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CN103649143B - Water soluble polyurethane resin composition, be coated with the highly adhesive polyester film of this water soluble polyurethane resin composition - Google Patents

Water soluble polyurethane resin composition, be coated with the highly adhesive polyester film of this water soluble polyurethane resin composition Download PDF

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Publication number
CN103649143B
CN103649143B CN201280034728.5A CN201280034728A CN103649143B CN 103649143 B CN103649143 B CN 103649143B CN 201280034728 A CN201280034728 A CN 201280034728A CN 103649143 B CN103649143 B CN 103649143B
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Prior art keywords
water soluble
polyurethane resin
soluble polyurethane
polyester film
resin composition
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Expired - Fee Related
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CN201280034728.5A
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CN103649143A (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

The invention provides monohydroxy vinyl ether compound and water that a kind of hydrophilic compounds, (D) following general formula (2) represented with (A) polyvalent alcohol, (B) polymeric polyisocyanate, (C) following general formula (1) represent for neccessary composition, and the water soluble polyurethane resin composition to the cohesiveness after the binding property of synthetic resins, coating and resistance to blocking excellence.The present invention also provides a kind of highly adhesive polyester film, and it has the easy bonding coat of at least water soluble polyurethane resin composition described in coated on one side at polyester film.The feature of water soluble polyurethane resin composition of the present invention is, (the C in described (C) composition 2h 4-O) nthe amount of the alkylene oxide unit represented is 3 ~ 20 quality % of the solids component be made up of described (A) ~ (D) composition, and the content of described (D) composition is 3 ~ 25 quality % of described solids component.

Description

Water soluble polyurethane resin composition, be coated with the highly adhesive polyester film of this water soluble polyurethane resin composition
Technical field
The present invention relates to the highly adhesive polyester film of water soluble polyurethane resin composition and this water soluble polyurethane resin composition of at least coated on one side at polyester film base material, in detail, relate to the cohesiveness after the binding property to synthetic resins, coating and the water soluble polyurethane resin composition of resistance to blocking excellence, and with the binding property of base material film and energy line curing resin the excellent and highly adhesive polyester film that the transparency of film (mist degree) is excellent.
Background technology
Urethane resin due to the film or molding with wear resistance, binding property, non-adhesive, caoutchouc elasticity etc. can be made into, so be widely used in coating, tackiness agent, binding agent, coating agent etc.
In recent years, from the safety perspective of environmental pollution, labour hygiene etc., many water soluble polyurethane resin compositions are reported, but compared 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.
When water soluble polyurethane resin composition is used as laminated gravure printing ink or coating agent, except needs water tolerance, thermotolerance, outside the physical properties excellent of tensile properties etc., to the adaptation of ink and substrate agent, bonding and resistance to blocking also need excellence, such as, report and the water soluble polyurethane resin that specific hydroxycarboxylic acid reacts, and adopt their printing-ink binding agent (patent documentation 1), the water soluble polyurethane resin composition that polyester glycol and hydroxyl value are the polyvalent alcohol of more than 3 is have employed as polyhydroxy reactant, and adopt the plastics film coating agent (patent documentation 2) etc. of this water soluble polyurethane resin composition.
But the performance of these carbamate resins can not make people's fully satisfaction.
Further, in recent years, water soluble polyurethane resin composition also starts to use as using the coating layer for the purpose of the binding property improving the polyester film used as optical thin film.
In polyester film, especially the Biaxially oriented polyester film of optics is used to, it is excellent in the transparency, dimensional stability, mechanical characteristics, thermotolerance, electrology characteristic, barrier properties for gases, chemical proofing etc., 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.
But, in these purposes, when when coating or laminated other materials, there is the problem causing binding property to worsen because used material is different on polyester film.
Further, as one of fusible method improveing polyester film, there will be a known at the various resin of the surface coated of polyester film, thus the method for the coating layer with highly adhesive energy is set.
Such as, disclose the acrylic resin (patent documentation 3) of trimeric cyanamide as linking agent, using oxazoline as the acrylic resin of linking agent, carbamate resins or vibrin (patent documentation 4), copolymer polyester resin and urethane resin (patent documentation 5), the technology that specific urethane resin is used as coating agent (patent documentation 6 ~ 9).
But, 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), compared with the situation of the surfacer of use solvent based, 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 have the shortcoming that cannot obtain sufficient engaging force.
In addition, with regard to there is the polyester film of the hard coat of the coating layer and active energy line curing resin layer etc. of highly adhesive, due to the factor of the refringence etc. of above-mentioned coating layer and above-mentioned polyester film and hard coat, there is the problem that such as mist degree uprises, the transparency reduces.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2004-231813 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-234931 publication
Patent documentation 3: Japanese Unexamined Patent Publication 08-281890 publication
Patent documentation 4: Japanese Unexamined Patent Publication 11-286092 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2000-229395 publication
Patent documentation 6: Japanese Laid-Open Patent Publication 61-261326 publication
Patent documentation 7: Japanese Unexamined Patent Publication 01-218832 publication
Patent documentation 8: Japanese Unexamined Patent Publication 02-158633 publication
Patent documentation 9: Japanese Unexamined Patent Publication 2009-220376 publication
Summary of the invention
The problem that invention will solve
Thus the first object of the present invention is, provide with the binding property of synthetic resins or ink, be coated with after cohesiveness and the water soluble polyurethane resin composition of resistance to blocking excellence.
Further, the second object of the present invention is, provides excellent with the binding property of base material film and energy line curing resin, the highly adhesive polyester film that the transparency (mist degree) of film is excellent simultaneously.
The method of dealing with problems
In order to realize above-mentioned all objects, present inventor has performed and concentrate on studies, it found that, by using the water soluble polyurethane resin composition using the hydrophilic compounds with ad hoc structure as neccessary composition can solve above-mentioned problem, thus completes the present invention.
Namely, the invention provides a kind of water soluble polyurethane resin composition, it is the monohydroxy vinyl ether compound that represents of hydrophilic compounds, (D) the following general formula (2) represented using (A) polyvalent alcohol, (B) polymeric polyisocyanate, (C) following general formula (1) and the water water soluble polyurethane resin composition as neccessary composition, it is characterized in that, in described (C) composition by (C 2h 4-O) nwhile the alkylene oxide unit represented is the amount of 3 ~ 20 quality % of the solids component be made up of described (A) ~ (D) composition, the content of described (D) composition is 3 ~ 25 quality % of described solids component.
The present invention also provides a kind of coating agent, it is characterized in that, containing 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 that at least described in the coated on one side of polyester film, water soluble polyurethane resin composition forms.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 be made up of active energy line curing resin.
Wherein, the R in formula 1for the residue that eliminates a hydroxyl from 2 ~ 4 yuan of alcohol or the group represented by RNHCO-, R 2for methyl or ethyl, n is the integer of 5 ~ 35, and described R is the residue eliminating an isocyanate group from the trimer compound of vulcabond.
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 eliminating the residue of a hydroxyl from 3 yuan of alcohol, n is the integer of 10 ~ 20.
Further, preferably, the median size of the dispersate in described water soluble polyurethane resin composition is at 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 surface coated of polyester film water soluble polyurethane resin composition of the present invention, mist degree can be obtained low, transparent good, simultaneously also good with the binding property of hard coat highly adhesive polyester film.
