CN1791634A - Aqueous polyolefin resin dispersion, process for producing the same, and water-based coating material comprising the same - Google Patents

Abstract

An aqueous polyolefin resin dispersion which contains a polyolefin resin comprising 50 to 98 wt.% units of a C3-6 unsaturated hydrocarbon and 0.5 to 20 wt.% units of an unsaturated carboxylic acid and a basic compound and contains substantially no aids for aqueous-dispersion preparation which have a boiling point of 185 DEG C or higher at normal pressure. The polyolefin resin in the aqueous dispersion has a number-average particle diameter of 1 mum or smaller.

Description

Aqueous polyolefin resin dispersion, its manufacture method and use its water-borne coatings

Technical field

The present invention relates to not contain high boiling point Water-borne modification auxiliary agent and various base materials are had aqueous polyolefin resin dispersion, its manufacture method of good adhesion and use its water-borne coatings.

Background technology

Because polyolefin resin, especially acrylic resin has excellent electrology characteristic, mechanical characteristic, chemical property, plastic property, sanitation performance, recycles performance etc., is being used in a large number aspect center many.Yet polyolefin resin does not contain polar group in its molecular chain usually, thereby existence is difficult to coating and agglutinating problem.For this reason, for the coating and the bonding of acrylic resin, propose to use with the method for chlorinated polypropylene as the resin of main component.Yet chlorinated resin is emitted objectionable impuritiess such as sour gas when burning, thereby grows to even greater heights the strong transformation of wishing to the chlorine-free material in recent years along with the care to environment.So, developed modified polyolefin resin with modifications such as acid.

For modified polyolefin resin being used for coating and agglutinating purposes, must liquefy resin.For example, adopted a) use molten resin, b) resin dissolves or be scattered in the organic solvent use, c) resin disperseed the method used in aqueous medium.Yet, for a), exist purposes limited, make it be difficult to the problem of attenuation with the equilibrium of the melt viscosity of resin; And b) with c) compare, from the angle to the control of hazardous product, working space environmental improvement etc. such as environment protection, resources conservation, law, the use of organic solvent is had restricted trend, therefore wish to adopt c) method.

Based on above-mentioned background, extensively carrying out for the research of the Water-borne modification of modified polyolefin resin.For example, put down in writing among JP-A-6-73250, JP-A-6-80738, JP-A-6-80844, JP-A-6-80845, JP-A-6-256592, JP-A-8-3376, JP-A-8-67726, JP-A-8-67726, JP-A-8-92427, the JP-B-8-2895574 in aqueous medium, using various tensio-active agents to modified polyolefin resin (mainly being polypropylene) stable dispersion.Also have, in JP-B-2610559, put down in writing the aqueous polyvalent alcohol of necessary use.

Yet tensio-active agent as described above is nonvolatile, remain in after the drying in the filming of modified polyolefin resin, thereby at its consumption for a long time, the water tolerance of filming just significantly descends.Even for example when a small amount of, also make the interfacial characteristics acute variation, the performances such as cohesiveness with base material are produced baneful influence.Furtherly, have ooze out from filming may, thereby not only bad, and make the danger of the performance time to time change of filming in addition to environment, health.Also have, because the wetting ability height of aqueous polyvalent alcohol only is difficult to make resin to carry out complete Water-borne modification with many alcohol.In fact, among the JP-B-2610559 just and used tensio-active agent, this moment just to produce the problems referred to above.For example,, only just can make the resin Water-borne modification, following problems is also arranged with aqueous polyvalent alcohol even improve the carboxyl-content of resin.That is to say because how pure boiling point height, how alcohol arranged with the dry back of low temperature, short period of time is still remaining in filming, can to the water tolerance of filming and with the generation ill effects such as cohesiveness of base material.And then, since many alcohol have ooze out from filming may, thereby not only bad, and make the danger of performance time to time change in addition to environment, health.Also have, make how alcohol volatilizees, need high temperature dry for a long time, this also is disadvantageous to industrialization, also has the problem that makes the base material distortion because of the condition variation.

From such viewpoint, the applicant has proposed not contain the modified polyolefin resin aqueous dispersion (JP-A-2003-119328) of nonvolatile Water-borne modification auxiliary agents such as tensio-active agent.Yet, use modified polyvinyl resin hereinto, therefore, though good to nylon or poly cohesiveness, the cohesiveness of acrylic resin is still left some room for improvement.

Below open fire coating.Chlorine-free polyolefin resin as described above is applied in water-borne coatings as tackiness agent.Wherein, used for packing foods film etc. is very high for the requirement of non-chlorine, water system.Usually, the film of used for packing foods after applying material on the base material film on the lamination polyolefin resin film etc. form.

On the other hand, in the lamination process technology, have: on base material film after the coating process, coating tackify paint on application face is the method (extruding layer platen press) that tack coat comes the lamination molten resin with this tackifier coating: above-mentioned tackifier coating as tack coat and on this tackifier coating the method (dried laminating) of bonding various films; And do not use the tackify paint and on the application face of base material film the direct method (hereinafter referred to as " contact laminating ") of lamination molten resin etc.Wherein from economy, resources conservation, environment aspect, contact laminating is favourable.

This wherein, the coating as using the chlorine-free polyolefin resin is known that the material of being put down in writing among JP-A-8-120205, JP-A-2002-226758, the JP-A-2003-313483.

Yet the coating of putting down in writing in these documents when dry, has the close-burning problem that lacks with the propylene base material under the lesser temps about room temperature.And then the contact laminating suitability is also not enough, and room for improvement is arranged.

Summary of the invention

At above-mentioned present situation, the present invention aims to provide and does not add the non-volatile compounds or the higher-boiling compound that remain in after the drying in filming, makes modified polyolefin resin fine and be evenly dispersed in the aqueous dispersion of the characteristic of in the aqueous medium, not losing modified polyolefin resin and use its coating.Particularly, the present invention aims to provide cohesiveness, the good water-borne coatings of contact laminating suitability to various base materials.

The inventor etc. have carried out meticulous research in order to solve above-mentioned problem, and finding can stable dispersion in the aqueous medium that does not add non-volatile Water-borne modification auxiliary agent such as tensio-active agent or high boiling point Water-borne modification auxiliary agent with the polyolefin resin of specific composition.And then find that the water-borne coatings that contains this aqueous dispersion is good to the cohesiveness and the contact laminating suitability of various base materials, thereby has finished the present invention.

Main points of the present invention are as follows.

(1) aqueous polyolefin resin dispersion, it is characterized by, contain the unsaturated hydrocarbons of the carbonatoms 3～6 that comprises 50～98 quality % and unitary polyolefin resin of unsaturated carboxylic acid and the basic cpd of 0.5～20 quality %, boiling point is at the Water-borne modification auxiliary agent of 185 ℃ or higher temperature when being substantially free of normal pressure, and the number average bead diameter of this polyolefin resin in aqueous dispersion is at 1 μ m or littler.

(2) aqueous polyolefin resin dispersion of above-mentioned (1) is characterized by, and the unsaturated hydrocarbons of contained carbonatoms 3～6 is propylene and/or butylene in polyolefin resin.

(3) aqueous polyolefin resin dispersion of (1) or (2) is characterized by, and polyolefin resin further contains ethene.

(4) laminate is characterized by, and has removed the layer that medium forms in layers on substrates amasss by any aqueous polyolefin resin dispersion from (1) to (3).

(5) manufacture method of aqueous polyolefin resin dispersion, it is characterized by, it is the method that is used to make the aqueous polyolefin resin dispersion of above-mentioned (1), and boiling point was less than 185 ℃ organic solvent and water heating under 80～220 ℃ temperature in encloses container, the operation that stirs when it had comprised the unitary polyolefin resin of unsaturated carboxylic acid of the unsaturated hydrocarbons of the carbonatoms 3～6 that comprises 50～98 quality % and 0.5～20 quality %, basic cpd, normal pressure.

(6) water-borne coatings, it is characterized by, contain the unsaturated hydrocarbons of the carbonatoms 3～6 that comprises 50～98 quality % and the unitary polyolefin resin of unsaturated carboxylic acid (A) of 0.5～20 quality %, other resin (B) and pigment or the dyestuff (C) that adds as required, and (A) and mass ratio (B) (A)/(B) be 100/0～10/90, the number average bead diameter of polyolefin resin (A) is 1 μ m or littler.

(7) processed goods is characterized by, and is coated with (6) described water-borne coatings is housed on base material.

(8) (7) described processed goods is characterized by, and base material is a thermoplastic resin film.

(9) film is characterized by, and the easy tack coat of thickness 0.01～10 μ m is set at least on 1 of thermoplastic resin film, so on this easy tack coat the described water-borne coatings of application (6).

(10) laminated film is characterized by, and on the application face of above-mentioned (8) or (9) described thermoplastic resin film laminate layers is set.

(11) manufacture method of laminated film is characterized by, and lamination fused polyethylene or polypropylene on the application face of above-mentioned (8) or (9) described thermoplastic resin film form laminate layers.

The aqueous dispersion that can not added the polyolefin resin of non-volatile Water-borne modification auxiliary agents such as tensio-active agent or high boiling point Water-borne modification auxiliary agent, number average bead diameter 1 μ m or littler fine and stable specific composition by the present invention.Because film non-volatile Water-borne modification auxiliary agents such as not containing tensio-active agent or the high boiling Water-borne modification auxiliary agent that obtain of aqueous dispersion thus, can not damage the original characteristic of polyolefin resin, particularly, even drying for low temperature, short period of time, its water tolerance, with cohesiveness, the heat sealability excellence of base material, and these performances almost do not change for a long time.So, be adapted at using in the purposes such as tackiness agent in various paints, coating, printing ink, the binding agent.Particularly, the water-borne coatings that contains aqueous polyolefin resin dispersion of the present invention has the good cohesiveness and the suitability of contact laminating to various base materials.Also have, because manufacture method of the present invention does not need to use high speed whipping apptss such as homogenizer or mixed type emulsor, can simplified apparatus and reduce cost.

Embodiment

Explain the present invention below.

Polyolefin resin at first is described.

Polyolefin resin of the present invention is to contain 50～98 quality %, preferred 60～98 quality %, more preferably 70～98 quality %, the further chlorine-free polyolefin resin of the unsaturated hydrocarbons of the carbonatoms 3～6 of preferred 80～98 quality %.When the presence of unsaturates less than 50 quality % of carbonatoms 3～6, descend for the cohesiveness of polyolefine materials such as polypropylene; When surpassing 98 quality %, owing to reduced the unitary content of unsaturated carboxylic acid described later relatively, and make the Water-borne modification of resin become difficult.The unsaturated hydrocarbons of carbonatoms 3～6 has been enumerated, chain olefines and dienes such as divinyl and isoprene such as propylene, 1-butylene, iso-butylene, 1-amylene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 1-hexene.Wherein, from easy to manufacture, the Water-borne modification of resin easily, various materials are had cohesiveness, adhesive equal angles, serve as preferably with propylene composition or butylene composition (1-butylene, iso-butylene etc.), also can and use the two.Polyolefin resin of the present invention also preferably further contains the ethene composition of 2～50 quality % except the unsaturated hydrocarbons of above-mentioned carbonatoms 3～6.By containing the ethene composition, improved the Water-borne modification and the film performance of resin.

The particularly preferred formation of polyolefin resin of the present invention is the 3 composition resins that contain propylene composition, butylene composition, ethene composition, when the summation of this 3 composition was 100 mass parts, its composition was: propylene composition 8～90 mass parts, butylene composition 8～90 mass parts and ethene composition 2～50 mass parts.

