CN103135158A - Method of manufacturing polarizing plate - Google Patents
Method of manufacturing polarizing plate Download PDFInfo
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- CN103135158A CN103135158A CN2012104412497A CN201210441249A CN103135158A CN 103135158 A CN103135158 A CN 103135158A CN 2012104412497 A CN2012104412497 A CN 2012104412497A CN 201210441249 A CN201210441249 A CN 201210441249A CN 103135158 A CN103135158 A CN 103135158A
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- protective film
- polaroid
- adhesive layer
- transparent protective
- polarization plates
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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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/0073—Optical laminates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/28—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
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- Mechanical Engineering (AREA)
- Nonlinear Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Ophthalmology & Optometry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polarising Elements (AREA)
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Abstract
The invention provides a method of manufacturing a polarizing plate. By using the method, even if a polarizer with low moisture content is used, a polarizing plate having good adhesive adhesion of the polarizer and a transparent protective film can be obtained. According to the method, the polarizing plate is manufactured by arranging a transparent protective film on at least one side of the polarizer of the polarizing plate by an adhesive. The method comprises: step (1), in which the back of the transparent protective film is coated by a water adhesive for polarizing plates and dried, and a coating-state adhesive layer, the water contact angle of which can be changed within 30 seconds, is formed on the transparent protective film; step (2), in which a polarizer having a water content of 12-25 weight% is adhered to the transparent protective film by the adhesive layer; and step (3), in which the adhesive layer is dried.
Description
Technical field
The present invention relates to the method for making method of polarization plates.In addition, the invention still further relates to the polarization plates, the blooming that have used this polaroid, and the image display device such as liquid crystal indicator, organic EL display, PDP that has used this polaroid, polarization plates, blooming.
Background technology
For liquid crystal indicator, due to its image forming mode, be absolutely necessary at the both sides of the glass substrate that forms liquid crystal panel surface configuration polaroid.Polaroid usually, after with dichroic material such as iodine, polyvinyl alcohol mesentery being dyeed, uses crosslinking chemical to carry out crosslinked, carries out uniaxial tension and masking, thereby obtains.Therefore above-mentioned polaroid easily shrinks owing to making by stretching.In addition, polyvinyl alcohol mesentery is owing to having used hydrophilic polymer, so especially easily distortion under humidified condition.In addition, a little less than the physical strength due to film self, the problem that therefore exists film to split.Therefore, use polarization plates, polarization plates in the both sides of polaroid or one-sided transparent protective film with triacetyl cellulose etc. fit to have replenished intensity.Above-mentioned polarization plates is fitted and is made by polaroid and transparent protective film being sticked with glue agent.
For example, when polaroid and transparent protective film are fitted to make polarization plates, the water system tackifier (patent documentation 1) that adopts the aqueous solution of using the polyvinyl alcohol resin that contains acetoacetyl and crosslinking chemical to relate to.Humidity resistance, the water tolerance of having put down in writing this water system tackifier are good.In addition, proposed by the viscosity of using tackifier liquid be the tackifier of 3～20mP as (25 ℃) as above-mentioned water system tackifier, obtain the good polarization plates (patent documentation 2) of outward appearance.In patent documentation 1,2, the adhesive solvent of coating polaroid or transparent protective film is not implemented drying, polaroid and transparent protective film are fitted.
In addition; proposed by after making the adhesive solvent drying of coating polaroid or transparent protective film form adhesive layer; make aqueous solution be present in these binding faces, thereby polaroid and transparent protective film are fitted to make the method (patent documentation 3) of polarization plates.Patent documentation 3 has been put down in writing by being pre-formed adhesive layer, compares with patent documentation 1,2, can make the few polarization plates of open defect.In addition, proposed to have coordinated the tackifier of metallic compound colloid can improve the knick point defective (patent documentation 4) of the polarization plates that obtains in containing the polyvinyl alcohol resin of acetoacetyl.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-189615 communique
Patent documentation 2: TOHKEMY 2002-365432 communique
Patent documentation 3: TOHKEMY 2005-128490 communique
Patent documentation 4: TOHKEMY 2009-122664 communique
Summary of the invention
On the other hand, during the manufacturing of polarization plates, as polaroid, the orientation of the low polyvinyl alcohol resin of moisture rate improves, so optical characteristics (degree of polarization etc.) is good.But in patent documentation 3, the degree of drying of preformed adhesive layer is high, and adhesive layer is difficult to water-soluble.Therefore, in the low situation of the moisture rate of polaroid, the aqueous solution that adhesive layer utilization is sometimes added is difficult to dissolve fully, sometimes causes the poor attachment of polaroid and transparent protective film in the polarization plates that obtains.In addition, for the tackifier that has coordinated the metallic compound colloid in containing the polyvinyl alcohol resin of acetoacetyl, also there is the problem of above-mentioned same poor attachment.
