alcohol resin and make the polarizing coating of this dichromatic pigment orientation, fits the protecting film being made up of cyclic olefine resin by adhesive, the method manufacturing polarization plates, wherein,
Making the described protecting film being made up of cyclic olefine resin, according to mode less than 0.5% of the turbidity value of this protecting film, and the organic solvent exposure without solute containing ester ring type hydrocarbon and essence, then by described adhesive and the laminating of described polarizing coating.
(4) manufacture method of a kind of polarization plates; it is to adsorb dichromatic pigment in polyvinyl alcohol resin and make the one side of polarizing coating of this dichromatic pigment orientation; by the first protecting film that adhesive laminating is made up of cyclic olefine resin; at the second protecting film that the another side of polarizing coating is made up of thermoplastic resin by adhesive laminating; the method manufacturing polarization plates; wherein
Making described the first protecting film being made up of cyclic olefine resin, according to mode less than 0.5% of the turbidity value of this first protecting film, and the organic solvent exposure without solute containing ester ring type hydrocarbon and essence, then by described adhesive and the laminating of described polarizing coating.
(5) manufacture method as described in (3) or (4), wherein,
Described ester ring type hydrocarbon is the compound shown in following formula (I),
In formula, m is the integer of 2～6, and R is hydrogen atom or the alkyl of carbon number 1～5.
(6) manufacture method as according to any one of (3)～(5), wherein,
Described organic solvent is in addition to outside described ester ring type hydrocarbon, possibly together with the mixed solvent of the organic solvent that will not make described cyclic olefine resin generation substantial variations because of contact.
(7) manufacture method as described in (6), wherein,
The organic solvent that will not make cyclic olefine resin generation substantial variations is organic acid Arrcostab.
(8) manufacture method as described in (7), wherein,
Organic acid Arrcostab is acetas.
(9) manufacture method as described in (8), wherein,
Acetas is ethyl acetate, isopropyl acetate or propyl acetate.
(10) manufacture method as according to any one of (1)～(9), wherein,
The described protecting film being made up of cyclic olefine resin with described organic solvent exposure before there is phase difference value in the face of more than 30nm, and in the face of this protecting film after this contact, phase difference value contacts in the way of reducing less than 3nm compared to phase difference value in the face before this contact.
(11) manufacture method as according to any one of (1)～(10), wherein,
When making the described protecting film being made up of cyclic olefine resin with described organic solvent exposure, implement the operation making this organic solvent dry simultaneously.
(12) manufacture method as according to any one of (1)～(11), wherein,
Described adhesive is water system adhesive.
(13) manufacture method as described in (12), wherein,
Described adhesive contains polyvinyl alcohol resin.
According to the present invention, in the polarization plates of the protecting film being made up of cyclic olefine resin by adhesive laminating on the polarizing coating being made up of polyvinyl alcohol resin, it is possible to improve the bonding force of polarizing coating and cyclic olefine resin molding.Particularly can suppress the erosion of cyclic olefine resin molding, it is possible to manufacture and can either be maintained as the high-performance of polarization plates, improve again the polarization plates of bonding force between polarizing coating and cyclic olefine resin molding.
Detailed description of the invention
In the present invention, polyvinyl alcohol resin it is adsorbed with dichromatic pigment and makes the protecting film being made up of cyclic olefine resin by adhesive laminating on the polarizing coating of its orientation, thus making polarization plates.Cyclic olefine resin molding can be fitted on the two sides of polarizing coating, it is also possible at single-sided lamination.When the single-sided lamination cyclic olefine resin molding of polarizing coating, it is preferable that in opposite to that face still by the protecting film being made up of thermoplastic resin that adhesive laminating is other.Hereinafter, sometimes the protecting film being made up of cyclic olefine resin is called " the first protecting film ", the other protecting film being made up of thermoplastic resin is called " the second protecting film ".First, each component parts of the polarization plates utilizing the present invention to manufacture is illustrated.
[polarizing coating]
The polarizing coating used in the present invention, specifically, is be adsorbed with dichromatic pigment in polyvinyl alcohol resin film and make the polarizing coating of its orientation.Before the absorption of dichromatic pigment, in absorption, or after absorption, by by polyvinyl alcohol resin film uniaxial tension, it is possible to make this dichromatic pigment orientation in the stretching direction.Polyvinyl alcohol resin is by obtaining the resin saponification of polyvinyl acetate system.As polyvinyl acetate system resin, except the polyvinyl acetate as the homopolymer of vinyl acetate, vinyl acetate and can with the copolymer of other monomer of its copolymerization can be enumerated, for instance vinyl-vinyl acetate copolymer etc..As can with other monomer of vinyl acetate copolymerization, for instance, can enumerate unsaturated carboxylic acid class, unsaturated sulfonic acid class, above-mentioned with ethylene be representative olefines, vinyl ethers, there is the acrylic amide etc. of ammonium.
The saponification degree of polyvinyl alcohol resin is generally 85～100 moles of %, it is preferable that 98 moles of more than %.Polyvinyl alcohol resin can also be modified, for instance can also use with the modified polyvinyl formal of aldehydes, polyvinyl acetal, polyvinyl butyral resin etc..It addition, the degree of polymerization of polyvinyl alcohol resin is generally in the scope of 1000～10000, it is preferable that be in the scope of 1500～5000.
Material by this polyvinyl alcohol resin masking, it is possible to use with the form of the reel film (Japanese original text: former anti-Off ィ Le system) of polarizing coating.The method of masking polyvinyl alcohol resin is not particularly limited, it is possible to be filmed by known suitable method.The thickness of the reel film being made up of polyvinyl alcohol resin is not particularly limited, for instance be 10～150 μm of degree.
Polarizing coating generally goes through following operation and manufactures: dyeed by polyvinyl alcohol resin film with dichromatic pigment, make the operation (dyeing treatment process) that this dichromatic pigment adsorbs, the operation (boric acid treatment process) that the polyvinyl alcohol resin film boric acid aqueous solution being adsorbed with dichromatic pigment is processed, with, carry out the operation (washing treatment process) washed after the process of this boric acid aqueous solution.
It addition, during the manufacture of polarizing coating, polyvinyl alcohol resin film is carried out uniaxial tension, for uniaxial tension, it is possible to carried out before dyeing treatment process, it is also possible to carry out in dyeing treatment process, it is also possible to carry out after dyeing treatment process.When carrying out uniaxial tension after the treatment process that dyes, this uniaxial tension can carry out before boric acid treatment process, it is also possible to carries out in boric acid treatment process.It is of course also possible to carry out uniaxial tension in these multiple stages.When uniaxial tension, it is possible to undertaken by passing through between the roller separately different in circular velocity, it is also possible to carry out with hot-rolling method of clamping.Furthermore it is possible to be the dry type stretching carrying out stretching etc. in an atmosphere, it is also possible to be that the wet type carrying out when making it swelling with solvent stretching stretches.Draw ratio is generally about 3～8 times.
Utilize dichromatic pigment that polyvinyl alcohol resin film is dyeed, for instance, it is possible to by polyvinyl alcohol resin film immersion is carried out in the aqueous solution containing dichromatic pigment.As dichromatic pigment, iodine, dichroic organic dye etc. specifically can be used.In dichroic organic dye, including the dichromatic direct dyes comprising the bis-azo compounds such as C.I.DIRECTRED39, comprise the dichromatic direct dyes of the compound such as trisazo-, four azos.It should be noted that for polyvinyl alcohol resin film, it is preferable that before dyeing processes, it is implemented in the impregnation process in water.
When using iodine as dichromatic pigment, generally utilize the method impregnating polyvinyl alcohol resin film in the aqueous solution containing iodine and potassium iodide and carry out dyeing.Content of iodine in this aqueous solution is generally 0.01～1 weight portion relative to water 100 weight portion, and the content of potassium iodide is generally 0.5～20 weight portion relative to water 100 weight portion.When using iodine as dichromatic pigment, the temperature of the aqueous solution for dyeing is generally 20～40 DEG C, it addition, the dip time (dyeing time) in this aqueous solution is generally 20～1800 seconds.
On the other hand, when using dichroic organic dye as dichromatic pigment, generally utilize the method impregnating polyvinyl alcohol resin film in the aqueous solution comprising water miscible dichroic organic dye and carry out dyeing.The content of the dichroic organic dye in this aqueous dye solutions is generally 1 × 10 relative to water 100 weight portion-4～10 weight portions, it is preferable that 1 × 10-3～1 weight portion, it is preferred that 1 × 10-3～1 × 10-2Weight portion.This aqueous solution can also contain the inorganic salts such as sodium sulfate as dyeing assistant.When using dichroic organic dye as dichromatic pigment, the temperature of the aqueous dye solutions for dyeing is generally 20～80 DEG C, it addition, the dip time (dyeing time) in this aqueous solution is generally 10～1800 seconds.
For boric acid treatment process, by the polyvinyl alcohol resin film immersion with dichromatic pigment dyeing is implemented in boric acid aqueous solution.Boric acid content in boric acid aqueous solution is generally 2～15 weight portions relative to water 100 weight portion, is preferably 5～12 weight portions.When use iodine is as the dichromatic pigment in above-mentioned dyeing treatment process, the boric acid aqueous solution used in this operation preferably comprises potassium iodide.In this case, the content of the potassium iodide in boric acid aqueous solution is generally 0.1～15 weight portion relative to water 100 weight portion, it is preferable that 5～12 weight portions.Dip time in boric acid aqueous solution is generally 60～1200 seconds, it is preferable that 150～600 seconds, it is preferred that 200～400 seconds.The temperature of boric acid aqueous solution is generally more than 50 DEG C, it is preferable that 50～85 DEG C, more preferably 60～80 DEG C.
In ensuing washing treatment process, process by such as above-mentioned borated polyvinyl alcohol resin film immersion being implemented in water washing.The temperature of the water in washing process is generally 5～40 DEG C, and dip time is 1～120 second.Washing generally implements dried after processing, and obtains polarizing coating.Air drier, far infra-red heater etc. such as can be used to implement dried.The temperature of dried is generally 30～100 DEG C, it is preferable that 50～80 DEG C.The time of dried is generally 60～600 seconds, it is preferable that 120～600 seconds.
By above operation, it is possible to be produced on and be adsorbed with dichromatic pigment in the polyvinyl alcohol resin film of uniaxial tension and make the polarizing coating of its orientation.The thickness of this polarizing coating can be set to about 5～40 μm.
[cyclic olefine resin molding]
In the present invention, with cyclic olefine resin molding be formed at least one face of polarizing coating arrange the first protecting film, by adhesive, this cyclic olefine resin molding is fitted in polarizing coating.
So-called cyclic olefine resin, for instance, there is the thermoplastic resin of the monomeric unit being made up of the cyclic olefin (cycloolefin) of norborene, multi-ring norborneol alkene monomer etc, also referred to as thermoplastic cyclic olefin system resin.This cyclic olefine resin can be the use of the hydride of the ring opening copolymer thing of the ring-opening polymerization polymer of above-mentioned cycloolefin, cycloolefin of more than two kinds, it is possible to is the addition polymer of cycloolefin and chain olefin or the aromatic compound etc. with polymerism double bond as such in vinyl.Cyclic olefine resin can also import polar group.
When the copolymer of the aromatic compound using cycloolefin and have chain olefin and/or vinyl constitutes the first protecting film; as chain olefin; ethylene, propylene etc. can be enumerated; additionally; as the aromatic compound with vinyl, styrene, α-methyl styrene, core alkyl-substituted styrene etc. can be enumerated.In such copolymer, the monomeric unit being made up of cycloolefin can be 50 moles of below %, it is preferred to 15～50 moles of about %.Particularly when the terpolymer of the aromatic compound using cycloolefin and chain olefin and have vinyl constitutes the first protecting film, the monomeric unit being made up of cycloolefin can set that as few amount compared as discussed above.In such terpolymer, the monomeric unit being made up of chain olefin is generally 5～80 moles of %, and the monomeric unit being made up of the aromatic compound with vinyl is generally 5～80 moles of %.
