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CN103649143A - Aqueous polyurethane resin composition, and highly-adhesive polyester film to which said aqueous polyurethane resin composition has been applied - Google Patents

Aqueous polyurethane resin composition, and highly-adhesive polyester film to which said aqueous polyurethane resin composition has been applied Download PDF

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Publication number
CN103649143A
CN103649143A CN201280034728.5A CN201280034728A CN103649143A CN 103649143 A CN103649143 A CN 103649143A CN 201280034728 A CN201280034728 A CN 201280034728A CN 103649143 A CN103649143 A CN 103649143A
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Prior art keywords
polyurethane resin
resin composition
water soluble
acid
soluble polyurethane
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CN103649143B (en
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藤田直博
柏崎史
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Adeka Corp
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Adeka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided are: an aqueous polyurethane resin composition having excellent adhesiveness to synthetic resins, and tackiness and blocking resistance after application, said composition having (A) a polyol, (B) a polyisocyanate, (C) a hydrophilic compound represented by general formula (1), (D) a monohydroxy vinyl ether compound represented by general formula (2), and water as essential components; and a highly-adhesive polyester film having a highly-adhesive layer obtained by applying the aqueous polyurethane resin composition to at least one surface of the polyester film. The aqueous polyurethane resin composition is characterized in that the amount of an alkylene oxide unit represented by (C2H4-O)n in the (C) component is 3 to 20 mass% of the solid content comprising the (A) to (D) components, and the content of the (D) component is 3 to 25 mass% of the aforementioned solid content.

Description

Water soluble polyurethane resin composition, be coated with the highly adhesive polyester film that this water soluble polyurethane resin composition forms
Technical field
The highly adhesive polyester film that the present invention relates to water soluble polyurethane resin composition and form at this water soluble polyurethane resin composition of at least coated on one side of polyester film base material, in detail, relate to cohesiveness after binding property to synthetic resins, coating and the water soluble polyurethane resin composition of resistance to blocking excellence, and with the excellent highly adhesive polyester film of the binding property transparency (mist degree) excellent and film of base material film and energy line curing resin.
Background technology
Urethane resin has filming or molding of wear resistance, binding property, non-adhesive, caoutchouc elasticity etc. owing to being made into, so be widely used in coating, tackiness agent, binding agent, coating agent etc.
In recent years, safety perspective from environmental pollution, labour hygiene etc., many water soluble polyurethane resin compositions have been reported, but compare with the composition of solvent based or solvent-free class, water soluble polyurethane resin composition has water tolerance, thermotolerance, the problem of the poor properties of binding property etc.
Using water soluble polyurethane resin composition as laminated while using with gravure printing ink or coating agent, except needs water tolerance, thermotolerance, outside the physical properties excellent of tensile properties etc., adaptation to ink and substrate agent, bonding and resistance to blocking also need excellence, for example, reported with specific hydroxycarboxylic acid and reacted the water soluble polyurethane resin forming, and adopt their binding agent for printing-ink (patent documentation 1), as polyhydroxy reactant, having adopted polyester glycol and hydroxyl value is the water soluble polyurethane resin composition of 3 above polyvalent alcohols, and adopt coating agent for plastics film (patent documentation 2) of this water soluble polyurethane resin composition etc.
Yet the performance of these carbamate resins can not make people fully satisfied.
And in recent years, water soluble polyurethane resin composition also starts to improve the coating layer that the binding property of the polyester film use as optical thin film is object and use as take.
In polyester film, especially be used to the Biaxially oriented polyester film that optics is used, it is excellent at aspects such as the transparency, dimensional stability, mechanical characteristics, thermotolerance, electrology characteristic, barrier properties for gases, chemical proofings, therefore except being used to wrapping material, plate-making material, display material, transfer materials, window subsides material etc., also be used at thin film switch, or anti-reflection film used in flat-panel monitor etc., the optical thin film of diffusion sheet, prismatic lens etc., in transparent touch-sensitive panel etc.
Yet, in these purposes, when coating on polyester film or laminated other materials, exist because of the different problems that cause binding property to worsen of used material.
And, as improveing one of fusible method of polyester film, the known various resins of surface coated that have at polyester film, thus setting has the method for the coating layer of highly adhesive energy.
For example, acrylic resin (patent documentation 3) using trimeric cyanamide as linking agent is disclosed, acrylic resin using oxazoline as linking agent, carbamate resins or vibrin (patent documentation 4), copolymer polyester resin and urethane resin (patent documentation 5), the technology (patent documentation 6～9) of using specific urethane resin as coating agent.
Yet, with regard to this existing highly adhesive coating layer, when using the active energy line curing resin of UV cured resin etc. as top coat (hard coat), with use the situation of the surfacer of solvent based and compare, because the active energy line curing resin penetration of cured resin etc. is low to the degree of easy bonding coat, make the effect of easy bonding coat swelling little, so there is the shortcoming that cannot obtain sufficient engaging force.
In addition, with regard to thering is the polyester film of hard coat of the coating layer of highly adhesive and active energy line curing resin layer etc.,, there is the problem such as mist degree uprises, the transparency reduces in the factor due to the refringence of above-mentioned coating layer and above-mentioned polyester film and hard coat etc.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-231813 communique
Patent documentation 2: TOHKEMY 2002-234931 communique
Patent documentation 3: Japanese kokai publication hei 08-281890 communique
Patent documentation 4: Japanese kokai publication hei 11-286092 communique
Patent documentation 5: TOHKEMY 2000-229395 communique
Patent documentation 6: Japanese kokai publication sho 61-261326 communique
Patent documentation 7: Japanese kokai publication hei 01-218832 communique
Patent documentation 8: Japanese kokai publication hei 02-158633 communique
Patent documentation 9: TOHKEMY 2009-220376 communique
Summary of the invention
The problem that invention will solve
Thereby the first object of the present invention is, provide and the binding property of synthetic resins or ink, cohesiveness after coating and the water soluble polyurethane resin composition of resistance to blocking excellence.
And the second object of the present invention is, provides excellent with the binding property of base material film and energy line curing resin, simultaneously the excellent highly adhesive polyester film of the transparency (mist degree) of film.
The method of dealing with problems
In order to realize above-mentioned all objects, the inventor concentrates on studies, it found that, usings the hydrophilic compounds with ad hoc structure and can solve above-mentioned problem as the water soluble polyurethane resin composition of neccessary composition, thereby completed the present invention by using.
; the invention provides a kind of water soluble polyurethane resin composition; its be using hydrophilic compounds that (A) polyvalent alcohol, (B) polymeric polyisocyanate, (C) following general formula (1) represent, the monohydroxy vinyl ether compound that (D) following general formula (2) represents and water as the water soluble polyurethane resin composition of neccessary composition; it is characterized in that, in described (C) composition by (C 2h 4-O) nin the time of the amount of 3～20 quality % of serve as reasons described (the A)～solids component that (D) composition forms of the alkylene oxide unit representing, 3～25 quality % that the content of described (D) composition is described solids component.
The present invention also provides a kind of coating agent, it is characterized in that, contains described water soluble polyurethane resin composition.
The present invention also provides a kind of highly adhesive polyester film, it is characterized in that, has easy bonding coat, and described easy bonding coat is at least at water soluble polyurethane resin composition described in the coated on one side of polyester film, to form.And,
The present invention also provides a kind of optical thin film, it is characterized in that, on the urethane resin layer of described highly adhesive polyester film, also has the hard coat consisting of active energy line curing resin.
Figure BDA0000456232290000031
Wherein, the R in formula 1for removed the residue of a hydroxyl or the group being represented by RNHCO-, R from 2～4 yuan of alcohol 2for methyl or ethyl, the integer that n is 5～35, described R for having removed the residue of an isocyanate group from the trimer compound of vulcabond.
Figure BDA0000456232290000032
Wherein, the R in formula 3for the alkylidene group of carbonatoms 2～9, m is 1 or 2.
Preferably, the R of described general formula (1) 1for removed the residue of a hydroxyl, the integer that n is 10～20 from 3 yuan of alcohol.
And preferably, the median size of the dispersate in described water soluble polyurethane resin composition is below 100nm.
The effect of invention
The adaptation of water soluble polyurethane resin composition of the present invention and base material, cohesiveness and resistance to blocking are excellent, are suitable for use as coating agent or tackiness agent.Particularly, by the water soluble polyurethane resin composition of the present invention of the surface coated at polyester film, can obtain that mist degree is low, the transparency is good, simultaneously with the binding property of hard coat also good highly adhesive polyester film.
Embodiment
The hydrophilic compounds that water soluble polyurethane resin composition of the present invention contains (A) polyvalent alcohol, (B) polymeric polyisocyanate, (C) described general formula (1) expression, monohydroxy vinyl ether compound and the water that (D) described general formula (2) represents.
For described (A) polyvalent alcohol, be not particularly limited, for example, can enumerate polyether glycol class, polyester polyols alcohols, polyester-polycarbonate polyalcohols and crystallinity or noncrystalline polycarbonate polyol class etc.
As the example of described polyether glycol class, can enumerate oxyethane and/or propylene oxide adduct that number-average molecular weight is less than the amine compound etc. of 200 small molecules polyalcohols, dihydroxyphenyl propane or quadrol etc., and polytetramethylene ether diol etc.