The object of the present invention is to provide the manufacture method of polarization plates, wherein, even used in the situation of the low polaroid of moisture rate, also can access the good polarization plates of cementability of polaroid and transparent protective film.
The inventor is in order to solve above-mentioned problem, and further investigation repeatedly found that the manufacture method that adopts polarization plates shown below etc. can realize above-mentioned purpose, has completed the present invention.
That is, the present invention relates to the manufacture method of polarization plates, it is provided with the manufacture method of the polarization plates of transparent protective film for the one side at least at polaroid by adhesive layer, it is characterized in that, comprising:
Operation (1) after the water system tackifier that polarization plates is used is coated above-mentioned transparent protective film, makes its drying, is formed on the adhesive layer that is coated with membrane stage that changed for the contact angle of water with interior generation in 30 seconds on transparent protective film;
Operation (2) is fitted by polaroid and transparent protective film that above-mentioned adhesive layer is 12～25 % by weight with moisture rate; With
Operation (3) makes above-mentioned adhesive layer dry.
In the manufacture method of above-mentioned polarization plates, as above-mentioned water system tackifier, be preferably the polyethenol series tackifier that contains polyvinyl alcohol resin.Above-mentioned polyvinyl alcohol resin preferably has hydrophilic long-chain functional group at side chain.
For the manufacture method of polarization plates of the present invention, in operation (1), with patent documentation 3 similarly, adhesive layer is formed at transparent protective film, but this adhesive layer is not state as high in degree of drying patent documentation 3, but is coated with membrane stage.This semiarid adhesive layer that is coated with membrane stage for example, can be controlled and be coated with membrane stage to satisfy until the time (beginning is by the water-soluble time) that changes for the contact angle of water occurs at the appointed time.By controlling in this wise the membrane stage that is coated with of adhesive layer, can guarantee to a certain extent moisture in the adhesive layer that is formed by the water system tackifier, even in the situation that the moisture rate of polaroid is low also can be well that polaroid and transparent protective film is bonding.
In addition, for the manufacture method of polarization plates of the present invention, the above-mentioned adhesive layer that is coated with membrane stage that forms on transparent protective film, tackifier is formed by the water system tackifier, can be polarized the moisture dissolving in sheet.Therefore, for the manufacture method of polarization plates of the present invention, add aqueous solution unnecessary especially as patent documentation 3.In addition, during the formation of the adhesive layer that is coated with membrane stage of above-mentioned operation (1), in advance the moisture in this adhesive layer is removed.Therefore, polaroid and transparent protective film can be carried out at high speed, drying process (3) can be carried out expeditiously, also favourable aspect throughput rate.
In addition, for the adhesive layer of the high state of in the past degree of drying, usually, as polaroid, it is necessary that moisture rate surpasses 25 % by weight, but for the manufacture method of polarization plates of the present invention, can use moisture rate is the following polaroids of 25 % by weight.Like this, for the manufacture method of polarization plates of the present invention, can use moisture rate is the following polaroids of 25 % by weight, therefore can improve the optical characteristics (degree of polarization etc.) of the polarization plates that obtains.The image display devices such as this polarization plates can realize that inner evenness is excellent, the liquid crystal indicator (LCD) of high degree of resolution and high-contrast, el display device (ELD).
Embodiment
In the present invention, the one side at least that is provided at polaroid is provided with the manufacture method of the polarization plates of transparent protective film by adhesive layer.
There is no particular restriction to polaroid, can use various polaroids.As polaroid, can enumerate such as making polyvinyl alcohol mesentery, part formalizing polyvinyl alcohol mesentery, ethylene vinyl acetate copolymer pastern divide the product of the dichroic material such as the hydrophilic macromolecule film such as saponification film absorption iodine, dichroic dye and uniaxial tension, the polyenoid such as the desalination acid treatment thing of the processed thing of polyvinyl alcohol (PVA), Polyvinylchloride are alignment films etc.In these, the polaroid that is preferably formed by dichroic substance such as polyvinyl alcohol mesentery and iodine.There is no particular restriction to the thickness of these polaroids, usually, is 5～80 μ m left and right.The thickness of polaroid is preferably 15～35 μ m.If the thickness of polaroid is excessively thin, when fitting with transparent protective film, easily sustain damage.On the other hand, if the thickness of polaroid is blocked up, there is the tendency of drying efficiency variation, not preferred aspect throughput rate.
