CN102648094B - Highly adhesive thermoplastic resin film - Google Patents

Highly adhesive thermoplastic resin film Download PDF

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Publication number
CN102648094B
CN102648094B CN201080054922.0A CN201080054922A CN102648094B CN 102648094 B CN102648094 B CN 102648094B CN 201080054922 A CN201080054922 A CN 201080054922A CN 102648094 B CN102648094 B CN 102648094B
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China
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film
coating layer
carbodiimide
easy
thermoplastic resin
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CN102648094A (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
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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
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    • 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
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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
    • C08G18/08—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
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    • 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
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    • 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
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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
    • C08G18/28—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
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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
    • C08G18/703—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
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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
    • C08G18/75—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
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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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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    • 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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    • 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
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    • 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
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C09D175/06—Polyurethanes from polyesters
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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
    • 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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    • 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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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

Easy-adhesion thermoplastic resin film
Technical field
The present invention relates to the easy-adhesion thermoplastic resin film of adaptation and humidity resistance excellence.In detail, relate to as be mainly used in display etc., easy-adhesion thermoplastic resin film that the base material of the functional membrane 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 is applicable to.
Background technology
Usually, as the base material of the functional membrane that the component of liquid crystal display (LCD) uses, employ the transparent thermoplastic resin film that PETG (PET), acrylic resin, Merlon (PC), triacetyl cellulose (TAC), polyolefin etc. are formed.
When using the base material of aforesaid thermoplastic resin film as various functional membrane, the stacked functional layer meeting various uses.Such as; for liquid crystal display (LCD), can enumerate the diaphragm (hard conating) preventing the damage on surface, the anti-reflection layer (AR layer) mirrored preventing outer light, for the light harvesting of light, diffusion layers of prisms, improve the functional layer such as light diffusion layer of brightness.In such base material, especially, polyester film is due to the transparency, dimensional stability, good chemical resistance, and price comparison is low, and the base material therefore as various functional membrane uses widely.
Usually, when the such Biaxially oriented thermoplastic film of double axial orientated polyester film, Biaxially orientated polyamide film, due to crystalline orientation to heavens, therefore there is the shortcoming be short of with the adaptation of various coating, adhesive, ink etc. in film surface.Therefore, the method adopting various method imparting easy-adhesion at Biaxially oriented thermoplastic surface resin film is proposed so far.
Such as, generally the surface of the known thermoplastic resin film at base material arranges the coating layer being main composition composition with various resins such as polyester, acrylic resin, polyurethane, acrylic resin grafted polyesters, thus gives the method for base material film easy-adhesion.In this rubbing method, industrially implement on the thermoplastic resin film before crystalline orientation completes, by the solution containing aforementioned resin or with decentralized medium by the water-based coating solution of the dispersion of resin dispersion in base material film, after drying, at least stretch on single shaft direction, following enforcement heat treatment, completes the method (so-called online rubbing method) of the orientation of thermoplastic resin film; After the manufacture of thermoplastic resin film, after this film is coated with the coating fluid of water system or solvent system, carry out dry method (so-called off-line rubbing method).
The displays such as LCD, PDP, using hard coat film as the portable equipment etc. of component, no matter within doors, outside room, use in various environment.Especially, for portable equipment, requirement sometimes can tolerate the humidity resistance in bathroom, high temperature and humidity area etc.For the optical functional film used in such purposes, require the high adhesion that splitting does not occur under hot and humid yet.Therefore, in following patent document, disclosing by adding crosslinking agent in coating fluid, when adopting the coating layer of online rubbing method to be formed, in coating layer resin, forming cross-linked structure, thus impart the easy-adhesion thermoplastic resin film of humidity resistance.
Patent document 1: Japanese Unexamined Patent Publication 2000-141574 publication
Patent document 2: Japan Patent No. 3900191 publication
Patent document 3: Japan Patent No. 3737738 publication
Patent document 4: Japanese Unexamined Patent Publication 2007-253512 publication
Patent document 5: Japanese Unexamined Patent Publication 2000-355086 publication
Patent document 6: Japan Patent No. 2544792 publication
Summary of the invention
The problem that invention will solve
In order to alleviate earth environment load, having in family's electrical article of display etc., expecting the long lifetime on existing basis.Therefore, as in the functional membrane that component uses, also think and also keep adaptation to be necessary for a long time under hot and humid.But easy-adhesion film disclosed in above-mentioned patent document, although the adaptation that initial display is good, in the Long-Time Service under hot and humid, the reduction of dhering strength is inevitable.Due to the reduction of such adaptation, existing cannot the problem of long term maintenance initial performance.
The present invention in view of above-mentioned problem, object be to provide cause hardly thought in the past inevitable hot and humid under coating layer deterioration, namely hot and humid under the easy-adhesion thermoplastic resin film of reduction of adaptation.
It should be noted that, in the present invention said hot and humid under adaptation, after meaning stacked light-cured type acrylic resin layer, be positioned over 80 DEG C, 95%RH, under the environment of 48 hours, use stroke lattice device (Cutter guide) of clearance gap 2mm, form through light-cured type acrylic resin layer in light-cured type acrylic resin aspect and arrive 100 latticed cut channels of base material film, next, by cellophane adhesive tape joining in latticed cut channel face, with rubber friction, make it completely closely sealed, adaptation when 5 times peeled off fiercely for same position, it is the evaluation method adopting the general JISK5600-5-6 used to record, adaptation under strict criterion, problem of the present invention is, so hot and humid under adaptation display to be equal to the adaptation shown in the initial stage or adaptation more than it.
For solving the means of problem
The present inventor conducts in-depth research to solve above-mentioned problem, found that by using the coating layer comprising specific polyurethane resin and/or specific mylar and carbodiimide compound, realize hot and humid lower adaptation and improve such fact of overturning technology general knowledge in the past, thus complete the present invention.As recorded like that in above-mentioned patent document, for technology general knowledge so far, adaptation in order to improve coating layer can be thought, wishes and crosslinking agent with have can with the mixed with resin of the functional group of its reaction, form cross-linked structure to heavens when coating layer is formed.But, present invention finds and substantially do not have and the polyurethane resin of this functional group of carboxylic acid group of carbodiimide radical reaction and/or mylar by using, make carbodiimide remaining in coating layer substantially not have cross-linked structure or to make the degree of cross linking become low state, even if can realize also maintaining the such fact in contrast to the prior art of high adhesion under hot and humid, thus complete the present invention.
Aforesaid problem can be realized by following solution.
(1) a kind of easy-adhesion thermoplastic resin film, be the easy-adhesion thermoplastic resin film having coating layer at least one mask of base material film, aforementioned coating layer contains polyurethane resin and/or number-average molecular weight more than 15000 that (a) take polycarbonate polyol as constituent and does not substantially have mylar and (b) carbodiimide compound of carboxylic acid group.
(2) above-mentioned easy-adhesion thermoplastic resin film, wherein, aforementioned polyurethane resin has polyoxyalkylenes.
(3) above-mentioned easy-adhesion thermoplastic resin film, wherein, previous polyesters resin comprises the dicarboxylic acid component shown in following formula (1) and/or the diol component shown in following formula (2).
(1) HOOC-(CH 2) n-COOH (in formula, n is the integer of 4≤n≤10)
(2) HO-(CH 2) n-OH (in formula, n is the integer of 4≤n≤10)
(4) above-mentioned easy-adhesion thermoplastic resin film, wherein, previous polyesters resin comprises naphthalenedicarboxylic acid as sour composition.
(5) above-mentioned easy-adhesion thermoplastic resin film, wherein, aforementioned coating layer using with polycarbonate polyol be the polyurethane resin of constituent and carbodiimide compound as principal component, comprise the carbodiimide of 0.5 ~ 3.5mmol/g in aforementioned coating layer.
(6) above-mentioned easy-adhesion thermoplastic resin film, wherein, aforementioned coating layer is with number-average molecular weight more than 15000 and substantially do not have the mylar of carboxylic acid group and carbodiimide compound is principal component, containing the carbodiimide of 0.3 ~ 3.3mmol/g in coating layer.
(7) above-mentioned easy-adhesion thermoplastic resin film, wherein, aforementioned coating layer using take polycarbonate polyol as the polyurethane resin of constituent, number-average molecular weight more than 15000 and not there is the mylar of carboxylic acid group and carbodiimide compound substantially as principal component, containing the carbodiimide of 0.1 ~ 2.0mmol/g in coating layer.
(8) above-mentioned easy-adhesion polyester film, wherein, aforementioned carbodiimide compound is water-soluble, and turbidity is less than 2.5%.
(9) laminating thermoplastic's resin molding, it is formed by the stacked functional layer of at least 1 layer selected from hard conating, light diffusion layer, prism-like lens jacket, electromagnetic wave absorbing layer, near infrared ray barrier layer, transparency conducting layer on the aforementioned coating layer of above-mentioned easy-adhesion thermoplastic resin film.
The effect of invention
First effect of easy bonding thermoplastic resin film of the present invention is, excellent with the adaptation (humidity resistance) of optical functional layer under hot and humid.Therefore, as preferred embodiment, the adaptation in above-mentioned high temperature, high humidity treatment and initial adaptation are equal or improve.As preferred embodiment of the present invention, when easy bonding polyester film of the present invention is used as the base material of lens sheet, good with the adaptation of lens jacket under hot and humid.
