JP2021169574A - Resin composition, gas barrier material, coating agent, and laminate - Google Patents

Abstract

To provide a resin composition excellent in quick-drying properties during coating and capable of providing a coating film excellent in barrier properties under high humidity.SOLUTION: The resin composition contains a trioctahedral smectite, a vinyl resin having a hydroxyl group, and a solvent. The trioctahedral smectite contains at least one kind selected from the group consisting of sodium ions, ammonium ions, and lithium ions as interlayer ions and has an aspect ratio of 1,000 or more and 15,000 or less. The solvent contains an alcohol, and the content of the alcohol is 25-55 mass% based on the total amount of the solvent.SELECTED DRAWING: None

Description

The present invention relates to resin compositions.

Packaging materials used for packaging foods and the like are required to have functions such as protection of contents, retort resistance, heat resistance, transparency, and processability. Gas barrier properties are especially important for maintaining the quality of the contents. Recently, not only packaging materials but also materials used for electronic materials such as solar cells and semiconductors are required to have high gas barrier properties.

Patent Document 1 describes that by combining a resin having a hydroxyl group and an isocyanate compound with a plate-like inorganic compound such as a clay mineral and a light blocking agent, properties such as gas barrier properties are improved.

Further, Patent Document 2 describes a material containing modified clay as a main constituent component. By using modified clay and using additives as necessary, the modified clay crystals are oriented and densely laminated. It is said that a film material having mechanical strength, gas barrier property, water resistance, thermal stability and flexibility that can be used as a self-supporting film can be obtained.

International Publication No. 2013/027609 Japanese Unexamined Patent Publication No. 2007-277078

Conventionally, the filler used for the purpose of improving the barrier property is a layered silicate (clay). Since the layered silicate exhibits excellent dispersibility in water, after applying a dispersion liquid containing polyvinyl alcohol, which is a water-soluble resin, a layered silicate, and water, as a packaging material having a barrier property on a base film. , A coating film obtained by drying is provided.
However, since the dispersion medium is water, it has a problem of poor drying property. Further, since this coating film has a high affinity with water, there is also a problem that the barrier property is poor under high humidity.

An object of the present invention is to provide a resin composition capable of providing a coating film having excellent quick-drying property at the time of coating and excellent barrier property under high humidity.

The present inventors have a 3-octhedral smectite having an aspect ratio of 1000 or more and 15000 or less, which contains at least one selected from the group consisting of sodium ion, ammonium ion, and lithium ion as interlayer ions, and a hydroxyl group. By combining a vinyl resin and a solvent containing a predetermined amount of alcohol, it is possible to obtain a resin composition capable of providing a coating film having excellent quick-drying property at the time of coating and excellent barrier property under high humidity. We have found and completed the present invention.

That is, in one aspect, the present invention contains a 38-hedron smectite, a vinyl resin having a hydroxyl group, and a solvent, and the 3 octahedral smectite contains sodium ion, ammonium ion, and interlayer ions as interlayer ions. It is a 3-octhedral smectite containing at least one selected from the group consisting of lithium ions and having an aspect ratio of 1000 or more and 15000 or less. The solvent contains alcohol, and the alcohol content is 20 with respect to the total amount of the solvent. A resin composition of ~ 55% by mass is provided.

The resin composition may further contain a polycarboxylic acid. The hydroxide value of the vinyl resin having a hydroxyl group may be 800 to 1500.

According to the present invention, it is possible to provide a resin composition having a good thixotropy index and excellent oxygen barrier property and water vapor barrier property.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, the upper limit value and the lower limit value described individually can be arbitrarily combined.

The resin composition of one embodiment contains a 38-octahedral smectite, a vinyl resin having a hydroxyl group, and a solvent.

<3 Octahedral smectite>
The basic structure of clay minerals is composed of a tetrahedral sheet of Si—O and an octahedral sheet of Al—O, etc., and the cations entering the octahedral sheet are ^{divalent ions such as Mg 2+} , or a part of them is Li. ^In the case of monovalent ions such as +, it is called a tri-octahedron. The cation exchange capacity of the 3 octahedral smectite is usually 60-150 meq / 100 g. As specific structures of smectite, saponite, hectorite, and stevensite are known. The 3-octahedral smectite of the present invention is preferably hectorite.

The 3-octahedral smectite of the present invention is characterized by having an aspect ratio of 1000 or more and 15000 or less. If the aspect ratio is less than 1000, the gas barrier property may be inferior. If it is larger than 15,000, the dispersibility in the resin is poor. It is preferably 1000 or more and 13000 or less, and particularly preferably 1000 or more and 10000 or less.

