CN102648094A - Highly adhesive thermoplastic resin film - Google Patents

Highly adhesive thermoplastic resin film Download PDF

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Publication number
CN102648094A
CN102648094A CN2010800549220A CN201080054922A CN102648094A CN 102648094 A CN102648094 A CN 102648094A CN 2010800549220 A CN2010800549220 A CN 2010800549220A CN 201080054922 A CN201080054922 A CN 201080054922A CN 102648094 A CN102648094 A CN 102648094A
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China
Prior art keywords
film
easy
thermoplastic resin
coating layer
carbodiimide
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Granted
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CN2010800549220A
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CN102648094B (en
Inventor
伊藤晃侍
山崎淳史
矢吹宽子
泽田薰
水野直树
东浦真哉
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Toyobo Co Ltd
Toyo Textile Co Ltd
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Toyo Textile Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • 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
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
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    • 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
    • C09J7/35—Heat-activated
    • 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
    • B32B2369/00—Polycarbonates
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane

Abstract

Disclosed is a highly adhesive thermoplastic resin film which is substantially free from decrease in adhesion under high temperature high humidity conditions. Specifically disclosed is a highly adhesive thermoplastic resin film which comprises a coating layer on at least one surface of a base film. The highly adhesive thermoplastic resin film is characterized in that the coating layer contains (a) a urethane resin that contains a polycarbonate polyol as a component, and/or a polyester resin that does not substantially contain a carboxylic acid group and has a number average molecular weight of not less than 15,000, and (b) a carbodiimide compound.

Description

The easy-adhesion thermoplastic resin film
Technical field
The present invention relates to the excellent easy-adhesion thermoplastic resin film of adaptation and humidity resistance.At length say, relate to as being mainly used in the easy-adhesion thermoplastic resin film that base materials display etc., functional membranes such as hard coat film, antireflection film, light diffusing sheet, prism-like lens, near infrared ray barrier film, transparent and electrically conductive film, antiglare film are fit to.
Background technology
Usually; The base material of the functional membrane that uses as the member of LCD (LCD), the transparent thermoplastic resin film that has used PETG (PET), acrylic resin, Merlon (PC), triacetyl cellulose (TAC), polyolefin etc. to form.
Use under the situation of aforesaid thermoplastic resin film as the base material of various functional membranes the range upon range of functional layer that meets various uses.For example, for LCD (LCD), can enumerate the functional layers such as light diffusion layer of the diaphragm (hard conating) of the damage that prevents the surface, the layers of prisms that prevents the anti-reflection layer of mirroring (AR layer) of outer light, the light harvesting that is used for light, diffusion, raising brightness.In such base material, especially, polyester film is owing to the transparency, dimensional stability, chemical-resistant excellence, and price comparison is low, and therefore the base material as various functional membranes uses widely.
Usually, under the situation of the Biaxially oriented thermoplastic film that double axial orientated polyester film, Biaxially orientated polyamide film are such, the film surface is because crystalline orientation to heavens, therefore has the shortcoming with the adaptation shortcoming of various coating, adhesive, China ink etc.Therefore, the method that adopts the whole bag of tricks to give easy-adhesion at the Biaxially oriented thermoplastic surface resin film has been proposed so far.
For example, it is the coating layer of main composition composition that the surface of general known thermoplastic resin film at base material is provided with various resins such as polyester, acrylic resin, polyurethane, acrylic resin grafted polyesters, thereby gives the method for base material film easy-adhesion.In this rubbing method; Implemented in the industry on the thermoplastic resin film before crystalline orientation is accomplished; To contain the solution of aforementioned resin or the water-based coating fluid of the dispersion of resin dispersion coated base material film, after the drying, on the single shaft direction, stretch at least with decentralized medium; Next implement heat treatment, accomplish the method (so-called online rubbing method) of the orientation of thermoplastic resin film; After the manufacturing of thermoplastic resin film, behind the coating fluid of coating water system or solvent system on this film, carry out dry method (so-called off-line rubbing method).
Display such as LCD, PDP, with hard coat film portable as member, no matter within doors, outside the room, in various environment, use with equipment etc.Especially, for the portable equipment of using, requirement sometimes can tolerate the humidity resistance in bathroom, many wetlands of high temperature district etc.For the optical functional film that in such purposes, uses, require the high adaptation that splitting does not take place yet hot and humid down.Therefore, in following patent documentation, disclose, in the coating layer resin, formed cross-linked structure when adopting the coating layer of online rubbing method to form, thereby given the easy-adhesion thermoplastic resin film of humidity resistance through in coating fluid, adding crosslinking agent.
Patent documentation 1: TOHKEMY 2000-141574 communique
Patent documentation 2: No. 3900191 communique of Japan Patent
Patent documentation 3: No. 3737738 communique of Japan Patent
Patent documentation 4: TOHKEMY 2007-253512 communique
Patent documentation 5: TOHKEMY 2000-355086 communique
Patent documentation 6: No. 2544792 communique of Japan Patent
Summary of the invention
The problem that invention will solve
In order to alleviate earth environment load, have in the tame electrical article etc. of display the long lifetime of expectation on existing basis.Therefore, in the functional membrane as the member use, think that also it is necessary also keeping adaptation for a long time at hot and humid time.But, disclosed easy-adhesion film in the above-mentioned patent documentation, though show good adaptation at first, the reduction of dhering strength is inevitable in the long-term use under hot and humid.Because the reduction of such adaptation, the problem that existence can't the long term maintenance initial performance.
The present invention is in view of above-mentioned problem, purpose be to provide cause hardly thought in the past the coating layer under inevitably hot and humid deterioration, be the easy-adhesion thermoplastic resin film of the reduction of the adaptation under hot and humid.
Need to prove, said adaptation under hot and humid among the present invention, mean range upon range of light-cured type acrylic resin layer after; Be positioned under 80 ℃, 95%RH, 48 hours environment, that uses clearance gap 2mm draws lattice device (Cutter guide), forms 100 latticed cut channels that connect light-cured type acrylic resin layer and arrive base material film in light-cured type acrylic resin aspect; Next, the cellophane adhesive tape joining in latticed cut channel face, is rubbed with rubber; Make its complete driving fit; Adaptation when peeling off 5 times fiercely for same position is the evaluation method that adopts the general JISK5600-5-6 record of using, the adaptation under the strict criterion; Problem of the present invention is, shows in such adaptation under hot and humid to be equal to the adaptation shown in the initial stage or adaptation more than it.
Be used to solve the means of problem
The inventor furthers investigate in order to solve above-mentioned problem; The result finds to comprise specific polyurethane resin and/or the specific mylar and the coating layer of carbodiimide compound through use; Realize that hot and humid adaptation down improves such fact of overturning technological general knowledge in the past, thereby accomplished the present invention.Such like record in the above-mentioned patent documentation, for technological general knowledge so far, can think in order to improve the adaptation of coating layer, hope and crosslinking agent and have can with the mixed with resin of the functional group of its reaction, when coating layer forms, form cross-linked structure to heavens.But; The present invention has found polyurethane resin and/or the mylar do not have basically with this functional group of carboxylic acid group of carbodiimide radical reaction through using; Do not make carbodiimide remaining in coating layer not have cross-linked structure basically or to make the degree of cross linking become low state; Even can realize also keeping the such fact opposite of high adaptation down, thereby accomplish the present invention with prior art hot and humid.
Aforesaid problem can realize through following solution.
(1) a kind of easy-adhesion thermoplastic resin film; Be the easy-adhesion thermoplastic resin film that coating layer is arranged at least one mask of base material film, aforementioned coating layer contains polyurethane resin that (a) is constituent with the polycarbonate polyol and/or number-average molecular weight more than 15000 and do not have carboxylic acid group's mylar and (b) carbodiimide compound basically.
(2) above-mentioned easy-adhesion thermoplastic resin film, wherein, aforementioned polyurethane resin has polyoxyalkylenes.
(3) above-mentioned easy-adhesion thermoplastic resin film, wherein, aforementioned mylar comprises the diol component shown in dicarboxylic acids composition shown in the following formula (1) and/or the following formula (2).
(1) HOOC-(CH 2) n-COOH (in the formula, n is the integer of 4≤n≤10)
(2) HO-(CH 2) n-OH (in the formula, n is the integer of 4≤n≤10)
(4) above-mentioned easy-adhesion thermoplastic resin film, wherein, aforementioned mylar comprises naphthalenedicarboxylic acid as sour composition.
(5) above-mentioned easy-adhesion thermoplastic resin film, wherein, aforementioned coating layer will be with the polycarbonate polyol polyurethane resin and the carbodiimide compound of constituent as principal component, comprise the carbodiimide of 0.5～3.5mmol/g in the aforementioned coating layer.
(6) above-mentioned easy-adhesion thermoplastic resin film, wherein, aforementioned coating layer with number-average molecular weight more than 15000 and the mylar and the carbodiimide compound that do not have the carboxylic acid group basically be principal component, contain the carbodiimide of 0.3～3.3mmol/g in the coating layer.
(7) above-mentioned easy-adhesion thermoplastic resin film; Wherein, Aforementioned coating layer will be with the polycarbonate polyol polyurethane resin, number-average molecular weight of constituent more than 15000 and the mylar and the carbodiimide compound that do not have the carboxylic acid group basically as principal component, contain the carbodiimide of 0.1～2.0mmol/g in the coating layer.
(8) above-mentioned easy-adhesion polyester film, wherein, aforementioned carbodiimide compound is water-soluble, turbidity is below 2.5%.
(9) a kind of range upon range of thermoplastic resin film, it forms through 1 layer the functional layer of from hard conating, light diffusion layer, prism-like lens jacket, electromagnetic wave absorbing layer, near infrared ray barrier layer, transparency conducting layer, selecting in the aforementioned coating layer laminated of above-mentioned easy-adhesion thermoplastic resin film at least.
The effect of invention
First effect that is prone to bonding thermoplastic resin film of the present invention is, under hot and humid and adaptation (humidity resistance) excellence optical functional layer.Therefore, as preferred embodiment, the equal or raising of adaptation in above-mentioned high temperature, the high humidity treatment and initial adaptation.As preferred embodiment of the present invention, when easy bonding polyester film of the present invention was used as the base material of lens sheet, the adaptation with lens jacket under hot and humid was good.
