CN104520738B - Polyester film for polarizer protection, polarizing plate and liquid crystal display device - Google Patents

Polyester film for polarizer protection, polarizing plate and liquid crystal display device Download PDF

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Publication number
CN104520738B
CN104520738B CN201380042126.9A CN201380042126A CN104520738B CN 104520738 B CN104520738 B CN 104520738B CN 201380042126 A CN201380042126 A CN 201380042126A CN 104520738 B CN104520738 B CN 104520738B
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resin
polaroid
mylar
layer
polyvinyl alcohol
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CN104520738A (en
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中谷充晴
黑岩晴信
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Toyobo Co Ltd
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Toyobo 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
    • 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
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is a polyester film for polarizer protection, which has high transmittance and excellent adhesion to a polarizer. A polyester film for polarizer protection, which has, on at least one surface, a layer that is highly adhesive to a polarizer, and wherein the highly adhesive layer contains a polyester resin (A), a polyvinyl alcohol resin (B) and a crosslinking agent (C). The polyester resin (A) has an acid value of 20 KOHmg/g or less. The polyvinyl alcohol resin (B) has a saponification degree of 60-85% by mole. Another surface of the polyester film, said another surface being on the reverse side of the above-mentioned one surface, has an average absolute reflectance of 6% or less with respect to light having a wavelength of 400-700 nm.

Description

Polaroid protection mylar, Polarizer and liquid crystal indicator
Technical field
The present invention relates to for the polaroid protection mylar protecting polaroid.Specifically, be related to transmitance high, With polaroid protection mylar polaroid excellent in adhesion.
Background technology
In liquid crystal display device, due to its image forming mode the two of the glass substrate forming liquid crystal panel surface Side configures Polarizer.Polarizer generally has following structure: formed by dichroic material such as polyvinyl alcohol film and iodine The two sides of polaroid is fitted with polaroid protective film by hydrophilic adhesive such as polyvinyl alcohol resins.As for protecting partially Shake the protecting film of piece, from the aspect of optical characteristics, the transparency, so far always using cellulose triacetate film.
However, the durability of Triafol T is insufficient, using with cellulose triacetate film under high temperature or high humidity As polaroid protective film Polarizer when, the performance of the Polarizer such as degree of polarization, tone reduces sometimes.Additionally, being in recent years The slimming of reply display and require Polarizer filming, but from the perspective of keeping moisture isolation characteristic, three acetic acid There is boundary in the filming of cellulose membrane.Accordingly, as the polaroid protective film with durability and moisture barrier, Propose using mylar (referring to patent documentation 1～5).
The surface of the cellulose triacetate film as polaroid protective film implements alkali process etc., has and glues with hydrophilic Connect the high affinity of agent.Therefore, the protecting film being formed by cellulose triacetate film be coated with the inclined of hydrophilic adhesive The piece that shakes has high cementability.However, mylar is insufficient with the cementability of hydrophilic adhesive, especially for passing through Stretch processing and for there is the mylar of orientation, this tendency is more notable.Therefore, in patent documentation 1～3 and 5 it is Raising with polaroid or the cementability of hydrophilic adhesive of coating polaroid and propose and arrange easily on mylar Adhesive linkage.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 8-271733 publication
Patent documentation 2: Japanese Unexamined Patent Publication 8-271734 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2009-157361 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2010-277028 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2011-8170 publication
Content of the invention
Problems to be solved by the invention
Mylar is low with the affinity of water, has aromatic dicarboxylic acid this as the mylar of dicarboxylic acid component Tendency is particularly significant.Additionally, the mylar having crystal orientation by stretching is lower with the affinity of water.And polarize Piece, it is coated in the bonding agent on polaroid, polyvinyl alcohol resin is main component, has high hydrophilic.Due to this The difference of property, mylar is low with the affinity of polaroid, this bonding agent it is difficult to both generals are bonding securely.Therefore, even if It is the mylar with adhesive layer disclosed in patent documentation 1～3 and 5, compared with cellulose triacetate film, obtain not yet Obtain sufficient cementability.Therefore, when the Polarizer using existing mylar as protecting film for the life-time service is as display member, Sometimes can float between protecting film/polaroid, peel off, lead to polarized light property to reduce by the change of the water quantities in polaroid, The visual variation such as blank occurs.
Additionally, compared with the cellulose triacetate film being typically used as polaroid protective film, mylar is used as inclined Shake piece protecting film Polarizer due to mylar refractive index be higher than cellulose triacetate film, therefore exist and reflected by surface The problem of the reduction of transmitance more than the scattering of light causing etc.
Under this present situation, the problem of the present invention is to provide a kind of polaroid protection mylar, and it has makes to gather Ester film and polaroid or the bonding securely means of polyvinyl alcohol resin layer being coated on the bonding agent on polaroid etc., and And the transmitance of light is high.
For solution to problem
The present inventor etc. conduct in-depth research to solve the above problems and inquire into, thus visualizing in polyester Between film and polyvinyl alcohol resin layer, setting contains the polyester based resin high with the affinity of mylar and polyethenol series The high polyvinyl alcohol resin of the affinity of resin bed and the layer of cross-linking agent.However, the present inventor etc. finds only to combine merely What these compositions cannot give full play to that each composition brings makes the mylar function closely sealed with polyvinyl alcohol resin layer.Therefore, The present inventor etc. is day and night studied, it was found that in above-mentioned design, by being made using the polyester resin with certain acid number For polyester resin, and then, using there is the polyvinyl alcohol resin of certain saponification degree as polyvinyl alcohol resin, can be effective Play the bonding effect of the high resin bed of the respective and affinity that each composition brings.
The present inventor etc. are based on above-mentioned cognition and have carried out further in-depth study, it was found that passing through to adopt and hydroxyl The high cross-linking agent of the reactivity of base, can further bonding mylar and polaroid, bonding agent etc. securely polyethylene Alcohol resin.
It moreover has been found that, by by the ripple in the face contrary with the face being provided with above-mentioned easily bonding with polaroid adhesive layer The average reflectance of the absolute reflectance under long 400～700nm controls below 6% such that it is able to provide transmitance high inclined Shake piece protection mylar.The present inventor etc. have carried out further discussion based on these opinions and have investigated, thus completing The present invention.
Hereinafter, the typical example of the present invention is shown.
1st.
A kind of polaroid protection mylar, it is to have the poly- of easily bonding with polaroid adhesive layer in one side Ester film, aforementioned adhesive layer contains polyester based resin (a), polyvinyl alcohol resin (b) and cross-linking agent (c), aforementioned Polyester The acid number of resin (a) is below 20kohmg/g, and the saponification degree of aforementioned polyvinyl alcohol resin (b) is 60～85 moles of %, aforementioned The average absolute reflectance of the light of wavelength 400～700nm in the face contrary with aforementioned one side of mylar is less than 6%.
2nd.
Polaroid protection mylar according to the 1st, wherein, has refractive index than poly- in aforementioned contrary face The low low-index layer of ester film.
3rd.
Polaroid protection mylar according to the 1st or the 2nd, wherein, aforementioned low-index layer be selected from At least one functional layer in the group being made up of hard conating, antiglare layer and anti-reflection layer.
4th
Polaroid protection mylar according to any one of the 1st～the 3rd, wherein, aforementioned polyester resin A () contains the 5- sulfoisophthalic acid composition in dicarboxylic acid component for 1～15 mole of %.
5th
Polaroid protection mylar according to any one of the 1st～the 4th, wherein, aforementioned crosslinking agent (c) For isocyanate compound or melamine compound.
6th
Polaroid protection mylar according to any one of the 1st～the 5th, wherein, aforementioned adhesive layer In, the mass ratio of polyester based resin (a), polyvinyl alcohol resin (b) and cross-linking agent (c) meets following formula.
0.8≤(a)/(b)≤5
2≤((a)+(b))/(c)≤50
7th
A kind of Polarizer, it is the two-sided Polarizer with polaroid protective film in polaroid, at least one polaroid Protecting film is the polaroid protection mylar any one of the 1st～the 6th.
8.th
A kind of image display device, it has at least one Polarizer described in the 7th.
The effect of invention
The polaroid protection mylar of the present invention poly- second representated by bonding agent thereon with polaroid or coating Enol resin excellent in adhesion.Additionally, the transmitance of the light of the mylar of the present invention is also high, can suitably be used as The protecting film of polaroid.By using this present invention mylar as the protecting film of polaroid, can much less expensively make Make durability and water preventing ability is better than conventional Polarizer.Additionally, the excellent in te pins of durability of the Polarizer of the present invention, therefore with conventional phase Than can filming further.Therefore, by using the Polarizer of the present invention, liquid crystal display can be made to be thinned further.
Specific embodiment
(mylar)
It is the thin film being mainly made up of polyester resin as the mylar that base material uses in the present invention.Here, " main The thin film being made up of polyester resin " refers to the thin film being formed by the resin combination containing polyester resin more than 50 mass %, It is meant that containing polyester resin more than 50 mass % when being blended with other polymers, with during other monomers copolymerization it is meant that containing There are the polyester structural units of 50 moles of more than %.Preferably mylar contains the polyester resin of more than 90 mass %, more preferably More than 95 mass %, more preferably 100 mass %.
As polyester resin, material is not particularly limited, it is possible to use dicarboxylic acid component and glycol component polycondensation shape The copolymer becoming or its blending resin.As dicarboxylic acid component, for example, can include: p-phthalic acid, M-phthalic acid, adjacent benzene Dioctyl phthalate, 2,5- naphthalenedicarboxylic acid, 2,6- naphthalenedicarboxylic acid, 1,4- naphthalenedicarboxylic acid, 1,5- naphthalenedicarboxylic acid, biphenyl carboxylic acid, hexichol oxygen Base ethane dicarboxylic acids, diphenyl sulphone (DPS) carboxylic acid, anthracene dicarboxylic acids, 1,3- Pentamethylene. diacid, 1,3- cyclohexane diacid, 1,4- hexamethylene two Acid, hexahydro terephthalic acid, hexahydro M-phthalic acid, malonic acid, dimethyl malonic acid, succinic acid, 3,3- diethyl succinic acid, 1,3-propanedicarboxylic acid, 2,2- dimethylated pentanedioic acid, adipic acid, 2- methyl adipic acid, trimethyladipic acid, 1,5-pentanedicarboxylic acid., Azelaic Acid, dimerization Acid, decanedioic acid, suberic acid, dodecanedioic acid etc..
As the glycol component constituting polyester resin, for example, can include: ethylene glycol, propylene glycol, 1,6- hexanediol, new Pentanediol, 1,2- cyclohexanedimethanol, 1,4 cyclohexane dimethanol, 1,10- decanediol, 1,3- propylene glycol, 1,4- butanediol, 1, 5- pentanediol, 1,6-HD, 2,2- double (4- hydroxy phenyl) propane, double (4- hydroxy phenyl) sulfone etc..