The small molecules polyalcohols that is less than 200 as described number-average molecular weight, for example, can enumerate ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, Diethylene Glycol, triethylene glycol, 2-butyl-2-ethyl-1, ammediol, 1, 4-butyleneglycol, neopentyl glycol, 3-methyl-2, 4-pentanediol, 2, 4-pentanediol, 1, 5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 6-hexylene glycol, 1, 7-heptanediol, 3, 5-heptanediol, 1, 8-ethohexadiol, 2-methyl isophthalic acid, 8-ethohexadiol, 1, the aliphatic diol of 9-nonanediol etc., cyclohexanedimethanol, the ester ring type glycol of cyclohexanediol etc., trimethylolethane, TriMethylolPropane(TMP), hexose alcohols, pentose alcohols, glycerine, Polyglycerine, tetramethylolmethane, Dipentaerythritol, 3 yuan of above polyvalent alcohols of tetra methylol propane etc.
As described polyester polyols alcohols, can enumerate by described number-average molecular weight and be less than the polyvalent alcohol of 200 small molecules polyvalent alcohol etc. and the polycarboxylic acid of Bi Qi stoichiometric number amount still less or the direct esterification reaction of its ester formative derivative or polyester polyol that transesterification reaction obtains, and the polyester polyol being obtained by the direct esterification reaction of described polyvalent alcohol and lactone or the hydroxycarboxylic acid that obtained by its hydrolysis reaction.
As above-mentioned polycarboxylic acid, for example, can enumerate oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, bay diacid, 2-methylsuccinic acid, 2-methyl hexanodioic acid, 3-methyl hexanodioic acid, 3-methylglutaric acid, 2-methyl suberic acid, 3, 8-dimethyl sebacic acid, 3, 7-dimethyl sebacic acid, hydrogenated dimer acids, the aliphatic dicarboxylic acid class of dimeracid etc., phthalic acid, terephthalic acid, m-phthalic acid, the aromatic dicarboxylic acid class of naphthalic acid etc., the ester ring type omega-dicarboxylic acids of cyclohexane dicarboxylic acid etc., trimellitic acid, trimesic acid, the tricarboxylic acids of the trimer of Castor Oil Fatty Acid etc., 4 yuan of above carboxylic acids of Pyromellitic Acid etc.
As the ester formative derivative of described polycarboxylic acid, can enumerate the acid anhydrides of above-mentioned polycarboxylic acid, the carboxylic acid halides compound of muriate, bromide etc., the lower aliphatic ester of methyl esters, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, pentyl ester etc. etc.
As described lactone, can enumerate γ-hexalactone, δ-caprolactone, 6-caprolactone, dimethyl-6-caprolactone, δ-valerolactone, γ-valerolactone, gamma-butyrolactone etc.
As the example of described polyester-polycarbonate polyalcohols, can enumerate the polyester glycol of polycaprolactone polyol etc. and the resultant of reaction of alkylene carbonate and react by the resultant of reaction of ethylene carbonate and polyvalent alcohol the resultant of reaction obtaining with organic dicarboxylic acid.
And, example as described crystallinity or noncrystalline polycarbonate polyol class, can enumerate 1, ammediol, 1,4-butyleneglycol, 1, the resultant of reaction of the cyclic carbonate of the diaryl carbonate of the glycol of 6-hexylene glycol, Diethylene Glycol, polypropylene glycol and/or polytetramethylene glycol etc., photoreactive gas, diphenyl carbonate etc. or propylene carbonate etc. etc.
The number-average molecular weight of described polyether glycol class, polyester polyols alcohols, polyester-polycarbonate polyalcohols, crystalline polycarbonate polyalcohols and noncrystalline polycarbonate polyol class is preferably 300～5000, and more preferably 500～3000.
In water soluble polyurethane resin composition of the present invention, owing to can making the adaptation under damp and hot become good, therefore in these polyalcohols, particularly preferably use polycarbonate polyol class.
In the present invention, described polyvalent alcohol can only be used a kind, and also two or more kinds may be used.
And, also can be used together the small molecules polyalcohols that these polyvalent alcohols and above-mentioned number-average molecular weight are less than 200.
For described (B) polymeric polyisocyanate, be not particularly limited, for example, can enumerate vulcabond and in 1 molecule, there is polymeric polyisocyanate of more than 3 isocyanate group etc.
Example as vulcabond, can enumerate tolylene diisocyanate, ditan-4, 4 '-vulcabond, to phenylene vulcabond, xylylene diisocyanate, 1, 5-naphthalene diisocyanate, 3, 3 '-dimethyl diphenyl-4, 4 '-vulcabond, dianisidine vulcabond, the aromatic diisocyanate class of tetramethyl-benzene dimethyl vulcabond etc., isophorone diisocyanate, dicyclohexyl methyl hydride-4, 4 '-vulcabond, trans and/or cis-1, 4-cyclohexyl diisocyanate, the ester ring type diisocyanates of sub-norcamphyl vulcabond etc., 1, 6-hexamethylene diisocyanate, 2, 2, 4 and/or (2, 4, 4)-trimethyl hexamethylene diisocyanate, the aliphatic diisocyanate class of lysinediisocyanate etc. etc.
As there is the example of more than 3 polymeric polyisocyanate of isocyanate group in 1 molecule, can enumerate triphenylmethane triisocyanate, 1-methylbenzene-2, 4, 6-triisocyanate, dimethyl triphenyl methane tetraisocyanate, isocyanic ester more than 3 functionality that formed by these mixtures etc., the carbodiimide modified of these isocyanic ester more than 3 functionality, isocyanurate-modified, the modifier of biuret modified grade, these are carried out to the blocked isocyanate of end-blocking by various end-capping reagents, the isocyanuric acid ester of above-mentioned vulcabond (trimer) and biuret trimer etc.
In these, based on easy acquisition and can obtain the viewpoint of the water soluble polyurethane resin composition that weathering resistance and intensity etc. are excellent, preferably use in the present invention aliphatic diisocyanate or ester ring type vulcabond, wherein, particularly preferably use 1,6-hexamethylene diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, isophorone diisocyanate.
In the present invention, these polymeric polyisocyanates can only be used a kind, and also two or more kinds may be used.
As the R in the hydrophilic compounds being represented by general formula (1) of described (C) 1, be from 2～4 yuan of alcohol, to have removed the residue of a hydroxyl or the group being represented by RNHCO-.
Example as above-mentioned 2～4 yuan of alcohol, can enumerate ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 1, 4-butyleneglycol, neopentyl glycol, 3-methyl-2, 4-pentanediol, 2, 4-pentanediol, 1, 5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 6-hexylene glycol, 1, 7-heptanediol, 3, 5-heptanediol, 1, 8-ethohexadiol, 2-methyl isophthalic acid, 8-ethohexadiol, 1, 9-nonanediol, 1, the aliphatic diol of 10-decanediol etc., and cyclohexanedimethanol for example, 2 yuan of alcohols of the ester ring type glycol of cyclohexanediol etc. etc., trimethylolethane, TriMethylolPropane(TMP), glycerine, two glycerine, tetramethylolmethane, 3～4 yuan of alcohols of tetra methylol propane etc.
In water soluble polyurethane resin composition of the present invention, (C) hydrophilic compounds enters in carbamate main chain owing to being easy to group, so R 1be preferably the residue of having removed a hydroxyl from 3～4 yuan of alcohol, wherein, based on do not cause viewpoint, the R of crosslinking reaction or end termination reaction when by hydrophilic compounds (C) and (B) reaction of isocyanic ester forms carbamate 1be preferably the residue of having removed a hydroxyl from 3 yuan of alcohol, be particularly preferably the residue of having removed a hydroxyl from TriMethylolPropane(TMP).
And, as the R in the described group being represented by RNHCO-, be from the trimer compound of vulcabond, to have removed the residue of an isocyanate group.
As the vulcabond that forms described trimer compound, the vulcabond of enumerating in the time of can being set forth in described (B) isocyanic ester of explanation.
In these, based on easy acquisition and can obtain the viewpoint of the water soluble polyurethane resin composition that weathering resistance and intensity etc. are excellent, preferably use aliphatic diisocyanate or ester ring type vulcabond, wherein, particularly preferably 1,6-hexamethylene diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, isophorone diisocyanate.
The integer that n in described general formula (1) is 5～35, but water dispersible based on resulting carbamate prepolymer becomes good viewpoint, more preferably 10～20 integer.
Described (D) in the monohydroxy vinyl ether compound that described general formula (2) represents, as by R 3the example of 2～9 the alkylidene group representing, for example, can enumerate ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, sub-sec-butyl, the sub-tertiary butyl, pentylidene, sub-sec.-amyl sec-pentyl secondary amyl, sub-tert-pentyl, hexylidene, cyclohexylidene, sub-heptyl, octylene, sub-iso-octyl, 2-ethyl hexylidene, sub-tertiary octyl group, nonamethylene, sub-different nonyl etc.
And m is 1 or 2, but is preferably 1.
As the object lesson of the compound being represented by general formula (2), can enumerate the hydroxyl vinyl ether compound of hydroxymethyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxyl amyl group vinyl ether, 6-hydroxyl hexyl vinyl ether, 9-hydroxyl nonyl vinyl ether, Diethylene Glycol mono vinyl ether etc.
