CN100588995C - Polarizing disk and producing method thereof - Google Patents
Polarizing disk and producing method thereof Download PDFInfo
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- CN100588995C CN100588995C CN200410081907A CN200410081907A CN100588995C CN 100588995 C CN100588995 C CN 100588995C CN 200410081907 A CN200410081907 A CN 200410081907A CN 200410081907 A CN200410081907 A CN 200410081907A CN 100588995 C CN100588995 C CN 100588995C
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- film
- resin
- polaroid
- polyvinyl alcohol
- bonding agent
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
To enhance adhesion force of both by using a proper adhesive when laminating a protection film consisting of cycloolefin resin on a polyvinyl alcohol polarizing film to make a polarizing plate. The polarizing plate laminates a cycloolefin resin film through an adhesive layer on at least one sided face of the polarizing film consisting of a polyvinyl alcohol resin. The adhesive layer provides the polarizing plate comprising a composition blending an urethane resin, an oxetane compound and an epoxy compound. The urethane resin is preferably a polyester ionomer urethane resin. In addition, a method for manufacturing the polarizing plate is provided by laminating the cycloolefin resin film through a water-based adhesive blending the urethane resin, the oxetane compound and the epoxy compound for the polarizing film consisting of the polyvinyl alcohol resin.
Description
Technical field
The present invention relates to a kind of polaroid and manufacture method thereof that on the polaroid that constitutes by polyvinyl alcohol resin, is bonded with the cyclic olefine resin film.
Background technology
Usually polaroid has following structure; promptly; the one or both sides of the polarization film that constitutes at the polyvinyl alcohol resin by absorption dichromatism pigment and orientation are by getting involved the stacked transparent resin film of bond layer, as being that the protective film of the acetate fiber prime system of representative forms with the triacetyl cellulose.Be situated between as required afterwards and help other optical thin film and described polaroid is attached on the liquid crystal cells, thereby constitute the component parts of liquid crystal indicator with bonding agent.
Along with the expansion of purposes, liquid crystal indicator is used in the various environment, therefore its component parts has been proposed high environment resistant requirement.For example, in the liquid crystal indicator of mobile purposes that with the mobile phone is representative, require it under wet heat condition, also can use, thereby also proposed the requirement of high moisture-proof heat durability being used in wherein polaroid.But after long-time the exposure, its polarization property descended the polaroid of structure easily, and can produce the problem that peel off easily at the interface between polarization film and cellulose acetate film under hygrothermal environment in the past.
For addressing the above problem, as the protective film of polaroid, the someone has proposed to use the method for thermoplasticity cyclic olefine resin.For example: the spy opens in the flat 5-212828 communique (patent documentation 1), and the one side of having put down in writing at the polyethenol series thin slice at least is a resin flake by the stacked thermoplasticity saturated norbornene of acrylic adhesives, adds the method that thermo-compressed becomes polaroid then.In the Te Kaiping 6-51117 communique (patent documentation 2); having put down in writing folded at least one surface layer of polyethenol series polarization film is the protective film that resin constitutes by the thermoplasticity saturated norbornene; thereby make the method for polaroid, enumerated stacked bonding agent, styrene butadiene rubbers class bonding agent, the epoxies biliquid curing type bonding agent etc. used of the dry type that forms behind mixing polyurethane series resin solution and the polyisocyanate resin solution as the bonding agent that is used for wherein.In addition; the spy opens the one side of having put down in writing in the 2000-321430 communique (patent documentation 3) at the polyethenol series polarization film at least; the bond layer of the potpourri by intervening acts polyethenol series bonding agent and dual liquid type bonding agent; come the stacked protective film that constitutes by annular ethylene series resin, thereby make the method for polaroid.Have, the spy opens in the 2000-321432 communique (patent documentation 4) again, and having put down in writing with the polyurethanes bonding agent is that the protective film that constitutes of resin is bonding with the polyethenol series polarization film with by the thermoplasticity saturated norbornene, thereby makes the method for polaroid.
But when using bonding agent (being also referred to as pressure adhesive) such as acrylic compounds, the thickness of itself is 10～50 μ m, therefore must have certain thick.And dry type is stacked with containing organic solvent in bonding agent and styrene butadiene rubbers class bonding agent, the epoxies biliquid curing type bonding agent etc., and therefore the health to environment and operator has harmful effect.And then when the above-mentioned bonding agent that contains organic solvent is applicable in the past without the polaroid manufacturing equipment of organic solvent the time, can bring scrap build problems such as adding of antiknock device.In addition, use bonding agents such as general known polyethenol series and polyurethanes, acrylic compounds, vinyl acetate class, when bonding, under the different combination condition of two kinds of films, cementability also may not be all very abundant with polyethenol series polarization film and cyclic olefine resin film.
On the other hand, somebody's proposed to try method that in the past triacetyl cellulose etc. is used as protective film, and itself and polyethenol series polarization film bonding also proposed various schemes.For example: the spy opens in the flat 8-101307 communique (patent documentation 5), discloses polyethenol series polarization film and support (protective film) the stacked polaroid that forms of bonding agent by being made of the pure and mild aliphatics polyvalent isocyanate of polyester polyols.