In addition, in the preferred mode of the present invention, except first effect, even range upon range of under the situation of hard conating, also can suppress interference of light striped, visibility is excellent.
In addition, in the preferred mode of the present invention, except first effect, anti-adhesive is excellent.
The specific embodiment
(thermoplastic resin film)
Constitute the thermoplastic resin of the thermoplastic resin film that uses as base material among the present invention; Can use polyamide, PETG, polybutylene terephthalate (PBT)s such as vistanexes such as polyethylene, polypropylene, nylon 6, nylon 66, gather 2; 6-(ethylene naphthalate), poly terephthalic acid methylene ester and as copolymer composition for example diol components such as diethylene glycol (DEG), neopentyl glycol, PAG and adipic acid, decanedioic acid, phthalic acid, M-phthalic acid, 2, dicarboxylic acids such as 6-naphthalenedicarboxylic acid one-tenth the mylar that copolymerization forms etc. that grades.Wherein, from mechanical strength, chemical-resistant aspect, preferred polyester resin.
The preferred mylar that uses among the present invention; Can use PETG, polybutylene terephthalate (PBT), gather 2; 6-(ethylene naphthalate), poly terephthalic acid methylene ester and as copolymer composition diol components such as diethylene glycol (DEG), neopentyl glycol, PAG for example; With adipic acid, decanedioic acid, phthalic acid, M-phthalic acid, 2, dicarboxylic acids such as 6-naphthalenedicarboxylic acid become the mylar that the copolymerization that grades forms etc.
The preferred mylar that uses among the present invention, mainly with PETG, PTT, polybutylene terephthalate (PBT), PEN at least a kind as constituent.In these mylar, from the balance of rerum natura and cost, most preferably PETG.In addition, these polyester films can improve chemical-resistant, hear resistance, mechanical strength etc. through biaxial stretch-formed.
In addition, aforesaid biaxially oriented polyester film can be an individual layer, also can be multilayer.In addition, so long as produce in the scope of effect of the present invention, in each layer, can make as required and contain various additives in the mylar at these.As additive, can enumerate for example anti-oxidant, photostabilizer, anti-gelating agent, organic wetting agent, antistatic additive, ultra-violet absorber, surfactant etc.
In addition, for wearing characters such as the property handled such as the sliding that improves film, coiling property, anti-adhesive, mar proof, scratch resistances, make sometimes and contain inactive particle in the polyester film.But, be used under the situation of optics with the base material film of member, require to keep the transparency of height, simultaneously the property handled excellence.Particularly, under the situation of optics with the base material film use of member, the full light transmittance of preferred easy-adhesion polyester film is more than 85%, and is more preferably more than 87%, further preferred more than 88%, further preferred more than 89%, preferred especially more than 90%.
In addition, for high vividness, the content of the inactive particle in the preferred substrates film is the least possible.Therefore, preferably become the top layer that only makes film and contain the multilayer of particle and constitute, perhaps make to be substantially free of particle in the film and only to make and contain particulate in the coating layer.
Especially,, make under the situation that is substantially free of inactive particle in the polyester film,, also preferably make and contain inorganic in the water system coating fluid and/or hear resistance macromolecule particle, form concavo-convex at painting layer surface in order to improve the processing property of film from the aspect of the transparency.
Need to prove; So-called " being substantially free of inactive particle "; For example be under the situation of inorganic particulate, when adopting x-ray fluorescence analysis that the element from particle is carried out quantitative analysis, mean become below the 50ppm, below the preferred 10ppm, the content below the detectable limit most preferably.This is because even energetically particle is not added in the base material film, the dirt that adheres to from the production line in the manufacturing process of pollutant component, material resin or the film of external foreign matter or device is sometimes peeled off and sneaked in the film.
In addition, from taking into account the aspect of high transparent and the property handled simultaneously, only in the top layer, adding inactive particle also is preferred mode.For example, process under the situation of 3 layers of formation, preferably in outermost layer (A layer under the situation of A layer/B layer/A layer), contain particle, in central core (B layer), be substantially free of particle.
The kind of contained particle and content can be inorganic particulates in the outermost layer; It also can be organic filler; Do not have special qualification, but metal oxides such as illustration silica, titanium dioxide, talcum, kaolinite, calcium carbonate, calcium phosphate, barium sulfate etc. are inactive inorganic particulate for polyester.These inactive inorganic particulates, all can use separately a kind of, also can be with more than 2 kinds and use.
Aforesaid particle, preferred average grain diameter is 0.1～3.5 μ m.If average grain diameter less than lower limit, can't obtain the property handled fully sometimes.If surpass the upper limit, the transparency reduces sometimes.The content of outermost inorganic particulate is preferably 0.01～0.20 quality % with respect to constituting outermost polyester.If not enough lower limit can't obtain the property handled fully.If surpass the upper limit, the transparency reduces.
In addition, require under the situation of reflectivity, highly concealed type, can use in base material film and add empty visualization reagent and the high white films of hole containing ratio.In addition, for the purposes that requires mouldability, can use the moulding of having given mouldability as mylar interpolation copolymer composition to use film.
The thickness of the base material film that uses among the present invention does not have special restriction, can in the scope of 30～500 μ m, at random determine according to the specification of using.The upper limit of the thickness of base material film, preferred 350 μ m are preferably 250 μ m especially.On the other hand, the preferred 50 μ m of the lower limit of thickness, more preferably 75 μ m are preferably 100 μ m especially.If the not enough lower limit of thickness, it is not enough that rigidity, mechanical strength become easily.On the other hand, if thickness surpasses the upper limit, cost raises sometimes.
(coating layer)
Be provided with in the easy-adhesion thermoplastic resin film of the present invention and comprise polyurethane resin that (a) is constituent with the polycarbonate polyol and/or number-average molecular weight more than 15000 and not have carboxylic acid group's mylar basically be important with (b) coating layer of carbodiimide compound.Wherein, be the coating layer of principal component with above-mentioned (a) and (b) preferably.Wherein, so-called " principal component " means in all solids composition contained in coating layer and contains more than the 50 quality %.
Thought in the past,, hoped to import energetically cross-linked structure from the aspect of the humidity resistance that improves coating layer.But, found in the application of the present invention that through making coating layer be above-mentioned formation, thereby humidity resistance improves.Through such formation, the mechanism that the adaptation under hot and humid improves is not fully aware of, but the inventor thinks and is described below.Basically do not have in the coating layer of the present invention for the carboxylic acid group of the functional group of carbodiimide radical reaction, so coating layer when forming unreacted carbodiimide remaining in coating layer.On the other hand, the mylar in hot and humid coating layer down causes hydrolysis, ester linkage breaking, and it is terminal to produce the carboxylic acid group.Therefore, the carboxylic acid end reaction of unreacted carbodiimide and generation forms crosslinked.We can say, think and carry out selfreparing, thereby can prevent the coated film strength deterioration under hot and humid through the deterioration of coated film intensity that hydrolysis is produced.
That is, in the coating layer of the present invention, do not contain as carboxyl or its salt of demonstration with the functional group of carbodiimide high response, perhaps few, so unreacted carbodiimide exists in a large number in the coating layer.On the other hand, there are functional groups such as carboxyl in the resin that in range upon range of functional layer, uses, for example light-cured type acrylic resin and the unreacted reactant.And, in as the thermoplastic resin of base material film, also there is functional group.Under hot and humid environment, infer that the functional group and the carbodiimide that exist in these functional layer and/or the base material film interact, and obtain firm adaptation.
The present invention, by the way, can raising and the adaptation (humidity resistance) under hot and humid of lens jacket and then other functional layer.Below formation of the present invention is further detailed.
(polyurethane resin)
The polyurethane resin that uses among the present invention as constituent, contains polyol component, polyisocyanates composition at least, also contains cahin extension agent as required.Polyurethane resin of the present invention is that these constituents are macromolecular compound main, that form through the urethane bond copolymerization.The invention is characterized in that the constituent as polyurethane resin has polycarbonate polyol.To contain in the coating layer of the present invention with the Merlon be the polyurethane resin of constituent through making, and can improve humidity resistance.Need to prove that the constituent of these polyurethane resins can be through evaluations such as nuclear magnetic resonance spectroscopies.
As the polycarbonate polyol of the constituent of polyurethane resin of the present invention, can enumerate PCDL, Merlon triol etc., can preferably use PCDL.As the PCDL of the constituent of polyurethane resin of the present invention, can enumerate for example through making ethylene glycol, propane diols, 1, ammediol, 1; 4-butanediol, 1; 5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, 1; 9-nonanediol, 1; 8-nonanediol, neopentyl glycol, diethylene glycol (DEG), DPG, 1,4-cyclohexanediol, 1, the PCDL that obtains with the reaction of carbonates such as for example dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene more than a kind or 2 kinds of glycols such as 4-cyclohexanedimethanol, bisphenol-A etc.As the number-average molecular weight of PCDL, be preferably 300～5000, more preferably 500～3000.
Among the present invention; Constitutive molar ratio as the polycarbonate polyol of the constituent of polyurethane resin when whole polyisocyanates compositions of polyurethane resin are counted 100 moles of %, is preferably 3～100 moles of %; More preferably 5～50 moles of % further are preferably 6～20 moles of %.Under the low situation of aforementioned component mol ratio, can't obtain the effect of the durability that polycarbonate polyol produces sometimes.In addition, under the high situation of aforementioned component mol ratio, the initial stage adaptation reduces sometimes.
Polyisocyanates as the constituent of polyurethane resin of the present invention; Can enumerate the for example isomers class, 4 of toluene di-isocyanate(TDI); Aromatic series aliphatic diisocyanate class, IPDIs and 4 such as aromatic diisocyanate class, eylylene diisocyanate such as 4-methyl diphenylene diisocyanate; 4-dicyclohexyl methyl hydride diisocyanate, 1; Ester ring type diisocyanates, hexamethylene diisocyanates and 2 such as two (isocyanatomethyl) cyclohexanes of 3-; 2, aliphatic diisocyanate classes such as 4-trimethyl hexamethylene diisocyanate, or addition in advance such as single or a plurality of and trimethylolpropane forms with these compounds polyisocyanates.