As the content of (C) hydrophilic compounds in water soluble polyurethane resin composition of the present invention, be preferably make in general formula (1) by (C 2h 4-O) nthe alkylene oxide unit representing reaches the amount of 3～20 quality % of carbamate prepolymer solids component, more preferably reaches the amount of 5～16 quality %.Wherein, the quality of carbamate prepolymer solids component refers to (A)～(D) total amount of composition.
If alkylene oxide unit is less than 3 quality %, the water dispersible variation of carbamate prepolymer, if while surpassing the amount of 20 quality %, the tendency that has tensile strength that carbamate resins films and the Physical properties of coating film of the adaptation of base material etc. is reduced.
And as the content of (D) monohydroxy vinyl ether compound, 3～25 quality % for carbamate prepolymer solids component, are preferably 5～20 quality %.
If (D) content of monohydroxy vinyl ether compound is less than 3 quality %, binding property effect of the present invention becomes insufficient, if surpass the amount of 25 quality %, has the tendency of the deleterious of the viscosity of highly adhesive polyester film of the present invention or mist degree etc.
Moreover, as described (A)～(D) the blending amount of composition, be preferably and make all isocyanate group equivalents with respect to (A)～(D) ratio (NCO/OH) of all hydroxyl equivalents of composition reaches 1.1～2.5 blending amount, more preferably make above-mentioned ratio reach 1.2～2.0 blending amount, be particularly preferably and make above-mentioned ratio reach 1.3～1.8 blending amount.
All hydroxyl equivalents refer to (A) polyvalent alcohol, (C) hydrophilic compounds and (D) total amount of the hydroxyl equivalent of monohydroxy vinyl ether compound, all isocyanate group equivalents refer to the isocyanurate equivalent of (B) isocyanic ester, or when (C) hydrophilic compounds contains isocyanate group, refer to (B) composition and (C) total amount of the isocyanate group equivalent of composition.
If described NCO/OH is than more than 1.0 and be less than 1.1, due to the higher molecular quantification of carbamate prepolymer, produce the tendency of the water dispersible variation of carbamate prepolymer, there is the situation of the variation such as storage stability of water soluble polyurethane resin, if surpass 2.5, in the performance of water soluble polyurethane resin, likely have problems, for example, when the water-dispersion of prepolymer, because causing violent foaming etc., the carbonic acid gas of following the reaction of isocyanate group and water to generate produces the problem in manufacture, or produce and to film to the tendency of the deleterious of the binding property of substrate resin etc. etc.
And, described NCO/OH ratio is less than at 1.0 o'clock, becomes the carbamate prepolymer of terminal hydroxyl, but water dispersible based on terminal isocyanate prepolymer is excellent, be easy to come by chain extension the viewpoint of polymer quantification etc. simultaneously, conventionally preferably manufacture terminal isocyanate prepolymer.
For the manufacture method of water soluble polyurethane resin composition of the present invention, there is no particular limitation, can use known method, for example, make (A) polyvalent alcohol and (B) isocyanic ester, (C) hydrophilic compounds, the reaction of (D) monohydroxy vinyl ether compound, add even as required the reaction of radical ion imported agent, thereby synthesis of carbamates prepolymer, the carbamate prepolymer obtaining is carried out to water-dispersion and make after carbamate resins, in water, with extender, carry out the method for chain extension.
In carbamate prepolymer synthetic, can use as required reaction is inertia and the solvent large with the affinity of water.
As carbamate prepolymer being carried out to the method for water-dispersion, have (1) to add to make it after prepolymer the prepolymer hybrid system of disperseing in water, and (2) add in prepolymer and make it the phase transfer method that disperses etc. after water.
When carbamate prepolymer is carried out to water-dispersion, while adding ionic group neutralizing agent and/or emulsifying agent if be necessary, both can add in water, also can add in carbamate prepolymer, but these emulsifying agents normally be added in water.
As above-mentioned to reaction, be inertia and the solvent large with the affinity of water, preferred example is acetone, methylethylketone, dioxan, tetrahydrofuran (THF), METHYLPYRROLIDONE etc.
As the usage quantity of these solvents, total amount 100 mass parts of the composition of described raw material (A) used when manufacturing prepolymer～(D) and radical ion imported ingredient, are 3～100 mass parts.
And, if while using boiling point to be the solvent below 100 ℃, preferably, after having synthesized water soluble polyurethane resin, by underpressure distillation etc., remove solvent in these solvents.
As above-mentioned ionic group imported agent, there are anionic property group imported agent and cationic group imported agent.
As the example of anionic property group imported agent, can enumerate the polyalcohols that dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl butanic acid, dihydroxymethyl valeric acid etc. contain carboxyl, and BDO-2-sulfonic acid etc. contains sulfonic polyalcohols.
And, as the example of cationic group imported agent, can enumerate N, N-dialkyl group alkanol amine, N-methyl-N, N-diethanolamine, N-butyl-N, the N-alkyl-N of N-diethanolamine etc., N-dialkanol amine, and three alkanol amines.
And, as the blending amount of ionic group imported agent, be preferably 0～30 quality % of the carbamate prepolymer being formed by described (A)～(D) composition and ionic group imported agent, more preferably 0～20 quality %, is particularly preferably 0～10 quality %.If the content of ionic group imported agent surpasses 30 quality %, along with the focusing energy increase of amino-formate bond, cause the viscosity rise of carbamate prepolymer, thus the problem of generation water-dispersion change difficulty etc.
As described ionic group neutralizing agent, there are anionic property group neutralizing agent and cationic group neutralizing agent.
Example as anionic property group neutralizing agent, can enumerate the trialkyl amines of Trimethylamine, triethylamine, tributylamine etc., N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, the N of N-dipropyl thanomin, 1-dimethylamino-2-methyl-2-propanol etc., N-dialkyl group alkanol amine, N-alkyl-N, the tertiary amine compound of three alkanol amines of N-dialkanol amine, trolamine etc. etc., the basic cpd of ammonia, trimethyl ammonium oxyhydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide etc.
And, example as cationic group neutralizing agent, except enumerating the organic carboxyl acid of formic acid, acetic acid, lactic acid, succsinic acid, pentanedioic acid, citric acid etc., the organic sulfonic acid of tosic acid, alkyl sulfonate esters etc., the mineral acid of hydrochloric acid, phosphoric acid, nitric acid, sulfonic acid etc., outside the epoxy compounds of epihalohydrins etc. etc., also can enumerate the quaternizing agent of dialkyl group sulfuric acid, halogenated alkyl etc.
As the usage quantity of described ionic group neutralizing agent, with respect to ionic group 1 equivalent, be preferably 0.5～2.0 equivalent, more preferably 0.8～1.5 equivalent.
If the usage quantity of neutralizing agent is less than described 0.5 equivalent or more than 2.0 equivalents, likely cause the storage stability of water soluble polyurethane resin or the physical property of water soluble polyurethane resin film strength, stretching etc. to reduce.
Example as described emulsifying agent, can enumerate the cationic surfactant of common anionic surfactant and nonionic surfactant and primary amine salt, secondary amine salt, tertiary ammonium salt, quaternary ammonium salt and pyridinium salt etc., in addition also can enumerate, the known emulsifying agents such as amphoterics of betaine type, sulfuric acid ester type and sulfonic acid type etc.
As above-mentioned anionic surfactant, can enumerate sodium lauryl sulphate, dodecyl sulphate potassium, the alkylsurfuric acid salt of ammonium lauryl sulfate etc., Brij-35 sodium sulfate, the polyoxyethylene ether sulfate class of Voranol EP 2001 ammonium sulfate etc., natrium sulforicinoleicum, the an alkali metal salt of sulfonated alkane, the alkylsulfonate of the ammonium salt of sulfonated alkane etc., sodium laurate, triethanolamine oleate, the soap of sylvic acid trolamine etc., Phenylsulfonic acid sodium salt, the alkylaryl sulphonate of the alkali metal sulfates of alkalescence phenolic hydroxyl group ethene etc., high sulfonated alkyl naphathalene, naphthene sulfonic acid formalin condenses, dialkyl sulfosuccinates, laureth sulfate, polyxyethylated aryl-sulfate, polyoxyethylene ether phosphate, Voranol EP 2001 acetate, N-acyl amino hydrochlorate, N-acyl methyl taurine salt etc.
As described nonionic surfactant, can enumerate the fatty acid part ester class of the polyvalent alcohol of sorbitol anhydride mono-laurate, sorbitan mono-oleic acid ester etc., cithrol class, polyglycerol fatty acid ester class, the oxyethane of the alcohol of carbonatoms 1～18 and/or propylene oxide adduct, the oxyethane of alkylphenol and/or propylene oxide adduct, the oxyethane of aklylene glycol and/or Alkylenediamine and/or propylene oxide adduct etc.
As the alcohol that forms the carbonatoms 1～18 of these nonionic surfactants, can enumerate methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, 2-butanols, the trimethyl carbinol, amylalcohol, primary isoamyl alcohol, tertiary amyl alcohol, hexanol, octanol, decyl alcohol, lauryl alcohol, cardanol, palmityl alcohol, stearyl alcohol etc.
As described alkylphenol, can enumerate phenol, methylphenol, 2,4-DI-tert-butylphenol compounds, 2,5-DI-tert-butylphenol compounds, 3,5-DI-tert-butylphenol compounds, 4-(1,3-tetramethyl butyl) phenol, 4-isooctyl phenol, 4-nonylphenol, 4-tert-octyl phenol, 4-dodecyl phenol, 2-(3,5-dimethyl heptyl) phenol, 4-(3,5-dimethyl heptyl) phenol, naphthols, dihydroxyphenyl propane, Bisphenol F etc.