With iodine, polyvinyl alcohol mesentery is dyeed and the polaroid of uniaxial tension, for example, can dye by the aqueous solution that polyvinyl alcohol (PVA) be impregnated in iodine, make by being stretched to 3～7 times of former length.Also can impregnated in as required the aqueous solution of boric acid, potassium iodide etc.And then, washed in polyvinyl alcohol mesentery can being impregnated in water before dyeing as required.By polyvinyl alcohol mesentery is washed, dirt, the antiblocking agent on polyvinyl alcohol mesentery surface can be cleaned, and by making the polyvinyl alcohol mesentery swelling, also have the inhomogeneous effect such as inhomogeneous that prevents from dyeing.Stretching can be carried out after with iodine staining, but also the Edge Coloring limit stretches, and also can use iodine staining after stretching.Also can be in the aqueous solution of boric acid, potassium iodide etc., stretch in water-bath.
In addition, as polaroid, using moisture rate is the polaroid of 12～25 % by weight.In the present invention, under being low moisture rate below 25 % by weight, also can use the moisture rate of polaroid.And then, be also can use below 23 % by weight at the moisture rate of polaroid.Aspect the good polarization plates of acquisition optical characteristics, the moisture rate of preferred polaroid is low.In addition, drying efficiency in drying process (3) improves, and the throughput rate aspect that can improve speed of production is preferred.On the other hand, if the moisture rate of polaroid is too low, improve as the rigidity of the film of polaroid, easily sustain damage, open defect easily occurs.From this aspect, more than the moisture rate of polaroid is preferably 12 % by weight.The moisture rate of such polaroid, the condition that generally can utilize the drying in the manufacturing process of polaroid to process is adjusted, as required the damping treatment process can be set in addition, be implemented in the spraying of dipping in water-bath, water droplet or heat drying again, drying under reduced pressure.
The material of the transparent protective film that arranges as the one or both sides that are formed on above-mentioned polaroid, the material that preferably clear, physical strength, thermal stability, moisture barrier property, isotropy etc. are excellent.Can enumerate styrenic, the polycarbonate based polymers etc. such as the acrylic acid series polymeric compounds such as cellulose-based polymkeric substance, polymethylmethacrylate such as the based polymer such as the polyester such as polyethylene terephthalate, PEN, diacetyl cellulose, triacetyl cellulose, polystyrene, acrylonitrile styrene copolymer (AS resin).in addition, example as the polymkeric substance that forms above-mentioned transparent protective film, also can enumerate tygon, polypropylene, polyolefin with ring system or norborene structure, the polyolefin polymkeric substance that ethylene propylene copolymer is such, vinyl chloride-based polymer, nylon, the acid amides based polymers such as aromatic polyamide, the imide series polymkeric substance, the sulfone based polymer, the polyethersulfone based polymer, the polyetheretherketone based polymer, the polyphenylene sulfide based polymer, vinyl alcohol system polymer, the vinylidene chloride based polymer, the vinyl butyral based polymer, the polyarylate based polymer, the polyoxymethylene based polymer, the epoxy based polymer, or the blend of above-mentioned polymkeric substance etc.In addition; usually stick with glue the agent layer transparent protective film is pasted on polaroid; as transparent protective film, can use heat-curing resin or the ultraviolet curing resins such as (methyl) acrylic acid series, polyurethane series, propenoic methyl carbamate system, epoxy system, silicon-type.Can contain the suitable adjuvant arbitrarily more than a kind in transparent protective film.As adjuvant, can enumerate such as ultraviolet light absorber, antioxidant, lubricant, plastifier, release agent, anti-coloring agent, fire retardant, nucleator, antistatic agent, pigment, colorant etc.The content of the above-mentioned thermoplastic resin in transparent protective film is preferably 50～100 % by weight, 50～99 % by weight more preferably, and more preferably 60～98 % by weight, be particularly preferably 70～97 % by weight.The content of the above-mentioned thermoplastic resin in transparent protective film is in the following situation of 50 % by weight, and the high transparent that might thermoplastic resin originally has etc. can not manifest fully.
As transparent protective film of the present invention, preferably use at least a kind that selects from celluosic resin (polymkeric substance), polycarbonate resin (polymkeric substance), cyclic polyolefin resin (polyolefin with ring system or norborene structure) and (methyl) acrylic resin.Particularly in the situation that used the diaphragm that is formed by triacetyl cellulose, effect of the present invention is remarkable.
The thickness of transparent protective film can suitably determine, generally from aspects such as the workability such as intensity, treatability, thin layers, is about 1～500 μ m.Particularly preferably 1～300 μ m, more preferably 5～200 μ m.