In the said polyolefins resin, for the copolymerization form of each composition without limits, enumerated random copolymerization, block copolymerization etc., considered, preferred random copolymerization from easy polymeric angle.Also can mix the polyolefin resin of two or more in constituent ratio of the present invention.

Except mentioned component, also can contain 20 quality % of polyolefin resin total amount or other composition still less.Other composition has been enumerated, carbonatoms 6 or more chain olefines or dienes such as 1-octene, norbornylene class; (methyl) esters of acrylic acids such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate; Maleic acid esters such as dimethyl maleate, ethyl maleate, dibutyl maleinate; (methyl) acrylic amide; Alkyl vinyl such as methylvinylether, ethyl vinyl ether ethers; Vinyl esters such as vinyl formate, vinyl-acetic ester, propionate, trimethylacetic acid vinyl acetate, tertiary monocarboxylic acid (バ-サ チ Star Network acid) vinyl acetate and the vinyl alcohol that the vinyl esters saponification is obtained with basic cpd etc.; Vinylformic acid 2-hydroxy methacrylate, (methyl) glycidyl acrylate, (methyl) vinyl cyanide, vinylbenzene, substituted phenylethylene, vinyl halides class, meta-halo ethylene class, carbon monoxide, sulfurous gas etc. also can use their mixture.

Wherein, calm easily Water-borne modification and raising are considered the close-burning angle of various base material, are served as preferred to contain (methyl) acrylate.The object lesson of (methyl) acrylate has been enumerated, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) decyl acrylate, (methyl) lauryl acrylate, (methyl) Octyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl etc.

Consider from the angle of dispersiveness, the unsaturated carboxylic acid unit that 0.5～20 quality % must be arranged in the structure of polyolefin resin of the present invention, this unit serves as preferred to contain 0.5～15 quality %, contain 0.5～12 quality % for more preferably, contain 1～10 quality % for further preferred, contain 1～8 quality % for preferred especially.When unsaturated carboxylic acid unit less than 0.5 quality %, there is polyolefin resin to be difficult to the trend of Water-borne modification, on the other hand, when surpassing 20 quality %, although the Water-borne modification of resin becomes easily, have a declining tendency with the cohesiveness of polyolefin material such as polypropylene.

The unsaturated carboxylic acid unit is introduced by unsaturated carboxylic acid or its acid anhydrides.Its object lesson has been enumerated, outside vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride, equisetic acid, aconitic anhydride, fumaric acid, Ba Dousuan, citraconic acid, methylfumaric acid, the allyl group succsinic acid etc., also can use such intramolecularly (in the monomeric unit) such as half ester, half amide of unsaturated dicarboxylic acid that the compound of at least 1 carboxyl or anhydride group is arranged.Wherein, considering from the angle that is incorporated into polyolefin resin easily, serve as preferably with maleic anhydride, vinylformic acid, methacrylic acid, and maleic anhydride is for more preferably.The unsaturated carboxylic acid unit is so long as copolymerization gets final product in polyolefin resin, and its form has no particular limits, and for example can enumerate random copolymerization, block copolymerization, graft copolymerization etc.The acid anhydrides unit that is incorporated in the polyolefin resin is taked acid anhydride structure easily under drying regime, and in containing the aqueous medium of basic cpd described later the time, has its part or all of open loop to become the trend of the structure of carboxylic acid or its salt.

For being incorporated into the method for going in the polyolefin resin, the unsaturated carboxylic acid unit has no particular limits, for example can enumerate in the presence of radical initiator, polyolefin resin and unsaturated carboxylic acid under the fusing point of polyolefin resin or higher temperature heating and melting, make the method for its reaction; After polyolefin resin dissolved, heating in the presence of radical initiator, stir the method that the method that makes its reaction etc. makes unsaturated carboxylic acid unit and polyolefin resin graft copolymerization in organic solvent.From consideration easy and simple to handle, the kind method was preferred in the past.

The radical initiator that uses in graft copolymerization for example can be enumerated azo nitriles such as organo-peroxide class, Diisopropyl azodicarboxylate such as ditertiary butyl peroxide, diisopropylbenzyl superoxide, tertbutyl peroxide, tert butyl isopropyl benzene peroxide, benzoyl peroxide, dilauryl superoxide, cumyl hydroperoxide, tert butyl peroxy benzoate, ethyl diethyldithiocarbamate ketone peroxide, di-t-butyl two mistake phthalic acid esters.They can suitably select with temperature of reaction to use.

The weight-average molecular weight of polyolefin resin serves as preferred with 5000～150000, and 20000～120000 for more preferably, and 30000～100000 for further preferred, and 35000～90000 for preferred especially, and 40000～80000 for most preferably.When weight-average molecular weight less than 5000 the time, descend the resulting trend of filming and wanting hardening to become fragile with the cohesiveness of base material; And weight-average molecular weight surpasses at 150000 o'clock, and is in distress so that the trend of resin Water-borne modification.Have, the weight-average molecular weight of resin can be that standard is tried to achieve with the polystyrene resin with gel permeation chromatography (GPC) again.

Aqueous dispersion of the present invention is the said polyolefins resin dispersion or be dissolved in the aqueous medium.Aqueous medium described here is meant with water to be the liquid of main component, also can contain water-miscible organic solvent described later or basic cpd.

The number average bead diameter that is scattered in the polyolefin resin particle in the aqueous dispersion of the present invention is necessary for 1 μ m or littler.From low temperature make film, the viewpoint of the tone of filming considers, with 0.5 μ m or littler serve as preferably, for more preferably, 0.005～0.2 μ m is for further preferred at 0.005～0.3 μ m.When number average bead diameter surpassed 1 μ m, low temperature was made film and is significantly worsened, and the storage stability of aqueous dispersion descends.Make the angle of film and storage stability from low temperature and consider, weight average particle diameter with 2 μ m or littler serve as preferably, at 1 μ m or littler of more preferably, for further preferred, 0.01～0.3 μ m is for preferred especially at 0.005～0.5 μ m.By making particle diameter little, improved the tone that sticking power, low temperature are made film properties and filmed.

The number average bead diameter of polyolefin resin and weight average particle diameter are to measure with the general employed dynamic light scattering method of particle diameter of measuring particulate matter.

Resin containing ratio in the aqueous dispersion of the present invention can wait suitably by the thickness of film forming condition, target resin coating film and performance and select, and has no particular limits.But, considering from the angle that appropriateness keeps the viscosity of coating composition and presents the good formation ability of filming, serve as preferably with 1～60 quality %, and 3～55 quality % are for more preferably, and 5～50 quality % are for further preferred, and 10～45 quality % are for preferred especially.

Aqueous dispersion of the present invention is characterised in that, boiling point was at the Water-borne modification auxiliary agent of 185 ℃ or higher temperature when it was substantially devoid of normal pressure.When being meant normal atmosphere during described normal pressure.Thereby, have excellent cryodrying coating characteristic, particularly water tolerance, with cohesiveness, the heat sealability excellence of base material, these performances almost do not change for a long time.Boiling point described in this specification sheets all is meant the boiling point under the normal pressure.Also have, under normal pressure, do not have the Water-borne modification auxiliary agent of boiling point to be considered to be the Water-borne modification auxiliary agent of boiling point of the present invention at 185 ℃ or higher temperature.

Here, described " Water-borne modification auxiliary agent " is meant, in making aqueous dispersion, with reagent or the compound that promotes that Water-borne modification adds with making aqueous dispersion stabilize to purpose.

Described " boiling point is at the Water-borne modification auxiliary agent of 185 ℃ or higher temperature when being substantially devoid of normal pressure " is meant that auxiliary agent that need not be such when making (resin Water-borne modification) does not contain this auxiliary agent in the consequently resulting dispersion.So,, within the scope of not damaging effect of the present invention, contain less than degree also harmless with respect to 0.1 quality % of polyolefin resin composition though be zero for preferred especially with such Water-borne modification auxiliary agent content.

Boiling point is at the Water-borne modification auxiliary agent of 185 ℃ or higher temperature during normal pressure of the present invention, for example can enumerate sour modified compound, water-soluble polymer, many alcohol of tensio-active agent described later, the compound with protective colloid action, modified waxes class, high acid value etc.

Tensio-active agent has been enumerated, cationic surfactant, aniorfic surfactant, nonionic surface active agent, amphoterics, fluorine are tensio-active agent, reactive surfactant, except generally in emulsion polymerization, using, also comprise the emulsifying agent class.For example, aniorfic surfactant has been enumerated, senior carboxylic acid such as the sulfuric acid of higher alcohols, senior alkyl sulfonic acid and salt thereof, oleic acid, stearic acid, palmitinic acid and salt, alkyl benzene sulphonate (ABS) and salt thereof, polyoxyethylene alkyl sulfuric ester salt, polyoxyethylene alkyl phenyl ether sulfuric acid, sulfo-succinic acid vinyl ester etc.Nonionic surface active agent has been enumerated, and polyoxyethylene alkyl oxide, polyoxyethylene alkyl phenyl ether, cithrol, oxyethane propylene oxide block copolymer, polyoxyethylene fatty amide, PEP-101 etc. have dehydrated sorbitol derivatives such as the compound of polyoxyethylene structure and polyoxyethylene sorbitan fatty acid esters etc.The example of amphoterics has, lauryl betaine, lauryl dimethyl amine oxide etc.Reactive surfactant has been enumerated, the compound of alkyl propenyl phenol polyethylene oxide affixture and the two keys of their sulfuric acid, allyl group alkylphenol polyethylene oxide affixture and their sulfuric acid, allyl group dialkyl group phenol polyethylene oxide affixture and their responding property such as sulfuric acid.

Compound with protective colloid action; the modified waxes class; the sour modified compound of high acid value; water-soluble polymer has been enumerated, polyvinyl alcohol; carboxy-modified polyvinyl alcohol; carboxymethyl cellulose; Natvosol; hydroxypropylcellulose; treated starch; Polyvinylpyrolidone (PVP); polyacrylic acid and salt thereof; contain the carboxyl polyethylene wax; contain carboxylated polypropylene wax; contain carboxyl polyethylene-weight-average molecular weight such as propylene wax usually 5000 or lower acid modified polyolefin wax class and salt thereof; vinylformic acid-copolymer-maleic anhydride and salt thereof; vinylbenzene-(methyl) acrylic copolymer; ethene-(methyl) acrylic copolymer; iso-butylene-maleic anhydride alternate copolymer; (methyl) vinylformic acid-unsaturated carboxylic acid content such as (methyl) acrylate copolymer are at 20 quality % or higher carboxylic polymkeric substance and salt thereof; poly-methylene-succinic acid and salt thereof; amino water-soluble acrylic copolymers is arranged; gelatin; Sudan Gum-arabic; the compound that casein etc. generally use as the dispersion stabilizer of particulate.

Boiling point has been enumerated at many alcohol of 185 ℃ or higher temperature, glycols, polyoxy aklylene glycol class, polyvalent alcohol, polyester polyol, the many alcohol of acrylic acid or the like, the many alcohol of urethane etc.Ethylene glycol, glycol ether, triglycol, propylene glycol, butyleneglycol, glycerine etc. specifically can have been enumerated.

Aqueous dispersion of the present invention contains basic cpd.The basic cpd carboxyl in the polyolefin resin that partly or entirely neutralized has thus prevented aggegation between the particulate by the electric repulsion between the carboxyl anion that generates, and gives aqueous dispersion with stability.Though boiling point is less than 185 ℃ during the normal pressure of such basic cpd, it is preferred waiting for water tolerance, drying property.When boiling point during at 185 ℃ or higher temperature, drying is difficult to make it to overflow from resin coating film, especially has the situation that makes the water tolerance of filming and worsen with the cohesiveness of base material etc. when cryodrying.