As described aklylene glycol, can enumerate ethylene glycol, 1,2-PD, 1,3-PD, 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, BDO, neopentyl glycol, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, 2,4-diethyl-1,5-PD, 1,6-hexylene glycol etc.
And, as Alkylenediamine, can enumerate compound that the alcohol hydroxyl group of these aklylene glycols replaced by amino etc.
As oxyethane and the propylene oxide adduct of these compounds, can be random affixture, can be also blocked adduct.
As described cationic surfactant, can enumerate lauryl trimethyl ammonium muriate, stearyl trimethyl ammonium muriate, distearyl dimethyl ammonium chloride, didecyldimethyl ammonium muriate, lauryl benzyl dimethyl ammonium muriate, didecyldimethyl ammonium muriate, alkyl pyridine bromide and tetrahydroglyoxaline lauroleate etc.
As described amphoterics, can enumerate the betaine type of the metal-salt etc. of Oleum Cocois fatty acyl amido propyl-dimethyl acetic acid trimethyl-glycine, lauryl dimethyl amino acid trimethyl-glycine, 2-alkyl-N-carboxyl methyl-N-hydroxymethyl imidazolinium betaine, lauryl hydroxyl sulfo betaine, lauroyl amido ethyl hydroxyethyl carboxyl methyl betaine, hydroxypropyl phosphoric acid, amino acid pattern, sulfuric acid ester type and the sulfonic acid type etc. of the metal-salt of β-lauryl alanine etc.
For the usage quantity of described emulsifier component, there is no particular limitation, but the viewpoint of the physical property based on by the resulting painting film strength of coating water soluble polyurethane resin composition, stretching etc., total amount 100 mass parts with respect to urethane resin solids component, be preferably 0～30 mass parts, more preferably 0～20 mass parts.If surpass 30 mass parts, likely cause the physical property of above-mentioned carbamate resins film to reduce.
As described extender, can use from as described in number-average molecular weight be less than compound 200 small molecules weight polyalcohol compound and small molecules polyamine compounds, that suitably select normally used extender.
As this extender composition, for example, except can enumerating above-mentioned small molecules glycols, also can enumerate quadrol, propylene diamine, hexamethylene-diamine, tolylene diamine, piperazine, the small molecules Diamines of 2-methylpiperazine etc., polypropyleneoxide diamine, the polyether diamine class of polyethyleneoxide diamine etc., menthane diamines, isophorone diamine, sub-norcamphyl diamines, amino-ethyl cyclo-imino ethanol, two (4-amino-3-methyl bicyclic hexyl) methane, diamino-dicyclohexyl methane, two (amino methyl) hexanaphthene, two (the 3-aminopropyls)-2,4,8 of 3,9-, the ester ring type Diamines of 10-tetra-oxaspiros (5,5) undecane etc., m-xylene diamine, α-(/ p-aminophenyl) ethamine, mphenylenediamine, diaminodiphenyl-methane, diamino diphenyl sulfone, diamino diethyl-dimethyl ditan, diamino diethyl ditan, dimethyl sulphide is for tolylene diamine, diethyl toluene diamine, α, the polyamines of α '-bis-(4-aminophenyl)-to aromatic diamines of diisopropyl benzene etc. etc., amber acid dihydrazide, adipic dihydrazide, sebacic dihydrazide, O-phthalic acid dihydrazide, hydrazine hydrate, 1,6-hexa-methylene two (N, N-dimethylamino urea), 1,1,1 ', 1 '-tetramethyl--4, the hydrazine class of 4 '-(two pairs of phenylenes of methylene radical) diaminourea etc., and water etc.
Usage quantity as described extender composition, viewpoint based on carbamate resins physical property etc., the ratio that is preferably the isocyanate group equivalent of the carbamate prepolymer of isocyanate reaction base equivalent before with respect to chain extension reaction that makes extender reaches 0.1～1.0 amount.
In the water soluble polyurethane resin composition the present invention relates to, also can blending there is the compound of unsaturated link(age).
As the compound with unsaturated link(age), for example, can enumerate ethene, propylene, butylene, iso-butylene, amylene, vinyl acetate, vinyl alcohol, vinylbenzene, vinyl cyanide, (methyl) vinylformic acid, toxilic acid, methylene-succinic acid, β-crotonic acid, (methyl) acrylate, urethane acrylate and epoxy acrylate etc.
As described (methyl) acrylate, can enumerate (methyl) vinylformic acid and methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, 2-butanols, isopropylcarbinol, the trimethyl carbinol, the alkyl alcohols of octanol etc., with ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 1, 4-butyleneglycol, neopentyl glycol, 3-methyl-2, 4-pentanediol, 2, 4-pentanediol, 1, 5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl-2, the small molecules glycols of 4-pentanediol etc., with 2-methyl cellosolve, 4-methoxybutanol, the ether alcohol class of MPEG-550 etc., or with the ester cpds of polyether glycol of polyoxyethylene glycol etc. etc.
And, in the aqurous ployurethane composition the present invention relates to, can use reaction terminating agent as required.
As this reaction terminating agent, can enumerate alkylol cpd, monoamine compound etc.These both can use a kind, also can mix two or more and use.As above-mentioned alkylol cpd, can enumerate methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, octanol etc., as this monoamine compound, can enumerate ethamine, propylamine, 2-propylamine, butylamine, 2-butylamine, TERTIARY BUTYL AMINE, the alkylamine of isobutylamine etc., aniline, monomethylaniline, nonox, the aromatic amine of naphthylamines etc., hexahydroaniline, the ester ring type amine of methyl cyclohexylamine etc., 2-methoxyethyl amine, 3 methoxypropyl amine, 2-(2-methoxy ethoxy) the ether amine of ethamine etc., thanomin, Propanolamine, butylethanolamine, 1-amino-2-methyl-2-propyl alcohol, 2-amino-2-methyl propyl alcohol, diethanolamine, diisopropanolamine (DIPA), dimethylaminopropyl thanomin, dipropanolamine, N-Mono Methyl Ethanol Amine, the alkanolamine of N-ehtylethanolamine etc. etc.
And in water soluble polyurethane resin composition of the present invention, mixed cross-linker is used as required.As linking agent, there are internal crosslinker and outside cross-linking agent, internal crosslinker mixes when carbamate prepolymer synthetic, and outside cross-linking agent is blended in water soluble polyurethane resin.
As described internal crosslinker, for example, can enumerate the melamine compound of trimeric cyanamide, monomethylol trimeric cyanamide, dihydroxymethyl trimeric cyanamide, trimethylol melamine, tetra methylol trimeric cyanamide, pentamethylol melamine, hexamethylolmelamine, the melamine methylol that methylates, butylated methylol melamine etc., or the small molecules polyol compound with 3 hydroxyls of TriMethylolPropane(TMP) etc. etc.
In these, preferably use the trimeric cyanamide to the excellent dispersion of water soluble polyurethane resin composition.
As described outside cross-linking agent, can enumerate the affixture of urea, trimeric cyanamide, benzoguanamine etc. and formaldehyde, the aminoresin of alkylether compounds being formed by the alcohol of these affixtures and carbonatoms 1～6 etc., multi-functional epoxy compounds, multi-functional isocyanate compound, blocked isocyanate compounds, multi-functional nitrogen heterocycle propane compound etc.
And, when water soluble polyurethane resin is anionic property, the compound that can react with the anionic property group of carboxyl or sulfonic group etc. can be used as linking agent.As this compound, for example, can enumerate epoxy compounds, water dispersible isocyanic ester, carbodiimide compound, ethylenimine compounds, trimeric cyanamide compounds and the chelates of zinc etc. of oxazoline compounds, water-soluble epoxy resin etc.In these, preferably use oxazoline compounds, epoxy compounds or the carbodiimide compound being easy to anionic property radical reaction.
And water soluble polyurethane resin composition of the present invention can suitably dilute afterwards and use, and was not particularly limited for its solid component concentration.Based on dispersed or form film, the viewpoint of operability during molding etc., solid component concentration is preferably 1～65 quality %, more preferably 5～50 quality %.
As the median size of the dispersate in water soluble polyurethane resin composition of the present invention, the value in the mensuration according to dynamic light scattering method is preferably below 100nm, more preferably, below 50nm, is particularly preferably below 35nm.
Particularly, to be coated with water soluble polyurethane resin composition of the present invention as the highly adhesive polyester film of easy bonding coat during for optical thin film, if the median size of described dispersate, over 100nm, exists the haze value of film to uprise, the tendency of transparent variation.On the other hand, median size is less, and haze value declines thereupon, also change is good thereupon for the transparency.