As cahin extension agent; Can enumerate ethylene glycol, diethylene glycol (DEG), 1; 4-butanediol, neopentyl glycol and 1, thiodiglycol class or water such as alkamine, thiodiglycol such as two amines such as polyalcohols such as glycols such as 6-hexylene glycol, glycerine, trimethylolpropane and pentaerythrite, ethylenediamine, hexamethylene diamine and piperazine, monoethanolamine and diethanol amine.
Coating layer of the present invention preferably uses the coating fluid of water system, the online rubbing method setting of stating after the employing.Therefore, hope that polyurethane resin of the present invention is water-soluble.If the use water soluble polyurethane resin, then the compatibility with carbodiimide compound can increase, and the transparency can improve.Need to prove that so-called aforesaid " water-soluble " means for water or contain the aqueous solution dissolving less than the water miscible organic solvent of 50 quality %.
Water-soluble in order to give polyurethane resin, can in the molecule carbamate skeleton, sulfonic acid (salt) base or carboxylic acid (salt) base be imported (copolymerization).Sulfonic acid (salt) base is a highly acid, because its moisture pick-up properties, is difficult to keep moisture-proof sometimes, and it is comparatively suitable therefore to import weakly acidic carboxylic acid (salt) base.
For carboxylic acid (salt) base is imported polyurethane resin, for example, as polyol component, the polyol compound that dihydromethyl propionic acid, dimethylolpropionic acid etc. is had the carboxylic acid group imports as copolymer composition, forms agent with salt and neutralizes.As the concrete example of salt formation agent, can enumerate N-dialkyl group alkanolamine such as N-alkyl morpholine class, N-dimethylethanolamine, N-diethyl ethylene diamine such as trialkyl amines such as ammonia, trimethylamine, triethylamine, tri-isopropyl amine, Tri-n-Propylamine, tri-n-butylamine, N-methylmorpholine, N-ethylmorpholine.These can use separately, also can be with also using more than 2 kinds.
Water-soluble in order to give; Use has under the situation of polyol compound as copolymer composition of carboxylic acid (salt) base; The constitutive molar ratio of the polyol compound in the polyurethane resin with carboxylic acid (salt) base; When whole polyisocyanates compositions of polyurethane resin are counted 100 moles of %, be preferably 3～60 moles of %, more preferably 10～40 moles of %.Under the situation of aforementioned component mol ratio less than 3 moles of %, water dispersible becomes difficult sometimes.In addition, the aforementioned component mol ratio surpasses under the situation of 60 moles of %, and the remaining carbodiimide when forming owing to coating layer reduces, and therefore humidity resistance descends sometimes.
But, use under the situation of the polyurethane resin imported carboxylic acid as polyurethane resin as stated, sometimes in coating fluid with the carbodiimide radical reaction, the unreacted carbodiimide when coating layer forms reduces.Therefore, hope do not have carboxylic acid (salt) base in the coating layer basically.Therefore, water-soluble in order to give polyurethane resin, it is preferred embodiment of the present invention replacing carboxylate group and importing polyoxyalkylenes.Use as polyurethane resin under the situation of the polyurethane resin that has imported polyoxyalkylenes, do not have carboxyl in the coating layer basically.Therefore, unreacted carbodiimide is stably remaining, can bring into play more excellent humidity resistance.
As the polyoxyalkylenes that imports polyurethane resin, can enumerate polyoxyethylene groups, polyoxypropylene base, polytetramethylene glycol chain etc., these can use separately, also can be with also using more than 2 kinds.Wherein, can preferably use polyoxyethylene groups.
For polyoxyethylene groups is imported polyurethane resin; For example; With the hydroxyl with respect to single end-capped polyoxyethylene glycol, the NCO of vulcabond is after excessive ratio is carried out the urethane reaction, as required unreacted polyisocyanates to be removed can to make polyisocyanates and single end-capped polyoxyethylene glycol (with the alkoxyl ethylene glycol of the alkyl list end-capped of carbon number 1～20); Thereby obtain containing the monoisocyanates of polyoxyethylene chain; Next, make the monoisocyanates that contains polyoxyethylene chain and the vulcabond that obtain carry out allophanic acid esterification reaction, thereby obtain.
Water-soluble in order to give; Polyoxyethylene groups is imported under the situation of polyurethane resin; The constitutive molar ratio of the polyoxyethylene groups in the polyurethane resin is counted whole polyisocyanates compositions of polyurethane resin under the situation of 100 moles of %, is preferably 3 moles more than the %; More preferably 10 moles more than the %, further be preferably 20 moles more than the %.Under the situation of aforementioned component mol ratio less than 3 moles of %, water dispersible becomes difficult sometimes.
Only use under the situation of polyurethane resin as (a) composition, aforementioned polyurethane resin preferably contains in coating layer more than the 10 quality % below the 90 quality %.Especially, require under the situation of high adaptation as lens jacket, more preferably below the above 80 quality % of 20 quality %.Under the many situation of the content of polyurethane resin, hot and humid adaptation down reduces, under the opposite poor situation, and the reduction of the adaptation at initial stage.
Only use under the situation of aforementioned polyurethane resin as (a) composition, the following 0.5mmol/g that is limited to of the concentration of the carbodiimide in the coating layer is preferably 0.7mmol/g; 1.0mmol/g more preferably; On be limited to 3.5mmol/g, be preferably 3.3mmol/g, more preferably 3.0mmol/g.If not enough above-mentioned lower limit can't obtain the adaptation under sufficient high temperature, the high humidity sometimes.If surpass the above-mentioned upper limit, relatively the ratio of polycarbonate-based polyurethane resin diminishes, and adaptation, particularly initial stage adaptation reduce sometimes.
(mylar)
The mylar that uses among the present invention, preferably conduct is few with the carboxylic acid group of the reactive group of carbodiimide.More preferably, do not have the carboxylic acid group basically.Wherein what is called does not have the carboxylic acid group basically, is meant the carboxylic acid group of not containing beyond the terminal groups.As the method for stipulating the carboxylic acid group, can enumerate the mensuration of acid number, the so-called mylar that does not have the carboxylic acid group basically is that acid number is, more preferably below the 2KOHmg/g, further is preferably the mylar below the 1KOHmg/g below the 3KOHmg/g.
The number-average molecular weight of mylar is to be necessary more than 15000.Under the low situation of number-average molecular weight, because terminal carboxylic acid group increases, sometimes with the carbodiimide radical reaction.In addition, not only promote hydrolysis, the reparation that can't fully film can't obtain the adaptation under hot and humid, and also reduces with the adaptation of base material film.In addition, more preferably more than 20000, as long as can make, preferred number average molecular weight is higher for above-mentioned number-average molecular weight.But big if number-average molecular weight becomes, also the dissolubility in coating fluid reduces sometimes, and therefore above-mentioned number-average molecular weight is preferably below 60000.
Mylar; As sour composition; Can enumerate terephthalic acid (TPA), M-phthalic acid, phthalic acid, phthalic anhydride, 2; 6-naphthalenedicarboxylic acid, 1,4-cyclohexane cyclohexanedimethanodibasic, adipic acid, decanedioic acid, trimellitic acid, Pyromellitic Acid, dimeric dibasic acid, 5-sodiosulfoisophthalic acid, 4-sodium sulfo group naphthalene-2,7-dioctyl phthalate etc.As diol component, can enumerate ethylene glycol, propane diols, 1,4-butanediol, neopentyl glycol, diethylene glycol (DEG), 1,6-hexylene glycol, 1, the ethylene oxide adduct of 4-cyclohexanedimethanol, benzene dimethanol, bisphenol-A etc.Be provided with in the film of the present invention under the situation of the hard conating that mainly formed by acrylic resin etc., because the refractive index of coating layer and other layers is poor, the generation interference fringe becomes problem sometimes aspect visibility.Therefore, obtain the more naphthalenedicarboxylic acid of high index of refraction from improving the inhibition effect of humidity resistance, iris shape color, preferably containing as sour composition.
In addition, the inhibition aspect of the iris shape color when being provided with hard conating as the composition of mylar, preferably contains the dicarboxylic acids composition of following formula (1) and/or the diol component of following formula (2).The dicarboxylic acids composition of the following formula (1) in the mylar and/or the diol component of following formula (2) are preferred more than 10%, and be more preferably more than 15%, further preferred more than 20%.In addition, the dicarboxylic acids composition of the following formula (1) in the above-mentioned mylar and/or the diol component of following formula (2) are preferred below 70%, and be more preferably below 60%, further preferred below 50%.Surpass under the situation of the above-mentioned upper limit, filming sometimes exceedingly becomes soft, and humidity resistance reduces.Under the situation of not enough above-mentioned lower limit, the flexibility of mylar reduces sometimes, the excessive hardening of filming, and adaptation reduces.
(1) HOOC-(CH 2) n-COOH (in the formula, n is the integer of 4≤n≤10)
(2) HO-(CH 2) n-OH (in the formula, n is the integer of 4≤n≤10)
Mylar, can use for water, or water miscible organic solvent (aqueous solution that for example contains alcohol less than 50 quality %, alkyl cellosolve, ketone system, ether system) perhaps, organic solvent (for example toluene, ethyl acetate etc.) dissolving or the mylar that disperses.
Under the situation of mylar with the use of water system masking liquid form, use the mylar of water-soluble or water dispersible, for so water-solubleization or aqueous dispersionization, preferably make the compound that contains sulphonate-base, the compound copolymerization of carboxylate-containing base.For this reason; Except aforesaid dicarboxylic acids composition; In order to give the polyester water dispersible; Preferably in the scope of 1～10 mole of %, use 5-sulfoisophthalic acid or its alkali metal salt, can enumerate for example sulfo group terephthalic acid (TPA), 5-sulfoisophthalic acid, 4-sulfo group naphthalene M-phthalic acid-2,7-dicarboxylic acids and 5-(4-sulfophenoxy) M-phthalic acid or its alkali metal salt.