Cyclic olefine resin can be preferably used suitable commercially available product, for instance: Germany TOPAS advanced person polymer GmbH manufacture by " TOPAS " of Japan's polymer plastic sold, by " ア ト Application (ARTON) " of JSR sold, by " ゼ オ ノ ア " (ZEONOR) and " ゼ オ ネ ッ Network ス " (ZEONEX), " ア ペ Le " (APEL) (being trade name above) sold by Mitsui Chemicals, Inc. of Japan's ZEON sold etc..Such cyclic olefine resin is filmed when making film, can suitably use the known method such as solvent casting method, extrusion by melting.Additionally; " エ ス シ Na " (Escena) and " SCA40 " that such as sold can also be used by hydrops chemical industrial company, by " the ZEONOR film " of Japan's ZEON sold, by the commercially available cyclic olefine resin masking of the masking in advance such as " ARTON film " (being trade name above) of JSR sold as the first protecting film.
The cyclic olefine resin molding used in first protecting film can be through uniaxial tension or Biaxially stretched resin molding.At this moment stretching ratio is generally 1.1～5 times, it is preferable that 1.1～3 times.Phase contrast is given, it is possible to make phase retardation film by this stretching.In this face, phase difference value can be appropriately configured according to the kind of the liquid crystal cells applied, it is usually preferable to be set to more than 30nm.In face, the upper limit of phase difference value is not particularly limited, for instance reaches about 300nm and is sufficient to.
Although in the first protecting film use cyclic olefine resin molding preferably get over Bao Yuehao, but cross thin time decrease in strength, have the tendency of poor in processability, on the other hand, time blocked up, have the transparency decline, or polarization plates weight increase trend.From such a viewpoint, the thickness of the protecting film being made up of cyclic olefine resin is generally 5～200 μm, it is preferred to 10～150 μm, more preferably 20～100 μm.
The protecting film being made up of cyclic olefine resin uses adhesive described below to fit in polarizing coating.During both laminating, in order to improve cementability, it is possible to polarizing coating and/or the gluing of surfaces of protecting film fitted with it, implement plasma treatment, sided corona treatment, the surface treatments such as ultraviolet radiation processes, and flame (fire is scorching) processes, saponification process.Hereinafter, the adhesive used in the laminating of polarizing coating and cyclic olefine resin molding is illustrated.
[adhesive]
In the laminating of polarizing coating and cyclic olefine resin molding, use adhesive.For the adhesive of this use, as long as both to be embodied the material of bonding force, for instance, the adhesive of the water system being dissolved or dispersed in water by adhesive component, the curable adhesive containing active energy ray-curable compound can be enumerated.The surface considering polarizing coating is hydrophilic, it is preferable that the adhesive of the water system being dissolved or dispersed in by adhesive component in water.Water system adhesive is also preferred from the viewpoint that can control relatively thin by the adhesive layer after solidifying.In becoming the adhesive component of main constituent of water system adhesive, there are polyvinyl alcohol resin, polyurethane resin etc..
When using polyvinyl alcohol resin as the main constituent of water system adhesive, this polyvinyl alcohol resin can obtain by polyvinyl acetate system resin is carried out saponification.As polyvinyl acetate system resin, except the polyvinyl acetate as the homopolymer of vinyl acetate, can example vinyl acetate with can with other unitarily formed copolymers etc. of its copolymerization.As with other monomers of vinyl acetate copolymerization, can enumerating such as unsaturated carboxylic acid class, unsaturated sulfonic acid class, olefines, vinyl ethers, there is the acrylic amide etc. of ammonium.The polyvinyl alcohol resin used in adhesive preferably has the suitable degree of polymerization, for instance, when making the aqueous solution that concentration is 4 weight %, it is preferable that viscosity is in the scope of 4～50mPa sec, in the scope more preferably in 6～30mPa sec.
The saponification degree of the polyvinyl alcohol resin for using in adhesive, it does not have limit especially, it is generally preferable to be 80 moles of more than %, more preferably 90 moles of more than %.When the saponification degree of the polyvinyl alcohol resin used in adhesive is low, it is understood that there may be the resistance to water of adhesive layer is prone to insufficient trend.
Modified polyvinyl alcohol resin is preferably used in adhesive.As preferred modified polyvinylalcohol system resin, acetoacetyl modified polyvinyl alcohol resin, anion-modified polyvinyl alcohol system resin, cation-modified polyvinyl alcohol resin etc. can be enumerated.When using this modified polyvinylalcohol system resin, it is easy to obtain improving the effect of the resistance to water of adhesive layer.
For acetoacetyl modified polyvinyl alcohol resin, except the hydroxyl constituting polyvinyl alcohol skeleton, also there is acetoacetyl (CH3COCH2CO-), it is possible to have the such as acetyl group of group in addition etc..The state that this acetoacetyl is replaced with the hydrogen atom being typically constructed the hydroxyl of polyvinyl alcohol exists.Acetoacetyl modified polyvinyl alcohol resin can utilize and such as make the method that polyvinyl alcohol and acetyl ketene react manufacture.There is reactive high functional group and acetoacetyl due to acetoacetyl modified polyvinyl alcohol resin, therefore preferred in improving the durability raising of adhesive layer.
For the content of the acetoacetyl in acetoacetyl modified polyvinyl alcohol resin, as long as 0.1 mole of more than % is just not particularly limited.The content of acetoacetyl said here; it is that acetoacetyl is used the % value represented relative to the mole fraction of the total amount of the hydroxyl in polyvinyl alcohol resin, acetoacetyl and other ester groups (acetyl group etc.), is sometimes referred to as " acetoacetylate degree ".When the acetoacetylate degree in polyvinyl alcohol resin is lower than 0.1 mole of %, the effect of the resistance to water improving adhesive layer is not necessarily abundant.Acetoacetylate degree in polyvinyl alcohol resin is preferably 0.1～40 mole of about %, more preferably 1～20 mole of %, is particularly preferably 2～7 moles of %.When acetoacetylate degree is more than 40 moles of %, the raising effect of resistance to water diminishes.
For anion-modified polyvinyl alcohol system resin, except the hydroxyl constituting polyvinyl alcohol skeleton, possibly together with anionic property group, it is typically carboxyl (-COOH) or its salt, it is also possible to containing group such as acetyl group etc. in addition.The method that anion-modified polyvinyl alcohol system resin such as can utilize makes the unsaturated monomer with anionic property group (being typically carboxyl) and vinyl acetate copolymerization, then carry out saponification manufactures.On the other hand, for cation-modified polyvinyl alcohol resin, except the hydroxyl constituting polyvinyl alcohol skeleton, possibly together with cationic groups, it is typically tertiary amino or quaternary ammonium group, it is also possible to containing group such as acetyl group etc. in addition.The method that cation-modified polyvinyl alcohol resin can utilize such as makes the unsaturated monomer with cationic groups (being typically tertiary amino or quaternary ammonium group) and vinyl acetate copolymerization, then carry out saponification manufactures.
The adhesive used in the present invention is it is of course possible to containing two or more above-mentioned modified polyvinylalcohol system resin, additionally can also contain unmodified polyvinyl alcohol resin (concrete is the fully saponified thing of polyvinyl acetate or partly-hydrolysed thing) and above-mentioned modified polyvinylalcohol system resin both resins.
The polyvinyl alcohol resin constituting adhesive can suitably select to use from commercially available product.Specifically, can enumerate such as: as have high saponification degree polyvinyl alcohol by " PVA-117H " of Kuraray sold, by Japan synthetic chemical industry sold " GohsenolNH-20 "；" GohsefimerZ " by Japan's synthetic chemical industry sold as acetoacetyl modified polyvinyl alcohol is serial；As anion-modified polyvinyl alcohol by " KL-318 " and " KM-118 " of Kuraray sold, by Japan synthetic chemical industry sold " GohsenolT-330 "；As cation-modified polyvinyl alcohol by " CM-318 " of Kuraray sold, by " GohsefimerK-210 " etc. of Japan's synthetic chemical industry sold.
The concentration of the polyvinyl alcohol resin in adhesive is not particularly limited, when using with the form of aqueous solution, relative to 100 weight parts waters, polyvinyl alcohol resin is preferably in the scope of 1～20 weight portion, more preferably 1～15 weight portion, more preferably 1～10 weight portion, be particularly preferably in the scope of 2～10 weight portions.When the concentration of the polyvinyl alcohol resin in aqueous solution is too small, it is possible to easily make cementability decline, it addition, when its concentration is excessive, it is possible to easily make the optical characteristics of the polarization plates obtained decline.The water used in this adhesive can be pure water, ultra-pure water, tap water etc., it does not have limits especially, but from the viewpoint of keep the uniformity of adhesive layer, the transparency that are formed, it is preferable that pure water or ultra-pure water.Additionally can also add the alcohol such as methanol or ethanol in adhesive aqueous solution.
In the water system adhesive that polyvinyl alcohol resin is main constituent, it is possible to containing cross-linking agent.For cross-linking agent, as long as have the compound that polyvinyl alcohol resin is had reactive functional group, it is possible to use the cross-linking agent used in current polyethenol series adhesive without particular limitation.The compound that can become cross-linking agent is enumerated, for instance have: at least there is in molecule the isocyanate compound of 2 isocyanato-s base (-NCO) by functional group's difference；At least there is in molecule the epoxide of 2 epoxy radicals (-O-of crosslinking)；Single aldehyde or dialdehyde class；Organic titanic compound；The bivalence of magnesium, calcium, ferrum, nickel, zinc and aluminum etc or the inorganic salt of trivalent metal；The slaine of glyoxalic acid；Melamine methylol etc..
As the concrete example of the isocyanate compound becoming cross-linking agent, can enumerate: the adduct of toluene di-isocyanate(TDI), hydrogenated tolylene diisocyanate, trimethylolpropane and toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate, the ketoxime end-blocking thing of these isocyanate compounds or phenol end-blocking thing etc..
Concrete example as the epoxide becoming cross-linking agent, can enumerate: the water soluble polyamide epoxy resin etc. that Ethylene glycol diglycidyl ether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether or glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, diglycidylaniline, diglycidyl amine, the reactant making polyalkylene polyamine and dicarboxylic acids and polyamide polyamines and chloropropylene oxide are obtained by reacting.
As the concrete example of the single aldehydes becoming cross-linking agent, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde etc. can be enumerated, as the concrete example of dialdehyde, can enumerate: Biformyl, malonaldehyde, butanedial, glutaraldehyde, maleic dialdehyde, phthalic aldehyde etc..
For becoming the organic titanic compound of cross-linking agent, the pine company (MatsumotoFineChemicalCo., Ltd.) that originally refines of Japan sell the various organic titanic compound becoming cross-linking agent.By the homepage (the Internet<URL:http: //www.m-chem.co.jp/products/products1.html>, Heisei retrieval on November 18th, 22) of the organic titanic compound of the said firm, for the water solublity organic titanic compound suitable in the present invention, the chemical name, the order of the trade name of the said firm that claim according to the rational formula of its compound, the said firm are listed below organic titanic compound.
[(CH3)2CHO]2Ti[OCH2CH2N(CH2CH2OH)2]2: the said firm is called the trade name " OrgaticksTC-400 " of chemical name " double; two (triethanolamine) diisopropyl titanate esters ", the said firm
(HO)2Ti[OCH(CH3)COO-]2(NH4 +)2: the said firm is called the trade name " OrgaticksTC-300 " of chemical name " lactic acid titanium ammonium salt ", the said firm,
(HO)2Ti[OCH(CH3)COOH]2: the said firm is called chemical name " lactic acid titanium ", the trade name " OrgaticksTC-310 " of the said firm and " OrgaticksTC-315 ".
It addition, the slaine of glyoxalic acid is preferably alkali metal salt or alkali salt, can enumerate such as: sodiam glyoxlate, glyoxalic acid potassium, glyoxalic acid magnesium, calcium glyoxylate etc..
In these cross-linking agent, be suitable for using with above-mentioned water soluble polyamide epoxy resin be representative epoxide or aldehydes, melamine methylol, the alkali metal of glyoxalic acid or alkali salt etc..
