JPH11315222A - Water-based coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based coating material which can give a uniform coating film of excellent wettability even when applied by high-speed coating and can be desirably used, for example, to obtain coated film having a low oxygen permeability and excellent gas barrier properties, and to provide a process for producing the same. SOLUTION: There is provided the water-based coating material prepared by incorporating water, a surfactant, and a solid component comprising an inorganic layered compound and a resin 32 in a coating fluid. It is desirable that the solid component comprises at least either of a high hydrogen bond resin and an inorganic layered compound. The coating fluid forms a coating film after application and contains a surfactant for improving its affinity for a substrate or an anchor surface. The surface tension of the coating fluid contained in the water-based coating material is 50 mN/m or below in an equilibrated state, and the half-life t of the dynamic surface tension γSAA of the solution prepared by adding the surfactant to water is in the range: 0.01<t<1,000 (sec).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based paint suitable for high-speed coating.

[0002]

2. Description of the Related Art Generally, when a water-based paint is applied to a substrate,
It is known that the addition of a surfactant improves the affinity of a water-based paint for a substrate, that is, the wettability. This means that when the water-based paint is applied, a part of the water-based paint is repelled and no longer adheres to the substrate, and a so-called repelling that causes a point-like discontinuous portion in the coating film is eliminated by adding a surfactant. Things. This method utilizes the principle that unevenness in surface tension between the liquid constituting the water-based paint and the substrate on which the water-based paint is applied can be prevented by adding a surfactant.

[0003]

However, Du.
When the surface tension of the components of the water-based paint is determined by a measurement method such as the Nouy method, even when the surface tension of the liquid constituting the water-based paint is lower than the surface tension of the base material, repelling is observed during coating. There are many. This is because it takes time for the surfactant to reduce the surface tension of the liquid constituting the water-based paint, and repelling occurs during that time.

[0004] That is, in actual coating, there is a difference between the wettability obtained as a whole from the measurement results and the partial wettability at the interface during coating. Especially,
When using a water-based paint having wettability that causes such a divergence when performing high-speed coating, bleeding occurs at the time of coating, coating omission occurs after coating, and a good coating state cannot be maintained. There's a problem.

For example, when a coating film obtained by applying a water-based paint to a film base material or the like is used as a packaging material, a conventional coating film obtained by applying a water-based paint has a high oxygen content. There is a problem that permeability is high and so-called gas barrier properties are insufficient.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object thereof is to provide a uniform coating film having excellent wettability even when high-speed coating is performed, and Another object of the present invention is to provide a water-based paint suitably used for obtaining a coating film having low oxygen permeability and excellent gas barrier properties and a method for producing the same.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, used a liquid containing water, a surfactant, and a solid as a coating liquid contained in an aqueous paint. As a result, it has been found that the wettability to the base film at the time of coating is remarkably improved, and the present invention has been completed.

According to a first aspect of the present invention, there is provided a water-based paint containing a coating solution containing water, a surfactant, and a solid component. The surface tension at the time of equilibrium is 50 mN / m or less, and the half-life t of the dynamic surface tension value γ _SAA of water by the bubble pressure method when the surfactant is added to water is as follows:
It is characterized in that 0.01 <t <1000 (sec).

According to a second aspect of the present invention, in order to solve the above-mentioned problems, in addition to the first aspect, the water-based paint further has a surface tension at the time of equilibration of the coating liquid of 40 mN / m or less. Features.

According to the above configuration, since the water-based paint contains the above-mentioned surfactant, the time required to lower the surface tension of the coating liquid contained in the water-based paint is shortened. Can be prevented, and the wettability of the water-based paint can be improved.

According to a third aspect of the present invention, in order to solve the above-mentioned problems, in addition to the constitution of the first or second aspect, the solid content comprises at least one of a resin and an inorganic compound. It is characterized by:

According to a fourth aspect of the present invention, in order to solve the above-mentioned problems, in addition to the constitutions of the first to third aspects, the solid content is at least one of a high hydrogen bonding resin and an inorganic layered compound. It is characterized by being composed of one substance.

[0013] In order to solve the above-mentioned problems, the water-based paint according to the invention of claim 8 is characterized in that, in addition to the constitution of claim 4, the inorganic layered compound has an aspect ratio in the range of 50 to 5000. Features.

According to a ninth aspect of the present invention, in order to solve the above-mentioned problem, in addition to the constitution of the fourth aspect, the aspect ratio of the inorganic layered compound is in the range of 200 to 3000. Features.

According to the above arrangement, the inorganic layered compound is
While facing each other by the shape of the layer, and oriented so as to be substantially parallel to the surface direction of the coating film, a labyrinth effect of the inorganic layered compound is generated, and gas barrier properties with respect to the coating film of the water-based paint. Can be provided.

According to a fifth aspect of the present invention, in order to solve the above-mentioned problems, in addition to any one of the first to fourth aspects, the coating liquid contains a hydrophilic solvent. Features.

In order to solve the above-mentioned problems, the water-based paint according to the invention of claim 6 has, in addition to the constitution of claim 5, a solubility parameter of a hydrophilic solvent [hereinafter referred to as Solubilit.
yParameter (abbreviated as “SP value”) is 9 or more.

According to a seventh aspect of the present invention, in order to solve the above-mentioned problems, in addition to the constitution of the fifth or sixth aspect, the hydrophilic solvent contains one or more alcohols. And

According to the above configuration, the presence of the hydrophilic solvent in the coating solution allows the solid content contained in the coating solution to be dissolved or dispersed in the coating solution even if the solid content is poorly soluble in water. It becomes easier.

According to a tenth aspect of the present invention, in order to solve the above-mentioned problems, in addition to the constitution of the fourth aspect, the high hydrogen bonding resin further comprises a hydrogen bonding group or an ionic group. It is characterized in that it is contained at a concentration of 30 mol% or more and 50 mol% or less per unit weight of the hydrogen bonding resin.

According to an eleventh aspect of the present invention, in order to solve the above-mentioned problems, in addition to the constitution of the fourth aspect, the high hydrogen bonding resin may be polyvinyl alcohol, a modified polyvinyl alcohol, ethylene / Vinyl alcohol copolymer, modified ethylene / vinyl alcohol copolymer,
It is a compound selected from the group consisting of polysaccharides.

According to the above configuration, the solid content is stably dispersed or dissolved in the coating liquid because the high hydrogen bonding resin has hydrophilicity.

According to a twelfth aspect of the present invention, there is provided a method for producing a water-based coating composition, wherein the inorganic layered compound is swollen and cleaved in the coating solution to form the resin or the resin. It is characterized by being dispersed in a coating solution containing a resin.

According to the above method, since the inorganic layered compound is sufficiently dispersed in the coating solution, the inorganic layered compound is suitably used to obtain a coating film having excellent gas barrier properties due to a maze effect of the inorganic compound. Water-based paints can be produced.

According to a thirteenth aspect of the present invention, there is provided a method for applying a water-based paint, wherein the line speed is 150 m / m in continuous coating on a film-like material.
in or more.

According to a fourteenth aspect of the present invention, there is provided a method for applying a water-based paint according to the twelfth aspect of the present invention, in addition to the structure of the thirteenth aspect. It is characterized by using a water-based paint.

According to the above method, since the inorganic layered compound is sufficiently dispersed in the coating liquid, a coating film having excellent gas barrier properties can be obtained by a maze effect of the inorganic compound.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below with reference to FIGS.

The water-based paint according to the present invention is a water-based paint containing a coating liquid containing water, a surfactant and a solid content, and has a surface tension of 50 mN / at equilibrium of the coating liquid.
m, and when the surfactant is added to water, the half-life t of the dynamic surface tension value γ _SAA of water is 0.01
It can be obtained by using a coating liquid that satisfies <t <1000 (sec).

As the solid content, for example, at least one of a resin and an inorganic compound is used. As shown in FIG. 1, the coating film 3 formed by applying the water-based paint according to the present invention includes, as the solid content, a unit crystal layer 31 containing an inorganic compound and a resin 32.

The coating liquid according to the present invention is a liquid obtained by dispersing or dissolving the above-mentioned surfactant and solid content in water.
As the surfactant used in the present invention, as shown in FIG. 2, the adhesion between an object 1 such as a base film and a coating film 3 formed by applying the above-mentioned water-based paint. There is no particular limitation as long as it is able to improve the surface tension. For example, a nonionic surfactant is preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, and a nonionic surfactant.

