CN107075298A - Easy adhesive composition and the optical film and its manufacture method for having used said composition - Google Patents

Easy adhesive composition and the optical film and its manufacture method for having used said composition Download PDF

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Publication number
CN107075298A
CN107075298A CN201580060306.9A CN201580060306A CN107075298A CN 107075298 A CN107075298 A CN 107075298A CN 201580060306 A CN201580060306 A CN 201580060306A CN 107075298 A CN107075298 A CN 107075298A
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film
weight
parts
water
adhesive composition
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CN107075298B (en
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吉泽正浩
松本匡弘
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Okura Industrial Co Ltd
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Okura Industrial Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

The problem of the present invention is to provide the reduction for not only suppressing the initial performance when hot and humid lower long-time is used but also can meet the easy adhesive composition of humidity resistance under more harsh environment and the optical film of the adhesive layer formed by the easy adhesive composition is set at least one surface of thermoplastic resin film.The present invention provides a kind of easy adhesive composition, and it contains:100 parts by weight have the water-dispersible polyurethane resin of carboxyl, 1~25 parts by weight water-soluble carbodiimide compound and 1~25 parts by weight water dispersible carbodiimide compound;A kind of optical film, it is that the adhesive layer formed by the easy adhesive composition is set at least one surface of thermoplastic resin film.

Description

Easy adhesive composition and the optical film and its manufacture method for having used said composition
Technical field
The present invention relates to easy adhesive composition and the optical film with the adhesive layer being made up of the easy adhesive composition. The invention further relates to the manufacture method of the optical film and possesses the polarizer (polarizing plate, Polarizer) of the optical film And image display device.
Background technology
The acrylic acid series tree that known (methyl) acrylic polymer by by representative of polymethyl methacrylate is formed The optical characteristics such as adipose membrane light transmittance are excellent, and mechanical strength and shaping processability is harmonious excellent.Therefore, acrylic acid series tree Adipose membrane has been applied to be assembled in liquid crystal display device (LCD), plasma display panel (PDP), organic EL display (OLED) optical film of image display device as.
Optical film in the state of the stacking of other functional membranes generally with using.For example, regarding optical film as polaroid (polarizer) diaphragm is in use, at least one side of polaroid can be laminated in via hydrophilic adhesive layer.Obtain The polarizer can be used for image display device etc..In this case, the adaptation of optical film and polaroid is well important.
However, for acrylic resin film, it is poor with the cementability of hydrophilic adhesive to exist, close with polaroid The problem of conjunction property is insufficient such.Therefore, it is proposed to be set on the surface of acrylic resin film with polyester, acrylic acid tree Fat, polyurethane etc. help the resin of cementability for the adhesive layer of main component, assign easy-adhesion to acrylic resin film Method.
On the other hand, in recent years, used carrying equipment of the image display devices such as LCD etc. whether indoor or Used in outdoor various environment, even sometimes requiring that the humidity resistance that hot and humid environment is also resistant to.For being used for The polarizer of such purposes, it is desirable to also do not occur the high adhesion of splitting under hot and humid.
Therefore, in Japanese Unexamined Patent Publication 2009-193061 publications, as the polarizer of the excellent adhesion under hot and humid, Describe and the polymer for coordinating Ju You oxazolinyls is formed on the surface of (methyl) acrylic resin film as crosslinking agent Into adhesive layer scheme.In Japanese Unexamined Patent Publication 2014-35411 publications, describe to improve acrylic acid mesentery and polarisation The adaptation of piece, and set and be combined with polyester resin, polyvinyl alcohol resin and by isocyanate compound or melamine amination The adhesive layer of the crosslinking agent of compound formation.
The content of the invention
Invent problem to be solved
However, for the optical film with adhesive layer disclosed in above-mentioned document, although originally show good closely sealed Property, but in hot and humid lower long-time in use, can not be avoided with the adaptation reduction of polaroid.Due to such adaptation drop It is low, therefore there is the problem of can not maintaining initial performance (initial adaptation) for a long time so.In addition, disclosed in above-mentioned document Although humidity resistance of the optical film with adhesive layer in the environment of 40~60 DEG C, 60~90%RH or so is satisfactory, Humidity resistance under more harsh environment under (for example, 80 DEG C, 90%RH) fails satisfactory.
The present invention be in view of so the problem of and complete, problem, which is to provide, can not only suppress when hot and humid lower long Between initial performance when using reduction but also can meet humidity resistance under more harsh environment easy adhesive composition, And the optics of the adhesive layer formed by the easy adhesive composition is set at least one surface of thermoplastic resin film Film.
Means for solving the problems
By the present invention there is provided:
(1) easy adhesive composition, it contains:100 parts by weight have the water-dispersible polyurethane resin of carboxyl, 1~25 parts by weight Water-soluble carbodiimide compound and 1~25 parts by weight water dispersible carbodiimide compound.