Constitute the dicarboxylic acid component of polyester resin and glycol component can be respectively using one kind or two or more.Additionally, can To be properly added other hydroxyl moieties such as other sour composition, trimethylolpropanes such as trimellitic acid.
As polyester resin, specifically can include: polyethylene terephthalate, poly terephthalic acid propylene glycol Ester, polybutylene terephthalate (PBT), PEN etc., in the middle of these for physical property and cost balance and Preferably polyethylene terephthalate.Additionally, in order to control the optical characteristics such as polarity and contain other copolymer compositions, other Polymer is also preferred mode.From the perspective of the optical characteristics controlling mylar, as preferred copolymer composition, can Include: diethylene glycol, in side chain, there is being copolymerized into of norborene and grade.
The mylar of the present invention is used with thin film as polaroid protection, therefore preferably has the high transparency.This The transparency of the polaroid protection mylar of invention preferably its total light transmittance is more than 90%, more preferably more than 91%, More preferably more than 92%.Additionally, mist degree is preferably less than 3%, more preferably less than 2.5%, more preferably 2% Hereinafter, particularly preferably less than 1.5%.The total light transmittance of mylar for example can be according to the side described in embodiment described later Method measures.But, have aftermentioned antiglare layer the present invention mylar in terms of its characteristic not limited to this.
Sometimes for improve the sliding of mylar, the treatability such as windability and make to contain inert particle in thin film, but In order to keep the high transparency, the content of the inert particle in preferred film is as far as possible few.It is therefore preferable that making the table only in thin film The multilamellar containing granule for the layer is constituted, or, make to be substantially free of granule in thin film and only make to be layered at least single of mylar The adhesive layer in face contains microgranule.
Additionally, " being substantially free of granule " refers to, such as if inorganic particle, with fluorescent x rays analysis to deriving from The element of granule carries out being below 50ppm during quantitative analyses, the content below preferably below 10ppm, most preferably detection limit. Even if this is because, actively granule is not added in base film, sometimes also have pollutant component from alien material, On production line in the manufacturing process of material resin or thin film, device, the dirt of attachment is peeled off and is mixed in thin film.
Additionally, when base film being made multilamellar constituting, internal layer is substantially free of inert particle, so that outermost layer is contained lazy Two kinds of three layers of compositions of property granule can take into account the transparency and processability, is preferred.
In the present invention the thickness of thin film is not particularly limited, reduces the thickness of Polarizer for the slimming of display When spending, the thickness of thin film is preferably less than 200 μm, more preferably less than 100 μm.And for the machine keeping as protecting film For tool intensity, the thickness of thin film is preferably more than 10 μm, more preferably more than 12 μm, more preferably more than 20 μm.
Mylar as base material can be monolayer or layer stackup of more than two kinds.As long as additionally, In the range of the effect playing the present invention, can make to contain various additives as desired in thin film.As additive, example As included: antioxidant, photostabilizer, antigelling agent, organic wetting agent, antistatic additive, UV absorbent, surface activity Agent etc..When thin film has stacking composition, it is also preferred for containing additive according to the function of each layer as desired.For example, It is also preferred mode in order to prevent the light deterioration of polaroid in internal layer interpolation UV absorbent etc..
Mylar can by for example by above-mentioned polyester resin melt extrude into film like, with curtain coating drum be allowed to cool solidification Obtain to form method of thin film etc..Mylar as the present invention, it is possible to use in tensionless winkler foundation thin film, oriented film Any one, in terms of the durability such as mechanical strength, chemical proofing from the point of view of preferred oriented film.Mylar is that stretching is thin During film, its drawing process is not particularly limited, can be using longitudinal uniaxial stretching method, horizontal uniaxial stretching method, in length and breadth progressively Biaxial stretching process, in length and breadth simultaneously biaxial drawing method etc..
(adhesive layer)
The mylar of the present invention is in order to improve and polaroid and be arranged on the water system bonding agent of its one or two sides etc. The cementability of polyvinyl alcohol resin layer and be laminated with adhesive layer in its at least one side, described adhesive layer by containing acid number is The polyester based resin (a) of below 20kohmg/g, saponification degree are polyvinyl alcohol resin (b) and the crosslinking of 60～85 moles of % The resin combination of agent (c) is formed.
Although without being bound by theory, it is believed that by combining the specific Polyester tree that acid number is below 20kohmg/g Fat (a), saponification degree are specific polyvinyl alcohol resin (b) and the cross-linking agent (c) of 60～85 moles of %, polyester based resin and Polyvinyl alcohol resin forms independent domain unit in adhesive layer respectively, is formed and is generally also known as island structure Phase separation structure.It can be said that by the isolating construction forming this domain unit, the domain band being made up of polyester based resin Come the cementability with mylar and the domain being made up of polyvinyl alcohol resin bring with polyvinyl alcohol resin layer This two Function fitness of cementability take into account without mutually impaired.It can be said that cross-linking agent (c) is by making polyethenol series tree Fat (b) is crosslinked and condenses and promotes being formed and maintaining of this domain constructs.Hereinafter each composition of adhesive layer is carried out in detail Explanation.
(polyester based resin (a))
Used in the adhesive layer of the present invention, polyester based resin (a) is that dicarboxylic acid component is formed with glycol component polycondensation Copolymer, as dicarboxylic acid component and glycol component, it is possible to use previous materials.Viscous with mylar base material from improving From the perspective of connecing property, preferably use with the dicarboxylic acid component in mylar have same or similar structure, property two Carboxylic acid composition is as the dicarboxylic acid component of polyester based resin (a).Thus, for example using aromatic dicarboxylic acid as mylar During dicarboxylic acid component, preferably use aromatic dicarboxylic acid as the dicarboxylic acid component of polyester based resin (a).As this aromatic series Dicarboxylic acid component, most preferably p-phthalic acid and M-phthalic acid.Can with respect to whole dicarboxylic acid component with 10 moles of % with Under scope add other aromatic dicarboxylic acids to make its copolymerization.
Additionally, as the glycol component of polyester based resin (a), preferably using the glycol of ethylene glycol and side chain as being constituted into Point.It can be said that can aid in stress relaxation at adhesive layer by having branched structure, suitably play adaptation.Right In the glycol component of aforementioned side chain, for example, can include: 2，2-dimethyl-1，3-propanediol, 2- methyl -2- ethyl -1,3- Propylene glycol, 2- methyl -2- butyl -1,3- propylene glycol, 2- methyl-2-propyl -1,3- propylene glycol, 2- methyl -2- isopropyl -1,3- Propylene glycol, 2- methyl -2- n-hexyl -1,3- propylene glycol, 2,2- diethyl -1,3- propylene glycol, 2- ethyl -2- normal-butyl -1,3- Propylene glycol, 2- ethyl -2- n-hexyl -1,3- propylene glycol, 2,2- di-n-butyl -1,3- propylene glycol, 2- normal-butyl -2- propyl group -1, Ammediol and 2,2- di-n-hexyl -1,3- propylene glycol etc..
For the mol ratio of the glycol component of aforementioned side chain, with respect to whole glycol component, lower limit is preferably 10 and rubs You are %, particularly preferably 20 moles %.And the upper limit is preferably 80 moles of %, more preferably 70 moles %, particularly preferably 60 moles of %.Furthermore, it is possible to as desired and with diethylene glycol, propylene glycol, butanediol, hexanediol or Isosorbide-5-Nitrae-hexamethylene diformazan Alcohol etc..
From with the compatibility of polyvinyl alcohol resin (b) in terms of from the point of view of, used in the present invention, polyester based resin (a) is excellent Choosing uses water solublity or water-dispersed resin.For water solublity or the moisture dispersion of polyester based resin, preferably copolymerization contains The compound of the hydrophilic radicals such as sulphonate-base, carboxylate group.Wherein, from the acid number keeping polyester based resin (a) relatively low controlling System with cross-linking agent reactive while imparting hydrophilic from the perspective of, be suitably the dicarboxylic acid component with sulphonate-base. As the dicarboxylic acid component with sulphonate-base, for example, can include: sulfoterephthalic, 5- sulfoisophthalic acid, 4- Sulfo group naphthalene -2,7- dicarboxylic acids and 5- (4- sulfophenoxy) M-phthalic acid or its alkali metal salt, wherein particularly preferred 5- sulfo group M-phthalic acid.The dicarboxylic acid component with sulphonate-base preferably accounts for 1～15 the rubbing of dicarboxylic acid component of polyester resin (a) You are %, more preferably 1.5～12 moles %, more preferably 2～10 moles %.The dicarboxylic acid component with sulphonate-base is When more than above-mentioned lower limit, it is suitable for the water solublity of polyester based resin or moisture dispersion.Additionally, having sulfonic acid The dicarboxylic acid component of alkali be the above-mentioned upper limit below when, for the cementability of mylar base material for be suitable.
Polyester based resin (a) is less preferably as the carboxylic acid group of the reactive group with cross-linking agent (c).It can be said that due to logical Cross minimizing to there is the carboxyl with the reactivity of cross-linking agent and make the reactivity reduction with cross-linking agent, as a result, not with poly- second Enol system resin is thoroughly mixed, and can maintain the domain constructs being formed by crosslinked polyvinyl alcohol resin.From this From the point of view of angle, the acid number of polyester based resin (a) is below 20kohmg/g, preferably below 15kohmg/g, more preferably Below 10kohmg/g, more preferably below 8kohmg/g, still more preferably for below 5kohmg/g.Polyester based resin A the acid number of () theoretically can be obtained according to the result of the component analyses based on titrimetry described later or nmr etc..
Want to control in above range by the acid number of polyester based resin (a), preferably reduce for water solublity or moisture The introduction volume of the carboxylate group of dispersion, or using the hydrophilic radical beyond carboxylate group, or reduce polyester based resin Carboxylic acid terminal's concentration.Method as the carboxylic acid terminal's concentration reducing polyester based resin, it is preferred to use carboxylic acid terminal's base is carried out End modified polyester based resin, or using the big polyester based resin of the number-average molecular weight of polyester based resin.Therefore, polyester It is the number-average molecular weight preferably more than 5000, more preferably more than 6000, more preferably more than 10000 of resin (a).This Outward, preferably reduce the content of sour composition constituent, that there are more than 3 carboxyls as polyester based resin (a).
The glass transition temperature of polyester based resin (a) is not particularly limited, preferably 20～90 DEG C, more preferably 30 ～80 DEG C.When glass transition temperature is more than above-mentioned lower limit, it is suitable for resistance to adhesive, glass transition temperature For when below the above-mentioned upper limit, for the cementability of mylar base material for be suitable.