Examples of the anionic surfactant include a carboxylic acid type such as an aliphatic monocarboxylate, N-acyloylglutamate, an alkylbenzene sulfonate, a naphthalene sulfonate-formaldehyde condensate, and a dialkyl sulfosuccinate. Sulfonate type such as sulfonic acid type, alkyl sulfate salt, alkyl sulfate polyoxyethylene salt, etc., phosphate type such as alkyl phosphate salt, borate type such as alkyl borate salt, etc. Surfactants, fluorine-based anionic surfactants such as sodium perfluorodecanoate and sodium perfluorooctylsulfonate, and silicone-based anions having an anionic group such as a polymer having a polydimethylsiloxane group and a metal carboxylate. Surfactants.

Examples of the cationic surfactant include:
Amine salt types such as alkylamine salts, alkyltrimethylammonium salts, dialkyldimethylammonium salts,
A quaternary ammonium salt type such as an alkyldimethylbenzylammonium salt is exemplified.

Examples of the zwitterionic surfactant include carboxybetaine type such as N, N-dimethyl-N-alkylaminoacetic acid betaine and glycine such as 1-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine. Type.

Examples of the nonionic surfactant include ester types such as glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester, condensation polymers of polydimethylsiloxane groups and alkylene oxide adducts, and polysiloxane-polyoxyalkylene copolymers. Polymer, ether type such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block polymer, etc., ester ether type such as polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc., aliphatic alkanolamide And fluorine types such as perfluorodecanoic acid-diglycerin ester and perfluoroalkylalkylene oxide compounds.

Among the above surfactants, in particular, those having 6 carbon atoms
An alkali metal salt of a carboxylic acid having an alkyl chain of not more than 24 or less, an ether type nonionic surfactant such as polydimethylsiloxane-polyoxyethylene copolymer (silicone nonionic surfactant), Fluorinated nonionic surfactants such as alkyl ethylene oxide compounds (fluorinated nonionic surfactants)
Is preferred.

The amount of the surfactant may be adjusted from the viewpoint of the effect when the coating film 3 is formed, for example, when a coating liquid is used.
0.001 to 5% by weight is preferable in the coating solution,
03-0.5% by weight is more preferable, and 0.005-0.
1% by weight is particularly preferred.

The dynamic surface tension value γ of water when the surfactant according to the present invention is added to water γ The half-life t of _SAA is defined as the surface tension value γ (7) of water measured by the bubble pressure method.
2mN / m) is reduced to half (36mN / m) by adding a surfactant (Surface A).
ge, sec). The smaller the half-life t is, the faster the surface tension is reduced by the addition of the surfactant, so that repelling at the time of application of the water-based paint can be prevented.
The half-life t is preferably 0.01 <t <1000 (sec), and from the viewpoint of high-speed coating property, 0.01 <t <500.
(Sec) is more preferable, and 0.01 <t <60 (sec)
c) is most preferred.

If the surface tension of the coating solution at equilibrium is higher than the surface tension of the substrate on which the water-based paint is to be applied, undesired repelling occurs at the time of coating. The surface tension at the time of equilibration of the coating liquid is 50 mN / m or less, preferably 40 mN / m or less, in order to prevent repelling during high-speed coating.

The hydrophilic solvent used in the present invention includes:
Examples thereof include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butanol, pentanol, hexanol, and heptanol, acetone, cellosolve, and mixtures thereof.

The SP value of the hydrophilic solvent (Solubilit)
y Parameter is the cohesive energy density (Cohesive Energy Density,
CED). CED is CED = △ E / V
= (△ H-RT) / V. (ΔE = evaporation energy (ca1 / mole), V: molar volume (cc / m
ole), ΔH: latent heat of vaporization (cal / mole), R:
Gas constant (1.987 cal / mole · K), T: absolute temperature (K) The SP value of the hydrophilic solvent is particularly preferably 9 or more.

When a hydrophilic solvent is added, the mixing ratio is preferably 70% by weight or less, more preferably 50% by weight or less, particularly preferably 30% by weight or less, based on water.

The solid content according to the present invention is a component which becomes, for example, a coating film on the substrate after the application of the water-based paint and the application liquid contained in the water-based paint evaporates, for example. Examples of the solid content according to the present invention include resins and inorganic compounds described below.

The resin contained as one of the solid components according to the present invention is not particularly limited. For example, polyolefin resin, polyester resin, amide resin, acrylic resin, styrene resin, acrylonitrile resin, cellulose Resin, halogen-containing resin, hydrogen bonding resin,
Examples thereof include a liquid crystal resin, a polyphenylene oxide resin, a polymethylene oxide resin, a polycarbonate resin, a polysulfone resin, a polyethersulfone resin, and a polyetheretherketone resin. Specifically, a resin used as an object to be coated, which will be described later, can be cited as an example.

Preferred examples of the resin include a high hydrogen bonding resin having a hydrogen bonding group or an ionic group described later in the resin. The content of the hydrogen bonding group or the ionic group in the high hydrogen bonding resin (when both are included, the total amount of both) is usually 20 to 60% by weight, preferably 30 to 50% by weight. is there. The content of these hydrogen bonding groups and ionic groups can be determined, for example, by nuclear magnetic resonance (NMR).
( ¹ H-NMR, ¹³ C-NMR, etc.).

The above-mentioned hydrogen bonding group includes a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group,
Examples of the ionic group include a carboxylate group, a sulfonate ion group, a phosphate ion group, an ammonium group, and a phosphonium group. Among the hydrogen bonding groups or ionic groups, more preferable ones include a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonic acid ion group, and an ammonium group.

Specific examples of the high hydrogen bonding resin include, for example, polyvinyl alcohol and a vinyl alcohol fraction of 4
0 mol% or more ethylene / vinyl alcohol copolymer,
Examples include polysaccharides, polyacrylic acids and esters thereof, sodium polyacrylate, polybenzenesulfonic acid, sodium polybenzenesulfonate, polyethyleneimine, polyallylamine and quaternary ammonium salts thereof, polyvinyl thiol, and polyglycerin. Among the above-mentioned resins, more preferred are polyvinyl alcohol and polysaccharides.

The term "polyvinyl alcohol" as used herein means a polymer obtained by, for example, hydrolyzing or transesterifying (saponifying) the acetic ester portion of a vinyl acetate polymer (ie, a copolymer of vinyl alcohol and vinyl acetate). And a polymer obtained by saponifying a vinyl trifluoroacetate polymer, a vinyl formate polymer, a vinyl pivalate polymer, a t-butyl vinyl ether polymer, a trimethylsilyl vinyl ether polymer, etc. (for details of polyvinyl alcohol). See, for example, edited by the Poval Society, “The World of PVA”, 1992, Kobunshi Publishing Co .; Nagano et al., “Povar”, 1981, Kobunshi Publishing Co., Ltd.).

"Saponification" in polyvinyl alcohol
Is preferably 70% or more in terms of molar percentage, more preferably 85% or more, and particularly preferably 98% or more, a so-called fully saponified product. The degree of polymerization of polyvinyl alcohol is preferably from 100 to 5,000, more preferably from 200 to 3,000. Furthermore, the PVA referred to in the present invention may be modified with a small amount of a comonomer as long as the object of the present invention is not hindered.

The above-mentioned modified polyvinyl alcohol and ethylene-vinyl alcohol copolymer are defined as other unsaturated monomers copolymerizable with a vinyl acetate monomer on a vinyl ester resin during the production of polyvinyl alcohol, for example, Olefins such as ethylene, propylene, α-hexene and α-octene; unsaturated acids such as (meth) acrylic acid, crotonic acid, (anhydride) maleic acid, fumaric acid and itaconic acid, and alkyl esters and alkalis thereof. Salts, vinyl sulfonic acid, styrene sulfonic acid, 2-
Sulfonic acid-containing monomers such as acrylamide-2-methylpropanesulfonic acid and alkali salts thereof, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and trimethyl-2- (1
-(Meth) acrylamide-1,1-dimethylethyl)
Ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride,
Examples thereof include 1-vinyl-2-ethylimidazole and other quaternizable cationic monomers, styrene, alkyl vinyl ether, (meth) acrylamide, and others.

The ratio of these copolymer components is not particularly limited, but is 5 to 5 parts per vinyl alcohol unit.
0 mol% or less, preferably 30 mol% or less is preferable, and various forms obtained by any method such as random copolymerization, block copolymerization, and graft copolymerization are used as the form of copolymerization. .

