CN103339538B - Highly adhesive polyester film for protection of polarizers - Google Patents

Highly adhesive polyester film for protection of polarizers Download PDF

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Publication number
CN103339538B
CN103339538B CN201280007582.5A CN201280007582A CN103339538B CN 103339538 B CN103339538 B CN 103339538B CN 201280007582 A CN201280007582 A CN 201280007582A CN 103339538 B CN103339538 B CN 103339538B
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China
Prior art keywords
polyvinyl alcohol
mylar
quality
polaroid
resin
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CN201280007582.5A
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CN103339538A (en
Inventor
中谷充晴
熊谷荣二
东浦真哉
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Toyobo Co Ltd
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Toyobo Co Ltd
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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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2429/00—Presence of polyvinyl alcohol
    • 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
    • C09J2467/00—Presence of polyester
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • 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
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/50—Protective arrangements
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

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

Abstract

Provided is a highly adhesive polyester film for protecting polarizers, which has excellent adhesion to polarizers. A highly adhesive polyester film for protecting polarizers, which has a highly adhesive layer on at least one surface thereof, wherein the highly adhesive layer comprises a polyester resin (A), a polyvinyl alcohol resin (B) and a cross-linking agent (C), the polyester resin (A) has an acid value of 20 KOHmg/g or less, and the polyvinyl alcohol resin (B) has a degree of saponification of 60-85 mol%.

Description

Easy-adhesion mylar is used in polaroid protection
Technical field
The present invention relates to the polaroid protection easy-adhesion mylar for the protection of polaroid.Specifically, the polaroid protection easy-adhesion mylar excellent in adhesion with polaroid is related to.
Background technology
In liquid crystal display device, configure Polarizer due to its image forming mode in the both sides of the glass substrate forming liquid crystal panel surface.Polarizer has following structure usually: be fitted with polaroid protective film on the two sides of the polaroid formed by dichroic material such as polyvinyl alcohol film and iodine by hydrophilic adhesive such as polyvinyl alcohol resins.As the diaphragm for the protection of polaroid, from the aspect of optical characteristics, the transparency, use cellulose triacetate film so far always.
But the permanance of Triafol T is insufficient, when using the Polarizer using cellulose triacetate film as polaroid protective film under high temperature or high humidity, the performance of the Polarizer such as degree of polarization, tone reduces sometimes.In addition, require Polarizer filming to tackle the slimming of display in recent years, but from keeping the angle of moisture isolation characteristic, there is boundary in the filming of cellulose triacetate film.Therefore, as the polaroid protective film with permanance and moisture barrier, propose and use mylar (see patent documentation 1 ~ 5).
Surface as the cellulose triacetate film of polaroid protective film implements alkali treatment etc., has the compatibility high with hydrophilic adhesive.Therefore, the diaphragm formed by cellulose triacetate film has high cementability with the polaroid being coated with hydrophilic adhesive.But the cementability of mylar and hydrophilic adhesive is insufficient, particularly for had the mylar of orientation by stretch processing for, this tendency is more remarkable.Therefore, in patent documentation 1 ~ 3 and 5 in order to improve with polaroid or coat polaroid hydrophilic adhesive cementability and propose easy adhesive linkage be set on mylar.
prior art document
patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 8-271733 publication
Patent documentation 2: Japanese Unexamined Patent Publication 8-271734 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2009-157361 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2010-277028 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2011-8170 publication
Summary of the invention
the problem that invention will solve
The compatibility of mylar and water is low, has aromatic dicarboxylic acid remarkable especially as this tendency of the mylar of dicarboxylic acid component.In addition, the compatibility by stretching with the mylar of crystal orientation and water is lower.And polaroid, being coated on polaroid bonding agent, polyvinyl alcohol resin is principal ingredient, has high water wettability.Due to the difference of this character, the compatibility of mylar and polaroid, this bonding agent is low, is difficult to both bonding securely.Therefore, even have the mylar of easy adhesive linkage disclosed in patent documentation 1 ~ 3 and 5, compared with cellulose triacetate film, sufficient cementability is not obtained yet.Therefore; when Long-Time Service is using the existing mylar Polarizer that is diaphragm as display member; sometimes can float between diaphragm/polaroid, peel off, cause polarized light property to reduce by the change of the amount of moisture in polaroid, occur the visual variation such as blank.
Under this present situation, the object of problem of the present invention is to provide a kind of mylar, and it has the polyvinyl alcohol resin layer that makes mylar and polaroid or be coated on bonding agent on polaroid etc. means bonding securely.
for the scheme of dealing with problems
The present inventor etc. conduct in-depth research to solve the problem and inquire into and visualize the layer arranging between mylar and polyvinyl alcohol resin layer and contain the polyester resin high with the compatibility of mylar, the polyvinyl alcohol resin high with the compatibility of polyvinyl alcohol resin layer and crosslinking chemical.But the present inventor etc. find only to combine merely that these compositions cannot give full play to that each composition brings makes mylar and the closely sealed function of polyvinyl alcohol resin layer.Therefore, the present inventor etc. day and night study, found that, in above-mentioned design, by adopting the vibrin with certain acid number as vibrin, and then, adopt the polyvinyl alcohol resin with certain saponification degree as polyvinyl alcohol resin, effectively can play the bonding effect of the respective resin bed high with compatibility that each composition brings.
The present inventor etc. have carried out further deep research based on above-mentioned cognition, found that, by adopting the crosslinking chemical high with the reactivity of hydroxyl, and can the polyvinyl alcohol resin layer of further bonding mylar and polaroid, bonding agent etc. securely.The present inventor etc. have carried out further discussion and improvement based on these understanding, thus complete the present invention.
Typical example of the present invention is below shown.
1st technical scheme is a kind of polaroid protection easy-adhesion mylar; it is at least having the mylar of easy adhesive linkage at one side; described easy adhesive linkage contains polyester resin (A), polyvinyl alcohol resin (B) and crosslinking chemical (C); the acid number of described polyester resin (A) is below 20KOHmg/g, and the saponification degree of described polyvinyl alcohol resin (B) is 60 ~ 85 % by mole.
2nd technical scheme is aforementioned polaroid protection easy-adhesion mylar, and wherein, previous polyesters resin (A) is containing the 5-sulfoisophthalic acid composition of 1 ~ 15 % by mole accounting for dicarboxylic acid component.
3rd technical scheme is aforementioned polaroid protection easy-adhesion mylar, and wherein, aforementioned crosslinking agent (C) is isocyanate compound or melamine compound.
4th technical scheme is aforementioned polaroid protection easy-adhesion mylar, and wherein, in aforementioned easy adhesive linkage, the mass ratio of polyester resin (A), polyvinyl alcohol resin (B) and crosslinking chemical (C) meets following formula:
0.8≤（A）/（B）≤5
2≤（（A）+（B））/（C）≤50。
5th technical scheme is a kind of Polarizer, and it has polaroid protective film on the two sides of polaroid, and at least the polaroid protective film in the face of side is aforementioned polaroid protection easy-adhesion mylar.
the effect of invention
Polaroid protection easy-adhesion mylar of the present invention and polaroid or be coated with the excellent in adhesion of the polyvinyl alcohol resin layer representated by bonding agent thereon.Therefore, mylar of the present invention can be used as the diaphragm of polaroid aptly.By using this mylar of the present invention as the diaphragm of polaroid, the Polarizer that permanance and water preventing ability are better than in the past much less expensively can be manufactured.In addition, the excellent in te pins of durability of Polarizer of the present invention, therefore can further filming compared with the past.Therefore, by utilizing Polarizer of the present invention, the further slimming of liquid crystal display can be made.