The content of the polyester based resin (a) in adhesive layer is preferably below more than 40 mass % and 90 mass %, more excellent Elect below more than 45 mass % and 85% mass % as, more than more preferably 50 mass % and below 80 mass %.Polyester Be resin (a) content be above-mentioned lower limit more than when, for the cementability of mylar base material for be suitable, be above-mentioned When below the upper limit, for the cementability of polaroid/aqueous resin for be suitable.
(polyvinyl alcohol resin (b))
Polyvinyl alcohol resin is not particularly limited, for example, can include: by obtained from polyvinyl acetate saponification Polyvinyl alcohol；Its derivant；Have with same vinylacetate further the monomer of copolymerizable copolymer saponified；To poly- second Enol has carried out the modified polyvinylalcohol of acetalation, urethane, etherificate, grafting, Phosphation etc.；Deng.As front State monomer, can include: the unsaturated carboxylic acid such as maleic acid (acid anhydride), fumaric acid .beta.-methylacrylic acid, itaconic acid, (methyl) acrylic acid and its Esters；The alpha-olefins such as ethylene, propylene, (methyl) allyl sulphonic acid (sodium), sodium sulfonate (monoalkyl malate), sodium disulfonate alkane Base malate, n- n-methylolacrylamide, acrylamide alkyl sulfonic acid alkali salt, n- vinyl pyrrolidone, n- vinylpyridine Pyrrolidone derivant etc..These polyvinyl alcohol resins only and can also use two or more using a kind.
As polyvinyl alcohol resin (b) used in the present invention, can exemplify: vinyl alcohol-vinyl acetate copolymer, Polyvinyl alcohol-co-vinyl butyral copolymer, ethylene-vinyl alcohol copolymer, in the middle of these, optimal ethylene alcohol-vinylacetate is common Polymers, ethylene-vinyl alcohol copolymer.The degree of polymerization of polyvinyl alcohol resin (b) is not particularly limited, from coating fluid viscosity From the point of view of aspect, preferred degree of polymerization is less than 3000.
The copolymerization ratio of vinyl alcohol is represented with saponification degree.The saponification degree of the polyvinyl alcohol resin (b) of the present invention is preferably 60 moles of more than % and 85 mole of below %, more preferably 65 moles more than % and 83 mole of below %, more preferably 68 Mole more than % and 80 mole of below %, still more preferably for 70 moles of % less than 80 moles of %, further excellent Elect 71 moles of more than % and 78 mole of below %, particularly preferably 73 moles more than % and 75 mole of below % as.Polyvinyl alcohol It is the saponification degree of resin (b) for, when more than above-mentioned lower limit, more appropriately cross-linked structure can be formed with cross-linking agent (c).Additionally, it is poly- When the saponification degree of vinyl alcohol resin (b) is below the above-mentioned upper limit (or being less than it), can more appropriately play and Polyester tree The compatibility of fat (a).The saponification degree of vinyl alcohol resin can pass through the alkali needed for hydrolysis of the copolymerization units such as vinylacetate Consumption, the composition analysis based on nmr are obtaining.
As the content of polyvinyl alcohol resin (b), adhesive layer is preferably more than 10 mass % and 60 mass % Hereinafter, more than more preferably 15 mass % and below 55% mass %, more than more preferably 20 mass % and 50 mass % Below.When the content of polyvinyl alcohol resin (b) is more than above-mentioned lower limit, for the cementability with polaroid/aqueous resin Speech is suitable, when being below the above-mentioned upper limit, for the cementability of mylar base material for be suitable.
(cross-linking agent (c))
As cross-linking agent (c), as long as with hydroxyl, there is bridging property being not particularly limited, can include: melamine series, The compound of isocyanates system, carbodiimide system, oxazoline system, epoxy etc..Come in terms of the ageing stability of coating fluid See, preferably melamine series, isocyanates system, carbodiimide system, the compound of oxazoline system.And then, cross-linking agent preferably with poly- The hydroxyl of vinyl alcohol resin (b) suitably carries out tripolycyanamide based compound or the isocyanates based compound of cross-linking reaction. It can be said that this is because, carbodiimide system cross-linking agent and carboxyl reaction, and tripolycyanamide based compound or isocyanates system chemical combination Thing and hydroxyl reaction, thus more appropriately form cross-linked structure with the polyvinyl alcohol resin (b) as functional group with hydroxyl. Wherein, from the hydroxyl with polyvinyl alcohol resin suitably carry out cross-linking reaction and the transparency excellent from the perspective of, especially Preferably use isocyanates based compound.Additionally, in order to promote cross-linking reaction and as needed suitably using catalyst etc..
As isocyanate compound, it is possible to use the polyisocyanate of low molecule or high molecular diisocyanate or more than 3 yuan Cyanate.For example, as isocyanate compound, can include: 2,4 toluene diisocyanate, 2,6- toluene diisocynate Ester, 4,4 '-methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate, 2,2 '-diphenyl methane two isocyanide Acid esters, 1,5- naphthalene diisocyanate, 1,4- naphthalene diisocyanate, phenylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4 '-diphenyl ether diisocyanate, 2- nitro diphenyl -4,4 '-diisocyanate, 2,2 '-diphenyl propane -4,4 '-two Isocyanates, 3,3 '-dimethyl diphenylmethane -4,4 '-diisocyanate, 4,4 '-diphenylpropane diisocyanate, 3, 3 '-dimethoxydiphenyl -4, the aromatic diisocyanate class such as 4 '-diisocyanate, the virtue such as xylylene diisocyanate Fragrant race aliphatic diisocyanate class, isophorone diisocyanate and 4,4- dicyclohexyl methyl hydride diisocyanate, 1,3- are double The ester ring type diisocyanates such as (isocyanatomethyl) hexamethylene, hexamethylene diisocyanate and 2,2,4- trimethyl six is sub- The aliphatic diisocyanate class such as methyl diisocyanate, and the trimer of these isocyanate compounds.And then, can enumerate Go out the excess quantity of these isocyanate compounds and following compounds react obtained from high molecular end contain NCO Compound: ethylene glycol, propylene glycol, trimethylolpropane, glycerol, Sorbitol, ethylenediamine, monoethanolamine, diethanolamine, three ethanol The low molecule active dydrogen compounds such as amine, or polyester polyols alcohols, polyether polyols alcohols, the high molecular reactive such as polyamide-based hydrogenation close Thing.
As cross-linking agent (c) used in the present invention, blocked isocyanate based compound is also preferred.Sealed by adding Isocyanate terminated based compound, can more appropriately improve the ageing stability of coating fluid.
Blocked isocyanate based compound can make above-mentioned isocyanate compound and end-blocking by existing known method Agent carries out additive reaction to prepare.As isocyanate-terminated dose, for example, can include: phenol, cresol, xylenols, isophthalic The phenols such as diphenol, nitrophenol, chlorophenol；The thio phenols such as thiophenol, methyl thio phenol；Acetyl oxime, methyl ethyl ketoxime, hexamethylene The oximes such as ketoxime；The alcohols such as methanol, ethanol, propanol, butanol；The halogen substiuted alcohols such as 2-chloroethyl alcohol, the chloro- 2- propanol of 1,3- bis-；Uncle The tertiary alcohols such as butanol, tert-pentyl alcohol；3,5- dimethyl pyrazole, 3- methylpyrazole, 4- bromo- 3,5- dimethyl pyrazole, 4- nitro -3,5- The pyrazoles based compound such as dimethyl pyrazole；1,2,4- triazole etc. three azole compounds；Epsilon-caprolactams, δ-valerolactam, γ-fourth The lactams such as lactams, azetidinone；Aromatic amine；Acid imide；Acetylacetone,2,4-pentanedione, acetoacetate, malonic acid second Ester, diester malonate (dimethyl malenate, diethyl malonate, malonic acid di-n-butyl, malonic acid two (2- Octyl Nitrite)) Isoreactivity methylene compound；Thio-alcohol；Imines；Carbamide class；Biaryl compound class；Sodium sulfite etc..
As the content of cross-linking agent (c), adhesive layer is preferably below more than 2 mass % and 50 mass %, more excellent Elect below more than 5 mass % and 40% mass % as, more than more preferably 8 mass % and below 30 mass %.Cross-linking agent When the content of () is more than above-mentioned lower limit c, it is suitable for polyvinyl alcohol resin is cross-linked to form, is the above-mentioned upper limit When following, it is suitable for the cementability effect that performance resin glue brings.
Mix ratio (a)/(b) of polyester based resin (a) and polyvinyl alcohol resin (b) count preferably 0.8 in mass ratio～ 5, more preferably 1～4, more preferably 2～4, particularly preferably 2.5～3.5.When ()/(b) is more than above-mentioned lower limit a, right In with the cementability of mylar base material for be suitable, when being below the above-mentioned upper limit, for polaroid/aqueous resin It is suitable for cementability.
Mix ratio ((a)+(b))/(c) of polyester based resin (a) and polyvinyl alcohol resin (b) and cross-linking agent (c) presses matter Amount is preferably 2～50, more preferably 5～40, more preferably 8～30 than meter.((a)+(b))/(c) is more than above-mentioned lower limit When, it is suitable for the cementability effect that performance resin glue composition brings, when being below the above-mentioned upper limit, for phase It is suitable for separating the cementability effect brought.
The adhesive layer of the present invention is passed through using above-mentioned composition, with respect to polaroid, aqueous adhesive, particularly polyethylene The polaroid of alcohol system, aqueous adhesive, show the high adhesiveness equal with Triafol T.Specifically, based on described later Remaining area preferably more than 90%, more preferably more than 95% after adhesive test water system bonding agent 1 time is peeled off, enters One step is preferably 100%, and the remaining area after 5 continuous strippings is preferably more than 75%, more preferably more than 85%, further It is preferably more than 95%, the remaining area after 10 continuous strippings is preferably more than 50%, more preferably more than 80%, further It is preferably more than 90%, still more preferably for more than 93%, particularly preferably more than 95%.
(additive)
In the adhesive layer of the present invention, known interpolation can be added in the range of the effect not damaging the present invention Agent, such as surfactant, antioxidant, catalyst, heat-resisting stabilizing agent, weathering stabilizers, UV absorbent, organically easy Lubrication prescription, pigment, dyestuff, the granule of organic or inorganic, antistatic additive, nucleator etc..
In the present invention, in order to improve the resistance to adhesive of adhesive layer further, it is also excellent for adding granule in adhesive layer The mode of choosing.In the present invention as making the granule that contains in adhesive layer, for example, inorganic particle, organic polymer can be included Composition granule, described inorganic particle has: titanium oxide, barium sulfate, Calcium Carbonate, calcium sulfate, silicon dioxide, aluminium oxide, Talcum, kaolinite Soil, clay etc. or their mixture, and with other conventional inorganic particulates, such as calcium phosphate, Muscovitum, Strese Hofmann's hectorite., oxygen Change inorganic particles being applied in combination such as zirconium, tungsten oxide, lithium fluoride, calcium fluoride etc., described organic polymer particles have: benzene second The organic polymer particles of alkene system, acrylic compounds, melamine series, benzocarbamidine amine system, silicon-type etc..