The number-average molecular weight that preferably makes mylar is more than 15000, and in order to have the glass transition temperature of the degree that suppresses adhesion, in mylar, imports branched structure.But many if branched structure becomes, acid number also tends to uprise.Therefore, in the mylar of application of the present invention, 1 molecule has the ternary mol ratio that 3 above carboxyls or 1 molecule have 3 hydroxyls and all is being preferably 5.0 moles below the % in the dicarboxylic acids compositions, more preferably 1.0 moles below the %.
Only use under the situation of mylar as (a) composition, aforementioned mylar preferably contains in coating layer more than the 10 quality % below the 85 quality %.Require under the situation of high adaptation, more preferably below the above 80 quality % of 20 quality %.Under the many situation of the content of mylar, hot and humid adaptation down reduces, under the opposite poor situation, with the adaptation reduction of base material film.
Only use under the situation of aforementioned mylar as (a) composition, the following 0.3mmol/g that is limited to of the concentration of the carbodiimide in the coating layer is preferably 0.5mmol/g; 0.8mmol/g more preferably; On be limited to 3.3mmol/g, be preferably 3.0mmol/g, more preferably 2.8mmol/g.If not enough above-mentioned lower limit can't obtain the adaptation under sufficient high temperature, the high humidity sometimes.If surpass the above-mentioned upper limit, relatively the ratio of mylar diminishes, and adaptation, particularly initial stage adaptation reduce sometimes.
(polyurethane resin and mylar)
In addition, among the present invention,,, can improve coated film hardness through useful life longevity excellent aforementioned polycarbonate-based polyurethane resin and aforementioned mylar as (a) composition, when adaptation is excellent, the anti-adhesive of also performance excellence.
Mylar, from the aspect of adaptation, the preferred glass transition temperature is low, but from the aspect of anti-adhesive, the preferred glass transition temperature is high.Therefore, the glass transition temperature of mylar is preferably 10～100 ℃, more preferably 30～70 ℃.If glass transition temperature surpasses 100 ℃ high like this, melt viscosity raises, and is difficult to obtain enough molecular weight, and therefore, adaptation reduces.If glass transition temperature surpasses 10 ℃ and low, the anti-adhesive of film reduces.
The number-average molecular weight that preferably makes mylar is more than 15000, and is above-mentioned scope in order to make glass transition temperature, in mylar, imports branched structure.But if branched structure increases, acid number also tends to uprise.Therefore, in the mylar of application of the present invention, 1 molecule has 3 above carboxyls or 1 molecule has the ternary mol ratio of 3 above hydroxyls, preferably is 5.0 moles below the % in whole dicarboxylic acids compositions, more preferably 1.0 moles below the %.
As (a) composition, use under the situation of aforementioned polyurethane resin and aforementioned mylar, contain in preferred each the comfortable coating layer of the concentration of polyurethane resin and mylar below the above 80 quality % of 10 quality %.Require under the situation of high adaptation, more preferably below the above 70 quality % of 20 quality %.Under the many situation of the content of polyurethane resin, hot and humid adaptation down reduces, on the contrary, under the poor situation, the reduction of the adaptation at initial stage.In addition, under the many situation of the amount of mylar, hot and humid adaptation down reduces, on the contrary, and under the poor situation, with the adaptation and the reduction of anti-adhesive of base material film.
As (a) composition; Use under the situation of aforementioned polyurethane resin and aforementioned mylar, the following 0.1mmol/g that is limited to of the concentration of the carbodiimide in the coating layer is preferably 0.2mmol/g; 0.4mmol/g more preferably; On be limited to 2.0mmol/g, be preferably 1.8mmol/g, more preferably 1.5mmol/g.If not enough above-mentioned lower limit can't obtain enough high temperature, the adaptation under the high humidity sometimes.If surpass the above-mentioned upper limit, relatively the ratio of polyurethane resin and mylar diminishes, and adaptation, particularly initial stage adaptation reduce sometimes.
Among the present invention, even the resin beyond aforementioned polyurethane resin and/or the aforementioned mylar also can contain in order to improve adaptation.For example, can enumerate acrylic resin, mylar etc.Be preferably carboxylic acid group's poor resin.More preferably, be the resin that does not contain the carboxylic acid group.Under carboxylic acid group's situation how,, reduce with the carbodiimide that reacts the hot and humid carboxylic acid group who produces by polyurethane resin down with the carbodiimide radical reaction.
(carbodiimide compound)
Among the present invention, must contain carbodiimide compound.As carbodiimide compound, can enumerate single carbodiimide compound, gather carbodiimide compound.
As single carbodiimide compound, can enumerate for example dicyclohexylcarbodiimide, DIC, dimethyl carbodiimide, diisobutyl carbodiimide, dioctyl carbodiimide, t− Butyl isopropyl carbodiimide, diphenyl carbodiimide, Er − T− Butyl carbodiimide, Er − β − Naphthyl carbodiimide etc.
As gathering carbodiimide compound, can use the compound that adopts known method manufacturing in the past.For example, can come the synthesizing isocyanate end to gather carbodiimide through the condensation reaction of following carbon dioxide removal of vulcabond, thereby make.
Vulcabond as the synthesis material that gathers carbodiimide compound; Can enumerate the for example isomers class, 4 of toluene di-isocyanate(TDI); Aromatic series aliphatic diisocyanate class, IPDIs and 4 such as aromatic diisocyanate class, eylylene diisocyanate such as 4-methyl diphenylene diisocyanate; 4-dicyclohexyl methyl hydride diisocyanate, 1; Ester ring type diisocyanates, hexamethylene diisocyanates and 2,2 such as two (isocyanatomethyl) cyclohexanes of 3-, aliphatic diisocyanate classes such as 4-trimethyl hexamethylene diisocyanate.From the problem of xanthochromia, optimization aromatic aliphatic diisocyanate class, ester ring type diisocyanates, aliphatic diisocyanate class.
In addition, above-mentioned vulcabond can use the compound of monoisocyanates etc. and terminal isocyanate reaction, and molecular Control is used in the suitable degree of polymerization.Control the monoisocyanates of its degree of polymerization as the end-capped that is used for to gather like this carbodiimide, can enumerate for example phenyl isocyanate, toluene diisocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanates etc.In addition, except these, as the end-capped agent, can use to have-the OH base ,-NH 2Base ,-the COOH base ,-SO 2The compound of H base.
The condensation reaction of following carbon dioxide removal of vulcabond is carried out in the presence of the carbodiimide catalyst.As catalyst, can enumerate for example 1− Ben Ji − 2− Lin Zahuanwuwan − 1− Oxide, 3− Jia Ji − 2− Lin Zahuanwuwan − 1− Oxide, 1− Yi Ji − 2− Lin Zahuanwuwan − 1− Oxide, 3− Jia Ji − 1− Ben Ji − 2− Lin Zahuanwuwan − 1− Oxide, these 3− Phospholane oxides such as phospholane isomers etc., from reactive aspect, preferred 3− Jia Ji − 1− Ben Ji − 2− Lin Zahuanwuwan − 1− Oxide.Need to prove that the use amount of above-mentioned catalyst can be catalytic amount.
Above-mentioned list or gather carbodiimide compound; Hope remains on uniform dispersity when in water paint, cooperating; Therefore; Preferred use suitable emulsifying agent to carry out emulsification processing and form emulsion and use, perhaps additional hydrophilic segment and in gathering the molecular structure of carbodiimide compound under the form of self-emulsifying thing or under the form of dissolved matter, be matched with coating.
The carbodiimide compound that uses among the present invention can be enumerated water dispersible, water-soluble.Because good with other the compatibility of water-soluble resin, improve the transparency, the cross-linking reaction efficient of coating layer, so the preferred water dissolubility.
As the degree of polymerization of gathering carbodiimide compound (n), preferred 2～10, more preferably 3～7.Under the little situation of the degree of polymerization, cross-linking reaction rate variation reduces with the adaptation of functional layer, and under the big situation, with the compatibility variation of resin, turbidity rises sometimes.
It is water-soluble for carbodiimide compound is become; After can gathering carbodiimide through the condensation reaction synthesizing isocyanate end with carbon dioxide removal of isocyanates; Further make to have the hydrophily position addition that has with reactive functional group of NCO, thereby make.
As the hydrophily position; Can enumerate the quaternary ammonium salt of (1) dialkyl amido alcohol, the quaternary ammonium salt of dialkyl aminoalkyl amine etc.; (2) have the alkylsulfonate etc. of at least 1 reactive hydroxyl, gathering (ethylene oxide), gather (propylene oxide), gather (ethylene oxide) and gathering the mixture of (propylene oxide) etc. of end-capped carried out with alkoxyl in (3).The recurring unit of ethylene oxide and/or propylene oxide is preferred 3～50, and more preferably 5～35.Under the little situation of recurring unit, with the compatibility variation of resin, turbidity rises, under the big situation, and hot and humid sometimes cementability reduction down.Carbodiimide compound has imported under the situation at above-mentioned hydrophily position, becomes (1) cationic, (2) anionic property, (3) nonionic.Wherein, preferably with other ionic irrelevant, the nonionic that can be compatible of water-soluble resin.In addition, also in order to improve humidity resistance, preferably needn't import the nonionic of ionic hydrophilic group.
In addition, the carbodiimide equivalent of the carbodiimide compound that uses among the present invention does not have special qualification, particularly, for example, is preferably below 1000, more preferably below 500, further is preferably below 300.Above-mentioned carbodiimide equivalent surpasses under the situation of the upper limit, insufficient manifest with base material film, functional layer in the interaction of contained carboxyl etc., can't obtain durability, resistance to water satisfactorily sometimes.Need to prove that above-mentioned carbodiimide equivalent is the formula weight of every 1mol carbodiimide.Therefore, the value of this carbodiimide equivalent is more little, and the amount of the carbodiimide of expression in the polymer is many more, be worth greatly more, representes that the amount of the carbodiimide in the polymer is few more.
Aforementioned carbodiimide compound preferably contains in coating layer more than the 5 quality % below the 90 quality %.More preferably, be below the above 70 quality % of 10 quality %.Under the many situation of the content of carbodiimide compound, reduce with the adaptation of functional layer, on the contrary, under the poor situation, hot and humid sometimes adaptation reduction down.