For cross-linking agent, it is preferable that it is dissolved in together with polyvinyl alcohol resin in water and forms adhesive.But, as described below, owing to the cross-linked dosage in aqueous solution is trace, therefore, as long as its relative glassware for drinking water has the dissolubility of such as about at least 0.1 weight %, it is possible to use as cross-linking agent.Certainly, the compound of the dissolubility with the relative water being commonly referred to as water solublity degree also is suitable as the cross-linking agent for the present invention.
For the use level of cross-linking agent, can be appropriately designed according to the kind of polyvinyl alcohol resin etc., it is generally about 5～60 weight portions relative to polyvinyl alcohol resin 100 weight portion, is preferably 10～50 weight portions.By with this range fit cross-linking agent, good cementability can be obtained.As mentioned above; in order to improve the durability of adhesive layer, it is preferred to use acetoacetyl modified polyvinyl alcohol resin, in this case; relative to polyvinyl alcohol resin 100 weight portion, it is preferable that coordinate cross-linking agent with the ratio of 5～60 weight portions, more preferably 10～50 weight portions.When the use level of cross-linking agent is too much, cross-linking agent reaction carries out at short notice, it is possible to adhesive can be made to shift to an earlier date saponification, and its result becomes very short working life, is unsuitable for for commercial production.
In adhesive, in the scope not interfering with effect of the present invention, it is possible to coordinate the currently known suitable additives such as such as silane coupling agent, plasticizer, antistatic additive, microgranule.
When using polyurethane resin as the main constituent of water system adhesive, as the example of suitable adhesive, Polyester ionomer type polyurethane resin can be enumerated and there is the mixture of compound of glycidoxypropyl.Polyester ionomer type polyurethane resin described here is to have the polyurethane resin of polyester backbone, and has imported a small amount of ionic composition (hydrophilic component) wherein.Owing to this ionomer type polyurethane resin does not use emulsifying agent directly to occur emulsifying to form emulsion in water, use so being adapted in water system adhesive.It is known using Polyester ionomer type polyurethane resin as the method used in the adhesive of polarizing coating and protecting film, for instance, JP2005-070140-A, described in having in JP2005-181817-A and JP2005-208456-A.
In the laminating of polarizing coating and cyclic olefine resin molding, it is possible to use the curable adhesive containing active energy ray-curable compound.So-called " active energy ray-curable compound ", refers to by the compound that the irradiation of active energy ray can solidify.Active energy ray-curable compound, it is possible to be the compound of cationically polymerizable, it is also possible to be free-radical polymerised compound.As the example of cationically polymerizable compound, the epoxide in molecule with at least 1 epoxy radicals can be enumerated, there is in molecule the oxetane compound etc. of at least 1 oxetanes ring.It addition, as the example of free-radical polymerised compound, (methyl) the acryloyl based compound etc. with at least 1 (methyl) acryloxy can be enumerated in molecule.Additionally, so-called " (methyl) acryloxy ", refer to methacryloxy or acryloxy.
The active energy ray-curable compound used in this laminating preferably at least contains epoxide, thus, demonstrates better adaptation between polarizing coating and cyclic olefine resin molding.
From weatherability, refractive index, the viewpoint of cationically polymerizable etc. is set out, epoxide preferably in molecule epoxide without aromatic rings be main constituent.As epoxide without aromatic rings in molecule, it is possible to illustrate the glycidyl ether of the polyhydric alcohol with ester ring type ring, aliphatic epoxy compound, cycloaliphatic epoxy etc..As the epoxide being preferably used in such curable adhesive, it is described in detail in such as JP2004-245925-A, at this to its brief description.
There is the glycidyl ether of the polyhydric alcohol of ester ring type ring, can pass through aromatic polyol in the presence of a catalyst, on aromatic rings, carry out selective hydrogenation under pressurized conditions, and the core hydrogenated polyol thus obtained be carried out glycidyl ether and obtains.As aromatic polyol, for instance can enumerate: the bisphenol type compounds of bisphenol-A, Bisphenol F and bisphenol S etc；The novolac resin of phenol resol resins, cresol novolac resin and hydroxy benzaldehyde phenol resol resins etc；The compound etc. of the multifunctional type of tetrahydroxy diphenyl methane, tetrahydroxybenzophenone and polyvinylphenol etc.React with chloropropylene oxide by making the aromatic rings of such aromatic polyol hydrogenate the ester ring type polyhydric alcohol obtained, it is possible to glycidyl ether.As compound preferred in the glycidyl ether of such polyhydric alcohol with ester ring type ring, it is possible to enumerate the diglycidyl ether of the bisphenol-A of hydrogenation.
Aliphatic epoxy compound can be the poly epihydric alcohol base ether of aliphatic polyol or this alkylen oxide adducts.More specifically, the diglycidyl ether of BDO can be enumerated；The diglycidyl ether of 1,6-hexanediol；The triglycidyl group ether of glycerol；The triglycidyl group ether of trimethylolpropane；The diglycidyl ether of Polyethylene Glycol；The diglycidyl ether of propylene glycol；Addition is one kind or two or more on the aliphatic polyol of ethylene glycol, propylene glycol or glycerol etc oxyalkylene (oxirane, expoxy propane) and the poly epihydric alcohol base ether etc. of polyether polyol that obtains.
Cycloaliphatic epoxy refers to the compound at least in molecule with 1 epoxy radicals closed with ester ring type loops.At this, " epoxy radicals with the conjunction of ester ring type loops " refers to the oxygen atom-O-of the crosslinking in the structure shown in following formula (II), and in formula, n is the integer of 2～5.
[changing 1]
Eliminate (the CH in one or more this formula (II)2)nIn the compound that is bonded with other chemical constitution of the group of hydrogen atom can form cycloaliphatic epoxy.It addition, form (the CH of ester ring type ring2)nIn one or more hydrogen atom can suitably be replaced by the straight-chain alkyl such as methyl or ethyl.
In above epoxide; preferred cycloaliphatic epoxy; namely; the compound that at least 1 of epoxy radicals is combined into ester ring type ring; from the elastic modelling quantity of solidfied material height, between polarizing coating and protecting film, obtain good bonding viewpoint, it is particularly preferred that use and there is oxabicyclo hexane ring (in above formula (II) n=3) and the epoxide of oxa-bicyclo heptane ring (in above formula (II) n=4).Hereinafter, the concrete example of cycloaliphatic epoxy is enumerated.Here, compound name is first enumerated, thereafter, it is shown that chemical formula corresponding respectively, the chemical formula mark same-sign of compound name and correspondence thereof.
A:3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexane carboxylate,
B:3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylic acid ester,
C: ethylene double; two (3,4-epoxycyclohexane carboxylate),
D: double; two (3,4-epoxycyclohexyl-methyl) adipic acid (ester),
E: double; two (3,4-epoxy-6-methylcyclohexylmethyl) adipic acid (ester),
F: diethylene glycol double; two (3,4-epoxycyclohexyl-methyl ether),
G: ethylene glycol bis (3,4-epoxycyclohexyl-methyl ether),
H:2,3,14,15-diepoxy-7,11,18,21-tetra-oxa-three spiral shells-[5.2.2.5.2.2] heneicosane
I:3-(3,4-epoxycyclohexyl)-8,9-epoxy-1,5-dioxo spiro [5.5] hendecane,
J:4-vinyl cyclohexene dioxide,
K: limonene dioxide,
L: double; two (2,3-epoxycyclopentyl) ether,
M: dicyclopentadiene etc..
A:
B:
C:
D:
E:
F:
G:
H:
I:
J:
K:
L:
M:
In curable adhesive, epoxide can only be single use a kind, it is also possible to and use two or more.
It addition, except above-mentioned epoxide in curable adhesive, it is also possible to containing oxetane compound.By adding oxetane compound, the decrease in viscosity of curable adhesive, it is possible to accelerate curing rate.
Oxetane compound is the compound in molecule with at least 1 oxetanes ring (4 yuan of cyclic ethers), such as can enumerate 3-ethyl-3-hydroxymethyl oxetane, Isosorbide-5-Nitrae-bis-((3-ethyl-3-oxetanyl) methoxy) benzene, 3-ethyl-3-(phenoxymethyl) oxetanes, two ((3-ethyl-3-oxetanyl) methyl) ether, 3-ethyl-3-(2-Ethylhexoxymethyl) oxetanes, phenol novolac oxetanes etc..These oxetane compounds, can easily buy commercially available product, such as, the commodity sold in arbitrary East Asia synthesis (strain) can be enumerated and be called the commercially available products such as " AroneOxetaneOXT-101 ", " AroneOxetaneOXT-121 ", " AroneOxetaneOXT-211 ", " AroneOxetaneOXT-221 ", " AroneOxetaneOXT-212 ".The use level of oxetane compound is not particularly limited, and with active energy ray-curable chemical combination object for benchmark, is generally below 50 weight %, it is preferred to 10～40 weight %.
When curable adhesive contains the cationically polymerizable compound of epoxide, oxetane compound etc., this curable adhesive is generally mated light cationic polymerization initiators.When making with light cationic polymerization initiators, owing to room temperature can form adhesive layer, therefore consider that the necessity of the strain that the thermostability of polarizing coating or expansion cause can reduce, it is possible to polarizing coating and protecting film are fitted by adaptation well.Additionally, light cationic polymerization initiators owing to playing a role under the catalysis of light, even if therefore mixing in curable adhesive, the storage stability of curable adhesive, workability are also excellent.
About light cationic polymerization initiators, it is the irradiation by luminous ray, ultraviolet, X ray or electron beam isoreactivity energy line, produces cation kind or lewis acid, cause the material of the polyreaction of cationically polymerizable compound.Light cationic polymerization initiators can be arbitrary kind, and concrete example can enumerate such as aromatic diazonium salt；Aromatic iodonium salts, the such salt of aromatic series sulfonium salt；Iron-arene complex etc..
As aromatic diazonium salt, it is possible to enumerate following compound:
Benzene diazonium hexafluoro antimonate,
Benzene diazonium hexafluorophosphate,
Benzene diazonium hexafluoro borate etc..
It addition, as aromatic iodonium salts, it is possible to enumerate following compound:
Diphenyl iodonium four (pentafluorophenyl group) borate,
Diphenyl iodonium hexafluorophosphate,
Diphenyl iodonium hexafluoro antimonate,
Two (4-nonyl phenyl) iodine hexafluorophosphate etc..
As aromatic series sulfonium salt, it is possible to enumerate following compound:
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoro antimonate,
Triphenylsulfonium four (pentafluorophenyl group) borate,
The double; two hexafluorophosphate of 4,4 '-bis-(diphenyl sulfonium) diphenyl sulfur,
The double; two hexafluoro antimonate of 4,4 '-bis-[two (beta-hydroxy ethyoxyl) phenyl sulfonium] diphenyl sulfur,
The double; two hexafluorophosphate of 4,4 '-bis-[two (beta-hydroxy ethyoxyl) phenyl sulfonium] diphenyl sulfur,
7-[two (p-methylphenyl) sulfonium]-ITX hexafluoro antimonate,
7-[two (p-methylphenyl) sulfonium]-ITX four (pentafluorophenyl group) borate,
4-phenylcarbonyl group-4 '-diphenyl sulfonium-diphenyl sulfur hexafluorophosphate,
4-(to tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium-diphenyl sulfur hexafluoro antimonate,
4-(to tert-butyl-phenyl carbonyl)-4 '-two (p-methylphenyl) sulfonium-diphenyl sulfur four (pentafluorophenyl group) borate etc..
Additionally, as iron-arene complex, it is possible to enumerate such as following compound.
Dimethylbenzene-cyclopentadienyl group ferrum (II) hexafluoro antimonate, cumene-cyclopentadienyl group ferrum (II) hexafluorophosphoric acid ester, dimethylbenzene-cyclopentadienyl group ferrum (II) three (trimethyl fluoride sulfonyl) methanides etc..
nullThese light cationic polymerization initiators，Commercially available product can be readily available，Such as，If naming by trade name respectively，Then can enumerate chemical medicine company system of Japan " KayaradPCI-220 "、“KayaradPCI-620”、Associating carbide (UnionCarbide) company system " UVI-6990 "、DAICELCYTEC company system " UVACURE1590 "、(strain) ADEKA system " AdekaOptomerSP-150 "、“AdekaOptomerSP-170”、Cao Da company system of Japan " CI-5102 "、“CIT-1370”、“CIT-1682”、“CIP-1866S”、" CIP-2048S " and " CIP-2064S "、Green chemical company system " DPI-101 "、“DPI-102”、“DPI-103”、“DPI-105”、“MPI-103”、“MPI-105”、“BBI-101”、“BBI-102”、“BBI-103”、“BBI-105”、“TPS-101”、“TPS-102”、“TPS-103”、“TPS-105”、“MDS-103”、“MDS-105”、“DTS-102”、“DTS-103”、Sub-(Rhodia) company system " PI-2074 " in sieve ground、Deng.