Among these copolymers, a block copolymer obtained by copolymerizing a polycarboxylic acid component with a polyvinyl alcohol component is particularly preferably used, and when the polycarboxylic acid component is polymethacrylic acid, Particularly preferred. Further, the block copolymer is particularly preferably an AB block copolymer in which a polyacrylic acid chain is extended at one end of a polyvinyl alcohol chain, and the polyvinyl alcohol block component (a) Weight ratio of acrylic acid block component (b) (a) /
(B) is preferably 50/50 to 95/5,
In the case of 60/40 to 90/10, particularly preferable gas barrier properties are completed, and the bonding characteristics with the base material layer are remarkably completed. Further, among other modified forms, one particularly preferred form is a silyl group-modified polyvinyl alcohol resin composed of a saponified vinyl ester polymer modified with at least one compound having a silyl group in the molecule. is there.

The method for obtaining the modified polymer having such a composition is not particularly limited, but a silyl group is added to a vinyl alcohol polymer such as polyvinyl alcohol or modified polyvinyl acetate obtained by a conventional method. Reacting a compound having a silyl group into the polymer, or activating the terminal of polyvinyl alcohol or a modified product thereof, and introducing an unsaturated monomer having a silyl group in the molecule to the terminal of the polymer. Various modification methods such as graft copolymerization of the unsaturated monomer to a vinyl alcohol polymer molecular chain, a copolymer comprising a vinyl ester monomer and an unsaturated monomer having a silyl group in the molecule. And saponifying it, or polymerizing a vinyl ester in the presence of a silyl group-containing mercaptan or the like and saponifying it. Introducing silyl groups into Runado end,
Various methods such as are effectively used.

The modified polyvinyl alcohol-based resin obtained by such various methods may be any resin as long as it has a silyl group in the molecule. The silyl group contained in the molecule may be an alkoxyl group or a silyl group. Those having a reactive substituent such as an acyloxyl group and a hydrolyzate of a silanol group or a salt thereof are preferable, and among them, a silanol group is particularly preferable.

Compounds having a silyl group in the molecule used for obtaining these modified polyvinyl alcohol resins include trimethylchlorosilane, dimethylchlorosilane, methyltrichlorosilane, vinyltrichlorosilane, diphenyldichlorosilane, triethylfluorosilane. Organohalosilanes such as silane, organosilicon esters such as trimethylacetoxysilane and dimethyldiacetoxysilane, organoalkoxysilanes such as trimethylmethoxysilane and dimethyldimethoxysilane,
Examples include organosilanols such as trimethylsilanol and diethylsilanediol, aminoalkylsilanes such as N-amiethyltrimethoxysilane, and organosilicon isocyanates such as trimethylsiliconisocyanate. The degree of modification by these silylating agents can be arbitrarily adjusted depending on the type, amount and reaction conditions of the silylating agent used.

The unsaturated monomer used in the method for saponifying a copolymer of a vinyl ester monomer and an unsaturated monomer having a silyl group in the molecule is vinyltrimethoxysilane. Many vinylsilane-based compounds such as vinylalkoxysilane and vinylmethyldimethoxysilane represented by vinyltriethoxysilane, and alkyl- or allyl-substituted vinylalkoxysilane represented by vinyltriisopropoxysilane; Further, polyalkylene glycol-modified vinyl silanes in which a part or all of these alkoxy groups are substituted with a polyalkylene glycol such as polyethylene glycol can be given. Furthermore, 3- (meth) acrylamino-propyltrimethoxysilane, 3
(Meth) acrylamide-alkylsilane represented by-(meth) acrylamide-propyltriethoxysilane and the like can also be preferably used.

On the other hand, a method of polymerizing a vinyl ester in the presence of a mercaptan having a silyl group or the like and then saponifying the silyl group to introduce a silyl group into the terminal includes an alkoxysilylalkyl such as 3- (trimethoxysilyl) -propylmercaptan. Mercaptan is preferably used.

The suitable range varies depending on the degree of modification of the modified polyvinyl alcohol-based resin of the present invention, ie, the content of the silyl group, the degree of saponification, etc., but it is important for the gas barrier property which is the object of the present invention. It becomes a factor. The content of the silyl group is usually 30 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, as a monomer containing a silyl group, based on the vinyl alcohol unit in the polymer. And 2 mol% or less is particularly preferably used. Although the lower limit is not particularly limited, the effect is particularly remarkably exhibited when it is 0.1 mol% or more.

The silylation rate indicates the ratio of the silyl group introduced after the silylation to the amount of the hydroxyl group contained in the polyvinyl alcohol resin before the silylation.

The modified polyvinyl alcohol-based resin into which the silyl group has been introduced is alcohol or alcohol /
By heating and dissolving with a mixed solvent of water, the compound is dissolved in an alcohol solvent due to the presence of the introduced silyl group.
The modified polyvinyl alcohol-based resin dissolved in the solvent, on the other hand, partially crosslinks by reacting by a dealcoholization reaction and a dehydration reaction. In the above reaction, the presence of water is essential, and it is preferable to use a mixed solvent of alcohol / water.

Of course, these various polyvinyl alcohol resins may be used alone. However, as long as the object of the present invention is not impaired, they may be used as copolymers with other copolymerizable monomers or mixed with other monomers. It can be used in combination with other possible resin compounds. Examples of such a resin include polyacrylic acid or esters thereof, polyester resin, polyurethane resin, polyamide resin, epoxy resin, melamine resin, and others.

[0063] Polysaccharides are biopolymers synthesized in a biological system by polycondensation of various monosaccharides, and here also include those chemically modified based on them. Examples include cellulose and cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose and carboxymethylcellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan and the like.

The ethylene / vinyl alcohol copolymer (hereinafter referred to as EVOH) has a vinyl alcohol content of 40 mol% or more and 80 mol% or less, and more preferably 45 mol% to 75 mol%. It means a certain EVOH. In addition, the melt index of EVOH (temperature 190
The value measured under the conditions of ° C and a load of 2160 g; hereinafter, referred to as MI) is not particularly limited, but is 0.1 to 50 g / 10 minutes. Further, the EVOH referred to in the present invention may be modified with a small amount of a comonomer as long as the object of the present invention is not hindered.

The inorganic compound used in the present invention is not particularly limited. For example, an inorganic layered compound can be used. An inorganic layered compound is an inorganic compound in which unit crystal layers are stacked on each other to have a layered structure, and when cleaved, has a particle size of 5 μm or less and an aspect ratio of 50 to 5000 in gas barrier properties. Then, there is no particular limitation. As for the gas barrier properties, the aspect ratio is more preferably in the range of 200 to 3000. If the aspect ratio is less than 50, the gas barrier property is not sufficiently exhibited, and if the aspect ratio is more than 5000, it is technically difficult and economically expensive. Further, when the particle size is 3 μm or less, the transparency becomes better, and when the particle size is 1 μm or less, it is more preferable for applications where transparency is important.

Specific examples of the inorganic layered compound used in the present invention include graphite, phosphate derivative-type compounds (zirconium phosphate compounds, etc.), chalcogenides,
And clay minerals. Here, the “chalcogen compound” includes a group IV (Ti, Zr, Hf) and a group V (V,
Nb, Ta) and group VI (Mo, W) dichalcogenides, which are represented by the formula MX ₂ (M is the above element, and X is chalcogen (S, Se, Te)).

The particle size of the inorganic layered compound used in the present invention refers to a particle size obtained by a diffraction / scattering method in a dispersion medium. Although it is extremely difficult to measure the true particle size in a coating film, it is sufficiently swelled and cleaved with a dispersion medium of the same type as the dispersion medium used in the diffraction / scattering method, and is combined with the resin used for the coating film. In the case, in the resin 32 in the coating film 3 shown in FIG.
The particle size of the cleaved inorganic layered compound can be considered to correspond to the particle size of the cleaved inorganic layered compound in the dispersion medium.

(Method for Determining Average Particle Diameter) The method for determining the average particle diameter of particles in a liquid includes a method based on a diffraction / scattering method, a method based on a dynamic light scattering method, a method based on a change in electric resistance, and a method using an underwater microscope. A method by image processing or the like is possible.

In the dynamic light scattering method, when the resin and the particles coexist, the apparent liquid viscosity is different from that of the pure dispersion medium, so that it is difficult to evaluate the method. There is a problem of resolution in the method using image processing after photographing in a submerged microscope, and each method is difficult to use. diffraction/
In the method by the scattering method, when a resin solution, for example, a resin aqueous solution has substantially little scattering (that is, it is transparent), and scattering derived from particles is dominant, only particle size distribution of particles regardless of the presence or absence of resin is used. This is preferable because information can be obtained.