In addition, in the situation that the both sides of polaroid arrange transparent protective film, can use the diaphragm that is formed by identical polymeric material in its table, also can use the transparent protective film that is formed by different polymeric material etc.
To the face bonding with polaroid of transparent protective film, can implement easy bonding processing.As easy bonding processing, can enumerate the chemical treatments such as the dry process such as Cement Composite Treated by Plasma, corona treatment, alkali treatment (saponification processing), form the coating processing of easy adhesive linkage etc.In these, the coating processing, the alkali treatment that form easy adhesive linkage are preferred.For the formation of easy adhesive linkage, can use the various easy adhesivess such as polyol resin, polycarboxylic acid resin, vibrin.In addition, easily the thickness of adhesive linkage, be generally about 0.001～10 μ m, more preferably about 0.001～5 μ m, is particularly preferably about 0.001～1 μ m.
To that polaroid is the not bonding face of above-mentioned transparent protective film, can implement hard conating or antireflection process, take prevent from adhering to, diffusion or anti-dazzle processing as purpose.
In addition, above-mentioned anti-reflection layer, anti-adhesion layer, diffusing layer, antiglare layer etc. except can being arranged at transparent protective film self, can also in addition as optical layers, arrange with respect to transparent protective film independently.
Tackifier as being used to form the adhesive layer of above-mentioned polaroid and transparent protective film applying uses the water system tackifier.
As the water system tackifier, be not particularly limited, but illustration such as vinyl polymerization system, gelatin system, ethene base system latex system, polyurethane series, isocyanate-based, polyester system, epoxy system etc.As above-mentioned water system tackifier, preferred use contains the tackifier of polyvinyl etc., and as polyvinyl, preferably polyethylene alcohol is resin.Especially, use in the situation of polymer film as polaroid of polyethenol series, from the cementability aspect, the preferred tackifier that contains polyvinyl alcohol resin that uses.
For polyvinyl alcohol resin, can enumerate the polyvinyl alcohol (PVA) that polyvinyl acetate (PVA) is carried out saponification and obtain; Its derivant; And then and have multipolymer saponified of the monomer of copolymerizable with vinyl acetate; Polyvinyl alcohol (PVA) is carried out the modified polyvinylalcohol of acetalation, urethane, etherificate, grafting, Phosphation etc.As above-mentioned monomer, can enumerate unsaturated carboxylic acid and the ester classes thereof such as maleic acid (acid anhydride), fumaric acid, crotonic acid, itaconic acid, (methyl) acrylic acid; The alpha-olefin such as ethene, propylene, (methyl) allyl sulphonic acid (sodium), sodium sulfonate (monoalkyl maleate), sodium disulfonate alkyl maleate, N hydroxymethyl acrylamide, acrylamide alkyl sulfonic acid alkali metal salt, NVP, NVP derivant etc.
These polyvinyl alcohol resins can be used alone, and perhaps will also use more than two kinds.
Above-mentioned polyvinyl alcohol resin is not particularly limited, and from the cementability aspect, average degree of polymerization is 100～5000 left and right, is preferably 1000～4000, and average saponification degree is 85～100 % by mole of left and right, is preferably 90～100 % by mole.
Above-mentioned polyvinyl alcohol resin preferably has hydrophilic long-chain functional group at side chain.As the above-mentioned hydrophilic long-chain functional group that has at side chain, can enumerate such as acetoacetyl, carbonyl etc.From improving the aspect of permanance, tackifier more preferably is included in the polyvinyl alcohol resin that side chain has hydrophilic long-chain functional group (for example acetoacetyl).In addition, the polyvinyl alcohol resin that has hydrophilic long-chain functional group at side chain, owing to having water wettability, therefore swellability is excellent, and the absorbability of water is good, due to the existence of water, easy swelling (due to easy dissolving), even therefore in the situation that the moisture rate of polaroid is low, also can have good cementability, therefore preferred.
The polyvinyl alcohol resin that contains acetoacetyl obtains polyvinyl alcohol resin and diketen reaction by adopting known method.For example, can enumerate that polyvinyl alcohol resin is dispersed in the acetic acid equal solvent, add wherein the method for diketen; Polyvinyl alcohol resin is dissolved in dimethyl formamide Huo diox equal solvent in advance, adds wherein the method for diketen etc.In addition, also can enumerate the method that diketen gas or liquid diketen and polyvinyl alcohol (PVA) are directly contacted.