The present invention is also provided:
(2) the easy adhesive composition described in (1), wherein, foregoing water-soluble carbodiimide compound and foregoing water dispersible carbon two The weight ratio of group with imine moiety is 30:70~95:5 scope;
(3) the easy adhesive composition described in (1) or (2), wherein, relative to the foregoing weight of water-dispersible polyurethane resin 100 Part, also containing 0.1~15 parts by weight particulate;
(4) optical film, it possesses:Thermoplastic resin film and be arranged at the thermoplastic resin film at least one surface and by (1) adhesive layer of the easy adhesive composition formation any one of~(3);
(5) optical film described in (4), wherein, aforementioned thermoplastic resin film is formed by (methyl) acrylic resin;And,
(6) polarizer, it possesses:Polaroid and (4) or (5) that are coated to the surface of the polaroid and are protected to it are described Optical film.
The present invention and then offer:
(7) manufacture method of optical film, methods described includes following process:
The process that easy adhesive composition is coated at least one surface of thermoplastic resin film and film is formed, the easy bonding Composition dilutes through water solvent, and has containing 100 parts by weight water-dispersible polyurethane resin, 1~25 parts by weight of carboxyl Water-soluble carbodiimide compound and 1~25 parts by weight water dispersible carbodiimide compound;And
The process that foregoing dried coating film is formed into adhesive layer.
The effect of invention
Easy adhesive composition of the invention with above-mentioned composition can not only suppress first when hot and humid lower long-time is used The reduction of beginning performance, and can also maintain under more harsh environment high adhesion.Therefore, have for having used by this Invention easy adhesive composition formation adhesive layer optical film the polarizer for, it is hot and humid under optical film and polarisation The excellent adhesion of piece.It should be noted that in this specification, the term of " (methyl) acrylic acid " is used as methacrylic acid, third Olefin(e) acid or the general designation of both and use.The term of " (methyl) acrylonitrile " is similarly.
Brief description of the drawings
[Fig. 1] is the sectional view of one for schematically showing the optical film of the present invention;
[Fig. 2] is the sectional view of one for schematically showing the polarizer of the present invention.
Embodiment
[easy adhesive composition]
The easy adhesive composition of the present invention contains:Water-dispersible polyurethane resin with carboxyl (is hereinafter sometimes referred to simply as U trees Fat) and it is sub- as the water-soluble carbodiimide compound (hereinafter sometimes referred to simply as S compounds) and water dispersible carbon two of crosslinking agent Amines (hereinafter sometimes referred to simply as D compounds).The easy adhesive composition constituted as described above not only suppresses high in high temperature The reduction of initial performance when wet lower long-time is used, and under more harsh environment, adaptation is also excellent.
For the existing known adhesive layer for the purposes, in hot and humid lower long-time in use, closely sealed The reduction of property can not be avoided.However, in the present invention, suppress the reduction of the initial performance when hot and humid lower long-time is used, Excellent adhesion under hot and humid.Though its reason is indefinite, it is presumed as follows:S compounds are from D compounds respectively different Period forms cross-linked structure, in the following manner function.
That is, S compounds and the compatibility of other hydrophilic resins is good, and cross-linking reaction speed is fast, therefore in adhesive layer During formation, or earlier stage after its formation, the carboxyl formation cross-linked structure with U resins.On the other hand, D compounds and S chemical combination Thing is compared, and cross-linking reaction speed is slow, therefore, when adhesive layer is formed, the D compounds of remained unreacted in adhesive layer. Under hot and humid, when the U resins in adhesive layer are Polyester, polyester is hydrolyzed, and ester bond is cut off, and produces carboxylic acid group. Herein, it is believed that unreacted D compounds are reacted with the carboxylic acid group produced and form cross-linked structure, will be because easy to stick caused by hydrolysis The deterioration selfreparing of layer is connect, thus, the strength deterioration of the adhesive layer under suppression is hot and humid.
In addition, there is also the functional groups such as carboxyl in the functional layer or thermoplastic resin film for be laminated in adhesive layer.Recognize For under hot and humid, carboxyl present in these functional layers or thermoplastic resin film reacts with unreacted D compounds, formed Cross-linked structure, thus, suppresses the strength deterioration of adhesive layer.
As U resins, as long as there is the polyurethane resin of the water dispersible of carboxyl in intramolecular, you can not limit especially Use to system.U resins are for example manufactured using following methods.First, it is being inertia and compatible with water relative to isocyanates Make polyisocyanates and polyol reaction in organic solvent, form NCO end prepolymer.Then, make its with trip From carboxyl chain extender reaction, obtain wire carbamate prepolymer.Then, in the presence of nertralizer, in water, make Wire carbamate prepolymer carries out chain extension, while carrying out Water-borne modification, thus obtains U resins.It should be noted that herein So-called Water-borne modification is to instigate resin stably to disperse or emulsify in water.