Embodiment
The monohydroxy vinyl ether compound that 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) represent, (D) described general formula (2) represent and water.
Described (A) polyvalent alcohol is not particularly limited, such as, polyether polyols alcohols, polyester polyols alcohols, polyester polycarbonate polyols class and crystallinity or noncrystalline polycarbonate polyol class etc. can be enumerated.
As the example of described polyether polyols alcohols, oxyethane and/or propylene oxide adduct that number-average molecular weight is less than the small molecule polyol class of 200, the amine compound of dihydroxyphenyl propane or quadrol etc. etc. can be enumerated, and polytetramethylene ether diol etc.
The small molecule polyol class of 200 is less than as described number-average molecular weight, such as, ethylene glycol can be enumerated, 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, the polyvalent alcohol of more than 3 yuan of tetra methylol propane etc.
As described polyester polyols alcohols, the polyester polyol that the polyvalent alcohol of small molecule polyol being less than 200 etc. by described number-average molecular weight and the less polycarboxylic acid of amount of Bi Qi stoichiometric number or the direct esterification reaction of its ester formative derivative or transesterification reaction obtain can be enumerated, and the polyester polyol be obtained by reacting by described polyvalent alcohol and lactone or the direct esterification of hydroxycarboxylic acid that is obtained by reacting by its hydrolysis.
As above-mentioned polycarboxylic acid, such as, oxalic acid can be enumerated, 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., the carboxylic acid of more than 4 yuan of Pyromellitic Acid etc.
As the ester formative derivative of described polycarboxylic acid, the acid anhydrides of above-mentioned polycarboxylic acid can be enumerated, the carboxylic acid halides compound of muriate, bromide etc., the lower aliphatic ester etc. of methyl esters, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, pentyl ester etc.
As described lactone, γ-hexalactone, δ-caprolactone, 6-caprolactone, dimethyl-E-caprolactone, δ-valerolactone, γ-valerolactone, gamma-butyrolactone etc. can be enumerated.
As the example of described polyester polycarbonate polyols class, the resultant of reaction polyester glycol of polycaprolactone polyol etc. and the resultant of reaction of alkylene carbonate can enumerated and be obtained by reacting by resultant of reaction and the organic dicarboxylic acid of ethylene carbonate and polyvalent alcohol.
And, as the example of described crystallinity or noncrystalline polycarbonate polyol class, can 1 be enumerated, ammediol, 1, the resultant of reaction etc. of the cyclic carbonate of the diaryl carbonate of the glycol, photoreactive gas, diphenyl carbonate etc. of 4-butyleneglycol, 1,6-hexylene glycol, Diethylene Glycol, polypropylene glycol and/or polytetramethylene glycol etc. or propylene carbonate etc.
The number-average molecular weight of described polyether polyols alcohols, polyester polyols alcohols, polyester polycarbonate polyols class, crystalline polycarbonate polyalcohols and noncrystalline polycarbonate polyol class is preferably 300 ~ 5000, is more preferably 500 ~ 3000.
In water soluble polyurethane resin composition of the present invention, due to can make damp and hot under adaptation become good, therefore in these polyalcohols, particularly preferably use polycarbonate polyol class.
In the present invention, described polyvalent alcohol only can use a kind, and also two or more kinds may be used.
Further, also can be used together the small molecule polyol class that these polyvalent alcohols and above-mentioned number-average molecular weight are less than 200.
Described (B) polymeric polyisocyanate is not particularly limited, such as, vulcabond can be enumerated and there is the polymeric polyisocyanate etc. of more than 3 isocyanate group in 1 molecule.
As the example of vulcabond, tolylene diisocyanate can be enumerated, ditan-4, 4 '-vulcabond, to phenylene vulcabond, xylylene diisocyanate, 1, 5-naphthalene diisocyanate, 3, 3 '-dimethyl diphenyl-4, 4 '-vulcabond, dianisidine diisocyanate, the aromatic diisocyanate class of tetramethyl-xylylene diisocyanate 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 etc. of lysinediisocyanate etc.
As the example of polymeric polyisocyanate in 1 molecule with more than 3 isocyanate group, triphenylmethane triisocyanate can be enumerated, 1-methylbenzene-2, 4, 6-triisocyanate, dimethyl triphenyl methane tetraisocyanate, isocyanic ester more than 3 functionality be made up of these mixtures etc., the carbodiimide modified of isocyanic ester more than these 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 reagent, the isocyanuric acid ester (trimer) of above-mentioned vulcabond and biuret trimer etc.
In these, based on easily obtaining and the viewpoint of the excellent water soluble polyurethane resin composition such as weathering resistance and intensity can being obtained, preferably use aliphatic diisocyanate or ester ring type vulcabond in the present invention, wherein, particularly preferably use 1,6-hexamethylene diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, isophorone diisocyanate.
In the present invention, these polymeric polyisocyanates only can use a kind, and also two or more kinds may be used.
As the R in the hydrophilic compounds represented by general formula (1) of described (C) 1, be the residue eliminating a hydroxyl from 2 ~ 4 yuan of alcohol or the group represented by RNHCO-.
As the example of above-mentioned 2 ~ 4 yuan of alcohol, ethylene glycol can be enumerated, 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 such as cyclohexanedimethanol, 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 urethane backbone, so R owing to being easy to group 1from 3 ~ 4 yuan of alcohol, preferably eliminate the residue of a hydroxyl, wherein, based on the viewpoint, the R that do not cause crosslinking reaction or end termination reaction when the reaction by hydrophilic compounds (C) and (B) isocyanic ester forms carbamate 1from 3 yuan of alcohol, preferably eliminate the residue of a hydroxyl, be particularly preferably the residue eliminating a hydroxyl from TriMethylolPropane(TMP).
Further, as the R in the described group represented by RNHCO-, be the residue eliminating an isocyanate group from the trimer compound of vulcabond.
As the vulcabond forming described trimer compound, the vulcabond enumerated when described (B) isocyanic ester is described can be set forth in.
In these, based on easily obtaining and the viewpoint of the excellent water soluble polyurethane resin composition such as weathering resistance and intensity can being obtained, preferred use aliphatic diisocyanate or ester ring type vulcabond, wherein, particularly preferably 1,6-hexamethylene diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, isophorone diisocyanate.
N in described general formula (1) is the integer of 5 ~ 35, but becomes good viewpoint based on the water dispersible of obtained carbamate prepolymer, is more preferably the integer of 10 ~ 20.
In the monohydroxy vinyl ether compound represented by described general formula (2) of described (D), as by R 3the example of alkylidene group of represent 2 ~ 9, such as, 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 hexylen, sub-tertiary octyl group, nonamethylene, sub-different nonyl etc. can be enumerated.
Further, m is 1 or 2, but is preferably 1.
As the object lesson of the compound represented by general formula (2), the hydroxyvinyl ether compound of hydroxymethyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-Hydroxy pentyl vinyl ether, 6-hydroxyl hexyl vinyl ether, 9-hydroxynonyl vinyl ether, diethylene glycol monovinyl base ether etc. can be enumerated.
As the content of (C) hydrophilic compounds in water soluble polyurethane resin composition of the present invention, preferably make in general formula (1) by (C 2h 4-O) nthe alkylene oxide unit represented reaches the amount of 3 ~ 20 quality % of carbamate prepolymer solids component, is more preferably the amount reaching 5 ~ 16 quality %.Wherein, the quality of carbamate prepolymer solids component refers to the total amount of (A) ~ (D) composition.