The aspect ratio of the three octahedral smectites used in the present invention is an average aspect ratio calculated from the measured values of an atomic force microscope (AFM). Specifically, it is calculated from the measured values of the average particle diameter X and the unit thickness d by an atomic force microscope (AFM). 3 A dilute solution in which octahedral smectite was dispersed in water at 0.1-0.5% by mass was dropped onto a silicon wafer and then coated with a spin coater. The coating film from which water was removed by vacuum drying was measured by AFM to measure the average particle diameter X and the unit thickness d, and the average aspect ratio Z = X / d was calculated.

The 3-octhedral smectite of the present invention is characterized by containing at least one selected from the group consisting of sodium ion, ammonium ion, and lithium ion as interlayer ions.
The total of sodium ion equivalent, ammonium ion equivalent and lithium ion equivalent of 3 octahedral smectite may be 50 to 120 meq / 100 g.
3 The total of sodium ion equivalent, ammonium ion equivalent and lithium ion equivalent of octahedral smectite may be 50 meq / 100 g or more, 80 meq / 100 g or more, or 100 meq / 100 g or more, 120 meq / 100 g or less, or 110 meq / 100 g. It may be: 3 The ammonium ion equivalent of octahedral smectite is the amount of cations eluted in 1N potassium chloride solution, and the lithium ion equivalent is the amount of cations eluted in 1N ammonium acetate solution by ion chromatography. It can be obtained by doing.

The method of exchanging the interlayer ion (cation) of 3 octahedral smectite with ammonium ion or lithium ion may be a usual ion exchange method. For example, an aqueous dispersion of 3 octahedral smectite may be exchanged with ammonium ion, Alternatively, it may be a method of treating with a cation exchange resin in which lithium ions are retained in advance. The method may be a method of passing the aqueous dispersion through a column filled with an ion exchange resin, or a method of mixing the ion exchange resin and the aqueous dispersion and stirring them in a batch.

More specifically, for example, when the interlayer cations are exchanged for lithium ions, amberlite IR120B-H is treated with lithium hydroxide in advance to cause the ion exchange resin to retain the lithium ions. An aqueous dispersion having a concentration of 3 octahedral smectite of 2% or less is passed through a column packed with an ion exchange resin holding lithium ions at a rate of 1 mL / min. By drying the aqueous dispersion after passing the liquid in an oven at 110 ° C. overnight, a 3-octahedral smectite having lithium ions as interlayer ions can be obtained.

3 The content of octahedral smectite is more excellent than the total non-volatile content in the resin composition, for example, from the viewpoint of water vapor barrier property and oxygen barrier property (for example, oxygen barrier property under high humidity). It may be 5% by mass or more, and for example, from the viewpoint of further excellent moldability of the resin composition and improvement of adhesion to the substrate, 70% by mass or less and 60% by mass or less. , 50% by mass or less, or 45% by mass or less. The content of the 3 octahedral smectite is, for example, 5 to 70% by mass, 5 to 60% by mass, 5 to 50% by mass, or 5 to 44% by mass with respect to the total amount of the non-volatile content in the resin composition. It's okay. The non-volatile component means a component other than the solvent in the resin composition.

<Vinyl resin with hydroxyl group>
The resin composition contains a vinyl resin having a hydroxyl group. A vinyl resin having a hydroxyl group can be obtained, for example, by polymerizing an esterified product of an alcohol having a polymerizable double bond and then performing a saponification treatment.

The esterified product of the alcohol having a polymerizable double bond may be, for example, a vinyl ester. Examples of the vinyl ester include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.

Further, the vinyl resin having a hydroxyl group can be obtained, for example, by polymerizing or copolymerizing a vinyl monomer having a hydroxyl group, or copolymerizing a vinyl monomer having a hydroxyl group and a vinyl monomer having no hydroxyl group. The vinyl monomer having a hydroxyl group is a monomer having at least one group having a polymerizable double bond (for example, a vinyl group, a (meth) allyl group, or a (meth) acryloyl group) and a hydroxyl group. A vinyl monomer having no hydroxyl group is a monomer having at least one group having a polymerizable double bond (for example, a vinyl group, a (meth) allyl group, or a (meth) acryloyl group) and having no hydroxyl group. be. The (meth) allyl group means an allyl group or a metharyl group. The (meth) acryloyl group means an acryloyl group or a methacryloyl group.

Examples of the vinyl monomer having a hydroxyl group (hydroxyl-containing vinyl monomer) include (meth) allyl alcohol, vinyl alcohol, and alkenemonool or alkenediol having 4 to 12 carbon atoms such as 1-buten-3-ol; 2-. Alkene ether having a polymerizable double bond at the end such as hydroxyethyl propenyl ether; hydroxystyrene; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( 2-Hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; monoesteride of (meth) acrylate and ring-open polymerized ε-caprolactone; etc. Examples thereof include a hydroxyl group-containing vinyl monomer.