In addition, in preferred mode of the present invention, except the first effect, even if when stacked hard conating, also can suppress interference of light striped, visibility is excellent.
In addition, in preferred mode of the present invention, except the first effect, resistance to adhesive is excellent.
Detailed description of the invention
(thermoplastic resin film)
Form the thermoplastic resin as the thermoplastic resin film of base material use in the present invention, polyethylene can be used, the vistanexes such as polypropylene, nylon 6, the polyamides such as nylon66 fiber, PETG, polybutylene terephthalate (PBT), poly-2, 6-(ethylene naphthalate), poly terephthalic acid methylene ester, and as copolymer composition by such as diethylene glycol (DEG), neopentyl glycol, the diol components such as PAG and adipic acid, decanedioic acid, phthalic acid, M-phthalic acid, 2, the mylar etc. of the copolymerization such as dicarboxylic acid component such as 6-naphthalenedicarboxylic acid.Wherein, from mechanical strength, chemical-resistant aspect, preferred polyester resin.
The mylar preferably used in the present invention, PETG, polybutylene terephthalate (PBT), poly-2 can be used, 6-(ethylene naphthalate), poly terephthalic acid methylene ester and as copolymer composition by diol components such as such as diethylene glycol (DEG), neopentyl glycol, PAGs, with the mylar etc. of the copolymerization such as dicarboxylic acid component such as adipic acid, decanedioic acid, phthalic acid, M-phthalic acid, NDA.
The mylar preferably used in the present invention, mainly using PETG, PTT, polybutylene terephthalate (PBT), at least a kind of PEN as constituent.In these mylar, from the balance of physical property and cost, most preferably PETG.In addition, these polyester films, by biaxial stretch-formed, can improve chemical-resistant, heat resistance, mechanical strength etc.
In addition, aforesaid biaxially oriented polyester film can be individual layer, also can be multilayer.In addition, as long as produce in the scope of effect of the present invention, in these each layers, can make as required in mylar containing various additive.As additive, such as antioxidant, photostabilizer, anti-gel agent, organic wetting agent, antistatic additive, ultra-violet absorber, surfactant etc. can be enumerated.
In addition, in order to improve the wearing characters such as treatability, mar proof, scratch resistance such as the sliding of film, windability, resistance to adhesive, sometimes make in polyester film containing inactive particle.But when base material film for optics component, require the transparency maintaining height, treatability is excellent simultaneously.Particularly, when the base material film as optics component uses, the full light transmittance of preferred easy-adhesion polyester film is more than 85%, more preferably more than 87%, further preferably more than 88%, further preferably more than 89%, particularly preferably more than 90%.
In addition, in order to high vividness, the content of the inactive particle in preferred substrates film is the least possible.Therefore, preferably become and only make the multilayer that particle is contained on the top layer of film form, or make to be substantially free of particle in film and only make in coating layer containing particulate.
Especially, from the aspect of the transparency, when making to be substantially free of inactive particle in polyester film, in order to improve the treatability of film, also preferably making to contain inorganic and/or heat resistance polymer particles in water system coating fluid, being formed at painting layer surface concavo-convex.
It should be noted that, so-called " being substantially free of inactive particle ", such as, when being inorganic particulate, when adopting x-ray fluorescence analysis to carry out quantitative analysis to the element from particle, mean the content becoming below below 50ppm, preferably below 10ppm, most preferably detectable limit.This is because, even if energetically particle is not added in base material film, sometimes peel off from the dirt of the production line in the manufacturing process of the pollutant component of alien material, material resin or film or device attachment and be mixed in film.
In addition, from the aspect taking into account high transparent and treatability simultaneously, only in top layer, adding inactive particle is also preferred mode.Such as, when making 3 layers of formation, preferably in outermost layer (when A layer/B layer/A layer A layer), contain particle, in central core (B layer), be substantially free of particle.
Kind and the content of particle contained in outermost layer can be inorganic particulates, also can be organic filler, be not particularly limited, can illustrate the metal oxides such as silica, titanium dioxide, talcum, kaolinite, calcium carbonate, calcium phosphate, barium sulfate etc. is inactive inorganic particulate for polyester.These inactive inorganic particulates, all can be used alone one, and also two or more may be used.
Aforesaid particle, preferred average grain diameter is 0.1 ~ 3.5 μm.If average grain diameter is less than lower limit, sometimes sufficient treatability cannot be obtained.If exceed the upper limit, the transparency reduces sometimes.The content of outermost inorganic particulate, relative to the outermost polyester of formation, is preferably 0.01 ~ 0.20 quality %.If not enough lower limit, sufficient treatability cannot be obtained.If exceed the upper limit, the transparency reduces.
In addition, when requiring reflectivity, highly concealed type, can be used in base material film and add empty visualization reagent and the high white films of hole containing ratio.In addition, for the purposes requiring mouldability, mylar can be used as to add copolymer composition and impart the molding film of mouldability.
The thickness of the base material film used in the present invention, there is no particular restriction, at random can determine in the scope of 30 ~ 500 μm according to the specification used.The upper limit of the thickness of base material film, is particularly preferably 250 μm by preferably 350 μm.On the other hand, the lower limit of thickness preferably 50 μm, is more preferably 75 μm, is particularly preferably 100 μm.If thickness deficiency lower limit, rigidity, mechanical strength easily become not enough.On the other hand, if thickness exceedes the upper limit, cost raises sometimes.
(coating layer)
Arrange in easy-adhesion thermoplastic resin film of the present invention and comprise polyurethane resin and/or number-average molecular weight more than 15000 that (a) take polycarbonate polyol as constituent and not there is the mylar of carboxylic acid group substantially and the coating layer of (b) carbodiimide compound is important.Wherein, preferably with the coating layer that above-mentioned (a) and (b) are principal component.Wherein, so-called " principal component ", means in all solids composition contained in coating layer containing more than 50 quality %.
Thought in the past, and from the aspect of the humidity resistance of raising coating layer, ited is desirable to import cross-linked structure energetically.But, found by making coating layer be above-mentioned formation in the present patent application, thus humidity resistance improves.By such formation, the mechanism that the adaptation under hot and humid improves is not fully aware of, but the present inventor thinks as described below.Substantially do not have the carboxylic acid group for the functional group with carbodiimide radical reaction in coating layer of the present invention, when therefore coating layer is formed, unreacted carbodiimide is remaining in coating layer.On the other hand, the mylar in hot and humid lower coating layer causes hydrolysis, ester linkage breaking, produces carboxylic acid group's end.Therefore, the carboxylic acid terminal of unreacted carbodiimide and generation reacts, and is formed crosslinked.Can say, think and carry out selfreparing by the deterioration of coating film strength produced hydrolysis, thus can prevent at hot and humid lower coating film strength deteriorated.
That is, in coating layer of the present invention, not containing carboxyl or its salt of the functional group as display and carbodiimide high response, or seldom, therefore in coating layer, unreacted carbodiimide exists in a large number.On the other hand, there is the functional groups such as carboxyl in the resin used in stacked functional layer, such as light-cured type acrylic resin and 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 that exists in these functional layer and/or base material film and carbodiimide interact, obtain firmly adaptation.
The present invention, by the way, can improve the adaptation (humidity resistance) under hot and humid with lens jacket and then other functional layer.Below formation of the present invention is described in further detail.
(polyurethane resin)
The polyurethane resin used in the present invention, as constituent, at least containing polyol component, polyisocyanate component, as required also containing cahin extension agent.That to be these constituents is polyurethane resin of the present invention is main, by the macromolecular compound of urethane bond copolymerization.The invention is characterized in, as the constituent of polyurethane resin, to there is polycarbonate polyol.By making in coating layer of the present invention, containing the polyurethane resin taking Merlon as constituent, can humidity resistance be improved.It should be noted that, the constituent of these polyurethane resins can by qualifications such as nuclear magnetic resonance spectroscopies.
As the polycarbonate polyol of the constituent of polyurethane resin of the present invention, PCDL, Merlon triol etc. can be enumerated, preferably can use PCDL.As the PCDL of the constituent of polyurethane resin of the present invention, can enumerate such as by 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, 4-cyclohexanedimethanol, one kind or two or more and the such as dimethyl carbonate of the glycols such as bisphenol-A, diphenyl carbonate, ethylene carbonate, the PCDL etc. that the carbonates such as phosgene react and obtain.As the number-average molecular weight of PCDL, be preferably 300 ~ 5000, be more preferably 500 ~ 3000.
In the present invention, as the constitutive molar ratio of the polycarbonate polyol of the constituent of polyurethane resin, when whole polyisocyanate component of polyurethane resin are counted 100 % by mole, be preferably 3 ~ 100 % by mole, be more preferably 5 ~ 50 % by mole, more preferably 6 ~ 20 % by mole.When aforementioned component mol ratio is low, sometimes cannot obtain the effect of the durability that polycarbonate polyol produces.In addition, when aforementioned component mol ratio is high, initial stage adaptation reduces sometimes.