As polyisocyanates, for example, tetramethylene diisocyanate, ten dimethylene diisocyanates, 1 can be enumerated, 4- butane diisocyanates (1,4-butanediisocyanate), hexamethylene diisocyanate, 2,2,4- trimethyls six are sub- Methyl diisocyanate, 2,4,4- trimethyl hexamethylene diisocyanates, lysine diisocyanate, 2- methylpentane -1, The aliphatic diisocyanates such as 5- diisocyanate, 3- methylpentane -1,5- diisocyanate;IPDI, Hydrogenate XDI, 4,4 '-diphenylmethane diisocyanate, 1,4- cyclohexane diisocyanates, methyl The alicyclic diisocyanates such as double (isocyanatomethyl) hexamethylenes of cyclohexylene diisocyanate, 1,3-;Toluene diisocynate Ester, 2,2 '-methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate, the isocyanide of 4,4 '-diphenyl methane two Acid esters, 4,4 '-diphenyldimethyhnethane diisocyanate, 4,4 '-dibenzyl diisocyanate, 1,5- naphthalene diisocyanates, The aromatic diisocyanates such as XDI, 1,3- phenylene diisocyanates, 1,4- phenylene diisocyanates;Dioxane Base methyl diphenylene diisocyanate, tetraalkyl methyl diphenylene diisocyanate, α, α, α, α-tetramethylxylene two Araliphatic diisocyanates such as isocyanates etc..They can be used alone or two or more also can be combined and uses.
As polyalcohol, as long as having the compound of more than 2 hydroxyls in the molecule, it is not particularly limited, can Using arbitrary appropriate polyalcohol.For example, polyacrylic polyalcohol, PEPA, PPG, poly- carbon can be enumerated Acid esters polyalcohol etc..They can be used alone or two or more also can be combined and uses.In addition, in these, preferably using polyester Polyalcohol, for the Polyester polyurethane resin for having used PEPA, prevent it is hot and humid under adhesive layer The excellent performance of strength deterioration.
As the chain extender with free carboxyl, for example, dihydroxy carboxylic acids, dihydroxysuccinic acid etc. can be enumerated.As Dihydroxy carboxylic acids, for example, dihydroxymethyl alkanoic acid can be enumerated (for example, dihydroxymethyl acetic acid, dimethylolpropionic acid, dihydroxymethyl Propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid) etc. dihydroxyalkyl (alkylol) alkanoic acid.They can be used alone or Two or more can be combined and uses.
As nertralizer, for example, ammonia, N-methylmorpholine, triethylamine, dimethylethanolamine, methyl diethanol can be enumerated Amine, triethanolamine, morpholine, tripropylamine, monoethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol etc..They can be independent Using or also can be combined two or more and use.
In addition, as other workable chain extenders, can enumerate ethylene glycol, propane diols, BDO, neopentyl glycol, The low molecular weight diols such as furyl dimethyl carbinol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol compound and make they and oxirane, epoxy third Alkane, tetrahydrofuran etc. carry out PTMEG compound obtained from addition polymerization;By above-mentioned low molecular weight diols compound and amber The polyester two in end with hydroxyl that dicarboxylic acids and their acid anhydrides such as amber acid (acid anhydride), adipic acid, phthalic acid (acid anhydride) are obtained Alcohol;The polyalcohols such as trimethylolethane, trimethylolpropane;The amino alcohols such as MEA, diethanol amine, triethanolamine;Second two Two amine compounds such as amine, propane diamine, butanediamine, 1,6- hexamethylene diamines, phenylenediamine, toluenediamine, dimethylphenylene diamine, IPD Thing;Water, ammonia, hydrazine, binary hydrazides (bis- salt base acid ヒ De ラ ジ De) etc..They can be used alone or two or more also can be combined And use.
U resins have preferably 5000~600000, further preferred 10000~400000 number-average molecular weight and preferably 10 The above, further preferred 10~50, particularly preferred 20~45 acid number.By making acid number in above range, thus with conduct Crosslinking agent carbodiimide compound formation cross-linked structure, it is hot and humid under excellent adhesion.It is used as the tool of preferred U resins Style, can enumerate " Superflex (registration mark) " series, " ADEKA of ADEKA company systems of the first industrial pharmaceutical company system BONTIGHTER (registration mark) HUX " series, Mitsui Chemicals, Inc.'s system " TAKELAC (registration mark) W, WPB, WS " series, The commercially available U resins such as " HYDRAN (registration mark) " series of DIC company systems.
Operability consideration when being formed from adhesive layer, can be diluted easy adhesive composition with water solvent.It is used as water system Solvent, can be used water or water with hydrophilic organic solvent (for example, the alcohol such as methanol, ethanol, isopropanol, ethylene glycol, propane diols system Solvent;The ester series solvents such as ethyl acetate, butyl acetate, gamma-butyrolacton;The ketone series solvents such as acetone;Tetrahydrofuran, dioxa hexamethylene The ether series solvents such as alkane;The aprotic polar solvents such as 1-METHYLPYRROLIDONE) mixed solvent, particularly preferably water.
The content of U resins in easy adhesive composition is not particularly limited, it is considered to which painting work etc. is suitably set, For example, it is preferable to be 1~25 weight %, more preferably more preferably 3~20 weight %, 5~15 weight %.If easily bonding combination U resins in thing are above range, then operational excellent during adhesive layer formation, thus preferably.In addition, for easy bonding group For the solid state component amount of compound, it is considered to which painting work etc. is suitably set, preferably 1~30 weight %, more preferably 2 ~25 weight %, more preferably 3~20 weight %.