(Measurement of Average Particle Size by Diffraction / Scattering Method) In the measurement of particle size distribution and average particle size by the diffraction / scattering method, a dispersion obtained by dispersing a swollen and cleaved inorganic layered compound in an aqueous dispersion medium is subjected to light irradiation. The diffraction / scattering pattern obtained when the light is passed through is calculated by using the Mie scattering theory or the like to calculate the particle size distribution most consistent with the pattern.

As a commercially available device, a particle size measuring device (LS230, LS200, L
S100, manufactured by Coulter Co., Ltd.), laser diffraction particle size distribution analyzer (SALD2000, SALD2000A, S
ALD3000, manufactured by Shimadzu Corporation) Laser diffraction / scattering type particle size distribution analyzer (LA910, LA700, LA5)
00, manufactured by Horiba, and Microtrack SPA,
Microtrack FRA, manufactured by Nikkiso Co., Ltd.).

(Method of Measuring Aspect Ratio) The aspect ratio (Z) is a ratio obtained from the relationship of Z = L / a. Here, L is the particle diameter (volume-based median diameter) of the inorganic layered compound in the dispersion obtained by the particle diameter measurement method by the above-mentioned diffraction / scattering method, and a is the cleaved unit shown in FIG. This is the unit thickness of the crystal layer 31. The “unit thickness a” is a value determined based on the result of independently measuring the thickness of the inorganic layered compound by a powder X-ray diffraction method or the like described later.

More specifically, as schematically shown in the graph of FIG. 3 in which the horizontal axis represents 2θ and the vertical axis represents the intensity of the X-ray diffraction peak, the lowest angle side of the observed diffraction peaks is shown. From the angle θ corresponding to the peak, the Bragg equation (nλ = 2Dsi
The interval determined based on nθ, n = 1, 2, 3,... is defined as “unit thickness a” (for details of the powder X-ray diffraction method, for example, see “ Guide (a) ”, page 69 (1985) published by Kagaku Dojinsha).

When the resin composition corresponding to the coating film 3 obtained by removing the dispersion medium from the dispersion liquid was subjected to powder X-ray diffraction,
Normally, the plane distance between the dispersed inorganic layered compounds in the resin composition can be determined as the plane distance d shown in FIG.

More specifically, as shown in the graph of FIG. 4 in which the horizontal axis indicates 2θ and the vertical axis indicates the intensity of the X-ray diffraction peak, the diffraction corresponding to the above “unit thickness a” is shown. Of the diffraction peaks observed at a lower angle (larger interval) than the peak position, the interval corresponding to the peak at the lowest angle is defined as “plane interval d” (a <d).

As schematically shown in the graph of FIG. 5, when it is difficult to detect the peak corresponding to the “surface distance d” overlapping with the halo (or the background), it is difficult to detect the peak at a lower angle than 2θd. The area of the portion excluding the baseline is set as the peak corresponding to the “surface distance d”.
Here, “θd” is a diffraction angle corresponding to “(unit thickness a) + (width of single resin chain)”. (For details of the method of calculating the surface distance d, see, for example, Shuichi Iwata et al. Ed., "Encyclopedia of Clay", p. 35 and below and p. 271 and below, 1985,
(See Asakura Shoten Co., Ltd.)

As described above, the “integrated intensity” of the diffraction peak observed in the powder X-ray diffraction of the resin composition is 2 or more in relative ratio to the integrated intensity of the reference diffraction peak (corresponding to “distance d”). (More preferably 10 or more).

Normally, the difference between the above-mentioned surface distance d and “unit thickness a”, that is, the value of k = (da) (when converted to “length”) constitutes the resin composition. It is equal to or greater than the width of a single resin chain [k = (da) ≧ width of a single resin chain]. Such “the width of a single resin chain” can be obtained by simulation calculation or the like (for example, “Introduction to Polymer Chemistry”, pp. 103-110, 198).
1 year, see Chemical Doujinshi), 4-5 Å for polyvinyl alcohol (2-3 for water molecules)
Angstrom).

It is extremely difficult to directly measure the “true aspect ratio” of the inorganic layered compound in the coating film 3. Although the above aspect ratio Z = L / a is not always equal to the “true aspect ratio” of the inorganic layered compound in the coating film 3, the aspect ratio Z is “true” for the following reason. It is reasonable to approximate the "aspect ratio".

There is a relationship of a <d between the spacing d of the resin composition obtained by the powder X-ray diffraction method and the “unit thickness a” obtained by the powder X-ray diffraction measurement of the inorganic layered compound alone. And the value of (da) is the value of resin 1 in the composition.
If the width of the main chain or more, in the resin composition,
The resin is inserted between the layers of each inorganic layered compound. Therefore, approximating the thickness of the inorganic layered compound in the coating film 3 by the above “unit thickness a”, that is, the “true aspect ratio” of the inorganic layered compound in the coating film 3
Is adequately approximated by the “aspect ratio Z” in the dispersion liquid of the above-mentioned inorganic layered compound.

As described above, it is extremely difficult to measure the true particle size of the inorganic layered compound in the coating film 3.
The particle size of the inorganic layered compound in the resin 32 of the coating film 3 can be considered to correspond to the particle size L of the inorganic layered compound in the dispersion (resin / inorganic layered compound / dispersion medium).

However, since the particle diameter L in the dispersion obtained by the diffraction / scattering method is considered to be very unlikely to exceed the long diameter Lmax of the inorganic layered compound, the true aspect ratio (Lmax / a) is low. The possibility that the ratio is lower than the “aspect ratio Z” used in the present invention (Lmax / a <Z) is theoretically considerably low.

From the above two points, it is considered that the definition Z of the aspect ratio used in the present invention has sufficient validity. In the present specification, “aspect ratio” or “particle size” means “aspect ratio Z” defined above or “particle size L determined by a diffraction / scattering method”.

From the viewpoint of easily giving a large aspect ratio, an inorganic layered compound having a property of swelling and cleaving in a dispersion medium is preferably used.

The degree of “swelling / cleaving” of the inorganic layered compound used in the present invention into a dispersion medium can be evaluated by the following “swelling / cleaving” test. The swellability of the inorganic layered compound is preferably about 5 or more (more preferably, about 20 or more) in a swelling test described below. On the other hand, the cleavage property of the inorganic layered compound is preferably about 5 or more (and more preferably about 20 or more) in the cleavage test. In these cases, a liquid having a density smaller than the density of the inorganic layered compound is used as the dispersion medium. When the inorganic layered compound is a natural swellable clay mineral, it is preferable to use water as the dispersion medium.

<Swelling test> 100 mL of the dispersion medium was placed in a 100 mL measuring cylinder, and 2 g of the inorganic layered compound was added thereto.
Add slowly. After standing, the volume (mL) of the inorganic layered compound dispersed layer is read as the swelling value from the scale at the interface between the inorganic layered compound dispersed layer and the supernatant after 24 hours at 23 ° C. The larger the value, the higher the swelling property.

<Cleaving test> 30 g of an inorganic layered compound was slowly added to 1500 mL of a dispersion medium, and a dispersion machine [Despa MH-L, manufactured by Asada Tekko Co., Ltd., blade diameter 52 mm, rotation speed 3]
100 rpm, container capacity 3 L, distance 28 between bottom and blade
mm] at a peripheral speed of 8.5 m / sec for 90 minutes (23 ° C.), take 100 mL of the dispersion liquid, put it in a graduated cylinder and let stand for 60 minutes, and then, from the interface with the supernatant, the volume of the inorganic layered compound dispersed layer Read (mL) as cleavage value.

As the inorganic layered compound which swells and cleaves in the dispersion medium, a clay mineral which swells and cleaves in the dispersion medium is particularly preferably used. Such clay minerals are generally
A type having a two-layer structure having an octahedral layer having aluminum or magnesium as a central metal on the upper surface of a tetrahedral layer of silica, and an octahedral layer having a tetrahedral layer of silica having aluminum or magnesium as a central metal. Is classified into a type having a three-layer structure in which is narrowed from both sides. The former two-layer structure type includes kaolinite group and antigolite group, and the latter three-layer structure type includes smectite group, vermiculite group and mica group depending on the number of interlayer cations. Can be.