Examples of the vinyl monomer having no hydroxyl group (vinyl monomer containing no hydroxyl group) include olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene; halogenated olefins such as dichloroethylene and vinyl chloride; (meth) acrylic acid; (meth) acrylic. Acid ester; vinyl ester; maleic acid diester; fumaric acid diester; itaconic acid diester; (meth) acrylamide; styrene and its derivatives; vinyl ether; vinyl ketone; maleimide; allyl compound; (meth) acrylonitrile; vinylpyridine, N-vinylpyrrolidone, Compounds having a heterocyclic group substituted with a vinyl group such as vinylcarbazole, N-vinylimidazole and vinylcaprolactone; vinylamides such as N-vinylformamide and N-vinylacetamide can be mentioned.

Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, ( 2-Ethylhexyl acrylate, t-octyl acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic 2-Hydroxyethyl acid, -2-hydroxypropyl (meth) acrylate, -3-hydroxypropyl (meth) acrylate, -4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ( 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, -2-chloroethyl (meth) acrylate, (meth) ) Glycidyl acrylate, (meth) acrylate-3,4-epoxycyclohexylmethyl, vinyl (meth) acrylate, -2-phenylvinyl (meth) acrylate, -1-propenyl (meth) acrylate, (meth) Allyl acrylate, -2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, ( Triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β- (meth) acrylate Phenoxyethoxyethyl, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluororo (meth) acrylate Pentyl, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, ( Examples thereof include tribromophenyl (meth) acrylic acid, tribromophenyloxyethyl (meth) acrylic acid, and (meth) acrylic acid-γ-butyrolactone.

Examples of vinyl esters include the monomers exemplified above.

Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, dibutyl maleate and the like.

Examples of the fumaric acid diester include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

Examples of the itaconic acid diester include dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconate and the like.

Examples of (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-. Butylacryl (meth) amide, N-t-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholin, diacetoneacrylamide, N -Methylol acrylamide, N-hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N-diallyl (meth) acrylamide, N-allyl (meth) acrylamide and the like can be mentioned.

Examples of styrene derivatives include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, Examples thereof include α-methylstyrene.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, phenyl vinyl ether and the like.

Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone and the like.

Examples of maleimides include maleimide, butylmaleimide, cyclohexylmaleimide, phenylmaleimide and the like.

Examples of the allyl compound include allyl acetate, allyl alcohol, allylamine, N-allylaniline, allyl chloride, allyl bromide and the like.

The vinyl resin having a hydroxyl group may contain a hydroxyl group so that the hydroxyl value (unit: mgKOH / g) is in the range of, for example, 800 to 1500. The hydroxyl value of the vinyl resin having a hydroxyl group may be, for example, 800 or more, 900 or more, 950 or more, or 1000 or more, and may be 1500 or less, 1400 or less, or 1300 or less. The hydroxyl value of the vinyl resin having a hydroxyl group may be, for example, 800 to 1500, 900 to 1400, 950 to 1300, or 1000 to 1300. The hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070. Further, when a vinyl resin is synthesized and used, the hydroxyl value can be calculated from the monomer composition used.

When the vinyl resin having a hydroxyl group is a resin obtained by saponifying a polymer of an esterified product of an alcohol having a polymerizable double bond, the weight average molecular weight of the vinyl resin having a hydroxyl group is the vinyl resin before the saponification treatment. It can be converted from the weight average molecular weight of. The polystyrene-equivalent weight average molecular weight of the vinyl resin (vinyl resin having an acetoxy group (CH ₃ C (= O) O-)) before the saponification treatment by GPC (gel permeation chromatography) is not particularly limited, but is 300 or more. It may be 4000 or less.

The vinyl resin having a hydroxyl group is preferably a vinyl resin having a structural unit A (also referred to as partial structure A) represented by the following formula (1) (hereinafter, also referred to as “vinyl resin A”). In this case, since the vinyl resin A has a hydroxyl group, not only the cohesive force of the vinyl resin is improved by the interaction between the hydroxyl groups, but also the affinity with the 3-octahedral smectite is increased, and therefore the gas barrier is even higher. It will exert its sexuality. Further, since the vinyl resin A has the structural unit (A), not only the solubility in alcohol is improved, but also the resin composition can be imparted with water resistance, so that it has a water vapor barrier property and oxygen under high humidity. Further improvement in barrier properties can be expected.

式（１）中、ｍは、０又は１を表し、＊は、結合手を表す。ｍは、好ましくは０である。

In the formula (1), m represents 0 or 1, and * represents a bond. m is preferably 0.