Do not limit less than 185 ℃ basic cpd is special for boiling point, concrete example has been enumerated, ammonia, triethylamine, N, N-dimethylethanolamine, Isopropylamine, monoethanolamine, dimethylaminoethanol, DEAE diethylaminoethanol, ethamine, diethylamine, isobutylamine, dipropyl amine, 3-ethoxy propylamine, 3-diethyl amino propylamine, sec-butylamine, propylamine, n-Butyl Amine 99,2-methoxyethyl amine, 3 methoxypropyl amine, 2,2-dimethoxy-ethylamine, thanomin, morpholine, N-methylmorpholine, N-ethylmorpholine, pyrroles, pyridine etc.

The add-on of basic cpd serves as preferred with 0.5～3.0 times of equivalent with respect to the carboxyl in the polyolefin resin, and 0.8～2.5 times of equivalent is for more preferably, and 0.9～2.0 times of equivalent is for preferred especially.When less than 0.5 times of equivalent, do not see the effect that adds basic cpd, and when surpassing 3.0 times of equivalents, the time of drying that forms when filming is elongated, have the situation that the stability that makes aqueous dispersion worsens.

Among the present invention,, make that the particle diameter of dispersed particle is little, preferably when Water-borne modification, add organic solvent in order to promote the Water-borne modification of polyolefin resin.The amount of the organic solvent that uses with 50 quality % in the aqueous medium or lower serve as preferably, 1～45 quality % is for more preferably, 2～40 quality % are for further preferred, 3～35 quality % are for preferred especially.When organic quantity of solvent surpasses 50 quality %, can not be considered as aqueous medium basically, not only can not reach one of purpose of the present invention (environment protection), and sometimes because employed organic solvent can make the stability decreases of aqueous dispersion.

Consider from the angle that obtains good aqueous dispersion, organic solvent so that when being used in 20 ℃ to the solvability of water at 10g/L or higher organic solvent for preferred, 20g/L or higher for more preferably, 50g/L or higher for preferred especially.

From considering easily by the angle of removing filming, organic solvent during with normal pressure boiling point serve as preferably less than 185 ℃ organic solvent, 50 ℃ or higher and less than 185 ℃ for preferred especially.The organic solvent of 185 ℃ of boiling points or higher temperature is difficult to by dry and overflow from resin coating film, particularly the water tolerance of filming of cryodrying and worsen sometimes with the cohesiveness of base material.

The object lesson of the organic solvent that uses for example can be enumerated alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, sec.-amyl alcohol, tertiary amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butene alcohol, n-hexyl alcohol, hexalin; Ketones such as methylethylketone, methyl iso-butyl ketone (MIBK), ethyl butyl ketone, pimelinketone; Ethers such as tetrahydrofuran (THF), diox; Ester classes such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, acetate-3-methoxyl group butyl ester, methyl propionate, ethyl propionate, diethyl carbonate, methylcarbonate; Diol, derivatives such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate; And then have, 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, 3-methoxyl group-3-methyl isophthalic acid-butanols, methoxybutanol, acetonitrile, dimethyl formamide, N,N-DIMETHYLACETAMIDE, Pyranton, methyl aceto acetate, 1,2-dimethyl glycerine, 1,3-dimethyl glycerine, trimethylammonium glycerine etc.Also can mix these organic solvents of two or more and use.

Consider from the high angle of effect of the Water-borne modification that promotes resin, in above-mentioned organic solvent, preferred alcohol, n-propyl alcohol, Virahol, propyl carbinol, methylethylketone, pimelinketone, tetrahydrofuran (THF), diox, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether are preferred, the organic solvent that 1 hydroxyl arranged with the intramolecularly in the middle of these is for more preferably, from a small amount of interpolation the angle of resin Water-borne modification is considered, with the ethylene glycol alkyl ether for further preferred.

When making aqueous dispersion, having used above-mentioned organic solvent, handle its partial solvent is distilled to outside the system with the desolventizing that generally is referred to as " stripping " after the resin Water-borne modification, can reach the effect that reduces the organic solvent amount.Can be reduced to the organic solvent content in the aqueous dispersion 10 quality % or lower with stripping, if to 5 quality % or lower, be preferred from the environment aspect is said.In the stripping operation, distill away although can go up employed organic solvent in the Water-borne modification substantially all, the just essential for this reason decompression degree that improves device prolongs the operating time, therefore consider that from productive angle the lower limit of organic solvent amount is about 0.01 quality %.But,, especially, also can use resin well to not influence of aspect of performance even less than 0.01 quality %.

Steam stripped method has been enumerated, while thereby stir and heat the method that organic solvent is steamed at normal pressure or the following aqueous dispersion of decompression.Because of aqueous medium is distilled away the concentration of solids component is uprised, for example, thereby viscosity rises when causing the transaction capabilities variation, also can add entry in advance in aqueous dispersion.

Follow the manufacture method that aqueous polyolefin resin dispersion is described.

Have no particular limits for the method that obtains aqueous polyolefin resin dispersion of the present invention, can adopt described various compositions, be polyolefin resin, basic cpd, aqueous medium, organic solvent as required in vessel in heating, stirring method that can be airtight, this method be the most preferred.Method does not just have the special necessary Water-borne modification auxiliary agent that adds 185 ℃ of boiling points or higher temperature thus.

Can use the device as solid-liquid whipping appts or mulser well known to those skilled in the art as described container, can be pressurized to 0.1Mpa or higher device serves as preferred with use.Speed of rotation for stirring method and stirring has no particular limits, so that resin becomes the stirring at low speed of floating state degree to be advisable in aqueous medium.So, there is no need high-speed stirring (for example, 1,000rpm or higher), just can make aqueous dispersion with simple assembly.

Raw materials such as polyolefin resin, aqueous medium are joined in the said apparatus, preferably mix 40 ℃ or lower temperature.Then, temperature in the groove is remained in 60～220 ℃, preferred 80～200 ℃, further preferred 100～190 ℃, preferred especially 100～180 ℃, preferably continuing to be stirred to (does not for example have till the oversize particle, 5～120 minutes), make the abundant Water-borne modification of polyolefin resin, then, preferably under agitation be cooled to 40 ℃ or low temperature more, just can obtain aqueous dispersion.When temperature in the groove during less than 60 ℃, polyolefin resin is difficult to Water-borne modification; And when temperature surpasses 220 ℃ in the groove, have the possibility of the molecular weight and molecular weight of polyolefin resin.

Can as required further spray pulverization process thereafter.The so-called pulverization process of spraying is that aqueous polyolefin resin dispersion is under high pressure sprayed from the such pore of nozzle or slit, by resin particle each other or the mechanical energy of collisions such as resin particle and impingement plate make the further refinement of resin particle.The object lesson of the device of this purposes has been enumerated, super-voltage micro jet equipment (the マ イ Network ロ Off Le イ イ ザ one) M-110E/H that uniform mixer that A.P.V.GAULIN company makes or MIZUHO industrial make etc.

Adjust the method for the solid component concentration of the aqueous dispersion that obtains like this and enumerated, for example, aqueous medium is boiled off to obtain the method for required solid component concentration or dilute with water.

The aqueous dispersion of the present invention that adopts above-mentioned method for making to obtain is that its polyolefin resin is dispersed or dissolved in the aqueous medium and is modulated into liquid uniformly.Uniform liquid being meant described here do not see that in appearance aqueous dispersion has precipitation, is separated or the state of phenomenons so-called skinning, that local solid component concentration is different with other parts.

The using method of aqueous polyolefin resin dispersion of the present invention is described below.

Aqueous dispersion of the present invention has the excellent formation ability of filming, can use known film, for example, gravure cylinder is coated with, contrary roller coat, the line rod is coated with, methods such as scraper plate is coated with, air knife is coated with, curtain coating, spraying, dip-coating, brushing are evenly coated in various base materials surface, after near room temperature, condensing as required, come dry or dry and baking by carrying out heat treated, just can adhere to and form uniform resin coating film at various substrate surfaces.The heating unit of this moment uses common hot air circulation type baking oven or Infrared heaters etc. to get final product.The temperature of heating and heat-up time can be with waiting suitably and select as the characteristic of the base material of coated thing with in kind, the use level of solidifying agent described later, the angle of the economy of not associating is considered, Heating temperature serves as preferred with 30～250 ℃, 60～230 ℃ for more preferably, and 80～210 ℃ for preferred especially.Be divided into preferred heat-up time with 1 second～20,5 seconds～15 are divided into more preferably, 5 seconds～10 be divided into preferred especially.When adding linking agent, fully react in order to make carboxyl and linking agent in the polyolefin resin, preferably suitably select Heating temperature and time with the kind of linking agent.

The glue spread of aqueous dispersion of the present invention can suitably be selected with purposes, but is 0.01～100g/m with dried glue spread ²For preferably, 0.1～50g/m ²For more preferably, 0.2～30g/m ²For preferred especially.If at 0.01～100g/m ²The scope film forming just can obtain the resin coating film of excellent in uniformity.

In order to regulate glue spread, except applying device and its working conditions that suitable selection is used, the preferred aqueous dispersion that uses with the concentration that is suitable for target resin coating thickness.The concentration of this moment can be regulated by the composition that when modulation adds.Also can regulate by synthetic aqueous dispersion is suitably diluted or concentrates.

In order further to improve the performance of aqueous dispersion of the present invention, can add the aqueous dispersion, viscosity imparting agent, inorganic particulate, linking agent, pigment, dyestuff of other polymkeric substance etc.

As other the not special restriction of aqueous dispersion of polymkeric substance, for example can enumerate polyvinyl acetate, vinyl-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylate-copolymer-maleic anhydride, the styrene-maleic acid resin, the styrene butadiene resin, butadiene resin, the acrylonitrile-butadiene resin, poly-(methyl) acrylonitrile resin, (methyl) acrylamide resin, the chlorinated polyethylene resin, the chloro acrylic resin, vibrin, the modification of nylon resin, carbamate resins, rosin etc. are given the resin of viscosity, phenolic resin, silicone resin, aqueous dispersion such as Resins, epoxy also can mix in them two or more and use.

As inorganic particulate, can add layered inorganic compounds such as inorganic particulates such as metal oxides such as magnesium oxide, zinc oxide, stannic oxide, lime carbonate, silicon-dioxide, vermiculite, polynite, lithium montmorillonite, hydrotalcite, synthetic mica.Consider that from the angle of the stability of aqueous dispersion the median size of these inorganic particulates serve as preferably with 0.005～10 μ m, 0.005～5 μ m is for more preferably.Inorganic particulate also can two or more mix use.For shielding ultraviolet rays, can use zinc oxide, for antistatic, can use stannic oxide.

In order further to improve various film performances such as water tolerance and solvent resistance, with respect to the resin of 100 mass parts in aqueous dispersion, the linking agent that can add 0.01～80 mass parts serves as preferred to add 0.1～50 mass parts, and 0.5～30 mass parts is for more preferably.The add-on of linking agent is during less than 0.01 mass parts, and the degree that film performance improves diminishes, and when surpassing 80 mass parts, degradation such as processibility.Linking agent can use linking agent, intramolecularly with self-crosslinking have the functional group of a plurality of and carboxyl reaction compound, multiple tooth coordinate metal etc. is arranged, serve as preferred with the compound of isocyanate compound, melamine compound, urea compounds, epoxy compounds, carbodiimide compound, Han oxazolinyl, zirconates compound, silane coupling agent etc. wherein, these linking agents also can be used in combination.