Contain the acetoacetyl modification degree of the polyvinyl alcohol resin of acetoacetyl, as long as be that more than 0.1 % by mole, there is no particular restriction.If less than 0.1 % by mole, the water tolerance of adhesive layer is insufficient, is not suitable for.Acetoacetyl modification degree is preferably 0.1～40 % by mole of left and right, more preferably 1～20 % by mole, is particularly preferably 2～7 % by mole.If acetoacetyl modification degree surpasses 40 % by mole, the raising effect of water tolerance is little.Acetoacetyl modification degree is the value that adopts NMR to measure.
In addition, the adhesive layer that is formed by above-mentioned water system tackifier when the modulation of its aqueous solution, as required, also can coordinate crosslinking chemical, other the catalyzer such as adjuvant, acid.
As crosslinking chemical, can use with no particular limitation the crosslinking chemical for the polyethenol series tackifier.Can use and have at least 2 and have the compound of reactive functional group with above-mentioned polyvinyl alcohol resin.Can enumerate the Alkylenediamine class that such as ethylenediamine, triethylenediamine, hexamethylene diamine etc. has alkylidene and 2 amino; Toluene diisocyanate, HTDI, trimethylolpropane toluene diisocyanate addition product, triphenylmethane triisocyanate, di-2-ethylhexylphosphine oxide (4-phenylmethane triisocyanate), isophorone diisocyanate and the isocyanates such as their ketoxime end-blocking thing or phenol end-blocking thing; Ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerine two or triglycidyl ether, 1, the epoxiess such as 6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, diglycidylaniline, diglycidyl amine; The monobasic aldehydes such as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde; Glyoxal, the twain-aldehyde compound such as MDA, butanedial, glutaraldehyde, maleic dialdehyde, o-phthalaldehyde(OPA); The amino-formaldehyde resins such as condensation product of methylolurea, methylol melamine, alkylation methylolurea, alkylation methylolation melamine, acetylguanamine, benzoguanamine and formaldehyde; The zirconium compoundss such as acetic acid zirconium, zirconium nitrate, zirconium carbonate, zirconium hydroxide, zirconium oxychloride; The glyoxalic acid slaine (as metal, can be enumerated the transition metal such as alkaline-earth metal, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, zinc, the aluminium etc. such as alkaline metal such as lithium, sodium, potassium, magnesium, calcium.), the glyoxalic acid amine salt (as amine, can enumerate such as ammonia, monomethyl amine, dimethylamine, trimethylamine etc.) etc. glyoxylate; Have basic group more than 1 and amino acid or the sulfur-containing amino acid of the acidic-group more than 1; The acetal compounds such as dimethoxy acetaldehyde, diethoxy acetaldehyde, dialkoxy acetaldehyde; And salt and the oxide thereof of the divalent metal such as sodium, potassium, magnesium, calcium, aluminium, iron, nickel or trivalent metal.These can a kind of independent use, perhaps will more than two kinds and use.In these, the preferred basic group that has more than 1 and amino acid or the sulfur-containing amino acid of the acidic-group more than 1 of using.As basic group, preferred amino, as acidic-group, preferred carboxyl or sulfo group.As above-mentioned amino acid, can enumerate such as glycocoll, alanine, phenylalanine, valine, leucine, isoleucine, lysine, proline, serine, threonine, tryptophane, histidine, tyrosine, arginine, asparagine, aspartic acid, aspartame, glutamine, glutamic acid and these amino acid and (methyl) acrylic acid multipolymer etc.As above-mentioned sulfur-containing amino acid, can enumerate such as methionine, halfcystine, cystine and taurine etc.In these, particularly preferably use taurine etc. to have the sulfur-containing amino acid of sulfo group.In addition, as crosslinking chemical, can use the coupling agents such as silane coupling agent, titanium coupling agent.
The use level of above-mentioned crosslinking chemical can with respect to polyvinyl alcohol resin 100 weight portions, be generally about 0.1～50 weight portion according to the suitably designs such as kind of polyvinyl alcohol resin, is preferably about 0.2～30 weight portion, more preferably 0.5～20 weight portion.In this scope, obtain good cementability.
The manufacture method of polarization plates of the present invention comprises: tackifier is coated transparent protective film, form the operation (1) of adhesive layer on transparent protective film; Utilize above-mentioned adhesive layer with the operation (2) of polaroid and transparent protective film applying; With the operation that makes above-mentioned adhesive layer drying (3).Adopt this manufacture method, the one side at least that can access at polaroid is provided with the polarization plates of transparent protective film by adhesive layer.
In above-mentioned operation (1), make its drying after tackifier is coated transparent protective film, form the adhesive layer that is coated with membrane stage on transparent protective film.