Patent documentation 1 spy opens flat 5-212828 communique
Patent documentation 2 spies open flat 6-51117 communique
Patent documentation 3 spies open the 2000-321430 communique
Patent documentation 4 spies open the 2000-321432 communique
Patent documentation 5 spies open flat 8-101307 communique
Summary of the invention
The objective of the invention is, the stacked protective film that is made of the cyclic olefine resin on the polyethenol series polarization film and when making polaroid improves between the two bonding force by using suitable bonding agent.Another object of the present invention is to use the bonding agent that does not contain the water system of organic solvent in fact, the polaroid of manufacturing polyethenol series polarization film and cyclic olefine resin film strong bond.
Present inventors have carried out deep research according to above-mentioned purpose; when found that on the polyethenol series polarization film the stacked protective film that constitutes by the cyclic olefine resin; when having cooperated the potpourri of special component by using as bonding agent; can obtain the good polaroid of cementability of polarization film and protective film, thereby finish the present invention.
Promptly the invention provides a kind of polaroid, it is the polaroid that at least simultaneously forms by intervention bond layer stacked ring ethylene series resin film at the polarization film that is made of polyvinyl alcohol resin, contains oxetane compound in this bond layer at least.
Wherein, to be preferably polyester be ionomer type polyurethane resin to the urethane resin that constitutes bond layer.The cyclic olefine resin film can be configured in the one side of polarization film, also can be configured in the two sides of polarization film.When stacked ring ethylene series resin film at polarization film, the protective film that its another side can be stacked be made of the resin beyond the cyclic olefine resin is as acetate fiber prime system film.
The present invention also provides a kind of manufacture method of polaroid, in this method, on the polarization film that constitutes by polyvinyl alcohol resin, cooperated the water system bonding agent of urethane resin and oxetane compound and epoxy compound by intervention, come stacked ring ethylene series resin film.Wherein the water system bonding agent can use with the form that does not contain organic solvent in fact.
Compare with the situation of using bonding agent in the past, the present invention can produce the polyethenol series polarization film and the good polaroid of cementability of the protective film that is made of the cyclic olefine resin.In addition when making this polaroid; owing to do not need with an organic solvent; thereby have advantage aspect environment and the safety and sanitation, simultaneously can with in the past the identical device fabrication of the polaroid by transparent protective film/polarization film constituted, do not need big equipment investment.
Embodiment
The present invention below is described in detail in detail.Polaroid is the one or both sides at the polarization film that is made of polyvinyl alcohol resin, makes by the stacked transparent protective film of intervention bond layer.The polarization film that is made of polyvinyl alcohol resin specifically is the material that also is orientated at absorption dichromatism pigment on the polyvinyl alcohol resin film of unilateral stretching.Among the present invention, as the protective film of one side at least that is layered in described polarization film, employing be the cyclic olefine resin film, and bond layer can be obtained by the composition that has cooperated urethane resin, oxetane compound and epoxy compound.
The polyvinyl alcohol resin that constitutes polarization film can be by being that resin is implemented saponification and obtained to polyvinyl acetate (PVA).As polyvinyl acetate (PVA) is resin, except the homopolymer of vinyl acetate is the polyvinyl acetate (PVA), also can enumerate the vinyl acetate and the multipolymer etc. of other monomers of copolymerization with it.As can with other vinyl acetate copolymerized monomers, can enumerate unsaturated carboxylic acid class, unsaturated sulfonic acid class, olefines, vinyl ethers, have the acrylic amide of ammonium etc.The saponification degree of polyvinyl alcohol resin is generally 85～100mol%, and is preferred more than 98%.The further modification of this polyvinyl alcohol resin is used aldehydes modified polyethylene alcohol formal polyvinyl acetal etc. but for example also can use.In addition, the degree of polymerization of polyvinyl alcohol resin is generally 1,000～10, and 000, preferred 1,500～5,000.
This polyvinyl alcohol resin is made the starting material film that film behind the film can be used as polarization film.There is not particular determination for the method for polyvinyl alcohol resin being made film, can be with known method system film.Thickness to polyethenol series starting material film does not have particular determination, for example is 10 μ m～150 μ m.
Polarization film is usually through following operation manufacturing: with the operation of above-mentioned polyvinyl alcohol resin film unilateral stretching; With the dichromatism pigment polyvinyl alcohol resin film is dyeed, make it to adsorb the operation of this dichromatism pigment; Handle the operation of the polyvinyl alcohol resin film that has adsorbed the dichromatism pigment with boric acid aqueous solution; And the operation of washing after handling with this boric acid aqueous solution.
Unilateral stretching can be carried out before dyeing, also can carry out simultaneously with dyeing, can also carry out after dyeing.When carrying out unilateral stretching after dyeing, this unilateral stretching can be carried out before boric acid is handled, and also can carry out in boric acid is handled.Certainly, also can in above-mentioned a plurality of steps, carry out unilateral stretching.During unilateral stretching, can between the different roller of peripheral speed, carry out unilateral stretching, also can carry out unilateral stretching with hot-rolling.In addition, can adopt the dry type stretching that stretches in the atmosphere, also can adopt the wet type that after making it swelling, stretches to stretch with solvent.Stretching ratio is generally 3～8 times.
When the polyvinyl alcohol resin film being dyeed, for example in the aqueous solution that contains the dichromatism pigment, get final product polyvinyl alcohol resin is thin film dipped with the dichromatism pigment.As the dichromatism pigment, specifically can use iodine or dichroic dye.In addition, before handling, dyeing preferably in advance the polyvinyl alcohol resin film is carried out dip treating in the water.