When the vinyl resin having a hydroxyl group contains the structural unit A, the content of the structural unit A is preferably 85 mol% or more, more preferably 90 mol% or more, based on the total molar amount of the hydroxyl groups in the vinyl resin having a hydroxyl group. More preferably, it is 95 mol% or more, and preferably 99 mol% or less. The content of the structural unit A is preferably 85 mol% or more and 99 mol% or less, and more preferably 90 mol% or more and 99 mol% or less, based on the molar amount of the total hydroxyl group in the vinyl resin having a hydroxyl group. The content of the structural unit A in which m is 0 is preferably in the above range.

The vinyl resin having a hydroxyl group may contain a structural unit (other structural unit) other than the structural unit A. The other structural unit may be, for example, a structural unit B (also referred to as a partial structure B) represented by the following formula (2). The vinyl resin having a hydroxyl group preferably contains the structural unit A and further preferably the structural unit B. In one embodiment, the vinyl resin having a hydroxyl group may consist of only structural unit A and structural unit B. When the vinyl resin having a hydroxyl group contains the structural unit B, the film-forming property, the film strength, and the adhesiveness of the resin composition when formed into a molded product are further improved.

In the formula (2), R ¹ represents a hydrogen atom and an alkyl group having 1 to 2 carbon atoms, n represents 0 or 1, and * represents a bond. Specifically, R ¹ is a hydrogen atom, a methyl group or an ethyl group, and n is preferably 0. R ² is a hydrogen atom or an acetyl group. Here, R ¹ and R ² do not become hydrogen atoms at the same time.

The content of the structural unit B is 1 mol% or more with respect to the total molar amount of the hydroxyl groups in the vinyl resin having a hydroxyl group from the viewpoint of excellent water resistance. The content of the structural unit B is preferably 30 with respect to the total molar amount of the hydroxyl groups in the vinyl resin having a hydroxyl group from the viewpoint of excellent film forming property, film strength, adhesiveness of the composition, etc. when formed into a molded product. It is mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less. The content of the structural unit B is preferably 1 mol% or more and 30 mol% or less, more preferably 1 mol% or more and 15 mol% or less, and more preferably 1 mol% or more and 15 mol% or less, based on the molar amount of the entire hydroxyl group in the vinyl resin having a hydroxyl group. Is 1 mol% or more and 10 mol% or less. It is preferable that the content of the structural unit B in which R ¹ is a hydrogen atom, R ² is an acetyl group, and n is 0 is in the above range.

When the vinyl resin having a hydroxyl group contains structural units A and B, the molar% (A / (A + B) × 100) of the content of structural unit A with respect to the total content of structural unit A and structural unit B is gas barrier property. Is preferably 85 mol% or more and 99 mol% or less from the viewpoint of further improvement.

The method for producing the vinyl resin having the structural unit A and / or the structural unit B is not particularly limited, and the vinyl resin can be produced by a known and commonly used method. For example, a vinyl resin having a hydroxyl group can be produced by polymerizing an esterified product of a hydroxyl group-containing vinyl monomer corresponding to the structural unit A or B and then performing a saponification treatment.

Examples of the hydroxyl group-containing vinyl monomer corresponding to the structural unit A include vinyl alcohol, allyl alcohol, and crotyl alcohol. The ester in the esterified product of the hydroxyl group-containing vinyl monomer corresponding to the structural unit B may be an ester as exemplified above. Among the esterified products of the hydroxyl group-containing vinyl monomer corresponding to the structural unit B, vinyl acetate, allyl acetate, or crotyl acetate, which are acetates, are preferable. One type of these may be used, or two or more types may be used in combination.

Examples of the hydroxyl group-containing vinyl monomer corresponding to the structural unit B include isopropenyl alcohol, metallic alcohol, isobutenyl alcohol and the like. The esters in the esterified product of the hydroxyl group-containing vinyl monomer corresponding to the structural unit A are acetic acid ester, propanoic acid ester, butanoic acid ester, 2-methylpropanoic acid ester, pentanoic acid ester, 3-methylbutanoic acid ester, 2,2-. Examples thereof include dimethylpropanoic acid ester, hexanoic acid ester, cyclohexylcarboxylic acid ester, and benzoic acid ester. Among the esterified products of the hydroxyl group-containing vinyl monomer corresponding to the structural unit A, isopropenyl acetate, metharyl acetate, or isobutenyl acetate, which are acetic acid esters, are preferable. These may be used alone or in combination of two or more.

The vinyl resin having a hydroxyl group may be a homopolymer obtained by polymerizing a single monomer, or may be a copolymer obtained by copolymerizing a plurality of types of monomers. At this time, as the vinyl monomer, a monomer having each of a vinyl group, a (meth) allyl group, and a (meth) acryloyl group may be used in combination.