The coating of above-mentioned tackifier on transparent protective film, preferably the thickness of the adhesive layer after the drying process (3) carries out as the mode of 10～300nm left and right.The thickness of adhesive layer, from obtaining thickness in uniform face, the viewpoint that obtains sufficient bonding force is set out, and more preferably 10～200nm, be particularly preferably 20～150nm.In the situation of the thickness of adhesive layer less than 10nm, bonding force is not enough, surpasses in the situation of 300nm, and optics reliability and moisture-proof bonding force tend to reduce.
As the method for the thickness of regulating adhesive layer, there is no particular restriction, for example, can enumerate the method for the apparatus for coating of the solid component concentration of regulating adhesive solvent, tackifier.As the assay method of such adhesive layer thickness, there is no particular restriction, the preferred section Observe and measure that adopts SEM (scanning electron microscope), TEM (transmission electron microscope) that uses.
There is no particular restriction in the coating operation of above-mentioned tackifier, can adopt the various means such as gravure roll rubbing method, mouthful mould rubbing method, print roll coating method, spraying rubbing method, dip coated method, but from coating binder equably, preferred gravure roll rubbing method, mouthful mould rubbing method.
In addition, in above-mentioned operation (1), become the semiarid mode that is coated with membrane stage with the adhesive layer that forms and control on transparent protective film.Particularly, form contact angle for water at 30 seconds with the interior formation of pressure-sensitive adhesive layer that is coated with membrane stage that changes.The membrane stage that is coated with of above-mentioned adhesive layer judges as benchmark for the transformation period of the contact angle of water take adhesive layer.That is, the membrane stage that is coated with of above-mentioned adhesive layer can be described as the expression adhesive layer for the index of the swelling time (time that adhesive layer begins to dissolve) of water.Above-mentioned adhesive layer is for the transformation period of the contact angle of water, particularly, be the contact angle (the then angle at initial stage) of the water of adhesive layer after water contact adhesive layer until change time of 10 °.The transformation period of above-mentioned contact angle is below 30 seconds, is preferably below 15 seconds.If the transformation period of above-mentioned contact angle is below 30 seconds, even in the low situation of the moisture rate of polaroid, also can utilize the moisture in polaroid to make the adhesive layer swelling, improve cementability.In addition, the transformation period of above-mentioned contact angle is shorter, means adhesive layer more quickly by water-soluble solution, and is preferred from the viewpoint of high-speed production.
On the other hand, if the transformation period of above-mentioned contact angle surpasses 30 seconds, in the low situation of the moisture rate of polaroid, utilize the moisture of polaroid to make adhesive layer swelling difficulty, produce poor attachment.
The above-mentioned formation that is coated with the adhesive layer of membrane stage, for example, the tackifier of coating transparent protective film is dry to carry out by making.Drying condition is by the decisions such as kind of tackifier, preferred 30～100 ℃ of baking temperature, more preferably 40～90 ℃.In addition, be preferably 1～100 second drying time, more preferably 20～80 seconds.
By above-mentioned operation (1), after having formed the above-mentioned adhesive layer that is coated with membrane stage on transparent protective film, the operation (2) of utilizing above-mentioned adhesive layer that polaroid and transparent protective film are fitted.
Applying method in operation (2) is not particularly limited, for example, can adopts the applying method of utilizing roll-type laminating machine etc.In addition, in the situation that the two sides of polaroid arranges transparent protective film, can adopt simultaneously or any applying method successively.
Next, after bonding process (2), implement drying process (3).By drying process (3), form adhesive layer by the above-mentioned semiarid adhesive layer that is coated with membrane stage, obtain being provided with the polarization plates of transparent protective film by this adhesive layer in the one side at least of polaroid.
The drying condition of above-mentioned drying process (3) is 40～100 ℃ of baking temperatures, 1～10 minute drying time.Baking temperature is preferably 50～90 ℃, more preferably 60～80 ℃.In addition, be preferably 2～9 minutes drying time, more preferably 3～8 minutes.
Adopt polarization plates that manufacture method of the present invention obtains when reality is used, can be as using with the stacked blooming of other optical layers.Be not particularly limited for this optical layers, can use the optical layers of the formation that sometimes is used for liquid crystal indicators such as reflecting plate, half transmitting plate, polarizer (comprising 1/2,1/4 equiwavelength's plate), compensation film for angular field of view etc. more than 1 layer or 2 layers.Especially, preferably on polarization plates of the present invention further stacked reflecting plate or Transflective plate form reflection type polarizer or Semitransmissive polarization plates, on polarization plates further the elliptic polarization plate that forms of laminated phase-difference plate or circularly polarizing plate, the wide viewing angle polarization plates that forms at further stacked compensation film for angular field of view on polarization plates or on polarization plates further stacked brightness improve the polarization plates that film forms.
