JPH11256094A - Surface-treated resin molded item - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molded item having an excellent O2 impermeability even in a high-humidity atmosphere by forming a surface-treated layer comprising a specific ratio of an organic metal compound and a (meth)acrylic polymer and a solvent and giving a specific O2 permeability. SOLUTION: This surface-treated resin molded item has a surface-treated layer comprising an organic metal compound and/or its hydrolyzed condensate of formula I: R<1> O1M(OR<2> )n (wherein M is a metallic element [e.g. Si]; R<1> is H, a lower alkyl, an aryl, vinyl, SH bonded directly to a C chain or 4 (meth) acryloyl; R<2> is H, a lower alkyl or the like; m is 0 or more; n is 1 or more; and m+n is equal to the valence of M), a (meth)acrylic polymer having one or more kinds of functional groups selected from the group of carboxyl, hydroxy and amide (e.g. polyacrylamide), and a solvent (e.g. water) where the ratio of the organic metal compound and/or its hydrolyzed condensate to the (meth) acrylic polymer is shown in the formula. The surfacetreated resin molded item has an O2 permeability at 20 deg.C, 90% RH of not more than 20 cc/m<2> .24 hr.atm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated resin laminate having a gas-barrier surface-treated layer capable of exhibiting the same level of oxygen permeability as a low-humidity atmosphere even in a high-humidity atmosphere. is there.

[0002]

2. Description of the Related Art There is an increasing demand for gas barrier materials having extremely low permeability of gases such as oxygen, nitrogen, carbon dioxide, water vapor and the like in the field of packaging materials and the like. In order to impart gas barrier properties to a resin molded article such as a plastic film or sheet, an ethylene-vinyl alcohol copolymer,
Forming molded objects with gas-impermeable materials such as vinylidene chloride copolymer and polymethaxylylene adipamide; laminating or coating these gas-impermeable materials with other materials; film-forming aluminum foil There are known methods of laminating a metal oxide and vapor-depositing a metal oxide.

[0003] However, among the gas-impermeable materials, ethylene-vinyl alcohol copolymer and polymethaxylylene adipamide have a large hygroscopic property, and there is a problem that the gas barrier property is greatly reduced with the moisture absorption. Since the vinylidene chloride-based copolymer contains a chlorine atom, it may cause pollution. In addition, with the aluminum foil laminated film, the packaged contents cannot be seen from the outside,
The metal vapor-deposited film has a problem that the vapor-deposited layer is easily cracked at the time of packaging since the flexibility or the like is lowered, and the gas barrier property is lowered.

[0004] In order to solve these problems, it has been studied to perform a surface treatment of a plastic film using a polysiloxane having a dense molecular structure and having excellent weather resistance, hardness and chemical resistance. . For example, the present inventors have already filed applications for polysiloxane-based surface treatment compositions (Japanese Patent Application Laid-Open Nos. 8-165365 and 8-1653).
No. 66 etc.). These inventions disclose compositions containing a silane compound having an amino group and a compound having reactivity with an amino group as essential components, and have a water vapor permeability resistance and an oxygen permeability resistance under a high humidity atmosphere. Was successfully improved. However, the silane compound having an amino group is relatively expensive, and thus has a commercial problem that it is difficult to be used widely while having high performance.

[0005]

In the present invention, a new composition capable of exhibiting excellent oxygen permeation resistance even in a high-humidity atmosphere was found, and a gas-barrier surface-treated resin molding applicable to various fields was found. The challenge was to provide the body.

[0006]

Means for Solving the Problems The surface-treated resin molded product of the present invention comprises a solvent, an essential component (A): an organometallic compound represented by the following general formula (I) and / or a hydrolytic condensate thereof; ¹ _mM (OR ² ) _n (I) wherein M is a metal element and R ¹ may be the same or different and is a mercapto directly bonded to a hydrogen atom, a lower alkyl group, an aryl group, a vinyl group or a carbon chain. Represents a group or a (meth) acryloyl group, R ² may be the same or different and represents a hydrogen atom, a lower alkyl group or an acyl group, m is 0 or a positive integer, n is an integer of 1 or more,
And m + n is equal to the valence of the metal element M], and (B) a (meth) acrylic polymer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an amide group,

[0007]

(Equation 2)

Having a surface treatment layer formed from a composition for surface treatment containing at 20 ° C., 90% RH
Oxygen permeability at 20cc / m ² · 24hrs · atm
The following are the features that have the greatest features.

By combining an organometallic compound and / or a hydrolytic condensate thereof and a (meth) acrylic polymer having a highly polar functional group at a specific ratio, a low oxygen permeability even under a high humidity atmosphere can be obtained. A gas barrier layer can be formed.