More specifically, these clay minerals include kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectite. Light, tetrasilyl mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, zansophyllite, chlorite and the like can be mentioned.

Further, those obtained by treating a clay mineral with an organic substance (hereinafter sometimes referred to as an organically modified clay mineral) can also be used as an inorganic layered compound. See Clay Encyclopedia).

Among the above clay minerals, smectites, vermiculites, and micas are preferable, and smectites are more preferable, from the viewpoint of swelling or cleavage. Examples of the smectite group include montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, and hectorite.

The dispersion medium for swelling or cleaving the inorganic layered compound is, for example, in the case of a natural swellable clay mineral, water, alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol and diethylene glycol, dimethylformamide, dimethyl sulfoxide, Acetone and the like are mentioned, and alcohols such as water and methanol are more preferable.

In the case of organically modified clay minerals, aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as ethyl ether and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; n-pentane; aliphatic hydrocarbons such as n-hexane and n-octane, chlorobenzene, carbon tetrachloride,
Chloroform, dichloromethane, 1,2-dichloroethane,
Examples include halogenated hydrocarbons such as perchlorethylene, ethyl acetate, methyl methacrylate (MMA), dioctyl phthalate (DOP), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, and silicone oil.

From the viewpoint of the gas barrier properties of the laminated film obtained by applying the aqueous paint according to the present invention, water is preferred in that it can swell or cleave the above-mentioned inorganic layered compound.

The composition ratio of the inorganic layered compound and the high hydrogen bonding resin used as the solid content contained in the coating liquid is not particularly limited, but generally, the inorganic layered compound and the high hydrogen bonding resin are generally used. Is preferably in the range of 0/100 to 10/1 (inorganic layered compound / high hydrogen bonding resin). The higher the weight ratio of the inorganic layered compound is, the more excellent the gas barrier property of the laminated film obtained by applying the aqueous paint according to the present invention is, but in consideration of the bending resistance, it is 1/2.
The range of 0 to 2/1 is more preferable. In addition, the concentration of the inorganic layered compound and the high hydrogen bonding resin in the coating liquid is usually 1 to 15% by weight in total, preferably 4 to 1% by weight.
0% by weight.

When the resin used in the present invention is a high hydrogen bonding resin, a crosslinking agent for a hydrogen bonding group can be used for the purpose of improving the water resistance. Preferred examples of the crosslinking agent include coupling agents such as titanium-based coupling agents, silane-based coupling agents, melamine-based coupling agents, epoxy-based coupling agents, and isocyanate-based coupling agents, water-soluble epoxy compounds, Copper compounds, zirconium compounds, organometallic compounds and the like can be mentioned. From the viewpoint of improving water resistance, an organic metal compound, a zirconium compound, a water-soluble epoxy compound, and a silane coupling agent are more preferably used, and an organic metal compound such as an organic titanium compound is more preferable.

Specific examples of the zirconium compounds include zirconium halides such as zirconium oxychloride, zirconium hydroxychloride, zirconium tetrachloride and zirconium bromide; and mineral acids such as zirconium sulfate, basic zirconium sulfate and zirconium nitrate. Zirconium salts of organic acids such as zirconium formate, zirconium acetate, zirconium propionate, zirconium caprylate and zirconium stearate;
Examples include zirconium complex salts such as ammonium zirconium carbonate, sodium zirconium sulfate, ammonium zirconium acetate, sodium zirconium oxalate, sodium zirconium citrate, and zirconium ammonium citrate.

Specific examples of the water-soluble epoxy compound include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, glycidyl ether epoxy resin, heterocyclic epoxy resin, glycidylamine epoxy resin, and aliphatic epoxy resin. I can give it.

Examples of the silane coupling agent include amino silane coupling agents, vinyl or methacryloxy silane coupling agents, epoxy silane coupling agents, methyl silane coupling agents,
Chloro silane coupling agents and mercapto silane coupling agent systems are exemplified.

Preferable examples of the crosslinking agent for a hydrogen-bonding group include a reaction for forming a cross-linked structure by reacting with a plurality of functional groups of a high hydrogen-bonding resin, that is, an organic metal compound capable of a cross-linking reaction. For example, the above-mentioned organometallic compounds which react with a plurality of hydroxyl groups of polyvinyl alcohol and form a cross-linking by a coordination bond or an ionic bond between a metal atom of the organometallic compound and an oxygen atom of the hydroxyl group are preferable.

The above-mentioned organometallic compounds capable of undergoing a crosslinking reaction include:
Higher crosslinking reactivity and higher crosslinking efficiency than inorganic metal salts. However, if the cross-linking reactivity is too high, the cross-linking reaction proceeds in the coating solution and coating (coating) becomes impossible, but the cross-linking reactivity of the organometallic compound can be changed by appropriately changing the ligand. Easy to control. The organic metal compound is also superior to the inorganic metal salt in that it has the advantage that the reactivity is easily controlled. Among the organometallic compounds, an organometallic compound having a chelating ligand such as acetylacetonate has an appropriate crosslinking reactivity and is preferable as a crosslinking agent for a hydrogen bonding group.

Preferred examples of such organometallic compounds include organic titanium compounds, organic zirconium compounds, organic aluminum compounds, and organic silicon compounds.

Specific examples of the organic titanium compound include titanium orthoesters such as tetra-n-butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate and tetramethyl titanate; titanium acetylacetonate;
Titanium chelates such as titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium triethanolamine, titanium ethyl acetoacetate, and titanium acylates such as polyhydroxytitanium stearate. No.

Specific examples of the organic zirconium compound include zirconium normal propylate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium acetylacetonate bisethylacetoacetate and the like. No.

Specific examples of the organoaluminum compound include aluminum acetylacetonate, aluminum organic acid chelate and the like. Examples of the organic silicon compound include a silicon compound having a ligand included in the compounds exemplified as the organic titanium compound or the organic zirconium compound.

Among these, a chelate compound is preferable in terms of stability in a coating solution. In terms of the stability of the coating solution, the stability is greatly improved by setting the coating solution to be acidic. The above acidic conditions include a pH of 5
Or less, more preferably pH 3 or less. There is no particular lower limit on the pH of the coating solution, but usually the pH is 0.1.
5 or more. As the addition method, it is preferable to dilute with an alcohol and add. By including the step of mixing the resin and the crosslinking agent, a coating film in which the resin is crosslinked can be obtained.

The amount of the crosslinking agent to be added is not particularly limited, but the ratio K (K = CN / HN) of the number of moles of the crosslinking group (CN) of the crosslinking agent to the number of moles of the hydrogen bonding group (HN) of the resin is used. But,
It is preferable to use it in the range of 0.001 or more and 10 or less. More preferably, the molar ratio K is in the range of 0.01 or more and 1 or less.

The method of compounding or producing the coating film layer comprising the high hydrogen bonding resin and the inorganic layer compound is not particularly limited. From the viewpoint of uniformity or ease of operation at the time of compounding, for example, after mixing a liquid in which a resin is dissolved in a solvent and a dispersion in which an inorganic layered compound has been swollen and cleaved in advance with a dispersion medium, the solvent and the dispersion medium are mixed. (Method 1), a method of mixing a dispersion obtained by swelling and cleaving an inorganic layered compound with a dispersion medium and a resin, dissolving the resin in the dispersion medium, and then removing the dispersion medium (method 2). A) a method in which an inorganic layered compound is added to a solution obtained by dissolving a resin in a solvent, the inorganic layered compound is swelled and cleaved using the solvent as a dispersion medium to form a dispersion, and the solvent is removed (method 3). A method of hot-kneading the inorganic layered compound (method 4) can be used. The former three methods are preferably used from the viewpoint that a large aspect ratio of the inorganic layered compound can be easily obtained. In the former three cases, it is preferable to perform treatment using a high-pressure dispersion device from the viewpoint of dispersibility of the inorganic layered compound.

As a high-pressure dispersion device, for example, Microfluid
There is an ultrahigh-pressure homogenizer (trade name: Microfluidizer) manufactured by ics Corporation or a Nanomizer manufactured by Nanomizer, and a homogenizer manufactured by Manton-Gaulin, such as a homogenizer manufactured by Izumi Food Machinery.

In the above three methods, after removing the solvent or the dispersion medium from the system and coating, the obtained coated film is heat-aged at, for example, 110 ° C. or more and 220 ° C. or less. The water resistance (meaning of gas barrier properties after the water resistance environment test) of the coating film can be improved, which is preferable.