If alkylene oxide unit is less than 3 quality %, then the water dispersible of carbamate prepolymer is deteriorated, if during amount more than 20 quality %, then and the tensile strength that there is carbamate resins film and the tendency that the Physical properties of coating film of the adaptation of base material etc. is reduced.
Further, as the content of (D) monohydroxy vinyl ether compound, be 3 ~ 25 quality % of carbamate prepolymer solids component, be preferably 5 ~ 20 quality %.
If (D) content of monohydroxy vinyl ether compound is less than 3 quality %, then binding property effect of the present invention becomes insufficient, if more than the amount of 25 quality %, then there is the tendency of the deleterious of the viscosity or mist degree etc. of highly adhesive polyester film of the present invention.
Moreover, as the blending amount of described (A) ~ (D) composition, all isocyanate group equivalents are preferably made to reach the blending amount of 1.1 ~ 2.5 relative to the ratio (NCO/OH) of all hydroxyl equivalents of (A) ~ (D) composition, be more preferably the blending amount making above-mentioned ratio reach 1.2 ~ 2.0, be particularly preferably the blending amount making above-mentioned ratio reach 1.3 ~ 1.8.
All hydroxyl equivalents refer to the total amount of the hydroxyl equivalent of (A) polyvalent alcohol, (C) hydrophilic compounds and (D) 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 the total amount of the isocyanate group equivalent of (B) composition and (C) composition.
If described NCO/OH ratio is more than 1.0 and be less than 1.1, the tendency that the water dispersible then producing carbamate prepolymer due to the higher molecular quantification of carbamate prepolymer is deteriorated, there is the situation that the storage stability of water soluble polyurethane resin etc. is deteriorated, if more than 2.5, then likely have problems in the performance of water soluble polyurethane resin, such as, when the water-dispersion of prepolymer, violent foaming is caused to wait due to the carbonic acid gas generated with the reaction of isocyanate group and water and the problem that produces in manufacture, or produce film to the tendency etc. of the deleterious of the binding property of substrate resin etc.
And, when described NCO/OH ratio is less than 1.0, then become the carbamate prepolymer of terminal hydroxyl, but excellent based on the water dispersible of terminal isocyanate prepolymer, carry out the viewpoint of polymer quantification etc. simultaneously easily through chain extension, usually preferably manufacture terminal isocyanate prepolymer.
For the manufacture method of water soluble polyurethane resin composition of the present invention, there is no particular limitation, known method can be used, such as, make (A) polyvalent alcohol and (B) isocyanic ester, (C) hydrophilic compounds, the reaction of (D) monohydroxy vinyl ether compound, add the reaction of radical ion imported agent even as required, thus synthesis of carbamates prepolymer, the carbamate prepolymer obtained is carried out after water-dispersion carrys out obtained carbamate resins, in water, carry out the method for chain extension with extender.
In the synthesis of carbamate prepolymer, can use as required reaction for inertia and and the large solvent of the affinity of water.
As the method for carbamate prepolymer being carried out water-dispersion, make it after having (1) to add prepolymer in water disperse prepolymer hybrid system, and (2) in prepolymer, add water after make it disperse phase transfer method etc.
When carbamate prepolymer is carried out water-dispersion, when adding ionic group neutralizing agent and/or emulsifying agent if be necessary, both can add in water, and also can add in carbamate prepolymer, but these emulsifying agents are normally added in water.
As above-mentioned to reaction for inertia and and the large solvent of the affinity of water, preferred example is acetone, methylethylketone, dioxan, tetrahydrofuran (THF), METHYLPYRROLIDONE etc.
As the usage quantity of these solvents, relative to described raw material (A) ~ (D) composition used and total amount 100 mass parts of radical ion imported ingredient when manufacturing prepolymer, be 3 ~ 100 mass parts.
Further, if when using boiling point to be the solvent of less than 100 DEG C in these solvents, preferably after having synthesized water soluble polyurethane resin, remove solvent by underpressure distillation etc.
As above-mentioned ionic group imported agent, there are anionic property group imported agent and cationic groups imported agent.
As the example of anionic property group imported agent, dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl butanic acid, dihydroxymethyl valeric acid etc. can be enumerated containing the polyalcohols of carboxyl, and BDO-2-sulfonic acid etc. is containing sulfonic polyalcohols.
Further, as the example of cationic groups imported agent, N can be enumerated, N-dialkyl amine, N-methyl-N, N-diethanolamine, N-butyl-N, the N-alkyl-N of N-diethanolamine etc., N-dialkanol amine, and three alkanol amines.
Further, as the blending amount of ionic group imported agent, 0 ~ 30 quality % of the carbamate prepolymer be preferably made up of described (A) ~ (D) composition and ionic group imported agent, is more preferably 0 ~ 20 quality %, is particularly preferably 0 ~ 10 quality %.If the content of ionic group imported agent is more than 30 quality %, then causes the viscosity of carbamate prepolymer to rise along with the focusing energy increase of amino-formate bond, thus produce the problem that water-dispersion becomes difficulty etc.
As described ionic group neutralizing agent, there are anionic property group neutralizing agent and cationic groups neutralizing agent.
As the example of anionic property group neutralizing agent, the trialkyl amines of Trimethylamine, triethylamine, tributylamine etc. can be enumerated, N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, the N of N-dipropylethanolamine, 1-dimethylamino-2-methyl-2-propanol etc., N-dialkyl 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, as the example of cationic groups neutralizing agent, except the organic carboxyl acid of formic acid, acetic acid, lactic acid, succsinic acid, pentanedioic acid, citric acid etc. can be enumerated, 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, relative to ionic group 1 equivalent, be preferably 0.5 ~ 2.0 equivalent, be 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, then 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.
As the example of described emulsifying agent, 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. can be enumerated, in addition, the known emulsifying agents such as the amphoterics of betaine type, sulfuric acid ester type and sulfonic acid type etc. can also be enumerated.
As above-mentioned anionic surfactant, sodium lauryl sulphate can be enumerated, 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, naphthalenesulfonic 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, the fatty acid part ester class of the polyvalent alcohol of sorbitanmonolaureate, sorbitan mono-oleic acid ester etc. can be enumerated, 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 of the carbonatoms 1 ~ 18 of these nonionic surfactants of formation, 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. can be enumerated.
As described alkylphenol, phenol, methylphenol, 2 can be enumerated, 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, ethylene glycol, 1,2-PD, 1,3-PD, 2-methyl isophthalic acid can be enumerated, 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.
Further, as Alkylenediamine, the compound etc. that the alcohol hydroxyl group can enumerating these aklylene glycols is replaced by amino.
As oxyethane and the propylene oxide adduct of these compounds, can be random affixture, also can be blocked adduct.
As described cationic surfactant, 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. can be enumerated.
As described amphoterics, the betaine type of metal-salt etc. of coconut oil fat amidopropyl dimethyl acetic acid trimethyl-glycine, lauryl dimethyl amino acid betaine alkali, 2-alkyl-N-carboxymethyl group-N-hydroxymethylimidazole quinoline trimethyl-glycine, lauryl hydroxyl sulfo betaine, lauroyl amido ethyl hydroxy ethyl carboxymethyl group trimethyl-glycine, hydroxypropyl phosphoric acid can be enumerated, the amino acid pattern of the metal-salt of β-lauryl amino propionic acid etc., sulfuric acid ester type and sulfonic acid type etc.