Among the present invention,, in coating layer, can contain crosslinking agent beyond the carbodiimide compound, or have the resin of crosslinking group in order to improve coating strength.As crosslinking agent, can enumerate urea system, epoxy system, melamine system, isocyanate-based 、 oxazoline system, silanol system etc.In addition, in order to promote cross-linking reaction, suitably use catalyst etc. as required.
Among the present invention, also can make and contain particle in the coating layer.Particle can be enumerated inorganic particulates such as (1) silica, kaolinite, talcum, precipitated calcium carbonate, powdered whiting, zeolite, aluminium oxide, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, titanium dioxide, zirconium dioxide, tin oxide, satin white, titanium are black, alumina silicate, diatomite, calcium silicates, aluminium hydroxide, halloysite, magnesium carbonate, magnesium hydroxide, and (2) acrylic acid series or metha crylic, vinyl chloride, vinylacetate system, nylon, styrene/acrylic system, phenylethylene/butadiene system, polystyrene/acrylic acid series, polystyrene/isoprene, polystyrene/isoprene, methyl methacrylate/butyl methacrylate are, melamine is, the organic filler of polycarbonate-based, urea system, epoxy system, polyurethane series, phenolic aldehyde system, diallyl phthalate system, polyester system etc.
The preferred average grain diameter of aforementioned particles is the particle of 1～500nm.Average grain diameter is not had special qualification, and the aspect from the transparency of keeping film is preferably 1～100nm.
Aforementioned particles can contain the different particle of average grain diameter more than 2 kinds.
Need to prove that above-mentioned average grain diameter can be used transmission electron microscope (TEM), take the cross sections of stacked film, be determined at the maximum diameter of the particle more than 10 that the cross section of coating layer exists, obtain as their mean value with 120,000 times of multiplying powers.In addition, can adopt the coulter counter method to obtain.
As the content of particle, below the above 20 quality % of preferred 0.5 quality %.Under few situation, can not obtain sufficient anti-adhesive.In addition, resistance to marring variation.Under many situation, the not only transparent variation of coating layer, and coating strength reduces.
In the coating layer, the levelability when being coated with in order to improve, the deaeration of coating fluid also can contain surfactant.Surfactant can be any surfactants such as cation system, anion system, nonionic system, but preferred silicon is, acetylenic glycol is or fluorine is a surfactant.Also preferably in the scope of not damaging with the degree of the adaptation of functional layer, for example, the scope with 0.005～0.5 quality % in coating fluid contains these surfactants.
Easy-adhesion polyester film of the present invention, preferred turbidity value is below 2.5%, more preferably below 2.0%, further is preferably below 1.5%.Such easy-adhesion thermoplastic resin film, become through carbodiimide compound contained in the coating layer that makes aforementioned record water-soluble, thereby can improve with the compatibility of other resins.
Other are functional in order to give coating layer, can in the scope of not damaging with the degree of the adaptation of functional layer, contain various additives.As aforementioned additive, can enumerate for example fluorescent dye, fluorescent whitening agent, plasticizer, ultra-violet absorber, pigment dispersing agent, foam inhibitor, antifoaming agent, anticorrisive agent, antistatic additive etc.
Among the present invention,, can enumerate the coating fluid that contains solvent, particle, resin is coated polyester film, carry out dry method as the method that coating layer is set on thermoplastic resin film.As solvent, can enumerate the mixed stocker of organic solvent, water or water such as toluene and water miscible organic solvent, preferably,, preferably make water separately or in water, mixed the product of water miscible organic solvent from the environmental problem aspect.
Range upon range of thermoplastic resin film of the present invention; In the one side at least of the coating layer of aforesaid thermoplastic resin film, range upon range of at least 1 layer the optical functional layer of from hard conating, light diffusion layer, prism-like lens jacket, electromagnetic wave absorbing layer, near infrared ray barrier layer, transparency conducting layer, selecting and obtaining.
Do not have special qualification for the material that uses in the aforementioned optical functional layer.
(manufacturing of easy-adhesion thermoplastic resin film)
For the manufacturing approach of easy-adhesion thermoplastic resin film of the present invention, be that example describes with PETG (below be abbreviated as PET) film, be not limited to this certainly.
The PET resin fully after the vacuum drying, is supplied with extruder, about 280 ℃ fusion PET resin is melt extruded to the rotation chill roll with sheet, apply method through static and make its cooling curing PET sheet material that do not stretched from the T die.The aforementioned PET of stretching sheet material can be that individual layer constitutes, and also can be to adopt the multilayer of coetrusion to constitute.In addition, be substantially free of inactive particle in the preferred PET resin.
With the not stretching PET sheet material that obtains, use the roller that is heated to 80～120 ℃ 2.5～5.0 times of longitudinal stretchings, obtain uniaxial tension PET film.And then, control the end of film with clip, import the hot blast district that is heated to 70～140 ℃, stretch 2.5～5.0 times at width.Then, import 160～240 ℃ heat-treatment zone, carry out 1～60 second heat treatment, accomplish crystalline orientation.
In the stage arbitrarily of this film manufacturing process, the PET film at least the one side be coated with coating fluid, form aforementioned coating layer.Even forming on the two sides of PET film, coating layer do not have special problem yet.The solid component concentration of the resin combination in the coating fluid is preferably 2～35 weight %, is preferably 4～15 weight % especially.
Be used for this coating fluid is coated the method for PET film, can use known arbitrary method.The roll-type rubbing method that for example reverses, intaglio plate roll-type rubbing method, roller be can enumerate and rubbing method, mold pressing rubbing method, roller brush method, spraying process, airblade coating method, the excellent rubbing method that winds the line, tubular type scraper plate method, dip coating, curtain formula rubbing method etc. licked.Can these methods perhaps be made up separately and be coated with.
Among the present invention, coating layer through aforementioned coating fluid is coated not stretch or uniaxial tension after the PET film, after the drying, stretching on the single shaft direction at least, next heat-treat and form.
Among the present invention, the thickness of the coating layer that finally obtains is preferably 20～350nm, and dried coating weight is preferably 0.02～0.5g/m 2If the coating weight of coating layer is less than 0.02g/m 2, exist hardly for the effect of cementability.On the other hand, if coating weight surpasses 0.5g/m 2, then turbidity increases.
The coating layer of the easy-adhesion thermoplastic resin film that obtains among the present invention has good cementability for hard conating, light diffusion layer, prism-like lens jacket, electromagnetic wave absorbing layer, near infrared ray barrier layer, transparency conducting layer.Through range upon range of these optical functional layers, thereby even the range upon range of thermoplastic resin film of optics that under the moisture-proof thermal environment, also can keep the initial stage function for a long time can be provided.In addition, beyond optical applications, also obtain good adhesive strength.Particularly, can enumerate photosensitive layer, diazonium photosensitive layer, delustring layer, magnetosphere, ink-jet China ink held layer, hard conating, with ultraviolet curable resin, heat reactive resin, printer's ink or UV China ink, dry lamination or extrude the thin layer that the vacuum evaporation, electron beam evaporation plating, sputter, ion plating, CVD, plasma polymerization etc. of adhesive, metal or inorganic matter or their oxide of lamination etc. obtain, organic barrier layer etc.
Embodiment
Next, use embodiment and comparative example to the detailed description of the invention, the present invention is not limited to following embodiment certainly.In addition, the evaluation method of using among the present invention is described below.
(1) intrinsic viscosity
According to JIS K 7367-5, use phenol (60 quality %) and 1,1,2, the mixed solvent of 2-tetrachloroethanes (40 quality %) is measured down at 30 ℃ as solvent.
(2) reduced viscosity
With respect to resin 0.1g, use phenol (60 quality %) and 1,1,2, the mixed solvent 25mL of 2-tetrachloroethanes (40 quality %) measures down at 30 ℃ as solvent.
(3) glass transition temperature
According to JIS K7121; Use differential scanning calorimetry (Seiko instrument system, DSC6200); Make resin sample 10mg in 25～300 ℃ temperature range with 20 ℃ of/minute intensifications, will begin temperature as glass transition temperature by the extrapolation glass transition that the DSC curve obtains.
(4) resin is formed
Resin dissolves in heavy chloroform, is used system nuclear magnetic resonance spectroscopy meter (NMR) Gemini of Varian Associates, Inc. (US) 611 Hansen Way, Palo Alto, California 94303, U.S.A. 200, carry out 1H-NMR analyzes, by its integration each mole % ratio of forming when confirming that whole isocyanate prepolymer compositions are counted 100 moles of %.
(5) number-average molecular weight
Resin 0.03g is dissolved among the oxolane 10ml; Use GPC-LALLS device low angle light light-scattering photometer LS-8000 (TOSOH Co., Ltd's system, tetrahydrofuran solvent, reference: polystyrene); Use 30 ℃ of column temperature, flow 1ml/ branch, chromatographic column (the clear and system shodex KF-802 of electrician society, 804,806), measure number-average molecular weight.
(6) acid number
The sample of 1g (solid constituent) is dissolved in chloroform or the dimethyl formamide of 30ml, as indicator,, obtains the amount (mg) of the necessary KOH of carboxyl of the every 1g sample of neutralization with the potassium hydroxide-ethanol solution titration of 0.1N with phenolphthalein.
(7) carbodiimide value
With the carbodiimide compound freeze drying, use 1H-NMR analyzes this compound, by from the absorption peak strength of carbodiimide, from other the absorption peak strength of monomer, calculates the carbodiimide value.
(8) the full light transmittance of easy-adhesion polyester film
The full light transmittance of the easy-adhesion polyester film that obtains uses nephelometer (Japanese electric look system, NDH2000) to measure according to JIS K 7105.
(9) turbidity of easy-adhesion polyester film
The turbidity of the easy-adhesion polyester film that obtains uses nephelometer (Japanese electric look system, NDH2000) to measure according to JIS K 7136.
(10) the carbodiimide concentration in the coating layer is quantitative
For the coating aspect of the film that obtains in embodiment and the comparative example, adopt total reflection to absorb infrared measure and measure, as contrast, obtain the carbodiimide concentration in the coating layer with the absorbance that obtains specifically from base material film.