When using iodine, adopt the thin film dipped method that in the aqueous solution that contains iodine and potassium iodide, dyes of polyvinyl alcohol resin usually as the dichromatism pigment.The content of iodine is generally in per 100 weight parts waters and contains 0.01～1 weight portion in this aqueous solution, and the content of potassium iodide is generally in per 100 weight parts waters and contains 0.5～20 weight portion.The temperature of the aqueous solution that is used to dye is generally 20～40 ℃, and the time of flooding in this aqueous solution (dyeing time) is generally 20～1,800 seconds.
On the other hand, when using dichroic dye, adopt the thin film dipped method that in containing the aqueous solution of water-soluble dichroic dye, dyes of polyvinyl alcohol resin usually as the dichromatism pigment.The content of dichroic dye is generally in per 100 weight parts waters and contains 1 * 10 in this aqueous solution
-4～10 weight portions, preferred 1 * 10
-3～1 weight portion.Can also contain inorganic salts such as sodium sulphate in this aqueous solution as dyeing assistant.The temperature of the aqueous solution that is used to dye is generally 20～80 ℃, and the time of flooding in this aqueous solution (dyeing time) is generally 10～1,800 seconds.
Handling with the boric acid behind the dichromatism pigment dyeing, is by carrying out in containing the aqueous solution of boric acid the polyvinyl alcohol resin that is colored is thin film dipped.The amount that contains the aqueous solution mesoboric acid of boric acid is generally in per 100 weight parts waters and contains 2～15 weight portions, preferred 5～12 weight portions.When using iodine as the dichromatism pigment, this aqueous solution that contains boric acid preferably contains potassium iodide.Containing in the aqueous solution of boric acid the amount of potassium iodide is generally in per 100 weight parts waters and contains 0.1～15 weight portion, preferred 5～12 weight portions.Dip time in containing the aqueous solution of boric acid is generally 60～1, and 200 seconds, preferred 150～600 seconds, more preferably 200～400 seconds.The temperature that contains the aqueous solution of boric acid is generally more than 50 ℃, and preferred 50～85 ℃, more preferably 60～80 ℃.
Polyvinyl alcohol resin film after boric acid is handled will be handled through washing usually.Washing handle to be by carrying out in water through the polyvinyl alcohol resin that boric acid is handled is thin film dipped.The temperature of water was generally 5～40 ℃ during washing was handled, and dip time is generally 1～120 second.Dried is implemented in the washing back, obtains polarization film.Dried uses air drier or far infrared heater to carry out usually.The temperature of dried is generally 30～100 ℃, preferred 50～80 ℃.The time of dried is generally 60～600 seconds, preferred 120～600 seconds.
After as described above the polyvinyl alcohol resin film being carried out unilateral stretching, dichromatism pigment dyeing and boric acid processing, can obtain polarization film.The thickness of this polarization film is 5～40 μ m.Among the present invention,,, form polaroid by getting involved bond layer stacked ring ethylene series resin film in the one side at least of this polarization film.
The cyclic olefine resin is meant the thermoplastic resin that has by norborene or encircle the unit of the monomer that cyclic olefins (cycloolefin) such as norborneol alkene monomer are constituted more.This cyclic olefine resin can also be cycloolefin and chain alkene or the addition copolymer with aromatics of vinyl except being the hydrogenation thing of the ring-opening polymerization polymer of described cycloolefin or the ring opening copolymer thing that uses cycloolefin more than 2 kinds.In addition, importing has the material of polar group also effective.
When being made into cycloolefin and chain alkene or have the addition copolymer of aromatics of vinyl, ethene or propylene etc. be can enumerate as chain alkene, and styrene, α-Jia Jibenyixi, nuclear alkyl-substituted styrene etc. for example can be enumerated as aromatics with vinyl.In the above-mentioned multipolymer, the unit of the monomer that is made of cycloolefin is below the 50mol%, for example can be 15～50mol%.Particularly when the cyclic olefine resin is the terpolymer of cycloolefin and chain alkene and the aromatics with vinyl, the unit of the monomer that is made of cycloolefin can be above-mentioned fewer amount.In described terpolymer, the unit of the monomer that is made of chain alkene is generally 5～80mol%, and the unit of the monomer that is made of the aromatics with vinyl is generally 5～80mol%.
As the example of commercially available thermoplasticity cyclic olefine resin, can enumerate " Topas ", " ア-ト Application " by JSR (strain) sale that sells by the Ticona company of Germany, " ZEONOR " and " ZEONEX " that Japanese ZEON (strain) sells, " the ア ペ Le " that Mitsui Chemicals (strain) is sold etc.Above-mentioned cyclic olefine resin can be made film and use, can suitably adopt known method such as solvent cast method, extrusion by melting during the system film.As the cyclic olefine resin film of making film commercially available product is arranged also, " the エ ス シ-Na " and " SCA40 " of ponding chemical industry (strain) sale, " the ゼ オ ノ ア film " that (strain) オ プ テ ス sells etc. are for example arranged.
The thickness of protective film is got over Bao Yuehao, but if too thin, intensity can descend, the processability variation; And if too thick, the transparency can descend, can cause the weight of polaroid to become the problem that heavily waits.Therefore, the protective film particularly suitable depth of cyclic olefine resin film is 5～200 μ m, preferred 10～150 μ m, more preferably 20～100 μ m.