Embodiment
(mylar)
The mylar used as base material is in the present invention the film formed primarily of vibrin.Here, " film primarily of vibrin is formed " refers to the film formed by the resin combination of the vibrin containing more than 50 quality %, during with other polymer blendings, mean the vibrin containing more than 50 quality %, during with other monomer copolymerizations, mean the polyester structural units containing more than 50 % by mole.Preferred polyester film contains the vibrin of more than 90 quality %, is more preferably more than 95 quality %, more preferably 100 quality %.
As vibrin, material is not particularly limited, the multipolymer that dicarboxylic acid component and glycol component polycondensation can be used to be formed or its blending resin.As dicarboxylic acid component, include, for example out: terephthalic acid (TPA), m-phthalic acid, phthalic acid, 2, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, biphenyl carboxylic acid, diphenoxyethanedicarboxylic acid, diphenylsulphone carboxylic acid, anthracene dicarboxylic acid, 1, 3-cyclopentane diacid, 1, 3-cyclohexane diacid, 1, 4-cyclohexane diacid, six hydrogen terephthalic acid (TPA)s, six hydrogen m-phthalic acids, malonic acid, dimethyl malonic acid, succinic acid, 3, 3-diethyl succinic acid, glutaric acid, 2, 2-dimethylated pentanedioic acid, hexane diacid, 2-methyl hexane diacid, trimethyladipic acid, heptandioic acid, azelaic acid, dimer acid, decanedioic acid, suberic acid, dodecanedioic acid etc.
As the glycol component forming vibrin, include, for example out: ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, 1,2-CHDM, 1,4-CHDM, 1,10-decanediol, 1, ammediol, BDO, 1,5-PD, 1,6-hexanediol, 2,2-two (4-hydroxy phenyl) propane, two (4-hydroxy phenyl) sulfones etc.
The dicarboxylic acid component and the glycol component that form vibrin can use one kind or two or more respectively.In addition, other hydroxyl moieties such as other sour composition, trimethylolpropanes such as trimellitic acid can suitably be added.
As vibrin, specifically can list: polyethylene terephthalate, PTT, polybutylene terephthalate, PEN etc., in the middle of these for the balance of physical property and cost preferred polyethylene terephthalate.In addition, in order to control, the optical characteristics such as polarity contain other copolymer compositions, other polymkeric substance are also preferred modes.From the angle of optical characteristics controlling mylar, as preferred copolymer composition, can list: diethylene glycol, at side chain, there is being copolymerized into of norborene and grade.
Mylar of the present invention is used as protective film for polarizing plate, therefore preferably has the high transparency.The transparency of polaroid protection mylar of the present invention preferably its total light transmittance is more than 85%, is more preferably more than 87%, more preferably more than 88%, and be further preferably more than 89%, be particularly preferably more than 90%.In addition, mist degree is preferably less than 3%, is more preferably less than 2.5%, and more preferably less than 2%, be particularly preferably less than 1.5%.The total light transmittance of mylar such as can measure according to the method recorded in embodiment described later.
Sometimes in order to improve the sliding of mylar, the treatability such as windability and make containing inert particle in film, but in order to keep the high transparency, the content of the inert particle in preferred film is as far as possible few.Therefore, preferably make the multilayer only containing particle on the top layer of film and form, or, make the easy adhesive linkage only not making to be layered in fact at least one side of mylar in film containing particle contain particulate.
In addition, " in fact not containing particle " refers to, such as inorganic particle, being below 50ppm, being preferably below 10ppm, most preferably being the content of below detection limit when carrying out quantitative test with x-ray fluorescence analysis to the element deriving from particle.Even if this is because, initiatively do not add in base film by particle, sometimes deriving from the dirt that the production line in the manufacturing process of the pollutant component of alien material, material resin or film, device adhere to can peel off and be mixed in film.
In addition, when base film being made multilayer formation, internal layer in fact contains inert particle, only makes two kinds of three layers of formations that outermost layer contains inert particle can take into account the transparency and processability, is preferred.
Be not particularly limited the thickness of film in the present invention, when reducing the thickness of Polarizer in order to the slimming of display, the thickness of film is preferably less than 200 μm, more preferably less than 100 μm.And for the physical strength kept as diaphragm, the thickness of film is preferably more than 10 μm, is more preferably more than 12 μm, more preferably more than 20 μm.
Mylar as base material can be individual layer, also can be laminated by layer of more than two kinds.In addition, as long as in the scope playing effect of the present invention, can make in film containing various adjuvant as required.As adjuvant, include, for example out: antioxidant, photostabilizer, antigelling agent, organic wetting agent, antistatic agent, ultraviolet light absorber, surfactant etc.When film has stacked formation, it is also preferred for containing adjuvant according to the function of each layer as required.Such as, adding ultraviolet light absorber etc. in order to prevent the light of polaroid deteriorated at internal layer is also preferred mode.
Mylar is by such as melt extruding into film-form, making its cooling curing carry out film forming method etc. and obtain with curtain coating drum by above-mentioned vibrin.As mylar of the present invention, any one in tensionless winkler foundation film, oriented film can be used, from the viewpoint of the preferred oriented film of the permanance such as physical strength, chemical proofing.When mylar is oriented film, its drawing process is not particularly limited, longitudinal uniaxial stretching method, horizontal uniaxial stretching method, in length and breadth progressively biaxial stretching process, in length and breadth simultaneously biaxial stretching process etc. can be adopted.
(easy adhesive linkage)
Mylar of the present invention in order to improve with polaroid and be arranged on its one or two sides water system bonding agent etc. polyvinyl alcohol resin layer cementability and its at least one side be laminated with easy adhesive linkage, described easy adhesive linkage by be the polyester resin (A) of below 20KOHmg/g containing acid number, saponification degree is that the polyvinyl alcohol resin (B) of 60 ~ 85 % by mole and the resin combination of crosslinking chemical (C) are formed.Easy adhesive linkage can be arranged on the two sides of mylar, also only can arrange at the one side of mylar, arrange resin-coated layer not of the same race at another side.
Although not by theoretical restriction, can think, by combination acid number be the specific polyester resin (A) of below 20KOHmg/g, saponification degree is specific polyvinyl alcohol resin (B) and the crosslinking chemical (C) of 60 ~ 85 % by mole, polyester resin and polyvinyl alcohol resin form independently domain unit respectively in easy adhesive linkage, form the phase separation structure being usually also known as island structure.Can think, by forming the isolating construction of this domain unit, that what the domain be made up of polyester resin brought bring with the cementability of mylar and the domain that is made up of polyvinyl alcohol resin to take into account with these two Function fitness of cementability that are polyvinyl alcohol resin layer and can not be mutually impaired.Can think, crosslinking chemical (C) is by making polyvinyl alcohol resin (B) be cross-linked and condensing and promote the formation of this domain constructs and maintain.