The constitution in which the (meth) acrylic polymer (B) is polyacrylamide and the constitution in which m in the general formula representing the organometallic compound (I) is 0 are both preferred embodiments of the present invention. . A surface-treated resin molded article having an oxygen permeability at 20 ° C. and 90% RH of 3.0 times or less the oxygen permeability at 20 ° C. and 0% RH is considered to exhibit more excellent oxygen permeability. It can be used preferably.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The surface-treated resin molded article of the present invention
It has a surface treatment layer formed from a composition for surface treatment comprising an organometallic compound and / or a hydrolytic condensate thereof and a (meth) acrylic polymer having a highly polar functional group as essential components. The organometallic compound is polymerized by a hydrolysis-condensation reaction that can also be caused by moisture in the air, and forms a dense three-dimensional cured product. However, even when the organometallic compound is used alone for forming the surface treatment layer, only a brittle film is obtained, and gas barrier properties cannot be exhibited. On the other hand, a (meth) acrylic polymer having a highly polar functional group often forms a film even when used alone, and the polar functional group forms a hydrogen bond, thereby exhibiting good gas barrier properties. In a humid atmosphere, the hydrogen bonding is broken, and the gas barrier properties are extremely deteriorated.
However, the present inventors have found that, by combining the two at a specific ratio, a surface treatment layer exhibiting good gas barrier properties in which oxygen permeability under a low-humidity atmosphere and under a high-humidity atmosphere does not significantly change can be obtained. . Hereinafter, the present invention will be described in detail.

The composition for surface treatment used in the present invention comprises:
In order to prevent an increase in oxygen permeability in a high humidity atmosphere, an organometallic compound represented by the following general formula (I) and / or a hydrolytic condensate thereof must be contained as an essential component (A). . R ¹ _mM (OR ² ) _n (I) wherein M is a metal element and R ¹ may be the same or different and is directly connected to a hydrogen atom, a lower alkyl group, an aryl group, a vinyl group or a carbon chain. Represents a mercapto group or a (meth) acryloyl group, R ² may be the same or different and represents a hydrogen atom, a lower alkyl group or an acyl group, m is 0 or a positive integer, and n is an integer of 1 or more. ,
And m + n matches the valence of the metal element M. ]
“Lower alkyl group” refers to an alkyl group having 1 to 5 carbon atoms.

In the above general formula (I), the metal element M is S
i, Ti, Zr, and Al are preferred. Specific examples include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and methyltributoxysilane in which M in the above formula is Si. , Ethyltrimethoxysilane,
Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,
Dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxy Silane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxy Alkoxysilanes such as silane, phenyltrimethoxysilane, phenyltriethoxysilane, etc .; tetrahydroxysilane; tetraacetoxysilane, methyltriace Acyloxysilanes such as xysilane; silanols such as trimethylsilanol; titanium alkoxides such as titanium tetraethoxide, titanium tetraisopropoxide and titanium tetrabutoxide where M is Ti; zirconium tetraethoxide where M is Zr; Zirconium alkoxides such as zirconium tetraisopropoxide and zirconium tetrabutoxide; aluminum alkoxides such as aluminum triethoxide, aluminum triisopropoxide and aluminum tributoxide wherein M is Al; and one or more of these. Can be used.

Among these organometallic compounds, the general formula
M (OR) where m in (I) is 0^Two ) _n (Note that M and R^Two 
And n have the same meanings as described above).
This is preferable because a dense film can be formed quickly. This
Is a tetraalkoxysila of the above
, Tetrahydroxysilane, tetraacetoxysila
, Titanium tetraalkoxides, zirconium
Tetraalkoxides, aluminum trialkoxides
Kind.

[0015] In order to prevent evaporation of unreacted organometallic compounds when the resin composition is coated with the surface treatment composition and then dried while undergoing polycondensation, the organometallic compounds must be hydrolyzed and condensed before coating. It is preferable that the molecular weight be increased to a high molecular weight. For this hydrolysis-condensation reaction, a known acid or base catalyst can be used, and it is advantageous to carry out the reaction in a solvent described below. When the composition for surface treatment contains an organometallic compound that has not been hydrolyzed and condensed, in order to promote hydrolytic condensation while maintaining the stability of the composition, acetic acid, hydrochloric acid, nitric acid and the like are used. It is preferred to add an inorganic acid as a catalyst to the composition. If the hydrolysis-condensation occurs too rapidly, the composition may gel before coating.

The second essential component of the composition for surface treatment used in the present invention is a (meth) acrylic polymer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an amide group. (B). Carboxyl, hydroxyl and amide groups form hydrogen bonds,
The gas barrier property of the film becomes good. Further, these polar groups also have a function of improving the adhesion between the surface treatment layer, the resin molded body, and another resin layer formed on the resin molded body. Furthermore, the composition has good storage stability even when mixed with the essential component (A) to form a composition for surface treatment. When a polymer having no polar group or a non- (meth) acrylic polymer is used, the stability of the composition is poor,
It is not preferable because the essential component (A) and the polymer are separated or gelled. If the stability of the composition is poor, a uniform film cannot be obtained or the coating itself becomes difficult when a surface treatment layer is formed by coating on a resin molded article. From these viewpoints, in the present invention, a (meth) acrylic polymer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an amide group is defined as the second essential component (B). .