For the usage quantity of described emulsifier component, there is no particular limitation, but the viewpoint of the physical property based on the painting film strength, stretching etc. that are obtained by coating water soluble polyurethane resin composition, relative to total amount 100 mass parts of urethane resin solids component, be preferably 0 ~ 30 mass parts, be more preferably 0 ~ 20 mass parts.If more than 30 mass parts, then the physical property of above-mentioned carbamate resins film is likely caused to reduce.
As described extender, can use from as described in number-average molecular weight be less than 200 small-molecular-weight polyol compound and small molecules polyamine compounds, the compound suitably selected normally used extender.
As this extender composition, such as, except can enumerating above-mentioned small molecules glycols, also quadrol can be enumerated, 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-methyldicyclohexyl) methane, diamino-dicyclohexyl methane, two (amino methyl) hexanaphthene, the ester ring type Diamines of 3,9-two (3-aminopropyl)-2,4,8,10-tetra-oxaspiro (5,5) undecane etc., m-xylene diamine, α-(/ p-aminophenyl) ethamine, mphenylenediamine, diaminodiphenyl-methane, diamino diphenyl sulfone, diamino diethyl-dimethyl ditan, diamino diethyl ditan, dimethylthiotoluenediamine, diethyl toluene diamine, α, α '-the polyamines of bis-(4-aminophenyl)-to the 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, the hydrazine class of 1 ', 1 '-tetramethyl--4,4 '-(methylene radical two pairs of phenylenes) diaminourea etc., and water etc.
As the usage quantity of described extender composition, based on the viewpoint of carbamate resins physical property etc., the isocyanate reaction base equivalent of extender is preferably made to reach the amount of 0.1 ~ 1.0 relative to the ratio of the isocyanate group equivalent of the carbamate prepolymer before chain extension reaction.
In the water soluble polyurethane resin composition that the present invention relates to, also blending can have the compound of unsaturated link(age).
As the compound with unsaturated link(age), such as, 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. can be enumerated.
As described (methyl) acrylate, (methyl) vinylformic acid and methyl alcohol can be enumerated, 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 the polyether glycol of polyoxyethylene glycol etc. etc.
Further, in the aqurous ployurethane composition that the present invention relates to, reaction terminating agent can be used as required.
As this reaction terminating agent, alkylol cpd, monoamine compound etc. can be enumerated.These both can use a kind, also can mix two or more to use.As above-mentioned alkylol cpd, methyl alcohol can be enumerated, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, octanol etc., as this monoamine compound, ethamine can be enumerated, 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 etc. of N-ehtylethanolamine etc.
Further, in water soluble polyurethane resin composition of the present invention, can use by mixed cross-linker as required.As linking agent, have internal crosslinker and outside cross-linking agent, internal crosslinker mixes when the synthesis of carbamate prepolymer, and outside cross-linking agent is then blended in water soluble polyurethane resin.
As described internal crosslinker, such as, the melamine compound of trimeric cyanamide, monomethylol trimeric cyanamide, dihydroxymethyl trimeric cyanamide, trimethylol melamine, tetra methylol trimeric cyanamide, pentamethylol melamine, hexamethylolmelamine, methylate melamine methylol, butylated methylol melamine etc. can be enumerated, or the small molecule polyol compound etc. with 3 hydroxyls of TriMethylolPropane(TMP) etc.
In these, the trimeric cyanamide to the excellent dispersion of water soluble polyurethane resin composition is preferably used.
As described outside cross-linking agent, the affixture of urea, trimeric cyanamide, benzoguanamine etc. and formaldehyde can be enumerated, the aminoresin of the alkylether compounds be made up of 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.
Further, when water soluble polyurethane resin is anionic property, the compound that can carry out reacting with the anionic property group of carboxyl or sulfonic group etc. can be used as linking agent.As this compound, such as, the epoxy compounds of oxazoline compounds, water-soluble epoxy resin etc., water-dispersible isocyanate, carbodiimide compound, ethylenimine compounds, trimeric cyanamide compounds and chelates of zinc etc. can be enumerated.In these, preferably use is easy to and the oxazoline compounds of anionic property radical reaction, epoxy compounds or carbodiimide compound.
Further, water soluble polyurethane resin composition of the present invention suitably can dilute and use afterwards, is not particularly limited for its solid component concentration.Based on the viewpoint of operability when dispersed or formation film, molding etc., solid component concentration is preferably 1 ~ 65 quality %, is more preferably 5 ~ 50 quality %.
As the median size of the dispersate in water soluble polyurethane resin composition of the present invention, being preferably below 100nm according to the value in the mensuration of dynamic light scattering method, being more preferably below 50nm, being particularly preferably below 35nm.
Particularly, using be coated with the highly adhesive polyester film of water soluble polyurethane resin composition of the present invention as easy bonding coat be used for optical thin film time, if the median size of described dispersate is more than 100nm, then the tendency that the haze value that there is film uprises, the transparency is deteriorated.On the other hand, median size is less, then haze value declines thereupon, also change is good thereupon for the transparency.
In the coating that water soluble polyurethane resin composition of the present invention is suitable for being used in synthetic resins and bonding.Now, the synthetic resins as adherend or applied thing is not particularly limited.As this synthetic resins, such as, polypropylene can be enumerated, 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, vinyl chloride-maleic acid ester 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 (such as, maleic anhydride, phenyl maleimide, methyl methacrylate, divinyl, vinyl cyanide etc.) multipolymer (such as, AS resin, ABS resin, MBS resin, heat-resisting ABS resin etc.), polymethylmethacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral acetal, the linear polyesters of polyethylene terephthalate and polybutylene terephthalate etc., polyphenylene oxide, the polymeric amide of polycaprolactam and polyhexamethylene adipamide etc., polycarbonate, polycarbonate/ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, urethane, the thermoplastic resin of cellulosic resin etc. and their blend, or phenol resins, and can also urea resin be enumerated, melamine resin, epoxy resin, the heat-curing resin etc. of unsaturated polyester resin etc.
In addition, in the coating and bonding of the elastomerics etc. of synthetic polyisoprene, divinyl rubber, acrylonitrile-butadiene copolymer rubber, styrene butadiene copolymers rubber etc., water soluble polyurethane resin composition of the present invention can also be used.
Further, in water soluble polyurethane resin composition of the present invention, normally used various additive can be added as required.As these additives, such as, hindered amine light stabilizer can be enumerated, the various weather resisting agent of UV light absorber and antioxidant etc., the silane coupling agent of adaptation firm especially can be given to base material, 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-gelling agents, 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, such as, can 2 be enumerated, 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-piperidyl methyl methyl acrylate, 2, 2, 6, 6-tetramethyl--4-piperidyl methyl methyl acrylate, 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 of 4-bis--s-triazine polycondensate, 1, 6-two (2, 2, 6, 6-tetramethyl--4-piperidyl amino) hexane/2, the tertiary octyl amino of the chloro-6-of 4-bis--s-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-base-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-base-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 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 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-oxaspiro [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-oxaspiro [5.5] undecane etc.