The aging time is not limited, but it is necessary that the coated film reaches at least the set temperature. For example, in the case of a method using a hot medium such as a hot air dryer, the time is preferably 1 second to 100 minutes. There is no particular limitation on the heat source, as well as hot roll contact, heat medium contact (air, oil, etc.),
Various methods such as infrared heating and microwave heating can be applied.

The above aging treatment exerts a particularly excellent effect in improving the water resistance when the resin is a highly hydrogen-bonding resin.

As shown in FIG. 6, the high-pressure dispersion treatment is performed by passing a composition mixture containing particles or a dispersion medium to be dispersed through a plurality of thin tubes 11 at a high speed so as to collide with each other. Dispersion treatment is performed under special conditions such as high pressure.

In such a high-pressure dispersion treatment, the composition mixture is preferably passed through a thin tube 11 having a diameter of 1 μm to 1000 μm. When the composition mixture passes through the small tube 11, the maximum pressure condition is applied to the composition mixture. It is preferable that a pressure of 100 kgf / cm ² or more is applied.
/ Cm ² or more, more preferably 1000 kgf / cm ²
The above is particularly preferred. In addition, the composition mixture is a thin tube 11
When passing through the inside, the maximum arrival speed of the composition mixture is 1
00 m / s or more, and the heat transfer rate is 1
It is preferably at least 00 kcal / hr.

The principle of the high-pressure treatment in the high-pressure dispersion treatment apparatus used for the high-pressure dispersion treatment will be described schematically.
The composition mixture is sucked into the feeder tube 13 having a larger diameter than the thin tube 11 by the pump 12 and taken in. Subsequently, a high pressure is applied to the composition mixture in the feeder tube 13 by the pump 12. At this time,
Check valve provided on feeder tube 13 (not shown)
As a result, the composition mixture in the feeder tube 13 is
Extruded toward one. Therefore, the composition mixture is in a high-pressure and high-speed state in the thin tube 11, and each inorganic layer compound particle of the composition mixture collides with each other and the inner wall of the small tube 11, and the diameter of each inorganic layer compound particle is reduced. And the thickness, particularly the thickness, is subdivided and more uniformly dispersed, and is taken out of the discharge pipe 14 to the outside.

For example, in the case where the flow velocity at the point where the maximum velocity is instantaneously reached with respect to the composition mixture as the processed sample in the thin tube 11 is 300 m / s, the volume is 1 × 10 ^−3.
passes through a cube of m ³ at 1 / (3 × 10 ⁵ ) sec,
When the temperature of the composition mixture increases by 35 ° C., energy is transferred to the composition mixture by pressure loss. The heat transfer rate is such that the specific gravity of the composition mixture is 1 g / cm ^{3 and the} specific heat 1 cal /
At g ° C., it is 3.8 × 10 ⁴ kcal / hr.

The aging treatment here is particularly excellent when the resin is a highly hydrogen-bonding resin.

In the laminated film obtained by applying the aqueous paint according to the present invention, the thickness of the coating film is 1 n
m to 10 μm, 10 nm to 5 μm,
The thickness is preferably in the range of 0.1 μm to 2 μm. When transparency is required, the thickness is desirably 1 μm or less.

The laminated film obtained by applying the aqueous paint according to the present invention has an anchor coat layer (anchor layer).
May be made. For example, polyethyleneimine,
Titanium, polybutadiene, urethane and the like are not particularly limited, but an anchor layer composed of an isocyanate compound and an active hydrogen compound is preferable from the viewpoint of water resistance.

The isocyanate compounds include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), and hexamethylene diisocyanate (HDI).
I), 4,4'-methylenebiscyclohexyl isocyanate (H12MDI), isophorone diisocyanate (IP
DI).

Examples of the active hydrogen compound include, for example,
Low molecular weight polyols such as ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and trimethylolpropane; polyethylene glycol, polyoxypropylene glycol, ethylene oxide / propylene oxide copolymer And polyether polyols such as polytetramethylene ether glycol; polyester polyols such as poly-β-methyl-δ-valerolactone, polycaprolactone, and polyesters from diols / dibasic acids; and the like. Particularly, a low molecular weight polyol is preferable, and a diol in the low molecular weight polyol is more preferable. Here, the diol is ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol and the like, and dibasic acids such as adipic acid, azelaic acid, sebacic acid, isophthalic acid, and terephthalic acid. Other polyols include castor oil, liquid polybutadiene, epoxy resin, polycarbonate diol, acrylic polyol, and active hydrogen compounds such as neoprene.

The mixing ratio of the isocyanate compound and the active hydrogen compound is not particularly limited, but the amount to be added is determined in consideration of the equivalence relationship between the isocyanate group and the active hydrogen group, for example, —OH, —NH, and —COOH. preferable. For example, the ratio R (R = AN / mol) of the number of moles of isocyanate groups (AN) to the number of moles of active hydrogen groups (BN) of the active hydrogen compound
BN) is preferably 0.001 or more from the viewpoint of adhesive strength, and is preferably 10 or less from the viewpoint of tackiness and blocking. More preferably, the molar ratio R is in the range of 0.01 or more and 1 or less. Each mole number of the isocyanate group and the active hydrogen group can be determined by ¹ H-NMR and ¹³ C-NMR.

The method of laminating the anchor layer 2 on the object 1 is not particularly limited, but a coating method using an anchor coating agent solution obtained by dissolving an anchor coating agent containing an isocyanate compound and an active hydrogen compound in a solvent is used. preferable. Specific examples of the coating method include a direct gravure method, a reverse gravure method, a microgravure method, a roll coating method such as a two-roll beat coating method and a bottom feed three-reverse coating method, and a doctor knife method and a die coating method. Dip coating method,
Examples of the method include a bar coating method and a coating method combining these methods.

The solvent component in the anchor coating agent solution is mainly an organic solvent, and includes alcohols, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, esters, ketones, ethers, Halogenated hydrocarbons and mixed solvents thereof are exemplified.

[0125] The coating thickness obtained by applying the anchor coating agent solution to the object 1 in a film form is not particularly limited.
It is preferable that the dry thickness is set to be 0.01 μm to 5 μm. The larger the coating thickness, the better the heat sealing strength, but the lower the gelboflex resistance. Therefore, the coating thickness is more preferably 0.03 μm or more.
2.0 μm, more preferably 0.05 μm
1.0 μm.

The base layer used as the object 1 to be coated includes polyethylene (low density, high density), ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / octene copolymer. Polyolefin resin such as polymer, polypropylene, ethylene / vinyl acetate copolymer, ethylene / methyl methacrylate copolymer, ionomer resin, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, nylon-6, nylon -6, 6, meth-xylene diamine / adipic acid condensation polymer, amide resin such as polymethyl methacrylimide, acrylic resin such as polymethyl methacrylate, polystyrene, styrene / acrylonitrile copolymer, styrene / acrylonitrile / Butadiene copolymers, styrene such as polyacrylonitrile - acrylonitrile resin, cellulose triacetate, hydrophobic cellulose-based resins such as di cellulose acetate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, halogen-containing resins such as Teflon,
Hydrogen bonding resin such as polyvinyl alcohol, ethylene / vinyl alcohol copolymer, cellulose derivative, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyphenylene oxide resin, polymethylene oxide resin, liquid crystal resin, etc. Engineering plastic resin, kraft paper, high quality paper, imitation paper, glassine paper, parchment paper,
Synthetic paper and various cardboards are included.

Among them, biaxially oriented polypropylene, polyethylene terephthalate, biaxially oriented polypropylene coated with nylon or polyvinylidene chloride called K coat, polyethylene terephthalate,
Nylon, silica, alumina, aluminum-deposited polyethylene terephthalate, polypropylene, nylon, and OPP (AS-OP) for strong antistatic applications, as well as metals or metal oxides such as aluminum-deposited, silica-deposited, and alumina-deposited Biaxially oriented polypropylene (OPP), biaxially oriented polyethylene terephthalate (OPET), biaxially oriented nylon (ONy) and the like are preferably used.

The method for applying the coating film 3 to the object 1 or the object 1 on which the anchor layer 2 is laminated is not particularly limited, but a coating liquid is applied to the surface of the object 1. , Drying and heat treatment, and a method of laminating the resin composition film to the object 1 or the anchor layer 2 later, and particularly preferably the above-mentioned method. When coating, the resin contained in the coating liquid is preferably the above-mentioned high hydrogen bonding resin from the viewpoint of dispersibility.