By the protective film that this cyclic olefine resin constitutes, can stick on the one side of polarization film, also can stick on the two sides.When the protective film that is made of the cyclic olefine resin was pasted on the two sides of polarization film, 2 protective films can be identical type, also can be variety classeses.When the one side of polarization film is pasted the protective film that is made of the cyclic olefine resin, can paste the protective film that constitutes by the resin beyond the cyclic olefine resin in its opposite one side.As the suitable protective film that constitutes by the resin beyond the cyclic olefine resin, can enumerate the cellulose acetate based resin film of the protective film that in the past was widely used in polaroid.The cellulose acetate based resin film can be triacetylcellulose film or diacetyl cellulose film etc.Tri acetyl cellulose membrane can be sold " Off ジ タ Star Network TD80 ", " Off ジ タ Star Network TD80UF " and " Off ジ タ Star Network TD80UZ " by Fujiphoto (strain) company; " KC8UX2M " and " KC8UY " that sells by コ ニ カ ミ ノ Le タ オ プ ト (strain) company etc.The thickness of acetate fiber prime system protective film is 20～200 μ m.In addition; as other example of the protective film that constitutes by the resin beyond the cyclic olefine resin, the good film of optical transparences such as film that can enumerate the film that constitutes by polyester based resins such as polyethylene terephthalate, PEN, polybutylene terephthalates, constitute by polycarbonate-based resin.
In addition, in described protective film, can also be to implementing surface treatments such as non-glare treated, dura mater processing, electrostatic prevention processing, antireflection processing with the one side opposite with the one side of polarization film stickup.In addition, also can form the coating that constitutes by liquid crystal compounds or high-molecular weight compounds etc.When pasting the protective film that constitutes by the cyclic olefine resin on the two sides of polarization film; the surface of a side film is implemented above-mentioned surface treatment or is formed coating therein; when the one side at polarization film is pasted the protective film that is made of the cyclic olefine resin; and when another side is pasted the protective film that is made of in addition resin, can implement above-mentioned surface treatment or form coating on the surface of either side protective film.
Among the present invention,, by getting involved the stacked aforesaid cyclic olefine resin film of bond layer, thereby make polaroid in the one side at least of the aforesaid polarization film that constitutes by polyvinyl alcohol resin.Also can be at a stacked ring ethylene series resin film of polarization film, the stacked protective film that constitutes by the resin beyond the cyclic olefine resin of another side.Use therein bonding agent is to have cooperated the composition of urethane resin, oxetane compound and epoxy compound especially for the bonding bonding agent with the cyclic olefine resin film.When the stacked protective film that is made of the resin beyond the cyclic olefine resin of the one side of polarization film, this bonding agent is not limited to the material of afore mentioned rules, but considers from the easy construction aspect, generally is advisable with identical bonding agent on the two sides.
As urethane resin, can enumerate the polyethers urethane resin, polyester is urethane resin, acrylic compounds urethane resin etc., wherein preferred polyester is an ionomer type polyurethane resin.Polyester is that ionomer type polyurethane resin is meant to have the urethane resin of polyester construction, and wherein importing has a spot of ionic composition (hydrophilic component).This ionomer type polyurethane resin can be directly under the condition of not using emulsifying agent in water emulsification become emulsion, therefore be suitable as the bonding agent of water system.Polyester is that ionomer type polyurethane resin itself is known, and for example the spy opens in the flat 7-97504 communique, has put down in writing it and has been used as and makes phenol resin be dispersed in the example of the macromolecule dispersing agent in the aqueous medium.Aforesaid polyester system can be with following method manufacturing from poly-type polyurethane resin.
(1) compound (A), polyester polyol (B) and the polyisocyanate (C) that will contain hydrophilic group reacts the urethane resin that the contains hydrophilic group emulsification in water that obtains, and obtains the method for ionomer resin; (2) compound (A), polyester polyol (B) and the polyisocyanate (C) that contain hydrophilic group will be reacted and the polyurethane that contains terminal isocyano that imported hydrophilic group is dispersed in the water, and make it to obtain the method etc. of ionomer resin with the polyamine reaction.
The use therein compound (A) that contains hydrophilic group for example is 2-hydroxyethanesulfonic acid, sulfosuccinic acid, sulfanilic acid, 2,4-diaminotoluene sulfonic acid etc. contains sulfonic compound, 2,2-dihydromethyl propionic acid, dihydroxymaleic acid, 3,4-diamido benzoic acid etc. contain the poly suboxygen ethyl glycol that has 1 active hydrogen in the compound, polymkeric substance of carboxyl at least or polyoxyethylene-polyoxypropylene copolymer glycol etc.