As described UV light absorber, such as, can 2 be enumerated, 4-dihydroxy benaophenonel, ESCALOL 567, 2-hydroxyl-4-octyloxybenzophenone, 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 of 4--6-benzotriazole base phenol), 2-(2-hydroxyl-3-the tertiary butyl-5-carboxyl phenyl) macrogol ester of benzotriazole, 2-[2-hydroxyl-3-(2-acryloyl-oxyethyl)-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-[the 2-hydroxyl-3-tertiary butyl-5-(2-methacryloxyethyl) phenyl] benzotriazole, 2-[2-hydroxyl-3-tert-pentyl-5-(2-methacryloxyethyl) phenyl] benzotriazole, 2-[the 2-hydroxyl-3-tertiary butyl-5-(3-methacryloxypropyl) phenyl]-5-chlorobenzotriazole, 2-[2-hydroxyl-4-(2-methacryloxymethyl) phenyl] benzotriazole, 2-[2-hydroxyl-4-(3-methacryloxy-2-hydroxypropyl) phenyl] benzotriazole, the 2-(2-hydroxy phenyl of 2-[2-hydroxyl-4-(3-methacryloxypropyl) phenyl] benzotriazole etc.) benzotriazole category, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4, 6-phenylbenzene-1, 3, 5-triazine, 2-(2-hydroxyl-4-Hexyloxy-phenyl)-4, 6-phenylbenzene-1, 3, 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-[2-hydroxyl-4-(3-C12 ~ C13 mixed oxyalkyl-2-hydroxy propyloxy group) phenyl]-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-[2-hydroxyl-4-(2-acryloyloxyethoxy) phenyl]-4, two (the 4-aminomethyl phenyl)-1 of 6-, 3, 5-triazine, 2-(2, 4-dihydroxyl-3-allyl phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2, 4, 6-tri-(2-hydroxy-3-methyl-4-Hexyloxy-phenyl)-1, 3, the 2-(2-hydroxy phenyl of 5-triazine etc.)-4, 6-diaryl-1, 3, 5-triazines, 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, docosyl (3, 5-di-t-butyl-4-hydroxyl) benzoates of benzoic ether etc., 2-ethyl-2 '-oxyethyl group oxanilide, 2-oxyethyl group-4 ' the replacement oxanilide class of-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-salt or metallo-chelate.
As metal-salt or metallo-chelate, the salt or inner complex class etc. of nickel or chromium can be enumerated.
As described antioxidant, Phosphorus, phenols or sulphur class antioxidant can be enumerated.
As phosphorus antioxidants, such as, triphenyl phosphite can be enumerated, 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 (dinonylphenyl) phosphorous acid ester, three is (single, two mixing 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, trilauryl phosphite, dibutyl acid phosphorous acid ester, dilauryl acid phosphorous acid ester, three lauryl trithiophosphite, two (neopentyl glycol) Isosorbide-5-Nitrae-cyclohexanedimethyl 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 alkyl)-4,4 '-isopropylidene diphenylphosphite, two ［ 2,2 '-methylene-bis (4,6-diamyl phenyl) ］ isopropylidene diphenylphosphite, four (tridecyls) 4, two (the 2-tertiary butyl-5-methylphenol) diphosphites of 4 '-butylidene, six (tridecyl) 1,1,3-tri-(2-methyl-5-tert-butyl-hydroxy phenyl) butane GW-540, four even (2,4-di-tert-butyl-phenyl) biphenylen, three (2-[(2,4,7,9-tetra-even tertiary butyl dibenzo [d, f] [1,3,2] dioxaphosphepin ring in heptan-6-base) oxygen base] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, three (2-[(2,4,8,10-tetra-even tertiary butyl dibenzo [d, f] [1,3,2] dioxaphosphepin ring in heptan-6-base) 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] dioxaphosphepin ring in heptan-6-base] 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, such as, 2,6 ditertiary butyl p cresol can be enumerated, 2,6-phenylbenzene-4-octade-cyloxyphenol, 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, thiodiethylene two ［ (3,5-di-tert-butyl-hydroxy phenyl) propionic ester ］, 4,4 '-thiobis (6-tert-butyl-m-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-t-butylbenzyl) 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 Benzenes, 1,3,5-tri-［ (3,5-di-tert-butyl-hydroxy phenyl) propionyloxyethyl ］ isocyanuric acid ester, four idols methylene radical-3-(3 ', 5 '-di-t-butyl-4 ' and-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-methylhydrocinnamoyl acyloxy) and-1,1-dimethyl ethyl ］-2,4,8,10-tetra-oxaspiro ［ 5.5 ］ undecanes, triethylene glycol two ［ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester ］, tocopherol etc.
As described sulphur class antioxidant, such as, the dialkyl dipropionate class of two lauryls of thio-2 acid, two myristins, myristyl stearyl ester, distearyl ester etc. can be enumerated, and the β-alkylmercaptopropionates class of the polyvalent alcohol of tetramethylolmethane four (β-dodecy propionic ester) etc.
As described hindered amine light stabilizer, UV light absorber and antioxidant usage quantity separately, relative to total amount 100 mass parts of described (A) ~ (D) composition, be preferably 0.001 ~ 10 mass parts, be particularly more preferably 0.01 ~ 5 mass parts.If be less than 0.001 mass parts, then likely cannot obtain sufficient additive effect, if more than 10 mass parts, then 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, can be the method be added in polyvalent alcohol, the method be added in carbamate prepolymer, the method be added on when carrying out water-dispersion in aqueous phase, arbitrary method in the method for adding after water-dispersion, but from the viewpoint of processing ease, the method being preferably added on the method in polyvalent alcohol and being added in carbamate prepolymer.
As the purposes of water soluble polyurethane resin composition of the present invention, the binding agent of coating agent, tackiness agent, coating, surface-modifying agent, organic powder and/or inorganic powder, molding, material of construction, sealing agent, cast material, elastomerics, foam, plastic raw materials, fibre finish etc. can be enumerated.
More particularly, the coating, wood coating, fibre finish, cavernous body, powder puff, gloves, condom etc. of inorganic structure material of binding agent, steel plate coating, glass, slabstone, cement etc. of the plastics coating agent of highly adhesive polyester film coating agent, polyethylene, polypropylene, polyester, polycarbonate etc., 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, intaglio printing printing-ink can be enumerated.
And; as the film of coating water soluble polyurethane resin of the present invention, wrapping material can be enumerated, window pastes material, ink jet recording materials, replacing paper, polaroid protective film, photo induction agent film, liquid-crystal display/plasma display/organic EL/ e-book etc. the base material film etc. of display unit etc.In these purposes, be particularly suitable to be used in plastics coating agent or tackiness agent, the binding agent of intaglio printing printing-ink, optics highly adhesive polyester film.
About the kind of the polyester be used in highly adhesive polyester film of the present invention, as long as can film shape be processed into, to it, there is no particular limitation, but the polyester of aromatic dicarboxylic acid is preferably employed as the dicarboxylic acid of raw material, such as, polyethylene terephthalate, polyethylene glycol 2，6-naphthalene dicarboxylate, polybutylene terephthalate, poly-α, β-bis-(2-chlorophenoxy) ethane 4 can be enumerated, 4 ,-dicarboxylic acid glycol ester etc.Particularly based on the viewpoint of quality, economy etc., most preferably use polyethylene terephthalate (PET).