Examples of the coating method include a direct gravure method, a reverse gravure method, a microgravure method, a two-roll beat coating method, a roll coating method such as a bottom feed three-reverse coating method, a doctor knife method, a die coating method, and a dip coating method. Method, a spin coating method, a bar coating method, and a coating method combining these methods. As a method for continuous coating (continuous coating) on a film-like material such as the object 1 or the object 1 on which the anchor layer 2 is laminated, a line speed of 150 m / min or more is preferable.
50 m / min or more is more preferable.

In the film laminate of the present invention, as shown in FIG. 7, a sealant layer 4 for improving heat sealability may be further laminated on the coating film 3. The resin used for the sealant layer 4 is not particularly limited, but polyethylene (low density, high density), ethylene / propylene copolymer, ethylene / butene copolymer may be used due to heat sealing strength, food aroma, and desorption of resin odor. Polymer,
Ethylene / hexene copolymer, ethylene-4-methyl-1-
Pentene copolymer, ethylene / octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene / methyl methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / acrylic acid copolymer, ionomer resin, etc. Is preferably used. In particular, when the object to be coated 1 after coating is required to have the sealing property of the contents, the sealant layer 4 having high impact strength is preferable. Preferred examples of such a resin include polyethylene, ethylene-α-olefin copolymer, and polypropylene obtained using a metallocene catalyst or a late transition metal complex catalyst.

As a method for laminating the sealant layer 4,
Although not particularly limited, for example, a method in which the resin used for the sealant layer 4 is dissolved in a coating solution and coated on the coating film 3 made of an inorganic layered compound and a resin. Extrusion lamination method,
A preferred example is a method of dry laminating the sealant layer 4 on the coating film 3. The interface between the sealant layer 4 and the coating film 3 is corona-treated, ozone-treated,
An electron beam treatment or a treatment such as an anchor coating agent may be performed.

Further, as long as the effects of the present invention are not impaired,
Various additives such as an ultraviolet absorber, a crosslinking agent, a coloring agent, and an antioxidant may be mixed with at least one of the object 1, the anchor layer 2, the coating film 3, and the sealant layer 4.

[0133]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

The measuring methods of various physical properties are described below.

[Measurement of Surface Tension of Du Nouy Method] The static surface tension was measured using a Du Nouy measuring instrument.

[Measurement of Dynamic Surface Tension by Bubble Pressure Method] The dynamic surface tension was measured by the following method using a bubble breaker measuring device (BP2, manufactured by KRUSS).

A capillary was vertically inserted into a measuring solution composed of water and a surfactant contained in a petri dish, and gas (air) was blown from above the capillary. The pressure (mN / m) received from the measurement liquid by the bubbles generated from the lower end of the capillary inserted into the measurement liquid was measured by changing the conditions as follows. That is, the number of bubbles coming out of the capillary per second was changed, and the pressure applied to the bubbles from the measurement liquid was measured under each condition. In this case, the time taken for one bubble to grow and exit the capillary is plotted on the horizontal axis, and the pressure at that time is plotted on the vertical axis. From the above plot, the half-life t of the dynamic surface tension value γ _SAA is determined by the fact that the dynamic surface tension of water (the initial value is 72 mN / m)
The time required to reach 6 mN / m was determined by extrapolation.

[Measurement of Particle Size] Using a laser diffraction / scattering type particle size distribution analyzer (LA910, manufactured by HORIBA, Ltd.), a volume-based median of particles considered to be an inorganic layered compound present in a resin matrix of a medium. The diameter was measured as a particle diameter L. The undiluted liquid dispersion was measured with an optical path length of 50 μm in a paste cell, and the dilute liquid of the dispersion was measured with an optical path length of 4 mm by a flow cell method.

[Aspect Ratio Calculation] X-ray diffractometer (XD
-5A (manufactured by Shimadzu Corporation), the diffraction measurement of the inorganic layered compound alone and the resin composition by the powder method was performed. Thereby, the unit thickness a of the inorganic layered compound was obtained, and further, from the diffraction measurement of the resin composition, it was confirmed that there was a portion where the interplanar spacing d of the inorganic layered compound was widened. Using the particle diameter L obtained by the above-described method, the aspect ratio Z is calculated as follows: Z = L / a
It calculated by the formula of.

[Thickness Measurement] The thickness of 0.5 μm or more was measured with a commercially available digital thickness gauge (contact type thickness gauge, trade name: Ultra-high precision decimicro head MH-15M, manufactured by Nippon Kogaku Co., Ltd.). On the other hand, the thickness of less than 0.5 μm is determined by the gravimetric analysis method (the measured value of the weight of a film having a certain area is divided by the area and further divided by the specific gravity of the composition) or the actual coating film thickness by the IR method. A calibration curve with IR absorption was prepared and determined from the calibration curve. Further, in the case of measuring the coating film thickness of the resin composition of the present invention, the elemental analysis method [from the specific inorganic element analysis value of the laminate (derived from the coating film) and the specific element fraction of the inorganic layered compound alone] Method for determining the ratio between the coating film of the water-based paint of the present invention and the object to be coated 1).

[Oxygen Permeability Measurement] Based on JIS K7126, an oxygen permeability measuring device (OX-TRAN ML,
MOCON) under the conditions of 23 ° C. and 50% RH.

[Coating liquid 1] Dispersion pot [Product name: Despa MH]
-L, manufactured by Asada Tekko Co., Ltd.], 1410 g of ion-exchanged water (specific electric conductivity 0.7 μS / cm or less) was further added, and polyvinyl alcohol [PVA117H; manufactured by Kuraray Co., Ltd., saponification degree: 99.6%, Polymerization degree 1700] and stirring at a low speed (1500 rpm, peripheral speed 4.10 m / min)
And the mixture is stirred for 1 hour to dissolve.

Next, the temperature was lowered to 60 ° C. while stirring, and 92 g of 1-butanol and isopropyl alcohol 2
Nonionic surfactant SH3746 is added to 77 g of the mixed solution.
(Toray Dow Corning Co., Ltd.) was added and the liquid which added 0.18g was added. The SH 3746 du used here
The surface tension value by the Nooy method was set to 0.0
As a result of measurement as 1% by weight, it was 24 mN / m.
The half-life t by the bubble pressure method is 40 seconds.
c. Then, 40 g of natural montmorillonite (Kunipia F; manufactured by Kunimine Industries Co., Ltd.) was added as it was, and after confirming that montmorillonite was substantially precipitated in the liquid, high-speed stirring (3100 rpm, peripheral speed 8.47 m / m) was performed.
in) for 90 minutes to obtain a resin composition mixture (A) having a total solid content of 8% by weight as a coating liquid 1. (Powder X
The a value obtained from the line diffraction is 1.2156 nm, and the aspect ratio (Z) is 200 or more. [Coating liquid 2] 1779 g of ion-exchanged water (0.7 μS / cm or less) is placed in a dispersion kettle (trade name: Despa MH-L, manufactured by Asada Iron Works Co., Ltd.), and polyvinyl alcohol (PVA117H; 99.) Kuraray, saponification degree;
80 g of 6% and a degree of polymerization of 1700) and stirred under low speed (1
The temperature was raised to 95 ° C. at 500 rpm at a peripheral speed of 4.10 m / min, and the mixture was stirred for 1 hour to dissolve. Next, the temperature was lowered to 60 ° C. while stirring, and then the surfactant STO-277 was used.
(Diglycerin sesquiolate, manufactured by Marubishi Yuka Kogyo Co., Ltd.) 0.18 g is added. The surface tension value according to the Du Nouy method of STO-277 was set to a concentration in water of 0.01.
As a result of measurement as% by weight, it was 25.7 mN / m. Further, the half-life t of STO-277 was 1000 sec or more by the bubble pressure method. And natural montmorillonite (Kunipia F; Kunimine Industry Co., Ltd.)
) Was added as powder, and after confirming that montmorillonite had substantially precipitated in the solution, high-speed stirring (3100 rpm) was performed.
pm and a peripheral speed of 8.47 m / min) for 90 minutes to obtain a resin composition mixture (A) having a total solid content of 8% by weight as a coating liquid 2. (The a value obtained from powder X-ray diffraction is 1.2156 nm, and the aspect ratio (Z) is 200
That is all. Example 1 A 20 μm-thick biaxially oriented polypropylene (OPP) film (Pyrene P2102; manufactured by Toyobo Co., Ltd.) was used as a base material, and an anchor coat agent (ad coat) was applied on the object 1 to be coated. AD335 /
CATIO = 15/1 (weight ratio); Toyo Morton Co., Ltd.
Gravure coating (coating machine; Inoue Metal Industry Co., Ltd.):
Gravure coating method, coating speed 200m / min, drying temperature 80
° C). The dry thickness of the anchor coat layer is 0.05
μm. Further, as a TOP coating solution, the coating solution 1 is gravure coated (coating machine; Inoue Metal Industry Co., Ltd .: gravure coating method, coating speed 200 m / min, drying temperature 110 ° C.,
Using a smoother on the coated surface) to obtain a coated film.
The dry thickness of the coating layer was 0.4 μm. The coating condition was good. Then, as a result of measuring the oxygen permeability of the coated film, it was as good as 0.1 or less.