These light cationic polymerization initiators, it is possible to individually use, it is also possible to two or more mixes use.Wherein, especially aromatic series sulfonium salt, even if also having Ultraviolet Light in 300nm wavelength above region; therefore curable is excellent; can provide and there is good mechanical strength, additionally can provide the solidfied material with the polarizing coating good adaptation intermembranous with protection, it is thus preferred to use.
About the use level of light cationic polymerization initiators, relative to total 100 weight portion of the cationically polymerizable compound comprising epoxide or oxetane compound, it is common that 0.5～20 weight portion, it is preferable that 1～6 weight portion.When the use level of light cationic polymerization initiators is few, solidify insufficient, there is the trend that between mechanical strength, polarizing coating and protecting film, cementability reduces.On the other hand, when the use level of light cationic polymerization initiators is too much, the ionic substance in solidfied material increases, and therefore there is the probability of the endurance quality reduction of the hygroscopicity raising of solidfied material, gained adhesive layer.
Additionally, can with above-mentioned epoxide jointly containing promising free-radical polymerised (methyl) acryloyl based compound in curable adhesive, or can with epoxide and oxetane compound jointly containing promising free-radical polymerised (methyl) acryloyl based compound.By and with (methyl) acryloyl based compound, it is possible to expect the effect improving the hardness of adhesive layer, mechanical strength, and then, the adjustment of the viscosity of curable adhesive, curing rate etc. becomes easier to carry out.
As (methyl) acryloyl based compound, molecule can be enumerated and be contained within (methyl) acrylate monomer of at least 1 (methyl) acryloxy, two or more there is the compound reaction of functional group and there is in the molecule that obtains (methyl) acrylate oligomer etc. of at least 2 (methyl) acryloxies.These can individually use, it is also possible to two or more is also used.Two or more is the used time also, it can be two or more (methyl) acrylate monomer, can be two or more (methyl) acrylate oligomer, naturally it is also possible to and with more than a kind (methyl) acrylate monomer and more than a kind (methyl) acrylate oligomer.Additionally, so-called " (methyl) acrylate ", refer to acrylate or methacrylate.
In above-mentioned (methyl) acrylate monomer, can have multifunctional (methyl) acrylate monomer of (methyl) acryloxy of more than 3 in (methyl) acrylate monomers and molecule including 2 officials in molecule in simple function (methyl) acrylate monomer of 1 (methyl) acryloxy, molecule to have with 2 (methyl) acryloxies.
nullConcrete example as simple function (methyl) acrylate monomer，(methyl) tetrahydrofurfuryl acrylate can be enumerated、(methyl) acrylic acid 2-hydroxy methacrylate、(methyl) acrylic acid 2-or 3-hydroxy propyl ester、(methyl) acrylic acid 2-hydroxybutyl、2-hydroxyl-3-phenoxy propyl (methyl) acrylate，(methyl) Isobutyl 2-propenoate、(methyl) tert-butyl acrylate、(methyl) 2-EHA、(methyl) cyclohexyl acrylate、(methyl) acrylic acid dicyclopentenyl ester、(methyl) benzyl acrylate、(methyl) acrylic acid norbornene ester、(methyl) acrylate、Dicyclopentenyl oxygen base ethyl (methyl) acrylate、Dimethyl aminoethyl (methyl) acrylate，Ethyl carbitol (methyl) acrylate、Trimethylolpropane list (methyl) acrylate、Tetramethylolmethane list (methyl) acrylate、Phenoxy group Polyethylene Glycol (methyl) acrylate etc..
As simple function (methyl) acrylate monomer, it is possible to use (methyl) acrylate monomer containing carboxyl.
As simple function (methyl) acrylate monomer containing carboxyl, phthalic acid 2-(methyl) acrylyl oxy-ethyl ester, hexahydrophthalic acid 2-(methyl) acrylyl oxy-ethyl ester, carboxyethyl (methyl) acrylate, succinic acid 2-(methyl) acrylyl oxy-ethyl ester can be enumerated, N-(methyl) acryloyl-oxy-N ', N '-dicarboxy-methyl-P-pHENYLENE dI AMINE, trimellitic acid 4-(methyl) acrylyl oxy-ethyl ester etc..
As 2 officials' energy (methyl) acrylate monomers, representational enumerate: aklylene glycol two (methyl) esters of acrylic acid, polyether polyols two (methyl) esters of acrylic acid, halogeno alkylen glycol two (methyl) esters of acrylic acid, two (methyl) esters of acrylic acid of aliphatic polyol, two (methyl) esters of acrylic acid of hydrogenation bicyclopentadiene or tristane dialkanol, two (methyl) esters of acrylic acid of dioxane glycol or dioxane dialkanol, two (methyl) esters of acrylic acid of the alkylen oxide adducts of bisphenol-A or Bisphenol F, epoxy two (methyl) esters of acrylic acid etc. of bisphenol-A or Bisphenol F.
nullExample more specifically as 2 officials' energy (methyl) acrylate monomers，Ethylene glycol bisthioglycolate (methyl) acrylate can be enumerated、1，3-butanediol two (methyl) acrylate、1，4-butanediol two (methyl) acrylate、1，6-hexanediol two (methyl) acrylate、1，9-nonanediol two (methyl) acrylate、Neopentyl glycol two (methyl) acrylate、Trimethylolpropane two (methyl) acrylate、Tetramethylolmethane two (methyl) acrylate、Two trimethylolpropane two (methyl) acrylate、Diethylene glycol two (methyl) acrylate、Triethylene glycol two (methyl) acrylate、Dipropylene glycol two (methyl) acrylate、Tripropylene glycol two (methyl) acrylate、Polyethylene Glycol two (methyl) acrylate、Polypropylene glycol two (methyl) acrylate、Polytetramethylene glycol two (methyl) acrylate、Silicone two (methyl) acrylate、Two (methyl) acrylate of 3-hydroxypivalic acid DOPCP、2，Double; two [4-(methyl) acryl-oyloxyethoxy ethoxyl phenenyl] propane of 2-、2，Double; two [4-(methyl) acryl-oyloxyethoxy ethoxycyclohexyl] propane of 2-、Hydrogenation dicyclopentadienyl two (methyl) acrylate、Tricyclodecane Dimethanol two (methyl) acrylate、1，3-dioxane-2，5-bis-base two (methyl) acrylate (another name: dioxane glycol two (methyl) acrylate)、Acetal compound (chemical name: 2-(the 2-hydroxyl-1 of hydroxyl spy's valeral and trimethylolpropane，1-dimethyl ethyl)-5-ethyl-5-hydroxymethyl-1，3-dioxane) two (methyl) acrylate、Three (hydroxyethyl) isocyanuric acid ester two (methyl) acrylate etc..
nullCan above multifunctional (methyl) acrylate monomer as 3 officials，Representational have glycerol three (methyl) acrylate、Trimethylolpropane tris (methyl) acrylate、Double trimethylolpropane three (methyl) acrylate、Double trimethylolpropane four (methyl) acrylate、Tetramethylolmethane three (methyl) acrylate、Tetramethylolmethane four (methyl) acrylate、Dipentaerythritol four (methyl) acrylate、Dipentaerythritol five (methyl) acrylate、3 officials of dipentaerythritol six (methyl) acrylate etc. can poly-(methyl) acrylate of above aliphatic polyol，Additionally，Can enumerate 3 officials can poly-(methyl) acrylate of above halogenated polyol、Three (methyl) acrylate of the alkylen oxide adducts of glycerol、Three (methyl) acrylate of the alkylen oxide adducts of trimethylolpropane、1，1，1-tri-[(methyl) acryl-oyloxyethoxy ethyoxyl] propane、Three (hydroxyethyl) isocyanuric acid ester three (methyl) esters of acrylic acid etc..
On the other hand, in (methyl) acrylate oligomer, there are urethane (methyl) acrylate oligomer, polyester (methyl) acrylate oligomer, epoxy (methyl) acrylate oligomer etc..
So-called urethane (methyl) acrylate oligomer, is the compound in molecule with urethane bond (-NHCOO-) and at least 2 (methyl) acryloxies.Specifically, it is possible to be respectively provided with the urethane reaction product of (methyl) acrylate monomer containing hydroxyl of at least 1 (methyl) acryloxy and at least 1 hydroxyl and polyisocyanate in molecule, make polyalcohols and polyisocyanate reacts and in the carbamate compounds containing terminal isocyanate acid group conjunction base that obtains and molecule, be respectively provided with the urethane reaction product etc. of (methyl) acrylate monomer of at least 1 (methyl) acryloxy and at least 1 hydroxyl.
Contain (methyl) acrylate monomer as the hydroxyl used in above-mentioned urine alkylation reaction, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, glycerol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc. can be enumerated.
As being supplied in the polyisocyanate containing the urine alkylation reaction that (methyl) acrylate monomer carries out with this hydroxyl, hexamethylene diisocyanate can be enumerated, lysinediisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, toluene di-isocyanate(TDI), xylylene diisocyanate, diisocyanate isocyanates aromatic in these diisocyanate being hydrogenated with and obtain is (such as, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate etc.), triphenylmethane triisocyanate, two-or tri-isocyanate of dibenzyl benzene triisocyanate etc., with, the polyisocyanate etc. making above-mentioned diisocyanate multimerization and obtain.
It addition, close, as being used for by the reaction with polyisocyanate making, the polyalcohols used in the urethane compound of base containing terminal isocyanate acid group, outside the polyhydric alcohol of aromatic series, aliphatic and ester ring type, it be also possible to use PEPA, polyether polyol etc..Polyhydric alcohol as aliphatic and ester ring type, 1 can be enumerated, 4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, two trimethylolpropanes, tetramethylolmethane, dipentaerythritol, dihydroxymethyl heptane, dihydromethyl propionic acid, the acid of dihydroxymethyl butane, glycerol, hydrogenated bisphenol A etc..
PEPA, is the material obtained by the dehydration condensation of above-mentioned polyalcohols and polybasic carboxylic acid or its anhydride.Example for polybasic carboxylic acid or its acid anhydride, if the material can become acid anhydride marks " (acid anhydride) ", then can enumerate succinic acid (acid anhydride), adipic acid, maleic acid (acid anhydride), itaconic acid (acid anhydride), trimellitic acid (acid anhydride), PMA (acid anhydride), phthalic acid (acid anhydride), M-phthalic acid, p-phthalic acid, hexahydrophthalic acid (acid anhydride) etc..
Polyether polyol is except poly alkylene glycol, it is possible to be the polyoxy alkylidene modified polyalcohol etc. obtained by the reaction with oxyalkylene of above-mentioned polyalcohols or dihydroxy benzenes class.
So-called polyester (methyl) acrylate oligomer, has ester bond and the compound of at least 2 (methyl) acryloxies in molecule.Specifically, it is possible to use (methyl) acrylic acid, polybasic carboxylic acid or its anhydride and polyhydric alcohol, obtained by dehydration condensation.Example by the polybasic carboxylic acid used in dehydration condensation or its anhydride, if the material can become anhydride marks " (acid anhydride) ", then there are succinic acid (acid anhydride), adipic acid, maleic acid (acid anhydride), itaconic acid (acid anhydride), trimellitic acid (acid anhydride), PMA (acid anhydride), hexahydrophthalic acid (acid anhydride), phthalic acid (acid anhydride), M-phthalic acid, p-phthalic acid etc..Additionally, as the polyhydric alcohol used in dehydration condensation, 1 can be enumerated, 4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, two trimethylolpropanes, tetramethylolmethane, dipentaerythritol, dihydroxymethyl heptane, dihydromethyl propionic acid, the acid of dihydroxymethyl butane, glycerol, hydrogenated bisphenol A etc..