Each composition of following commute adhesive linkage is described in detail.
(polyester resin (A))
The polyester resin (A) used in easy adhesive linkage of the present invention is the multipolymer of dicarboxylic acid component and glycol component polycondensation, as dicarboxylic acid component and glycol component, can be used as the material of the mylar of aforementioned substrates.From improving the angle with the cementability of mylar base material, preferably use and the dicarboxylic acid component of dicarboxylic acid component as polyester resin (A) as the dicarboxylic acid component in the mylar of base material with same or similar structural property.Therefore, such as, when adopting the dicarboxylic acid component of aromatic dicarboxylic acid as mylar, preferably use aromatic dicarboxylic acid as the dicarboxylic acid component of polyester resin (A).As this aromatic dicarboxylic acid composition, most preferably terephthalic acid (TPA) and m-phthalic acid.Other aromatic dicarboxylic acids can be added relative to whole dicarboxylic acid component with the scope of less than 10 % by mole and make its copolymerization.
In addition, as the glycol component of polyester resin (A), preferably using the glycol of ethylene glycol and side chain as constituent.Can think, the stress relaxation at easy adhesive linkage place can be contributed to by having branched structure, playing adaptation aptly.For the glycol component of aforementioned side chain, include, for example out: 2, 2-dimethyl-1, ammediol, 2-methyl-2-ethyl-1, ammediol, 2-methyl-2-butyl-1, ammediol, 2-methyl-2-propyl-1, ammediol, 2-methyl-2-isopropyl-1, ammediol, 2-methyl-2-n-hexyl-1, ammediol, 2, 2-diethyl-1, ammediol, 2-ethyl-2-normal-butyl-1, ammediol, 2-ethyl-2-n-hexyl-1, ammediol, 2, 2-di-n-butyl-1, ammediol, 2-normal-butyl-2-propyl group-1, ammediol, and 2, 2-di-n-hexyl-1, ammediol etc.
For the mol ratio of the glycol component of aforementioned side chain, relative to whole glycol component, lower limit is preferably 10 % by mole, is particularly preferably 20 % by mole.And the upper limit is preferably 80 % by mole, more preferably 70 % by mole, be particularly preferably 60 % by mole.In addition, can as required and also with diethylene glycol, propylene glycol, butylene glycol, hexanediol or 1,4-CHDM etc.
From the viewpoint of the compatibility with polyvinyl alcohol resin (B), the polyester resin (A) used in the present invention preferably uses water-soluble or water-dispersed resin.In order to water-solubleization or the moisture dispersion of polyester resin, preferred copolymerization contains the compound of the hydrophilic radical such as sulphonate-base, carboxylate group.Wherein, from keeping lower control of acid number of polyester resin (A) to give hydrophilic angle with the reactive of crosslinking chemical simultaneously, the dicarboxylic acid component with sulphonate-base is suitably.As the dicarboxylic acid component with sulphonate-base, include, for example out: sulfoterephthalic, 5-sulfoisophthalic acid, 4-sulfo group naphthalene m-phthalic acid-2,7-dicarboxylic acid and 5-(4-sulfophenoxy) m-phthalic acid or its alkali metal salt, wherein especially preferred 5-sulfoisophthalic acid.The dicarboxylic acid component with sulphonate-base preferably accounts for 1 ~ 15 % by mole of the dicarboxylic acid component of vibrin (A), is more preferably 1.5 ~ 12 % by mole, more preferably 2 ~ 10 % by mole.The dicarboxylic acid component with sulphonate-base for more than above-mentioned lower limit time, be suitable for water-solubleization of polyester resin or moisture dispersion.In addition, the dicarboxylic acid component with sulphonate-base for below the above-mentioned upper limit time, be suitable for the cementability with mylar base material.
The carboxylic acid group preferably as the reactive group with crosslinking chemical (C) is less for polyester resin (A).Can think, owing to making to reduce with the reactivity of crosslinking chemical with reactive carboxyl of crosslinking chemical by reducing to have, as a result, not mix completely with polyvinyl alcohol resin, the domain constructs formed by crosslinked polyvinyl alcohol resin can be maintained.From this angle, the acid number of polyester resin (A) is below 20KOHmg/g, is preferably below 15KOHmg/g, is more preferably below 10KOHmg/g, more preferably below 8KOHmg/g, is further preferably below 5KOHmg/g.The acid number of polyester resin (A) can be obtained theoretically according to the result of the constituent analysis based on titrimetry described later or NMR etc.
The acid number of polyester resin (A) is wanted to control in above-mentioned scope, preferred minimizing is used for the introduction volume of the carboxylate group of water-solubleization or moisture dispersion, or the hydrophilic radical beyond employing carboxylate group, or the carboxylic acid terminal's concentration reducing polyester resin.As the method for carboxylic acid terminal's concentration of reduction polyester resin, preferably adopt the polyester resin having carried out end modified to carboxylic acid terminal's base, or adopt the polyester resin that the number-average molecular weight of polyester resin is large.Therefore, the number-average molecular weight of polyester resin (A) is preferably more than 5000, is more preferably more than 6000, and more preferably more than 10000.In addition, preferably reduce as polyester resin (A) constituent, the content of the sour composition with more than 3 carboxyls.
The glass transition temperature of polyester resin (A) is not particularly limited, is preferably 20 ~ 90 DEG C, is more preferably 30 ~ 80 DEG C.When glass transition temperature is more than above-mentioned lower limit, being suitable for resistance to adhesive, when glass transition temperature is below the above-mentioned upper limit, is suitable for the cementability with mylar base material.
The content of the polyester resin (A) in easy adhesive linkage is preferably more than 40 quality % and below 90 quality %, is more preferably more than 45 quality % and below 85% quality %, more preferably more than 50 quality % and below 80 quality %.When the content of polyester resin (A) is more than above-mentioned lower limit, be suitable for the cementability with mylar base material, for below the above-mentioned upper limit time, the cementability for the polyvinyl alcohol resin with polaroid, hydrophilic adhesive etc. is suitable.
(polyvinyl alcohol resin (B))
Polyvinyl alcohol resin is not particularly limited, include, for example out: the polyvinyl alcohol (PVA) that polyvinyl acetate (PVA) saponification is obtained; Its derivant; With same vinyl acetate, there is the saponified of the multipolymer of the monomer of copolymerizable further; Polyvinyl alcohol (PVA) is carried out to the modified polyvinylalcohol of acetalation, urethane, etherificate, grafting, Phosphation etc.; Deng.As aforementioned monomer, can list: 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 malate), sodium disulfonate alkyl malate, N hydroxymethyl acrylamide, acrylamide alkyl sulfonic acid alkali salt, NVP, NVP derivant etc.These polyvinyl alcohol resins only can use a kind, and also two or more kinds may be used.