Comparative Example 1 A coating film was obtained in the same manner as in Example 1 except that the coating liquid was changed to the coating liquid 2. Coating omission occurred and the coating state was poor. And
As a result of measuring the oxygen permeability in the same manner as in Example 1, 5
It was 0 or more.

[0145]

As described above, the water-based paint according to the first aspect of the present invention is a water-based paint containing a coating liquid containing water, a surfactant, and a solid content. Is less than 50 mN / m, and the half-life t of the dynamic surface tension value γ _SAA of water by the bubble pressure method when the surfactant is added to water is 0.01 <t.
<1000 (sec).

As described above, the water-based paint according to the second aspect of the present invention has a configuration in which the surface tension at the time of equilibration of the coating liquid is 40 mN / m or less, in addition to the configuration of the first aspect.

[0147] Therefore, when the water-based paint contains the above-mentioned surfactant, the time until the surface tension of the coating liquid contained in the water-based paint is reduced is shortened. Can be prevented, and the wettability of the water-based paint can be improved.

As described above, the water-based paint according to the third aspect of the invention has a configuration in which the solid content is made of at least one of a resin and an inorganic compound in addition to the configuration of the first or second aspect. .

As described above, the water-based paint according to the fourth aspect of the present invention has, in addition to the constitutions of the first to third aspects, a solid content of at least one of a high hydrogen bonding resin and an inorganic layered compound. This is the configuration that has become.

As described above, the water-based paint according to the invention of claim 8 has a structure in which the aspect ratio of the inorganic layered compound is in the range of 50 to 5000 in addition to the structure of claim 4.

As described above, the water-based paint according to the ninth aspect of the present invention has a configuration in which the aspect ratio of the inorganic layered compound is in the range of 200 to 3000 in addition to the configuration of the fourth aspect.

Therefore, the inorganic laminar compounds face each other due to the lamellar shape and are oriented so as to be substantially parallel to the surface direction of the coating film. Gas barrier properties can be imparted to a coating film made of an aqueous paint.

The water-based paint according to the fifth aspect of the present invention has a structure in which the coating liquid contains a hydrophilic solvent in addition to any one of the first to fourth aspects.

As described above, the water-based paint according to the invention of claim 6 has a constitution in which the solubility parameter (SP value) of the hydrophilic solvent is 9 or more in addition to the constitution of claim 5.

As described above, the water-based paint according to the invention of claim 7 has a structure in which the hydrophilic solvent contains one or more alcohols in addition to the structure of claim 5 or 6.

Therefore, the presence of the hydrophilic solvent in the coating liquid makes it easy to dissolve or disperse in the coating liquid even if the solid content contained in the coating liquid is poorly soluble in water. Become.

The water-based paint according to the tenth aspect of the present invention, as described above, has a structure in which the high hydrogen bonding resin has a hydrogen bonding group or an ionic group and a high hydrogen bonding resin. It is configured to contain a concentration of 30 mol% or more and 50 mol% or less per unit weight.

As described above, in the water-based paint according to the eleventh aspect of the present invention, in addition to the constitution of the fourth aspect, the high hydrogen-bonding resin comprises polyvinyl alcohol, a modified polyvinyl alcohol, and ethylene / vinyl alcohol copolymer. And a compound selected from the group consisting of polysaccharides, modified ethylene / vinyl alcohol copolymers, and polysaccharides.

Therefore, since the high hydrogen bonding resin has hydrophilicity, the solid content is stably dispersed or dissolved in the coating liquid.

According to a twelfth aspect of the present invention, there is provided a method for producing a water-based paint, wherein the inorganic layered compound is swollen and cleaved in the coating solution as described above, and the resin or the resin-containing coating is dispersed. It is a configuration to disperse in the working liquid.

Therefore, since the inorganic layered compound is sufficiently dispersed in the coating liquid, a water-based coating material preferably used for obtaining a coating film having excellent gas barrier properties due to a maze effect of the inorganic compound is obtained. Can be manufactured.

The method for applying a water-based paint according to the thirteenth aspect of the invention has a configuration in which the line speed is 150 m / min or more in continuous coating on a film-like material as described above.

According to a fourteenth aspect of the present invention, in order to solve the above-mentioned problems, in addition to the structure of the thirteenth aspect, the method of manufacturing a water-based paint according to the twelfth aspect is provided. This is a configuration using a water-based paint.

Therefore, since the inorganic layered compound is sufficiently dispersed in the coating solution, a coating film having excellent gas barrier properties can be obtained by the maze effect of the inorganic compound.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a coating film of a base film laminate coated with a water-based paint of the present invention.

FIG. 2 is a schematic sectional view showing an example of a film laminate having a coating film formed on a film.

FIG. 3 is an X-ray diffraction graph of the inorganic layered compound for calculating “unit thickness a” of the inorganic layered compound in the film laminate.

FIG. 4 is an X-ray diffraction graph of the inorganic layered compound for calculating the “plane spacing d” of the inorganic layered compound in the film laminate.

FIG. 5 is a graph for calculating the “plane spacing d” of the inorganic layered compound when the peak corresponding to the “plane spacing d” overlaps with a halo (or background) and is difficult to detect. It is an X-ray diffraction graph at the time.

FIG. 6 is an explanatory view schematically showing a high-pressure dispersion treatment used in the production of the water-based paint.

FIG. 7 is a schematic cross-sectional view showing another example of a film laminate in which a water-based paint of the present invention is applied and a coating film is formed on a base film.

[Explanation of symbols]

 31 unit crystal layer 32 resin

Claims (14)

[Claims] 1. A water-based paint containing a coating liquid containing water, a surfactant and a solid content, wherein the coating liquid has a surface tension at equilibrium of 50 mN / m or less, and Surface Tension γ _SAA of Water by Bubble Pressure Method when Additives are Added to Water
Wherein the half-life t is 0.01 <t <1000 (sec). 2. The surface tension at equilibrium of the coating liquid is 40 m.
The water-based paint according to claim 1, wherein the water-based paint is at most N / m. 3. The method according to claim 1, wherein the solid content comprises at least one of a resin and an inorganic compound.
Or the water-based paint according to 2. 4. The water-based coating composition according to claim 1, wherein the solid content comprises at least one of a high hydrogen bonding resin and an inorganic layered compound. 5. The water-based coating according to claim 1, wherein the coating liquid contains a hydrophilic solvent. 6. A water-based paint according to claim 5, wherein the solubility parameter of the hydrophilic solvent is 9 or more. 7. A water-based coating according to claim 5, wherein the hydrophilic solvent contains one or more alcohols. 8. An inorganic layered compound having an aspect ratio of 50 to 50.
The water-based paint according to claim 4, which is within a range of 5000. 9. An inorganic layered compound having an aspect ratio of 200
The water-based paint according to claim 4, wherein the water-based paint is within a range of -3000. 10. The high hydrogen-bonding resin contains a hydrogen-bonding group or an ionic group at a concentration of 20 mol% to 60 mol% per unit weight of the high hydrogen-bonding resin. 5. The water-based paint according to 4. 11. The high hydrogen bonding resin is at least one selected from the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, ethylene / vinyl alcohol copolymer, modified ethylene / vinyl alcohol copolymer, and polysaccharide. The aqueous paint according to claim 4, which is one compound. 12. The method for producing a water-based coating composition according to claim 1, wherein the inorganic layered compound is swollen and cleaved in the coating solution, and the resin or A method for producing a water-based paint, wherein the method is obtained by dispersing in a coating solution containing the resin. 13. The method according to claim 1, wherein the line speed is 150 m / min or more in the continuous coating on the film. 14. A coating method according to claim 13, wherein the water-based paint produced by the method for producing a water-based paint according to claim 12 is used.