That is, adopt the condition shown in following to absorb infrared measure with total reflection and measure, obtain infrared absorption spectroscopy, (infrared absorbency compares A to obtain ratio from the absorbance of carbodiimide and the absorbance of base material film (under the situation of PET film, being ethylene glycol) 2120/ A 1340).Need to prove, be at 2120 ± 10cm from the absorbance of carbodiimide -1The zone in have the value (A of height of the absworption peak of very big absorption 2120), be at 1340 ± 10cm from the absorbance of PET -1The zone in have the value (A of height of the absworption peak of very big absorption 1340).Baseline is the line of flank that connects the both sides of each very big absworption peak.
In addition, the thickness of coating layer is obtained by transmission electron microscope.The sample of stacked film is embedded in the visible-light curing type resin (the new EM society of Japan system, D-800), at room temperature is exposed to visible light and makes its curing.By the embedding block that obtains, use the ultra-thin section cutter that diamond cutter has been installed, make the ultra-thin section of the thickness of 70～100nm degree, dyeing is 30 minutes in the ruthenium tetroxide steam.And then after implementing the carbon vapor deposition, use transmission electron microscope (Jeol Ltd.'s system, TEM2010) pair cross-section to observe, and take pictures, measure the thickness of coating layer thus.Need to prove that shooting is in 10000～100000 times scope, suitably to set.
Compare A by the infrared absorbency that obtains 2120/ A 1340With the thickness of coating layer, use the calibration curve that makes by the known coating fluid of carbon-coated diimine concentration, the air-dry standard sample that forms in advance, obtain the carbodiimide concentration in the coating layer.
Need to prove; In the making of calibration curve; Make for coating that carbodiimide concentration is 0.5,1.4,2.7, the coating fluid (solvent: water/isopropyl alcohol=1/1 of 4.5mmol/g; Regulating and making solid component concentration with the combined amount of acrylic resin is 30 quality %) so that the thickness of dried coating layer is 50nm, 100nm, 200nm and the air-dry sample that forms, adopts total reflection to absorb infrared measure under the condition shown in following and measure infrared absorbency and compare A 2120/ A 1340, obtain You oxazolinyl concentration, coating layer thickness, infrared absorbency by the result who obtains and compare A 2120/ A 1340The following mathematical expression that these 3 variablees are formed is made into calibration curve.
(carbodiimide concentration)=A * (infrared absorbency compares A 2120/ A 1340)/(coating layer thickness)+B
(wherein, A, B serve as reasons and make the constant that the data that obtain are obtained through above-mentioned calibration curve)
(condition determination)
Device: the system FTS-60A/896 of Varian society
1 secondary reflection ATR annex: SPECTRA TECH corporate system Silver Gate
Optical crystal: Ge
Incidence angle: 45 °
Capacity of decomposition: 4cm -1
Integral number of times: 128 times
Need to prove, the thin thickness of coating layer, can't obtain under the situation of sufficient sensitivity, can the annex (for example ST Japan corporate system VeeMax) that the 1 secondary reflection annex that use replace with incidence angle bigger (65 degree) be measured.
(11) cementability
In the light-cured type acrylic resin aspect of the range upon range of polyester film that obtains, use stroke lattice device (Cutter guide) of clearance gap 2mm, form 100 latticed cut channels that connect light-cured type acrylic resin layer and arrive base material film.Next, with cellophane adhesive tape (ニ チ バ Application society system, No. 405; 24mm is wide) be pasted on latticed cut channel face, with the rubber friction so that its complete driving fit.Then; After the operation of carrying out vertically the cellophane adhesive tape being peeled off from the light-cured type acrylic resin aspect of range upon range of polyester film for 5 times; The number of the grid that visual calculating is peeled off from the light-cured type acrylic resin aspect of range upon range of polyester film is obtained the adaptation of light-cured type acrylic resin layer and base material film by following formula.Need to prove that the grid that part in the grid is peeled off also is calculated as the grid of peeling off, according to following criteria grade.
Adaptation (%)=(number of the grid that 1-peels off/100) * 100
◎: 100%, perhaps, the material damage of light-cured type acrylic resin layer
○：99～90％
△：89～70％
×：69～0％
(12) humidity resistance
With the range upon range of polyester film that obtains in hot and humid groove 80 ℃, the environment held of 95%RH 48 hours.Next, range upon range of polyester film is taken out, the often wet held of room temperature 12 hours.Then; Beyond the operation of carrying out vertically the cellophane adhesive tape being peeled off from the light-cured type acrylic resin aspect of range upon range of polyester film for 5 times; Adopt the adaptation of obtaining light-cured type acrylic resin layer and base material film with aforementioned (11) same method, according to following criteria grade.
◎: 100%, perhaps, the material damage of light-cured type acrylic resin layer
○：99～90％
△：89～70％
×：69～0％
(13) the interference spot property improved (iris shape color)
The range upon range of polyester film that obtains is cut out the area of 10cm (film width) * 15cm (film length direction), make sample film.Paste black glossy band (day eastern electrician's system, Vinyltape No21 at the opposing face of the hard conating of the sample film that obtains; Black).Above the face that is coated with firmly that makes this sample film is; As light source, seem the strongest position relation (be from the distance 40～60cm of light source, with respect to the vertical line of face 15～45 ° angle) with whites in 3 wavelength shapes daytimes (National パ Le Star Network, F.L 15EX-N 15W) from oblique upper visualization reflection.
With the result of visualization according to following criteria grade.Need to prove, observe with 5 observers that are proficient in this evaluation, with maximum grades as opinion rating.If 2 grades are under the situation of similar number, adopt the center of the grade that is divided into 3.
Zero: almost do not find iris shape color
△: few observation is to iris shape color
*: observe clearly iris shape color
(polymerization of mylar)
In the stainless steel autoclave that possesses agitator, thermometer and partial reflux formula cooler; Pack into dimethyl terephthalate (DMT) 194.2 mass parts, DMIP 184.5 mass parts, 5-sodiosulfoisophthalic acid dimethyl ester 14.8 mass parts, diethylene glycol (DEG) 233.5 mass parts, ethylene glycol 136.6 mass parts and tetra-n-butyl titanate 0.2 mass parts; From 160 ℃ to 220 ℃, with carrying out ester exchange reaction in 4 hours.Next, be warmed up to 255 ℃, after reaction system was slowly reduced pressure, reaction was 1 hour 30 minutes under the decompression of 30Pa, has obtained copolymer polyester resin (A-1).The copolymer polyester resin that obtains (A-1) is for faint yellow transparent.The reduced viscosity of the copolymer polyester resin that mensuration obtains (A-1) (reduce viscosity), the result is 0.70dl/g.The glass transition temperature that adopts DSC to obtain is 40 ℃.
Adopting uses the same method has obtained the copolymer polyester resin (A-2)～(A-7) of other composition.For these copolymer polyester resins, will adopt 1The composition that H-NMR measures (mole % ratio) and other characteristics are shown in table 1.
[table 1]
Figure BDA00001722371500231
(modulation of polyester water dispersion)
In the reactor that possesses agitator, thermometer and reflux, the mylar of packing into (A-1) 30 mass parts, ethylene glycol n-butyl ether 15 mass parts 110 ℃ of heating down, stir, with resin dissolves.After resin dissolves fully, under agitation at leisure water 55 mass parts are added in the polyester liquid.After the interpolation, under agitation liquid cools is arrived room temperature, make the milky polyester water dispersion (B-1) of solid constituent 30 quality %.Equally, replace mylar (A-1) and use mylar (A-2)～(A-7), make aqueous dispersion, process aqueous dispersion (B-2)～(B-7) respectively.
(polymerization of water-soluble carbodiimide compound)
In the flask that possesses thermometer, nitrogen ingress pipe, reflux cooler, dropping funel and agitator, drop into 3-methyl isophthalic acid-phenyl-2-phospholane-1-oxide 4 mass parts of tetramethylxylylene diisocyanate 200 mass parts, carbodiimide catalyst; Under blanket of nitrogen, 180 ℃ stirred 40 hours down, obtained the terminal durol dimethylene carbodiimide (degree of polymerization=5) of isocyanates.Next, the carbodiimide 94.5g, poly glycol monomethyl ether (molecular weight 220) 40.0g that obtain were reacted 24 hours down at 100 ℃.Under 50 ℃,, obtained the water-soluble carbodiimide compound (C-1) of the yellow transparent of solid constituent 40 quality % to wherein adding entry at leisure.The carbodiimide equivalent is 246.
(polymerization of water-soluble carbodiimide compound)
In the flask that possesses thermometer, nitrogen ingress pipe, reflux cooler, dropping funel and agitator, drop into 3-methyl isophthalic acid-phenyl-2-phospholane-1-oxide 4 mass parts of IPDI 200 mass parts, carbodiimide catalyst; Under blanket of nitrogen, 180 ℃ stirred 12 hours down, obtained the terminal isophorone carbodiimide (degree of polymerization=6) of isocyanates.Next, the carbodiimide 129.2g, poly glycol monomethyl ether (molecular weight 400) 80g that obtain were reacted 24 hours down at 100 ℃.Under 50 ℃,, obtained the water-soluble carbodiimide compound (C-2) of the yellow transparent of solid constituent 40 quality % to wherein adding entry at leisure.The carbodiimide equivalent is 349.
(polymerization of water-soluble carbodiimide compound)
In the flask that possesses thermometer, nitrogen ingress pipe, reflux cooler, dropping funel and agitator, drop into 4; 3-methyl isophthalic acid-the phenyl of 4-dicyclohexyl methyl hydride diisocyanate 200 mass parts, carbodiimide catalyst-2-phospholane-1-oxide 4 mass parts; Under blanket of nitrogen, in 180 ℃, stirred 10 hours; Obtained isocyanates end 4,4-dicyclohexyl methyl hydride (degree of polymerization=4).Next, the carbodiimide 113.6g, poly glycol monomethyl ether (molecular weight 400) 80g that obtain were reacted 24 hours.Under 50 ℃,, obtained the water-soluble carbodiimide compound (C-3) of the yellow transparent of solid constituent 40 quality % to wherein slowly adding entry.The carbodiimide equivalent is 484.