Water soluble polyurethane resin composition of the present invention be suitable for being used in synthetic resins coating and bonding in.Now, for the synthetic resins as adherend or applied thing, be not particularly limited.As this synthetic resins, for example, can enumerate polypropylene, high density polyethylene(HDPE), Low Density Polyethylene, straight-chain low density polyethylene, polybutene-1, the alpha-olefin polymer of poly-3-methylpentene etc., or ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer, the polyalkenes hydrocarbon of ethylene-propylene copolymer etc. and their multipolymer, polyvinyl chloride, polyvinylidene dichloride, chlorinatedpolyethylene, Chlorinated Polypropylene III, polyvinylidene difluoride (PVDF), chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinylchlorid-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinylchlorid-maleate copolymer, the halogen-containing resin of vinylchlorid-N-cyclohexylmaleimide multipolymer etc., petroleum resin, coumarone resin, polystyrene, polyvinyl acetate (PVA), acrylic resin, vinylbenzene and/or alpha-methyl styrene and other monomers (for example, maleic anhydride, phenyl maleimide, methyl methacrylate, divinyl, vinyl cyanide etc.) multipolymer (for example, AS resin, ABS resin, MBS resin, heat-resisting ABS resin etc.), polymethylmethacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral acetal, the straight chain polyester of polyethylene terephthalate and polybutylene terephthalate etc., polyphenylene oxide, the polymeric amide of polycaprolactam and polyhexamethylene adipamide etc., polycarbonate, polycarbonate/ABS resin, divide branched polycarbonate, polyacetal, polyphenylene sulfide, urethane, the thermoplastic resin of cellulosic resin etc. and their blend, or phenol resins, and can also enumerate urea resin, melamine resin, epoxy resin, the heat-curing resin of unsaturated polyester resin etc. etc.
In addition, the coating of elastomerics of synthetic polyisoprene, divinyl rubber, acrylonitrile-butadiene copolymer rubber, styrene butadiene copolymer rubber etc. etc. and bonding in, also can use water soluble polyurethane resin composition of the present invention.
And, in water soluble polyurethane resin composition of the present invention, can add as required normally used various additive.As these additives, for example, can enumerate hindered amine light stabilizer, the various weather resisting agent of UV light absorber and antioxidant etc., to base material, can give the silane coupling agent of firm especially adaptation, silica gel, tetraalkoxysilane and polycondensate thereof, sequestrant, and epoxy compounds, pigment, dyestuff, film coalescence aid, solidifying agent, outside cross-linking agent, viscosity modifier, flow agent, defoamer, anti-gel agent, radical scavenger, thermotolerance imparting agent, inorganic and organic filler, softening agent, lubricant, static inhibitor, toughener, catalyzer, thixotropic agent, sterilant, mould inhibitor, anticorrosive agent, and rust-preventive agent etc.
As described hindered amine light stabilizer, for example, can enumerate 2, 2, 6, 6-tetramethyl--4-piperidyl stearate, 1, 2, 2, 6, 6-pentamethyl--4-piperidyl stearate, 2, 2, 6, 6-tetramethyl--4-piperidyl benzoic ether, two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) sebate, two (1-octyloxy-2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, 1, 2, 2, 6, 6-pentamethyl--4-piperidino methyl methacrylic ester, 2, 2, 6, 6-tetramethyl--4-piperidino methyl methacrylic ester, four even (2, 2, 6, 6-tetramethyl--4-piperidyl)-1, 2, 3, 4-butane tetracarboxylic acid esters, four even (1, 2, 2, 6, 6-pentamethyl--4-piperidyl)-1, 2, 3, 4-butane tetracarboxylic acid esters, two (2, 2, 6, 6-tetramethyl--4-piperidyl) two (tridecyl)-1, 2, 3, 4-butane tetracarboxylic acid esters, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) two (tridecyl)-1, 2, 3, 4-butane tetracarboxylic acid esters, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl)-2-butyl-2-(3, 5-di-tert-butyl-4-hydroxyl benzyl) malonic ester, 1-(2-hydroxyethyl)-2, 2, 6, 6-tetramethyl--4-piperidine alcohols/ethyl succinate polycondensate, 1, 6-two (2, 2, 6, 6-tetramethyl--4-piperidyl amino) hexane/ethylene dibromide polycondensate, 1, 6-two (2, 2, 6, 6-tetramethyl--4-piperidyl amino) hexane/2, the chloro-6-morpholinyl-s-of 4-bis-triazine polycondensate, 1, 6-two (2, 2, 6, 6-tetramethyl--4-piperidyl amino) hexane/2, the tertiary octyl group amino-s-of the chloro-6-of 4-bis-triazine polycondensate, 1, 5, 8, 12-tetra-even ［ 2, two (N-butyl-the N-(2 of 4-, 2, 6, 6-tetramethyl--4-piperidyl) amino)-s-triazine-6-yl ］-1, 5, 8, 12-teteaazacyclododecane, 1, 5, 8, 12-tetra-even ［ 2, two (N-butyl-the N-(1 of 4-, 2, 2, 6, 6-pentamethyl--4-piperidyl) amino)-s-triazine-6-yl ］-1, 5, 8, 12-teteaazacyclododecane, 1, 6, 11-tri-［ 2, two (N-butyl-the N-(2 of 4-, 2, 6, 6-tetramethyl--4-piperidyl) amino)-s-triazine-6-base is amino ］ undecane, 1, 6, 11-tri-［ 2, two (N-butyl-the N-(1 of 4-, 2, 2, 6, 6-pentamethyl--4-piperidyl) amino)-s-triazine-6-base is amino ］ undecane, 3, 9-two [1, 1-dimethyl-2-［ three (2, 2, 6, 6-tetramethyl--4-piperidyl oxygen base ketonic oxygen base) butyl ketonic oxygen base ］ ethyl]-2, 4, 8, 10-tetra-oxaspiros [5.5] undecane, 3, 9-two [1, 1-dimethyl-2-［ three (1, 2, 2, 6, 6-pentamethyl--4-piperidyl oxygen base ketonic oxygen base) butyl ketonic oxygen base ］ ethyl]-2, 4, 8, 10-tetra-oxaspiros [5.5] undecane etc.
As described UV light absorber, for example, can enumerate 2,4 dihydroxyl benzophenone, ESCALOL 567, 2-hydroxyl-4-octyloxy benzophenone, 5, the 2-hydroxy benzophenone ketone of 5 '-methylene-bis (ESCALOL 567) etc., 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, the tertiary octyl phenyl of 2-(2-hydroxyl-5-) benzotriazole, 2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3,5-dicumylphenyl) benzotriazole, 2,2 '-methylene-bis (the tertiary octyl group-6-of 4-benzotriazole base phenol), 2-(2-hydroxyl-3-the tertiary butyl-5-carboxyl phenyl) macrogol ester of benzotriazole, 2-[2-hydroxyl-3-(2-acryloxy ethyl)-5-aminomethyl phenyl] benzotriazole, 2-[2-hydroxyl-3-(2-methacryloxyethyl)-5-tert-butyl-phenyl] benzotriazole, 2-[2-hydroxyl-3-(2-methacryloxyethyl) the tertiary octyl phenyl of-5-] benzotriazole, 2-[2-hydroxyl-3-(2-methacryloxyethyl)-5-tert-butyl-phenyl]-5-chlorobenzotriazole, 2-[2-hydroxyl-5-(2-methacryloxyethyl) phenyl] benzotriazole, 2-[2-hydroxyl-3-the tertiary butyl-5-(2-methacryloxyethyl) phenyl] benzotriazole, 2-[2-hydroxyl-3-tert-pentyl-5-(2-methacryloxyethyl) phenyl] benzotriazole, 2-[2-hydroxyl-3-the tertiary butyl-5-(3-methacryloxypropyl) phenyl]-5-chlorobenzotriazole, 2-[2-hydroxyl-4-(2-methacryloxy methyl) phenyl] benzotriazole, 2-[2-hydroxyl-4-(3-methacryloxy-2-hydroxypropyl) phenyl] benzotriazole, 2-[2-hydroxyl-4-(3-methacryloxypropyl) phenyl] the 2-(2-hydroxy phenyl of benzotriazole etc.) benzotriazole category, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4,6-phenylbenzene-1,3,5-triazines, 2-(2-hydroxyl-4-hexyloxy phenyl)-4,6-phenylbenzene-1,3,5-triazines, 2-(2-hydroxyl-4-octyloxyphenyl)-4, two (2,4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-, 2-[2-hydroxyl-4-(3-C12～C13 mixed oxyalkyl-2-hydroxyl propoxy-) phenyl]-4, two (2,4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-, 2-[2-hydroxyl-4-(2-acryloyl-oxy base oxethyl) phenyl]-4, two (4-the aminomethyl phenyl)-1,3,5-triazines of 6-, 2-(2,4-dihydroxyl-3-allyl phenyl)-4, two (2,4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-, the 2-(2-hydroxy phenyl of 2,4,6-tri-(2-hydroxy-3-methyl-4-hexyloxy phenyl)-1,3,5-triazines etc.)-4,6-diaryl-1,3,5-triazines class, phenyl salicylic acid esters, resorcinol monobenzoate, 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester, octyl group (3,5-di-t-butyl-4-hydroxyl) benzoic ether, dodecyl (3,5-di-t-butyl-4-hydroxyl) benzoic ether, tetradecyl (3,5-di-t-butyl-4-hydroxyl) benzoic ether, hexadecyl (3,5-di-t-butyl-4-hydroxyl) benzoic ether, octadecyl (3,5-di-t-butyl-4-hydroxyl) benzoic ether, the benzoates of docosyl (3,5-di-t-butyl-4-hydroxyl) benzoic ether etc., 2-ethyl-2 '-oxyethyl group oxanilide, the replacement oxanilide class of 2-oxyethyl group-4 '-dodecyl oxanilide etc., ethyl-alpha-cyano-β, β-diphenylacrylate ester, methyl-2-cyano group-3-methyl-3-(p-methoxyphenyl) cyanoacrylate of acrylate etc., various metal-salts or metallo-chelate.