As S compounds, as long as the water miscible compound in intramolecular with the carbodiimide of more than 2 is Can, it is not particularly limited, for example, the material being dissolved in the water can be enumerated, it is utilized along with organic diisocyanate chemical combination Then the condensation reaction of the decarboxylation (de- diacid charcoal element) of thing, the poly- carbodiimide in synthesizing isocyanate end, makes itself and hydrophily Organic compound (hydrophilic organic compound includes the functional group for having reactivity with NCO) reaction, uses hydrophily Segment poly- carbodiimide system resin obtained from terminal isocyanate is blocked.As S compounds, Nisshinbo can be used Chemical Inc. systems " Carbodilite (registration mark) SV-02 ", " Carbodilite (registration mark) V-02 ", " Carbodilite (registration mark) V-04 ", " Carbodilite (registration mark) V-10 ", " Carbodilite (registrars Mark) the commercially available product such as V-02-L2 ".
For the usage amount of S compounds, in terms of solid state component conversion, relative to the parts by weight of U resins 100, preferably 1 ~25 parts by weight, more preferably 3~20 parts by weight, more preferably 5~15 parts by weight.
As D compounds, as long as the compound in intramolecular with the water dispersible of the carbodiimide of more than 2 is Can, it is not particularly limited, for example, it is not dissolving but the material of differential scattered (emulsion) that can enumerate in water, it is using adjoint The condensation reaction of the decarboxylation of organic diisocyanate compound, the poly- carbodiimide in synthesizing isocyanate end, then, make its with Hydrophilic organic compound (hydrophilic organic compound includes the functional group for having reactivity with NCO) reaction, is used Hydrophilic segment poly- carbodiimide system resin obtained from terminal isocyanate is blocked.It is used as water dispersible carbodiimide chemical combination Thing, can be used Nisshinbo Chemical Inc. systems " Carbodilite (registration mark) E-01 ", " Carbodilite (notes Volume trade mark) the commercially available product such as E-02 ".
For the usage amount of D compounds, in terms of solid state component conversion, relative to the parts by weight of U resins 100, preferably 1 ~25 parts by weight, more preferably 1~20 parts by weight, more preferably 1~10 parts by weight.S chemical combination in easy adhesive composition The weight ratio (S/D) of thing and D compounds is usually 30:70~95:5 scope, preferably 40:60~90:10, more preferably 50:50~80:20.
For easy adhesive composition, according to required function, arbitrary appropriate particulate, preferably moisture can be contained Dissipate the particulate of property.As particulate, inorganic system's particulate, organic system particulate can be used.As inorganic system's particulate, for example, can enumerate The inorganic oxides such as silica, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talcum, clay, calcined kaolin, calcining Calcium silicates, afwillite, alumina silicate, magnesium silicate, calcium phosphate etc..As organic system particulate, for example, silicon-type tree can be enumerated Fat, fluorine resin, (methyl) acrylic resin, (methyl) Chelate resin etc..In these, preferred (methyl) acrylic Resin.For the particulate comprising (methyl) Chelate resin, the ability for suppressing caking (blocking) is more excellent, and The transparency is excellent, and muddy (haze) is not produced, is not coloured, therefore, influence of the easy bonding layer to optical characteristics is smaller yet.Separately Outside, although the intensity and adaptation of adhesive layer are reduced due to coordinating particulate, but are combined with comprising (methyl) acrylic tree The adhesive layer of the particulate of fat can suppress the reduction of the intensity and adaptation of adhesive layer, thus preferably.
The average grain diameter of particulate is not particularly limited, from the viewpoint of the transparency for maintaining adhesive layer, preferably 1~ 500nm, more preferably 50~350nm, more preferably 100~300nm.By using the particulate of such particle diameter, so that Be properly formed bumps on adhesive layer surface, can be effectively reduced thermoplastic resin film and adhesive layer contact surface and/ Or the frictional force of the mutual contact surface of adhesive layer, in addition, caking can be suppressed.Above-mentioned average grain diameter refers to, is spread out using laser Penetrate/the median particle diameter (d50) that measures of the formula particle size distribution of scattering.
For the content of particulate, in terms of solid state component conversion, relative to the parts by weight of U resins 100, preferably 0.1~ 15 parts by weight.More preferably 0.3~5 parts by weight, more preferably 0.5~3 parts by weight.
For easy adhesive composition, in order to improve coating strength, it can contain different from above-mentioned S and D compounds Crosslinking agent or the resin with crosslinking group.As crosslinking agent, can enumerate urea system, epoxy, melamine series, isocyanates system, Oxazoline system, silanol system etc..In addition, in order to promote cross-linking reaction, as needed, can be suitably using catalyst etc..
Easy adhesive composition can also contain arbitrary appropriate additive.As additive, for example, stably dispersing can be enumerated Agent, thixotropic agent, antioxidant, ultra-violet absorber, defoamer, thickener, dispersant, surfactant, catalyst, lubrication Agent, antistatic agent etc..
[optical film]
One of the optical film of the present invention is shown in Fig. 1.For the optical film 1 shown in Fig. 1, in thermoplastic resin film 2 A surface on there is the adhesive layer 3 that is formed by above-mentioned easy adhesive composition.It should be noted that the optics of the present invention Film also can form adhesive layer on two surfaces of thermoplastic resin film.