In aqueous dispersion of the present invention, can further add all ingredients such as flow agent, defoamer, mould inhibitor, pigment dispersing agent, UV light absorber, tackifier, weather resisting agent, fire retardant as required.

The resin combination and the various base material that obtain by aqueous dispersion of the present invention, for example, metal, glass, plastic former, film, synthetic paper, paper etc. have excellent cohesiveness, thereby are suitable for as paint, priming paint, coating (printing ink), binding agent on these base materials.Wherein, from the angle of good cohesiveness, contact laminating suitability is arranged for various base materials, using as priming paint or coating (printing ink) to more preferably, as the coating use for most preferably.

Next explanation contains the water-borne coatings of aqueous polyolefin resin dispersion of the present invention.

Water-borne coatings of the present invention is except containing polyolefin resin (A) as the resinous principle, the resin (B) that can also contain other, (A) with (B) mass ratio (A)/(B) in 100/0～10/90 scope, with 99/1～15/85 serves as preferred, 97/2～20/80 for more preferably, and 95/5～25/75 is further preferred.Even have only polyolefin resin (A), for just existing good cohesiveness, the contact laminating suitability of various base materials, but by having mixed other resin, can further improve anti-viscosity, to the adhesive power of specific base material.

Described other resin (B) is so long as just having no particular limits of using in water system, consider from the angle of weathering resistance, wear resistant, tint retention, economy, can use the resin of having stated, but serve as preferred with acrylic resin, polyurethanes resin, polyester resin especially.

Above-mentioned acrylic resin has been enumerated, the homopolymerization or the copolymer resins of (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate; (methyl) acrylic acid hydroxy ester classes such as (methyl) hydroxyethyl acrylate, (methyl) vinylformic acid hydroxypropyl ester, (methyl) hydroxybutyl acrylate; And by olefines such as ethene, propylene, iso-butylene, 1-butylene, vinylbenzene, vinyl toluenes; Vinyl esters such as vinyl formate, vinyl-acetic ester, propionate, trimethylacetic acid vinyl acetate, tertiary ethylene carbonate; Vinyl halides such as vinylchlorid, vinylidene chloride compounds; Carboxylic-acids such as vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, fumaric acid, Ba Dousuan; Nitriles such as (methyl) vinyl cyanide; The copolymer resins of amidess such as (methyl) acrylamide, N hydroxymethyl acrylamide, N,N-DMAA, N-N-isopropylacrylamide etc. and above-mentioned (methyl) alkyl acrylate.

Wherein, can use as the vinyl acetate esters resin: the homopolymer of vinyl-acetic ester or with the multipolymer of ethene, dibutyl maleinate, dibutyl fumarate, propionate, trimethylacetic acid vinyl acetate, tertiary ethylene carbonate etc.

The polyurethanes resin is meant the resin that contains amino-formate bond in main chain, obtains by for example many alkylol cpds and polyisocyanate compound reaction, and from the angle of the dispersiveness aqueous medium, serve as preferred with what have the anionic property group.Here said anionic property group is meant that carboxyl, sulfonic group, sulfate, phosphate etc. become anionic functional group in aqueous medium.

Have no particular limits as constituting the resinoid how pure composition of urethane, can enumerate water, ethylene glycol, glycol ether, triglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,2-propylene glycol, 1, ammediol, 1,6-hexylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, methyl isophthalic acid, 5-pentanediol, 1,8-ethohexadiol, 2-ethyl-1, low molecular weight diols classes such as 3-hexylene glycol, glycol ether, triglycol, dipropylene glycol; Low-molecular-weight polyol classes such as TriMethylolPropane(TMP), glycerine, tetramethylolmethane; The high molecular weight diol class such as many alkylol cpds, polyether glycol class, polyester glycol class that oxyethane or propylene oxide units are arranged; Bisphenols such as dihydroxyphenyl propane and Bisphenol F; The carboxyl of dimeracid is converted into the dimer diol of hydroxyl etc.

On the other hand, as the polymeric polyisocyanate composition, can use a kind or the mixture of two or more of known aromatic series, aliphatics and alicyclic diisocyanates.The object lesson of diisocyanates has been enumerated, inferior cresyl vulcabond, 4,4 '-'-diphenylmethane diisocyanate, 1, the 3-phenylene vulcabond, hexamethylene diisocyanate, eylylene diisocyanate, 1, the 5-naphthalene diisocyanate, isophorone diisocyanate, two メ リ-Le vulcabond, lysinediisocyanate, hydrogenation 4,4 '-'-diphenylmethane diisocyanate, the hydrogenation inferior cresyl vulcabond, the carboxyl of dimeracid is converted into the dimerization vulcabond of isocyanate group and their adduction object, the biuret body, chlorinated isocyanurates body etc.Also have, also can use in the diisocyanates 3 officials such as triphenylmethane triisocyanate, polymethylene multi-phenenyl isocyanate can or more polyfunctional polyisocyanates.

Also have,, also can use how pure composition with carboxyl, sulfonic group, sulfate, phosphate etc. in order in the polyurethanes resin, to introduce the anionic property group.

Many alkylol cpds with carboxyl have been enumerated, 3,5-dihydroxyl M-nitro benzoic acid, 2, two (methylol) propionic acid, 2 of 2-, two (hydroxyethyl) propionic acid, 2 of 2-, two (hydroxypropyl) propionic acid of 2-, two (methylol) acetate, two (4-hydroxy phenyl) acetate, 2, two (4-hydroxy phenyl) valeric acids of 2-, tartrate, N, N-dihydroxyethylglycin, N, two (2-the hydroxyethyl)-3-carboxyl propionic acid amides of N-etc.

Also can use chain length to prolong agent and suitably adjust the resinoid molecular weight of urethane.As chain length prolong agent enumerate have 2 or more can with the compound of reactive hydrogens such as the amino of isocyanic ester radical reaction or hydroxyl, for example, diamine compound, dihydrazide compound, glycols.

Polyester resin as above-mentioned other resin (B) is the resin that is made of dicarboxylic acid composition and glycol component.Dicarboxylic acid has been enumerated terephthalic acid, m-phthalic acid, phthalic acid, toxilic acid, hexanodioic acid, sebacic acid, palmitinic acid, 1,4-cyclohexane diacid etc.Glycol has been enumerated, ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, Diethylene Glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, triglycol etc.As required, also can with 3 officials can or copolymerization such as trimellitic acid of more polyfunctional acid or pure composition, pyromellitic acid, glycerine, TriMethylolPropane(TMP), tetramethylolmethane.Vibrin also can be the vibrin that polyoxyethylene glycol acid, poly(lactic acid), polycaprolactone, poly butylene succinate, polyethylene glycol succinate etc. have biological degradability.

In water-borne coatings, also can contain pigment or dyestuff.This pigment or dyestuff are so long as widely usedly in paint field just have no particular limits.As pigment, mineral dyes such as titanium dioxide, zinc oxide, chromic oxide, Cadmium Sulfide, lime carbonate, barium carbonate, barium sulfate, clay, talcum, lead chromate, ferric oxide, carbon black have been enumerated; Pigment dyestuffs such as azo class, two azo classes, condensation azo class, thioindigo class, ponsol blue RSV class, quinoline a word used for translation ketone, anthraquinone class, benzimidazoles, perylene Lei, perylene quinone (ペ リ ノ Application) class, phthalocyanines, halo phthalocyanines, naphthazin(e) class, dioxazines.Also have, enumerated substantive dyestuff and reactive dyestuffs, matching stain, cationic dyestuff, vat pigment, mordanting dye etc. as dyestuff.Above-mentioned pigment or dyestuff use separately or two or more are used in combination all harmless.In order to bring into play effect as coating, with respect to resin (A) and (B) total measure for 100 mass parts, the use level of pigment or dyestuff serves as preferred with 10～600 mass parts, 20～400 mass parts be further not preferably.When surpassing 600 mass parts, can not obtain enough sticking power and contact laminating suitability sometimes.

In order further to improve the performance of solvent resistance etc., in water-borne coatings of the present invention, also can cooperate linking agent.With respect to resin (A) and (B) total measure for 100 mass parts, the cooperation ratio of linking agent serves as preferred with the scope of 0.1～30 mass parts, the scope of 0.1～20 mass parts is for more preferably.In add-on during less than 0.1 mass parts, it is little that it adds effect, and sticking power and the contact laminating suitability downward trend that makes with base material arranged when surpassing 30 mass parts.As linking agent can use compound, intramolecularly with self-crosslinking have the functional group of a plurality of and carboxyl reaction compound, multiple tooth coordinate metal-salt etc. is arranged, serve as preferred for example with the compound of isocyanate compound, melamine compound, urea compounds, epoxy compounds, carbodiimide compound, Han oxazolinyl, zirconates compound, silane coupling agent etc.These linking agents can use separately, perhaps also can two or more be used in combination.

In the scope of not damaging its characteristic, in water-borne coatings of the present invention, can add pigment dispersing agent, wetting agent, defoamer, tackifier, freeze to melt stablizer, filming forms auxiliary agent, sanitas, mould inhibitor, rust-preventive agent, softening agent, antioxidant, UV light absorber, free radical and capture agent etc.

The manufacture method that is used to obtain water-borne coatings of the present invention has no particular limits, for example can enumerate [1] synthetic water-borne coatings in advance with contain said polyolefins resin (A) and the preferred aqueous dispersion blended method of other resin (B); [2] method of adding pigment or dyestuff in the aqueous dispersion that contains said polyolefins resin (A) and preferred other resin (B).

Here, so-called " synthetic in advance water-borne coatings " is meant the water-borne coatings that commercially available water-borne coatings etc. can use separately, for example, ア Network ワ series such as " the ア Network ワ エ コ-Le JW 224 " of Toyo Ink manufacturing company system, " ア Network ワ ALB ", " ア Network ワ キ Application グ S ", " ア Network ワ Off ロ Application テ "; マ リ-Application プ ラ ス the series such as " マ リ-Application プ ラ ス HR " of big Japanese ink corporate system; デ イ Star Network セ-Off series such as " デ イ Star Network セ-Off GK, BAG-C "; The オ デ エ コ ラ イ Application series of Japan's paint company system, the ア レ ス ア Network ア グ ロ ス series of Northwest paint company system, the G-series of goddess's printing ink industrial system etc.

Because the dispersing and mixing of aqueous dispersion and water-borne coatings is good, so the married operation time in the above-mentioned manufacture method [1] is short and simple.

On the other hand, in the manufacture method [2], for example, pigment or dyestuff are mixed to come the conditioned pigment bed material with water, other pigment dispersing agent, tackifier, defoamer etc., then this pigment bed material and the aqueous dispersion that contains the polyolefin resin (A) stated and preferred other resin (B) etc. being cooperated, also can be that pigment or dyestuff, water, polyolefin-containing resin (A) are cooperated simultaneously with the aqueous dispersion of other resin (B).

No matter be any one in the manufacture method [1] [2], when mixing, can use general mixing device, for example can enumerate dispersion machines such as mixing machine such as dissolver, homogenizer, uniform mixer or coating vibrator and ball mill, sand milling, suction pump, roller mill, kneader etc.

And then adjust the method for mixed solid component concentration, for example can enumerate the method that aqueous medium is distilled to desirable solid component concentration, viscosity and dilute with water.Also can add organic solvent in order to improve coating performance as lower boiling alcohols such as Virahols.