Epoxy (methyl) acrylate oligomer can be obtained by poly epihydric alcohol base ether and (methyl) acrylic acid additive reaction, has at least 2 (methyl) acryloxies in its molecule.As the poly epihydric alcohol base ether used in additive reaction, ethylene glycol diglycidyl base ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol-A diglycidyl ether etc. can be enumerated.
When coordinating (methyl) acryloyl based compound in curable adhesive, its amount is with all amount of active energy ray-curable compound for benchmark, it is preferred to below 20 weight %, more preferably below 10 weight %.When the use level of (methyl) acryloyl based compound is many, the adaptation between polarizing coating and protecting film has the tendency of decline.
Curable adhesive contain described above the free-radical polymerised compound such as (methyl) acryloyl based compound time, it is preferable that coordinate optical free radical polymerization initiator.As optical free radical polymerization initiator, as long as by the irradiation of active energy ray, the material of the polymerization of the free-radical polymerised compound of (methyl) acryloyl based compound etc. can be caused, it is possible to use known material.The concrete example of optical free radical polymerization initiator, can enumerate 1-Phenylethanone., 3-methyl acetophenone, benzyl dimethyl ketal, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-methyl isophthalic acid-[1-Phenylethanone. series initiators of 4-(methyl sulfur) phenyl-2-morpholino propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone etc.；Benzophenone, 4-chlorobenzophenone, 4, the benzophenone series initiators such as 4 '-diaminobenzophenone；The benzoin ether series initiators such as benzoin propyl ether, benzoin ethyl ether；The thiaxanthone series initiators such as ITX；Other also have, ton ketone, Fluorenone, camphorquinone, benzaldehyde, anthraquinone etc..
The use level of optical free radical polymerization initiator, relative to free-radical polymerised compound 100 weight portion of (methyl) acryloyl based compound etc., is generally 0.5～20 weight portion, it is preferable that 1～6 weight portion.When the amount of optical free radical polymerization initiator is few, solidifying insufficient, the cementability of mechanical strength, polarizing coating and protecting film has downward trend.Additionally, when the amount of optical free radical polymerization initiator is too much, active energy ray-curable compound (free-radical polymerised compound such as the curable compound of the cationically polymerizable containing epoxide and (methyl) acryloyl based compound) in curable adhesive becomes relatively fewer, and the endurance quality of the adhesive layer of gained likely declines.
Curable adhesive can also contain light sensitizer as required.By coordinating light sensitizer, the reactive raising of cationic polymerization and/or radical polymerization, it is possible to improve the mechanical strength of adhesive layer, cementability between polarizing coating and protecting film.As light sensitizer, for instance, carbonyl compound, organosulfur compound, persulfide, oxidoreduction based compound, azo and diazonium compound, halogen compounds, photo-reduction pigment etc. can be enumerated.The example more specifically of light sensitizer, can enumerate the benzoin derivatives of benzoin methyl ether, benzoin isopropyl ether and α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone etc；The benzophenone derivates of benzophenone, 2,4-dichloro benzophenones, o-benzoyl essence of Niobe, 4,4 '-bis-(dimethylamino) benzophenone and 4,4 '-bis-(diethylamino) benzophenone etc；The thioxanthone derivates of CTX, ITX etc；The anthraquinone derivative of 2-chloroanthraquinone, 2-methylanthraquinone etc；The acridone derivatives of N-methylacridine ketone, N-butyl acridone etc；Also have α, α-diethoxy acetophenone, benzyl, Fluorenone, ton ketone, uranyl compound, halogen compounds etc..These light sensitizers, it is possible to individually use, it is also possible to mix two or more and use.Active energy ray-curable compound entirety is being set to 100 weight portions by light sensitizer, it is preferable that coordinate with the ratio of 0.1～20 weight portion.
In curable adhesive, it is possible to add normally used known polymeric additive in macromolecule.Such as, the UV absorbent etc. of a secondary antioxidant of phenol system, amine system etc, the secondary antioxidant of sulfur system, hindered amine system light stabilizer (HALS), benzophenone series, benzotriazole system or benzoate system etc can be enumerated.
Curable adhesive can also contain solvent as required.Solvent can consider that the dissolubility constituting the composition of curable adhesive suitably selects.The example of general solvent, it is possible to enumerate the aliphatic hydrocarbon of normal hexane, hexamethylene etc；Toluene, dimethylbenzene etc aromatic hydrocarbon based；The alcohols of methanol, ethanol, propanol, isopropanol and n-butyl alcohol etc；The ketone of acetone, butanone, methyl iso-butyl ketone (MIBK) and Ketohexamethylene etc；The esters of methyl acetate, ethyl acetate and acetic acid butyl etc；The cellosolve class of methyl cellosolve, ethyl cellosolve and butyl cellosolve etc；The halogenated hydro carbons etc. of dichloromethane, chloroform etc.The viewpoint of the viscosity adjustment etc. that the mixing ratio of solvent can carry out according to the purpose in the processing such as film property goes out to send suitable decision.
[the second protecting film]
As it has been described above, fit on a face of polarizing coating during cyclic olefine resin molding, on the face of the opposition side of polarizing coating, it is possible to other the second protecting film being made up of thermoplastic resin of fitting.The second protecting film being made up of thermoplastic resin is also made by adhesive and fits in polarizing coating.Second protecting film can use such as acetate fiber prime system resin, polyolefin-based resins, acrylic resin, polyimides system resin, polycarbonate-based resin, polyester based resin etc., and this area was widely used in the appropriate materials forming material of protecting film in the past and constitutes.From the view point of production, cementability, in these, it is preferable that using cellulose acetate resin film as the second protecting film.From the view point of arrange easiness and the optical characteristics of surface-treated layer, as the second protecting film, it is preferable that cellulose acetate resin film.
Cellulose acetate resin film is the film being made up of cellulosic partially or completely acetas compound, can enumerate such as tri acetyl cellulose membrane, diacetyl cellulose film etc..As such cellulose acetate resin film, suitable commercially available product can be used, such as, " FujiTACTD80 " that Fujiphoto (strain) is sold, " FujiTACTD80UF " and " FujiTACTD80UZ ", " KC8UX2M " that Konica Minolta Optical Co., Ltd sells, " KC8UY " and " KC4UEW " etc. (more than, it is trade name).
The adhesive used in the laminating of the second protecting film and polarizing coating is not particularly limited; the above-mentioned various adhesive meant as the adhesive used in the laminating of polarizing coating and cyclic olefine resin molding can be used equally, it is preferred to use the adhesive identical with the adhesive used in above-mentioned cyclic olefine resin molding.When employing the laminating of these films of adhesive, in order to improve cementability, for the second protecting film and/or the bonding plane fitting in polarizing coating thereon, it is also possible to be appropriately carried out the surface treatment improved for above-mentioned cementability.The second protecting film is constituted, when using water system adhesive to fit in polarizing coating, as to one of preferred surface process that this cellulose acetate resin film is implemented, saponification being enumerated and process with cellulose acetate resin film.Saponification processes, by being carried out in the aqueous solution of the alkali of sodium hydroxide, potassium hydroxide etc by film immersion.
The film that second protecting film is preferably thin, but decrease in strength when crossing thin, have the tendency of poor in processability, and on the other hand, time blocked up, the transparency declines, and the weight of polarization plates has the tendency of increase.From such a viewpoint, the thickness of the second protecting film, when constituting with acetate fiber prime system resin, it is generally 10～200 μm, it is preferred to 20～150 μm, more preferably 30～100 μm.
Second protecting film, with on the face of face opposite side fitting in polarizing coating, it is possible to implement non-glare treated, hard painting process, antistatic process, reflection prevent the surface treatments such as process.
[manufacture method of polarization plates]
Hereinafter, the manufacture method of the polarization plates of the present invention is illustrated.As it has been described above, in the present invention, the protecting film being made up of cyclic olefine resin by adhesive laminating on polarizing coating, manufacture polarization plates.As required, the one side at polarizing coating is fitted the first protecting film being made up of cyclic olefine resin as described above, is also fitted on the another side of polarizing coating by adhesive by other the second protecting film being made up of thermoplastic resin.It addition, before fitting to polarizing coating, make the protecting film being made up of cyclic olefine resin in the turbidity value of this cyclic olefine resin molding is less than 0.5% scope with the essence organic solvent exposure without solute.By this process with organic solvent exposure, it is sometimes referred to as " solvent process " in this manual.
The organic solvent used during above-mentioned solvent is processed; from a kind of viewpoint; the organic solvent being set to make this cyclic olefine resin change when the cyclic olefine resin constituting the first protecting film with described above individually contacts is (following; it is sometimes referred to as " good solvent ") and; the mixture of the organic solvent (following, " poor solvent " is sometimes referred to as) of this cyclic olefine resin generation substantial variations is not made with this cyclic olefine resin when similarly individually contacting.
Certain organic solvent belongs to good solvent or poor solvent for cyclic olefine resin molding, it is possible to determined by following test.First, the cyclic olefine resin molding severing of protecting film will be become, take about 1.0g, in grams accurate weighing to arithmetic point 3, this quality will be set to Fg.It addition, still in grams accurately weighing organic solvent be about 99.0g to arithmetic point 3, this quality is set to Sg.In this organic solvent, by the resin molding thorough impregnation of above accurately weighing, place 24 hours.After 24 hours, observe the shape of resin molding of dipping, whether outward appearance changes.It addition, take the about 10.0g upper clear liquid that impregnated of the organic solvent of resin molding, still accurate weighing to arithmetic point 3 in grams, this quality is set to Lg.Thus, dry removing organic solvent, the solid constituent that weighing is remaining, this quality is set to Rg.The meltage of resin molding is obtained by these values.The consoluet situation of resin molding, defining the solution of [F (=about 1g)/{ F+S (=about 100g) } × 100 weight %] (=about 1 weight %), therefore dried solid constituent should remain [L (=about 10g) × F (=about 1g)/{ F+S (=about 100g) } g] (=about 0.1g).Therefore, by below formula (III), the dissolution rate of resin molding is calculated.
Thus, carrying out the resin molding after 24 h immersion in organic solvent, when shape, outward appearance not caused change and dissolution rate less than 1 weight %, this organic solvent is set to poor solvent.In addition, namely shape, outward appearance change or when dissolution rate is more than 1 weight %, and this organic solvent is set to good solvent.Certainly, there is also shape, outward appearance changes and dissolubility is more than 1 weight % situation, this organic solvent is good solvent.According to experiment, insoluble, but the state that the shape of film, outward appearance change, the state of the swelling state that can not rest on original shape and film generation albefaction is there is for film.
By the stretch ring olefin-based resin molding (trade name " ZEONOR film ", Japan ZEON (strain) system) of use in embodiment described later, as sample, in the experiment carry out multiple organic solvents, representative data collects in table 1 below." % " that represent dissolubility in table, is weight basis as described above.It addition, the material of " dissolution rate " field mark note "-", refer to and only carried out dipping experiment, after 24 h immersion, carry out visual inspection, but do not carry out the mensuration of dissolution rate.By the result of the visual inspection after 24 hours it can be seen that all substances dissolubility is nearly all speculated as zero.
[table 1]
By these result and the present inventor etc. experience up to now, hexamethylene, hexahydrotoluene, the dissolution rate of cyclic olefine resin close to 100%, is categorized as good solvent by the ester ring type hydro carbons such as ethyl cyclohexane.Additionally, although the aliphatic ethers such as toluene, dimethylbenzene etc. are aromatic hydrocarbon based, the halogenated hydro carbons such as dichloromethane, chloroform, Anaesthetie Ether, oxolane and, the dissolution rate of cyclic olefine resin has by the aliphatic hydrocarbon apoplexy due to endogenous wind such as pentane, hexane, heptane is more than 1%, also have less than 1%, but owing to the change of shape, outward appearance all can be caused, therefore still it is classified as described good solvent here.