Polyester polyol (B) except the polyester that the dehydration condensation by diol component and sour composition obtains, can also be polyester or its copolyester that the ring-opening polymerization by the cyclic ester compound of 6-caprolactone obtains.The diol component that is used for polyester polyol for example has ethylene glycol, propylene glycol, 1, ammediol, 1, the 4-butylene glycol, 1, the 5-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 1, the 6-hexanediol, neopentyl glycol, diglycol, triethylene glycol, tetraethylene glycol, polyglycol (molecular weight 300～6,000), dipropylene glycol, tripropylene glycol, 2,2-diethyl-1, ammediol, 2-butyl-2-ethyl-1, ammediol, 2-amyl group-2-propyl group-1, ammediol, 2-butyl-2-hexyl-1, ammediol, 2-ethyl-1, the 3-hexanediol, two hydroxyl-oxethyl benzene, 1, the 4-cyclohexanediol, 1,4 cyclohexane dimethanol, bisphenol-A, hydrogenated bisphenol A, p-dihydroxy-benzene and their alkylene oxide addition product etc.For example can enumerate succinic acid as sour composition, hexane diacid, azelaic acid, decanedioic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentane dicarboxylic acid, 1, the 4-cyclohexane dicarboxylic acid, terephthalic acid (TPA), m-phthalic acid, phthalic acid, 1, the 4-naphthalene dicarboxylic acids, 2, the 5-naphthalene dicarboxylic acids, 2, the 6-naphthalene dicarboxylic acids, naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 1, two (phenoxy group) ethane-p of 2-, p '-dicarboxylic acid, and the acid anhydrides of above-mentioned dicarboxylic acid or ester formation property derivant, the p-Para Hydroxy Benzoic Acid, the ester of p-(2-hydroxyl-oxethyl) benzoic acid and these hydroxycarboxylic acids formation property derivant etc.
In addition, polyester is in the ionomer type polyurethane resin, except above-mentioned polyester polyol, in the scope that does not influence effect of the present invention can also and with other high molecular weight polyols composition or the low-molecular-weight compound that contains active hydrogen.As high molecular weight polyols polyether glycol, polycarbonate polyol, polyacetal polyvalent alcohol, polyacrylate polyol, polyesteramide polyvalent alcohol, polythiaether polyvalent alcohol etc. are for example arranged.As the low-molecular-weight compound that contains active hydrogen ethylene glycol, neopentyl glycol, 1, diamine compounds such as polyols such as 6-hexanediol, glycerine, trimethylolpropane, ethylene diamin(e), piperazine etc. are for example arranged.Wherein, and with the low-molecular-weight compound that contains active hydrogen is comparatively ideal form.
Above-mentioned polyisocyanate (C) is the compound that has at least 2 isocyanos in the molecule, be specially 2,4-toluene support diisocyanate, phenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate etc.
The above-mentioned reaction that contains compound (A), polyester polyol (B) and the polyisocyanate (C) of hydrophilic group can be carried out under solvent-free, also can carry out in organic solvent.The resin that obtains can neutralize with amines such as non-volatile alkali such as NaOH or potassium hydroxide, triethylamine or dimethylethanolamine or ammonia, afterwards by just obtaining the aqueous liquid dispersion that polyester is an ionomer type polyurethane resin to wherein adding water.
When being when containing organic solvent in the ionomer type polyurethane resin, preferably after removing this organic solvent, grade re-uses by distilling because of with an organic solvent waiting the polyester that is obtaining in reacting.Because this urethane resin is the ionomer type, thereby can form extremely fine and stable colloid in water, becomes the water system bonding agent that does not contain the machine solvent.
Polyester is that the weight-average molecular weight of ionomer type polyurethane resin is preferably more than 5,000, and preferred weight-average molecular weight is more than 10,000 below 300,000.Its weight-average molecular weight is 5,000 when following, can not obtain the intensity of sufficient adhesive linkage, and be higher than at 300,000 o'clock, and the viscosity when making it become aqueous dispersions is bigger, is not easy operation.
This polyester is can become the water system bonding agent under the state of ionomer type polyurethane resin in being scattered in water.Consider that from being convenient to operating aspect the viscosity of this water system bonding agent is preferably 2, below the 000mPasec, more preferably 1, below the 000mPasec, below the preferred especially 500mPasec.The coating of the low more bonding agent of viscosity is easy more to be carried out, and the outward appearance of the polaroid that obtains is also good more.Polyester is the solid component concentration of ionomer type polyurethane resin in this water system bonding agent, considers from viscosity and bonding strength aspect, is preferably the scope of 10～70 weight %, more than the preferred especially 20 weight % and below the 50 weight %.
At polyester is can also further add surfactants such as polyglycol and polyoxyethylene in the aqueous dispersions of ionomer type polyurethane resin.And then can also add water soluble resins such as poly-hydroxyethyl methacrylate, poly-hydroxyethyl acrylate, polyacrylic acid, polyvinyl alcohol resin.
As being suitable for commercially available polyester of the present invention is ionomer type polyurethane resin, and " the Ha イ De ラ ソ AP-20 " that sold by big Japanese ink chemical industry (strain) company, " Ha イ De ラ ソ APX-101H " etc. are for example arranged.
The bonding agent that uses among the present invention is that except that above-mentioned urethane resin, being preferably polyester is outside the ionomer type polyurethane resin, also contains the water system bonding agent of oxetane compound and epoxy compound.With oxetane compound and epoxy compound, can improve the cementability between polarization film and the cyclic olefine resin film by also.