The drying of water-borne coatings of the present invention has no particular limits, and can carry out in the wide temperature range about 0～250 ℃, and is when the thermotolerance of base material is not high enough, comparatively practical with about 0～200 ℃.The thickness that also depends on drying temperature time of drying and film etc., though have no particular limits, usually can be 5 seconds～120 minutes scope.If temperature is 50～150 ℃, just obtained good filming at 5 seconds～3 minutes, then need can obtain good filming in about 30 minutes～120 minutes in room temperature (about 20 °).Because coating of the present invention can form good filming at a lower temperature, therefore can make contributions to the energy-conservation of manufacturing process.This be since the dispersion particle diameter of polyolefin resin 1 μ m or littler and miniaturization cause, (disperse particle diameter to surpass 1 μ m's) in this coating in the past and do not find, and be the very favorable effect of industrialization.

Water-borne coatings of the present invention and various base material have excellent sticking power, can use in the application of paper, synthetic paper, thermoplastic resin film, plastics, steel plate etc.Particularly, with thermoplastic resin film during, owing to can make laminated film and preferred with contact laminating as base material.Considering that from the angle that sticking power is good the resin of base material can use polyolefin resin, serves as preferred to use on acrylic resin, sour modified polypropylene resin, elastomer modified polypropylene resin wherein.

Thermoplastic resin film has been enumerated, by nylon 6 (being designated hereinafter simply as " Ny6 "), nylon 66, polyamide resins such as nylon 46, polyethylene terephthalate (being designated hereinafter simply as " PET "), PEN, Poly(Trimethylene Terephthalate), poly-naphthalic acid propylene glycol ester, polybutylene terephthalate, vibrin such as PBN, polyoxyethylene glycol acid, polyhydroxycarboxyliacid acids such as poly(lactic acid), polyethylene glycol succinate, aliphatic polyester-based resins such as poly butylene succinate are the Biodegradable resin of representative, polypropylene (being designated hereinafter simply as " PP "), modified polypropene, polyolefin resines such as polyethylene, polyimide resin, film and its lamination thing that polyarylate resin and their thermoplastic resins such as mixture constitute.Wherein, can preferably use the film that constitutes by polyester, polymeric amide, polyethylene, polypropylene.No matter these base material films are that unstretching film or stretched film are all passable, to its method for making also without limits.As long as the thickness of base material film has no particular limits, usually at 1～500 mu m range.On the application face of base material film, preferably carry out Corona discharge Treatment, also can steam coating silicon dioxide, aluminum oxide etc.

In order to improve the sticking power of water-borne coatings, to carry out application more thereon serve as preferred to set in advance easy tack coat on thermoplastic resin film.Can enumerate urethane resin, vibrin, polyolefin resin, acrylic resin etc. as the resin that constitutes easy tack coat.Wherein and since acid-modified polyolefin resin and base material film and water-borne coatings of the present invention the two excellent sticking power is all arranged, so be preferred.In acid-modified polyolefin resin, further optimal ethylene-(methyl) acrylic copolymer, ethene-(methyl) vinylformic acid-maleic anhydride terpolymer (also comprising maleic anhydride grafted polymer), with maleic anhydride or (methyl) vinylformic acid with ethene-polypropylene copolymer modified resins, with maleic anhydride or (methyl) vinylformic acid with polypropylene-butylene copolymer modified resins, with maleic anhydride or (methyl) vinylformic acid with ethene-polypropylene-butylene copolymer modified resins.Consider that from the angle of sticking power the content of sour compositions such as maleic anhydride or (methyl) vinylformic acid serve as preferably with 0.1～25 quality %, 0.5～15 quality % is for more preferably, and 0.5～10 quality % is for further preferred, and 1～8 quality % is for preferred especially.Easily the thickness of tack coat is so long as 0.01～10 μ m gets final product more preferably 0.05～5 μ m.

Have no particular limits for the method that water-borne coatings of the present invention is coated with on base material, can adopt that gravure cylinder is coated with, contrary roller coat, line rod are coated with, methods such as scraper plate is coated with, air knife is coated with, curtain coating, spraying, dip-coating, brushing.As method of printing, what can enumerate is intaglio printing, porous printing, silk screen printing, offset printing, letterpress, heat transfer write printing, ink jet printing, scrape, pressure roller printing, liner printing, form printing, label printing etc.

On the application face that is coated with the film that water-borne coatings of the present invention is housed, form laminate layers, when making laminated film, can wait and form laminate layers with extruding layer platen press, dried laminating, contact laminating.In the extruding layer platen press, on base material film application after the water-borne coatings, tackify paints such as coating imines class, isocyanates, titanate ester by molten polyethylene resin or acrylic resin on the lamination, obtain laminated film on application face.Dried laminating is the binding agent of coating polyurethanes resin etc. on the application face of base material film, and thermoplastic resin film in the applying obtains laminated film.Contact laminating is, on base material film application after the water-borne coatings, molten polyethylene resin or the direct lamination of acrylic resin on application face.Perhaps, the film contact laminating that handle is made of polyethylene or polypropylene on application face gets on and forms laminate layers, thereby obtains laminated film.

Because water-borne coatings of the present invention and base material have excellent sticking power, therefore can use any laminating method.Wherein, the most economic contact laminating is the most preferred method that can bring into play the performance of water-borne coatings of the present invention.

As the used polyvinyl resin of laminate layers so long as with the ethene composition is that main component gets final product, also can be alpha-olefins such as propylene, 1-butylene, 2-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, vinyl-acetic ester, (methyl) vinylformic acid, (methyl) acrylate etc. 2 yuan or polybasic multiple copolymer more, also can be sour modified polyethylene resins such as maleic anhydride, also can be the polyvinyl resin of having implemented high temperature oxidation process.

As the not special restriction of the three-dimensional arrangement of the used acrylic resin of laminate layers, for example can enumerate complete with or syndiotactic and the acrylic resin homopolymer of various tacticities is arranged, or with the propylene be main component and with the multipolymer of alpha-olefins such as ethene, 1-butylene, 2-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene.No matter these multipolymers are 2 yuan or more polybasic multiple copolymer or random copolymers, segmented copolymer all can.And then, also can be sour modified polypropylene resins and the acrylic resin of having implemented high temperature oxidation process such as maleic anhydride.They can use separately, also can multiple mixing use.

The glue spread of water-borne coatings of the present invention is suitably selected with its purposes, is 0.01～100g/m with dried glue spread ²For preferably, 0.1～50g/m ²For more preferably, 0.2～30g/m ²For preferred especially.So long as at 0.01～100g/m ²Film forming in the scope just can obtain the resin coating film of excellent in uniformity.

In order to regulate glue spread, except employed apparatus for coating of suitable selection and working conditions thereof, the concentration that the thickness that preferred use and target are filmed adapts, the water-borne coatings of viscosity.The concentration of this moment can be made up of the adding in when modulation and regulates, and also can regulate by suitably diluting a synthetic water-borne coatings or concentrate.

Embodiment

Specify the present invention with embodiment below, but the present invention is not limited in these embodiment.

Have, various characteristics described later is measured or is estimated with following method again.

[evaluation of aqueous polyolefin resin dispersion]

(1) the unitary content of unsaturated carboxylic acid

According to the acid value of JIS K5407 standard test polyolefin resin, value is obtained the content of unsaturated carboxylic acid thus.

(2) formation of the resin beyond the unsaturated carboxylic acid unit

At orthodichlorobenzene (d ₄) in, under 120 ℃, carry out ¹H-NMR, ¹³C-NMR analyzes (manufacturing of Varian company, 300MHz). ¹³C-NMR analyze to be to measure with having for the quantitative method of uncoupling of the gate pulse of usefulness.

(3) weight-average molecular weight of resin

With gpc analysis (post that eastern Cao company makes is the HLC-8020 of TSK-GEL), sample dissolution in tetrahydrofuran (THF), 40 ℃ of mensuration, is obtained weight-average molecular weight from the working curve made from the polystyrene standard sample.When being insoluble in tetrahydrofuran (THF), use orthodichlorobenzene.

(4) solid component concentration of aqueous dispersion

Taking by weighing an amount of polyolefin dispersion, 150 ℃ of heating, is it constant until the quality of resistates (solids component), obtains the polyolefin resin solid component concentration.

(5) number average of polyolefin resin particle and weight average particle diameter

The microtrack size-grade distribution meter UPA150 (No.9340 type) of machine dress corporate system asks its number average bead diameter (mn) and weight average particle diameter (mw) with day, and the specific refractory power of resin is taken as 1.5.

(6) working life

Estimate the outward appearance of aqueous dispersion when room temperature is placed 90 days with following 3 grades.

Zero: the outward appearance no change

△: find tackify

*: find curing, aggegation and generation throw out

Be evaluated as at 1 o'clock in outward appearance, also measure number average bead diameter with aforesaid method.

(7) containing ratio of organic solvent in the aqueous dispersion

The gas chromatograph GC-8A[that makes with company of Shimadzu Seisakusho Ltd. uses FID analyzer, carrier gas: nitrogen, column packed material (manufacturing of GL SCIENCES company) PEG-HT (5%)-Uniport HP (60/80 order), column dimension: diameter 3mm * 3m, sample add temperature (injection temperature): 180 ℃, column temperature: 80 ℃, internal standard material: propyl carbinol], aqueous dispersion as required and the material of dilute with water directly joins in the device, obtain the containing ratio of organic solvent.Limit of detection is 0.01 quality %.

The water tolerance of (8) filming

Being coated with dried glue spread with the Meyer rod on the face that is untreated of oriented polypropylene (PP) film (the OP U-1 that eastern セ ロ company makes, thickness 20 μ m) is about 2g/m ²Aqueous dispersion, 100 ℃ of dryings 2 minutes.After the dipping of making like this 1 day of filming in 40 ℃ warm water, visual assessment is coated with the state of face.

Zero: the outward appearance no change

△: the albefaction of filming

*: coating is dissolved or is peeled off

The sticking power evaluation of (9) filming

At oriented polypropylene (PP) film (the OP U-1 that eastern セ ロ company makes, thickness 20 μ m), biaxial stretch-formed polyethylene terephthalate (PET) film (EMBLETPET12 that UNITIKA company makes, thickness 12 μ m), going up dried glue spread with the coating of Meyer rod on the face that is untreated of biaxial stretch-formed nylon 6 (Ny6) film (EMBLEM that UNITIKA company makes, thickness 15 μ m) is about 2g/m ²Aqueous dispersion, 100 ℃ of dryings 2 minutes.On coated surface, stick self adhesive tape (TF-12 that NICHIBAN company makes) then, the release adhesive band of taking advantage of a situation.Visual observations is coated with the state of face, by following evaluation.

Zero: do not peel off fully

△: part takes place peel off

*: peel off fully

(10) heat seal strength evaluation

At stretching PP film (the OP U-1 that eastern セ ロ company makes, thickness 20 μ m) on the face that is untreated, aluminium foil (aluminium company of Mitsubishi make, thickness 15 μ m) goes up, on the good quality paper (big clear and system paper manufacturing) of A4 size respectively with the coating of Meyer rod upward dried glue spread be about 5g/m ²The masking liquid of aquosity dispersion, 100 ℃ of dryings 2 minutes.Then, other PP film is engaged respectively with the face that is coated with of good quality paper with the face that is coated with, other PP film of aluminium foil with the face that is coated with, other PP film of above-mentioned stretching PP film, press 3kg/cm in sealing with thermocompressor ², seal temperature pressed down 5 seconds for 110 ℃, obtained sample.It is wide that this sample is cut into 15mm, after pressure through after 1 day, under draw speed 200mm/ branch, stretching angle 180 degree, measure the stripping strength of filming with tensile testing machine (accurate universal testing machine 2020 types that INTESCO company makes), estimate its heat seal strength.