Mean diameter (the mean diameter of the number benchmark based on sem of the granule in adhesive layer.Similarly hereinafter) it is preferably 0.04～2.0 μm, more preferably 0.1～1.0 μm.When the mean diameter of inert particle is less than 0.04 μm, in film surface Concavo-convex formation become insufficient, therefore the treatability such as the sliding of thin film, batching property can reduce sometimes, and when fitting Processability reduces.Conversely, during more than 2.0 μm, being susceptible to particle detachment and not preferred.Granule density in adhesive layer is solid It is preferably 1～20 mass %, more preferably 5～15 mass % in body composition.
The thickness of adhesive layer suitably can set in the range of 0.001～2 μm in the present invention, wants to take into account processing Property and cementability, preferably 0.01～1 μm of scope, more preferably 0.02～0.8 μm, more preferably 0.05～0.5 μm. When the thickness of adhesive layer is less than 0.01 μm, cementability becomes insufficient.If the thickness of adhesive layer is more than 2 μm, sometimes Can stick together.
(low-index layer)
In order to improve the transmitance of the light of the polaroid protection mylar of the present invention, with the face phase being provided with adhesive layer The average absolute reflectance of the light of wavelength 400～700nm in anti-face is preferably less than 6%.Average absolute reflectance is more preferably For less than 5%, more preferably less than 4.5%.Average absolute reflectance is more than when 6% it is desirable to the visible ray passing through is thin The reflection on film surface becomes big, and transmitance reduces.Another face, when being less than 6%, using the teaching of the invention it is possible to provide is subject in the reflection of film surface The high polaroid protection mylar of suppression, transmitance.
To for controlling means to be within the above range not particularly limited average absolute reflectance, preferably in the present invention Mylar the surface layer contrary with the face being provided with adhesive layer fold low-index layer.Low-index layer refers to, refractive index ratio As the low layer of the mylar of base material, more specifically, it is the layer that refractive index is less than 1.60.Refractive index is less than 1.55 When, further preferably.The lower limit of refractive index is not particularly limited, and practicality is preferably more than 1.20, more preferably 1.25 more than.
As material used in aforementioned low-index layer, be not particularly limited, can suitably using polyester based resin, Polyurethane series resin, acrylic resin, polyvinyl alcohol resin, polycarbonate-based resin, fluorine resin, silicon-type resin Deng.These resins can be by any number of in drying, heat, chemical reaction or irradiating electron beam, radiation, ultraviolet and The resin compound being polymerized and/or being reacted, it is possible to use known material.In the middle of these, polyurethane series resin, acrylic acid Resinoid, fluorine resin refractive index relatively low, can suitably use.
(polyurethane resin)
Used in low-index layer, polyurethane resin includes at least polyol component, polyisocyanate component as composition Composition, preferably further comprises cahin extension agent as needed.Polyurethane resin is to pass through carbamic acid based on these constituents The macromolecular compound of ester bond copolymerization.
As polyol component, can include by polybasic carboxylic acid (for example, malonic acid, succinic acid, adipic acid, decanedioic acid, richness Horse acid, maleic acid, p-phthalic acid, M-phthalic acid etc.) or their anhydride and polyhydric alcohol (for example, ethylene glycol, diethyl two Alcohol, triethylene glycol, propylene glycol, butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, neopentyl glycol, 1,6- oneself two Alcohol etc.) polyester polyols alcohols, Polyethylene Glycol, polypropylene glycol, poly- ethylene propylene glycol obtained from reaction The polyether polyol such as (polyethylene propylene glycol), polytetramethylene ether diol, polyhexamethylene ether glycol Class, polycarbonate polyol class, polyolefin polyhydric alcohol class, acrylic polyol class etc..Wherein, as the structure of polyurethane resin Fatty family polycarbonate polyol heat-resisting, that hydrolytic resistance is excellent is preferably comprised in the polyol component becoming composition.The present invention Optical applications in, from the viewpoint of preventing xanthochromia it is also preferred that use fatty family polycarbonate polyol.
(polyester resin)
As polyester resin used in low-index layer, following material can be included.The equal molecule of number of polyester resin Amount is preferably more than 15000.When number-average molecular weight is low, the carboxylic acid group of end increases, and therefore promotes hydrolysis, not only cannot get high temperature Adaptation under high humidity, also can reduce the adaptation with base film.Additionally, above-mentioned number-average molecular weight more preferably 20000 with On, and then, as long as can manufacture, then higher is preferred.But, when increasing number-average molecular weight, sometimes to molten in coating fluid Solution property reduces, and therefore above-mentioned number-average molecular weight is preferably less than 60000.
With regard to polyester resin, as sour composition, p-phthalic acid, M-phthalic acid, phthalic acid, adjacent benzene can be included Dicarboxylic acid anhydride, 2,6 naphthalene dicarboxylic acid, 1,4- cyclohexane dicarboxylic acid, adipic acid, decanedioic acid, trimellitic acid, PMA, dimerization Acid, 5-sodium sulfo isophthalate, naphthalene -2,7- dicarboxylic acids -4- sodium sulfonate etc..As diol component, can include ethylene glycol, Propylene glycol, 1,4- butanediol, neopentyl glycol, diethylene glycol, 1,6-HD, 1,4 cyclohexane dimethanol, benzene dimethanol, bis-phenol Ethylene oxide adduct of a etc..
Polyester resin can be using being dissolved or dispersed in water or water miscible organic solution (for example, comprises less than 50 matter The alcohol of amount %, alkyl cellosolve, ketone system, the aqueous solution of ether system) or organic solution (for example, toluene, ethyl acetate etc.) Liquid.
When polyester resin is used in the form of water system coating fluidmn, it is possible to use the polyester tree of water solublity or water dispersible Fat, for this water solublity or moisture dispersion, preferably makes compound containing sulfonate groups, the compound of carboxylate-containing group Copolymerization.Therefore, in addition to foregoing dicarboxylic acids' composition, in order to give water dispersible to polyester, preferably with the model of 1～10 mole of % Enclose using 5- sulfoisophthalic acid and its alkali metal salt, for example, can include sulfoterephthalic, 5- sulfo group isophthalic diformazan Acid, 4- sulfo group naphthalene M-phthalic acid -2,7- dicarboxylic acids and 5- (4- sulfophenoxy) M-phthalic acid or its alkali metal salt.
In order to the number-average molecular weight of polyester resin is set to more than 15000, and there is the glass of the level of suppression adhesion Change transition temperature, import branched structure preferably in polyester resin.However, when branched structure becomes many, having what acid number also uprised Tendency.Therefore, polyester resin preferably, has the 3rd of the carboxyl of more than 3/1 molecule or the hydroxyl of more than 3/1 molecule the The mol ratio of composition is 5.0 moles of below %, more preferably 1.0 moles below % in whole dicarboxylic acid component.
(acrylic resin)
In acrylic resin used in low-index layer, it is not particularly limited, it is possible to use by with acrylic compounds, first The monomer of base acrylic compounds is to have the polymer that the polymerizable monomer of carbon-carbon double bond is formed as representative.They can be equal Anyone in polymers or copolymer.Additionally, also including being total to of these polymer and other polymer (such as polyester, polyurethane etc.) Polymers.For example, block copolymer, graft copolymer.Or, it is also included within polyester liquid or polyester dispersion and will have carbon The polymer (according to circumstances for the mixture of polymer) obtained from polymerizable monomer polymerization of carbon double bond.Similarly, also include In polyurethane solutions, polyurethane dispersing liquid by have carbon-carbon double bond polymerizable monomer be polymerized obtained from polymer (according to Situation is the mixture of polymer).Similarly, it is also included within other polymer solutions or dispersion liquid and will there is carbon-carbon double bond Polymer (according to circumstances for polymeric blends) obtained from polymerizable monomer polymerization.Additionally, in order to efficiently improve Total light transmittance, it is possible to use the low compound containing fluorine atom of refractive index.
As the above-mentioned polymerizable monomer with carbon-carbon double bond, it is not particularly limited, as especially representational chemical combination Thing, for example, can include acrylic acid, methacrylic acid .beta.-methylacrylic acid, itaconic acid, fumaric acid, maleic acid, various as citraconic acid Carboxyl group-containing monomer class and their salt；(methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (first Base) acrylic acid 4- hydroxybutyl, monobutyl hydroxyfumaric acid ester, various hydroxyl monomers as monobutyl hydroxyl itaconate Class；(methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Various as lauryl acrylate (methyl) esters of acrylic acid；(methyl) acrylamide, N-[2-(2-methyl-4-oxopentyl), n- methylol Such various nitrogen-containing compounds such as acrylamide or (methyl) acrylonitrile；Styrene, α-methyl styrene, divinylbenzene, Various styrene derivatives, vinyl acetate, various vinyl esters as propionate as vinyltoluene；γ- Such various siliceous polymerizable monomers such as methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane Class；Phosphorous vinyl monomer class；Vinyl chloride, vinylidene chloride, fluorothene, vinylidene fluoride, CTFE, tetrafluoro second Various haloalkene hydro carbons as alkene, chlorotrifluoroethylene, hexafluoropropene；Various conjugated dienes as butadiene.
Additionally, when giving hard painting propert to low-index layer, preferably using third being solidified using electron beam or ultraviolet Olefin(e) acid resinoid.Refer to that using the acrylic resin that electron beam or ultraviolet are solidified there is the sense of esters of acrylic acid The material of group, for example, can use the material containing following component: the polyester resin of lower molecular weight, polyether resin, acrylic acid Resinoid, epoxy resin, polyurethane resin, alkyd resin, spiral shell acetal resin, polybutadiene, the many olefine resins of polythiol The oligomer of (methyl) acrylate of the polyfunctional compound such as (polythiol-polyene resin), polyhydric alcohol etc. or pre- Polymers, and (methyl) ethyl acrylate as reactive diluent, (methyl) EHA, styrene, methyl Monofunctional monomer and the polyfunctional monomers such as styrene, n- vinyl pyrrolidone, for example, trimethylolpropane tris (methyl) propylene Acid esters, hexanediol (methyl) acrylate, tripropylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, Tetramethylolmethane three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,6-HD two (methyl) acrylic acid Ester, neopentyl glycol two (methyl) acrylate etc..
In the case of electron beam or ultraviolet curing resin, can mix as Photoepolymerizationinitiater initiater in aforementioned resin Acetophenones, benzophenone, rice Chi benzoylbenzoic acid ester (michler ' s benzoyl benzoate), α-amidoxim Ester, tetramethylthiuram monosulfide, thioxanthene ketone class, the n-butylamine as photosensitizer, triethylamine, three-normal-butyl phosphine etc. are making With.The addition of above-mentioned Photoepolymerizationinitiater initiater with respect to 100 mass parts electron beams or ultraviolet curing resin, preferably 0.1 ～10 mass parts.