As metal-salt or metallo-chelate, can enumerate the salt of nickel or chromium or inner complex class etc.
As described antioxidant, can enumerate Phosphorus, phenols or sulphur class antioxidant.
As Phosphorus antioxidant, for example, can enumerate triphenyl phosphorous acid ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, three (2,5-di-tert-butyl-phenyl) phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, three (dinonyl phenyl) phosphorous acid ester, three is (single, two mix nonyl phenyl) phosphorous acid ester, phenylbenzene acid phosphorous acid ester, 2,2 '-methylene-bis (4,6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, phenylbenzene decyl phosphorous acid ester, phenylbenzene octyl group phosphorous acid ester, two (nonyl phenyl) pentaerythritol diphosphites, phenyl diiso decyl phosphorous acid ester, tributyl phosphorous acid ester, three (2-ethylhexyl) phosphorous acid ester, three decyl phosphorous acid esters, three lauryl phosphorous acid esters, dibutyl acid phosphorous acid ester, dilauryl acid phosphorous acid ester, three lauryl trithiophosphite, two (neopentyl glycol) Isosorbide-5-Nitrae-hexanaphthene dimethyl diphosphites, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,5-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,4-dicumylphenyl) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite, four (C12～15 mixed alkyls)-4,4 '-isopropylidene phenylbenzene phosphorous acid ester, two ［ 2,2 '-methylene-bis (4,6-diamyl phenyl) ］ isopropylidene phenylbenzene phosphorous acid ester, four (tridecyls) 4, two (the 2-tertiary butyl-5-methylphenol) diphosphites of 4 '-butylidene, six (tridecyls) 1,1,3-tri-(2-methyl-5-tert-butyl-hydroxy phenyl) butane GW-540, four even (2,4-di-tert-butyl-phenyl) biphenylene two phosphinates, three (2-[(2, the even tertiary butyl dibenzo of 4,7,9-tetra-[d, f] [1,3,2] dioxa phospha ring-6-in heptan yl) oxygen base] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, three (2-[(2, the even tertiary butyl dibenzo of 4,8,10-tetra-[d, f] [1,3,2] dioxa phospha ring-6-in heptan yl) oxygen base] ethyl) amine, 2-(1,1-dimethyl ethyl)-6-methyl-4-[3-[[2,4,8,10-tetra-even (1,1-dimethyl ethyl) dibenzo [d, f] [1,3,2] dioxa phospha ring-6-in heptan yl] oxygen base] propyl group] phenol 2-butyl-2-ethyl glycol 2,4,6-tri-butyl-phenol list phosphorous acid ester etc.
As described phenol antioxidant, for example, can enumerate 2,6 ditertiary butyl p cresol, 2,6-phenylbenzene-4-octadecane oxygen base phenol, stearyl (3,5-di-tert-butyl-hydroxy phenyl) propionic ester, distearyl (3,5-di-tert-butyl-4-hydroxyl benzyl) phosphonic acid ester, tridecyl 3,5-di-tert-butyl-4-hydroxyl benzyl thioacetate, sulfo-di ethylene bis ［ (3,5-di-tert-butyl-hydroxy phenyl) propionic ester ］, 4,4 '-thiobis (6-tertiary butyl meta-cresol), 2-octylsulfo-4,6-bis-(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), two ［ two (4-hydroxyl-3-tert-butyl-phenyl) butyric acid of 3,3-］ diol ester, 4,4 '-butylidene two (2,6 di t butyl phenol), 4,4 '-butylidene two (the 6-tertiary butyl-3-methylphenol), 2,2 '-ethylenebis (4,6-DI-tert-butylphenol compounds), 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, two the 2-tertiary butyl-4-methyl-6-(2-hydroxyl-3-tertiary butyl-5-methyl-benzyl) and phenyl ］ terephthalate, 1,3,5-tri-(2,6-dimethyl-3-hydroxyl-4-tertiary butyl benzyl) isocyanuric acid ester, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl)-2,4,6-Three methyl Benzene, 1,3,5-tri-［ (3,5-di-tert-butyl-hydroxy phenyl) propionyloxy ethyl ］ isocyanuric acid ester, four idols methylene radical-3-(3 ', and 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester ］ methane, the 2-tertiary butyl-4-methyl-6-(2-acryloxy-3-the tertiary butyl-5-methyl-benzyl) phenol, 3,9-pair 2-(3-tertiary butyl-4-hydroxy-5-hydrogenated methyl cinnamoyloxy group) and-1,1-dimethyl ethyl ］-2,4,8,10-tetra-oxaspiros ［ 5.5 ］ undecane, triethylene glycol two ［ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester ］, tocopherol etc.
As described sulphur class antioxidant, for example, can enumerate the dialkyl group thiodipropionate class of two lauryls, two myristins, myristyl stearyl ester, distearyl ester etc. of thio-2 acid, and β-alkyl thiol propionic acid ester of the polyvalent alcohol of tetramethylolmethane four (β-dodecyl mercaptopropionic acid ester) etc.
As described hindered amine light stabilizer, UV light absorber and antioxidant usage quantity separately, with respect to described (A)～(D) total amount 100 mass parts of composition, be preferably 0.001～10 mass parts, particularly 0.01～5 mass parts more preferably.If be less than 0.001 mass parts, likely cannot obtain sufficient additive effect, if more than 10 mass parts, bring bad influence likely to dispersiveness and application physical property.
As the method for adding these hindered amine light stabilizers, UV light absorber or antioxidant, it can be the method arbitrarily in the method that is added on method in polyvalent alcohol, is added on method in carbamate prepolymer, is added on method in water while carrying out water-dispersion, adds after water-dispersion, but from the viewpoint of processing ease, be preferably added on the method in polyvalent alcohol and be added on the method in carbamate prepolymer.
As the purposes of water soluble polyurethane resin composition of the present invention, can enumerate binding agent, molding, material of construction, sealing agent, cast material, elastomerics, foam, plastic raw materials, fibre finish of coating agent, tackiness agent, coating, surface-modifying agent, organic powder and/or inorganic powder etc.
More particularly, can enumerate the coating agent for plastics, adhesive for laminate, agricultural film coating agent, temperature-sensitive paper coating agent, ink jetting paper coating agent, fiber coating agent, electronic unit coating agent, glass fibre sizing agent of highly adhesive coating agent, polyethylene, polypropylene, polyester, polycarbonate etc. for polyester film, binding agent of printing-ink for intaglio printing, coating that for steel plate, the inorganic structure material of coating, glass, slabstone, cement etc. is used, wood coating, fibre finish, cavernous body, powder puff, gloves, condom etc.
And; as the film that forms of coating water soluble polyurethane resin of the present invention, can enumerate the base material film etc. that wrapping material, window paste the display unit etc. of material, ink jet recording materials, replacing paper, polaroid protective film, photo induction agent film, liquid-crystal display/plasma display/organic EL/ e-book etc.In these purposes, be particularly suitable to be used in for coating agent or tackiness agent for plastics, intaglio printing the binding agent of printing-ink, optics with in highly adhesive polyester film.
About being used in the kind of the polyester in highly adhesive polyester film of the present invention, as long as can be processed into film shape, to it, there is no particular limitation, but preferably as the dicarboxylic acid of raw material, used the polyester of aromatic dicarboxylic acid, for example, can enumerate polyethylene terephthalate, polyethylene glycol 2，6-naphthalene dicarboxylate, polybutylene terephthalate, poly-α, β-bis-(2-chlorophenoxy) ethane 4,4 ,-dicarboxylic acid glycol ester etc.Particularly the viewpoint based on quality, economy etc., is most preferably used polyethylene terephthalate (PET).
And described polyester film can be any one in non-stretched film, single axle drawn membrane or biaxially oriented film, but while using with highly adhesive polyester film as optics, adopt specially single shaft or biaxially oriented film.
As the easy bonding coat of highly adhesive polyester film of the present invention, use water soluble polyurethane resin composition of the present invention.Now, in order further to improve smoothness, stationarity etc., preferably in composition, contain mineral-type particle or organic particle.
As the blending amount of described mineral-type particle or organic particle, solids component 100 mass parts with respect to water soluble polyurethane resin, are generally 0.5～10 mass parts, are preferably 1～5 quality %.
If described blending amount is less than 0.5 quality %, there is the inadequate situation of resistance to blocking of film, if surpass 10 quality %, hinder the transparency of film, thereby produce the tendency of the boldness reduction of image.
As inorganic particulate, can enumerate silicon-dioxide, aluminum oxide, zirconium white, kaolin, talcum, calcium carbonate, titanium oxide, barium oxide, carbon black, moly-sulfide, weisspiessglanz etc., but due to low price and there is the cause of multiple particle diameter, preferably use silicon-dioxide.
As organic filler, for example, can enumerate by using as the polystyrene with crosslinking structure of the compou nd synthesis that contains more than 2 carbon-to-carbon double bond in a part of Vinylstyrene or the organic filler that formed by polyacrylic ester, polymethacrylate resin etc.