As the polyvinyl alcohol resin used in the present invention (B), can exemplify: vinyl alcohol-vinyl acetate multipolymer, polyvinyl alcohol-co-vinyl butyral multipolymer, ethylene-vinyl alcohol copolymer, optimal ethylene alcohol-vinyl acetate co-polymer, ethylene-vinyl alcohol copolymer in the middle of these.The degree of polymerization of polyvinyl alcohol resin (B) is not particularly limited, from the viewpoint of coating fluid viscosity, preferred degree of polymerization is less than 3000.
The copolymerization ratio of vinyl alcohol represents with saponification degree.The saponification degree of polyvinyl alcohol resin of the present invention (B) is preferably more than 60 % by mole and less than 85 % by mole, be more preferably more than 65 % by mole and less than 83 % by mole, more preferably more than 68 % by mole and less than 80 % by mole, further be preferably more than 70 % by mole and be less than 80 % by mole, more preferably more than 71 % by mole and less than 78 % by mole again, are particularly preferably more than 73 % by mole and less than 75 % by mole.When the saponification degree of polyvinyl alcohol resin (B) is more than above-mentioned lower limit, more appropriately can form cross-linked structure with crosslinking chemical (C).In addition, when the saponification degree of polyvinyl alcohol resin (B) is below the above-mentioned upper limit (or being less than it), the compatibility with polyester resin (A) can more appropriately be played.The saponification degree of vinyl alcohol resin can by the quantity of alkali consumption needed for the hydrolysis of the copolymerization units such as vinyl acetate, obtain based on the composition analysis of NMR.
As the content of polyvinyl alcohol resin (B), in easy adhesive linkage, be preferably more than 10 quality % and below 60 quality %, be more preferably more than 15 quality % and below 55% quality %, more preferably more than 20 quality % and below 50 quality %.When the content of polyvinyl alcohol resin (B) is more than above-mentioned lower limit, the cementability for the polyvinyl alcohol resin layer with polaroid, bonding agent etc. is suitable, for below the above-mentioned upper limit time, be suitable for the cementability with mylar base material.
(crosslinking chemical (C))
As crosslinking chemical (C), be not particularly limited as long as there is bridging property with hydroxyl, can list: the compound of melamine class, isocyanates, carbodiimide Lei, oxazoline class, epoxies etc.From the viewpoint of the ageing stability of coating fluid, the compound of preferred melamine class, isocyanates, carbodiimide Lei, oxazoline class.And then crosslinking chemical preferably carries out melamine compounds or the isocyanate ester compound of cross-linking reaction aptly with the hydroxyl of polyvinyl alcohol resin (B).Can think, this is because, carbodiimide class crosslinking chemical and carboxyl reaction, and melamine compounds or isocyanate ester compound and hydroxyl reaction, thus more appropriately form cross-linked structure with the polyvinyl alcohol resin (B) as functional group with hydroxyl.Wherein, carry out cross-linking reaction aptly and the angle of transparency excellence from the hydroxyl with polyvinyl alcohol resin, particularly preferably use isocyanate ester compound.In addition, in order to promote that cross-linking reaction suitably uses catalyzer etc. as required.
As isocyanate compound, the polyisocyanates of low molecule or high molecular diisocyanate or more than 3 yuan can be used.Such as, as isocyanate compound, can list: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate, 2,2 '-methyl diphenylene diisocyanate, 1,5-naphthalene diisocyanate, Isosorbide-5-Nitrae-naphthalene diisocyanate, phenylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4 '-diphenyl ether diisocyanate, 2-nitro diphenyl-4,4 '-diisocyanate, 2,2 '-diphenyl propane-4,4 '-diisocyanate, 3,3 '-dimethyl diphenylmethane-4,4 '-diisocyanate, 4,4 '-diphenylpropane diisocyanate, 3, the aromatic diisocyanate classes such as 3 '-dimethoxydiphenyl-4,4 '-diisocyanate, the aromatic series aliphatic diisocyanate classes such as xylylene diisocyanate, isophorone diisocyanate and 4,4-dicyclohexyl methyl hydride diisocyanates, the ester ring type diisocyanates such as two (isocyanatomethyl) cyclohexanes of 1,3-, the aliphatic diisocyanate classes such as hexamethylene diisocyanate and 2,2,4-trimethyl hexamethylene diisocyanates, and the trimer of these isocyanate compounds.And then, high molecular end that the excess quantity of these isocyanate compounds and following compound react and obtain can be listed containing isocyanate-based compound: the low molecule active dydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerine, sorbierite, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, or polyester polyols alcohols, polyether polyols alcohols, the high molecular reactive hydrogen compound such as polyamide-based.
As melamine compound, can list and be substituted base-(CH 2) nin-O-R(formula, n is the integer of 1 ~ 3, and R is the alkyl of carbon number 1 ~ 4.) melamine compound that instead of, the R in previously described formula is preferably methyl.The above-mentioned substituent quantity that 1 melamine structure has is preferably 3 ~ 6.As the object lesson of melamine compound, can list: Sumitomo Chemical Co manufactures M-3, MK, M-6, M-100, MC etc. of Sumitex Resin series, methylated melamine resins MW-22, MX-706, MX-042 etc. that SANWA Chemical Co., Ltd. manufactures.
As the crosslinking chemical used in the present invention (C), blocked isocyanate compounds is also preferred.By adding blocked isocyanate compounds, the ageing stability of coating fluid more appropriately can be improved.
Blocked isocyanate compounds can make above-mentioned isocyanate compound and end-capping reagent carry out addition reaction to prepare by existing known method.As isocyanate-terminated dose, include, for example out: the phenols such as phenol, cresols, xylenols, resorcinol, nitrophenol, chlorophenol; The sulfo-phenols such as thiophenol, methyl thio phenol; The oximes such as acetyl oxime, methyl ethyl ketoxime, cyclohexanone-oxime; The alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols; The halogen substiuted alcohols such as chlorohydrin, 1,3-bis-chloro-2-propyl alcohol; The tertiary alcohols such as the tert-butyl alcohol, tert-pentyl alcohol; The lactams such as epsilon-caprolactams, δ-valerolactam, butyrolactam, azetidinone; Aromatic amine; Acid imide; Diacetone, acetoacetate, malonic ester isoreactivity methylene compound; Thio-alcohol; Imines class; Urea class; Biaryl compound class; Sodium bisulfite etc.
As the content of crosslinking chemical (C), be preferably more than 2 quality % and below 50 quality % in easy adhesive linkage, be more preferably more than 5 quality % and below 40% quality %, more preferably more than 8 quality % and below 30 quality %.When the content of crosslinking chemical (C) is more than above-mentioned lower limit, be suitable for being cross-linked to form of polyvinyl alcohol resin, for below the above-mentioned upper limit time, be suitable for the cementability effect brought of performance resin glue.
The compounding of polyester resin (A) and polyvinyl alcohol resin (B) count preferably 0.8 ~ 5 in mass ratio than (A)/(B), is more preferably 1 ~ 4, and more preferably 2 ~ 4, be particularly preferably 2.5 ~ 3.5.(A)/(B) for more than above-mentioned lower limit time, be suitable for the cementability with mylar base material, for below the above-mentioned upper limit time, the cementability for the polyvinyl alcohol resin layer with polaroid, bonding agent etc. is suitable.