Polarization plates of the present invention or blooming can be preferably used for the formation of the various devices such as liquid crystal indicator etc.The formation of liquid crystal indicator can be carried out according to prior art.Namely, liquid crystal indicator, usually by liquid crystal cells and polarization plates or blooming and the component parts such as illuminator are as required suitably assembled, assembling driving circuit etc. and forming, in the present invention, except using according to polarization plates of the present invention or this point of blooming, be not particularly limited, can carry out according to prior art.For liquid crystal cells, can use such as the liquid crystal cells of type arbitrarily such as TN type, STN type, π type.
The one or both sides that can be formed on liquid crystal cells have configured the liquid crystal indicator of polarization plates or blooming, backlight or reflecting plate have been used for the suitable liquid crystal indicators such as device of illuminator.In this case, can be arranged at the one or both sides of liquid crystal cells according to polarization plates of the present invention or blooming.In the situation that both sides arrange polarization plates or blooming, they can be identical, also can be different.And then, during the formation of liquid crystal indicator, can configure in suitable position more than 1 layer or 2 layers such as diffusing panel, antiglare layer, antireflection film, fender, prism array, lens arra sheet material, astigmatism plate, the suitable parts such as backlight.
Embodiment
Below use embodiment and comparative example, more specifically the present invention will be described, but the present invention is not limited by these embodiment and comparative example.
(the moisture rate assay method of polaroid)
Cut out the sample of 180mm * 500mm from the light polarizing film that obtains, measure its initial stage weight (W (g)).This sample is placed 2 hours in the dryer of 120 ℃ after, measure dry rear weight (D (g)).By these measured values, obtain moisture rate by following formula.
Moisture rate (%)={ (W-D)/W} * 100
(making of polaroid)
Use polyvinyl alcohol film (Kuraray (strain) system: VF-PS7500 of thick 75 μ m, wide 1000mm), the limit is flooded 60 seconds limits and is stretched to 2.5 times of stretching ratios in the pure water of 30 ℃, (weight ratio: pure water/iodine (I)/potassium iodide (KI)=100/0.01/1), dyeing is 45 seconds at the iodine aqueous solutions of 30 ℃, stretch so that stretching ratio is 5.8 times in 4 % by weight boric acid aqueous solutions, dipping is after 10 seconds in pure water, in the situation of the tension force of maintenance film, drying is 3 minutes under 60 ℃, has obtained polaroid.The thickness of this polaroid is 25 μ m, and moisture rate is 12 % by weight.It is designated as polaroid (1).
In the making of above-mentioned polaroid (1), change beyond drying condition, similarly make the different polaroid of moisture rate (2)-(5) from polaroid (1).Drying condition and moisture rate are as follows.
Polaroid (2): drying condition (40 ℃ lower 30 seconds), moisture rate 20 % by weight.
Polaroid (3): drying condition (40 ℃ lower 20 seconds), moisture rate 25 % by weight.
Polaroid (4): drying condition (40 ℃ lower 60 seconds), moisture rate 10 % by weight.
(modulation of tackifier A)
(Japanese synthetic chemical industry (strain) system: Ecomaty) (large Japanese ink chemical industry (strain) system: Watersol) 35 weight portions are dissolved in pure water 3760 weight portions, modulation tackifier A for 100 weight portions and crosslinking chemical with the PVA resin.
(modulation of tackifier B)
(Japanese synthetic chemical industry (strain) system: go one セ Off ア イ マ one Z: contain acetoacetyl) (large Japanese ink chemical industry (strain) system: Watersol) 35 weight portions are dissolved in pure water 3760 weight portions, modulation tackifier B for 100 weight portions and crosslinking chemical with the PVA resin.
(modulation of tackifier C)
For above-mentioned tackifier B (aqueous solution) 100 weight portions, add alumina gel aqueous solution (mean grain size 15nm, solid component concentration 10 % by weight, positive charge) 18 weight portions, modulation tackifier C.
Embodiment 1
(making of polarization plates)
With slit die, above-mentioned tackifier A is coated triacetyl cellulose (TAC) film (Fuji Photo Film Co., Ltd.'s system: UZ-80T of thick 80 μ m, moisture rate 1.4 % by weight) single face rear flank, under 65 ℃ dry 1 minute, obtained having the TAC film with adhesive layer of the adhesive layer that is coated with membrane stage of thick 0.1 μ m.Next, will fit in the TAC film of adhesive layer the two sides of above-mentioned polaroid with the roller machine.Then, implement the drying process of 5 minutes under 80 ℃, make polarization plates.
Embodiment 2～4 and comparative example 1～5
In embodiment 1, the kind of change tackifier as shown in table 1, the kind of polaroid (moisture rate) adopt method similarly to Example 1 to make polarization plates in addition.