Oxetane compound be have 4 Yuans cyclic ethers in the molecule, be the compound of oxetanes ring.As its example, can enumerate 3-ethyl-3-methylol oxetanes, 1, two [{ (3-ethyl-3-oxetanyl) methoxyl } methyl] benzene of 4-, 3-ethyl-3-(phenoxymethyl) oxetanes, two [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3-(2-ethyl hexyl oxy methyl) oxetanes, 3-ethyl-3-[(3-triethoxysilicane alkyl propoxyl group) methyl] oxetanes, oxetanyl silsesquioxane, novolaks oxetanes etc.Wherein, oxetanyl silsesquioxane is meant the silane compound with oxetanyl, for example has by making above-mentioned 3-ethyl-3-[(3-triethoxysilicane alkyl propoxyl group) methyl] oxetanes hydrolytic condensation netted polysiloxane compound that obtain, that have a plurality of oxetanyls.In the above-mentioned oxetane compound, 3-ethyl-3-methylol oxetanes that the dispersive property in the preferred water is good.The commercially available product of oxetanes for example has: " OXT-101 " that is sold by synthetic (strain) company in East Asia etc.
Epoxy compound be meant have 3 Yuans cyclic ethers in the molecule, be the compound of epoxide ring.For example can enumerate polyglycol diepoxy propyl ether, polypropylene glycol diepoxy propyl ether, poly-fourth support glycol diepoxy propyl ether, neopentyl glycol diepoxy propyl ether, two glycerine diepoxy propyl ethers, the ethylene glycol bisthioglycolate glycidyl ethers, propylene glycol diepoxy propyl ether, 1,4-butylene glycol diepoxy propyl ether, 1,6-hexanediol diepoxy propyl ether, bisphenol-A diepoxy propyl ether, Bisphenol F diepoxy propyl ether, resorcinol diepoxy propyl ether, glycerine three glycidyl ethers, the trimethylolpropane tris glycidyl ethers, the many glycidyl ethers of D-sorbite, the many glycidyl ethers of sorbitan, the many glycidyl ethers of pentaerythrite, the many glycidyl ethers of polyglycereol, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane etc.Wherein, the preferred good material of the dispersive property in water.The commercially available product of epoxy compound for example has: " CR-5L " that is sold by big Japanese ink chemical industry (strain) company, " the エ Port ラ イ ト 40E " and " エ Port ラ イ ト 80MF " that sold by company of common prosperity society chemistry (strain), by " KBM-303 ", " KBM-403 " of the sale of SHIN-ETSU HANTOTAI's chemical industry (strain) company, " KBE-403 " etc.
The mixing ratio of urethane resin, oxetane compound and epoxy compound, solid constituent 100 weight portions with urethane resin are benchmark, oxetane compound and epoxy compound be the scope of preferred 5～100 weight portions respectively, the further preferred range of oxetane compound and epoxy compound is 5～60 weight portions, the scope of preferred especially 5～30 weight portions.If the ratio of oxetane compound and epoxy compound is too descended, just can not obtain enough bonding strengths, and if this ratio is too big, not only the stability of bonding agent can descend, the viscosity of bonding agent also can become big and be difficult to operation.
As mentioned above, the invention is characterized in, use the water system bonding agent that contains urethane resin, oxetane compound and epoxy compound.Owing to do not need with an organic solvent in fact in this water system bonding agent, thereby do not worry giving environment and operator's health bring infringement, simultaneously by and with oxetane compound and epoxy compound, can obtain high bonding force.
The method of the protective film that constitutes with the bonding polarization film of bonding agent with by the cyclic olefine resin; make both bonding methods to have under the situation of the stacked protective film that constitutes by the resin beyond the cyclic olefine of the one side of polarization film; can adopt known method usually; for example available The tape casting, mayer rod are coated with that (マ イ ヤ-バ-コ-ト) method, engraved roll rubbing method, mould are coated with coating adhesive on the bonding plane of polarization film and/or protective film such as method, dip coating, spray-on process, and both are overlaped.The tape casting be make as the polarization film of applied thing or protective film in an approximate vertical direction, when general horizontal direction or tilted direction between the two move, the method that bonding agent stream is coated with in its surface.Behind the coating adhesive, clamp polarization film and protective film, they are pasted together with niproll etc.
In addition, in order to improve cementability, can also suitably carry out surface treatments such as Cement Composite Treated by Plasma, corona treatment, ultraviolet treatment with irradiation, flame treatment, saponification processing to the gluing of surfaces of polarization film and/or protective film.Handle the method in the aqueous solution that alkali such as being immersed in NaOH or potassium hydroxide is for example arranged as saponification.
With polarization film and protective film stacked after, carry out dried.Dried for example can be undertaken by the mode of blowing hot-air, and the temperature of this moment is 40～100 ℃, preferred 60～100 ℃ scope.Be 20～1200 seconds drying time.After the drying preferably further under the temperature of room temperature or a little higher than room temperature, for example slaking 12～600 hours under 20～50 ℃ of temperature.The thickness of dry back adhesive linkage is generally 0.001～5 μ m, more than the preferred 0.01 μ m, and below the preferred 2 μ m, more preferably below the 1 μ m.If the thickness of adhesive linkage is thicker than 5 μ m, the easy variation of the outward appearance of polaroid then.