The compounding of polyester resin (A) and polyvinyl alcohol resin (B) and crosslinking chemical (C) count preferably 2 ~ 50 in mass ratio than ((A)+(B))/(C), is more preferably 5 ~ 40, and more preferably 8 ~ 30.((A)+(B))/(C) for more than above-mentioned lower limit time, the cementability effect brought for performance resin glue composition is suitable, for below the above-mentioned upper limit time, the cementability effect brought for being separated is suitable.
Easy adhesive linkage of the present invention, by adopting above-mentioned composition, relative to polaroid, the aqueous adhesive of polaroid, aqueous adhesive, particularly polyvinyl alcohol, shows the high adhesiveness equal with Triafol T.Specifically, be preferably more than 90% based on the remaining area after the peeling off water system bonding agent 1 time of adhesive test described later, be more preferably more than 95%, more preferably 100%, remaining area after peeling off continuously for 5 times is preferably more than 75%, be more preferably more than 85%, the remaining area after more preferably peeling off continuously for more than 95%, 10 times is preferably more than 50%, be more preferably more than 80%, more preferably more than 90%, be further preferably more than 93%, be particularly preferably more than 95%.
(adjuvant)
In easy adhesive linkage of the present invention, known adjuvant can be added, such as the particle, antistatic agent, nucleator etc. of surfactant, antioxidant, catalyzer, heat-resisting stabilizing agent, weathering stabilizers, ultraviolet light absorber, organically easy lubrication prescription, pigment, dyestuff, organic or inorganic in the scope not damaging effect of the present invention.
In the present invention, in order to improve the resistance to adhesive of easy adhesive linkage further, in easy adhesive linkage, add particle is also preferred mode.In the present invention as the particle making to contain in easy adhesive linkage, include, for example out inorganic particle, organic polymer particles, described inorganic particle has: titanium dioxide, barium sulphate, calcium carbonate, calcium sulphate, silicon dioxide, aluminium oxide, talcum, porcelain earth, clay etc. or their potpourri, and with other conventional inorganic particulates, such as calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, the inorganic particle etc. that calcium fluoride etc. combinationally use, described organic polymer particles can list phenylethylene, acrylic compounds, melamine class, benzocarbamidine amine, silicone based etc.
The mean grain size of the particle in easy adhesive linkage is (based on the mean grain size of the number benchmark of SEM.Lower same) be preferably 0.04 ~ 2.0 μm, more preferably 0.1 ~ 1.0 μm.When the mean grain size of inert particle is less than 0.04 μm, become insufficient in the concavo-convex formation of film surface, therefore the treatability such as sliding, batching property of film can reduce sometimes, and processability when fitting reduces.Otherwise, during more than 2.0 μm, easily there is particle detachment and not preferred.Granule density in easy adhesive linkage is preferably 1 ~ 20 quality %, more preferably 5 ~ 15 quality % in solid constituent.
Easily the thickness of adhesive linkage suitably can set in the scope of 0.001 ~ 2.00 μm in the present invention, wants to take into account processability and cementability, is preferably the scope of 0.01 ~ 1.00 μm, is more preferably 0.02 ~ 0.80 μm, more preferably 0.05 ~ 0.50 μm.When the thickness of easy adhesive linkage is less than 0.01 μm, cementability becomes insufficient.If easily the thickness of adhesive linkage is more than 2.00 μm, then stick together sometimes.
(the polaroid protection manufacture of easy-adhesion mylar)
For the manufacture method of polaroid protection easy-adhesion mylar of the present invention, be described for polyethylene terephthalate (hereinafter referred to as PET) film, but be certainly not limited to this.
After fully carrying out vacuum drying to PET resin, supply extruder, to be expressed into the melting PET resin of about 280 DEG C with sheet-shaped molten from T mould and to rotate on chill roll, applies method carry out cooling curing and not stretched PET sheet by electrostatic.The aforementioned PET of stretching sheet can be that individual layer is formed, and also can be form based on the multilayer of coetrusion.
By not stretching to gained, PET sheet is implemented uniaxial tension or biaxial stretch-formedly makes crystal orientation.Such as, time biaxial stretch-formed, with the roller being heated to 80 ~ 120 DEG C be longitudinally stretched to 2.5 ~ 5.0 times obtain uniaxial tension PET film after, hold the end of film with clip, cause the hot blast district being heated to 80 ~ 180 DEG C, be stretched to 2.5 ~ 5.0 times in the width direction.In addition, during uniaxial tension, in stenter, 2.5 ~ 5.0 times are stretched to.The heat-treatment zone continuing to cause 140 ~ 240 DEG C after stretching carries out the thermal treatment in 1 ~ 60 second, completes crystal orientation.
Easy adhesive linkage can be arranged after the manufacture of film or in manufacturing process.Especially, from the viewpoint of throughput rate, preferably thin film fabrication operation any Duan Bands, namely not stretch or at least one side applied coating solution of PET film after uniaxial tension, form easy adhesive linkage.
For this coating solution can be used known arbitrary method in the method for PET film.Include, for example out: reverse roll rubbing method, photogravure rubbing method, engagement rubbing method, mould coater, roller brush method, spraying rubbing method, air knife rubbing method, coiling rod rubbing method, tubular type scrape the skill in using a kitchen knife in cookery (PipeDoctor, パ イ プ De Network タ ー) method, impregnation rubbing method, curtain coating processes etc.These methods separately or can combine and apply.
In the present invention, the thickness of the easy adhesive linkage finally obtained is preferably 0.03 ~ 0.20g/m 2.Be less than 0.03g/m 2time, cementability reduces, and is thicker than 0.20g/m 2time, adhesive, sliding reduce, therefore not preferred.
(Polarizer)
Polarizer of the present invention has polaroid protective film on the two sides of polaroid, and preferably at least the polaroid protective film in the face of side is aforementioned polaroid protection easy-adhesion mylar.The polaroid protective film of opposite side can be polaroid protection easy-adhesion mylar of the present invention, and it is also preferred for using with the film of cellulose triacetate film, acrylate film, the norborene class film free of birefringence that is representative.
As polaroid, such as, can enumerate the polyvinyl alcohol film containing dichroic material such as iodine.Polaroid protective film directly or fitted by bond layer and polaroid, and from the viewpoint of raising cementability, is fitted preferably by bonding agent.Now, easy adhesive linkage of the present invention is preferably configured in the unilateral or bonding agent aspect of polarization.As the polaroid being preferred for bonding mylar of the present invention, such as can enumerate the polaroid obtained as follows: dyeing absorption iodine, dichroic material on polyvinyl alcohol film, in boric acid aqueous solution, carry out uniaxial tension, keep extended state carry out washing and drying and obtain.The stretching ratio of uniaxial tension is generally about 4 ~ 8 times.As polyvinyl alcohol film, polyvinyl alcohol (PVA) is suitable, the commercially available products such as " Kuraray Vinylon " [Kuraray Co., Ltd.'s manufacture], " Tohcello Vinylon " [MitsuiChemicals Tohcello, Inc. manufacture], " day closes Vinylon " [Japanese synthetic chemistry Co., Ltd. manufactures] can be utilized.As dichroic material, can list: iodine, bis-azo compound, polymethin dyes etc.