On the other hand, the aliphatic alcohols such as the ketones such as butanone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, isopropanol, butanol, and the aliphatic ester such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate to the dissolubility of cyclic olefine resin less than 1%, do not cause the change of the shape of film, outward appearance, be therefore categorized as poor solvent.
Finding, in the above organic solvent enumerated, to dissolve cyclic olefine resin, even if the ester ring type hydrocarbon being categorized as good solvent is used alone, the bonding force to polarizing coating is also effective, and cyclic olefine resin will not be carried out excessive erosion.Therefore, in the present invention, considering from other starting point, the organic solvent that above-mentioned solvent uses in processing is set to the solvent containing ester ring type hydrocarbon.Ester ring type hydrocarbon typical case can be the compound shown in above-mentioned formula (I).When using ester ring type hydrocarbon, being arranged to except this ester ring type hydrocarbon, the mixed solvent containing poor solvent is advantageous for.It is mixed in the poor solvent of ester ring type hydrocarbon, for organic acid Arrcostab, it is preferable that the acetas of above citing.
In the present invention, it is very important for carrying out solvent process in the way of unduly corroding cyclic olefine resin molding, as unduly erosion index, the turbidity value of the cyclic olefine resin molding after adopting solvent to process.If the erosion development of cyclic olefine surface resin film, although the bonding force of polarizing coating improves, but become to damage the optical property of cyclic olefine resin molding.Here, solvent process is carried out with the turbidity value of the cyclic olefine resin molding after processing less than 0.5% mode.At this moment more preferably the turbidity value mode less than 0.3% processes, it is preferred that process in the way of less than 0.2%.Turbidity value has defined at JISK7136:2000 " the seeking method of the turbidity of plastics-transparent material ", is the value defined by (diffusional permeability/total light transmittance) × 100 (%).
Further, since solvent processes corrodes development deterioration, the phase contrast of film is eliminated, and in face, phase difference value has the tendency of decline.Therefore, stretch ring olefin-based resin molding and when giving phase difference value in face, in the face of the cyclic olefine resin molding processed based on solvent, the variable quantity of phase difference value is not as being also effective by the index of excessive erosion.Specifically, cyclic olefine resin molding is when having phase difference value in the face of more than 30nm before solvent processes, preferably by solvent process after face in phase difference value before treatment interior phase difference value than solvent decline less than 3nm in the way of, in other words, in face after solvent process, the mode that slippage (in the face after the interior phase difference value of before treatment of solvent-solvent process phase difference value) is below 3nm of before treatment relative to solvent interior phase difference value of phase difference value, carries out solvent process.More preferably in the face after solvent process, the slippage of before treatment relative to solvent interior phase difference value of phase difference value is below 2.5nm, it is particularly preferred that process in the way of below 2nm.When this slippage is big, when the polarization plates of gained is applied to liquid crystal indicator, it is possible to affect display characteristic.When being used alone ester ring type hydrocarbon in solvent processes, in this face, the slippage of phase difference value has the tendency increased slightly, therefore, from this viewpoint, re-uses it is also preferred that mix poor solvent in ester ring type hydrocarbon.
In the face of film, the refractive index in slow axis direction in the face of this film is set to n by phase difference value Rex, in face, the refractive index in leading phase shaft direction (direction orthogonal with slow axis in face) is set to ny, thickness is set to d, below formula (IV) value defined, it is possible to use commercially available various phase meters measure.
Re=(nx-ny)×d(IV)
When using mixed organic solvents, it is possible to determine blending ratio with reference to phase difference value in the turbidity value of cyclic olefine resin molding after solvent processes, face.
In the present invention, it is possible to through the operation of following (i)～(iii), manufacture polarization plates.At the first protecting film that the single-sided lamination of polarizing coating is made up of cyclic olefine resin, the another side at polarizing coating fit other the second protecting film being made up of thermoplastic resin time, adopt the operation of following (iv) further.
I () processes the solvent treatment process on the surface of cyclic olefine resin molding with the previously described essence organic solvent without solute,
(ii) drying process that above-mentioned organic solvent dries is made,
(iii) by processing with organic solvent and dry cyclic olefine resin molding, the mode being binding face with above-mentioned process face, the first bonding process of polarizing coating is fitted in by adhesive,
(iv) with on the face of the opposition side, face of the cyclic olefine resin molding of having fitted of above-mentioned polarizing coating, by the second bonding process of the second protecting film that adhesive laminating is made up of thermoplastic resin film.
In above-mentioned solvent treatment process (i), make cyclic olefine resin molding and previously described organic solvent exposure.Specifically, it is preferred to use the method that this organic solvent is coated with on the surface of cyclic olefine resin molding.The rubbing method used for this, can adopt the known methods such as the tape casting, Meyer stick coating method, gravure coating process, unfilled corner wheel rubbing method, doctor blade method, die coating method, dip coating, nebulization.To be processed can be the one side of cyclic olefine resin molding can also be two sides, and the face fitted at polarizing coating is implemented this process.
Then, in above-mentioned drying process (ii), the organic solvent being used in the surface processing cyclic olefine resin molding dries.Natural drying it is of course possible to, during heat drying, from the view point of prevent the deformation of film, it is preferable that be dried with the glass transition point temperature below of cyclic olefine resin molding.This drying process (ii) can be parallel with solvent treatment process (i), and preferred such parallel processing, when namely cyclic olefine resin molding being processed with organic solvent, carries out the operation making this organic solvent dry simultaneously.Specifically, it is possible to adopt and coated face is dried, while being coated with the method etc. of organic solvent.
In above-mentioned the first bonding process (iii), the mode being binding face with this process face by the cyclic olefine resin molding that processes with organic solvent, fit in polarizing coating by adhesive.Here applying method can be usual generally known method, such as can adopt by the tape casting, Meyer stick coating method, gravure coating process, unfilled corner wheel coating, doctor blade method, die coating method, dip coating, nebulization etc., at polarizing coating and/or fit in coating binder on the bonding plane of cyclic olefine resin molding thereon, the method that both are overlapped.Here, so-called the tape casting, be using as applied thing film in substantially vertical direction, general horizontal direction, or tilted direction between the two moves, while flowing down, on this surface, the method that adhesive makes it extend.After coating binder, clamp polarizing coating by pressure roller etc. and cyclic olefine resin molding makes it fit.It addition, adopt after the intermembranous adhesive that drips, when carrying out the method for pressurization uniform pressurization extension with roller etc., the material of the roller of use can be metal, rubber etc., by each roller used time between 2 rollers, it is possible to is same material, it is also possible to be unlike material.
After cyclic olefine resin molding being fitted in polarizing coating by adhesive, use and pass through to dry during water system adhesive, when additionally using curable adhesive, make adhesive layer solidify by irradiation active energy ray.Dried such as can be passed through to blow hot blast and carry out.This temperature is generally in the scope of 40～100 DEG C, it is preferable that in the scope of 60～100 DEG C.It addition, be generally 20～1200 seconds drying time.On the other hand, the active energy ray that active energy ray uses in irradiating can be ultraviolet, electron beam, X ray, it is seen that light etc., it is generally preferable to use ultraviolet.Active energy ray, intensity and amount needed for solidifying according to making adhesive layer are irradiated.
With on the polarization face of opposition side, face being fitted with cyclic olefine resin molding, fit other the second protecting film being made up of thermoplastic resin time, proceed above-mentioned the second bonding process (iv).In this operation, it is possible to adopt the method same with above-mentioned first bonding process (iii).Second bonding process (iv) preferably carries out with above-mentioned the first bonding process (iii) simultaneously.
The thickness of the adhesive layer obtained after drying or solidifying is generally about 0.01～5 μm, but can be less than 1 μm when employing water system adhesive.On the other hand, when employing curable adhesive, it is also preferred that be set to less than 2 μm.When adhesive layer is crossed thin, it is possible to bonding become insufficient, when adhesive layer is blocked up on the other hand, there is the probability of the bad order producing polarization plates.
[polarization plates]
The polarization plates thus obtained is the polarization plates that the bonding force between polarizing coating and cyclic olefine resin molding is improved.Namely can obtain with lower polarizing plate: it is adsorbed with dichromatic pigment in polyvinyl alcohol resin and makes the protecting film being made up of cyclic olefine resin by adhesive laminating on the polarizing coating of its orientation; utilize previously described organic solvent under the state processed in the way of the turbidity value of the above-mentioned protecting film being made up of cyclic olefine resin is less than 0.5% scope; fit in above-mentioned polarizing coating by above-mentioned adhesive, and the bonding force relative to polarizing coating by above-mentioned adhesive is more than 0.5N/25mm.And then following polarization plates can also be obtained, it is adsorbed with dichromatic pigment in polyvinyl alcohol resin and makes the one side of polarizing coating of its orientation fit the first protecting film of being made up of cyclic olefine resin by adhesive, the second protecting film being made up of thermoplastic resin by adhesive laminating in another face of polarizing coating, utilize previously described organic solvent by above-mentioned by the turbidity value of the first protecting film that cyclic olefine resin is constituted less than 0.5% scope in the way of under state that it is processed, above-mentioned polarizing coating is fitted in by above-mentioned adhesive, and the bonding force relative to polarizing coating by above-mentioned adhesive is more than 0.5N/25mm.In any polarization plates, the first protecting film being made up of cyclic olefine resin is more than 0.7N/25mm by the bonding force relative to polarizing coating of adhesive, more preferably more than 0.8N/25mm.
Here, cyclic olefine resin molding is relative to the value that the bonding force of polarizing coating is following mensuration.Namely; as described above; at the first protecting film that the one side of polarizing coating is made up of cyclic olefine resin by adhesive laminating; fit other the ratio being made up of thermoplastic resin above-mentioned cyclic olefine resin molding the second protecting film that the bonding force of polarizing coating is bigger by adhesive in another face of polarizing coating; and then as required; make adhesive dry or solidify, thus making polarization plates.In this cyclic olefine resin molding side, adhesive phase is set.From thus obtain with binding agent polarization plates, the test film of severing width 25mm × be about 200mm, this binding agent face is fitted in glass plate, after the bonding force for glass plate of binding agent is fully improved, utilize cupping machine, clamp the second protecting film and the polarizing coating of length direction one end (one side of wide 25mm) of test film, temperature 23 DEG C, under the atmosphere of relative humidity 60%, with crosshead speed (clamp translational speed) the 200mm/ condition divided, carry out 90 ° of disbonded tests based on JISK6854-1:1999 " adhesive-stripping adhesive strength test method-1: 90 degree stripping " standard.By Average peel force (unit is N/25mm) now, as the cyclic olefine resin molding bonding force relative to polarizing coating.
When this bonding force is too small, can be peeling-off at the interface of polarizing coating and cyclic olefine resin molding, after as mentioned above polarization plates being fitted in liquid crystal cells, it is necessary to when doing over again, only cyclic olefine resin molding residues on liquid crystal cells sometimes.On the other hand, this bonding force is the bigger the better, but it is set to when being worth greatly, utilize the process (erosion) of the cyclic olefine resin molding of organic solvent to become over, can improve the turbidity value etc. of cyclic olefine resin molding, damages optical characteristics.Therefore, carrying out solvent process under the state of the optical characteristics being representative with the turbidity value of cyclic olefine resin molding with maintenance, improving cyclic olefine resin molding is important relative to the bonding force of polarizing coating.
The polarization plates obtained by the present invention, in the face with the polarizing coating opposition side of the cyclic olefine resin molding fitting in polarizing coating, it is possible to arrange adhesive phase.This adhesive phase may be used for the laminating at liquid crystal cells of this polarization plates, the laminating to other functional membrane, for instance the laminating to phase retardation film, uses in the laminating of other layer.In binding agent, it is possible to use using the binding agent as substrate polymer such as acrylic acid series polymeric compounds, silicone-based polymer, polyester, polyurethane, polyethers.Wherein, it is preferable that selecting to use as acryloyl system binding agent, optical transparence is excellent, keep appropriateness wellability or cohesiveness, cementability is also excellent, and has weatherability, thermostability etc., does not float stripping etc. when heating, humidification and peels off the material of problem.In acryloyl system binding agent, it is preferably less than 25 DEG C with glass transition temperature, more preferably the mode of less than 0 DEG C coordinates (methyl) acrylic acid Arrcostab with alkyl that carbon number is less than 20 such as methyl, ethyl, butyl, with be made up of (methyl) acrylic acid, (methyl) Hydroxyethyl Acrylate etc. containing functional group acrylic monomer, weight average molecular weight be the acrylic acid series copolymer of more than 100,000 as substrate polymer, be useful.