A vinyl resin having a hydroxyl group can be obtained by polymerizing a vinyl monomer by radical polymerization, anionic polymerization, cationic polymerization or the like. A polymerization initiator may be used at the time of polymerization. Examples of the polymerization initiator include a thermal radical polymerization initiator, a photoradical polymerization initiator, an anionic polymerization initiator and a cationic polymerization initiator.

Examples of the thermal radical polymerization initiator include peroxides such as t-butyl peroxybenzoate, di-t-butyl peroxide, cumemper hydroxide, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide; azobisisobutylnitrile, Examples thereof include azo compounds such as azobis-2,4-dimethylvaleronitrile and azobiscyclohexanecarbonitrile.

Examples of the photoradical polymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 2,2-dimethoxy-1,2-diphenylethane-. Examples thereof include 1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like.

Examples of the anion polymerization initiator include organic alkali metals such as methyllithium, n-butyllithium, sec-butyllithium and t-butyllithium; organic alkaline earth metals such as methylmagnesium chloride and methylmagnesium bromide; lithium, sodium and potassium. Alkali metals such as, etc. can be mentioned.

Cationic polymerization initiators include protonic acids such as hydrochloric acid, sulfuric acid, perchloric acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid, fluorosulfonic acid; boron trifluoride, aluminum chloride, tetrachloride. Examples thereof include Lewis acids such as titanium, ferric chloride and ferric chloride.

In the embodiment, one kind of vinyl resin may be used alone, or a plurality of vinyl resins may be used in combination. The vinyl resin may be a linear polymer or a branched polymer. When the vinyl resin is a branched polymer, it may be comb-shaped or star-shaped.

The content of the vinyl resin having a hydroxyl group is 30% by mass or more, or 40% by mass or more, from the viewpoint that the water vapor barrier property and the oxygen barrier property are further excellent with respect to the total amount of the non-volatile content in the resin composition. It may be 95% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less from the viewpoint of further improving the moldability of the resin composition.

<Solvent>
The resin composition further contains a solvent. The solvent contains alcohol from the viewpoint of excellent drying property of the coating film. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, and methoxypropanol (1-methoxy-2-propanol, etc.). The alcohol may contain one kind alone or a combination of two or more kinds.

As the solvent, in addition to alcohol, for example, water, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like can be used. It may be further contained. Water, acetone, dimethylformamide and acetonitrile are preferred.
When used in combination with alcohol, water is preferably 45-55%, acetone is 5-10%, dimethylformamide is 5-20%, and acetonitrile is preferably 5-30% with respect to the total amount of the solvent.

The alcohol content is 20% by mass or more from the viewpoint of the effect of obtaining a good thixotropy index with respect to the total amount of the solvent, and is preferably 25% by mass from the viewpoint of more preferably exerting the effect. That is all. The alcohol content is 55% by mass or less from the viewpoint of the effect of being excellent in oxygen barrier property and water vapor barrier property with respect to the total amount of the solvent. The alcohol content may be 20 to 55% by mass and 25 to 55% by mass with respect to the total amount of the solvent.

The alcohol may contain ethanol from the viewpoint of being more excellent in drying property (blocking property). The alcohol may contain only ethanol, and may contain ethanol and alcohols other than ethanol. The alcohol other than ethanol may be, for example, at least one selected from the group consisting of methanol, 1-propanol, 2-propanol, and methoxypropanol. The content of ethanol in the alcohol may be 50% by mass or more, 80% by mass or more, 95% by mass or more, or 100% by mass with respect to the total amount of alcohol.

The content of the non-volatile component of the resin composition may be 1 to 10% by mass, preferably 2 to 9% by mass, and more preferably 6 to 9% by mass with respect to the total amount of the resin composition. ~ 9% by mass.

<Polycarboxylic acid>
The resin composition further contains a polycarboxylic acid. As used herein, the polycarboxylic acid means a compound having two or more carboxyl groups. As the polycarboxylic acid, a resin having two or more carboxyl groups (excluding vinyl resins having a hydroxyl group and a carboxyl group) can be used. Examples of the polycarboxylic acid include polyacrylic acid, polymaleic acid, polyaspartic acid, or a copolymer of polyacrylic acid and polymaleic acid.

The content of the polycarboxylic acid may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, and 30% by mass or less, based on the total content of the vinyl resin having a hydroxyl group and the polycarboxylic acid. It may be 25% by mass or less, or 20% by mass or less. When the resin composition contains a vinyl resin having a hydroxyl group and a resin other than the polycarboxylic acid (other resin), the content of the polycarboxylic acid is the total content of the vinyl resin having a hydroxyl group, the polycarboxylic acid and the other resin. It may be within the above range with respect to the amount.