As the polyisocyanates of the constituent of polyurethane resin of the present invention, the isomers class of such as toluene di-isocyanate(TDI) can be enumerated, 4, the aromatic diisocyanate classes such as 4-methyl diphenylene diisocyanate, the aromatic series aliphatic diisocyanate classes such as eylylene diisocyanate, IPDI and 4, 4-dicyclohexyl methyl hydride diisocyanate, 1, the ester ring type diisocyanates such as two (isocyanatomethyl) cyclohexanes of 3-, hexamethylene diisocyanate, with 2, 2, the aliphatic diisocyanate classes such as 4-trimethyl hexamethylene diisocyanate, or by polyisocyanates that is single for these compounds or multiple and the additions in advance such as trimethylolpropane.
As cahin extension agent, ethylene glycol, diethylene glycol (DEG), 1 can be enumerated, the thiodiglycol such as alkamine, thiodiglycol class or the water such as the Diamines such as the polyalcohols such as glycols, glycerine, trimethylolpropane and pentaerythrite, ethylenediamine, hexamethylene diamine and piperazine, monoethanolamine and diethanol amine such as 4-butanediol, neopentyl glycol and 1,6-hexylene glycol.
Coating layer of the present invention, preferably uses the coating fluid of water system, adopts online rubbing method described later to arrange.Therefore, wish that polyurethane resin of the present invention is water-soluble.If use water soluble polyurethane resin, then can increase with the compatibility of carbodiimide compound, the transparency can improve.It should be noted that, so-called aforesaid " water-soluble ", mean for water or containing the aqueous dissolution of water miscible organic solvent being less than 50 quality %.
Water-soluble in order to give polyurethane resin, in molecule carbamate skeleton, sulfonic acid (salt) base or carboxylic acid (salt) base can be imported (copolymerization).Sulfonic acid (salt) base is highly acid, due to its moisture pick-up properties, is sometimes difficult to maintain moisture-proof, therefore imports weakly acidic carboxylic acid (salt) base comparatively suitable.
In order to carboxylic acid (salt) base is imported polyurethane resin, such as, as polyol component, polyol compound dihydromethyl propionic acid, dimethylolpropionic acid etc. with carboxylic acid group imports as copolymer composition, neutralizes by salt forming agent.As the concrete example of salt forming agent, the N-dialkylalkanolamine classes such as N-alkyl morpholine class, N-dimethylethanolamine, N-diethyl ethylene diamine such as the trialkyl amines such as ammonia, trimethylamine, triethylamine, tri-isopropyl amine, Tri-n-Propylamine, tri-n-butylamine, N-methylmorpholine, N-ethylmorpholine can be enumerated.These can be used alone, and also two or more may be used.
Water-soluble in order to give, when the polyol compound that use has carboxylic acid (salt) base is as copolymer composition, the constitutive molar ratio with the polyol compound of carboxylic acid (salt) base in polyurethane resin, when whole polyisocyanate component of polyurethane resin are counted 100 % by mole, be preferably 3 ~ 60 % by mole, be more preferably 10 ~ 40 % by mole.When aforementioned component mol ratio is less than 3 % by mole, water dispersible becomes difficulty sometimes.In addition, when aforementioned component mol ratio is more than 60 % by mole, because remaining carbodiimide when coating layer is formed reduces, therefore humidity resistance declines sometimes.
But, as mentioned above as polyurethane resin use imported the polyurethane resin of carboxylic acid when, sometimes in coating fluid with carbodiimide radical reaction, unreacted carbodiimide when coating layer is formed reduces.Therefore, wish, in coating layer, not there is carboxylic acid (salt) base substantially.Therefore, water-soluble in order to give polyurethane resin, it is preferred embodiment of the present invention for replacing carboxylate group and importing polyoxyalkylenes.When having imported the polyurethane resin of polyoxyalkylenes as polyurethane resin use, in coating layer, substantially not there is carboxyl.Therefore, unreacted carbodiimide is stably remaining, can play more excellent humidity resistance.
As the polyoxyalkylenes importing polyurethane resin, can enumerate polyoxyethylene groups, polyoxypropylene base, polytetramethylene glycol chain etc., these can be used alone, and also two or more may be used.Wherein, preferably polyoxyethylene groups can be used.
In order to polyoxyethylene groups is imported polyurethane resin, such as, polyisocyanates and single end-capped polyoxyethylene glycol (the alkoxyl ethylene glycol by the alkyl list end-capped of carbon number 1 ~ 20) can be made with the hydroxyl relative to single end-capped polyoxyethylene glycol, the NCO of vulcabond is after excessive ratio carries out urine alkylation reaction, as required unreacted polyisocyanates is removed, thus the monoisocyanates obtained containing polyoxyethylene chain, next, the monoisocyanates containing polyoxyethylene chain making to obtain and vulcabond carry out allophanatization reaction, thus obtain.
Water-soluble in order to give, when polyoxyethylene groups is imported polyurethane resin, the constitutive molar ratio of the polyoxyethylene groups in polyurethane resin, when whole polyisocyanate component of polyurethane resin are counted 100 % by mole, be preferably more than 3 % by mole, be more preferably more than 10 % by mole, more preferably more than 20 % by mole.When aforementioned component mol ratio is less than 3 % by mole, water dispersible becomes difficulty sometimes.
When only using polyurethane resin as (a) composition, aforementioned polyurethane resin preferably in coating layer containing below more than 10 quality % 90 quality %.Especially, require when high adhesion, to be more preferably below more than 20 quality % 80 quality % as lens jacket.When the content of polyurethane resin is many, the adaptation under hot and humid reduces, and in contrary poor situation, the adaptation at initial stage reduces.
When only using aforementioned polyurethane resin as (a) composition, the lower limit of the concentration of the carbodiimide in coating layer is 0.5mmol/g, is preferably 0.7mmol/g, be more preferably 1.0mmol/g, the upper limit is 3.5mmol/g, is preferably 3.3mmol/g, is more preferably 3.0mmol/g.If not enough above-mentioned lower limit, the adaptation under sufficient high temperature, high humidity sometimes cannot be obtained.If exceed 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 used in the present invention, the carboxylic acid group preferably as the reactive group with carbodiimide is few.More preferably, substantially not there is carboxylic acid group.Wherein what is called does not have carboxylic acid group substantially, refers to not containing the carboxylic acid group beyond terminal groups.As the method specifying carboxylic acid group, the mensuration of acid number can be enumerated, the so-called mylar substantially without carboxylic acid group is acid number is below 3KOHmg/g, be more preferably the mylar of below 2KOHmg/g, more preferably below 1KOHmg/g.
The number-average molecular weight of mylar is more than 15000 is necessary.When number-average molecular weight is low, because the carboxylic acid group of end increases, sometimes with carbodiimide radical reaction.In addition, not only facilitation of hydrolysis, fully cannot carry out the reparation of film, cannot obtain hot and humid under adaptation, and also to reduce with the adaptation of base material film.In addition, above-mentioned number-average molecular weight more preferably more than 20000, as long as can manufacture, preferred number average molecular weight is higher.But if number-average molecular weight becomes large, the dissolubility also sometimes in coating fluid reduces, and therefore above-mentioned number-average molecular weight is preferably less than 60000.
Mylar, as sour composition, terephthalic acid (TPA), M-phthalic acid, phthalic acid, phthalic anhydride, 2 can be enumerated, 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, the ethylene oxide adduct etc. of ethylene glycol, propane diols, BDO, neopentyl glycol, diethylene glycol (DEG), 1,6-hexylene glycol, 1,4-CHDM, benzene dimethanol, bisphenol-A can be enumerated.When the hard conating etc. formed primarily of acrylic resin is set in film of the present invention, due to coating layer and the specific refractivity of other layers, produces interference fringe, sometimes in visibility, become problem.Therefore, from the inhibition improving humidity resistance, iris shape color, the naphthalenedicarboxylic acid obtaining more high index of refraction is preferably contained as sour composition.
In addition, from the suppression aspect of iris shape color when being provided with hard conating, as the composition of mylar, preferably containing the dicarboxylic acid component of following formula (1) and/or the diol component of following formula (2).The dicarboxylic acid component of the following formula (1) in mylar and/or the diol component of following formula (2) preferably more than 10%, more preferably more than 15%, further preferably more than 20%.In addition, the dicarboxylic acid component of the following formula (1) in above-mentioned mylar and/or the diol component of following formula (2) preferably less than 70%, more preferably less than 60%, further preferably less than 50%.When exceeding the above-mentioned upper limit, film exceedingly becomes soft sometimes, and humidity resistance reduces.When not enough above-mentioned lower limit, the flexibility of mylar reduces sometimes, and film is excessively hardening, and adaptation reduces.
(1) HOOC-(CH 2) n-COOH (in formula, n is the integer of 4≤n≤10)
(2) HO-(CH 2) n-OH (in formula, n is the integer of 4≤n≤10)
Mylar, can use for water or water miscible organic solvent (such as containing the aqueous solution being less than the alcohol of 50 quality %, alkyl cellosolve, ketone system, ether system) or, organic solvent (such as toluene, ethyl acetate etc.) dissolves or the mylar of dispersion.
When being used with water system masking liquid form by mylar, use mylar that is water-soluble or water dispersible, in order to so water-solubleization or moisture dispersion, preferably make containing the compound of sulphonate-base, the compound copolymerization of carboxylate-containing base.For this reason, except aforesaid dicarboxylic acid component, in order to give faling apart property of aqueous polyester, preferably in the scope of 1 ~ 10 % by mole, use 5-sulfoisophthalic acid or its alkali metal salt, such as sulfoterephthalic, 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 can be enumerated.