As optics of the present invention highly adhesive polyester film, for example, can adopt as described below known method suitably to manufacture.That is,
Pet resin is fully carried out being supplied to extrusion machine after vacuum-drying, by T mould, the melting pet resin utilization of approximately 280 ℃ is rotated to cooling roller melt extruded slabbing, utilize subsequently static to apply method and make it curing cooling, thereby obtain not stretching polyethylene terephthalate sheet.This polyethylene terephthalate sheet that do not stretch can be single layer structure, the multilayered structure also being formed by co-extrusion platen press.
And, preferably in pet resin, do not contain in fact the inert particle that causes that the transparency reduces, aluminum oxide or calcium carbonate etc.
The roller that the polyethylene terephthalate sheet utilization that do not stretch obtaining is heated to 80～120 ℃ stretches 2.5～5.0 times along its length, thereby as uniaxial extension pet film.
And then, with clip, clamp the end of film and guide to the hot blast district that is heated to 70～140 ℃, thereby broad ways stretches 2.5～5.0 times.Subsequently, the heat-treatment zone that guides to 160～240 ℃ carries out the thermal treatment of 1～60 second, thereby completes crystal orientation.
In any stage of this thin film fabrication operation, the coating fluid that contains water soluble polyurethane resin composition of the present invention at least coated on one side of pet film, thus form easy bonding coat.Easily bonding coat also can form on the two sides of pet film.
The solid component concentration of the resin combination in coating fluid is preferably 2～35 quality %, is particularly preferably 4～15 quality %.
As the coating process of described coating fluid, for example, can from brushing, roller coat, spraying, intaglio plate coating, inverse roller coating cloth, airblade coating, scraper coating, heavy curtain roller coat cloth, dip-coating, bar painting, scraper for coating etc., suitably select.
And, with regard to the thickness of described easy bonding coat, as final dry thickness, be 0.005～5 μ m, be preferably 0.05～2 μ m, more preferably the scope of 0.05～0.5 μ m.
If the thickness of described easy bonding coat is less than 0.005 μ m, cannot fully obtain the binding property with energy line curing resin.And, if the thickness of coating layer surpasses 5 μ m, film deadlocked adhesion phenomenon each other easily occurs during by pellicular cascade, or the film after coating being processed for the high strength of film is when redraw, and exists and easily adheres to the tendency on roller.When particularly having formed easy bonding coat on the two sides of film, the problem of adhesion can obviously occur.
On described easy bonding coat, in the scope of impact effect not, can and with water soluble polyurethane resin composition of the present invention and other resins.As other above-mentioned resins, for example, can enumerate the Vinylite of acrylic resin, vibrin, Synolac, polyvinyl alcohol etc., but in the present invention, particularly preferably and with water-soluble polyester or polyvinyl alcohol.
And during with above-mentioned other resins, the blending ratio as the solids component with respect to water soluble polyurethane resin composition of the present invention, is preferably 0/100～50/50 by quality ratio, more preferably 20/80～40/60.
As the solvent beyond the water using in coating fluid, can be at the alcohols that is less than the scope mixed ethanol of 50 quality %, Virahol, phenylcarbinol etc.In addition, in the scope of the 10 quality % lower than coating fluid, also can be at soluble scope mixed alcohols organic solvent in addition.
But the total amount of alcohols and other organic solvents is preferably the 50 quality % that are less than coating fluid.
The glue spread of described coating fluid is preferably 0.05g/m 2～0.8g/m 2, 0.1g/m more preferably 2～0.5g/m 2.
And in highly adhesive polyester film of the present invention, the glue spread of dried easy bonding coat is preferably at 0.01g/m 2above and be less than 1g/m 2.
If dried glue spread is less than 0.01g/m 2, binding property can reduce, if dried glue spread is at 1g/m 2above, be subject to being easy to generate coating spot after the impact of drying oven inner drying wind.
As easy adhering polyester film of the present invention, the viewpoint based on realizing high transparent, its mist degree is preferably and is less than 3.0%, is more preferably less than 2.0%, is particularly preferably and is less than 1.0%.
As optical thin film of the present invention, by being further set on the easy bonding coat of highly adhesive polyester film of the present invention, the hard coat consisting of active energy line curing resin obtains.
Above-mentioned active energy line curing resin can from have two keys such as acryl, use after suitably selecting known UV cured resin or electron beam curing resin etc.; but in the present invention, particularly preferably use urethane acrylate resin, Epocryl and unsaturated polyester resin etc.
Below, according to embodiment and comparative example, the present invention is done further and described in detail, but the present invention is not subject to these any restriction.
The manufacture of carbamate prepolymer
Production Example 1～6
According to the blending amount shown in aftermentioned table 1, mix (A) polyvalent alcohol, (B) polymeric polyisocyanate, (C) hydrophilic compounds, (D) monohydroxy vinyl ether compound, and 80～100 ℃ of reactions 2～3 hours.
Confirm that isocyanate content has arrived the amount of regulation, is made as PP-1～PP-6 by the carbamate prepolymer obtaining.
Compare Production Example 1～5
Use (A) of the blending amount shown in table 2 as described later～(D) composition, by the method identical with Production Example, manufactured carbamate prepolymer PP-7～PP-11.
Embodiment 1
The manufacture of water soluble polyurethane resin
Carbamate prepolymer PP-1～the PP-6 being obtained by described Production Example is injected in water, and makes solids component reach 20 quality %, at 30～40 ℃, disperse 30 minutes subsequently.
Secondly, it is (following that the amount that is 0.9 with respect to the ratio (NH/-NCO) of the isocyanate group equivalent of carbamate prepolymer according to amino equivalent is added quadrol, be designated as EDA), thereby carry out chain extension reaction, stir subsequently 1～2 hour until by IR(infrared spectrophotometer) can confirm isocyanate group disappearance, thus obtained water soluble polyurethane resin composition PUD-1～PUD-6.
Comparative example 1
Utilization, by described carbamate prepolymer PP-7～PP-11 that relatively Production Example obtains, has obtained water soluble polyurethane resin composition PUD-7～PUD-11 by the method identical with embodiment 1.
For the median size of the water soluble polyurethane resin disperseing in the composition being obtained by embodiment 1 and comparative example 1, by adopting the dynamic light scattering method of the LB-550 of Horiba Ltd's system to measure.The results are shown in table 1 and table 2.
Table 1
Figure BDA0000456232290000221
* 1: polycarbonate diol, Mw1000(Asahi Chemical Corp system)
* 2: methyl pentanediol/adipate polyester glycol, Mw1000(Kuraray Co., Ltd. system)
* 3: polytetramethylene glycol, Mw1000(hodogaya chemical Co., Ltd. system)
* 4: cyclohexanedimethanol
* 5: TriMethylolPropane(TMP)
* 6: isophorone diisocyanate
* 7: dicyclohexyl methyl hydride-4,4 '-vulcabond
* 8:Perstorp company system, ProductName Ymer N120, OH official can radix 2, Mw1000
* 9:HDI(hexamethylene diisocyanate) isocyanuric acid ester+methoxyl group PEG-1000,1/1 molar reactive compound
* 10: hydroxybutyl mono vinyl ether
* 11: hydroxyethyl mono vinyl ether
* 12: Diethylene Glycol mono vinyl ether
* 13: cyclohexanedimethanol mono vinyl ether
Table 2
Figure BDA0000456232290000231
*: cyclohexanedimethanol divinyl ether
Use metering bar coater, the water soluble polyurethane resin composition being obtained by embodiment 1 and comparative example 1 is coated on to surface on the stretched polypropene film of Corona discharge Treatment.
For the coated thin film obtaining, according to following condition evaluating adaptation, cohesiveness and resistance to blocking.The results are shown in table 3 and table 4.
Cohesiveness evaluation method
Coated thin film, for the drying regime of coated face, is evaluated by finger touch and by following standard after dry 24 hours at 25 ℃.
◎: it is upper that resin is not attached to finger, do not see fingerprint on coated face completely.
Zero: though resin is not attached to finger above, on coated face, slightly can see fingerprint.
△: resin is attached on finger slightly.
*: resin is attached on finger.
Resistance to blocking evaluation method
Coated thin film, after 50 ℃ of heating are dried for 30 minutes, is applied to 0.5kg/cm under the state fitting tightly each other at coated face 2loading, and be placed in the temperature of 40 ℃.From placement starts, after 24 hours, whether the position of observing coated face laminating has adhesion, and evaluates by following standard.
◎: there is no adhesion completely.
Zero: have very slight adhesion.
△: have a little adhesion.
*: there is adhesion.
The evaluation method of ink adaptation
Coated thin film, is coated with after ink as test film after 30 minutes 50 ℃ of heating on coated face.Using the ink face of this test film as outside, the temperature of 180 ℃, carried out bending machining.By on the ink face of the wide transparent adhesive tape of the 18mm bending machining portion that is attached to test film with pressure, whether have ink detachment, and evaluate by following standard if peeling off by force rear observation.
◎: ink face is completely not abnormal.
Zero: ink face has very slight peeling off.
△: ink face has a little to peel off.
*: ink face is peeled off completely.