Carried out following evaluation for the polarization plates that obtains in above-described embodiment and comparative example.Evaluation result is shown in table 1.
The contact angle transformation period of＜water 〉
For the semiarid adhesive layer that is coated with membrane stage that forms on transparent protective film, make water contact, through the time ground observe the contact angle of water.Mensuration changes the time of 10 ° to contact angle from the contact angle (initial stage angle) in the moment that the water for above-mentioned adhesive layer contacts.The confirmation of the mensuration of contact angle, the variation of contact angle (mensuration of time) adopts dynamic Contact horn cupping based on sessile drop method (consonance section length of schooling, contact angle meter) to carry out.
＜cementability 〉
Carry out the interface peel of polaroid and transparent protective film from the end of the polarization plates that obtains, the situation of peeling off is designated as " * ", the situation that will not peel off is designated as " zero ".
The mensuration of＜degree of polarization 〉
The degree of polarization of polarization plates uses spectrophotometer with the integrating sphere V7100 of system (the Japanese light splitting Co., Ltd.) to measure the spectral transmission of the wavelength light of 380～780nm.
Need to prove, degree of polarization by with 2 identical polarization plates with the transmissivity of the overlapping situation of the parallel mode of both axis of homology (parallel transmissivity: Tp) with transmissivity (the quadrature transmissivity: Tc) be applied to following formula and obtain of the overlapping situation of both modes of axis of homology quadrature.
Degree of polarization (%)={ (Tp-Tc)/(Tp+Tc) }
1/2* 100
For each transmissivity, these transmissivities are the Y values of having measured, having carried out the correction of visual sense degree according to the 2 degree visuals field (illuminant-C) of JIS Z8701.Degree of polarization when in table, expression monomer transmissivity is 42.8%.
[table 1]
Claims (3)
1. the manufacture method of a polarization plates is that the one side at least at polaroid is provided with the manufacture method of the polarization plates of transparent protective film by adhesive layer, it is characterized in that, comprising:
Operation (1) makes its drying after the water system tackifier used of coating polarization plates on described transparent protective film, is formed on the adhesive layer that is coated with membrane stage that changed with interior contact angle for water in 30 seconds on transparent protective film;
Operation (2) is fitted by polaroid and transparent protective film that described adhesive layer is 12～25 % by weight with moisture rate; And
Operation (3) makes described adhesive layer dry.
2. the manufacture method of polarization plates as claimed in claim 1, is characterized in that, described water system tackifier is the polyethenol series tackifier that contains polyvinyl alcohol resin.
3. the manufacture method of polarization plates as claimed in claim 2, is characterized in that, described polyvinyl alcohol resin has hydrophilic long-chain functional group at side chain.
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| JP2011254046A JP5975625B2 (en) | 2011-11-21 | 2011-11-21 | Manufacturing method of polarizing plate |
| JP2011-254046 | 2011-11-21 |
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| CN106104323A (en) * | 2014-03-05 | 2016-11-09 | 富士胶片株式会社 | Polarizer composition, polaroid protective film, polarizer, polarizer and liquid crystal indicator |
| CN110741291A (en) * | 2017-06-13 | 2020-01-31 | 日东电工株式会社 | Laminate, method for producing laminate, polarizing plate, and method for producing polarizing plate |
| CN115083319A (en) * | 2021-09-10 | 2022-09-20 | 荣耀终端有限公司 | Display assembly, terminal equipment and processing method of display assembly |
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| JP6456710B2 (en) * | 2015-02-16 | 2019-01-23 | 住友化学株式会社 | Manufacturing method of laminated polarizing plate and manufacturing method of polarizing plate |
| KR101960263B1 (en) | 2017-07-07 | 2019-07-15 | 박웅기 | Bollard |
| KR102301282B1 (en) * | 2018-06-19 | 2021-09-13 | 삼성에스디아이 주식회사 | Polarizing plate, adhesive for the same and optical display apparatus comprising the same |
| KR102680758B1 (en) * | 2019-08-23 | 2024-07-02 | 산진 옵토일렉트로닉스 (난징) 컴퍼니 리미티드 | Adhesive composition for polarizing plate, polarizing plate comprising same and image display apparatus comprising same |
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| KR101967931B1 (en) | 2019-04-10 |
| JP5975625B2 (en) | 2016-08-23 |
| JP2013109152A (en) | 2013-06-06 |
| KR20130056172A (en) | 2013-05-29 |
| TW201329540A (en) | 2013-07-16 |
| CN103135158B (en) | 2016-10-26 |
| TWI567430B (en) | 2017-01-21 |
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