(polymerization of water dispersible carbodiimide compound)
In the flask that possesses thermometer, nitrogen ingress pipe, reflux cooler, dropping funel and agitator, drop into 3-methyl isophthalic acid-phenyl-2-phospholane-1-oxide 4 mass parts of tetramethylxylylene diisocyanate 200 mass parts, carbodiimide catalyst; Under blanket of nitrogen, 180 ℃ stirred 40 hours down, obtained the terminal durol dimethylene carbodiimide (degree of polymerization=10) of isocyanates.Next, the carbodiimide 169.7g, poly glycol monomethyl ether (molecular weight 400) 80g that obtain were reacted 24 hours.Under 50 ℃,, obtained the water dispersible carbodiimide compound (C-4) of solid constituent 40 quality % to wherein slowly adding entry.The carbodiimide equivalent is 250.
(be constituent, have the polymerization of the polyurethane resin of polyoxyethylene groups) with the polycarbonate polyol
In the reactor that possesses thermometer, nitrogen ingress pipe and agitator; The limit import the nitrogen limit pack into hexamethylene diisocyanate 627.1 mass parts, be heated to methoxy poly (ethylene glycol) 372.9 mass parts of 50 ℃ number-average molecular weight 1000,80 ℃ of reactions 6 hours down.Behind the NCO content that arrives regulation, with rotating thin film distiller (ス ミ ス formula) unreacted hexamethylene diisocyanate is removed, obtained containing the monoisocyanates (D) of polyoxyethylene groups.This number-average molecular weight that contains in the calculating of monoisocyanates (D) of polyoxyethylene chain is the 1168g/ mole.
Next, in the reactor that possesses thermometer, nitrogen ingress pipe, agitator, at room temperature the limit imports nitrogen limit diethanol amine 83.9 mass parts of packing into.Add monoisocyanates (D) 916.1 mass parts that contain polyoxyethylene chain while cooling off, reacted 3 hours down at 60 ℃.With the generation of infrared spectrum affirmation urea key, obtained containing the polyalcohol (D) of polyoxyethylene groups.
In the four-hole boiling flask that possesses backflow cooling tube, nitrogen ingress pipe, thermometer, agitator; Pack into as 1 of polyisocyanates; Two (methyl isocyanate) 53.69 mass parts of 3-cyclohexane, as PCDL 88.6 mass parts, neopentyl glycol 14.97 mass parts, above-mentioned polyalcohol (D) 52.87 mass parts, acetonitrile 60 mass parts, N-methyl pyrrolidone 30 mass parts that contain polyoxyethylene groups of the number-average molecular weight 2000 of hydrophobicity macromolecular polyol as organic solvent; Under blanket of nitrogen, reacting liquid temperature is adjusted to 75～78 ℃; Add the stannous octoate of 0.06 mass parts, be reacted to reactivity more than 99% with 7 hours as catalysts.Next, it is cooled to 30 ℃, has obtained the terminal prepolymer of NCO.Next, but in the reaction vessel of the homogeneous phase dispersion machine that possesses high-speed stirred, add water 450g, be adjusted to 25 ℃, the limit mixes the limit with 2000min-1 and adds the terminal prepolymer of NCO, carries out aqueous dispersion.Then, decompression is removed the part of acetonitrile and water down, thus the water soluble polyurethane resin (D-1) of modulation solid constituent 35%.
(is the polymerization of the polyurethane resin of constituent with the polycarbonate polyol)
In the four-hole boiling flask that possesses agitator, serpentine condenser, nitrogen ingress pipe, silica dehydrator pipe and thermometer, drop into 1; PCDL 112.70 mass parts of two (isocyanatomethyl) cyclohexane 72.96 mass parts of 3-, dihydromethyl propionic acid 12.60 mass parts, neopentyl glycol 11.74 mass parts, number-average molecular weight 2000 and as acetonitrile 85.00 mass parts, N-methyl pyrrolidone 5.00 mass parts of solvent; Under blanket of nitrogen, 75 ℃ stirred 3 hours down, confirm that reactant liquor has arrived the amine equivalent of regulation.Next, this reactant liquor cooled to 40 ℃ after, add triethylamine 9.03 mass parts, obtained polyurethane prepolymer D solution.Next, but in the reaction vessel of the homogeneous phase dispersion machine that possesses high-speed stirred, add water 450g, be adjusted to 25 ℃, the limit mixes with 2000min-1, and the limit is added the terminal prepolymer of NCO and carried out aqueous dispersion.Then, under reduced pressure the part of acetonitrile and water is removed, thus the water soluble polyurethane resin (D-2) of modulation solid constituent 35%.
Adopting uses the same method has obtained the water soluble polyurethane resin (D-3)～(D-4) of other composition.For these water soluble polyurethane resins, will adopt 1The composition that H-NMR measures (mole % ratio) and other characteristics are shown in table 2.
[table 2]
Embodiment 1
(1) modulation of coating fluid
Following paint is mixed, make coating fluid.The number-average molecular weight of mylar is 20000.
Figure BDA00001722371500262
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.07 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Surfactant 0.05 quality %
(silicon system, solid component concentration 100 quality %)
(2) manufacturing of easy-adhesion polyester film
As pleurodiaphragmatic in terspace material polymer, with intrinsic viscosity be 0.62dl/g and the PET resin granular material that is substantially free of particle under the decompression of 133Pa, 135 ℃ dry 6 hours down.Then, supply with extruder, under about 280 ℃, melt extrude slabbing, chilling solidifies its driving fit on the rotation cool metal roller of 20 ℃ of surface temperatures remaining on, and the PET sheet material has obtained not stretching.
This PET sheet material that do not stretch is heated to 100 ℃ with the roller group and the infrared heater that heat, stretches 3.5 times at length direction with roller group then, obtained uniaxial tension PET film with peripheral speed difference.
Next, aforementioned coating fluid is applied to the one side of PET film with the print roll coating method after, 80 ℃ dry 20 seconds down.Need to prove, regulate so that the dried coating weight of final (biaxial stretch-formed back) is 0.15g/m 2Then; On width, stretch 4.0 times under 120 ℃ with stenter, under the state that the length of the width of film is fixing, 230 ℃ of heating 0.5 second down; And then under 230 ℃, carry out the relaxation processes of 10 seconds 3% width, obtained the easy-adhesion polyester film of thick 100 μ m.
Evaluation result is shown in table 3.
(3) manufacturing of range upon range of polyester film
In the coating aspect of aforesaid easy-adhesion polyester film, use #10 winds the line the excellent hard conating formation that is coated with following composition with coating fluid (C-1), and drying is 1 minute under 70 ℃, and solvent is removed.Next, for the film that has been coated with hard conating, use high-pressure mercury light irradiation 300mJ/cm 2Ultraviolet ray, obtained having the range upon range of polyester film of the hard conating of thickness 5 μ m.
Hard conating forms uses coating fluid
MEK 39.00 quality %
Toluene 26.00 quality %
Dipentaerythritol acrylate 22.83 quality %
(Xin Zhong village chemistry system A-DPH)
Polyethyleneglycol diacrylate 11.17 quality %
(Xin Zhong village chemistry system A-400)
Photoepolymerizationinitiater initiater 1.00 quality %
(Ciba corporate system Irgacure 184)
Comparative example 1
Except the polyester water dispersion (B-6) that polyester water dispersion is become molecular weight 8000, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Comparative example 2
Except the polyester water dispersion (B-7) that polyester water dispersion is become acid number 50KOHmg/g, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Comparative example 3
Except water-soluble carbodiimide compound (C-1) being become epoxide (the system Denacol EX-521 of Nagase ChemX society solid component concentration 100%), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Comparative example 4
Except water-soluble carbodiimide compound (C-1) being become melamine compound (the system ベ of DIC society Star カ ミ Application M-3 solid component concentration 60%), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Embodiment 2
Except coating fluid being become the following coating fluid, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Figure BDA00001722371500281
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.07 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Surfactant 0.05 quality %
(silicon system, solid component concentration 100 quality %)
Embodiment 3
Except coating fluid being become the following coating fluid, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Figure BDA00001722371500291
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.07 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Surfactant 0.05 quality %
(silicon system, solid component concentration 100 quality %)
Embodiment 4
Except coating fluid being become the following coating fluid, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Figure BDA00001722371500292
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.07 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Surfactant 0.05 quality %
(silicon system, solid component concentration 100 quality %)
Embodiment 5
Except water-soluble carbodiimide compound (C-1) is become the water-soluble carbodiimide compound (C-2), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Embodiment 6
Except water-soluble carbodiimide compound (C-1) is become the water-soluble carbodiimide compound (C-3), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Embodiment 7
Except the polyester water dispersion (B-2) that polyester water dispersion is become molecular weight 15000, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Embodiment 8
Except the polyester water dispersion (B-3) that polyester water dispersion is become molecular weight 23000, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Embodiment 9
Except the polyester water dispersion (B-4) that polyester water dispersion is become molecular weight 46000, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 1.
Embodiment 10
The polyester water dispersion (B-5) that polyester water dispersion is become molecular weight 50000 has likewise obtained easy-adhesion polyester film and range upon range of polyester film with embodiment 1 in addition.
Embodiment 11
Water-soluble carbodiimide compound (C-1) is become water dispersible carbodiimide compound (C-4) in addition, likewise obtained easy-adhesion polyester film and range upon range of polyester film with embodiment 1.
[table 3]
Figure BDA00001722371500311
Embodiment 12
(1) modulation of coating fluid
Following paint is mixed, make coating fluid.
Figure BDA00001722371500321
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.07 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Surfactant 0.05 quality %
(silicon system, solid component concentration 100 quality %)
(2) manufacturing of easy-adhesion polyester film
As pleurodiaphragmatic in terspace material polymer, with intrinsic viscosity be 0.62dl/g and the PET resin granular material that is substantially free of particle under the decompression of 133Pa, 135 ℃ dry 6 hours down.Then, supply with extruder, under about 280 ℃, melt extrude slabbing, remaining on chilling on the rotation cool metal roller of 20 ℃ of surface temperatures, its driving fit is solidified, the PET sheet material has obtained not stretching.