(11) the heat seal strength evaluation after the prolonged preservation

It is wide that the sample that the PP film of making by the method shown in above-mentioned (10) is sealed each other is cut into 15mm, after under 40 ℃, 90%RH condition, preserving 30 days, under draw speed 200mm/ branch, stretching angle 180 degree, measure the stripping strength of filming with tensile testing machine (accurate universal testing machine 2020 types of the INTESCO that INTESCO company makes), estimate the heat seal strength after its prolonged preservation.

[evaluation of water-borne coatings]

(1) concentration of resinous principle in the commercial coating and pigment composition (quality %)

Taking by weighing an amount of commercial coating, 150 ℃ of heating, is it constant until the quality of resistates (solids component), obtains the quality of resistates.And then, place resistates toluene to stir 2 hours at 70 ℃, elimination insolubles then is taken as the quality of pigment composition to dried quality, obtains pigment composition concentration.

Quality from the resistates of front is deducted the resinous principle quality that quality after the pigment composition weight is taken as the commercial coating, obtain the resinous principle concentration of commercial coating.

(2) working life

With following 3 grades estimate synthetic coating at room temperature place 90 days outward appearance.

Zero: the outward appearance no change

△: find tackify

*: find curing, aggegation

In the evaluation of (3) below～(6), the biaxial stretch-formed PET film that uses is the EMBLET PET12 (thickness 12 μ m) that UNITIKA company makes, biaxial stretch-formed Ny6 film is the EMBLEM (thickness 15 μ m) that UNITIKA company makes, and stretching PP film is the OP U-1 (thickness 20 μ m) that eastern セ ロ company makes.

(3) water tolerance evaluation

On the corona treatment face of biaxial stretch-formed PET film,, after 80 ℃ of dryings, resulting film was placed 1 day in room temperature with synthetic water-borne coatings in the application of intaglio plate inspection machine.Thereafter, the cloth that water has bedewed is wiped several times on the application face of film, and the state of visual observations application face estimates as follows.

Zero: the outward appearance no change

△: application face tarnishes

*: the coating of application face has dissolved fully

(4) sticking power evaluation (I)

Go up with excellent coating machine coating at the high rigid polypropylene plate (thickness 1cm) of having cleaned the surface with ethanol and to go up water-borne coatings, to make dried coating thickness be 5 μ m, 50 ℃ and 80 ℃ of difference dryings 5 minutes.According to the sticking power evaluation that JIS K5400 8.5.2. standard is filmed, tear stripping 1mm * 1mm * 100 a checker part with self adhesive tape (TF-12 that NICHIBAN company makes), residual number is estimated not peel off.Below " n/100 " expression test back in 100 checkers, have n not to be stripped from and residual time.

(5) sticking power evaluation (II)

With the intaglio plate inspection machine synthetic paint spraying on the non-corona treatment face of base material film, respectively dry 120 minutes of 80 ℃ of dryings 30 seconds, room temperature (20 ℃).On application face, stick self adhesive tape (TF-12 that NICHIBAN company makes) then, the release adhesive band of taking advantage of a situation.The state of visual observations application face is estimated as follows.

Zero: do not peel off fully

△: part takes place peel off

*: peel off fully

(6) contact laminating intensity

As base material film,, carry out drying with biaxial stretch-formed Ny6 film using synthetic coating in the application of intaglio plate inspection machine on the corona treatment face of this base material film.Then, at 300 ℃ of fused PE resins (the SUMIKASEN L211 that sumitomo chemical company is made) or the PP resin (homopolymer of propylene of using thickness 50 μ m on extrusion machine (VE-40 that limit, the field plastics machinery company makes) lamination on the application face of film, 164 ℃ of melt-flow speed 4g/10 branch, fusing points), make laminated film.This laminated film is cut into the wide test piece of 15mm, after 1 day after making film, in the stripping strength between mensuration laminate layers and the application face under draw speed 200mm/ branch, stretching angle 180 degree, estimate contact laminating intensity (mN/15mm) with tensile testing machine (accurate universal testing machine 2020 types of the INTESCO that INTESCO company makes).

(manufacturing of polyolefin resin " P-1 ")

280g propene-1-butene-ethylene-dien terpolymer (BESTPLAST 708 that HULS JAPAN company makes, propene/but-1-ene/ethene=64.8/23.9/11.3 quality %) is inserted in the four-hole boiling flask heating and melting under nitrogen atmosphere.Then, temperature in the system is remained on 170 ℃, stir down respectively with 1 hour adding 32.0g as the maleic anhydride of unsaturated carboxylic acid and 6.0g, reacted then 1 hour as the diisopropylbenzyl superoxide of radical initiator.After reaction terminating, resulting reactant is put in a large amount of acetone, resin is separated out.With acetone further this resin wash several times to remove after the unreacted maleic anhydride, drying under reduced pressure in the drying under reduced pressure machine obtains polyolefin resin " P-1 ", table 1 shows the characteristic of resulting resin.

(manufacturing of polyolefin resin " P-2 ")

Remove with outside propene-1-butene-ethylene-dien terpolymer (BESTPLAST 408 that HULS JAPAN company makes, propene/but-1-ene/ethene=12.3/82.2/5.5 quality %), make similarly to Example 1, obtain polyolefin resin " P-2 ".Table 1 shows the characteristic of resulting resin.

(manufacturing of polyolefin resin P-3)

280g propylene-ethylene copolymers (propylene/ethylene=81.8/18.2 quality %, weight-average molecular weight 85000) is inserted in the four-hole boiling flask heating and melting under nitrogen atmosphere.Then, temperature in the system is remained on 180 ℃, stir down respectively with 2 hours adding 35.0g as the maleic anhydride of unsaturated carboxylic acid and 6.0g, reacted then 1 hour as the ditertiary butyl peroxide of radical initiator.After reaction terminating, resulting reactant is put in a large amount of acetone, resin is separated out.With acetone further this resin wash several times to remove after the unreacted maleic anhydride, drying under reduced pressure in the drying under reduced pressure machine obtains polyolefin resin " P-3 ", table 1 shows the characteristic of resulting resin.

(manufacturing of polyolefin resin " P-4 ")

100g propene-1-butene-ethylene-dien terpolymer (BESTPLAST 708 that HULS JAPAN company makes, propene/but-1-ene/ethene=64.8/23.9/11.3 quality %), 500g toluene is inserted in the four-hole boiling flask that stirrer, cooling tube and dropping funnel are housed heating and melting under nitrogen atmosphere.Then, temperature in the system is remained on 110 ℃, stir to add with 1 hour down and contain the n-heptane solution of 1.0g as the 20g of the diisopropylbenzyl superoxide of radical initiator.Then, to splash into 7.0g in 1 hour as maleic anhydride, the 10.0g lauryl acrylate of unsaturated carboxylic acid with contain the n-heptane solution of the 10g of 0.5g diisopropylbenzyl superoxide, react 30 fens kinds then respectively.After reaction terminating, cool to room temperature thereafter, is put into resulting reactant in a large amount of acetone, and resin is separated out.With acetone further this resin wash several times to remove after the unreacted reactant, drying under reduced pressure in the drying under reduced pressure machine obtains polyolefin resin " P-4 ", table 1 shows the characteristic of resulting resin.

Table 1

Polyolefin resin	Constitute/(quality %)					Weight-average molecular weight
							Propylene	Butylene	Ethene	Acrylate	Maleic anhydride
	P-1	60.7	22.4	10.6	0							6.3	40,000
P-2						11.5	77.3	5.2	0	6.0	55,000
	P-3	75.4	0	16.8	0							7.8	38,000
P-4						57.9	21.3	10.1	6.5	4.2	50,000

Embodiment 1

Use have well heater can be airtight the stirrer of Glass Containers of withstand voltage 1L capacity, 60.0g polyolefin resin " P-1 ", 45.0g ethylene glycol n-butyl ether (with the pure medicine corporate system of light, superfine, 171 ℃ of boiling points), the N of 6.9g, the N-dimethylethanolamine is (with the pure medicine corporate system of light, superfine, 134 ℃ of boiling points) and 188.1g distilled water join in the above-mentioned Glass Containers.Stir under the speed of rotation 300rpm of stirring rake then, the result does not see the precipitation of resin at container bottom, confirms to become floating state.Remaining on this state then connects heater power source after 10 minutes and heats.In the maintenance system, further stirred 60 minutes under the condition of 140 ℃ of temperature.Then, air cooling is still stirred with speed of rotation 300rpm, until cool to room temperature (about 25 ℃).With 300 purpose stainless steel filter made devices (line footpath 0.035mm, plain weave) pressure filtration (air press 0.2MPa), obtain milky white yellow uniformly aqueous polyolefin resin dispersion " E-1 " thereafter.At this, almost there is not cull on the strainer.Table 2 shows the various characteristics and the film performance of aqueous dispersion.

Embodiment 2～4

Except the kind by the kind, amount and the basic cpd that change the organic solvent that is added shown in the table 2, other carry out similarly to Example 1, obtain aqueous dispersion " E-2 "～" E-4 ".Table 2 shows the various characteristics and the film performance of resulting aqueous dispersion.Here, what use as organic solvent is Virahol (with the pure medicine corporate system of light, superfine), propyl carbinol (with the pure medicine corporate system of light, superfine), and its boiling point is respectively 82 ℃ and 118 ℃; What basic cpd was used is triethylamine (with the pure medicine corporate system of light, superfine), and boiling point is 90 ℃.

Embodiment 5,6

Use " P-3 " as the polyolefin resin except embodiment 5 uses " P-2 ", embodiment 6, other carry out similarly to Example 1, obtain aqueous dispersion " E-5 ", " E-6 ".Table 2 shows the various characteristics and the film performance of resulting aqueous dispersion.

Embodiment 7

Use have well heater can be airtight the stirrer of Glass Containers of withstand voltage 1L capacity, the n-propyl alcohol of 60.0g polyolefin resin " P-4 ", 90.0g (with the pure medicine corporate system of light, superfine, 97 ℃ of boiling points), the triethylamine of 6.2g is (with the pure medicine corporate system of light, superfine, 89 ℃ of boiling points) and 143.8g distilled water join in the Glass Containers.Stir under the speed of rotation 300rpm of stirring rake then, the result does not see the precipitation of resin at container bottom, confirms to become floating state.Remaining on this state then connects heater power source after 10 minutes and heats.Temperature further stirred 60 minutes down for 140 ℃ in the maintenance system.Then, air cooling is still stirred with speed of rotation 300rpm, until cool to room temperature (about 25 ℃), use 300 purpose stainless steel filter made devices (line footpath 0.035mm, plain weave) pressure filtration (air is pressed 0.2MPa), obtain milky white yellow aqueous polyolefin resin dispersion " E-7 " uniformly thereafter.Table 2 shows the various characteristics and the film performance of the aqueous dispersion that obtains.

Embodiment 8

Aqueous polyolefin resin dispersion " E-1 " and " E-5 " are mixed, stir, make that solids component mass ratio separately is 75/25, obtain aqueous dispersion " E-8 ".Table 2 shows the various characteristics and the film performance of aqueous dispersion.

Embodiment 9

In two mouthfuls of round-bottomed flasks that " E-1 " that 250g is obtained by embodiment 1 and 90g distilled water join 0.5L, mechanical stirrer (メ カ ニ カ Le ス -ラ-) and Li Bixi type water cooler are set, heat flask, steam aqueous medium with oil bath.When steaming the aqueous medium of about 90g, stop heating, cool to room temperature.After the cooling, the liquid component in the flask with 300 purpose stainless steel filter made devices (line footpath 0.035mm, plain weave) pressure filtration (air is pressed 0.2MPa), is obtained the uniform aqueous polyolefin resin dispersion of oyster white " E-9 ".Table 2 shows the various characteristics and the film performance of the aqueous dispersion that obtains.Organic solvent containing ratio in this aqueous dispersion is 2.5 quality %.