Preferably make the number-average molecular weight of mylar be more than 15000, and in order to have the glass transition temperature of the degree suppressing adhesion, in mylar, import branched structure.But if branched structure becomes many, acid number also tends to uprise.Therefore, in the mylar of the present patent application, 1 molecule has the ternary mol ratio that more than 3 carboxyls or 1 molecule have 3 hydroxyls and be preferably less than 5.0 % by mole in whole dicarboxylic acid component, is more preferably less than 1.0 % by mole.
When only using mylar as (a) composition, previous polyesters resin preferably in coating layer containing below more than 10 quality % 85 quality %.When requiring high adhesion, be more preferably below more than 20 quality % 80 quality %.When the content of mylar is many, the adaptation under hot and humid reduces, and in contrary poor situation, reduces with the adaptation of base material film.
When only using previous polyesters resin as (a) composition, the lower limit of the concentration of the carbodiimide in coating layer is 0.3mmol/g, is preferably 0.5mmol/g, be more preferably 0.8mmol/g, the upper limit is 3.3mmol/g, is preferably 3.0mmol/g, is more preferably 2.8mmol/g.If not enough above-mentioned lower limit, the adaptation under sufficient high temperature, high humidity sometimes cannot be obtained.If exceed 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, in the present invention, as (a) composition, by foregoing polycarbonates system polyurethane resin and the previous polyesters resin of useful life longevity excellence, coated film hardness can be improved, while excellent adhesion, also play excellent resistance to adhesive.
Mylar, from the aspect of adaptation, preferred glass transition temperature is low, but from the aspect of resistance to adhesive, preferred glass transition temperature is high.Therefore, the glass transition temperature of mylar is preferably 10 ~ 100 DEG C, is more preferably 30 ~ 70 DEG C.If glass transition temperature is high like this more than 100 DEG C, melt viscosity raises, and is difficult to obtain enough molecular weight, and therefore, adaptation reduces.If glass transition temperature is low more than 10 DEG C, the resistance to adhesive of film reduces.
Preferably make the number-average molecular weight of mylar be more than 15000, and in order to make glass transition temperature be above-mentioned scope, in mylar, import branched structure.But if branched structure increases, acid number also tends to uprise.Therefore, in the mylar of the present patent application, 1 molecule has the ternary mol ratio that more than 3 carboxyls or 1 molecule have more than 3 hydroxyls, is preferably less than 5.0 % by mole in whole dicarboxylic acid component, is more preferably less than 1.0 % by mole.
As (a) composition, when using aforementioned polyurethane resin and previous polyesters resin, containing below more than 10 quality % 80 quality % in the preferred each comfortable coating layer of concentration of polyurethane resin and mylar.When requiring high adhesion, be more preferably below more than 20 quality % 70 quality %.When the content of polyurethane resin is many, the adaptation under hot and humid reduces, and on the contrary, in poor situation, the adaptation at initial stage reduces.In addition, when the amount of mylar is many, adaptation under hot and humid reduces, and on the contrary, in poor situation, reduces with the adaptation of base material film and resistance to adhesive.
As (a) composition, when using aforementioned polyurethane resin and previous polyesters resin, the lower limit of the concentration of the carbodiimide in coating layer is 0.1mmol/g, be preferably 0.2mmol/g, be more preferably 0.4mmol/g, the upper limit is 2.0mmol/g, is preferably 1.8mmol/g, is more preferably 1.5mmol/g.If not enough above-mentioned lower limit, the adaptation under enough high temperature, high humidity sometimes cannot be obtained.If exceed the above-mentioned upper limit, relatively the ratio of polyurethane resin and mylar diminishes, and adaptation, particularly initial stage adaptation reduce sometimes.
In the present invention, even if the resin beyond aforementioned polyurethane resin and/or previous polyesters resin, also can contain to improve adaptation.Such as, acrylic resin, mylar etc. can be enumerated.Be preferably the poor resin of carboxylic acid group.More preferably, be not containing the resin of carboxylic acid group.When carboxylic acid group is many, with carbodiimide radical reaction, the carbodiimide reacted with the carboxylic acid group produced by polyurethane resin under hot and humid reduces.
(carbodiimide compound)
In the present invention, carbodiimide compound must be contained.As carbodiimide compound, single carbodiimide compound, poly-carbodiimide compound can be enumerated.
As single carbodiimide compound, such as dicyclohexylcarbodiimide, DIC, dimethyl carbodiimide, diisobutyl carbodiimide, dioctyl carbodiimide, t & #8722 can be enumerated; Butyl diisopropylcarbodiimide, diphenyl carbodiimide, two & #8722; T & #8722; Butyl carbodiimide, two & #8722; β & #8722; Naphthyl carbodiimide etc.
As poly-carbodiimide compound, the compound adopting known method to manufacture can be used.Such as, the condensation reaction by the adjoint carbon dioxide removal of vulcabond carrys out synthesizing isocyanate end and gathers carbodiimide, thus manufactures.
As the vulcabond of the synthesis material of poly-carbodiimide compound, the isomers class of such as toluene di-isocyanate(TDI) can be enumerated, 4, the aromatic diisocyanate classes such as 4-methyl diphenylene diisocyanate, the aromatic series aliphatic diisocyanate classes such as eylylene diisocyanate, IPDI and 4, 4-dicyclohexyl methyl hydride diisocyanate, 1, the ester ring type diisocyanates such as two (isocyanatomethyl) cyclohexanes of 3-, hexamethylene diisocyanate and 2, 2, the 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, the compound that above-mentioned vulcabond can use monoisocyanates etc. and terminal isocyanate to react, uses molecular Control in the suitable degree of polymerization.As the monoisocyanates for like this end-capped of poly-carbodiimide being controlled its degree of polymerization, such as phenyl isocyanate, toluene diisocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate etc. can be enumerated.In addition, in addition to these, as end-capped agent, can use and there is-OH base ,-NH 2base ,-COOH base ,-SO 2the compound of H base.
The condensation reaction of the adjoint carbon dioxide removal of vulcabond, carries out under the existence of carbodiimidization catalyst.As catalyst, such as 1 & #8722 can be enumerated; Phenyl & #8722; 2 & #8722; Phospholane & #8722; 1 & #8722; Oxide, 3 & #8722; Methyl & #8722; 2 & #8722; Phospholane & #8722; 1 & #8722; Oxide, 1 & #8722; Ethyl & #8722; 2 & #8722; Phospholane & #8722; 1 & #8722; Oxide, 3 & #8722; Methyl & #8722; 1 & #8722; Phenyl & #8722; 2 & #8722; Phospholane & #8722; 1 & #8722; Oxide, these 3 & #8722; The phospholane oxides etc. such as phospholane isomers, from reactive aspect, preferably 3 & #8722; Methyl & #8722; 1 & #8722; Phenyl & #8722; 2 & #8722; Phospholane & #8722; 1 & #8722; Oxide.It should be noted that, the use amount of above-mentioned catalyst can be catalytic amount.
Above-mentioned list or poly-carbodiimide compound, uniform dispersity is remained on when wishing to coordinate in water paint, therefore, the suitable emulsifying agent of preferred use carries out emulsification processing and forms emulsion to use, or in the molecular structure of poly-carbodiimide compound additional hydrophilic segment and be matched with coating under the form of self-emulsifying thing or under the form of dissolved matter.
The carbodiimide compound used in the present invention, can enumerate water dispersible, water-soluble.Because the compatibility of the water-soluble resin with other is good, improve the transparency, the cross-linking reaction efficiency of coating layer, therefore preferred water dissolubility.
As the degree of polymerization (n) of poly-carbodiimide compound, preferably 2 ~ 10, be more preferably 3 ~ 7.When the degree of polymerization is little, cross-linking reaction rate is deteriorated, and reduces with the adaptation of functional layer, when large, sometimes with the compatibility poor of resin, and turbidity rising.
Become water-soluble to make carbodiimide compound, after gathering carbodiimide by the condensation reaction synthesizing isocyanate end with carbon dioxide removal of isocyanates, make further with having the hydrophilic portion addition with reactive functional group of NCO, thus manufacture.
As hydrophilic portion, the quaternary ammonium salt etc. of the quaternary ammonium salt of (1) dialkyl amido alcohol, dialkyl aminoalkyl amine can be enumerated, (2) have the alkylsulfonate etc. of at least 1 reactive hydroxyl, (3) have carried out the mixture etc. of poly-(ethylene oxide), poly-(propylene oxide) of end-capped, poly-(ethylene oxide) and poly-(propylene oxide) with alkoxyl.The recurring unit of ethylene oxide and/or propylene oxide preferably 3 ~ 50, is more preferably 5 ~ 35.When recurring unit is little, with the compatibility poor of resin, turbidity rises, when large, and hot and humid lower cementability reduction sometimes.Carbodiimide compound, when having imported above-mentioned hydrophilic portion, becomes (1) cationic, (2) anionic property, (3) nonionic.Wherein, preferably with ionic irrelevant, the nonionic that can be compatible of other water-soluble resin.In addition, also in order to improve humidity resistance, the nonionic of ionic hydrophilic group need not preferably be imported.