As the thermoplastic resin for constituting thermoplastic resin film, for example, the cellulose-based tree such as triacetyl cellulose can be enumerated Fat, polyester based resin, polyether sulfone system resin, polycarbonate-based resin, polyamide series resin, polyimides system resins, polyolefin It is resin, cyclic polyolefin hydrocarbon system resin, (methyl) acrylic resin, polyarylate system resin, polystyrene resin, polyethylene Alcohol system resin etc..They can be used alone or two or more also can be combined and uses.In these, for (methyl) acrylic acid series For resin (hereinafter sometimes referred to simply as ACR), due to poor with the cementability of hydrophilic adhesive, therefore, when using ACR, The effect of invention is particularly significant.
ACR glass transition temperature (hereinafter referred to as Tg) is preferably more than 115 DEG C, more preferably more than 120 DEG C, enters one Step is preferably more than 125 DEG C.It is used as main component for more than 115 DEG C of ACR by making thermoplastic resin film comprising Tg, can be formed The thermoplastic resin film of excellent in te pins of durability.In addition, above-mentioned Tg higher limit is not particularly limited, consider from viewpoints such as formabilities, Usually less than 170 DEG C.
As ACR, for example, can enumerate poly- (methyl) acrylate such as polymethyl methacrylate, methyl methacrylate- (methyl) acrylic copolymer, methyl methacrylate-(methyl) acrylate copolymer, methyl methacrylate-acrylic acid Ester-(methyl) acrylic copolymer, (methyl) acrylate-styrene copolymer (MS resins etc.), with alicyclic alkyl Polymer (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate-(methyl) propylene Sour norborny ester copolymer etc.).In above-mentioned substance, poly- (methyl) the acrylic acid C1-6 alkane such as preferably poly- (methyl) methyl acrylate Base ester, more preferably using methyl methacrylate as main component (50~100 weight %, preferably 70~100 weight %) methyl Methyl acrylate system resin.
As ACR concrete example, for example, " ACRYPET (the registrations of Mitsubishi Rayon Co., Ltd.s system can be enumerated Trade mark) VH ", " ACRYPET (registration mark) VRL20A ", pass through high Tg obtained from intramolecular crosslinking, intramolecular cyclization reaction (methyl) acrylic resin.
For ACR, from the aspect of with high-fire resistance, high transparency, high mechanical properties, have preferably in main chain Circular structure.As the ACR in main chain with ring structure, for example, can enumerate with glutaric anhydride structure or glutarimide The resin (WO2007/26659 publications, WO2005/108438 publications) of structure, with maleic anhydride structure or N- substitution horse Carry out the resin (Japanese Unexamined Patent Application 57-153008 publications, Japanese Unexamined Patent Publication 2007-31537 publications) of imide structure, with interior Resin (Japanese Unexamined Patent Publication 2006-96960 publications, Japanese Unexamined Patent Publication 2006-171464 publications, the Japanese Unexamined Patent Publication of ester ring structure 2007-63541 publications, Japanese Unexamined Patent Publication 2008-191426 publications).
Thermoplastic resin film can contain additive.As additive, resist for example, hindered phenol series, phosphorus system, sulphur system etc. can be enumerated Oxidant;The stabilizers such as resistance to light stabilizer, weathering stabilizers, heat stabilizer;The reinforcing materials such as glass fibre, carbon fiber;It is ultraviolet Light absorbers;Near infrared ray absorption;Fire retardant;The antistatics such as anion system, cation system, the surfactant of nonionic system Agent;The colouring agents such as inorganic pigment, organic pigment, dyestuff;Organic filler, inorganic filler;Modifier;Organic filler, nothing Machine filler;Plasticizer;Lubricant;Fire retardant;Phase difference depressant etc..
As the manufacture method of thermoplastic resin film, it is not particularly limited, for example, using arbitrary appropriate mixing side Thermoplastic resin and other polymers, additive etc. are sufficiently mixed by method, and thermoplastic resin composition is made in advance, then by it Carry out film shaping.Or also respective solution can be respectively prepared in thermoplastic resin and other polymer, additive etc., so Mixed afterwards, uniform mixed liquor is made, then carry out film shaping.
In order to manufacture thermoplastic resin composition, for example, being mixed using homogenizer (omni-mixer) etc. is arbitrary appropriate Conjunction machine, above-mentioned film raw material is pre-mixed, and is then extruded obtained mixture and is kneaded.In this case, it is mixed available for extrusion The kneading machine of refining is not particularly limited, for example, the extruders such as single screw extrusion machine, double screw extruder, pressurization can be used to mediate The arbitrary appropriate mixer such as machine.
The method shaped as film, for example, solution casting method (the tape casting), extrusion by melting, rolling process, compression can be enumerated The arbitrary appropriate film forming process such as forming process.In these film forming processes, preferred molten extrusion molding.
As extrusion by melting, for example, T modulus methods, inflation method etc. can be enumerated.Forming temperature is preferably 150~350 DEG C, more Preferably 200~300 DEG C.
When carrying out film shaping using T modulus methods, by the leading section of known single screw extrusion machine, double screw extruder T moulds are installed, film forming is moulded using the T, then by film roll around can obtain the film of web-like.
Thermoplastic resin film can be any of unstretching film or stretched film.In the case of for stretched film, Ke Yishi Monadic stretching membrane or biaxially-stretched film it is any.In the case of for biaxially-stretched film, can be synchronous double-shaft stretching or Successively biaxial drawing film it is any.Carried out it is biaxial stretch-formed in the case of, mechanical strength improve, film properties improve.