Further, described polyester film can be any one in non-stretched film, single axle drawn membrane or biaxially oriented film, but when using with highly adhesive polyester film as optics, then adopts single shaft or biaxially oriented film specially.
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 to improve smoothness, stationarity etc. further, preferably in the composition containing mineral-type particle or organic particle.
As the blending amount of described mineral-type particle or organic particle, relative to solids component 100 mass parts of water soluble polyurethane resin, be generally 0.5 ~ 10 mass parts, be preferably 1 ~ 5 quality %.
If described blending amount is less than 0.5 quality %, then there is the situation that the resistance to blocking of film is insufficient, if more than 10 quality %, then hinder the transparency of film, thus the tendency that the boldness producing image reduces.
As inorganic particulate, silicon-dioxide, aluminum oxide, zirconium white, kaolin, talcum, calcium carbonate, titanium oxide, barium oxide, carbon black, moly-sulfide, weisspiessglanz etc. can be enumerated, but there is the cause of multiple particle diameter due to low price, preferably use silicon-dioxide.
As organic filler, such as, can enumerate by the polystyrene with crosslinking structure used as the compou nd synthesis containing more than 2 carbon-to-carbon double bonds in a part of Vinylstyrene or the organic filler etc. be made up of polyacrylic ester, polymethacrylate resin.
As optics highly adhesive polyester film of the present invention, such as, known method can be adopted as described below suitably to manufacture.That is,
Extrusion machine is supplied to after pet resin is fully carried out vacuum-drying, by T mould, the melting pet resin of about 280 DEG C is utilized rotation cooling roller melt extruded slabbing, utilize electrostatic to apply method subsequently and make it solidification cooling, thus the polyethylene terephthalate sheet that do not stretched.This polyethylene terephthalate sheet that do not stretch can be single layer structure, may also be the multilayered structure formed by co-extrusion platen press.
Further, preferably in pet resin in fact not containing causing that the transparency reduces, aluminum oxide or calcium carbonate etc. inert particle.
The roller being heated to 80 ~ 120 DEG C is utilized to stretch 2.5 ~ 5.0 times along its length the polyethylene terephthalate sheet that do not stretch obtained, thus as uniaxial extension pet film.
And then, clamp the end of film with clip and guide to the hot blast district being heated to 70 ~ 140 DEG C, thus stretching 2.5 ~ 5.0 times in the width direction.Subsequently, the heat-treatment zone guiding to 160 ~ 240 DEG C carries out the thermal treatment of 1 ~ 60 second, thus completes crystal orientation.
In any stage of this thin film fabrication operation, contain the coating fluid of water soluble polyurethane resin composition of the present invention at least coated on one side of pet film, thus form easy bonding coat.Easy bonding coat also can be formed 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, such as, suitably can select from brushing, roller coat, spraying, intaglio plate coating, the coating of inverse roller coating cloth, airblade coating, scraper, heavy curtain roller coat cloth, dip-coating, bar painting, scraper for coating etc.
Further, with regard to the thickness of described easy bonding coat, be 0.005 ~ 5 μm as final dry thickness, be preferably 0.05 ~ 2 μm, be more preferably the scope of 0.05 ~ 0.5 μm.
If the thickness of described easy bonding coat is less than 0.005 μm, then fully cannot obtain the binding property with energy line curing resin.Further, if the thickness of coating layer is more than 5 μm, then will easily there is film adhesion phenomenon deadlocked each other during pellicular cascade, or when the film after coating process being redrawn in order to the high strength of film, there is the tendency easily adhered on roller.The problem of adhesion can obviously occur when particularly defining easy bonding coat on the two sides of film.
On described easy bonding coat, in the scope of not impact effect, can and with water soluble polyurethane resin composition of the present invention and other resins.As other above-mentioned resins, such as, the Vinylite of acrylic resin, vibrin, Synolac, polyvinyl alcohol etc. can be enumerated, but in the present invention, particularly preferably and with water-soluble polyester or polyvinyl alcohol.
And during with other above-mentioned resins, as the Blend proportion of the solids component relative to water soluble polyurethane resin composition of the present invention, be preferably 0/100 ~ 50/50 by quality ratio, be more preferably 20/80 ~ 40/60.
As the solvent beyond the water used in coating fluid, the alcohols of scope mixed ethanol, Virahol, phenylcarbinol etc. of 50 quality % can be less than.In addition, in the scope of the 10 quality % lower than coating fluid, also can organic solvent beyond soluble scope mixed alcohols.
But the total amount of alcohols and other organic solvents is preferably less than 50 quality % of coating fluid.
The glue spread of described coating fluid is preferably 0.05g/m 2~ 0.8g/m 2, be more preferably 0.1g/m 2~ 0.5g/m 2.
Further, 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, then binding property can reduce, if dried glue spread is at 1g/m 2above, be then easy to after being subject to the impact of drying oven inner drying wind generate coating spot.
As easy adhering polyester film of the present invention, based on the viewpoint realizing high transparent, its mist degree is preferably less than 3.0%, is more preferably and is less than 2.0%, is particularly preferably and is less than 1.0%.
As optical thin film of the present invention, by arranging the hard coat that is made up of active energy line curing resin further and obtain on the easy bonding coat of highly adhesive polyester film of the present invention.
Above-mentioned active energy line curing resin can from have the double bonds such as acryl, suitably select known UV cured resin or electron beam curing resin etc. after use; 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 done and further describe in detail, but the present invention is by these any restriction.
The manufacture of carbamate prepolymer
Production Example 1 ~ 6
According to the mixing of blending amount (A) polyvalent alcohol, (B) polymeric polyisocyanate, (C) hydrophilic compounds, (D) monohydroxy vinyl ether compound shown in aftermentioned table 1, and 80 ~ 100 DEG C of reactions 2 ~ 3 hours.
Confirm that isocyanate content reaches the amount of regulation, the carbamate prepolymer obtained is set to PP-1 ~ PP-6.
Relatively Production Example 1 ~ 5
Use (A) ~ (D) composition of the blending amount as shown in aftermentioned table 2, manufacture carbamate prepolymer PP-7 ~ PP-11 by the method identical with Production Example.
Embodiment 1
The manufacture of water soluble polyurethane resin
Carbamate prepolymer PP-1 ~ the PP-6 obtained by described Production Example is injected in water, and makes solids component reach 20 quality %, subsequently 30 ~ 40 DEG C of dispersions 30 minutes.
Secondly, quadrol is added relative to the amount that the ratio (-NH/-NCO) of the isocyanate group equivalent of carbamate prepolymer is 0.9 (following according to amino equivalent, be designated as EDA), thus carry out chain extension reaction, stir subsequently 1 ~ 2 hour until by IR(infrared spectrophotometer) isocyanate group disappearance can be confirmed, thus obtain water soluble polyurethane resin composition PUD-1 ~ PUD-6.
Comparative example 1
Utilize by the described carbamate prepolymer PP-7 ~ PP-11 comparing Production Example and obtain, obtain 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 disperseed in the composition obtained by embodiment 1 and comparative example 1, measured by the dynamic light scattering method of the LB-550 adopting Horiba Ltd.Result is shown in table 1 and table 2.
Table 1
* 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 Inc., ProductName YmerN120, OH official energy 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 monovinyl base ether
* 13: cyclohexanedimethanol mono vinyl ether
Table 2
*: cyclohexanedimethanol divinyl base ether
Use metering bar coater, the water soluble polyurethane resin composition obtained is coated on surface by embodiment 1 and comparative example 1 on the stretched polypropene film of Corona discharge Treatment.