In addition, the carbodiimide equivalent of the carbodiimide compound used in the present invention, is not particularly limited, and particularly, such as, is preferably less than 1000, is more preferably less than 500, more preferably less than 300.When above-mentioned carbodiimide equivalent exceedes the upper limit, insufficiently manifest the interaction with contained carboxyl in base material film, functional layer etc., sometimes cannot obtain durability, resistance to water satisfactorily.It should be noted that, above-mentioned carbodiimide equivalent is the formula weight of every 1mol carbodiimide.Therefore, the value of this carbodiimide equivalent is less, represents that the amount of the carbodiimide in polymer is more, is worth larger, represents that the amount of the carbodiimide in polymer is fewer.
Aforementioned carbodiimide compound, preferably contains below more than 5 quality % 90 quality % in coating layer.More preferably, be below more than 10 quality % 70 quality %.When the content of carbodiimide compound is many, reduce with the adaptation of functional layer, on the contrary, in poor situation, the adaptation under sometimes hot and humid reduces.
In the present invention, in order to improve coating strength, can containing the crosslinking agent beyond carbodiimide compound or the resin with crosslinking group in coating layer.As crosslinking agent, urea system, epoxy, melamine system, isocyanate-based, oxazoline system, silanol system etc. can be enumerated.In addition, in order to promote cross-linking reaction, suitably catalyst etc. is used as required.
In the present invention, also can make in coating layer containing particle.Particle can enumerate (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 is black, alumina silicate, diatomite, calcium silicates, aluminium hydroxide, halloysite, magnesium carbonate, the inorganic particulates such as magnesium hydroxide, (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 system, melamine system, polycarbonate-based, urea system, epoxy, polyurethane series, phenolic aldehyde system, diallyl phthalate system, the organic filler of Polyester etc.
The preferred average grain diameter of aforementioned particles is the particle of 1 ~ 500nm.Average grain diameter is not particularly limited, from the aspect of the transparency of maintenance film, is preferably 1 ~ 100nm.
Aforementioned particles can contain the different particle of average grain diameter of more than two kinds.
It should be noted that, above-mentioned average grain diameter can use transmission electron microscope (TEM), with the cross section of multiplying power 120,000 times shooting stacked film, the maximum diameter of the particle of more than 10 that the cross section being determined at coating layer exists, the mean value as them is obtained.In addition, coulter counter method can be adopted to obtain.
As the content of particle, preferably below more than 0.5 quality % 20 quality %.When few, sufficient resistance to adhesive can not be obtained.In addition, resistance to marring is deteriorated.When many, not only the transparency of coating layer is deteriorated, and coating strength reduces.
In coating layer, levelability during in order to improve coating, 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 system, acetylenic glycol system or fluorine system surfactant.Also preferably do not damage the scope with the degree of the adaptation of functional layer, such as, in coating fluid, contain these surfactants with the scope of 0.005 ~ 0.5 quality %.
Easy-adhesion polyester film of the present invention, preferred turbidity value is less than 2.5%, is more preferably less than 2.0%, more preferably less than 1.5%.Such easy-adhesion thermoplastic resin film, by making carbodiimide compound contained in the coating layer of foregoing description become water-soluble, thus can improve with the compatibility of other resins.
In order to give coating layer, other are functional, can not damaging with in the scope of the degree of the adaptation of functional layer, containing various additive.As aforementioned additive, such as fluorescent dye, fluorescent whitening agent, plasticizer, ultra-violet absorber, pigment dispersing agent, foam inhibitor, defoamer, anticorrisive agent, antistatic additive etc. can be enumerated.
In the present invention, as the method arranging coating layer on thermoplastic resin film, can enumerate by the coating solution containing solvent, particle, resin in polyester film, carry out dry method.As solvent, the mixed stocker of the organic solvents such as toluene, water or water and water miscible organic solvent can be enumerated, preferably, from environmental problem aspect, preferably be used alone water or in water, be mixed with the product of water miscible organic solvent.
Laminating thermoplastic's resin molding of the present invention, in at least one side of the coating layer of aforesaid thermoplastic resin film, the stacked optical functional layer of at least 1 layer selected from hard conating, light diffusion layer, prism-like lens jacket, electromagnetic wave absorbing layer, near infrared ray barrier layer, transparency conducting layer and obtaining.
The material used in aforementioned optical functional layer is not particularly limited.
(manufacture of easy-adhesion thermoplastic resin film)
For the manufacture method of easy-adhesion thermoplastic resin film of the present invention, be described for PETG (hereinafter abbreviated as PET) film, be certainly not limited to this.
After PET resin fully vacuum drying, supply extruder, is expressed into rotation chill roll by the melting PET resin of about 280 DEG C with sheet-shaped molten from T-shaped die head, applies method make its cooling curing and the PET sheet that do not stretched by electrostatic.The aforementioned PET sheet that do not stretch can be that individual layer is formed, and also can be to adopt the multilayer of coetrusion to form.In addition, inactive particle is substantially free of in preferred PET resin.
By the PET sheet that do not stretch obtained, with being heated to the roller of 80 ~ 120 DEG C longitudinal stretching 2.5 ~ 5.0 times, obtain uniaxial tension PET film.And then, hold the end of film with clip, import the hot blast district being heated to 70 ~ 140 DEG C, stretch 2.5 ~ 5.0 times at width.Then, import the heat-treatment zone of 160 ~ 240 DEG C, carry out the heat treatment of 1 ~ 60 second, complete crystalline orientation.
In the arbitrary stage of this film manufacturing process, at least one applied coating solution of PET film, form aforementioned coating layer.Even if coating layer is formed also without special problem on the two sides of PET film.The solid component concentration of the resin combination in coating fluid is preferably 2 ~ 35 % by weight, is particularly preferably 4 ~ 15 % by weight.
For by the method for this coating solution in PET film, known arbitrary method can be used.Such as reverse roll rubbing method, gravure roll rubbing method, roller can be enumerated and lick rubbing method, mold pressing rubbing method, roller brush method, spraying process, air knife coating method, coiling rod rubbing method, tubular scraper method, dip coating, curtain coating processes etc.Can by these methods separately or combination be coated with.
In the present invention, coating layer, by aforementioned coating liquid being coated the PET film do not stretched or after uniaxial tension, after drying, at least single shaft direction stretches, next heat-treats and formed.
In the present invention, the thickness of the coating layer finally obtained is preferably 20 ~ 350nm, and dried coating weight is preferably 0.02 ~ 0.5g/m 2.If the coating weight of coating layer is less than 0.02g/m 2, the effect of cementability is existed hardly.On the other hand, if coating weight is more than 0.5g/m 2, then turbidity increases.
The coating layer of the easy-adhesion thermoplastic resin film obtained in 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.By these optical functional layers stacked, even if thus can provide also can keep the stacked thermoplastic resin film of the optics of initial stage function for a long time under wet-heat resisting environment.In addition, beyond optical applications, good adhesive strength is also obtained.Particularly, can enumerate photosensitive layer, diazonium photosensitive layer, extinction layer, magnetosphere, ink jet ink by hold layer, hard conating, dry lamination black with ultraviolet curable resin, heat reactive resin, printer's ink or UV or extrude the adhesive of lamination etc., thin layer, organic barrier layer etc. that the vacuum evaporation, electron beam evaporation plating, sputtering, ion plating, CVD, plasma polymerization etc. of metal or inorganic matter or their oxide obtain.
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 used in the present invention is as described below.
(1) intrinsic viscosity
According to JIS K 7367-5, use the mixed solvent of phenol (60 quality %) and 1,1,2,2-tetrachloroethanes (40 quality %) as solvent, measure at 30 DEG C.
(2) reduced viscosity
Relative to resin 0.1g, use the mixed solvent 25mL of phenol (60 quality %) and 1,1,2,2-tetrachloroethanes (40 quality %) as solvent, measure at 30 DEG C.
(3) glass transition temperature
According to JIS K7121, use differential scanning calorimetry (Seiko instrument system, DSC6200), make resin sample 10mg with 20 DEG C/minute of intensifications in the temperature range of 25 ~ 300 DEG C, using the extrapolation glass transition obtained by DSC curve, temperature is as glass transition temperature.
(4) resin composition
By resin dissolves in heavy chloroform, use Varian Associates, Inc. (US) 611 Hansen Way, Palo Alto, California 94303, U.S.A. nuclear magnetic resonance spectroscopy meter (NMR) Gemini 200, carry out 1h-NMR analyzes, by its integration than each % by mole ratio formed determined when whole isocyanate prepolymer composition being counted 100 % by mole.
(5) number-average molecular weight
Resin 0.03g is dissolved in oxolane 10ml, use GPC-LALLS device low angle light light-scattering photometer LS-8000 (TOSOH Co., Ltd's system, tetrahydrofuran solvent, reference: polystyrene), use column temperature 30 DEG C, flow 1ml/ divides, chromatographic column (Showa electrician society shodex KF-802,804,806), measure number-average molecular weight.
(6) acid number
The sample of 1g (solid constituent) is dissolved in chloroform or the dimethyl formamide of 30ml, using phenolphthalein as indicator, with the potassium hydroxide-ethanol solution titration of 0.1N, obtains the amount (mg) of the necessary KOH of carboxyl neutralizing every 1g sample.
(7) carbodiimide value
By carbodiimide compound freeze drying, use 1h-NMR analyzes this compound, by the absorption peak strength of the absorption peak strength from carbodiimide, the monomer from other, calculates carbodiimide value.