As the curing of above-mentioned film, it is not particularly limited, irradiate preferably by ultraviolet and carry out.Using ultraviolet When being solidified, preferably use the ultraviolet of the wave-length coverage of 190～380nm.Solidification using ultraviolet for example can utilize Metal halide lamp, high voltage mercury lamp, low pressure mercury lamp, ultrahigh pressure mercury lamp, carbon arc lamp, biuret light fluorescent lamp etc. are carrying out.As electronics The concrete example of electron gun, can include cockcroft-walton type, van de graaff type, resonance transformer type, insulating core change The various electron-beam accelerators of depressor type, linear type, dynamitron type, high-frequency type etc..
(fluorine resin)
As fluorine resin used in low-index layer, it is not particularly limited, can be suitably using following material. As fluorine resin, such as preferred 1- (methyl) acryloxy -1- perfluoroalkyl methane, 1- (methyl) acryloxy -2- Double acryloxy -1,1,10,10- tetrahydrochysene the perfluoro decane of perfluoroalkyl ethane, 1,10-, the double acryloxy -2,9- of 1,10- Double acryloxy -2,10- dihydroxy-the 4,4,5,5,6,6,7,7- of dihydroxy -4,4,5,5,6,6,7,7- octafluoro decane, 1,9- Octafluoro decane, 2,9- double acryloxy -1,10- dihydroxy -4,4,5,5,6,6,7,7- octafluoro decane, 1,2- bis- (methyl) third Alkene acyloxy -3- perfluoroalkyl butane, 2- hydroxyl -1h, 1h, 2h, 3h, 3h- perfluoroalkyl -2 ', 2 '-bis- { (methyl) acryloyls Epoxide methyl } propionic ester, α, ω-two (methyl) acryloyloxymethyl perfluoroalkane, α, β, ψ, ω-four { (methyl) acryloyl Epoxide }-α h, α h, β h, γ h, γ h, χ h, χ h, ψ h, ω h, ω h- perfluoroalkane etc..
(polyvinyl alcohol resin)
As polyvinyl alcohol resin used in low-index layer, it is not particularly limited, it is possible to use with this specification The same polyvinyl alcohol resin of polyvinyl alcohol resin used in adhesive layer.
In order to reduce the refractive index of aforementioned low-index layer, it is possible to use the microgranule of existing known organic or inorganic.Example As silicon oxide particle, organic resin microgranule etc. can be included.Additionally, the use of hollow silica particles being also preferred.Hollow Silicon dioxide microparticle is to make silicon dioxide (silicon dioxide；sio2) be generally formed into spherical, in its inside the shell, there is hollow bulb Microgranule.The mean diameter of hollow silica particles is preferably 10～100nm, more preferably 20～60nm.Hollow silica When the mean diameter of microgranule is less than 10nm, the manufacture of hollow silica particles becomes difficult, not preferably.On the other hand, averagely When particle diameter is more than 100nm, scattering of light becomes big, and reflection in the film becomes big, and surface reflectivity uprises.
The thickness of aforementioned low-index layer preferably meets 400≤4n d (nm)≤700.(n in formula represents low-refraction The refractive index of layer, d represents thickness.) even more than this scope, it is possible to use, but, by meeting this scope, can be suitable The reflection on ground suppression surface, improves transmitance.
Between aforementioned low-index layer and mylar, it is possible to have other layers, have and make mylar and low folding Penetrating closely sealed anchor coat of rate layer etc. is also preferred embodiment.
Aforementioned low-index layer can be at least one having in hard painting propert, anti-glare, antireflection, antistatic behaviour etc. The functional layer of function.Now, between functional layer and mylar, it is possible to have other layers.With regard to low as functional layer , it is also possible to arrange other layers between mylar and low-index layer, this other layer is with low-index layer integrally for index layer Ground constitutes the functional layer with hard painting propert, anti-glare, antireflection, at least one function in antistatic behaviour.Either which kind of Structure, low-index layer configures in outermost layer, is preferred at the aspect of the transmitance improving thin film.Hereinafter, to functional layer Illustrate, but be not limited to following structures illustrating, this is self-evident.
(hard conating)
With regard to giving hard painting propert to low-index layer, as previously mentioned.It should be noted that setting as used in hard conating Fat is it is preferred that using the aforementioned resin being solidified using electron beam or ultraviolet, being preferably and utilize electron beam or ultraviolet The acrylic resin being solidified.
(antiglare layer)
Method as giving anti-glare to low-index layer, it is possible to use known technology.For example, it is possible in polyester Form concaveconvex shape on film, make outside light scattering, thus prevent by exterior light reflection, as the fall of visuality that causes of projection Low.As forming concavo-convex method, have: coating comprises big particle diameter or has the resin of the granule of aggregation, in film surface shape The method becoming concaveconvex shape；Or, being laminated in layer surface and have irregular thin film, transferring concaveconvex shape, thus forming antiglare layer Method；Without aforementioned particles, form concavo-convex method using nano impression, it is possible to use a kind or be applied in combination two or more.
As resin used in antiglare layer, it is possible to use the tree same with aforementioned electronic bundle or ultraviolet curing resin Fat.Can be using a kind or mix two or more and use from aforementioned described resin.Additionally, in order to adjust plasticity, surface The physical property such as hardness are it is also possible to mix the resin not solidified because of electron beam or ultraviolet.Do not solidify because of electron beam or ultraviolet Resin in, polyurethane, cellulose derivative, polyester, acrylic resin, polyvinyl butyral resin, polyethylene can be included Alcohol, polrvinyl chloride, polyvinyl acetate, Merlon, polyamide etc..
As the concrete example of granule used in antiglare layer, for example, preferably include silica dioxide granule, aluminium oxide Granule, tio2The granule of the inorganic compound such as granule or poly methyl methacrylate particle, acrylic-styrene copolymerization Composition granule, crosslink propylene acids granule, melamine particles, crosslinked melamine particles, polycarbonate pellets, polrvinyl chloride The resin particles such as grain, benzoguanamine granule, crosslinked benzoguanamine granule, granules of polystyrene, crosslinked polystyrene particle.As Shape, can be suitably using the perfect spherical particle that protrusion of surface shape is neat, it is possible to use the layer such as Talcum, bentonite The erose granule such as shape inorganic compound.In addition it is also possible to be applied in combination different granules of more than two kinds to use. Can be not limited in this respect with raw material types for two or more it is also possible to particle diameter is for two or more.
For example, 0.5～10 μm of the particle diameter of granule used in antiglare layer, more preferably 0.5～5 μm, more preferably 0.5～3 μm, still more preferably for 0.5～1.5 μm.Additionally, the content of aforementioned particles is 1～50 weight % with respect to resin, More preferably 2～30 weight %.
The thickness of antiglare layer is preferably 0.5 μm～20 μm, more preferably 1 μm～20 μm, more preferably 1 μm～ 10μm.
The mist degree of the polaroid protection mylar with antiglare layer of the present invention is preferably 1～50%.More preferably 1 ～30%, more preferably 1～10%.
As antiglare layer used in the present invention it is also possible to suitably using Japanese Unexamined Patent Publication 6-18706, Japanese Unexamined Patent Publication 10-20103, Japanese Unexamined Patent Publication 2009-227735, Japanese Unexamined Patent Publication 2009-86361, Japanese Unexamined Patent Publication 2009-80256, Japanese Unexamined Patent Publication 2011-81217, Japanese Unexamined Patent Publication 2010-204479, Japanese Unexamined Patent Publication 2010-181898, Japanese Unexamined Patent Publication 2011-197329, Japan are special Open the antiglare layer described in 2011-197330, Japanese Unexamined Patent Publication 2011-215393 etc..
(anti-glare anti-reflection layer)
Antiglare layer can be laminated between the low-index layer of the present invention and mylar, make anti-glare anti-reflection layer. The stacking of anti-glare anti-reflection layer can use known technology.Now, the refractive index by making antiglare layer is higher than low-refraction Layer is such that it is able to keep the effect of the present invention.
Used in the present invention, anti-glare anti-reflection layer preferably uses Japanese Unexamined Patent Publication 2001-281405, Japanese Unexamined Patent Publication 2004- 125958th, the anti-glare disclosed in Japanese Patent 4225675, Japanese Unexamined Patent Publication 2009-47938, Japanese Unexamined Patent Publication 2009-157234 etc. Anti-reflection layer.
(anti-reflection layer)
Can be between low-index layer and mylar, autopolyester film side rises and stacks gradually middle index layer, high folding Penetrate rate layer, or be only laminated high refractive index layer, make anti-reflection layer.As anti-reflection layer it is also possible to not damage the present invention's It is laminated using known technology other than the above in the range of effect.
(high refractive index layer, middle index layer)
The high refractive index layer of the anti-reflection layer of the mylar of the present invention, middle index layer are by inorganic material, You Jicai Material etc. combines and constitutes.The refractive index of high refractive index layer is higher than low-index layer, is more than 1.60 to be preferable, preferably 1.60～1.90.During less than 1.60, cannot get sufficient anti-reflection effect, the resin bed more than 1.90 is difficult to by wet To be formed.The refractive index of middle index layer is less than high refractive index layer and is higher than low-index layer, preferably 1.50～1.65 model Enclose.
With regard to constituting the material of high refractive index layer and middle index layer, be not particularly limited, it is possible to use inorganic material and Organic material.With regard to the forming method of high refractive index layer and middle index layer, can be sunk by chemical deposition (cvd) method, physics Long-pending (pvd) method, a kind of vacuum vapour deposition especially belonging to physical deposition methods, sputtering method, saturating using inorganic matters oxide Bright thin film, preferably by the method for full wet type coating.
During using wet to be formed, high refractive index layer is preferably as follows and is formed: coating composition is coated with, so that solvent is done After dry, irradiated using heating, ionization radial line or being applied in combination of two kinds of means is solidified, thus being formed, described coating Compositionss contain: the oxide containing at least one metal in ti, zr, in, zn, sn, al and sb inorganic micro- Grain；The curable resins with polymerizable group more than 3 senses (is set used in the hard conating that can also use the present invention Fat)；Solvent and polymerization initiator.During using curable resin, initiator, after coating by using thermally and/or electrically from spoke The polyreaction of ray and make curable resin solidify, such that it is able to form high refractive index layer.Middle index layer is except rolling over high Penetrate outside the refractive index difference of rate layer, especially can be formed using identical material etc..