In the polaroid of the present invention, can also paste optically functional film by getting involved bonding agent on the surface of protective film.For example there is substrate surface to be coated with liquid crystal compounds and optical compensating film as optically functional film through being orientated, can see through certain polarized light and reflect the reflective polarizing separating film of incompatible polarized light with it, the phase-contrast film that constitutes by polycarbonate-based resin, the phase-contrast film that constitutes by cyclic polyolefin hydrocarbon system resin, the surface has the film that has anti-dazzle function of concaveconvex shape, the film that antireflection is handled has been implemented on the surface, the surface has the reflective film of reflection function, have reflection function concurrently and see through the semi-penetration film etc. of function.Be coated with liquid crystal compounds and have as being equivalent to substrate surface: " the WV film " sold by Fujiphoto (strain) company, " the NH film " and " NR film " (being trade name) sold by Nippon Oil(Nippon Mitsubishi Oil) (strain) company etc. through the commercially available product of optical compensating film of orientation.Reflecting with it as being equivalent to see through certain polarized light, the commercially available product of the reflective polarizing separating film of incompatible polarized light has: sell " DBEF " (trade name) etc. by Minnesota Mining andManufacturing company (3M society) (is Sumitomo 3M (strain) in Japan).In addition, the commercially available product as the phase-contrast film that is equivalent to be made of cyclic polyolefin hydrocarbon system resin has: " ア-ト Application " that is sold by JSR (strain) company, " the エ ス シ-Na " sold by ponding chemical industry (strain) company, " ゼ オ ノ ア film " (being trade name) of being sold by (strain) オ プ テ ス etc.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to embodiment.The % of expression content and use amount and part in the example, short of signalment is all with weight basis.
Embodiment 1
With average degree of polymerization be about 2400, saponification degree is more than the 99.9mol% and the polyvinyl alcohol film of thick 75 μ m, be used for 5 times of formula method unilateral stretchings, and then under the condition that keeps extended state, dipping is 1 minute in 60 ℃ of pure water, afterwards, be in 28 ℃ of dippings 60 seconds in 0.05/5/100 the aqueous solution in the weight ratio of iodine/potassium iodide/water.Be in 72 ℃ of dippings 300 seconds in the aqueous solution of 8.5/8.5/100 in the weight ratio of potassium iodide/boric acid/water afterwards.The pure water of following with 26 ℃ washed 20 seconds, afterwards, 65 ℃ of dryings, had obtained adsorbing in the polyvinyl alcohol (PVA) polarization film of iodine and orientation.
In addition, at polyester is water-based emulsion (" the Ha イ De ラ Application AP-20 " of big Japanese ink chemical industry (strain) system of ionomer type polyurethane resin, solid component concentration 30%, viscosity 30mPasec) in 100 part, oxetane compound " the OXT-101 " (chemical name: 3-ethyl-3-methylol oxetanes) 5 parts, epoxy compound " KBM-303 " (chemical name: the 2-(3 of SHIN-ETSU HANTOTAI's chemical industry (strain) system that adds East Asia synthetic (strain) system, the 4-epoxycyclohexyl) ethyl trimethoxy silane) 5 parts, and make bonding agent with this.To stick on the two sides of the polarization film that obtains previously through the protective film by the thick 40 μ m that norbornene resin constituted (" the ゼ オ ノ ア film " of (strain) オ プ テ ス system) of corona treatment by getting involved described bonding agent; 80 ℃ of dryings 5 minutes, obtain polaroid.Afterwards 40 ℃ of slakings 6 days.On the surface of this polaroid, insert cutter with angle along seeing through direction of principal axis with respect to 45 ° of film normal direction inclinations, carry out the disbonded test of polarization film and this protective film, the result does not peel off fully.
Embodiment 2
The protective film that sticks on the polarization film is made as; one side is " the ゼ オ ノ ア film " by the thick 100 μ m that norbornene resin constituted through corona treatment; another side is the film of handling through surperficial saponification by the thick 80 μ m that triacetyl cellulose constituted (" the Off ジ タ Star Network film " of Fujiphoto (strain) system); 40 ℃ of slakings 8 days; in addition, similarly make polaroid with embodiment 1.The polaroid that obtains is carried out the disbonded test same with embodiment 1, and does not all peel off fully on the two sides.
Embodiment 3
Except another epoxy compound " CR-5L " (multi-functional epoxy's propyl ether) with big Japanese ink chemical industry (strain) system replaces the epoxy compound " KBM-303 " and embodiment 1 similarly makes polaroid.The polaroid that obtains is carried out the disbonded test same with embodiment 1, and the result does not peel off fully.
Comparative example 1
Except in bonding agent, mismatching epoxy compound " KBM-303 " and embodiment 1 similarly make polaroid.The protective film of the polaroid that obtains is stripped from easily.
Comparative example 2
In 100 parts in water, add 3 parts of carboxy-modified polyvinyl alcohol (PVA) (" the Network ラ レ Port バ-Le KL318 " of (strain) Network ラ レ system) and water soluble polyamide epoxy resin (" ス ミ レ-ズ resin 650 " (aqueous solution of solid component concentration 30%) 1.5 parts of Sumitomo Chemical (strain) system, make bonding agent, and 40 ℃ of slakings 4 days, in addition, similarly make polaroid with embodiment 1.The protective film of the polaroid that obtains is stripped from easily.
Claims (7)
1. polaroid, be by getting involved the polaroid that bond layer stacked ring ethylene series resin film forms on the one side at least of the polarization film that constitutes by polyvinyl alcohol resin, it is characterized in that, contain urethane resin, oxetane compound and epoxy compound in the described bond layer.