(8) the full light transmittance of easy-adhesion polyester film
The full light transmittance of the easy-adhesion polyester film obtained, according to JIS K 7105, uses nephelometer (Japanese electric look system, NDH2000) to measure.
(9) turbidity of easy-adhesion polyester film
The turbidity of the easy-adhesion polyester film obtained, according to JIS K 7136, uses nephelometer (Japanese electric look system, NDH2000) to measure.
(10) the carbodiimide concentration in coating layer quantitative
For the coating aspect of the film obtained in embodiment and comparative example, adopt total reflection to absorb infrared measure and measure, with the absorbance obtained specifically from base material film in contrast, obtain the carbodiimide concentration in coating layer.
Namely, adopt following shown in condition total reflection absorb infrared measure measure, obtain infrared absorption spectroscopy, (infrared absorbency compares A to the ratio obtaining from the absorbance of carbodiimide and the absorbance (when PET film, being ethylene glycol) of base material film 2120/ A 1340).It should be noted that, the absorbance from carbodiimide is at 2120 ± 10cm -1region in there is the value (A of the height of the absworption peak of maximum absorption 2120), the absorbance from PET is at 1340 ± 10cm -1region in there is the value (A of the height of the absworption peak of maximum absorption 1340).Baseline is the line of the flank of the both sides connecting each maximum absorption peak.
In addition, the thickness of coating layer is obtained by transmission electron microscope.The sample of stacked film is embedded in visible light curable resin (new EM society of Japan system, D-800), is at room temperature exposed to visible ray and makes it solidify.By the embedding block obtained, use the ultra-thin section cutter having installed diamond cutter, make the ultra-thin section of the thickness of 70 ~ 100nm degree, dye 30 minutes in ruthenium tetroxide steam.And then after implementing carbon evaporation, use transmission electron microscope (Jeol Ltd.'s system, TEM2010) pair cross-section to observe, take pictures, measure the thickness of coating layer thus.It should be noted that, shooting suitably sets in the scope of 10000 ~ 100000 times.
A is compared by the infrared absorbency obtained 2120/ A 1340with the thickness of coating layer, use in advance by the calibration curve being coated with the known coating fluid of carbodiimide concentration, air-dry standard sample is made, obtain the carbodiimide concentration in coating layer.
It should be noted that, in being made of calibration curve, make carbodiimide concentration be 0.5 for coating, 1.4,2.7, the coating fluid (solvent: water/isopropyl alcohol=1/1 of 4.5mmol/g, regulate with the combined amount of acrylic resin and make solid component concentration be 30 quality %) to make the thickness of dried coating layer for 50nm, 100nm, 200nm and air-dry sample, adopt 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 by the result obtained, coating thickness, infrared absorbency compare A 2120/ A 1340a following mathematical expression of these 3 variable compositions, is made into calibration curve.
(carbodiimide concentration)=A × (infrared absorbency compares A 2120/ A 1340)/(coating thickness)+B
(wherein, A, B are by the constant being made the data that obtain by above-mentioned calibration curve and obtaining)
(condition determination)
Device: Varian society FTS-60A/896
1 secondary reflection ATR annex: SPECTRA TECH Inc. Silver Gate
Optical crystal: Ge
Incidence angle: 45 °
Capacity of decomposition: 4cm -1
Integral number of times: 128 times
It should be noted that, the thickness of coating layer is thin, when cannot obtain sufficient sensitivity, the annex (such as ST Japan Inc. VeeMax) that the 1 secondary reflection annex used can be replaced with incidence angle larger (65 degree) measures.
(11) cementability
In the light-cured type acrylic resin aspect of the laminated polyester film obtained, use that clearance gap 2mm's draw lattice device (Cutter guide), form through light-cured type acrylic resin layer and arrive 100 latticed cut channels of base material film.Next, by cellophane adhesive tape (ニ チ バ Application society system, No. 405; 24mm is wide) be pasted on latticed cut channel face, with rubber friction to make it completely closely sealed.Then, after carrying out the operation of vertically being peeled off from the light-cured type acrylic resin aspect of laminated polyester film by cellophane adhesive tape for 5 times, the number of the grid that visual calculating is peeled off from the light-cured type acrylic resin aspect of laminated polyester film, is obtained the adaptation of light-cured type acrylic resin layer and base material film by following formula.It should be noted that, the grid that part in grid is peeled off also is calculated as the grid of stripping, according to following standard divided rank.
Adaptation (%)=(number/100 of the grid that 1-peels off) × 100
◎: 100% or, the material damage of light-cured type acrylic resin layer
○：99～90％
△：89～70％
×：69～0％
(12) humidity resistance
By the laminated polyester film that obtains in hot and humid groove 80 DEG C, place 48 hours under the environment of 95%RH.Next, laminated polyester film is taken out, room temperature often wet lower placement 12 hours.Then, carry out beyond the operation of vertically cellophane adhesive tape being peeled off from the light-cured type acrylic resin aspect of laminated polyester film for 5 times, the method same with aforementioned (11) is adopted to obtain the adaptation of light-cured type acrylic resin layer and base material film, according to following standard divided rank.
◎: 100% or, the material damage of light-cured type acrylic resin layer
○：99～90％
△：89～70％
×：69～0％
(13) interference spot improvement (iris shape color)
The laminated polyester film obtained is cut out the area of 10cm (film width) × 15cm (film length direction), be made sample film.The opposing face of the hard conating of the sample film obtained paste black glossy band (day east electrician's system, Vinyltape No21; Black).Make the hard painting face of this sample film for above, using 3 wavelength shape whites in daytime (National パ Le Star Network, F.L 15EX-N 15W) as light source, seem the strongest position relationship (the distance 40 ~ 60cm from light source, the vertical line relative to face are the angle of 15 ~ 45 °) from oblique upper visualization reflection.
By the result of visualization according to following standard divided rank.It should be noted that, observe, using maximum grades as opinion rating with 5 observers being proficient in this evaluation.If when 2 grades are identical number, adopt the center being divided into the grade of 3.
Zero: almost do not find iris shape color
△: observe iris shape color on a small quantity
×: observe clearly iris shape color
(polymerization of mylar)
In the stainless steel autoclave possessing agitator, thermometer and partial reflux formula cooler, load dimethyl terephthalate (DMT) 194.2 mass parts, DMIP 184.5 mass parts, 5-sodiosulfoisophthalate 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 DEG C to 220 DEG C, carried out ester exchange reaction with 4 hours.Next, be warmed up to 255 DEG C, after reaction system is slowly reduced pressure, react 1 hour 30 minutes under the decompression of 30Pa, obtain copolymer polyester resin (A-1).The copolymer polyester resin (A-1) obtained is pale yellow transparent.Measure the reduced viscosity (reduceviscosity) of the copolymer polyester resin (A-1) obtained, result is 0.70dl/g.The glass transition temperature adopting DSC to obtain is 40 DEG C.
Adopting uses the same method obtains copolymer polyester resin (A-2) ~ (A-7) of other composition.For these copolymer polyester resins, will adopt 1the composition (% by mole ratio) that H-NMR measures and other characteristics are shown in table 1.
[table 1]
(modulation of polyester water dispersion)
In the reactor possessing agitator, thermometer and reflux, load mylar (A-1) 30 mass parts, ethylene glycol n-butyl ether 15 mass parts, heat at 110 DEG C, stir, by resin dissolves.After resin dissolves completely, under agitation at leisure water 55 mass parts is added in polyester liquid.After interpolation, under agitation by liquid cools to 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), making aqueous dispersion, make aqueous dispersion (B-2) ~ (B-7) respectively.
(polymerization of water-soluble carbodiimide compound)
3-methyl isophthalic acid-phenyl-2-phospholane-1-oxide 4 mass parts of tetramethylxylylene diisocyanate 200 mass parts, carbodiimidization catalyst is dropped in the flask possessing thermometer, nitrogen ingress pipe, reflux cooler, dropping funel and agitator, stir 40 hours under nitrogen atmosphere, at 180 DEG C, obtain isocyanates end tetramethylxylene carbodiimide (degree of polymerization=5).Next, carbodiimide 94.5g, poly glycol monomethyl ether (molecular weight 220) 40.0g obtained is reacted 24 hours at 100 DEG C.At 50 DEG C, add water at leisure wherein, obtain the water-soluble carbodiimide compound (C-1) of the yellow transparent of solid constituent 40 quality %.Carbodiimide equivalent is 246.
(polymerization of water-soluble carbodiimide compound)
3-methyl isophthalic acid-phenyl-2-phospholane-1-oxide 4 mass parts of IPDI 200 mass parts, carbodiimidization catalyst is dropped in the flask possessing thermometer, nitrogen ingress pipe, reflux cooler, dropping funel and agitator, stir 12 hours under nitrogen atmosphere, at 180 DEG C, obtain isocyanates end isophorone carbodiimide (degree of polymerization=6).Next, carbodiimide 129.2g, poly glycol monomethyl ether (molecular weight 400) 80g obtained is reacted 24 hours at 100 DEG C.At 50 DEG C, add water at leisure wherein, obtain the water-soluble carbodiimide compound (C-2) of the yellow transparent of solid constituent 40 quality %.Carbodiimide equivalent is 349.