(inorganic particles)
As above-mentioned inorganic particles, the preferably oxide of metal (example ti, zr, in, zn, sn, sb, al), from refractive index Viewpoint is set out, most preferably zirconic microgranule.But, from the viewpoint of electric conductivity, preferably use with sb, in, sn at least 1 Plant the inorganic particles as main component for the oxide of metal.By changing the amount of inorganic particles such that it is able to be adjusted to regulation Refractive index.When being used zirconium oxide as main component, the mean diameter of the inorganic particles in layer is preferably 1～120nm, enters One step is preferably 5～100nm, more preferably 10～100nm.Within the range, can suppress mist degree, dispersion stabilization, by The adaptation with upper strata that is concavo-convex bringing of the appropriateness on surface becomes good, is preferred.
Using zirconium oxide as the inorganic particles preferred index of main component for 1.9～2.8, more preferably 2.1～ 2.8, most preferably 2.2～2.8.The addition of inorganic particles is different according to each layer, in high refractive index layer, with respect to high refraction The overall solid constituent of rate layer, is 40～90 mass %, preferably 50～85 mass %, more preferably 60～80 matter Amount %.In middle index layer, with respect to the solid constituent of middle index layer entirety, it is 1～60 mass %, preferably 3～50 matter Amount %.
The thickness of the anti-reflection layer being made up of low-index layer, high refractive index layer is different according to the structure of anti-reflection layer, Preferably each layer is and visible wavelength identical thickness or its following thickness.For example, reflection is reduced to luminous ray performance The light of 500≤4nh d (nm)≤750 and low-index layer during effect, is met with the blooming nh d of high refractive index layer The mode learning thickness nl d satisfaction 400≤4nl d (nm)≤650 is designed.Wherein, nh, nl be respectively high refractive index layer, The refractive index of low-index layer, d is the thickness of layer.
As anti-reflection layer used in the present invention it is also possible to suitably special using Japanese Unexamined Patent Publication 2003-177209, Japan Open 2008-262187, Japanese Unexamined Patent Publication 2010-170089, Japanese Unexamined Patent Publication 2004-309711, Japanese Unexamined Patent Publication 2011-191735, day In this JP 2004-322380, Japanese Unexamined Patent Publication 2009-3354, Japanese Unexamined Patent Publication 2010-72039, Japanese Unexamined Patent Publication 2010-256705 The anti-reflection layer recorded.
In the low-index layer of the present invention, in addition to the composition of above-mentioned record, as needed it is also possible to not lose invention Effect in the range of comprise other compositions.As other compositions, do not limit, for example, it is possible to add inorganic or organic face Material, polymer, polymerization initiator, polymerization inhibitor, antioxidant, dispersant, surfactant, light stabilizer, levelling agent, antistatic Agent, UV absorbent, catalyst, infrared absorbent, fire retardant, defoamer, electrically conductive microparticle, electroconductive resin etc..
The function of above-mentioned record can be separately provided only one kind it is also possible to combination is multiple by the low-index layer of the present invention.
(the polaroid protection manufacture of easy-adhesion mylar)
For the polaroid protection manufacture method of easy-adhesion mylar of the present invention, with poly terephthalic acid second two Illustrate as a example alcohol ester (hereinafter referred to as pet) thin film, but be certainly not limited to this.
After pet resin is fully vacuum dried, it is supplied in extruder, from t mould by about 280 DEG C of melting pet tree Fat is expressed on rotation chill roll with sheet-shaped molten, carries out cooling and solidifying by electrostatic applying method and obtains non-stretched pet piece.Aforementioned Non-stretched pet piece can be that monolayer is constituted or the multilamellar based on coetrusion is constituted.
Implement to be stretched uniaxially or biaxially to make crystal orientation by pet piece non-stretched to gained.For example twin shaft draws When stretching, it is longitudinally stretched with the roller being heated to 80～120 DEG C after obtaining uniaxial tension pet thin film to 2.5～5.0 times, with folder Son holds the end of thin film, causes the hot blast area being heated to 80～180 DEG C, is stretched to 2.5～5.0 times in the width direction.Additionally, During uniaxial tension, it is stretched to 2.5～5.0 times in stenter.The heat-treatment zone continuing to cause 140～240 DEG C after stretching carries out 1 The heat treatment of～60 seconds, completes crystal orientation.
Adhesive layer can be arranged after the manufacture of thin film or in manufacturing process.Especially, from the point of view of in terms of the productivity ratio, excellent Be selected in thin film fabrication operation any stage, i.e. at least single spreading of the pet thin film after non-stretched or uniaxial tension apply Cloth liquid, forms adhesive layer.
For this coating solution can be used known arbitrary method in the method for pet thin film.For example can enumerate Go out: reverse roll rubbing method, gravure coating process, engagement rubbing method, die coating machine method, roller brush method, spraying process, air knife coating method, line Rod coating method, tubular type doctor blade method (pipe doctor) method, dip coating, curtain coating processes etc..These methods individually or are combined Get up to be coated.
In the present invention, the thickness of the adhesive layer finally giving is preferably 0.03～0.20g/m2.Less than 0.03g/m2 When, cementability reduces, and is thicker than 0.20g/m2When, adhesive, sliding reduce, and it is not preferable.
In the present invention, it is also possible to arrange in the same manner as adhesive layer during setting low-index layer.
(Polarizer)
The Polarizer of the present invention has polaroid protective film, the preferably at least polaroid in the face of side on the two sides of polaroid Protecting film is aforementioned polaroid protection easy-adhesion mylar.The polaroid protective film of opposite side can be the inclined of the present invention Shake piece protection easy-adhesion mylar, using with cellulose triacetate film, acrylate film, norborene system thin film is The thin film free of birefringence representing is also preferred.
As polaroid, for example, can enumerate the polyvinyl alcohol film containing dichroic material such as iodine.Polaroid protective film Fit with polaroid directly or by bond layer, and from improve cementability in terms of from the point of view of, preferably fitted by bonding agent.This When, the adhesive layer of the present invention is preferably configured in the unilateral or bonding agent aspect of polarization.As being preferred for the poly- of the bonding present invention The polaroid of ester film, for example, can enumerate the polaroid obtaining as follows: dyeing absorption iodine, dichromatic on polyvinyl alcohol film Material, carries out uniaxial tension in boric acid aqueous solution, keeps extended state to be washed and be dried and obtain.The drawing of uniaxial tension Stretch generally 4～8 times about of multiplying power.As polyvinyl alcohol film, polyvinyl alcohol is suitable, it is possible to use " kuraray Vinylon " [Kuraray Co., Ltd.'s manufacture], " tohcello vinylon " [mitsui chemicals tohcello, Inc. manufacture], the commercially available product such as " day close vinylon " [synthesis KCC of Japan manufactures].As dichroic material, can arrange Enumerate: iodine, bis-azo compound, polymethin dyes etc..
From the perspective of thinning bond layer, coat the material of the preferred water system of bonding agent of polaroid, i.e. by bonding Agent composition is dissolved in water or is scattered in material obtained from water.It is, for example possible to use polyvinyl alcohol resin, polyurethane resin etc. As main component, in order to improve cementability and as needed using being compounded with isocyanates based compound, epoxide etc. Compositionss.The thickness of bond layer is preferably less than 10 μm, more preferably less than 5 μm, more preferably less than 3 μm.
Be used polyvinyl alcohol resin as bonding agent main component when, except partly-hydrolysed polyvinyl alcohol, complete soap Change beyond polyvinyl alcohol, can also be using carboxy-modified polyvinyl alcohol, acetoacetyl modified polyvinyl alcohol, methylol-modified poly- This modified polyvinyl alcohol resin of vinyl alcohol, amino modified polyvinyl alcohol.Polyvinyl alcohol resin in bonding agent Concentration is preferably 1～10 mass %, more preferably 2～7 mass %.
The polaroid protection mylar of the present invention is preferred for viewing side or the light source side polarisation of viewing side Polarizer The light source side of plate, in particular for light source side Polarizer light source side when, it is possible to increase the brightness of liquid crystal indicator, so excellent Choosing.When the light source side of light source side Polarizer uses the polaroid protection mylar of the present invention, light can be become from averagely The incident configuration in the low side of reflectance, improves the brightness of liquid crystal indicator.Herein, " light source side " refers to, image display dress It is the light source side of starting point with image-display units (for example, liquid crystal cells) in the middle of 2 Polarizers used in putting, " viewing side " is Refer to, with image-display units for starting point and light source side opposite side.
Embodiment
Then, describe the present invention in detail with embodiment, comparative example and reference example, but the present invention be certainly not limited to Under embodiment.Additionally, evaluation methodology is as follows used in the present invention.
(1) glass transition temperature
According to jis k7121, using differential scanning calorimetry (DSC) (seiko instruments inc. manufacture, dsc6200), 10mg resin sample is made to heat up within the temperature range of 25～300 DEG C with the speed of 20 DEG C/min, outer by obtained by dsc curve Push away glass transition started temperature as glass transition temperature.
(2) number-average molecular weight
0.03g resin is dissolved in 10ml oxolane, using gpc-lalls device low angle light light-scattering photometer ls- 8000 (TOSOH Co., Ltd's manufacture, tetrahydrofuran solvent, references: polystyrene), 30 DEG C of column temperature, flow 1ml/ minute, use Chromatographic column (Showa Denko K. K manufactures shodex kf-802,804,806) measures number-average molecular weight.
(3) resin composition
Resin is dissolved in deuterochloroform, using varian, inc. manufactures magnetic nuclear resonance analyzer (nmr) gemini-200 and enters OK1H-nmr analyzes, and determines each mole % ratio forming by its integration ratio.
(4) acid number
The sample of 1g (solid constituent) is dissolved in chloroform or the dimethylformamide of 30ml, is used as indicator using phenolphthalein The potassium hydroxide-ethanol solution of 0.1n is titrated, and obtains the amount (mg) of the koh needed for carboxyl neutralizing every 1g sample.
(5) saponification degree
Quantitation is carried out using sodium hydroxide to the remaining acetoxy group (mole %) of polyvinyl alcohol resin according to jis-k6726, Using its value as saponification degree (mole %).Same sample is carried out with 3 mensure, is averaged value as saponification degree (mole %).
(6) total light transmittance of polaroid protection mylar
The total light transmittance foundation jis k 7105 of polaroid protection mylar, using scopometer (Japan's electricity color strain formula Commercial firm's manufacture, ndh2000) measure.It should be noted that from polaroid protective film and the face opposition side with adhesive layer Face applies light to measure.
(7) mist degree of polaroid protection mylar
Polaroid protects the mist degree of mylar according to jis k 7136, using scopometer (Japan's electricity color Co. Ltd. system Make, ndh2000) measure.It should be noted that applying from the face of polaroid protective film and the face opposition side with adhesive layer Light is measuring.