For the coated thin film obtained, adaptation, cohesiveness and resistance to blocking according to following condition evaluating.Result is shown in table 3 and table 4.
Cohesiveness evaluation method
By coated thin film 25 DEG C of dryings after 24 hours, for the drying regime of coated face, evaluated by following standard by finger touch.
◎: resin is not attached on finger, and coated face does not see fingerprint completely.
Zero: though resin is not attached on finger, coated face can see fingerprint slightly.
△: resin is attached on finger slightly.
×: resin is attached on finger.
Resistance to blocking evaluation method
By coated thin film after 50 DEG C of heating carry out drying in 30 minutes, under the state that coated face fits tightly each other, apply 0.5kg/cm 2loading, and to be placed in the temperature of 40 DEG C.From placement starts after 24 hours, whether the position observing coated face laminating has adhesion, and evaluates by following standard.
◎: do not have adhesion completely.
Zero: have very slight adhesion.
△: have a little adhesion.
×: there is adhesion.
The evaluation method of ink adaptation
Coated thin film, coated face is coated with after ink as test film after 30 minutes 50 DEG C of heating.Using the ink surface of this test film as outside, carry out bending machining the temperature of 180 DEG C.By in the ink surface in the bending machining portion being attached to test film with pressure for transparent adhesive tape wide for 18mm, after peeling off by force, whether observation has ink detachment, and evaluates by following standard.
◎: ink surface is completely not abnormal.
Zero: ink surface has very slight stripping.
△: ink surface has a little stripping.
×: ink surface is peeled off completely.
Table 3
Embodiment 1-1 1-2 1-3 1-4 1-5 1-6
Water soluble polyurethane resin is numbered PUD-1 PUD-2 PUD-3 PUD-4 PUD-5 PUD-6
Use prepolymer is numbered 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) relative to carbamate prepolymer (total amount of (A) ~ (D) composition)
Table 4
Comparative example 1-1 1-2 1-3 1-4 1-5
Water soluble polyurethane resin is numbered PUD-7 PUD-8 PUD-9 PUD-10 PUD-11
Use prepolymer is numbered 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) relative to carbamate prepolymer (total amount of (A) ~ (D) composition)
Embodiment 2
The manufacture of highly adhesive polyester film
Be be supplied to extrusion machine after the polyethylene terephthalate of 0.65 by the dry intrinsic viscosity of ordinary method, sheet is squeezed into after carrying out melting at 290 DEG C, utilize electrostatic to apply casting to cool fast in cooling rotating roller, thus make the PET film that do not stretch.
Utilize roller stretching method the PET film that do not stretch obtained longitudinally, at 85 DEG C to be stretched 2.5 times, stretch 1.3 times at 95 DEG C subsequently.Then, after being coated with water soluble polyurethane resin composition PUD-1 ~ PUD-6 respectively, transversely stretching 3.2 times at 120 DEG C, and heat-treat at 225 DEG C, thus obtain each highly adhesive polyester film.
Comparative example 2
By the method identical with embodiment 2, each highly adhesive polyester film that utilized water soluble polyurethane resin composition PUD-7 ~ PUD-11 to manufacture.
Mist degree is evaluated
The each highly adhesive polyester film manufactured 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 JISK7361(ISO13468) method measure, evaluate by following standard subsequently.Result is shown in table 5 and table 6.
◎: be less than 1.0%(very good)
More than zero: 1.0%, 3%(is less than good)
More than △: 3.0%, 5%(is less than 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 obtained, be coated with the active energy line curing resin be made up of the urethane acrylate 40 parts of dipentaerythritol acrylate 30 parts, 4 functionality, bisphenol-a epoxy acrylate 27 parts and 1-hydroxycyclohexylphenylketone 3 parts, and the thickness after making it solidify is 3 μm.Use and there is the high voltage mercury lamp that 120W/cm irradiates energy, irradiate about 15 seconds from the irradiation distance of 150mm, thus obtain the laminated polyester film (optical thin film) with hard coat.
Binding property is evaluated
After the laminated polyester film obtained being placed in each condition of following (1) ~ (3), according to JIS-K5400, use cutting guide rail that clearance gap is 1mm cut out through by rete and arrive 100 lattice-shapeds of base material film cut line.Subsequently, transparent adhesive tape is pasted onto on the cut surface of lattice-shaped, carries out wiping with eraser, thus after making it to adhere to completely, peel off fast with the peel angle of 90 °, observe release surface subsequently, and by following standard, binding property is evaluated.
Result is shown in table 5 and table 6.
Adhesion test condition
(1) normality binding property: 23 DEG C/relative humidity 65%, 24 hours
(2) moistening binding property: 60 DEG C/relative humidity 90%, 100 hours
(3) wet-heat resisting binding property: 60 DEG C/relative humidity 90%, 300 hours
After above-mentioned each condition places the specified time, after 23 DEG C × relative humidity 65% places 24 hours, implement test.
Binding property judgement criteria
◎: it is very good that stripping area is less than 5%()
Zero: peel off area more than 5%, to be less than 15%(good)
△: peel off area more than 15%, to be less than 20%(good a little)
×: peel off area (bad) more than 20%
Table 5
Embodiment 2-1 2-2 2-3 2-4 2-5 2-6
Water soluble polyurethane resin is numbered 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 19 -->
Mist degree ◎ ◎ ○ ○ ○ ◎
Binding property: normality ◎ ◎ ◎ ◎ ◎ ◎
Binding property: moistening ◎ ◎ ○ ◎ ◎ ◎
Binding property: heat-resisting ◎ ◎ ○ ◎ ◎ ◎
*: numerical value is the content (quality standard) relative to carbamate prepolymer (total amount of (A) ~ (D) composition)
Table 6
Comparative example 2-1 2-2 2-3 2-4 2-5
Water soluble polyurethane resin is numbered 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) relative to carbamate prepolymer (total amount of (A) ~ (D) composition)
Can confirm, as highly adhesive polyester film of the present invention, the hard coat for the energy-line solidifying type acrylic resin of electron beam or ultraviolet etc. or type siloxane heat-curing resin etc. has good binding property, and the transparency is excellent simultaneously.
Further, can confirm, by the median size of the carbamate resins disperseed in the present compositions 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 arranging the hard coat be made up of energy ray-curable resin on easy bonding coat, 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, dried layer conjunction or adhesive tape etc.
Industrial applicibility
As water soluble polyurethane resin composition of the present invention, for the binding property of synthetic resins and cohesiveness when being coated on synthetic resin film and resistance to blocking excellent, therefore can be used as laminated gravure printing ink binding agent or coating agent, coating etc.The synthetic resin film being 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 employing water soluble polyurethane resin composition of the present invention; its mist degree is low and while having the good transparency; the optical thin film employing this easy adhering polyester film has excellent adaptation under the condition requiring wet-heat resisting etc., is therefore particularly suitable for the display unit etc. being used as polarized light protective film, picture photosensitive agent film, liquid-crystal display/plasma display/organic EL/ e-book etc.