(polymerization of water-soluble carbodiimide compound)
4 are dropped in the flask possessing thermometer, nitrogen ingress pipe, reflux cooler, dropping funel and agitator, 3-methyl isophthalic acid-phenyl-2-phospholane-1-oxide 4 mass parts of 4-dicyclohexyl methyl hydride diisocyanate 200 mass parts, carbodiimidization catalyst, under nitrogen atmosphere, stir 10 hours in 180 DEG C, obtain isocyanates end 4,4-dicyclohexyl methyl hydride (degree of polymerization=4).Next, at 100 DEG C, carbodiimide 113.6g, poly glycol monomethyl ether (molecular weight 400) 80g obtained is made to react 24 hours.At 50 DEG C, slowly add water wherein, obtain the water-soluble carbodiimide compound (C-3) of the yellow transparent of solid constituent 40 quality %.Carbodiimide equivalent is 484.
(polymerization of water dispersible carbodiimide compound)
3-methyl isophthalic acid-phenyl-2-phospholane-1-oxide 4 mass parts of tetramethylxylylene diisocyanate 200 mass parts, carbodiimidization catalyst is dropped in the flask possessing thermometer, nitrogen ingress pipe, reflux cooler, dropping funel and agitator, stir 40 hours under nitrogen atmosphere, at 180 DEG C, obtain isocyanates end tetramethylxylene carbodiimide (degree of polymerization=10).Next, at 100 DEG C, carbodiimide 169.7g, poly glycol monomethyl ether (molecular weight 400) 80g obtained is made to react 24 hours.At 50 DEG C, slowly add water wherein, obtain the water dispersible carbodiimide compound (C-4) of solid constituent 40 quality %.Carbodiimide equivalent is 250.
(be constituent with polycarbonate polyol, there is the polymerization of the polyurethane resin of polyoxyethylene groups)
In the reactor possessing thermometer, nitrogen ingress pipe and agitator, limit imports nitrogen limit and loads hexamethylene diisocyanate 627.1 mass parts, is heated to methoxy poly (ethylene glycol) 372.9 mass parts of the number-average molecular weight 1000 of 50 DEG C, reacts 6 hours at 80 DEG C.After the isocyanate group content arriving regulation, with rotating thin film distiller (ス ミ ス formula), unreacted hexamethylene diisocyanate is removed, obtain the monoisocyanates (D) containing polyoxyethylene groups.Should the number-average molecular weight contained in the calculating of the monoisocyanates (D) of polyoxyethylene chain be 1168g/ mole.
Next, in the reactor possessing thermometer, nitrogen ingress pipe, agitator, at room temperature limit imports nitrogen limit loading diethanol amine 83.9 mass parts.Monoisocyanates (D) 916.1 mass parts containing polyoxyethylene chain is added on cooling limit, limit, reacts 3 hours at 60 DEG C.Confirm the generation of urea key with infrared spectrum, obtain the polyalcohol (D) containing polyoxyethylene groups.
Possessing backflow cooling tube, nitrogen ingress pipe, thermometer, in the four-hole boiling flask of agitator, be loaded as 1 of polyisocyanates, 3-cyclohexane two (methyl isocyanate) 53.69 mass parts, as PCDL 88.6 mass parts of the number-average molecular weight 2000 of hydrophobic macromolecules polyalcohol, neopentyl glycol 14.97 mass parts, above-mentioned polyalcohol (D) 52.87 mass parts containing polyoxyethylene groups, as acetonitrile 60 mass parts of organic solvent, 1-METHYLPYRROLIDONE 30 mass parts, under nitrogen atmosphere reacting liquid temperature is adjusted to 75 ~ 78 DEG C, add the stannous octoate of 0.06 mass parts as catalysts, reactivity more than 99% is reacted to 7 hours.Next, be cooled to 30 DEG C, obtained NCO end prepolymer.Next, possess can high-speed stirred homogeneous phase dispersion machine reaction vessel in add water 450g, be adjusted to 25 DEG C, while be uniformly mixed limit with 2000min-1 to add NCO end prepolymer, carry out aqueous dispersion.Then, under decompression, a part for acetonitrile and water is removed, thus the water soluble polyurethane resin (D-1) of modulation solid constituent 35%.
(taking polycarbonate polyol as the polymerization of the polyurethane resin of constituent)
1 is dropped in the four-hole boiling flask possessing agitator, serpentine condenser, nitrogen ingress pipe, silica dehydrator pipe and thermometer, 3-two (isocyanatomethyl) cyclohexane 72.96 mass parts, dihydromethyl propionic acid 12.60 mass parts, neopentyl glycol 11.74 mass parts, PCDL 112.70 mass parts of number-average molecular weight 2000 and acetonitrile 85.00 mass parts, 1-METHYLPYRROLIDONE 5.00 mass parts as solvent, stir 3 hours under nitrogen atmosphere, at 75 DEG C, confirm that reactant liquor reaches the amine equivalent of regulation.Next, after this reactant liquor is cooled to 40 DEG C, add triethylamine 9.03 mass parts, obtain polyurethane prepolymer solution D.Next, possess can high-speed stirred homogeneous phase dispersion machine reaction vessel in add water 450g, be adjusted to 25 DEG C, while be uniformly mixed with 2000min-1, limit is added NCO end prepolymer and is carried out aqueous dispersion.Then, under reduced pressure a part for acetonitrile and water is removed, thus the water soluble polyurethane resin (D-2) of modulation solid constituent 35%.
Adopting uses the same method obtains water soluble polyurethane resin (D-3) ~ (D-4) of other composition.For these water soluble polyurethane resins, will adopt 1the composition (% by mole ratio) that H-NMR measures and other characteristics are shown in table 2.
[table 2]
Embodiment 1
(1) modulation of coating fluid
Following paint is mixed, is made coating fluid.The number-average molecular weight of mylar is 20000.
(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) manufacture of easy-adhesion polyester film
As film raw polymer, intrinsic viscosity is 0.62dl/g and the PET resin pellet being substantially free of particle under the decompression of 133Pa, at 135 DEG C dry 6 hours.Then, supply extruder, at about 280 DEG C, melt extrude slabbing, on the rotation cool metal roller remaining on surface temperature 20 DEG C, chilling makes its closely sealed solidification, obtains the PET sheet that do not stretch.
Roller group and the infrared heater of the PET sheet that this do not stretched heating are heated to 100 DEG C, then stretch 3.5 times by the roller group with peripheral speed difference at length direction, obtain uniaxial tension PET film.
Next, after aforementioned coating liquid print roll coating method is applied to the one side of PET film, drying 20 seconds at 80 DEG C.It should be noted that, the dried coating weight carrying out regulating to make final (after biaxial stretch-formed) is 0.15g/m 2.Then, stretch in the direction of the width at 120 DEG C 4.0 times with stenter, under the state that the length of the width by film is fixing, heat 0.5 second at 230 DEG C, and then at 230 DEG C, carry out the relaxation processes of width of 10 seconds 3%, obtain the easy-adhesion polyester film of thick 100 μm.
Evaluation result is shown in table 3.
(3) manufacture of laminated polyester film
In the coating aspect of aforesaid easy-adhesion polyester film, use the hard conating formation coating fluid (C-1) of the following composition of #10 coiling rod coating, at 70 DEG C, drying 1 minute, removes solvent.Next, for the film being coated with hard conating, use high-pressure mercury light irradiation 300mJ/cm 2ultraviolet, obtain the laminated polyester film of the hard conating with thickness 5 μm.
Hard conating formation coating fluid
MEK 39.00 quality %
Toluene 26.00 quality %
Dipentaerythritol acrylate 22.83 quality %
(Xin Zhong village chemistry A-DPH processed)
Polyethyleneglycol diacrylate 11.17 quality %
(Xin Zhong village chemistry A-400 processed)
Photoepolymerizationinitiater initiater 1.00 quality %
(Ciba Specialty Chemicals Irgacure 184)
Comparative example 1
Except the polyester water dispersion (B-6) polyester water dispersion being become molecular weight 8000, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
Comparative example 2
Except the polyester water dispersion (B-7) polyester water dispersion being become acid number 50KOHmg/g, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
Comparative example 3
Except water-soluble carbodiimide compound (C-1) being become epoxide (Nagase ChemX society Denacol EX-521 solid component concentration 100%), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
Comparative example 4
Except water-soluble carbodiimide compound (C-1) being become melamine compounds (DIC society ベ Star カ ミ Application M-3 solid component concentration 60%), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
Embodiment 2
Except being become by coating fluid except following coating fluid, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
(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 being become by coating fluid except following coating fluid, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
(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 being become by coating fluid except following coating fluid, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
(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 being become except water-soluble carbodiimide compound (C-2) by water-soluble carbodiimide compound (C-1), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
Embodiment 6
Except being become except water-soluble carbodiimide compound (C-3) by water-soluble carbodiimide compound (C-1), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
Embodiment 7
Except the polyester water dispersion (B-2) polyester water dispersion being become molecular weight 15000, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
Embodiment 8
Except the polyester water dispersion (B-3) polyester water dispersion being become molecular weight 23000, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
Embodiment 9
Except the polyester water dispersion (B-4) polyester water dispersion being become molecular weight 46000, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
Embodiment 10
Beyond the polyester water dispersion (B-5) polyester water dispersion being become molecular weight 50000, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 1.