2. polaroid as claimed in claim 1, wherein, urethane resin is that polyester is an ionomer type polyurethane resin.
3. polaroid as claimed in claim 1 or 2, wherein, the stacked cyclic olefine resin film of stating to some extent is laminated with acetate fiber prime system film on the another side on the one side of polarization film.
4. polaroid as claimed in claim 1 or 2 wherein, is laminated with the cyclic olefine resin film on the two sides of polarization film.
5. the manufacture method of a polaroid is characterized in that, on the polarization film that is made of polyvinyl alcohol resin, is combined with the water system bonding agent of urethane resin and oxetane compound and epoxy compound, stacked ring ethylene series resin film by intervention.
6. method as claimed in claim 5 wherein, does not contain organic solvent in fact in the water system bonding agent.
7. polaroid, be by getting involved the polaroid that bond layer stacked ring ethylene series resin film forms on the one side at least of the polarization film that constitutes by polyvinyl alcohol resin, it is characterized in that, this bond layer is obtained by composition, and described composition is made up of urethane resin, oxetane compound and epoxy compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003424584A JP4432487B2 (en) | 2003-12-22 | 2003-12-22 | Polarizing plate and manufacturing method thereof |
| JP2003424584 | 2003-12-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1637442A CN1637442A (en) | 2005-07-13 |
| CN100588995C true CN100588995C (en) | 2010-02-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200410081907A Expired - Fee Related CN100588995C (en) | 2003-12-22 | 2004-12-16 | Polarizing disk and producing method thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4432487B2 (en) |
| KR (1) | KR20050063688A (en) |
| CN (1) | CN100588995C (en) |
| TW (1) | TW200521503A (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080075857A (en) * | 2005-12-12 | 2008-08-19 | 코니카 미놀타 옵토 인코포레이티드 | Process for producing polarizer, polarizer, and liquid- crystal display |
| JP4802820B2 (en) * | 2006-03-31 | 2011-10-26 | 大日本印刷株式会社 | Polymer laminate, retardation film, and method for producing polymer laminate |
| JP2007279621A (en) * | 2006-04-12 | 2007-10-25 | Sumitomo Chemical Co Ltd | Polarizing plate and manufacturing method for polarizing plate with tacky adhesive agent |
| JP5083810B2 (en) * | 2007-07-23 | 2012-11-28 | 住友化学株式会社 | Polarizing plate and manufacturing method thereof |
| JP2009114279A (en) * | 2007-11-05 | 2009-05-28 | Omron Corp | Adhesive for bonding metal and molding material, composite material containing the same, and usage of composite material |
| US20110300387A1 (en) | 2009-02-20 | 2011-12-08 | Seong-Jun Park | Modified polyvinyl alcohol resins and adhesive, polarizer, and display device containing the same |
| JP2010250104A (en) * | 2009-04-16 | 2010-11-04 | Dainippon Printing Co Ltd | Optical functional film, method for manufacturing optical functional film, and polarizing plate |
| KR101219096B1 (en) | 2009-07-03 | 2013-01-11 | 주식회사 엘지화학 | Adhesive composition for polarizer and polarizer prepared by using the same |
| JP4877429B2 (en) * | 2009-08-21 | 2012-02-15 | Ｄｉｃ株式会社 | Cationic polymerizable adhesive and polarizing plate obtained using the same |
| KR101564658B1 (en) * | 2010-08-04 | 2015-10-30 | 코오롱인더스트리 주식회사 | Optical film |
| US9977163B2 (en) | 2013-04-11 | 2018-05-22 | Sumitomo Chemical Company, Limited | Orientation layer for optically anisotropic film |
| KR102329698B1 (en) | 2013-08-09 | 2021-11-23 | 스미또모 가가꾸 가부시키가이샤 | Process for producing long circularly polarizing plate and long circularly polarizing plate |
| US9625629B2 (en) | 2013-12-05 | 2017-04-18 | Sumitomo Chemical Company, Limited | Process for producing optically anisotropic film |
| US9606279B2 (en) | 2013-12-05 | 2017-03-28 | Sumitomo Chemical Company, Limited | Process for producing optically anisotropic film |
| JP2015138162A (en) | 2014-01-23 | 2015-07-30 | 住友化学株式会社 | Optical anisotropic film |
| WO2018021013A1 (en) * | 2016-07-28 | 2018-02-01 | 住友化学株式会社 | Polarizing plate |
| WO2018173637A1 (en) * | 2017-03-22 | 2018-09-27 | 株式会社Adeka | Aqueous polyurethane resin composition |
| KR20210066022A (en) * | 2017-03-23 | 2021-06-04 | 닛토덴코 가부시키가이샤 | Optical laminate |
-
2003
- 2003-12-22 JP JP2003424584A patent/JP4432487B2/en not_active Expired - Fee Related
-
2004
- 2004-11-30 TW TW093136820A patent/TW200521503A/en unknown
- 2004-12-16 CN CN200410081907A patent/CN100588995C/en not_active Expired - Fee Related
- 2004-12-17 KR KR1020040107518A patent/KR20050063688A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CN1637442A (en) | 2005-07-13 |
| TW200521503A (en) | 2005-07-01 |
| KR20050063688A (en) | 2005-06-28 |
| JP4432487B2 (en) | 2010-03-17 |
| JP2005181817A (en) | 2005-07-07 |
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