From the angle of thinning bond layer, coat the material of the preferred water system of bonding agent of polaroid, that is, by bonding agent component dissolves in water or the material that is scattered in water and obtains.Such as, polyvinyl alcohol resin, urethane resin etc. can be used as principal ingredient, in order to improve the composition that cementability has used isocyanate ester compound, epoxy compound etc. as required compounding.The thickness of bond layer is preferably less than 10 μm, is more preferably less than 5 μm, more preferably less than 3 μm.
When using the principal ingredient of polyvinyl alcohol resin as bonding agent; except partly-hydrolysed polyvinyl alcohol (PVA), fully saponified polyvinyl alcohol (PVA), the polyvinyl alcohol resin of carboxy-modified polyvinyl alcohol (PVA), acetoacetyl modified polyvinyl alcohol (PVA), methylol-modified polyvinyl alcohol (PVA), this modification of amino modified polyvinyl alcohol (PVA) can also be used.The concentration of the polyvinyl alcohol resin in bonding agent is preferably 1 ~ 10 quality %, is more preferably 2 ~ 7 quality %.
Embodiment
Then, describe the present invention in detail with embodiment, comparative example and reference example, but the present invention is not limited to following embodiment certainly.In addition, the evaluation method used in the present invention is as follows.
(1) glass transition temperature
According to JIS K7121, use differential scanning calorimeter (Seiko Instruments Inc. manufacture, DSC6200), 10mg resin sample is heated up in the temperature range of 25 ~ 300 DEG C with the speed of 20 DEG C/min, and using the extrapolation Glass Transition obtained by DSC curve, temperature is as glass transition temperature.
(2) number-average molecular weight
0.03g resin is dissolved in 10ml tetrahydrofuran, use the manufacture of GPC-LALLS device low angle light light scattering photometer LS-8000(TOSOH Co., Ltd, tetrahydrofuran solvent, reference: polystyrene), column temperature 30 DEG C, flow 1ml/ minute, uses chromatographic column (Showa Denko K. K manufactures shodex KF-802,804,806) to measure number-average molecular weight.
(3) resin composition
Resin is dissolved in deuterochloroform, uses Varian, Inc. to manufacture magnetic nuclear resonance analyzer (NMR) Gemini-200 and carry out 1h-NMR analyzes, by its integration than determining each % by mole ratio formed.
(4) acid number
By 1g(solid constituent) sample be dissolved in chloroform or the dimethyl formamide of 30ml, carry out titration using phenolphthalein as the potassium hydroxide-ethanol solution of indicator 0.1N, obtain the amount (mg) of the KOH needed for carboxyl neutralizing every 1g sample.
(5) saponification degree
The remaining acetoxy group (% by mole) of NaOH to polyvinyl alcohol resin is used to carry out quantitatively, using its value as saponification degree (% by mole) according to JIS-K6726.Carry out 3 times to same sample to measure, using its mean value as saponification degree (% by mole).
(6) total light transmittance of polaroid protection mylar
The total light transmittance of polaroid protection mylar, according to JIS K7105, uses nephelometer (manufacture of Japanese electricity Se Co., Ltd., NDH2000) to measure.
(7) mist degree of polaroid protection mylar
The mist degree of polaroid protection mylar, according to JIS K7136, uses nephelometer (manufacture of Japanese electricity Se Co., Ltd., NDH2000) to measure.
(8) PVA cementability
The polyvinyl alcohol water solution (Kuraray Co., Ltd. manufactures PVA117) of solid component concentration 5 quality % is adjusted in the easy adhesive linkage surface coiling rod coating of polaroid protection mylar; the thickness of dried polyvinyl alcohol resin layer is made to be 2 μm, with 70 DEG C of dryings 5 minutes.For the ease of judging, use the polyvinyl alcohol water solution adding orchil.For the evaluation object film made, on the glass plate of thickness 5mm posting double faced adhesive tape, the face contrary with the face being formed with polyvinyl alcohol resin layer of the laminate film of evaluation object is attached at above-mentioned double faced adhesive tape.Then, use the cutter guide of clearance gap 2mm to be formed and run through the otch that polyvinyl alcohol resin layer arrives 100 lattice-shapeds of base film.Then, by adhesive strip (Nichiban Co., Ltd. manufactures Cellotape(registered trademark) CT-24; 24mm is wide) be attached to the cut sides of lattice-shaped.When attaching with the air that rubber pressing interface is residual make its completely closely sealed after, implement 1 time, 5 times, 10 times by carrying out vertical operation of peeling off suddenly to adhesive strip.Count the number of the unstripped grid of polyvinyl alcohol resin layer, as PVA cementability.That is, PVA layer complete unstripped time, the bonding rate of PVA is denoted as 100, PVA layer when all peeling off, and the bonding rate of PVA is denoted as 0.In addition, that partly peels off in 1 grid is also included within the number of stripping.
(polymerization of vibrin)
In the stainless steel autoclave possessing stirring machine, thermometer and partial reflux formula refrigeratory, add 194.2 mass parts dimethyl terephthalate (DMT), 184.5 mass parts dimethyl isophthalate, 14.8 mass parts dimethyl-5-sulfoisophthalic acid sodium, 233.5 mass parts diethylene glycols, 136.6 mass parts ethylene glycol and 0.2 mass parts tetra-n-butyl titanate esters, carry out ester exchange reaction with the temperature of 160 DEG C ~ 220 DEG C with 4 hours.Then, be warming up to 255 DEG C, after reaction system is slowly reduced pressure, react 1 hour 30 minutes under the decompression of 30Pa, obtain copolymer polyester resin (A-1).Gained copolymer polyester resin (A-1) is pale yellow transparent.Measure the reduced viscosity of copolymer polyester resin (A-1), result is 0.70dl/g.Glass transition temperature based on DSC is 40 DEG C.
Use the same method and obtain copolymer polyester resin (A-2) ~ (A-5) of other compositions.These copolymer polyester resins are used 1the composition (% by mole ratio) that H-NMR records and other characteristics are shown in table 1.
[table 1]
(preparation of polyester water dispersion)
In the reactor that stirring machine, thermometer and reflux be housed, add 30 mass parts vibrin (A-1), 15 mass parts ethylene glycol n-butyl ethers, with 110 DEG C of heating, stir resin dissolves.After resin dissolves completely, while stirring 55 mass parts water are slowly added in polyester liquid.After interpolation, liquid is cooled to room temperature while stirring, makes the milky polyester water dispersion (Aw-1) of solid constituent 30 quality %.Vibrin (A-2) ~ (A-5) is similarly used to replace vibrin (A-1) to make aqueous dispersion, respectively as polyester water dispersion (Aw-2) ~ (Aw-5).
(preparation of polyvinyl alcohol water solution)
In the container that stirring machine and thermometer be housed, add 90 mass parts water, slowly add the polyvinyl alcohol resin (Kuraray Co., Ltd.'s manufacture) (B-1) of the 10 mass parts degree of polymerization 500 while stirring.After interpolation, liquid is heated to 95 DEG C while stirring, makes resin dissolves.After dissolving, be cooled to room temperature while stirring, make the polyvinyl alcohol water solution (Bw-1) of solid constituent 10 quality %.Polyvinyl alcohol resin (B-2) ~ (B-7) is similarly used to replace polyvinyl alcohol resin (B-1) to make aqueous solution, respectively as (Bw-2) ~ (Bw-7).The saponification degree of polyvinyl alcohol resin (B-1) ~ (B-7) is shown in table 2.