<Other ingredients>
The resin composition may further contain a modifier. Examples of the modifier include a coupling agent, a silane compound, an acid anhydride and the like. When the resin composition contains these modifiers, the wettability of the 3-octahedral smectite is improved, and the dispersibility in the resin composition is further improved. As the modifier, one type may be used alone, or a plurality of types may be used in combination.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like.

Examples of the silane coupling agent include an epoxy group-containing silane coupling agent, an amino group-containing silane coupling agent, a (meth) acrylic group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent. Examples of the epoxy group-containing silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4 epoxycyclohexyl). ) Ethyltrimethoxysilane and the like. Examples of the amino group-containing silane coupling agent include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-triethoxysilyl-N- (1,3-dimethyl). Butylidene) Propylamine, N-phenyl-γ-aminopropyltrimethoxysilane and the like can be mentioned. Examples of the (meth) acrylic group-containing silane coupling agent include 3-acryloyloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane. Examples of the isocyanate group-containing silane coupling agent include 3-isocyanatepropyltriethoxysilane and the like.

Examples of the titanium coupling agent include isopropyltriisostearoyl titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyldiacyl titanate, isopropyltris (dioctylpyrophosphate) titanate, and tetraoctylbis (ditridecyl). Examples thereof include phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.

Examples of the zirconium coupling agent include zirconium acetate, ammonium zirconium carbonate, zirconium fluoride and the like.

Examples of the aluminum coupling agent include acetalkoxyaluminum diisopropyrate, aluminum diisopropoxymonoethylacetate, aluminumtrisethylacetate, aluminumtrisacetylacetonate and the like.

Examples of the silane compound include alkoxysilane, silazane, and siloxane. Examples of alkoxysilanes include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and hexyltri. Examples thereof include methoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane and the like. Examples of the silazane include hexamethyldisilazane and the like. Examples of the siloxane include hydrolyzable group-containing siloxane.

Examples of acid anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methyl. Hexahydrophthalic anhydride alkenyl succinic anhydride and the like can be mentioned.

The content of the modifier is preferably 0.1 to 30% by mass with respect to the total amount of the 38-octahedral smectite. When the content of the modifier is 0.1% by mass or more, the dispersibility of the 3-octahedral smectite in the resin composition becomes better. When the content of the modifier is 30% by mass or less, the influence of the modifier on the mechanical properties of the resin composition can be further suppressed. The blending amount of the modifier is preferably 0.3 to 20% by mass, more preferably 0.5 to 15% by mass.

The resin composition may contain various additives (excluding vinyl resins having hydroxyl groups, trihahedral smectites, modifiers and compounds corresponding to solvents). Additives include, for example, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, etc. Examples thereof include oxygen scavengers (compounds having an oxygen scavenging function), antistatic agents and the like. These various additives are used alone or in combination of two or more.

Among the additives, examples of the inorganic filler include inorganic substances such as metals, metal oxides, resins and minerals, and composites thereof. Specific examples of the inorganic filler include alumina, titanium, zirconia, copper, iron, silver, mica, talc, aluminum flakes, glass flakes, clay minerals and the like. Among these, clay minerals may be used in combination for the purpose of improving the gas barrier property.

Examples of the compound having an oxygen trapping function include low molecular weight organic compounds that react with oxygen such as hindered phenol compounds, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, and pyrogallol, and cobalt, manganese, nickel, and iron. , Transition metal compounds such as copper and the like.

Examples of the tackifier include xylene resin, terpene resin, phenol resin, rosin resin and the like. By adding a tackifier, the tackiness to various film materials immediately after application can be improved. The amount of the tackifier added is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin composition.

<Molded body>
The molded product of the embodiment can be obtained by molding the above-mentioned resin composition. The molded product may be made of a resin composition, or may be made of a cured product of the resin composition. The molding method is arbitrary and may be selected in a timely manner depending on the intended use. The shape of the molded body is not limited, and it may be in the form of a plate, a sheet, or a film, may have a three-dimensional shape, may be coated on a base material, and may be a base material. It may be molded so as to exist between the substrates.

When producing a plate-shaped or sheet-shaped molded body, the resin composition is molded by using, for example, an extrusion molding method, a flat press, a deformed extrusion molding method, a blow molding method, a compression molding method, a vacuum molding method, an injection molding method, or the like. There is a way to do it. When producing a film-shaped molded product, for example, melt extrusion method, solution casting method, inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotary molding, Coating molding can be mentioned. When the resin composition is cured by heat or active energy rays, the resin composition may be molded by various curing methods using heat or active energy rays.

When the resin composition is liquid, it may be molded by coating. As a coating method, a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, a doctor blade method, a curtain coating method, a slit coating method, a screen printing method, an inkjet method, a dispense method, etc. Can be mentioned.