Draft temperature is preferably near glass transition temperature as the thermoplastic resin composition of film raw material, it is specific and Speech, preferably in the range of (- 30 DEG C of glass transition temperature)~(+100 DEG C of glass transition temperature), more preferably in (glass Change -20 DEG C of transition temperature)~(+80 DEG C of glass transition temperature) in the range of.Draft temperature less than (glass transition temperature- 30 DEG C) when, sufficient stretching ratio may be cannot get.Conversely, when draft temperature is higher than (+100 DEG C of glass transition temperature), Cause the flowing (flow) of resin combination, it may not be possible to the stretching stablized.
Than the stretching ratio of definition it is preferably 1.1~25 times with area, more preferably 1.3~10 times.Stretching ratio is less than At 1.1 times, it may not be possible to obtain being improved by the toughness for stretching and bringing.When stretching ratio is more than 25 times, it may not be possible to obtain with Improve the corresponding effect of stretching ratio (raising of toughness).
For draw speed, in one direction, preferably 10~20,000%/min, more preferably 100~10, 000%/min.When draw speed is less than 10%/min, the consuming time is needed in order to obtain sufficient stretching ratio, manufacturing cost can It can increase.When draw speed is more than 20,000%/min, fracture of stretched film etc. may be caused.
For thermoplastic resin film, in order that its optical isotropy, mechanical property are stabilized, can be in stretch processing It is heat-treated afterwards (annealing) etc..The condition of heat treatment can be using arbitrary appropriate condition.
The thickness of thermoplastic resin film is preferably 5~200 μm, more preferably 10~100 μm., may when thickness is less than 5 μm Cannot as optical film sufficient intensity.When thickness is more than 200 μm, transparency reduction may be not suitable anymore for as optics Film is used.
The thickness of adhesive layer can be set as to arbitrary appropriate value.Preferably 0.1~10 μm, more preferably 0.1~5 μm, particularly preferably 0.2~1.0 μm.By being set as such scope, so that the adaptation with other functional membranes It is excellent, it can suppress occur phase difference in adhesive layer.
As needed, it can form various on the surface of the opposite side in the surface with being formed with adhesive layer of optical film Functional layer.On functional layer, for example, antistatic backing, bond layer, adhesive linkage, adhesive layer, anti-dazzle (nonglare) can be enumerated The stain-proofing layers such as layer, photocatalysis layer, anti-reflection layer, hard conating, ultraviolet blocking layer, infrared ray barrier layer, blocking electromagnetic waves layer, resistance Gas-bearing formation etc..
Optical film can be used as such as polarizing plate protective film, phase retardation film, compensation film for angular field of view, optical diffusion film, reflectance coating, counnter attack Film, antiglare film, brightness raising film, touch panel is penetrated to be used with conducting film.In addition, in these, being protected particularly preferable as polaroid Cuticula is used.
[polarizer]
Next, one of the polarizer of the explanation present invention.The polarizer 10 shown in Fig. 2 has following structures:In thermoplastic resin Have on one surface of adipose membrane 2 and optical film 1 is obtained by the adhesive layer 3 that above-mentioned easy adhesive composition is formed, described On the surface of the adhesive layer side of optical film 1, via bonding agent 5, polaroid 6 is laminated with.It should be noted that, although not scheming Show, but the polarizer 10 can have the diaphragm being laminated via bond layer on the side opposite with optical film 1 of polaroid 6.
, can be using arbitrary appropriate polaroid according to purpose as polaroid.For example, can enumerate in polyethenol series The hydrophilic macromolecule films such as film, part formalizing polyvinyl alcohol mesentery, the partly-hydrolysed film of vinyl-vinyl acetate copolymer system The upper absorption dichroic material such as iodine or dichroic dyestuff, and polaroid, the dehydration of polyvinyl alcohol obtained from carrying out uniaxial tension The polyolefin (polyene) such as processed material, sour (dechlorination) processed material of desalination of polyvinyl chloride are alignment films etc..In these, in poly- second The polarisation dichroic of polaroid, than high, is special obtained from the dichroic materials such as iodine are adsorbed on enol mesentery and uniaxial tension is carried out It is not preferred.The thickness of these polaroids is not particularly limited, usually 1~80 μm or so.
, can be using arbitrary appropriate bonding agent as the bonding agent for forming bond layer.It is preferred that bond layer by comprising The adhesive composite of polyvinyl alcohol resin is formed.
, can be using arbitrary appropriate protection as the diaphragm for the side opposite with optical film 1 for being arranged at polaroid 6 Film, is formed using the material same with above-mentioned thermoplastic resin.
[image display device]
The image display device of the present invention possesses the above-mentioned polarizer.As the concrete example of image display device, it can enumerate electroluminescent Luminous (EL) display, plasma display (PD), field-emitter display (FED:Field Emission Display) this Self-luminous display device, the liquid crystal display device (LCD) of sample.
[manufacture method of optical film]
In the preferred manufacture method of the optical film of the present invention, the moisture that will be diluted and contained with water solvent has carboxyl dissipates Property polyurethane resin, water-soluble carbodiimide compound and water dispersible carbodiimide compound easy adhesive composition coating In at least one surface of thermoplastic resin film, film (painting process) is formed, next by dried coating film, easily bonding is formed Layer (drying process).