[table 2]
B-1 B-2 B-3 B-4 B-5 B-6 B-7
Saponification degree (% by mole) 88 83 79 74 70 67 40
(polymerization of blocked polyisocyanates crosslinking chemical)
In the flask that stirring machine, thermometer, reflux condenser be housed, add the polyisocyanate compound (Asahi Chemical Corp manufactures, DURANATE TPA) with isocyanurate structure that 100 mass parts take hexamethylene diisocyanate as raw material, 55 mass parts propylene glycol monomethyl ether acetate, 30 mass parts poly glycol monomethyl ethers (mean molecular weight 750), keep 4 hours with 70 DEG C under nitrogen atmosphere.Then, reacting liquid temperature is cooled to 50 DEG C, drips 47 mass parts methyl ethyl ketoximes.The infrared spectrum of assaying reaction liquid, the absorption confirming isocyanate group disappears, and obtains the blocked polyisocyanates aqueous dispersions (C-1) of solid constituent 75 quality %.
Embodiment 1
(1) preparation of coating fluid
Mix following smears, the mass ratio making polyester resin (A)/polyvinyl alcohol resin (B) is the coating fluid of 70/30.Polyester water dispersion uses the aqueous dispersion (Aw-1) being dispersed with the vibrin that acid number is 2KOHmg/g, and polyvinyl alcohol water solution uses and is dissolved with the aqueous solution (Bw-4) that saponification degree is the polyvinyl alcohol (PVA) of 74 % by mole.
Water 40.61 quality %
Isopropyl alcohol 30.00 quality %
Polyester water dispersion (Aw-1) 11.67 quality %
Polyvinyl alcohol water solution (Bw-4) 15.00 quality %
Blocked isocyanate class crosslinking chemical (C-1) 0.67 quality %
Particle 1.25 quality %
(silicon dioxide gel of mean grain size 100nm, solid component concentration 40 quality %)
Catalyzer
(organic tin compound solid constituent concentration 14 quality %) 0.3 quality %
Surfactant 0.5 quality %
(silicon class, solid component concentration 10 quality %)
(2) manufacture of polaroid protection mylar
As film raw material polymkeric substance, by limiting viscosity (solvent: phenol/tetrachloroethane=60/40) for 0.62dl/g and in fact not containing the PET resin pellet of particle under the decompression of 133Pa, with 135 DEG C of dryings 6 hours.Then, supply extruder, melt extrude slabbing with about 280 DEG C, the closely sealed solidification of chilling on the rotation cool metal roller remaining surface temperature 20 DEG C, do not stretched PET sheet.
Be heated to 100 DEG C with warmed-up roller group and the infrared heater PET sheet that this not stretched, be then longitudinally stretched to 3.5 times by the roller group with difference, obtain uniaxial tension PET film.
Then, after with roller rubbing method aforementioned coating liquid being coated on the one side of PET film, with 80 DEG C of drying 15 seconds.In addition, the dried coating weight carrying out adjusting to make final (after biaxial stretch-formed) is 0.12g/m 2.Then 4.0 times are stretched to stenter in the width direction with 150 DEG C; secure film Width length state under; heated for 0.5 second with 230 DEG C, carry out the relaxation processes of the Width in 10 seconds 3% further with 230 DEG C, obtain the polaroid protection mylar of thickness 38 μm.Evaluation result is shown in table 3.
Embodiment 2
Polyester water dispersion is changed to and is dispersed with the aqueous dispersion (Aw-2) that acid number is the vibrin of 4KOHmg/g, in addition obtain polaroid protection mylar similarly to Example 1.
Embodiment 3
Polyester water dispersion is changed to and is dispersed with the aqueous dispersion (Aw-3) that acid number is the vibrin of 6KOHmg/g, in addition obtain polaroid protection mylar similarly to Example 1.
Embodiment 4
Saponification degree polyvinyl alcohol water solution being changed to polyvinyl alcohol (PVA) is the polyvinyl alcohol water solution (Bw-3) of 79 % by mole, in addition obtains polaroid protection mylar similarly to Example 1.
Embodiment 5
The saponification degree changing to polyvinyl alcohol (PVA) is the polyvinyl alcohol water solution (Bw-2) of 83 % by mole, in addition obtains polaroid protection mylar similarly to Example 1.
Embodiment 6
Changing to the following smears of mixing makes the mass ratio of polyester resin (A)/polyvinyl alcohol resin (B) be 60/40, in addition obtains polaroid protection mylar similarly to Example 1.
Water 37.28 quality %
Isopropyl alcohol 30.00 quality %
Polyester water dispersion (Aw-1) 10.00 quality %
Polyvinyl alcohol water solution (Bw-4) 20.00 quality %
Blocked isocyanate class crosslinking chemical (C-1) 0.67 quality %
Particle 1.25 quality %
(silicon dioxide gel of mean grain size 100nm, solid component concentration 40 quality %)
Catalyzer
(organic tin compound solid constituent concentration 14 quality %) 0.3 quality %
Surfactant 0.5 quality %
(silicon class, solid component concentration 10 quality %)
Embodiment 7
Changing to the following smears of mixing makes the mass ratio of polyester resin (A)/polyvinyl alcohol resin (B) be 80/20, in addition obtains polaroid protection mylar similarly to Example 1.
Water 43.95 quality %
Isopropyl alcohol 30.00 quality %
Polyester water dispersion (Aw-1) 13.33 quality %
Polyvinyl alcohol water solution (Bw-4) 10.00 quality %
Blocked isocyanate class crosslinking chemical (C-1) 0.67 quality %
Particle 1.25 quality %
(silicon dioxide gel of mean grain size 100nm, solid component concentration 40 quality %)
Catalyzer
(organic tin compound solid constituent concentration 14 quality %) 0.3 quality %
Surfactant 0.5 quality %
(silicon class, solid component concentration 10 quality %)
Embodiment 8
Changing to the following smears of mixing makes the mass ratio of polyester resin (A)/polyvinyl alcohol resin (B) be 50/50, in addition obtains polaroid protection mylar similarly to Example 1.
Water 33.95 quality %
Isopropyl alcohol 30.00 quality %
Polyester water dispersion (Aw-1) 8.33 quality %
Polyvinyl alcohol water solution (Bw-4) 25.00 quality %
Blocked isocyanate class crosslinking chemical (C-1) 0.67 quality %
Particle 1.25 quality %
(silicon dioxide gel of mean grain size 100nm, solid component concentration 40 quality %)
Catalyzer
(organic tin compound solid constituent concentration 14 quality %) 0.3 quality %
Surfactant 0.5 quality %
(silicon class, solid component concentration 10 quality %)
Embodiment 9
The composition of coating fluid is changed as follows, in addition obtains polaroid protection mylar similarly to Example 1.