<Laminated body>
The laminate of the embodiment includes a base material and the molded product described above on the base material. The laminated body may have a two-layer structure or may have a three-layer structure or more.

The material of the base material is not particularly limited and may be appropriately selected depending on the intended use. Examples thereof include wood, metal, plastic, paper, silicon and modified silicon, and the base material obtained by joining different materials. There may be. The shape of the base material is not particularly limited, and may be any shape depending on the purpose, such as a flat plate, a sheet shape, or a three-dimensional shape having a curvature on the entire surface or a part thereof. Further, there are no restrictions on the hardness, thickness, etc. of the base material.

The laminated body can be obtained by laminating the above-mentioned molded body on the base material. The molded product to be laminated on the base material may be formed by direct coating or direct molding on the base material, or the molded product of the resin composition may be laminated. In the case of direct coating, the coating method is not particularly limited, and the spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, etc. Examples include a screen printing method and an inkjet method. In the case of direct molding, in-mold molding, insert molding, vacuum forming, extrusion laminating molding, press molding and the like can be mentioned. When a molded product made of a cured product of a resin composition is laminated, an uncured or semi-cured resin composition layer may be laminated on a substrate and then cured, or a cured product layer obtained by completely curing the resin composition. May be laminated on the substrate.

Further, the laminate may be obtained by applying a substrate precursor to a cured product of the resin composition and curing it, and the substrate precursor or the resin composition is uncured or semi-cured. It may be obtained by adhering in a state and then curing. The precursor of the base material is not particularly limited, and examples thereof include various curable resin compositions. Further, a laminate may be prepared by using the resin composition of the embodiment as an adhesive.

<Gas barrier material>
Since the resin composition is excellent in water vapor barrier property and oxygen barrier property, it can be suitably used as a gas barrier material. The gas barrier material may be any material containing the above-mentioned resin composition.

<Coating agent>
The resin composition can be suitably used as a coating agent. The coating agent may be any one containing the above-mentioned resin composition. The coating method of the coating agent is not particularly limited. As a specific method, various coating methods such as roll coating and gravure coating can be exemplified. Further, the coating device is not particularly limited. Since the resin composition has a high gas barrier property, it can be suitably used as a coating agent for a gas barrier.

<Adhesive>
Since the resin composition has excellent adhesiveness, it can be suitably used as an adhesive. The form of the adhesive is not particularly limited, and it may be a liquid or paste-like adhesive, or it may be a solid adhesive. Since the resin composition has a high gas barrier property, this adhesive can be suitably used as an adhesive for a gas barrier.

In the case of a liquid or paste-like adhesive, the method of use is not particularly limited, but the adhesive may be adhered and cured after being applied to the adhesive surface or injected into the interface of the adhesive surface.

In the case of a solid adhesive, an adhesive formed into a powder, a chip, or a sheet may be placed at the interface of the adhesive surface and thermally melted to adhere and cure.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

<Preparation of resin composition>
The following vinyl resins 1 and 2 were prepared as vinyl resins.
-Vinyl resin 1 (polyvinyl alcohol, hydroxyl value: 1250, manufactured by Japan Vam & Poval Co., Ltd., JF-03)
-Vinyl resin 2 (polyvinyl alcohol, hydroxyl value: 1000, manufactured by Japan Vam & Poval Co., Ltd., JP-05)

65 parts by mass of ion-exchanged water and 25 parts by mass of 1-propanol are mixed, and 8.1 parts by mass of vinyl resin 1 and 1.9 parts of polyacrylic acid (Julimer AC-10L manufactured by Toa Synthetic Co., Ltd.) are added thereto. A part by mass was added, and the mixture was heated at 85 ° C. for 5 hours to obtain a resin solution 1. Resin solutions 2 to 5 were prepared in the same manner except that the formulations shown in Table 1 (unit: parts by mass) were used.

Using ion-exchanged water, ethanol, 1-propanol, and 3-octahedral smectite, viscosity dispersions 1 to 9 were prepared based on the blending amounts shown in Table 2. The 3 octahedral smectites used are as follows.
Sodium-type hectorite 1 (Na-HTT ₁ ): NHT-CF manufactured by Topy Industries, Ltd., aspect ratio 5000, sodium ion equivalent 110 meq / 100 g
Ammonium type hectorite ₁ (NH 4 -HTT _1): obtained by the Na-HTT ₁ by ion exchange. Ammonium ion equivalent 110 meq / 100 g.
Lithium-type hectorite 1 (Li-HTT ₁ ): Obtained by ion exchange of the above Na-HTT _1. Lithium ion equivalent 110meq / 100g
Sodium-type hectorite 2 (Na-HTT ₂ ): Laponite RD manufactured by BYK, aspect ratio 50, sodium ion equivalent total 110 meq / 100 g