, can be using arbitrary appropriate method as the method that easy adhesive composition is coated with painting process.For example, can lift Go out scraping article rubbing method, rolling method, gravure coating process, bar type rubbing method, gap nozzle rubbing method (slot orifice Coating), curtain coating method, jetting type rubbing method (fountain coating) etc..The coated film formed in painting process Thickness thickness required when can form adhesive layer according to the coated film is suitably adjusted.
Implement surface treatment in the surface of the easy adhesive composition of coating of preferred pair thermoplastic resin film.As surface treatment, Preferably Corona discharge Treatment, corona treatment.By implementing Corona discharge Treatment, can improve thermoplastic resin film with it is easy to stick Connect the adaptation of layer.
Drying process is not particularly limited, using known method.It is 50 typically as drying temperature More than DEG C, preferably more than 90 DEG C, more preferably more than 110 DEG C.By making drying temperature be above range, color can be made into The excellent optical film of fastness (color resistance) (especially hot and humid under).The upper limit of drying temperature is preferably less than 200 DEG C, enters one Step is preferably less than 180 DEG C.
Using the manufacture method of the optical film of the present invention, by light of the non-stretched thermoplastic resin film manufacture as stretched film When learning film, and, it is necessary to a certain when manufacturing the optical film as biaxially-stretched film by the thermoplastic resin film through uniaxial tension Time point stretches to these thermoplastic resin films.The stretching of thermoplastic resin film can be carried out before the formation of adhesive layer, Also it can be carried out after the formation of adhesive layer.In addition, can also carry out the formation of adhesive layer and the drawing of thermoplastic resin film simultaneously Stretch.
When the formation of progress adhesive layer simultaneously and the stretching of thermoplastic resin film, such as after painting process, in heating The thermoplastic resin film of coated film under atmosphere to being formed with easy adhesive composition is stretched.By in order to be stretched And to the heat of film application so that the coated film of the easy adhesive composition formed on the surface of thermoplastic resin film is dried, shape Into adhesive layer.If so operated, the stretch processing of film and the drying of easy adhesive composition can be carried out simultaneously, productivity ratio is excellent It is different, thus preferably.
Embodiment
Hereinafter, the present invention is illustrated by embodiment in further detail.It should be noted that the present invention is not by following reality Apply the limitation of example.
As raw material, following materials is used:
< U resins >
Emulsion [the first industrial pharmaceutical company system, Superflex (registration mark) of water-dispersible polyurethane resin with carboxyl 210, solid state component amount is 35 weight %]
< S compounds (1) >
The aqueous solution [Nisshinbo Chemical Inc. systems, Carbodilite (notes containing water-soluble carbodiimide compound Volume trade mark) V-02-L2, solid state component amount is 40 weight %]
< S compounds (2) >
The aqueous solution [Nisshinbo Chemical Inc. systems, Carbodilite (notes containing water-soluble carbodiimide compound Volume trade mark) V-10, solid state component amount is 40 weight %]
< D compounds >
Emulsion [the Nisshinbo Chemical Inc. systems, Carbodilite (registrars of water dispersible carbodiimide compound Mark) E-02, solid state component amount is 40 weight %]
< particulates >
[ponding chemical industrial company system, ADVANCELL NS K-001 are put down emulsion containing acrylic particulate (PAN particulates) Equal particle diameter is 150nm, and solid state component amount is 20 weight %].
Embodiment 1~5 and comparative example 1~10
1. the manufacture of easy adhesive composition
In the way of as the solid state component amount (unit is parts by weight) shown in table 1 and 2, each composition shown in mixture table 1 and 2, Manufacture easy adhesive composition.It should be noted that using ion exchange water as the water solvent of easy adhesive composition, with solid-state It is prepared by the mode that component amount turns into 8 weight %.
2. the manufacture of optical film
Using single screw extrusion machine (φ=20.0mm, L/D=25) and clothes hanger type T moulds (wide 150mm), in 280 DEG C, by acrylic acid Based resin composition [Tg:135 DEG C, melt viscosity:700Pa s (temperature be 270 DEG C, shear rate be 100 (1/sec))] Grain melting extrusion, to the chill roll for remain 110 DEG C on discharge molten condition above-mentioned resin combination, is formed thickness be 100 μ M acrylic resin film.Next, using scraping strip coating machine, be coated with a surface of acrylic resin film according to The easy adhesive composition that aforesaid way is obtained, then puts into air drier, is dried 90 seconds in 100 DEG C.Then, using platform Formula stretching-machine, by the film uniaxial tension (stretching ratio:2.5 times), manufacture on the surface of the acrylic resin film of 40 μm of thickness The optical film of the upper adhesive layer with 0.3 μm of thickness.
3. the manufacture of the polarizer
In the adhesive layer side pva coating system adhesive composite of the optical film obtained in the manner described above.In addition, Implement unilateral pva coating system bonding agent of the thickness of saponification process for 40 μm of tri acetyl cellulose membrane (diaphragm) Composition.Next, being coated with layer stackup light via polyethenol series bonding agent respectively in thickness for the both sides of 30 μm of polaroid Film and diaphragm are learned, obtained layered product is put into air drier (70 DEG C), drying in 5 minutes is carried out, the polarizer is manufactured. In addition, the both sides for being similarly formed in polaroid are provided with the benchmark of the evaluation of the diaphragm formed by triacetyl cellulose Inclined device.