The formation of adhesive phase; such as carry out in the following way: dissolve in the organic solvent of toluene, ethyl acetate etc or disperse the adhesive composition being representative with above-mentioned substrate polymer; the solution of preparation 10～40 weight %; protecting film is formed adhesive phase, is moved the mode etc. being attached in polarization plates to be formed adhesive phase.Except coordinating above-mentioned substrate polymer in binding agent, generally also coordinate cross-linking agent.And then, during for fitting on liquid crystal cell, it is preferable that coordinate silane coupler.The thickness of adhesive phase determines according to this bonding force etc., is generally the scope of 1～50 μm.
Binding agent can coordinate glass fibre, glass microballoon, resin microbeads, the filler being made up of the inorganic powders such as metal powder etc., pigment, coloring agent, antioxidant, UV absorbent etc. as required.In UV absorbent, there are salicylate based compound, benzophenone based compound, benzotriazole based compound, cyanoacrylate based compound, nickel complex salt based compound etc..
Embodiment
Hereinafter, enumerate embodiment, specifically describe the present invention further, but the present invention is not limited by these examples.In example, represent the part and the % that make consumption and content, be then weight basis as do not illustrated.It addition, phase difference value and thickness direction phase difference value in the face of film, use prince to measure the measuring difference of phases device " KOBRA-21ADH " that machine (strain) is made, measure by rotating inspection photon method with the monochromatic light of wavelength 559nm.
The making of [manufacturing example 1] polarizing coating
By average degree of polymerization about 2400,99.9 moles of more than % of saponification degree, thickness 75 μm polyvinyl alcohol film be immersed in the pure water of 30 DEG C after, in the aqueous solution that weight ratio is 0.02/2/100 of iodine/potassium iodide/water, carry out dip dyeing with 30 DEG C.Then, impregnate with 56.5 DEG C in the aqueous solution that weight ratio is 12/5/100 of potassium iodide/boric acid/water, carry out boric acid process.It follows that after being carried out with the pure water of 8 DEG C, be dried at 65 DEG C, obtain the polarizing coating that gas absorption quantity in polyvinyl alcohol has the thickness about 30 μm of iodine.Stretching and mainly carry out in the operation that iodine staining and boric acid process, total stretching ratio is 5.3 times.
The preparation of [manufacturing example 2] adhesive compound
Acetoacetyl modified polyvinyl alcohol (trade name " GohsefimerZ-200 ", synthetic chemical industry company of Japan system, the viscosity of 4% aqueous solution=12.4mPa sec, saponification degree=99.1 mole %) is dissolved in pure water, prepares the aqueous solution of 10% concentration.By this acetoacetyl modified polyvinyl alcohol water solution; with the sodiam glyoxlate becoming cross-linking agent; with the former: the solids by weight of the latter mixes than the mode for 1:0.1; and then relative to 100, water; the mode pure water dilution being 2.5 with acetoacetyl modified polyvinyl alcohol, prepares adhesive compound.
[reference examples]
(A) protecting film
One side at the stretch ring olefin-based resin molding (trade name " ZEONOR film ", Japan ZEON (strain) system, phase difference value=90nm in face, thickness direction phase difference value=79nm) of thickness 25 μm implements sided corona treatment, as a protecting film.The turbidity value of this film uses the turbidity transmitance meter (in (strain) village " HR-100 " of color technical research institute) based on JISK7361-1:1997 " test method-of the total light transmittance of plastics-transparent material 1: single beam method " standard to be measured, and result is shown in table 2.It addition, the one side at the cellulose acetate resin film (trade name " KC4UEW ", Konica Minolta optics (strain) is made) of thickness 40 μm implements sided corona treatment, as another protecting film.
(B) making of polarization plates
The two sides of the polarizing coating made in manufacturing example 1, it is coated manufacturing the adhesive compound of preparation in example 2 under the atmosphere of 23 DEG C, an adhesive coated face is fitted the above-mentioned stretch ring olefin-based resin molding through sided corona treatment, another adhesive coated face is fitted the above-mentioned cellulose acetate resin film through sided corona treatment, above-mentioned laminating be respectively using its sided corona treatment face as with the binding face of polarizing coating in the way of, use laminating apparatus (" LPA3301 " that FUJIPURA (strain) makes) to carry out.It is dried 5 minutes at 80 DEG C, makes polarization plates.
(C) evaluation of bonding force
After the cyclic olefine surface resin film of the polarization plates of above-mentioned making implements sided corona treatment, acryloyl system adhesive sheet of fitting in this sided corona treatment face.Determining wide 25mm from the polarization plates with binding agent obtained, length is about the test film of 200mm, after this binding agent face is fitted in soda-lime glass, in autoclave, at pressure 5kgf/cm2, temperature 50 C condition carries out the pressurized treatments of 20 minutes, further, temperature 23 DEG C, under the atmosphere of relative humidity 60%, places 1 day.In this condition, use universal tensile testing machine (" AG-1 " of (strain) Shimadzu Seisakusho Ltd.), clamp cellulose acetate resin film and the polarizing coating of length direction one end (one side of wide 25mm) of test film, temperature 23 DEG C, under the atmosphere of relative humidity 60%, crosshead speed (clamp translational speed) 200mm/ divides under condition, carry out 90 ° of disbonded tests (based on JISK6854-1:1999 " adhesive-stripping adhesive strength test method-1: 90 degree stripping "), evaluate the bonding force between cyclic olefine resin molding and polarizing coating.Show the result in table 2.
[embodiment 1]
In above-mentioned reference examples; one side at the stretch ring olefin-based resin molding used as a protecting film; use coating machine (bar coater that the first physics and chemistry (strain) is made), be coated with and be coated with toluene: the organic solvent that butanone=1:9 (volume ratio) mixes.This coating is while drying while carrying out to applicator surface aerator.Method shown in (A) of the turbidity value reference examples of the cyclic olefine resin molding after process being measured, result illustrates in table 2.
Though it addition, visualization solvent process after the uneven result in the surface of cyclic olefine resin molding see not please, but examine the state that can confirm that inequality.Similarly, phase difference value in the cyclic olefine resin molding mensuration face after solvent is processed, to obtain and changed (when declining than phase difference value before treatment, being set to negative value) by value before treatment (90nm), this difference is-0.3nm.In below example and comparative example, cyclic olefine resin molding after solvent is processed, in the same manner as this example, carry out the mensuration of phase difference value in the observation dough-making powder of the mensuration of turbidity value, surface inequality, turbidity value is shown in " turbidity value " hurdle of table 2, surface inequality is evaluated according to following 3 grades, and result is shown in " inequality " hurdle of table 2, film before treatment in the face occurred, the change of phase difference value is shown in " Re change " hurdle of table 2.
(metewand of the surface inequality of the film after solvent process)
Nothing: not can confirm that inequality completely.
Weak: not see, examine and can confirm that inequality (state of embodiment 1).
Strong: can clearly to confirm inequality.
Thus on the solvent process face of the stretch ring olefin-based resin molding processed through solvent, polarizing coating one side is fitted in after implementing sided corona treatment, another face at polarizing coating, fit the cellulose acetate resin film through sided corona treatment same with reference examples, additionally, make polarization plates in the same manner as reference examples.Bonding force between cyclic olefine resin molding and the polarizing coating of the polarization plates obtained is evaluated with the method same with (C) of reference examples, result is illustrated in table 2.
[embodiment 2]
Mixed solvent is changed to toluene: beyond butanone=2:8 (volume ratio), make polarization plates similarly to Example 1, be evaluated.The turbidity value of the cyclic olefine resin molding after being processed by solvent, the observed result that surface is uneven, the change of phase difference value in dough-making powder, and the bonding force between cyclic olefine resin molding and the polarizing coating of polarization plates are summarized in table 2.
[comparative example 1]
Mixed solvent is changed to toluene: beyond butanone=3:7 (volume ratio), make polarization plates similarly to Example 1, be evaluated.The turbidity value of the cyclic olefine resin molding after being processed by solvent, the observed result that surface is uneven, the change of phase difference value in dough-making powder, and the bonding force between cyclic olefine resin molding and the polarizing coating of polarization plates are summarized in table 2.
[embodiment 3]
At the one side of the stretch ring olefin-based resin molding identical with the film used as a protecting film in embodiment 1, use the coating machine coating hexamethylene identical with embodiment 1, carried out solvent process.Here, all evaporate be dried owing to coating terminates rear hexamethylene, so not carrying out aerator blowing.The turbidity value of the cyclic olefine resin molding after being processed by solvent, the observed result that surface is uneven, in dough-making powder, the change of phase difference value is summarized in table 2.It addition, after the solvent of the stretch ring olefin-based resin molding that such hexamethylene is processed processes face enforcement sided corona treatment, be supplied in the laminating for polarizing coating one side, in addition, make polarization plates similarly to Example 1.Bonding force between cyclic olefine resin molding and the polarizing coating of the polarization plates obtained method being similarly to Example 1 evaluated, result illustrates in table 2.
[embodiment 4]
The one side of the stretch ring olefin-based resin molding identical with the film used as a protecting film in embodiment 1, uses the coating machine coating hexahydrotoluene identical with embodiment 1, carries out solvent process.In this embodiment, applicator surface is dried while applying with aerator.The turbidity value of the cyclic olefine resin molding after being processed by solvent, the observed result that surface is uneven, in dough-making powder, the change of phase difference value is summarized in table 2.It addition, to after the solvent process face enforcement sided corona treatment of the stretch ring olefin-based resin molding processed with hexahydrotoluene, be supplied in the laminating to polarizing coating one side, in addition, make polarization plates similarly to Example 1.Bonding force between cyclic olefine resin molding and the polarizing coating of the polarization plates obtained with the method evaluation that embodiment 1 is same, illustrates in table 2 by result.
[embodiment 5]
Organic solvent is changed to ethyl cyclohexane, and other carry out experiment similarly to Example 4, and result is summarized in table 2.
[embodiment 6～13]
Organic solvent is set to as the hexahydrotoluene of good solvent or ethyl cyclohexane and the mixed solvent as the ethyl acetate of poor solvent, isopropyl acetate or propyl acetate, each combination and volume such as table 2 are arranged, other carry out experiment similarly to Example 4, and result is summarized in table 2.
[embodiment 14 and 15]
Organic solvent being set to the mixed solvent of the heptane as good solvent and the butanone as poor solvent, is arranged by both volumes such as table 2, other carry out experiment similarly to Example 4, and result is summarized in table 2.
[comparative example 2]
Organic solvent is changed to heptane, and other carry out experiment similarly to Example 4, and result is summarized in table 2.
[table 2]
As shown in table 2, in the reference examples employing the cyclic olefine resin molding not carrying out solvent process, the bonding force between polarizing coating and cyclic olefine resin molding is low.On the other hand, what the ratio of the toluene in the toluene/butanone mixed solvent used in solvent processes improved is prone in the comparative example 1 of erosion cyclic olefine resin molding, bonding force between polarizing coating and cyclic olefine resin molding improves, but the turbidity value of cyclic olefine resin molding is high to 0.6%, it is impossible to meet optical characteristics during polarization plates.On the other hand, the ratio of the toluene in the toluene/butanone mixed solvent used in being processed by solvent is set in the embodiment 1 and 2 of 10 volume % or 20 volume %, the turbidity value of cyclic olefine resin molding is maintained at the low value of 0.1%, it is possible to improve the bonding force between polarizing coating and cyclic olefine resin molding.