Water 40.87 quality %
Isopropyl alcohol 30.00 quality %
Polyester water dispersion (Aw-1) 1.67 quality %
Polyvinyl alcohol water solution (Bw-4) 15.00 quality %
Melamine class crosslinking chemical (C-2) 0.71 quality %
(NIKALAC MX-042 SANWA Chemical Co., Ltd. manufactures solid component concentration 70%)
Particle 1.25 quality %
(silicon dioxide gel of mean grain size 100nm, solid component concentration 40 quality %)
Surfactant 0.5 quality %
(silicon class, solid component concentration 10 quality %)
Embodiment 10
Polyvinyl alcohol water solution is changed to the aqueous solution (Bw-5) that the saponification degree being dissolved with polyvinyl alcohol (PVA) is the polyvinyl alcohol (PVA) of 70 % by mole, in addition obtain polaroid protection mylar similarly to Example 1.
Embodiment 11
Polyvinyl alcohol water solution is changed to the aqueous solution (Bw-6) that the saponification degree being dissolved with polyvinyl alcohol (PVA) is the polyvinyl alcohol (PVA) of 67 % by mole, in addition obtain polaroid protection mylar similarly to Example 1.
Embodiment 12
The composition of coating fluid is changed as follows, in addition obtains polaroid protection mylar similarly to Example 1.
Water 40.33 quality %
Isopropyl alcohol 30.00 quality %
Polyester water dispersion (Aw-1) 11.67 quality %
Polyvinyl alcohol water solution (Bw-2) 15.00 quality %
Oxazoline class crosslinking chemical (C-3) 1.25 quality %
(EPOCROS WS-500, Nippon Shokubai Co., Ltd's manufacture, solid component concentration 40 quality %)
Particle 1.25 quality %
(silicon dioxide gel of mean grain size 100nm, solid component concentration 40 quality %)
Surfactant 0.5 quality %
(silicon class, solid component concentration 10 quality %)
Embodiment 13
Polyester water dispersion is changed to and is dispersed with the aqueous dispersion (Aw-5) that acid number is the vibrin of 10KOHmg/g, in addition obtain polaroid protection mylar similarly to Example 1.
Comparative example 1
Changing to the following smears of mixing makes the mass ratio of polyester resin (A)/polyvinyl alcohol resin (B) be 100/0, in addition obtains polaroid protection mylar similarly to Example 1.
Water 50.62 quality %
Isopropyl alcohol 30.00 quality %
Polyester water dispersion (Aw-1) 16.66 quality %
Blocked isocyanate class crosslinking chemical (C-1) 0.67 quality %
Particle 1.25 quality %
(silicon dioxide gel of mean grain size 100nm, solid component concentration 40 quality %)
Catalyzer
(organic tin compound solid constituent concentration 14 quality %) 0.3 quality %
Surfactant 0.5 quality %
(silicon class, solid component concentration 10 quality %)
Comparative example 2
Changing to the following smears of mixing makes the mass ratio of polyester resin (A)/polyvinyl alcohol resin (B) be 0/100, in addition obtains polaroid protection mylar similarly to Example 1.
Water 17.28 quality %
Isopropyl alcohol 30.00 quality %
Polyvinyl alcohol water solution (Bw-4) 50.00 quality %
Blocked isocyanate class crosslinking chemical (C-1) 0.67 quality %
Particle 1.25 quality %
(silicon dioxide gel of mean grain size 100nm, solid component concentration 40 quality %)
Catalyzer
(organic tin compound solid constituent concentration 14 quality %) 0.3 quality %
Surfactant 0.5 quality %
(silicon class, solid component concentration 10 quality %)
Comparative example 3
Polyester water dispersion is changed to and is dispersed with the aqueous dispersion (Aw-4) that acid number is the vibrin of 25KOHmg/g, in addition obtain polaroid protection mylar similarly to Example 1.
Comparative example 4
Polyvinyl alcohol water solution is changed to and is dissolved with the aqueous solution (Bw-1) that saponification degree is the polyvinyl alcohol (PVA) of 88 % by mole, in addition obtain polaroid protection mylar similarly to Example 1.
Comparative example 5
Polyvinyl alcohol water solution is changed to and is dissolved with the aqueous solution (Bw-7) that saponification degree is the polyvinyl alcohol (PVA) of 40 % by mole, in addition obtain polaroid protection mylar similarly to Example 1.
Comparative example 6
Change to smears, not mixed cross-linker that mixing is following, in addition obtain polaroid protection mylar similarly to Example 1.
Water 41.58 quality %
Isopropyl alcohol 30.00 quality %
Polyester water dispersion (Aw-1) 11.67 quality %
Polyvinyl alcohol water solution (Bw-4) 15.00 quality %
Particle 1.25 quality %
(silicon dioxide gel of mean grain size 100nm, solid component concentration 40 quality %)
Surfactant 0.5 quality %
(silicon class, solid component concentration 10 quality %)
Reference example 1
The result using TAC film (Fuji Photo Film Co., Ltd.'s manufacture, thickness 80 μm, saponification process) to carry out aforementioned adhesive test as polaroid protection film is shown.
[table 3]
utilizability in industry
Polaroid protection easy-adhesion mylar of the present invention has the high adhesiveness with polaroid and water system bonding agent.Therefore, polaroid protection component can be used as aptly.

Claims (6)

1. an easy-adhesion mylar is used in polaroid protection, and it is the mylar at least at one side with easy adhesive linkage,
Described easy adhesive linkage contains polyester resin (A), polyvinyl alcohol resin (B) and crosslinking chemical (C),
The acid number of described polyester resin (A) is below 20KOHmg/g,
The saponification degree of described polyvinyl alcohol resin (B) is 60 ~ 85 % by mole, and wherein, described saponification degree measures as follows: use the remaining acetoxy group of NaOH to polyvinyl alcohol resin to carry out quantitatively, using its value as saponification degree according to JIS-K6726.
2. polaroid protection easy-adhesion mylar according to claim 1, wherein, described polyester resin (A) is containing the 5-sulfoisophthalic acid composition of 1 ~ 15 % by mole accounting for dicarboxylic acid component.
3. polaroid protection easy-adhesion mylar according to claim 1 and 2, wherein, described crosslinking chemical (C) is isocyanate compound or melamine compound.
4. polaroid protection easy-adhesion mylar according to claim 1 and 2; wherein; in described easy adhesive linkage, the mass ratio of polyester resin (A), polyvinyl alcohol resin (B) and crosslinking chemical (C) meets following formula:
0.8≤(A)/(B)≤5
2≤((A)+(B))/(C)≤50。
5. polaroid protection easy-adhesion mylar according to claim 3; wherein; in described easy adhesive linkage, the mass ratio of polyester resin (A), polyvinyl alcohol resin (B) and crosslinking chemical (C) meets following formula:
0.8≤(A)/(B)≤5
2≤((A)+(B))/(C)≤50。
6. a Polarizer, it has polaroid protective film on the two sides of polaroid,
At least polaroid protection easy-adhesion mylar of the polaroid protective film in the face of side according to any one of Claims 1 to 5.
CN201280007582.5A 2011-02-02 2012-02-01 Highly adhesive polyester film for protection of polarizers Active CN103339538B (en)

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