Embodiment 11
Water-soluble carbodiimide compound (C-1) is become beyond water dispersible carbodiimide compound (C-4), obtains easy-adhesion polyester film and laminated polyester film similarly to Example 1.
[table 3]
Embodiment 12
(1) modulation of coating fluid
Following paint is mixed, is made coating fluid.
(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) manufacture of easy-adhesion polyester film
As film raw polymer, intrinsic viscosity is 0.62dl/g and the PET resin pellet being substantially free of particle under the decompression of 133Pa, at 135 DEG C dry 6 hours.Then, supply extruder, at about 280 DEG C, melt extrude slabbing, chilling on the rotation cool metal roller remaining on surface temperature 20 DEG C, makes its closely sealed solidification, obtains the PET sheet that do not stretch.
Roller group and the infrared heater of the PET sheet that this do not stretched heating are heated to 100 DEG C, then stretch 3.5 times by the roller group with peripheral speed difference at length direction, obtain uniaxial tension PET film.
Next, after adopting rolling method aforementioned coating liquid to be applied to the one side of PET film, drying 20 seconds at 80 DEG C.It should be noted that, the dried coating weight carrying out adjusting to make final (after biaxial stretch-formed) is 0.15g/m 2.Then, stretch in the direction of the width at 120 DEG C 4.0 times with stenter, under the state that the length of the width by film is fixing, heat 0.5 second at 230 DEG C, at 230 DEG C, carry out the relaxation processes of the width of 10 seconds 3% again, obtain the easy-adhesion thermoplastic resin film of thick 100 μm.
Evaluation result is shown in table 4.
Comparative example 5
Except polyurethane resin is become with PEPA be constituent polyurethane resin (D-5) except, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
Comparative example 6
Except polyurethane resin is become with PPG be constituent polyurethane resin (D-6) except, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
Comparative example 7
Except water-soluble carbodiimide compound (C-1) being become epoxide (NagaseChemteX Inc. Denacol EX-521 solid component concentration 100%), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
Comparative example 8
Except water-soluble carbodiimide compound (C-1) being become melamine compounds (DIC society ベ Star カ ミ M-3 solid component concentration 60%), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
Embodiment 13
Except being become by coating fluid except following coating fluid, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
(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 being become by coating fluid except following coating fluid, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
(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 being become by coating fluid except following coating fluid, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
(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 being become except water-soluble carbodiimide compound (C-2) by water-soluble carbodiimide compound (C-1), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
Embodiment 17
Except being become except water-soluble carbodiimide compound (C-3) by water-soluble carbodiimide compound (C-1), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
Embodiment 18
Except being become except polyurethane resin (D-2) by polyurethane resin (D-1), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
Embodiment 19
Except being become except polyurethane resin (D-3) by polyurethane resin (D-1), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
Embodiment 20
Except being become except polyurethane resin (D-4) by polyurethane resin (D-1), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
Embodiment 21
Except being become except water dispersible carbodiimide compound (C-4) by water-soluble carbodiimide compound (C-1), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 12.
[table 4]
Embodiment 22
(1) modulation of coating fluid
Mix following paint, be made coating fluid.
(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) manufacture of easy-adhesion polyester film
As film raw polymer, intrinsic viscosity is 0.62dl/g and the PET resin pellet being substantially free of particle under the decompression of 133Pa, at 135 DEG C dry 6 hours.Then, supply extruder, at about 280 DEG C, melt extrude slabbing, chilling on the rotation cool metal roller remaining on surface temperature 20 DEG C, makes its closely sealed solidification, obtains the PET sheet that do not stretch.
Roller group and the infrared heater of the PET sheet that this do not stretched heating are heated to 100 DEG C, then stretch 3.5 times by the roller group with peripheral speed difference at length direction, obtain uniaxial tension PET film.
Next, after adopting rolling method aforementioned coating liquid to be applied to the one side of PET film, drying 20 seconds at 80 DEG C.It should be noted that, the dried coating weight carrying out adjusting to make final (after biaxial stretch-formed) is 0.15g/m 2.Then, stretch in the direction of the width at 120 DEG C 4.0 times with stenter, under the state that the length of the width by film is fixing, heat 0.5 second at 230 DEG C, at 230 DEG C, carry out the relaxation processes of the width of 10 seconds 3% again, obtain the easy-adhesion polyester film of thick 100 μm.
Evaluation result is shown in table 5.
(3) manufacture of laminated polyester film
On the SUS plate keeping the thick 1mm cleaned (SUS304), place the following light-cured type acrylic acid series coating fluid of about 5g, overlap with the coating aspect of film sample and light-cured type acrylic acid series coating fluid phase ground connection, on film sample, use the hand loading rubber rollers of wide 10cm, diameter 4cm to carry out crimping light-cured type acrylic acid series coating fluid is expanded.Next, from face side, use high-pressure mercury light irradiation 800mJ/cm 2ultraviolet, light-cured type acrylic resin is solidified.From SUS plate by have thick 20 μm light-cured type acrylic resin layer film sample peel off, obtain laminated polyester film.
Light-cured type acrylic acid series coating fluid
Light-cured type acrylic resin 60.00 quality %
(Xin Zhong village chemistry 4G processed)
Light-cured type acrylic resin 20.00 quality %
(Xin Zhong village chemistry A-TMMT processed)
Light-cured type acrylic resin 10.00 quality %
(Xin Zhong village chemistry A-BPE-4 processed)
Light-cured type acrylic resin 8.00 quality %
(Xin Zhong village chemistry U-6HA processed)
Photoepolymerizationinitiater initiater 2.00 quality %
(Ciba Specialty Chemicals Irgacure 184)
Embodiment 23
Except the polyester water dispersion (B-1) polyester water dispersion being become molecular weight 20000, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 22.
Embodiment 24
Except the polyester water dispersion (B-3) polyester water dispersion being become molecular weight 23000, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 22.
Embodiment 25
Except being become by coating fluid except following coating fluid, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 22.
(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 being become by coating fluid except following coating fluid, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 22.
(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 being become by coating fluid except following coating fluid, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 22.
(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 being become by coating fluid except following coating fluid, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 22.
(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 being become by coating fluid except following coating fluid, obtain easy-adhesion polyester film and laminated polyester film similarly to Example 22.
(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 being become except water-soluble carbodiimide compound (C-3) by water-soluble carbodiimide compound (C-1), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 22.
Embodiment 31
Except being become except water dispersible carbodiimide compound (C-4) by water-soluble carbodiimide compound (C-1), obtain easy-adhesion polyester film and laminated polyester film similarly to Example 22.
[table 5]
Industry utilizes possibility
Easy bonded polyester film of the present invention, due to the adaptation of optical functional layer and hot and humid under adaptation (humidity resistance) excellent, be therefore suitable as the base material film of the optical functional films such as antireflection film that be mainly used in display etc., that employ 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 (6)

1. an easy-adhesion thermoplastic resin film, be the easy-adhesion thermoplastic resin film having coating layer at least one mask of base material film, thermoplastic resin film is polyester film, and described coating layer contains:
A () take polycarbonate polyol as the polyurethane resin of constituent and/or number-average molecular weight more than 15000 and does not substantially have the mylar of carboxylic acid group,
(b) carbodiimide compound,
Described carbodiimide compound has and has carried out poly-(ethylene oxide) of end-capped with alkoxyl and/or carried out poly-(propylene oxide) chain of end-capped with alkoxyl,
Wherein, in described coating layer, the content of carbodiimide meets the following conditions:
When described coating layer using with polycarbonate polyol be the polyurethane resin of constituent and carbodiimide compound as principal component time, containing the carbodiimide of 0.5 ~ 3.5mmol/g in described coating layer;
When described coating layer is not with number-average molecular weight more than 15000 and when substantially having the mylar of carboxylic acid group and carbodiimide compound for principal component, containing the carbodiimide of 0.3 ~ 3.3mmol/g in coating layer;
When described coating layer using take polycarbonate polyol as the polyurethane resin of constituent, number-average molecular weight more than 15000 and when not there is the mylar of carboxylic acid group and carbodiimide compound substantially as principal component, containing the carbodiimide of 0.1 ~ 2.0mmol/g in coating layer.
2. easy-adhesion thermoplastic resin film as claimed in claim 1, wherein, described polyurethane resin has polyoxyalkylenes.
3. easy-adhesion thermoplastic resin film as claimed in claim 1, wherein, described mylar is containing the dicarboxylic acid component shown in following formula (1) and/or the diol component shown in following formula (2):
(1) HOOC-(CH 2) n-COOH (in formula, n is the integer of 4≤n≤10)
(2) HO-(CH 2) n-OH (in formula, n is the integer of 4≤n≤10).
4. easy-adhesion thermoplastic resin film as claimed in claim 1, wherein, described mylar contains naphthalenedicarboxylic acid as sour composition.
5. easy-adhesion thermoplastic resin film as claimed in claim 1, wherein, described carbodiimide compound is water-soluble, and turbidity is less than 2.5%.
6. laminating thermoplastic's resin molding, it is formed by stacked at least 1 one functional layer selected from hard conating, light diffusion layer, prism-like lens jacket, electromagnetic wave absorbing layer, near infrared ray barrier layer, transparency conducting layer on the described coating layer of the easy-adhesion thermoplastic resin film described in any one in Claims 1 to 5.
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