Table 3
Embodiment 1-1 1-2 1-3 1-4 1-5 1-6
Water soluble polyurethane resin numbering PUD-1 PUD-2 PUD-3 PUD-4 PUD-5 PUD-6
Use prepolymer numbering PP-1 PP-2 PP-3 PP-4 PP-5 PP-6
(C) composition alkylene oxide content * 12% 19% 5.8% 11% 13% 12%
(D) component content * 12% 6.3% 17% 11% 13% 12%
Cohesiveness ◎ ○ ◎ ◎ ◎ ◎
Resistance to blocking ◎ ○ ◎ ◎ ◎ ◎
Ink adaptation ◎ ○ ◎ ◎ ◎ ◎
*: numerical value is the content (quality standard) with respect to carbamate prepolymer ((A)～(D) total amount of composition)
Table 4
Comparative example 1-1 1-2 1-3 1-4 1-5
Water soluble polyurethane resin numbering PUD-7 PUD-8 PUD-9 PUD-10 PUD-11
Use prepolymer numbering PP-7 PP-8 PP-9 PP-10 PP-11
(C) composition alkylene oxide content * 2.2% 14% 31% 11% 13%
(D) component content * 12% 2.0% 12% 32% 13%
Cohesiveness ○ △ △ × ◎
Resistance to blocking ○ △ × × ◎
Ink adaptation △ △ ◎ ○ ×
*: numerical value is the content (quality standard) with respect to carbamate prepolymer ((A)～(D) total amount of composition)
Embodiment 2
The manufacture of highly adhesive polyester film
After the polyethylene terephthalate that is 0.65 by the dry intrinsic viscosity of ordinary method, be supplied to extrusion machine, at 290 ℃, carry out being squeezed into sheet after melting, utilize static apply casting in cooling rotating roller, carry out cooling fast, thereby made the PET film that do not stretch.
Utilize roller stretching method by the not stretching PET film obtaining longitudinally, at 85 ℃, stretch 2.5 times, at 95 ℃, stretch 1.3 times subsequently.Then, be coated with respectively after water soluble polyurethane resin composition PUD-1～PUD-6, along laterally stretching 3.2 times at 120 ℃, and heat-treat at 225 ℃, thereby obtained each highly adhesive polyester film.
Comparative example 2
By the method identical with embodiment 2, utilize water soluble polyurethane resin composition PUD-7～PUD-11 to manufacture each highly adhesive polyester film.
Mist degree is evaluated
Each highly adhesive polyester film of manufacturing in embodiment 2 and comparative example 2 is cut into the square size of 50mm, use mist degree determinator (HM-150, Murakami K. K.'s dye technology institute system) and by according to JIS K7361(ISO13468) method measure, by following standard, evaluate subsequently.The results are shown in table 5 and table 6.
◎: be less than 1.0% (very good)
Zero: 1.0% above, be less than 3% (well)
△: more than 3.0%, be less than 5% (bad a little)
*: more than 5.0% (bad)
The manufacture of laminated polyester film
Moreover, on the easy bonding coat of each highly adhesive polyester film obtaining, coating is by 27 parts of 40 parts of urethane acrylates, bisphenol-a epoxy acrylates and 3 parts of active energy line curing resins that form of 1-hydroxycyclohexylphenylketone of 30 parts of dipentaerythritol acrylates, 4 functionality, and the thickness after it is solidified is 3 μ m.Use has the high voltage mercury lamp that 120W/cm irradiates energy, irradiates approximately 15 seconds, thereby obtained having the laminated polyester film (optical thin film) of hard coat from the irradiation distance of 150mm.
Binding property is evaluated
The laminated polyester film obtaining is placed in after each condition of following (1)～(3), according to JIS-K5400, use cutting guide rail that clearance gap is 1mm to cut out to connect by rete and arrive base material film 100 lattice-shapeds cut line.Subsequently, transparent bonding adhesive tape sticking, on the cut surface of lattice-shaped, is carried out to wiping with eraser, thereby after making it to adhere to completely, with the peel angle of 90 °, peel off fast, observe subsequently release surface, and by following standard, binding property is evaluated.
The results are shown in table 5 and table 6.
Adhesion test condition
(1) normality binding property: 23 ℃/relative humidity 65%, 24 hours
(2) moistening binding property: 60 ℃/relative humidity 90%, 100 hours
(3) wet-heat resisting binding property: 60 ℃/relative humidity 90%, 300 hours
In above-mentioned each condition, place after the specified time, after 23 ℃ * relative humidity 65% is placed 24 hours, implemented test.
Binding property judgement criteria
◎: peel off area and be less than 5% (very good)
Zero: peel off area more than 5%, be less than 15% (well)
△: peel off area more than 15%, be less than 20% (good a little)
*: peel off area more than 20% (bad)
Table 5
Embodiment 2-1 2-2 2-3 2-4 2-5 2-6
Water soluble polyurethane resin numbering PUD-1 PUD-2 PUD-3 PUD-4 PUD-5 PUD-6
(C) composition alkylene oxide content * 12% 19% 5.8% 11% 13% 12%
(D) component content * 12% 6.3% 17% 11% 13% 12%
Urethane resin median size (nm) 26 23 87 45 48 32
Mist degree ◎ ◎ ○ ○ ○ ◎
Binding property: normality ◎ ◎ ◎ ◎ ◎ ◎
Binding property: moistening ◎ ◎ ○ ◎ ◎ ◎
Binding property: heat-resisting ◎ ◎ ○ ◎ ◎ ◎
*: numerical value is the content (quality standard) with respect to carbamate prepolymer ((A)～(D) total amount of composition)
Table 6
Comparative example 2-1 2-2 2-3 2-4 2-5
Water soluble polyurethane resin numbering PUD-7 PUD-8 PUD-9 PUD-10 PUD-11
(C) composition alkylene oxide content * 2.2% 14% 31% 11% 13%
(D) component content * 12% 2.0% 12% 32% 13%
Urethane resin median size (nm) 480 30 28 120 160
Mist degree × △ × × ○
Binding property: normality × △ × △ △
Binding property: moistening × × × △ ×
Binding property: heat-resisting × × × △ ×
*: numerical value is the content (quality standard) with respect to carbamate prepolymer ((A)～(D) total amount of composition)
Can confirm, as highly adhesive polyester film of the present invention, for the energy-line solidifying type acrylic resin of electron beam or ultraviolet ray etc. or the hard coat of type siloxane heat-curing resin etc., to have good binding property, the transparency is excellent simultaneously.
And, can confirm, by the median size of the carbamate resins disperseing in composition of the present invention is adjusted to below 35nm, the transparency of highly adhesive polyester film of the present invention is able to further raising.
Can confirm thus; as highly adhesive polyester film of the present invention; by easily on bonding coat, the hard coat consisting of energy ray-curable resin being set, in the optical applications of the applicable anti-reflection film at the parts as liquid-crystal display, plasma display, organic EL and e-book etc., light diffusing sheet, near infrared ray blocking thin film, transparent conducting film, anti-dazzle thin-membrane and polarized light protective film etc.And then, be also applicable to the base material film as magnetic recording medium, photo photosensitive material, ink jet recording materials, dry laminated or adhesive tape etc.
Industrial applicibility
As water soluble polyurethane resin composition of the present invention, cohesiveness and resistance to blocking for the binding property of synthetic resins and while being coated on synthetic resin film are excellent, therefore can be used as laminated with gravure printing ink binding agent or coating agent, coating etc.The synthetic resin film that is coated with water soluble polyurethane resin composition of the present invention can be used as wrapping material, window pastes material, ink jet recording materials, replacing paper etc.
And; as the highly adhesive polyester film that has used water soluble polyurethane resin composition of the present invention; its mist degree is low and have good transparent time; the optical thin film that has used this easy adhering polyester film is requiring to have excellent adaptation under the condition of wet-heat resisting etc., is therefore particularly suitable for being used as the display unit of polarized light protective film, picture photosensitive agent film, liquid-crystal display/plasma display/organic EL/ e-book etc. etc.

Claims (6)

1. a water soluble polyurethane resin composition, it take the hydrophilic compounds of (A) polyvalent alcohol, (B) polymeric polyisocyanate, (C) following general formula (1) expression, monohydroxy vinyl ether compound and the water of (D) following general formula (2) expression are neccessary composition, it is characterized in that
(C in described (C) composition 2h 4-O) nthe amount of the alkylene oxide unit representing is that the content of described (D) composition is 3～25 quality % of described solids component by 3～20 quality % of described (A)～solids component that (D) composition forms,
Figure FDA0000456232280000011
Wherein, the R in formula 1for removed the residue of a hydroxyl or the group being represented by RNHCO-, R from 2～4 yuan of alcohol 2for methyl or ethyl, the integer that n is 5～35, described R has removed the residue of an isocyanate group from the trimer compound of vulcabond,
Figure FDA0000456232280000012
Wherein, the R in formula 3for the alkylidene group of carbonatoms 2～9, m is 1 or 2.
2. water soluble polyurethane resin composition as claimed in claim 1, wherein, the R of described general formula (1) 1from 3 yuan of alcohol, to have removed the residue of a hydroxyl, the integer that n is 10～20.
3. water soluble polyurethane resin composition as claimed in claim 1 or 2, wherein, the median size of dispersate is below 100nm.
4. coating agent or a tackiness agent, is characterized in that, contains water soluble polyurethane resin composition as claimed in claim 1.
5. a highly adhesive polyester film, it is at least one mask of polyester film, to have the highly adhesive polyester film of easy bonding coat, it is characterized in that, described easy bonding coat is the layer that coating water soluble polyurethane resin composition as claimed in claim 1 forms.
6. an optical thin film, is characterized in that, on the easy bonding coat of highly adhesive polyester film as claimed in claim 5, also has the hard coat consisting of active energy line curing resin.
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