This PET sheet material that do not stretch is heated to 100 ℃ with the roller group and the infrared heater that heat, stretches 3.5 times at length direction with roller group then, obtained uniaxial tension PET film with peripheral speed difference.
Next, after the employing rolling method was applied to the one side of PET film with aforementioned coating fluid, drying was 20 seconds under 80 ℃.Need to prove, adjust so that the dried coating weight of final (biaxial stretch-formed back) is 0.15g/m 2Then; On width, stretch 4.0 times under 120 ℃ with stenter; Under the state that the length of the width of film is fixing; 230 ℃ of down heating 0.5 second, under 230 ℃, carry out the relaxation processes of 10 seconds 3% width again, obtained the easy-adhesion thermoplastic resin film of thick 100 μ m.
Evaluation result is shown in table 4.
Comparative example 5
Except polyurethane resin being become with the PEPA is the polyurethane resin (D-5) of constituent, has likewise obtained easy-adhesion polyester film and range upon range of polyester film with embodiment 12.
Comparative example 6
Except polyurethane resin being become with the PPG is the polyurethane resin (D-6) of constituent, has likewise obtained easy-adhesion polyester film and range upon range of polyester film with embodiment 12.
Comparative example 7
Except water-soluble carbodiimide compound (C-1) being become epoxide (Nagase ChemteX corporate system Denacol EX-521 solid component concentration 100%), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 12.
Comparative example 8
Except water-soluble carbodiimide compound (C-1) being become melamine compound (the system ベ of DIC society Star カ ミ M-3 solid component concentration 60%), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 12.
Embodiment 13
Except coating fluid being become the following coating fluid, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 12.
Figure BDA00001722371500331
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.07 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Surfactant 0.05 quality %
(silicon system, solid component concentration 100 quality %)
Embodiment 14
Except coating fluid being become the following coating fluid, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 12.
Figure BDA00001722371500332
Figure BDA00001722371500341
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.07 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Surfactant 0.05 quality %
(silicon system, solid component concentration 100 quality %)
Embodiment 15
Except coating fluid being become the following coating fluid, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 12.
Figure BDA00001722371500342
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.07 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Surfactant 0.05 quality %
(silicon system, solid component concentration 100 quality %)
Embodiment 16
Except water-soluble carbodiimide compound (C-1) is become the water-soluble carbodiimide compound (C-2), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 12.
Embodiment 17
Except water-soluble carbodiimide compound (C-1) is become the water-soluble carbodiimide compound (C-3), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 12.
Embodiment 18
Except polyurethane resin (D-1) is become the polyurethane resin (D-2), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 12.
Embodiment 19
Except polyurethane resin (D-1) is become the polyurethane resin (D-3), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 12.
Embodiment 20
Except polyurethane resin (D-1) is become the polyurethane resin (D-4), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 12.
Embodiment 21
Except water-soluble carbodiimide compound (C-1) is become the water dispersible carbodiimide compound (C-4), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 12.
[table 4]
Figure BDA00001722371500361
Embodiment 22
(1) modulation of coating fluid
Mix following paint, make coating fluid.
Figure BDA00001722371500371
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.54 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
(2) manufacturing of easy-adhesion polyester film
As pleurodiaphragmatic in terspace material polymer, with intrinsic viscosity be 0.62dl/g and the PET resin granular material that is substantially free of particle under the decompression of 133Pa, 135 ℃ dry 6 hours down.Then, supply with extruder, under about 280 ℃, melt extrude slabbing, remaining on chilling on the rotation cool metal roller of 20 ℃ of surface temperatures, its driving fit is solidified, the PET sheet material has obtained not stretching.
This PET sheet material that do not stretch is heated to 100 ℃ with the roller group and the infrared heater that heat, stretches 3.5 times at length direction with roller group then, obtained uniaxial tension PET film with peripheral speed difference.
Next, after the employing rolling method was applied to the one side of PET film with aforementioned coating fluid, drying was 20 seconds under 80 ℃.Need to prove, adjust so that the dried coating weight of final (biaxial stretch-formed back) is 0.15g/m 2Then; On width, stretch 4.0 times under 120 ℃ with stenter, under the state that the length of the width of film is fixing, 230 ℃ of heating 0.5 second down; Under 230 ℃, carry out the relaxation processes of 10 seconds 3% width again, obtained the easy-adhesion polyester film of thick 100 μ m.
Evaluation result is shown in table 5.
(3) manufacturing of range upon range of polyester film
On the SUS of the thick 1mm that keeps clean plate (SUS304); Place the following light-cured type acrylic acid series coating fluid of about 5g; With the coating aspect and the ground connection coincidence mutually of light-cured type acrylic acid series coating fluid of film sample, on the film sample, use the hand loading rubber rollers of wide 10cm, diameter 4cm to carry out crimping so that the expansion of light-cured type acrylic acid series coating fluid.Next, from the face side, use high-pressure mercury light irradiation 800mJ/cm 2Ultraviolet ray, the light-cured type acrylic resin is solidified.The film sample that will have the light-cured type acrylic resin layer of thick 20 μ m from the SUS plate is peeled off, and has obtained range upon range of polyester film.
Light-cured type acrylic acid series coating fluid
Light-cured type acrylic resin 60.00 quality %
(Xin Zhong village chemistry system 4G)
Light-cured type acrylic resin 20.00 quality %
(Xin Zhong village chemistry system A-TMMT)
Light-cured type acrylic resin 10.00 quality %
(Xin Zhong village chemistry system A-BPE-4)
Light-cured type acrylic resin 8.00 quality %
(Xin Zhong village chemistry system U-6HA)
Photoepolymerizationinitiater initiater 2.00 quality %
(Ciba corporate system Irgacure 184)
Embodiment 23
Except the polyester water dispersion (B-1) that polyester water dispersion is become molecular weight 20000, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 22.
Embodiment 24
Except the polyester water dispersion (B-3) that polyester water dispersion is become molecular weight 23000, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 22.
Embodiment 25
Except coating fluid being become the following coating fluid, likewise obtain easy-adhesion polyester film and range upon range of polyester film with embodiment 22.
Figure BDA00001722371500381
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.54 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Embodiment 26
Except coating fluid being become the following coating fluid, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 22.
Figure BDA00001722371500392
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.54 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Embodiment 27
Except coating fluid being become the following coating fluid, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 22.
Figure BDA00001722371500393
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.54 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Embodiment 28
Except coating fluid being become the following coating fluid, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 22.
Figure BDA00001722371500401
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.54 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Embodiment 29
Except coating fluid being become the following coating fluid, easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 22.
Figure BDA00001722371500402
(Ludox of average grain diameter 40nm, solid component concentration 40 quality %)
Particle 0.54 quality %
(Ludox of average grain diameter 450nm, solid component concentration 40 quality %)
Embodiment 30
Except water-soluble carbodiimide compound (C-1) is become the water-soluble carbodiimide compound (C-3), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 22.
Embodiment 31
Except water-soluble carbodiimide compound (C-1) is become the water dispersible carbodiimide compound (C-4), easy-adhesion polyester film and range upon range of polyester film have likewise been obtained with embodiment 22.
[table 5]
Figure BDA00001722371500411
Utilize possibility on the industry
Easy bonded polyester film of the present invention; Because with the adaptation of optical functional layer and hot and humid following adaptation (humidity resistance) excellence, so be suitable as the base material film of optical functional films such as being mainly used in antireflection film display etc., that used hard coat film and this film, light diffusing sheet, prism-like lens, near infrared ray barrier film, transparent and electrically conductive film, antiglare film.

Claims (9)

1. an easy-adhesion thermoplastic resin film is the easy-adhesion thermoplastic resin film that coating layer is arranged at least one mask of base material film, and said coating layer contains:
(a) with the polycarbonate polyol be polyurethane resin and/or the number-average molecular weight of constituent more than 15000 and do not have carboxylic acid group's mylar basically,
(b) carbodiimide compound.
2. easy-adhesion thermoplastic resin film as claimed in claim 1, wherein, said polyurethane resin has polyoxyalkylenes.
3. easy-adhesion thermoplastic resin film as claimed in claim 1, wherein, said mylar contains the diol component shown in dicarboxylic acids composition shown in the following formula (1) and/or the following formula (2):
(1) HOOC-(CH 2) n-COOH (in the formula, n is the integer of 4≤n≤10)
(2) HO-(CH 2) n-OH (in the formula, n is the integer of 4≤n≤10).
4. easy-adhesion thermoplastic resin film as claimed in claim 1, wherein, said mylar contains naphthalenedicarboxylic acid as sour composition.
5. easy-adhesion thermoplastic resin film as claimed in claim 1; Wherein, Said coating layer will be with the polycarbonate polyol polyurethane resin and the carbodiimide compound of constituent as principal component, in said coating layer, contain the carbodiimide of 0.5～3.5mmol/g.
6. easy-adhesion thermoplastic resin film as claimed in claim 1; Wherein, Said coating layer with number-average molecular weight more than 15000 and the mylar and the carbodiimide compound that do not have the carboxylic acid group basically be principal component, in coating layer, contain the carbodiimide of 0.3～3.3mmol/g.
7. easy-adhesion thermoplastic resin film as claimed in claim 1; Wherein, Said coating layer will be with the polycarbonate polyol polyurethane resin, number-average molecular weight of constituent more than 15000 and the mylar and the carbodiimide compound that do not have the carboxylic acid group basically as principal component, in coating layer, contain the carbodiimide of 0.1～2.0mmol/g.
8. easy-adhesion thermoplastic resin film as claimed in claim 1, wherein, said carbodiimide compound is water-soluble, turbidity is below 2.5%.
9. range upon range of thermoplastic resin film, its at least 1 one functional layer of from hard conating, light diffusion layer, prism-like lens jacket, electromagnetic wave absorbing layer, near infrared ray barrier layer, transparency conducting layer, selecting through the said coating layer laminated of each the described easy-adhesion thermoplastic resin film in claim 1～8 forms.
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