Comparative example 1

Except using Nucrel N1050H (ethylene-methacrylic acid copolymer, methacrylic acid content 10 quality % that DU PONT-MITSUI POLYCHEMICALS company makes, hereinafter referred to as " P-5 ") as outside the polyolefin resin, other methods according to embodiment 1 obtain aqueous dispersion.Because this aqueous dispersion is tackify after cooling, water is diluted to it after the solid component concentration 10 quality %, and the material after strainer is filtered is as aqueous dispersion " H-1 ".Table 2 shows the various characteristics and the film performance of the aqueous dispersion that obtains.

Comparative example 2

Replace the ethylene glycol n-butyl ether except add non-volatile Water-borne modification auxiliary agent NOIGEN EA-190D (nonionic surface active agent that the first industrial drugmaker makes) by 7 mass parts with respect to resin solid composition 100 mass parts, other carry out the Water-borne modification of resin according to the method for embodiment 1.But resin does not almost have Water-borne modification, and residual on strainer have a large amount of resins.That is to say that light adds NOIGEN EA-190D, resin basically can not Water-borne modification.Therefore as shown in table 2, ethylene glycol n-butyl ether (15 quality %/aqueous dispersion total amount) is merged use with NOIGEN EA-190D (7 mass parts/resin solid composition 100 mass parts), carry out the Water-borne modification of resin by the method for embodiment 1, obtained aqueous dispersion " H-2 ".Table 2 shows the various characteristics and the film performance of aqueous dispersion.

Comparative example 3

Except with 1,4-butyleneglycol (with the pure medicine corporate system of light, superfine, 224 ℃ of boiling points) replaces outside the ethylene glycol n-butyl ether, and other carry out Water-borne modification by method similarly to Example 1.But resin does not almost have Water-borne modification, and residual on strainer have a large amount of resins.That is to say, only add 1,4-butyleneglycol, resin basically can not Water-borne modification.Therefore, add 1, the 4-butyleneglycol makes 15 quality % of its liquid total mass that becomes " E-1 " that obtain with respect to embodiment 1, with this as aqueous dispersion " H-3 ".Table 2 shows the various characteristics and the film performance of the aqueous dispersion that obtains.

Comparative example 4

Except with 1,2-propylene glycol (with the pure medicine corporate system of light, superfine, 187 ℃ of boiling points) replaces outside the ethylene glycol n-butyl ether, and other carry out Water-borne modification by method similarly to Example 1.But resin does not almost have Water-borne modification, and residual on strainer have a large amount of resins.That is to say, only add 1,4-propylene glycol, resin basically can not Water-borne modification.Therefore, add 1, the 4-propylene glycol makes 15 quality % of its liquid total quality that becomes " E-1 " that obtain with respect to embodiment 1, with this as aqueous dispersion " H-4 ".Table 2 shows the various characteristics and the film performance of the aqueous dispersion that obtains.

Table 2

					Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
																		Aqueous dispersion					E-1	E2	E-3	E-4	E-5	E-6	E-7	E-8	E-9	H-1	H-2	H-3	H-4
Add	Polyolefin resin				P-1	P-1	P-1	P-1	P-2	P-3	P-4	P-1、P-2	P-1	P-5	P-1	P-1	P-1
																		Basic cpd				DMEA	TEA	DMEA	DMEA	DMEA	DMEA	TEA	E-1 mixes (the solids component mass ratio is 75/25) with E-5	DMEA	DMEA	DMEA	In E-1, added 1, the material of 4-butyleneglycol	In E-1, added 1, the material of 2-propylene glycol
	Organic solvent (quality %)			Bu-EG	15	10	-	-	15	15	-	15	15	15
															BuOH	-	-	-	45	-	-	-	-	-	-
				IPA	-	-	-	-	-	-	30	-	-	-
															NPA	-	-	-	-	-	-	-	-	-	-
				Tensio-active agent	Kind			-	-	-	-	-	-	-												-	-	EA-190D
	Amount (mass parts/solid resin composition 100 mass parts)														0	0	0	0	0	0	0	0	0	7
					The dispersion characteristic	Solids component (quality %)				20.1	20.0	19.9	19.5	20.0											20.0	19.9	20.0	20.8		10.0	21.2	17.0			17.0
Particle diameter (μ m)			mn	0.082											0.120	0.156	0.257	0.090	0.095	0.083	0.084	0.068	0.155	0.080					0.085				0.086
						mw	0.185	0.489	0.766	1.035	0.218	0.286	0.294	0.266											0.195	0.860	0.170	0.188		0.180
			Working life												Outward appearance	○	○	○	○	○	○	○	○	○					○		○	○	○
mn	0.085	0.098				0.160	0.275	0.090	0.095	0.088	0.088	0.090	-	0.080											0.087	0.087
															Organic solvent content (quality %)				15	10	25	45	l5	15			30	15	25	7.5	15	27.8	27.8
Water tolerance					○	○	○	○	○	○	○	○	○	○											×	△								△
															Sticking power			PP		○	○	○	○	○			○	○	○	○	×	△	△		△
PET		○	○	○	○	○	△	○	○	○	×	△	△	△
																		Ny6		○	○	○	○	○	○	○	○	○	×	△	△	△
Heat seal strength (N/15mm)			PP/PP 1)		5.8	5.5	5.6	5.5	8.5	4.5	7.6	7.2	7.2	0.4																			3.6	4.2	4.4
															PP/Al 2)		5.5	5.4	5.2	5.3	7.5	4.5	7.9	6.0	6.0	0.5	3.5	4.0	4.1
			PP/ paper 3)		Base material damages	Base material damages	Base material damages	Base material damages	Base material damages	Base material damages	Base material damages	Base material damages	Base material damages	Base material damages																Base material damages	Base material damages	Base material damages
															Long term thermal sealing strength (N/15mm)					5.8	5.4	5.6	5.5	8.3	4.4	8.5	7.0	5.3	0.3				1.2	1.8	2.0

1) stretching propylene/stretching propylene

2) stretching propylene/aluminium foil

3) stretching propylene/good quality paper

Basic cpd: DMEA:N, N-dimethylethanolamine, TEA: triethylamine

Organic solvent: Bu-EG: ethylene glycol positive group ether, BuOH: propyl carbinol, IPA: Virahol, NPA: n-propyl alcohol

Tensio-active agent: EA-19OD:NOIGEN EA-19OD

Embodiment 10

The aqueous polyolefin resin dispersion that is obtained by embodiment 1 " E-1 " is mixed with the aqueous dispersion of other polymkeric substance.What use as other the aqueous dispersion of polymkeric substance is polyurethane aqueous dispersions (ADEKA BONTIGHTER HUX-380, Asahi Electro-Chemical Co. Ltd's system).

In detail, after " E-1 " stirred, add for " E-1 " solids component 100 mass parts, count the above-mentioned aqueous dispersion of 50 mass parts by the solids component amount, in 30 minutes (material that obtains is called " M-1 ") of stirring at room.Table 3 shows the close-burning evaluation result of filming that liquid thus obtains.

Embodiment 11～13

The aqueous polyolefin resin dispersion " E-1 " that embodiment 1 is obtained mixes with linking agent.What linking agent was used is that (CYMEL 327 for melamine compound, Mitsui Cytec Inc. makes, embodiment 11), (Bayhydur 3100 for isocyanate compound, Sumitomo Bayer Urethane Co., Ltd makes, embodiment 12), Han oxazolinyl compounds (embodiment 13 for EPOCROS WS-700, Japanese catalyst Co. manufacturing).

In detail, after " E-1 " stirred, adding for E-1 solids component 100 mass parts, be the above-mentioned linking agent of the amount shown in the table 3 by the amount of solid component meter, in stirring at room 10 minutes (resulting material is called " M-2 "～" M-4 ").Table 3 shows the close-burning evaluation result of filming that is obtained by these liquid.

Embodiment 14

Solids component with respect to the aqueous polyolefin resin dispersion that is obtained by embodiment 1 " E-1 " is 100 mass parts, mixing is scaled the aqueous dispersion as the carbon black of pigment of containing of 80 mass parts by solids component, and (LION company makes, LION PASTE W-376R), with making water-borne coatings " M-5 " under the propeller agitation.Table 3 shows the close-burning evaluation result of filming that liquid thus obtains.

Table 3

		Embodiment 10	Embodiment 11	Embodiment 12	Embodiment 13	Embodiment 14
							Masking liquid		M-1	M-2	M-3	M-4	M-5
Aqueous polyolefin resin dispersion		E-1	E-1	E-1	E-1	E-1
							Additive	Kind	HUX-380	CYMEL 327	Bayhydur 3100	WS-700	W-376R
Amount (mass parts)	50	10	10	15	80
						Sticking power		PP	○	○	○	○	○
PET	○	○	○	○	○
							Ny6	○	○	○	○	○

Additive types: HUX-380: urethane resin water-based dispersion; CYMEL327: melamine resin;

Bayhydur 3100: isocyanate compound; WS-700: Han oxazolinyl compound; W-376R: carbon black dispersion

In embodiment 1～9, because do not add the Water-borne modification auxiliary agent of non-volatile Water-borne modification auxiliary agent such as tensio-active agent or high boiling point (for example boiling point is 185 ℃ or higher temperature), the number average bead diameter that can obtain polyolefin resin is in 1 μ m or littler fine and stabilized aqueous dispersion.Even what aqueous dispersion obtained thus films under lower temperature, short period of time exsiccant condition its water tolerance, cohesiveness, heat sealability excellence.And then owing to do not contain tensio-active agent etc. in filming, even prolonged preservation, its heat sealability does not almost change yet.Also have, even when having added other resin water dispersion, linking agent, pigment (embodiment 10～14), superperformances such as its cohesiveness do not descend yet.

Relative therewith, because the composition of the polyolefin resin of comparative example 1 is different with the present invention, so poor to cohesiveness, the heat sealability of PP etc.Comparative example 2～4th has added surfactant-based (the non-volatile Water-borne modification auxiliary agent) or the many alcohol (1 of high boiling point that use in the method in the past, 4-butyleneglycol (224 ℃ of boiling points), 1,2-propylene glycol (187 ℃ of boiling points)) material, filming of obtaining thus compared with each embodiment, and its water tolerance, cohesiveness, heat sealability descend significantly.Particularly, the heat sealability after the prolonged preservation significantly descends.Also have, only how pure adding is, and its resin is difficult to Water-borne modification (comparative example 3,4) basically.

Reference example 1

(modulation of polyolefin resin dispersion " S-1 ")

Reduce the add-on (8 quality % of aqueous dispersion) of the ethylene glycol n-butyl ether among the embodiment 1, obtain aqueous dispersion S-1.It is 1.22 μ m and 1.98 μ m that the number average bead diameter of such polyolefin resin, weight average particle diameter become respectively, becomes bigger than 1 μ m.

Reference example 2

(modulation of polyolefin resin dispersion " S-2 ")

Except using BONDINE HX8290 (ethylene-propylene acetoacetic ester-copolymer-maleic anhydride that sumitomo chemical company is made, maleic anhydride content is 2～3 quality %) " P-6 " as outside the polyolefin resin, other methods by embodiment 1 obtain aqueous dispersion " S-2 ".