(8) pva cementability
Adjust to solid component concentration 5 matter in the adhesive layer surface wire rod coating, dip coated of polaroid protection mylar The polyvinyl alcohol water solution (Kuraray Co., Ltd. manufacture pva117) of amount % is so that the thickness of dried polyvinyl alcohol resin layer Spend for 2 μm, with 70 DEG C of dryings 5 minutes.For the ease of judging, using the polyvinyl alcohol water solution adding orchil.For The evaluation object thin film making, on the glass plate of thickness 5mm posting double faced adhesive tape, by the laminate film of evaluation object and shape One-tenth has the contrary face in the face of polyvinyl alcohol resin layer to be attached at above-mentioned double faced adhesive tape.Then, using the cutter guide of clearance gap 2mm Form the otch running through 100 lattice-shapeds that polyvinyl alcohol resin layer reaches base film.Then, by adhesive tape (nichiban Co., ltd. manufactures cellotape (registered trade mark) ct-24；24mm width) it is attached to the cut sides of lattice-shaped.Use rubber when attaching Skin press interface residual air make it completely closely sealed after, by adhesive tape is carried out the vertical operation peeled off suddenly implement 1 time, 5 times, 10 times.Count the number of the unstripped grid of polyvinyl alcohol resin layer, as pva cementability.That is, pva layer is not shelled completely From when, pva bonding rate is denoted as 100, pva layer when all peeling off, and pva bonding rate is denoted as 0.In addition, peeling off in 1 grid interior part The number being also included within stripping in.
(9) average reflectance
With regard to the assay method of the meansigma methodss of the absolute reflectance of the low-index layer of polaroid protection laminate film, The mensure back side (adhesive layer) of mylar paste black belt (Nitto Denko Corp manufactures, ethylene adhesive tape no21: Black).Then, using spectrophotometer (Shimadzu Seisakusho Ltd., uv-3150), with angle of incidence: 5 °, wavelength feed speed: at a high speed (about 700nm/min), sampling interval: 0.5nm, spectral bandwidth: 1nm, to low-index layer surface measurements wave-length coverage 300～800nm Absolute reflectance, calculate the meansigma methodss of 400～700nm, as average reflectance.
(10) refractive index of low-index layer
In the polaroid protection laminated polyester film of the present invention, the refractive index of the low-index layer of setting is by following Method measures.Coating fluid used in low-index layer is applied on glass plate in the way of dried thickness is about 4 μm, After drying, solidification, will be measured using Abbe refractomecer (atago co., ltd. manufacture, nar-4t, mensure wavelength 589nm) The value arriving is as the refractive index of low-index layer.
(polymerization of polyester resin)
Add 194.2 mass in the stainless steel autoclave possessing blender, thermometer and partial reflux formula cooler Part dimethyl terephthalate (DMT), 184.5 mass parts dimethyl isophthalate, 14.8 mass parts dimethyl isophthalate -5- Sodium sulfonate, 233.5 mass parts diethylene glycols, 136.6 mass parts ethylene glycol and 0.2 mass parts tetra-n-butyl titanate esters, with 160 DEG C～220 DEG C of temperature carried out ester exchange reaction with 4 hours.Then, it is warming up to 255 DEG C, after slow for reaction system decompression, React 1 hour 30 minutes under the decompression of 30pa, obtain copolymer polyester resin (a-1).Gained copolymer polyester resin (a-1) is light Yellow transparent.Measure the reduced viscosity of copolymer polyester resin (a-1), result is 0.70dl/g.Glass transition based on dsc Temperature is 40 DEG C.
Obtain copolymer polyester resin (a-2)～(a-5) of other compositions with same method.To these copolymer polyester resins With1The composition (mole % ratio) that h-nmr records and other characteristics are shown in table 1.
[table 1]
(preparation of polyester water dispersion)
30 mass parts polyester resin (a-1), 15 matter are added in the reactor possessing blender, thermometer and reflux Resin is dissolved by amount part ethylene glycol n-butyl ether with 110 DEG C of heating, stirring.After resin is completely dissolved, while stirring by 55 mass Part water is added slowly in polyester liquid.After interpolation, liquid is cooled to while stirring room temperature, makes solid constituent 30 mass % Milky polyester water dispersion (aw-1).Similarly replace polyester resin (a-1) using polyester resin (a-2)～(a-5) Make aqueous dispersion, respectively as polyester water dispersion (aw-2)～(aw-5).
(preparation of polyvinyl alcohol water solution)
Add 90 mass parts water in the container possessing blender and thermometer, be slowly added 10 mass parts while stirring and gather Right 500 polyvinyl alcohol resin (Kuraray Co., Ltd.'s manufacture) (b-1).After interpolation, liquid is heated to while stirring 95 DEG C, so that resin is dissolved.After dissolving, it is cooled to room temperature while stirring, make the polyvinyl alcohol water solution of solid constituent 10 mass % (bw-1).Similarly polyvinyl alcohol resin (b-1) is replaced to make aqueous solution using polyvinyl alcohol resin (b-2)～(b-7), respectively As (bw-2)～(bw-7).The saponification degree of polyvinyl alcohol resin (b-1)～(b-7) is shown in table 2.
[table 2]
b-1 b-2 b-3 b-4 b-5 b-6 b-7
Saponification degree (mole %) 88 83 79 74 70 67 40
(polymerization of blocked polyisocyanates cross-linking agent)
Add 100 mass parts with hexa-methylene two Carbimide. in the flask possessing blender, thermometer, reflux condenser Ester be raw material have isocyanurate structure polyisocyanate compound (Asahi Chemical Corp manufacture, Duranate tpa), 55 mass parts propylene glycol monomethyl ether acetate, 30 mass parts poly glycol monomethyl ether (mean molecule quantities 750), kept 4 hours with 70 DEG C under nitrogen atmosphere.Then, reacting liquid temperature is cooled to 50 DEG C, Deca 47 mass parts butanone Oxime.Measure the infrared spectrum of reactant liquor, the absorption confirming NCO disappears, and obtains the end-blocking of solid constituent 75 mass % Polyisocyanates aqueous dispersions (c-1).
(synthesis of polyurethane resin d-1u)
Make the polyurethane resin d- using fatty family polycarbonate polyol as constituent according to below step 1.To in 4 mouthfuls of flasks possessing blender, dimroth condenser, nitrogen ingress pipe, silica dehydrator pipe and thermometer, put into 4, 4- methyl diphenylene diisocyanate 43.75 mass parts, dimethylolpropionic acid 12.85 mass parts, number-average molecular weight 2000 poly- Hexa-methylene carbonate diol 153.41 mass parts, dibutyl tin laurate 0.03 mass parts and the acetone as solution 84.00 mass parts, in a nitrogen atmosphere, at 75 DEG C stirring 3 hours it is thus identified that reactant liquor reaches the amine equivalent of regulation.Then, will After this reactant liquor is cooled to 40 DEG C, adds triethylamine 8.77 mass parts, obtain polyurethane prepolymer solution.Then, have can Add water 450g in the reaction vessel of the mixer for well-distribution carrying out high-speed stirred, adjust to 25 DEG C, while with 2000min-1Stirring is mixed Interpolation polyurethane prepolymer solution in conjunction side carries out moisture and dissipates.Then, remove a part for acetone and water under reduced pressure, thus preparing The water soluble polyurethane resin of solid constituent 35%.Obtained using fatty family polycarbonate polyol as constituent The glass transition temperature of polyurethane resin (d-1u) is -30 DEG C.
(formation of low-index layer d-1)
Prepare low-index layer coating fluid (d-1) according to following composition.
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Surfactant 0.60 mass %
(silicon systems, solid component concentration 10 mass %)
(formation of low-index layer d-2)
Prepare low-index layer coating fluid (d-2) according to following composition.
Water 56.37 mass %
Isopropanol 30.00 mass %
Acrylic resin 9.13 mass %
(rx2035a, nippon carbide industries co., inc. manufacture, solid constituent 46%)
Blocked isocyanate system cross-linking agent (c-1) 2.40 mass %
Granule 1.50 mass %
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Surfactant 0.60 mass %
(silicon systems, solid component concentration 10 mass %)
(formation of low-index layer d-3)
Prepare low-index layer coating fluid (d-3) according to following composition.
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Surfactant 0.60 mass %
(silicon systems, solid component concentration 10 mass %)
(formation of hard conating d-4)
The face of the face opposition side bonding with same polaroid of mylar manufacturing in aftermentioned embodiment, using #10 line The hard conating formation coating fluid of the following composition of rod coating, is dried 1 minute at 70 DEG C, removes solvent.Then, for being coated with The thin film of hard conating, using high voltage mercury lamp radiation 300mj/cm2Ultraviolet, obtain the polarization with the hard conating of 5 μm of thickness Piece protecting film.
Hard conating formation coating fluid
Butanone 65.00 mass %
Dipentaerythritol acrylate 27.20 mass %
(Xin Zhong village chemistry manufactures a-dph)
Polyethyleneglycol diacrylate 6.80 mass %
(Xin Zhong village chemistry manufactures a-400)
Photoepolymerizationinitiater initiater 1.00 mass %
(ciba specialty chemicals corp manufactures irgacure184)
(formation of antiglare layer d-5)
The face of the face opposition side bonding with same polaroid of mylar manufacturing in aftermentioned embodiment, using #5 bar It is coated with the antiglare layer formation coating fluid of following compositions, is dried 1 minute at 70 DEG C, remove solvent.Then, anti-for being coated with The thin film of dizzy layer, using high voltage mercury lamp radiation 300mj/cm2Ultraviolet, the antiglare layer (d-5) obtaining there is 5 μm of thickness inclined Shake piece protecting film.
Antiglare layer formation coating fluid
(ciba specialty chemicals corp irgacure184)
(formation of anti-reflection layer d-6)
The face of the face opposition side bonding with same polaroid of mylar manufacturing in aftermentioned embodiment, using bar coater It is coated with the middle index layer formation coating fluid of following compositions, after being dried 1 minute at 70 DEG C, using high voltage mercury lamp radiation The ultraviolet of 400mj/cm2, obtains the middle index layer of 5 μm of dry film thickness.Then, on the middle index layer being formed, Using bar coater, the high refractive index layer formation coating fluid of following compositions is formed by the method same with middle index layer, Then thereon the low-index layer formation coating fluid of following compositions is formed by the method same with middle index layer, obtain To the polaroid protection mylar being laminated with anti-reflection layer (d-6).
Middle index layer is formed uses coating fluid (refractive index 1.52)
High refractive index layer is formed uses coating fluid (refractive index 1.64)
Low-index layer is formed uses coating fluid (refractive index 1.42)
Embodiment 1
(1) preparation of the coating fluid of adhesive layer
Mix following smearss, the mass ratio making polyester based resin (a)/polyvinyl alcohol resin (b) is 70/30 painting Cloth liquid.Polyester water dispersion is using the aqueous dispersion (aw-1) being dispersed with the polyester resin that acid number is 2kohmg/g, polyvinyl alcohol Aqueous solution is using the aqueous solution (bw-4) being dissolved with the polyvinyl alcohol that saponification degree is 74 moles of %.