For the polarizer obtained in the manner described above, evaluation as follows is carried out.Evaluation result is shown in table 1 and 2.
(1) initial adaptation
The test film of 25mm × 250mm size is cut out from the polarizer obtained in the manner described above, to the optics of test film Bonding processing is implemented on the surface of film, then, is fitted in glass plate, obtains test sample.Then, in the polaroid of sample Otch is cut out between optical film, polaroid and diaphragm is held, according to the floating of Japanese bonding agent industrial standard JAI 13-1996 Roller method (Floating-roller method), determines the stripping adhesive strength under the conditions of 90 degree.It should be noted that for base The quasi- polarizer, also determines stripping adhesive strength under identical condition.It is viscous to peeling off according to measurement result according to following standard Intensity is connect to be evaluated;
○:Compared with the benchmark polarizer, stripping adhesive strength is more preferable or is equal extent,
△:Compared with the benchmark polarizer, stripping adhesive strength is worse,
×:It is not closely sealed, it is impossible to determine;
(2) humidity resistance (60 DEG C, 90%RH)
It is permanent that test sample obtained from operating as described above is put into the constant temperature that temperature is 60 DEG C, humidity is 90%RH In wet machine, implement to place the heat treatment of 250 hours and 500 hours, in addition, grasped in the same manner as the evaluation with initial adaptation Make, determine and peel off adhesive strength.According to following standard, evaluated according to measurement result peeling off adhesive strength;
◎:Compared with the benchmark polarizer, adhesive strength is peeled off more preferably,
○:Stripping adhesive strength with the benchmark polarizer is equal extent,
△:Compared with the benchmark polarizer, stripping adhesive strength is worse,
×:It is not closely sealed, it is impossible to determine;
(3) humidity resistance (80 DEG C, 90%RH)
It is permanent that test sample obtained from operating as described above is put into the constant temperature that temperature is 80 DEG C, humidity is 90%RH In wet machine, implement to place the heat treatment of 100 hours, in addition, operated in the same manner as the evaluation with initial adaptation, determine and peel off Adhesive strength.According to following standard, evaluated according to measurement result peeling off adhesive strength;
◎:Compared with the benchmark polarizer, adhesive strength is peeled off more preferably,
○:Stripping adhesive strength with the benchmark polarizer is equal extent,
△:Compared with the benchmark polarizer, stripping adhesive strength is worse,
×:It is not closely sealed, it is impossible to determine.
[table 1]
[table 2]
As shown in table 1, for using containing the water-dispersible polyurethane resin (U resins) with carboxyl, water-soluble carbon two The implementation that the easy adhesive composition of group with imine moiety (S compounds) and water dispersible carbodiimide compound (D compounds) is made For the optical film of example 1~5, not only show that the reduction of the initial performance under hot and humid (60 DEG C, 90%RH) is suppressed, it is high When being used for a long time under warm high humidity and polaroid excellent adhesion result, and show even in harsh hot and humid Adaptation also excellent result under environment (80 DEG C, 90%RH).On the other hand, as shown in table 2, for without crosslinking agent or only For the optical film of comparative example 1~7 containing S compounds, the knot that the hot and humid lower adaptation with polaroid is reduced is shown Really.In addition, for the optical film of the comparative example 8~10 only containing D compounds, showing that hot and humid lower long-time is used When excellent adhesion, but the result of initial adaptation difference.

Claims (7)

1. easy adhesive composition, it contains:
100 parts by weight have carboxyl water-dispersible polyurethane resin,
1~25 parts by weight water-soluble carbodiimide compound and
1~25 parts by weight water dispersible carbodiimide compound.
2. easy adhesive composition according to claim 1, wherein, foregoing water-soluble carbodiimide compound and foregoing moisture The weight ratio for dissipating property carbodiimide compound is 30:70~95:5 scope.
3. easy adhesive composition according to claim 1 or 2, wherein, relative to the poly- ammonia of the foregoing water dispersible of 100 parts by weight Ester resin, also containing 0.1~15 parts by weight particulate.
4. optical film, it possesses:
Thermoplastic resin film and
It is arranged at least one surface of the thermoplastic resin film and as the easy bonding group any one of claim 1 ~ 3 The adhesive layer of compound formation.
5. optical film according to claim 4, wherein, aforementioned thermoplastic resin film is by (methyl) acrylic resin shape Into.
6. the polarizer, it possesses:
Polaroid and
The optical film described in claim 4 or 5 for being coated to the surface of the polaroid and being protected to it.
7. the manufacture method of optical film, this method includes following process:
The process that easy adhesive composition is coated at least one surface of thermoplastic resin film and film is formed, the easy bonding Composition dilutes through water solvent, and has containing 100 parts by weight water-dispersible polyurethane resin, 1~25 parts by weight of carboxyl Water-soluble carbodiimide compound and 1~25 parts by weight water dispersible carbodiimide compound;And
The process that foregoing dried coating film is formed into adhesive layer.
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