It addition, in hexamethylene, hexahydrotoluene or ethyl cyclohexane are used for the embodiment 3～5 that solvent processes, similarly, the turbidity value of cyclic olefine resin molding remains the low value of 0.1%, it is possible to improve the bonding force between polarizing coating and cyclic olefine resin molding.Only in these examples, in the embodiment 4 especially employing hexahydrotoluene in solvent process and the embodiment 5 employing ethyl cyclohexane, being processed by solvent, in the face of cyclic olefine resin molding, the decline of phase difference value has the tendency increased slightly.On the other hand, use is mixed as in the embodiment 6～13 of the ethyl acetate of poor solvent in as these ester ring type hydrocarbon of good solvent, both the decline of phase difference value in the face of cyclic olefine resin molding was suppressed at below 3nm, it is possible to improve the bonding force between polarizing coating and cyclic olefine resin molding.Employ in these embodiments 3～13 of ester ring type hydrocarbon, compared with the embodiment 1 and 2 employing toluene, uneven generation after solvent can be suppressed to process, it is also possible to the good appearance of retaining ring olefin-based resin molding and visuality, it is possible to improve the bonding force relative to polarizing coating.
The heptane as good solvent is used to carry out in the comparative example 2 of solvent process, bonding force between polarizing coating and cyclic olefine resin molding improves, but the turbidity value of cyclic olefine resin molding is high to 0.5%, also confirms after additionally processing that surface is uneven, therefore can not meet optical characteristics during polarization plates.On the other hand, heptane mix in the embodiment 14 and 15 used as the butanone of poor solvent, improve surface inequality, when suppressing the decline of phase difference value in the rising dough-making powder of turbidity value of cyclic olefine resin molding, it is possible to improve the bonding force between polarizing coating and cyclic olefine resin molding.

Claims (17)

1. a manufacture method for polarization plates, it is to adsorb dichromatic pigment the protecting film making the polarizing coating of this dichromatic pigment orientation be made up of cyclic olefine resin by adhesive laminating in polyvinyl alcohol resin, the method manufacturing polarization plates, wherein,
Make the described protecting film being made up of cyclic olefine resin, according to mode less than 0.5% of the turbidity value of this protecting film, contact with the essence mixed organic solvents without solute, then fit with described polarizing coating by described adhesive,
Described mixed organic solvents be because of contact make this cyclic olefine resin change organic solvent with will not because contacting the mixture of the organic solvent making this cyclic olefine resin generation substantial variations,
Described the organic solvent that this cyclic olefine resin changes is made to be when implementing the contact test that the sample of the described protecting film being made up of cyclic olefine resin impregnates 24 hours because of contact; the shape of this sample, outward appearance change; or dissolution rate now is more than 1 weight %
Described will not be when implementing the contact test that the sample of the described protecting film being made up of cyclic olefine resin impregnates 24 hours because contacting the organic solvent that make this cyclic olefine resin generation substantial variations; the shape of this sample, outward appearance do not change; and dissolution rate now is less than 1 weight %
The described protecting film being made up of cyclic olefine resin has phase difference value in the face of more than 30nm with described mixed organic solvents before contacting, and in the face of this protecting film after contact, phase difference value contacts in the way of reducing less than 3nm compared to phase difference value in the face before contact.
2. the manufacture method of a polarization plates; it is to adsorb dichromatic pigment in polyvinyl alcohol resin and make the one side of polarizing coating of this dichromatic pigment orientation fit the first protecting film of being made up of cyclic olefine resin by adhesive; at the second protecting film that the another side of polarizing coating is made up of thermoplastic resin by adhesive laminating; the method manufacturing polarization plates; wherein
Make described the first protecting film being made up of cyclic olefine resin, according to mode less than 0.5% of the turbidity value of this first protecting film, contact with the essence mixed organic solvents without solute, then fit with described polarizing coating by described adhesive,
Described mixed organic solvents be because of contact make this cyclic olefine resin change organic solvent with will not because contacting the mixture of the organic solvent making this cyclic olefine resin generation substantial variations,
Described the organic solvent that this cyclic olefine resin changes is made to be when implementing the contact test that the sample of the described protecting film being made up of cyclic olefine resin impregnates 24 hours because of contact; the shape of this sample, outward appearance change; or dissolution rate now is more than 1 weight %
Described will not be when implementing the contact test that the sample of the described protecting film being made up of cyclic olefine resin impregnates 24 hours because contacting the organic solvent that make this cyclic olefine resin generation substantial variations; the shape of this sample, outward appearance do not change; and dissolution rate now is less than 1 weight %
Described the first protecting film being made up of cyclic olefine resin has phase difference value in the face of more than 30nm with described mixed organic solvents before contacting, and in the face of this first protecting film after contact, phase difference value contacts in the way of reducing less than 3nm compared to phase difference value in the face before contact.
3. a manufacture method for polarization plates, it is to adsorb dichromatic pigment the protecting film making the polarizing coating of this dichromatic pigment orientation be made up of cyclic olefine resin by adhesive laminating in polyvinyl alcohol resin, the method manufacturing polarization plates, wherein,
Make the described protecting film being made up of cyclic olefine resin, according to mode less than 0.5% of the turbidity value of this protecting film, and the organic solvent exposure without solute containing ester ring type hydrocarbon and essence, then by described adhesive and the laminating of described polarizing coating,
The described protecting film being made up of cyclic olefine resin with described organic solvent exposure before there is phase difference value in the face of more than 30nm; and by contact after this protecting film face in phase difference value compared to contact before face in phase difference value reduce less than 3nm in the way of contact
Described ester ring type hydrocarbon is represented by following formula (I),
In formula, m is the integer of 2～6, and R is hydrogen atom or the alkyl of carbon number 1～5.
4. the manufacture method of a polarization plates; it is to adsorb dichromatic pigment in polyvinyl alcohol resin and make the one side of polarizing coating of this dichromatic pigment orientation fit the first protecting film of being made up of cyclic olefine resin by adhesive; at the second protecting film that the another side of polarizing coating is made up of thermoplastic resin by adhesive laminating; the method manufacturing polarization plates; wherein
Make described the first protecting film being made up of cyclic olefine resin, according to mode less than 0.5% of the turbidity value of this first protecting film, and the organic solvent exposure without solute containing ester ring type hydrocarbon and essence, then by described adhesive and the laminating of described polarizing coating,
Described the first protecting film being made up of cyclic olefine resin with described organic solvent exposure before there is phase difference value in the face of more than 30nm; and by contact after this first protecting film face in phase difference value compared to contact before face in phase difference value reduce less than 3nm in the way of contact
Described ester ring type hydrocarbon is represented by following formula (I),
In formula, m is the integer of 2～6, and R is hydrogen atom or the alkyl of carbon number 1～5.
5. a manufacture method for polarization plates, it is to adsorb dichromatic pigment the protecting film making the polarizing coating of this dichromatic pigment orientation be made up of cyclic olefine resin by adhesive laminating in polyvinyl alcohol resin, the method manufacturing polarization plates, wherein,
By the film uniaxial tension being made up of cyclic olefine resin being prepared the described protecting film being made up of cyclic olefine resin,
Make the described protecting film being made up of cyclic olefine resin, according to mode less than 0.5% of the turbidity value of this protecting film, contact with the essence mixed organic solvents without solute, then fit with described polarizing coating by described adhesive,
Described mixed organic solvents be because of contact make this cyclic olefine resin change organic solvent with will not because contacting the mixture of the organic solvent making this cyclic olefine resin generation substantial variations,
Described the organic solvent that this cyclic olefine resin changes is made to be when implementing the contact test that the sample of the described protecting film being made up of cyclic olefine resin impregnates 24 hours because of contact; the shape of this sample, outward appearance change; or dissolution rate now is more than 1 weight %
Described will not be when implementing the contact test that the sample of the described protecting film being made up of cyclic olefine resin impregnates 24 hours because contacting the organic solvent that make this cyclic olefine resin generation substantial variations; the shape of this sample, outward appearance do not change, and dissolution rate now is less than 1 weight %.
6. the manufacture method of a polarization plates; it is to adsorb dichromatic pigment in polyvinyl alcohol resin and make the one side of polarizing coating of this dichromatic pigment orientation fit the first protecting film of being made up of cyclic olefine resin by adhesive; at the second protecting film that the another side of polarizing coating is made up of thermoplastic resin by adhesive laminating; the method manufacturing polarization plates; wherein
By the film uniaxial tension being made up of cyclic olefine resin being prepared described the first protecting film being made up of cyclic olefine resin,
Make described the first protecting film being made up of cyclic olefine resin, according to mode less than 0.5% of the turbidity value of this first protecting film, contact with the essence mixed organic solvents without solute, then fit with described polarizing coating by described adhesive,
Described mixed organic solvents be because of contact make this cyclic olefine resin change organic solvent with will not because contacting the mixture of the organic solvent making this cyclic olefine resin generation substantial variations,
Described the organic solvent that this cyclic olefine resin changes is made to be when implementing the contact test that the sample of the described protecting film being made up of cyclic olefine resin impregnates 24 hours because of contact; the shape of this sample, outward appearance change; or dissolution rate now is more than 1 weight %
Described will not be when implementing the contact test that the sample of the described protecting film being made up of cyclic olefine resin impregnates 24 hours because contacting the organic solvent that make this cyclic olefine resin generation substantial variations; the shape of this sample, outward appearance do not change, and dissolution rate now is less than 1 weight %.
7. a manufacture method for polarization plates, it is to adsorb dichromatic pigment the protecting film making the polarizing coating of this dichromatic pigment orientation be made up of cyclic olefine resin by adhesive laminating in polyvinyl alcohol resin, the method manufacturing polarization plates, wherein,
By the film uniaxial tension being made up of cyclic olefine resin being prepared the described protecting film being made up of cyclic olefine resin,
Making the described protecting film being made up of cyclic olefine resin, according to mode less than 0.5% of the turbidity value of this protecting film, and the organic solvent exposure without solute containing ester ring type hydrocarbon and essence, then by described adhesive and the laminating of described polarizing coating.
8. the manufacture method of a polarization plates; it is to adsorb dichromatic pigment in polyvinyl alcohol resin and make the one side of polarizing coating of this dichromatic pigment orientation fit the first protecting film of being made up of cyclic olefine resin by adhesive; at the second protecting film that the another side of polarizing coating is made up of thermoplastic resin by adhesive laminating; the method manufacturing polarization plates; wherein
By the film uniaxial tension being made up of cyclic olefine resin being prepared described the first protecting film being made up of cyclic olefine resin,
Making described the first protecting film being made up of cyclic olefine resin, according to mode less than 0.5% of the turbidity value of this first protecting film, and the organic solvent exposure without solute containing ester ring type hydrocarbon and essence, then by described adhesive and the laminating of described polarizing coating.
9. the manufacture method according to claim 7 or 8, wherein,
Described ester ring type hydrocarbon is represented by following formula (I),
In formula, m is the integer of 2～6, and R is hydrogen atom or the alkyl of carbon number 1～5.
10. the manufacture method according to claim 3 or 4 or 7 or 8, wherein,
Described ester ring type hydrocarbon is at least one in hexamethylene, hexahydrotoluene and ethyl cyclohexane.
11. according to the manufacture method described in claim 3 or 4 or 7 or 8, wherein,
Described organic solvent is in addition to outside described ester ring type hydrocarbon, possibly together with the mixed solvent of the organic solvent that will not make described cyclic olefine resin generation substantial variations because of contact,
Described will not be when implementing the contact test that the sample of the described protecting film being made up of cyclic olefine resin impregnates 24 hours because contacting the organic solvent that make this cyclic olefine resin generation substantial variations; the shape of this sample, outward appearance do not change, and dissolution rate now is less than 1 weight %.
12. manufacture method according to claim 11, wherein,
The described organic solvent that will not make cyclic olefine resin generation substantial variations is organic acid Arrcostab.
13. manufacture method according to claim 12, wherein,
Organic acid Arrcostab is acetas.
14. manufacture method according to claim 13, wherein,
Acetas is ethyl acetate, isopropyl acetate or propyl acetate.
15. the manufacture method according to any one of claim 1～8, wherein,
When making the described protecting film being made up of cyclic olefine resin with described organic solvent exposure, implement the operation making this organic solvent dry simultaneously.
16. the manufacture method according to any one of claim 1～8, wherein,
Described adhesive is water system adhesive.
17. manufacture method according to claim 16, wherein,
Described adhesive contains polyvinyl alcohol resin.
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