Claims (4)

1. a highly adhesive polyester film, it is the highly adhesive polyester film having easy bonding coat at least one mask of polyester film, it is characterized in that,
Described easy bonding coat is the layer of coating water soluble polyurethane resin composition,
The monohydroxy vinyl ether compound that the hydrophilic compounds that described water soluble polyurethane resin composition represents with (A) polyvalent alcohol, (B) polymeric polyisocyanate, (C) following general formula (1), (D) following general formula (2) represent and water are for neccessary composition
(C in described (C) composition 2h 4-O) nthe amount of the alkylene oxide unit represented is 3 ~ 20 quality % of the solids component be made up of described (A) ~ (D) composition, and the content of described (D) composition is 3 ~ 25 quality % of described solids component,
Wherein, the R in formula 1for the group represented by RNHCO-, R 2for methyl or ethyl, n is the integer of 5 ~ 35, and described R is the residue eliminating an isocyanate group from the trimer compound of vulcabond,
Wherein, the R in formula 3for the alkylidene group of carbonatoms 2 ~ 9, m is 1 or 2.
2. highly adhesive polyester film as claimed in claim 1, wherein, the median size of the dispersate in described water soluble polyurethane resin composition is at below 100nm.
3. highly adhesive polyester film as claimed in claim 1 or 2, wherein, described polyester film is pet film.
4. an optical thin film, is characterized in that, on the easy bonding coat of highly adhesive polyester film as claimed in claim 1, also has the hard coat be made up of active energy line curing resin.
CN201280034728.5A 2011-07-22 2012-05-14 Water soluble polyurethane resin composition, be coated with the highly adhesive polyester film of this water soluble polyurethane resin composition Expired - Fee Related CN103649143B (en)

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Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5869893B2 (en) * 2012-01-24 2016-02-24 株式会社Adeka Glass fiber sizing agent, glass fiber for fiber reinforced resin, and fiber reinforced synthetic resin composition containing aqueous polyurethane resin composition
JP6121204B2 (en) * 2013-03-15 2017-04-26 富士フイルム株式会社 Touch panel laminate and method for manufacturing touch panel laminate
JP6148067B2 (en) * 2013-05-20 2017-06-14 日本カーバイド工業株式会社 Vinyl ether resin composition
JP6164929B2 (en) * 2013-05-20 2017-07-19 日本カーバイド工業株式会社 Vinyl ether resin compound containing carbonate skeleton
KR101657356B1 (en) 2013-09-30 2016-09-19 주식회사 엘지화학 Opticla film including coated functional layer, polarizing plate and image display device comprising the same
WO2015046971A1 (en) * 2013-09-30 2015-04-02 주식회사 엘지화학 Optical film including functional coating layer and polarizing plate and image display device including same
JP5758039B1 (en) * 2014-10-27 2015-08-05 第一工業製薬株式会社 Aqueous dispersion of polyurethane resin and coating agent for plastic film using the same
CN104327487A (en) * 2014-11-06 2015-02-04 苏州佰格斯电子科技有限公司 Corrosion-resistant and weather-resistant sealant
US10268066B2 (en) * 2015-01-09 2019-04-23 Samsung Display Co., Ltd. Photosensitive resin composition, color conversion panel using the same and display device
WO2016208284A1 (en) * 2015-06-26 2016-12-29 Dic株式会社 Steel sheet surface treatment agent and steel sheet with coating film thereof
JP6655395B2 (en) * 2016-01-06 2020-02-26 株式会社Adeka Water-based polyurethane resin composition and optical film using the composition
JP6628628B2 (en) * 2016-02-16 2020-01-15 第一工業製薬株式会社 Polyurethane aqueous dispersion and process for producing polyurethane aqueous dispersion
CN106010008A (en) * 2016-07-06 2016-10-12 广州城建职业学院 Latex paint
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CN106349854A (en) * 2016-08-29 2017-01-25 王小艳 Exterior wall coating
JP6946314B2 (en) 2016-09-27 2021-10-06 株式会社Adeka Water-based polyurethane resin composition
CN108250390B (en) 2016-12-29 2020-07-28 万华化学集团股份有限公司 Aqueous dispersion of polyurethane or polyurethane-urea, preparation method and application
CN107232734A (en) * 2017-05-16 2017-10-10 江门建欢化妆用品有限公司 A kind of Wet-dry type powder puff and preparation method thereof
KR102438334B1 (en) * 2018-01-19 2022-08-31 도요보 가부시키가이샤 Easily Adhesive Polyester Film
JP7102751B2 (en) * 2018-01-31 2022-07-20 Ｕｂｅ株式会社 Polycarbonate polyol and aqueous polyurethane resin dispersion
JP2020105237A (en) * 2018-12-26 2020-07-09 三洋化成工業株式会社 Polyurethane resin aqueous dispersion
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KR102379084B1 (en) 2021-09-30 2022-03-24 윤미라 (Ultraviolet curable resin composition and manufacturing method of UV curable laminate sheet comprising same
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6565696B1 (en) * 1997-12-23 2003-05-20 Henkel Kommanditgesellschaft Auf Aktien Laminating adhesive hardenable by radiation and use of same
CN1786055A (en) * 2005-11-15 2006-06-14 华南理工大学 Bicompenent high solid content aqueous polyurethane, its preparation method and application
CN101146842A (en) * 2005-03-29 2008-03-19 株式会社艾迪科 Water-dispersible polyurethane composition
CN101160335A (en) * 2005-03-23 2008-04-09 佩什托普特殊化学股份公司 Aqueous polyurethane dispersion

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0151418B1 (en) 1994-12-27 1998-10-15 김충세 Water Dispersed Urethane Resin Composition
JPH10120736A (en) * 1996-10-21 1998-05-12 Dainippon Ink & Chem Inc Curable resin composition, FRP molded product and coating material
AU2003258609A1 (en) * 2002-08-14 2004-03-03 Novartis Ag Radiation-curable prepolymers
JP4140002B2 (en) * 2003-01-30 2008-08-27 荒川化学工業株式会社 Binder for printing ink and printing ink composition
CN101014640A (en) * 2004-08-30 2007-08-08 三菱聚酯薄膜公司 Removable polyester film
KR101218146B1 (en) * 2005-11-08 2013-01-03 도레이첨단소재 주식회사 Biaxially-stretched polyester film for optical use
JP5561517B2 (en) * 2009-08-24 2014-07-30 荒川化学工業株式会社 Active energy ray-curable oligomer, active energy ray-curable resin composition, cured film, and plastic film.
EP2316867B1 (en) 2009-10-31 2012-05-09 Bayer MaterialScience AG Tin-free, aqueous polyurethane dispersions
CN101875254B (en) * 2010-06-18 2012-07-25 海南赛诺实业有限公司 Anti-ultraviolet barrier coating film and manufacturing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6565696B1 (en) * 1997-12-23 2003-05-20 Henkel Kommanditgesellschaft Auf Aktien Laminating adhesive hardenable by radiation and use of same
CN101160335A (en) * 2005-03-23 2008-04-09 佩什托普特殊化学股份公司 Aqueous polyurethane dispersion
CN101146842A (en) * 2005-03-29 2008-03-19 株式会社艾迪科 Water-dispersible polyurethane composition
CN1786055A (en) * 2005-11-15 2006-06-14 华南理工大学 Bicompenent high solid content aqueous polyurethane, its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
新型非离子水性聚氨酯的制备及性能研究;张海龙等;《涂料工业》;20110601;第41卷(第6期);第46-50页 *

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