The resin solutions (10 parts by mass) and clay dispersion (1.4-20 parts by mass) shown in Tables 1 and 2 are combined to form the resins of the types shown in Tables 3-1 to 3-3. Compositions were prepared and each was evaluated.
Table 3 shows the content of polycarboxylic acid with respect to the total content of vinyl resin having a hydroxyl group and polycarboxylic acid, the content of 3 octahedral smectite with respect to the total amount of non-volatile content (components other than solvent), and the content of alcohol with respect to the total amount of solvent. The content, the content of ethanol with respect to the total amount of alcohol, and the content of non-volatile components (components other than solvent) in the resin composition are also shown.

Moreover, the resin composition obtained by the above-mentioned method was used as a coating liquid. The amount of coating after drying each coating liquid on the corona-treated surface of a corona-treated 12 μm PET (polyethylene terephthalate) film (trade name: E-5100, manufactured by Toyobo Co., Ltd.) is 0. It was coated so as to be .5 g / m ^2. Immediately after coating, the PET film after coating was heat-treated in a dryer at 80 ° C. for 1 minute. As a result, a molded product of each resin composition was formed on the PET film to obtain a laminated film.

<Evaluation>
The obtained laminated film was evaluated for oxygen permeability and water vapor permeability. The evaluation results are shown in Tables 3-1 to 3-3. The evaluation of oxygen permeability and water vapor permeability was carried out by the following method.

(Measurement of oxygen permeability)
The oxygen permeability is measured according to JIS-K7126 (isopressure method), using the oxygen permeability measuring device "OX-TRAN1 / 50" manufactured by Mocon, at a temperature of 23 ° C., 75% RH, and a temperature of 23 ° C. , 90% RH atmosphere. In addition, RH represents relative humidity.

(Measurement of water vapor permeability)
The measurement of the water vapor transmittance was carried out in an atmosphere of 40 ° C. and 90% RH using a moisture permeable cup according to "Method for Permeation Humidity Test of Moisture-Proof Packaging Material" JIS Z0208.

(Measurement of film forming property)
The coated surface of the obtained laminated film was observed with an optical microscope, and the film-forming property was evaluated as "A" when the coated surface was smooth and "B" when the coated surface was not smooth. In addition, the case where the film could not be formed was evaluated as "C".

(Measurement of blocking property)
Immediately after preparing the laminated film, it was heat-treated in a dryer at 60 ° C. for 5 seconds, immediately folded in three, and weighted at 5 kgf for 24 hours. After that, the laminated body Y folded in three is opened, and at that time, "A" if there is no resistance or sound between the coated surface and the base material surface, and "B" if there is no resistance but there is sound. , When the film was stuck, it was evaluated as "C" to evaluate the blocking property.

(Evaluation of thixotropy index)
The viscosity of the coating liquid was evaluated from the thixotropy index (TI). TI was calculated from the ratio of viscosity values at 6 rpm and 60 rpm (viscosity at 6 rpm / viscosity at 60 rpm) using a B-type viscometer. The evaluation was made on the following three stages.
A: TI is less than 2 B: TI is 2 or more and less than 3 C: TI is 3 or more

Since the resin composition of the present invention can provide a coating film having excellent barrier properties under high humidity, it can be suitably used as a gas barrier material. Further, since it is excellent in quick-drying property at the time of coating, it can be suitably used as a coating agent, and a laminate having the resin composition of the present invention or a coating agent containing the resin composition as a coating film (coating layer). Can be suitably used as a packaging material.

Claims (9)

3 Contains octahedral smectite, vinyl resin having a hydroxyl group, and a solvent.
The 3 octahedral smectite is a 3 octahedral smectite having an aspect ratio of 1000 or more and 15000 or less, which contains at least one selected from the group consisting of sodium ion, ammonium ion, and lithium ion as interlayer ions.
The solvent contains alcohol
A resin composition in which the content of the alcohol is 25 to 55% by mass with respect to the total amount of the solvent. The resin composition according to claim 1, wherein the 3 octahedral smectite is hectorite. The resin composition according to claim 1 or 2, further containing a polycarboxylic acid. The resin composition according to any one of claims 1 to 3, wherein the vinyl resin has a hydroxyl value of 800 to 1500. A gas barrier material containing the resin composition according to any one of claims 1 to 4. A coating agent containing the resin composition according to any one of claims 1 to 4. A laminate having a base material and a coating layer obtained by coating the coating agent according to claim 6 on the base material. The laminate according to claim 7, wherein the coat layer has a thickness of 0.1 to 5 μm. The laminate according to claim 7 or 8, which is used as a packaging material.