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Catalyst
(organotin based compound solid component concentration 14 mass %) 0.3 mass %
Surfactant 0.5 mass %
(silicon systems, solid component concentration 10 mass %)
(2) manufacture of polaroid protection mylar
As film raw material polymer, by intrinsic viscosity (solvent: phenol/sym-tetrachloroethane=60/40) be 0.62dl/g and The pet resin granular material being substantially free of granule is under the decompression of 133pa, with 135 DEG C of dryings 6 hours.Then, it is supplied to extruder In, melt extrude slabbing with about 280 DEG C, cool down chilling in metallic roll in the rotation remaining 20 DEG C of surface temperature closely sealed solid Change, obtain non-stretched pet piece.
With warmed-up roller group and infrared heater, this non-stretched pet piece is heated to 100 DEG C, then with having circumference speed The roller group of degree difference is longitudinally stretched to 3.5 times, obtains uniaxial tension pet thin film.
Then, with roller rubbing method by the coating solution of the coating fluid of aforementioned adhesive layer and low-index layer d-1 in pet Thin film two-sided after, with 80 DEG C of dryings 15 seconds.In addition, being adjusted so that the dried painting of final (after biaxial stretch-formed) Cloth amount is 0.12g/m2.Then it is stretched to 4.0 times with stenter in the width direction with 150 DEG C, in the width side securing thin film To length in the state of, with 230 DEG C heat 0.5 second, carry out the pine of the width of 10 seconds 3% further with 230 DEG C Relaxation is processed, and obtains the polaroid protection mylar of 38 μm of thickness.Evaluation result is shown in table 3.
Embodiment 2
The moisture that the polyester water dispersion of adhesive layer is changed to be dispersed with the polyester resin that acid number is 4kohmg/g dissipates Body (aw-2), in addition obtains polaroid protection mylar similarly to Example 1.
Embodiment 3
The moisture that the polyester water dispersion of adhesive layer is changed to be dispersed with the polyester resin that acid number is 6kohmg/g dissipates Body (aw-3), in addition obtains polaroid protection mylar similarly to Example 1.
Embodiment 4
The saponification degree that the polyvinyl alcohol water solution of adhesive layer is changed to polyvinyl alcohol is the polyvinyl alcohol of 79 moles of % Aqueous solution (bw-3), in addition obtains polaroid protection mylar similarly to Example 1.
Embodiment 5
The saponification degree being changed to the polyvinyl alcohol of adhesive layer is the polyvinyl alcohol water solution (bw-2) of 83 moles of %, except this Outside obtain polaroid protection mylar similarly to Example 1.
Embodiment 6
Adhesive layer is changed to mix the matter that following smearss make polyester based resin (a)/polyvinyl alcohol resin (b) Amount ratio is 60/40, in addition obtains polaroid protection mylar similarly to Example 1.
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Catalyst
(organotin based compound solid component concentration 14 mass %) 0.3 mass %
Surfactant 0.5 mass %
(silicon systems, solid component concentration 10 mass %)
Embodiment 7
Adhesive layer is changed to mix the matter that following smearss make polyester based resin (a)/polyvinyl alcohol resin (b) Amount ratio is 80/20, in addition obtains polaroid protection mylar similarly to Example 1.
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Catalyst
(organotin based compound solid component concentration 14 mass %) 0.3 mass %
Surfactant 0.5 mass %
(silicon systems, solid component concentration 10 mass %)
Embodiment 8
Adhesive layer is changed to mix the matter that following smearss make polyester based resin (a)/polyvinyl alcohol resin (b) Amount ratio is 50/50, in addition obtains polaroid protection mylar similarly to Example 1.
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Catalyst
(organotin based compound solid component concentration 14 mass %) 0.3 mass %
Surfactant 0.5 mass %
(silicon systems, solid component concentration 10 mass %)
Embodiment 9
Will be as follows for the coating fluid composition change of adhesive layer, in addition obtain polaroid protection similarly to Example 1 Use mylar.
(nikalac mx-042 sanwa chemical co., ltd. manufacture solid component concentration 70%)
Granule 1.25 mass %
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Surfactant 0.5 mass %
(silicon systems, solid component concentration 10 mass %)
Embodiment 10
The saponification degree that the polyvinyl alcohol water solution of adhesive layer is changed to be dissolved with polyvinyl alcohol is the poly- of 70 moles of % The aqueous solution (bw-5) of vinyl alcohol, in addition obtains polaroid protection mylar similarly to Example 1.
Embodiment 11
The saponification degree that the polyvinyl alcohol water solution of adhesive layer is changed to be dissolved with polyvinyl alcohol is the poly- of 67 moles of % The aqueous solution (bw-6) of vinyl alcohol, in addition obtains polaroid protection mylar similarly to Example 1.
Embodiment 12
Will be as follows for the coating fluid composition change of adhesive layer, in addition obtain polaroid protection similarly to Example 1 Use mylar.
(epocros ws-500, Nippon Shokubai Co., Ltd's manufacture, solid component concentration 40 mass %)
Granule 1.25 mass %
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Surfactant 0.5 mass %
(silicon systems, solid component concentration 10 mass %)
Embodiment 13
The moisture that the polyester water dispersion of adhesive layer is changed to be dispersed with the polyester resin that acid number is 10kohmg/g dissipates Body (aw-5), in addition obtains polaroid protection mylar similarly to Example 1.
Embodiment 14
The coating fluid of low-index layer is changed to d-2, in addition obtains polaroid protection similarly to Example 1 and use Mylar.
Embodiment 15
The coating fluid of low-index layer is changed to d-3, in addition obtains polaroid protection similarly to Example 1 and use Mylar.
Embodiment 16
The low-index layer d-1 of embodiment 1 forms d-4, in addition obtains polaroid similarly to Example 1 and protect Shield mylar.
Embodiment 17
The low-index layer d-1 of embodiment 1 forms d-5, in addition obtains polaroid similarly to Example 1 and protect Shield mylar.
Embodiment 18
The low-index layer d-1 of embodiment 1 forms d-6, in addition obtains polaroid similarly to Example 1 and protect Shield mylar.
Embodiment 19
The thickness making low-index layer d-1 is 0.06g/m2, in addition obtain polaroid protection similarly to Example 1 Use mylar.
Embodiment 20
The thickness making low-index layer d-1 is 0.18g/m2, in addition obtain polaroid protection similarly to Example 1 Use mylar.
Comparative example 1
The coating fluid of adhesive layer is changed to mix following smearss and makes polyester based resin (a)/polyethenol series tree The mass ratio of fat (b) is 100/0, in addition obtains polaroid protection mylar similarly to Example 1.
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Catalyst
(organotin based compound solid component concentration 14 mass %) 0.3 mass %
Surfactant 0.5 mass %
(silicon systems, solid component concentration 10 mass %)
Comparative example 2
The coating fluid of adhesive layer is changed to mix following smearss and makes polyester based resin (a)/polyethenol series The mass ratio of resin (b) is 0/100, in addition obtains polaroid protection mylar similarly to Example 1.
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Catalyst
(organotin based compound solid component concentration 14 mass %) 0.3 mass %
Surfactant 0.5 mass %
(silicon systems, solid component concentration 10 mass %)
Comparative example 3
Polyester water dispersion is changed to be dispersed with the aqueous dispersion (aw-4) of the polyester resin that acid number is 25kohmg/g, In addition obtain polaroid protection mylar similarly to Example 1.
Comparative example 4
Polyvinyl alcohol water solution is changed to be dissolved with the aqueous solution (bw-1) of the polyvinyl alcohol that saponification degree is 88 moles of %, In addition obtain polaroid protection mylar similarly to Example 1.
Comparative example 5
Polyvinyl alcohol water solution is changed to be dissolved with the aqueous solution (bw-7) of the polyvinyl alcohol that saponification degree is 40 moles of %, In addition obtain polaroid protection mylar similarly to Example 1.
Comparative example 6
The coating fluid of adhesive layer is changed to mix following smearss and not mixed cross-linker, in addition with enforcement Example 1 similarly obtains polaroid protection mylar.
(silicon dioxide gel of mean diameter 100nm, solid component concentration 40 mass %)
Surfactant 0.5 mass %
(silicon systems, solid component concentration 10 mass %)
Comparative example 7
It is not provided with low-index layer, in addition obtain polaroid protection mylar similarly to Example 1.
Comparative example 8
The thickness making low-index layer d-1 is 0.02g/m2, in addition obtain polaroid protection similarly to Example 1 Use mylar.
Reference example 1
It is shown with tac thin film (Fuji Photo Film Co., Ltd.'s manufacture, 80 μm of thickness, saponification process) to protect as polaroid Shield carries out the result of aforementioned adhesive test with thin film.
[table 3]
Industrial applicability
The polaroid protection easy-adhesion mylar of the present invention and polaroid/water system bonding agent have high adhesiveness, And transmitance is also high, can suitably be used as polaroid and protect component.

Claims (8)

1. a kind of polaroid protection mylar, it is the polyester in easily bonding with the polaroid adhesive layer of one side stacking Thin film,
Described adhesive layer contains polyester based resin (a), polyvinyl alcohol resin (b) and cross-linking agent (c),
The acid number of described polyester based resin (a) is below 20kohmg/g,
The saponification degree of described polyvinyl alcohol resin (b) is 60～85 moles of %,
The average absolute reflectance of the light of wavelength 400～700nm in the face contrary with described one side of described mylar is 6% Below.
2. polaroid protection mylar according to claim 1, wherein, has refractive index ratio in described contrary face The low low-index layer of described mylar.
3. polaroid protection mylar according to claim 2, wherein, described low-index layer is to apply selected from hard At least one functional layer in the group of layer, antiglare layer and anti-reflection layer composition.
4. polaroid protection mylar according to claim 1 and 2, wherein, described polyester based resin (a) is contained It is the 5- sulfoisophthalic acid composition of 1～15 mole of % in dicarboxylic acid component.
5. polaroid protection mylar according to claim 1 and 2, wherein, described cross-linking agent (c) is isocyanates Compound or melamine compound.
6. polaroid protection mylar according to claim 1 and 2, wherein, in described adhesive layer, Polyester tree The mass ratio of fat (a), polyvinyl alcohol resin (b) and cross-linking agent (c) meets following formula:
0.8≤(a)/(b)≤5,
2≤((a)+(b))/(c)≤50.
7. a kind of Polarizer, it is the two-sided Polarizer with polaroid protective film in polaroid, and at least one polaroid is protected Cuticula is the polaroid protection mylar any one of claim 1～6.
8. a kind of image display device, it has the Polarizer described at least one claim 7.
CN201380042126.9A 2012-08-07 2013-08-06 Polyester film for polarizer protection, polarizing plate and liquid crystal display device Active CN104520738B (en)

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