Embodiment 15

Is polyolefin resin dispersion " E-1 " and crylic acid resin water borne coating (Toyo Ink company makes, Aquaecol JW 224) 50/50 to cooperate by resin solid composition quality ratio, mixes with the coating vibrator, obtains coating " J-1 ".Resulting coating " J-1 " is coated on the various base material films and drying after, carry out the evaluation of water tolerance, sticking power, contact laminating suitability, table 4 shows its result.

Embodiment 16,17

Except using polyolefin resin dispersion " E-5 ", " E-6 ", other carry out similarly to Example 15, make coating " J-2 " (embodiment 16) and " J-3 " (embodiment 17), carry out the evaluation of various rerum naturas, and table 4 shows its result.

Embodiment 18,19

Except (Toyo Ink company makes with crylic acid resin water borne coating polyolefin resin dispersion " E-1 ", Aquaecol JW 224) cooperate than 75/25,20/80 by the resin solid composition quality outside, other carry out similarly to Example 15, make coating " J-4 " (embodiment 18) and J-5 (embodiment 19), carry out the evaluation of various rerum naturas, table 4 shows its result.

Embodiment 20

Titanium oxide (the TIPAQUE CR-50 of stone former industry corporate system), 0.5 mass parts tackifier (the NACALAI TESQUE corporate system of 60 mass parts as pigment, Natvosol), 1 mass parts dispersion agent (the SN Dispersant5468 of SAN NOPCO corporate system), 38.5 mass parts distilled water match, mix with homogenizer., with coating vibrator carry out dispersing of pigments, obtain the pigment bed material thereafter.To wherein cooperating 200 mass parts polyolefin resin dispersions " E-1 ", mix with the coating vibrator, make coating " J-6 ", carry out the evaluation of various rerum naturas.Table 4 shows its result.

Embodiment 21

The coating that is obtained by embodiment 20 " J-6 " is mixed than 70/30 usefulness coating vibrator by the resin solid composition quality with water-based polyurethane aqueous dispersion (Hydran of big Japanese ink chemical industrial company system), make coating " J-7 ", carry out the evaluation of various rerum naturas, table 4 shows its result.

Embodiment 22

The coating that is obtained by embodiment 20 " J-6 " is mixed than 70/30 usefulness coating vibrator by the resin solid composition quality with waterborne polyester class aqueous dispersion (KA-5034 that UNITIKA company makes), make coating " J-8 ", carry out the evaluation of various rerum naturas, table 4 shows its result.

Embodiment 23

Cooperate polyfunctional isocyanate's compound (Sumitomo Bayer Urethane Co. in resin 100 mass parts in the coating that obtains by embodiment 15 " J-1 " as linking agent, Ltd makes, Bayhydur 3100, the about 17 quality % of isocyanate group containing ratio) making its solids component is 3 mass parts, mix with the coating vibrator, make water-borne coatings " J-9 ", carry out the evaluation of various rerum naturas, table 4 shows its result.

Embodiment 24

Cooperate melamine resin (Mitsui Cytec Inc. manufacturing in resin 100 mass parts in the coating that obtains by embodiment 21 " J-7 " as linking agent, CYMEL 327) to make its solids component be 5 mass parts, mix with the coating vibrator, make water-borne coatings " J-10 ", carry out the evaluation of various rerum naturas, table 4 shows its result.

Table 4

			Embodiment 15		Embodiment 16		Embodiment 17		Embodiment 18		Embodiment 19		Embodiment 20		Embodiment 21		Embodiment 22		Embodiment 23		Embodiment 24		Comparative example 5		Comparative example 6		Comparative example 7		Comparative example 8
																															The dispersion characteristic	Kind		E-1		E-5		E-6		E-1		E-1		E-1		E-1		E-1		E-1		E-1		E-1		S-1		H-1		S-2
Particle diameter (μ m)	mn	0.062		0.060		0.085		0.062		0.062		0.062		0.062		0.062		0.062		0.062		0.062		1.22		0.155		0.068
																														mw		0.098		0.085		0.215		0.098		0.098		0.098		0.098		0.098		0.098		0.098		0.098		1.98		0.860		0.089
		Kind		J-1		J-2		J-3		J-4		J-5		J-6		J-7		J-8		J-9		J-10		H-5		H-6		H-7																																H-8
Polyolefin resin (A)																														P-1		P-2		P-3		P-1		P-1		P-1		P-1		P-1		P-1		P-1		P-1		P-1		P-5		P-6
		Other resin (B)		Acrylic acid or the like		Acrylic acid or the like		Acrylic acid or the like		Acrylic acid or the like		Acrylic acid or the like		-		Urethane		Polyester		Acrylic acid or the like		Urethane		Acrylic acid or the like		Acrylic acid or the like		Acrylic acid or the like																														Acrylic acid or the like
(A)/(B) (mass ratio)																														50/50		50/50		50/50		75/25		20/80		100/0		70/30		70/30		50/50		70/30		5/95		5O/50		50/50		50/50
		Pigment or dyestuff (C) 1)(mass parts)		200		200		200		100		320		150		105		105		200		105		380		200		200																														200
Linking agent (mass parts/resin 100 mass parts)																														-		-		-		-		-		-		-		-		Isocyanic ester 3		Melamine 5		-		-		-		-
		Working life		○		○		○		○		○		○		○		○		○		○		○		○		○																														○
Water tolerance																														○		○		○		○		○		○		○		○		○		○		○		○		○		○
		Sticking power (I)	50℃	100/100		100/100		80/100		100/100		60/100		100/100		100/100		100/100		100/100		100/100		0/.00		0/100		0/100
80℃	100/100																													100/100		100/100		100/100		90/100		100/00		100/100		100/100		100/100		100/100		0/.00		30/.00		0/100
			Sticking power (II)	Temperature	80℃	RT 2)	80℃	RT 2)	80℃	RT 2)	80℃	RT 2)	80℃	RT 2)	80℃	RT 2)	80℃	RT 2)	80℃	RT 2)	80℃	RT 2)	80℃	RT 2)	80℃	RT 2)	80℃	RT 2)	80℃																											RT 2)	80℃	RT 2)
PET	○	○																												○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	△	×	○	×	×	×	○	○
				Ny6	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	△	○	×	×																											×	○	○
PP	○	○																												○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	×	×	×	×	×	×	△	×
				Contact laminating intensity (mN/15mm)	PE	2895		2950		1870		3250		1315		2685		3220		3100		2550		2870		0		1210																												10		3200
PP	2910		3005																											1915		3290		1530		2700		3400		3150		2620		2890		0		1415		10		980

1) with respect to (A) value with (B) total 100 mass parts

2) room temperature (20 ℃)

Comparative example 5

Except polyolefin resin dispersion " E-1 " and crylic acid resin water borne coating (Toyo Ink corporate system, Aquaecol JW 224) presses the resin solid composition quality than outside 5/95 cooperation, other carry out similarly to Example 15, make coating " H-5 ", carry out the evaluation of various rerum naturas, it the results are shown in the table 4.

Comparative example 6

Except using dispersion " S-1 ", other carry out the modulation of coating similarly to Example 15, make coating " H-6 ", carry out the evaluation of various rerum naturas, and it the results are shown in the table 4.

Comparative example 7

Except using dispersion " H-1 ", other carry out the modulation of coating similarly to Example 15, make coating " H-7 ", carry out the evaluation of various rerum naturas, and it the results are shown in the table 4.

Comparative example 8

Except using dispersion " S-2 ", other carry out the modulation of coating similarly to Example 15, make coating " H-8 ", carry out the evaluation of various rerum naturas, and it the results are shown in the table 4.

Embodiment 25

Coat aqueous dispersion " E-6 " on the corona treatment face of biaxial stretch-formed Ny6 film (EMBLEM that UNITIKA company makes, thickness 15 μ m), making dry back film thickness is 1 μ m, 120 ℃ of dryings 2 minutes, easy tack coat is set.Coating process " J-1 " on the easy bonding aspect of this film after the drying, carries out the evaluation of contact laminating suitability.After doing like this, the contact laminating intensity of PE, PP is respectively 4240mN/15mm, 4400mN/15mm.

Among the embodiment 15～24, even under the drying conditions of low temperature, short period of time, the sticking power of itself and polypropylene base is also very excellent, and then contact laminating suitability excellence.In embodiment 25,, improved contact laminating intensity by being provided with easy tack coat.

Relative therewith, the content of the polyolefin resin of comparative example 5 is outside scope of the present invention, and is poor for applicability with the sticking power and the contact laminating of various base materials.Also have, comparative example 6 is because the particle diameter of polyolefin resin has surpassed 1 μ m, the poor adhesive force of the polypropylene base during for cryodrying.In the comparative example 7, because the composition of polyolefin resin is different with the present invention, with the sticking power and the non-constant of contact laminating suitability of base material film.In the comparative example 8, because the composition of polyolefin resin is different with the present invention, when being base material film with the polypropylene, sticking power and contact laminating are poor for applicability.

Claims (11)

1. aqueous polyolefin resin dispersion, it is characterized in that, contain the unsaturated hydrocarbons of the carbonatoms 3～6 that comprises 50～98 quality % and unitary polyolefin resin of unsaturated carboxylic acid and the basic cpd of 0.5～20 quality %, boiling point when being substantially devoid of normal pressure is at the Water-borne modification auxiliary agent of 185 ℃ or higher temperature, and the number average bead diameter of this polyolefin resin in aqueous dispersion is 1 μ m or littler.

2. the aqueous polyolefin resin dispersion described in the claim 1 is characterized in that, the unsaturated hydrocarbons of the carbonatoms 3～6 that contains in the described polyolefin resin is propylene and/or butylene.

3. the aqueous polyolefin resin dispersion described in the claim 1 or 2 is characterized in that, further contains ethene in the described polyolefin resin.

4. the lamination thing is characterized in that, by having removed amassing on base material layer by layer that medium forms in wantonly 1 the described aqueous polyolefin resin dispersion in the claim 1 to 3.

5. the manufacture method of aqueous polyolefin resin dispersion, it is used to make the aqueous polyolefin resin dispersion described in the claim 1, it is characterized in that the boiling point when comprising the unitary polyolefin resin of unsaturated carboxylic acid of unsaturated hydrocarbons of carbonatoms 3～6 that comprises 50～98 quality % and 0.5～20 quality %, basic cpd, normal pressure is lower than the operation that 185 ℃ organic solvent and water heat, stir in encloses container, under 80～220 ℃ of temperature.

6. water-borne coatings, it is characterized in that, contain the unsaturated hydrocarbons of the carbonatoms 3～6 that comprises 50～98 quality % and the unitary polyolefin resin of unsaturated carboxylic acid (A), other resin (B) as required and pigment or the dyestuff (C) of 0.5～20 quality %, and its (A) and mass ratio (A)/(B) (B) are 100/0～10/90, and the number average bead diameter of polyolefin resin (A) is 1 μ m or littler.

7. processed goods is characterized in that, on base material application the water-borne coatings described in the claim 6.

8. the processed goods described in the claim 7 is characterized in that, described base material is a thermoplastic resin film.

9. film is characterized in that, is provided with the easy tack coat of thickness 0.01～10 μ m at least on 1 of thermoplastic resin film, and and then on this easy tack coat application the water-borne coatings described in the claim 6.

10. laminated film is characterized in that, is provided with laminate layers on the application face of the thermoplastic resin film described in claim 8 or 9.

11. the manufacture method of laminated film is characterized in that, lamination molten polyethylene or polypropylene on the application face of the thermoplastic resin film described in claim 8 or 9 form laminate layers.