The (meth) acrylic polymer is synthesized from a monomer having an acryloyl group or a methacryloyl group, that is, a (meth) acrylic monomer. A part or all of the monomer has a monomer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an amide group together with an acryloyl group or a methacryloyl group (monomer B -1).

As the carboxyl group-containing monomer, acrylic acid or methacrylic acid is used. As the hydroxyl group-containing monomer, 2-hydroxyethyl (meth) acrylate or 2-hydroxyethyl (meth) acrylate is used.
Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, caprolactone-modified hydroxy (meth) acrylate (for example, Daicel Manufactured by Kagaku Kogyo Co .; Plaxel FM) and the like. Examples of amide group-containing monomers include acrylamide, methacrylamide, methylalkoxy (meth) acrylamide, N, N
-Dimethylaminopropyl (meth) acrylamide,
N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diethylpropyl (meth) acrylamide and the like can be mentioned. One or more of these monomers B-1 may be mixed and used as a monomer component.

In order to synthesize the (meth) acrylic polymer, another (meth) acrylic monomer (hereinafter, referred to as monomer B-2) may be used together with the monomer B-1. . Specific examples of the monomer B-2 include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth)
Acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (Meth) acrylate alkyl esters such as (meth) acrylate, methylcyclohexyl (meth) acrylate, and tertiary butylcyclohexyl (meth) acrylate; epoxy group-containing monomers such as glycidyl (meth) acrylate; methacryloyloxyethyl acid phos (Meth) acryloyloxyalkyl acid phosphates such as phosphates and their alkylene oxide adducts, (meth) acryloyloxyalkyl acid phosphites Or an alkylene oxide adduct thereof, or a phosphoric acid group-containing ester compound of an epoxy group-containing vinyl monomer such as glycidyl (meth) acrylate or methyl glycidyl (meth) acrylate with phosphoric acid or phosphorous acid or an acid ester thereof. Monomer; N,
N'-dimethylaminoethyl (meth) acrylate; sulfoethyl (meth) acrylate; (meth) acrylonitrile; 2,4-dihydroxybenzophenone or 2,2 ', 4
-Trihydroxybenzophenone and glycidyl (meth)
2-hydroxy-4 obtained by reacting with acrylate
-[3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2,2'-dihydroxy-4
UV-absorbing monomers such as-[3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone.

In a small amount (about 10% by weight or less in the monomer component), aromatic monomers such as styrene, α-methylstyrene and vinyltoluene; vinyl esters such as vinyl acetate; Nitrogen-containing monomers such as vinylimidazole; halogen-containing monomers such as vinyl chloride and vinylidene chloride; vinyl ethers; (meth) acrylic monomers such as sulfonic acid group-containing monomers such as vinylsulfonic acid and styrenesulfonic acid A monomer other than the monomer may be copolymerized.

Preferred among the (meth) acrylic polymers of the essential component (B) are homopolymers of any one of the above monomers (B-1) or (B- 2 in 1)
It is a copolymer of at least one kind of monomer. Further, a copolymer of one or more monomers in (B-1) and one or more monomers in (B-2) is also preferably used.
The amount of the at least one kind of monomer is preferably larger than the amount of at least one kind of the monomer (B-2) in order to increase the number of polar functional groups in the polymer.

Among the (meth) acrylic polymers, the most preferred is polyacrylamide, which is a surface treatment layer that has very excellent properties such as storage stability, gas barrier properties and humidity dependency of the surface treatment composition. Can be formed. In addition, since the polarity of the amide group is large, the surface treatment layer adheres well to corona discharge treatment or the like even in a polyolefin-based molded article having poor adhesion.

The composition for surface treatment comprises an essential component (A) of an organometallic compound and / or a hydrolytic condensate thereof, and an essential component (B) of a (meth) acrylic polymer.

[0024]

(Equation 3)

It is necessary that it be contained so that
When (A) / (B) is less than 0.5, the gas barrier property in a high humidity atmosphere is deteriorated. However, (A) becomes (B)
If it exceeds 3.0 times, the amount of (B), that is, the (meth) acrylic polymer having a polar group decreases, and the gas barrier property itself becomes insufficient, which is not preferable. A more preferable ratio is such that (A) / (B) is in the range of 1.5 to 2.0.

The composition for surface treatment used in the present invention comprises:
In addition to the essential components (A) and (B), a solvent is contained,
It is in the form of a solution. This is because the presence of the solvent facilitates the hydrolysis-condensation reaction, and is easy to handle when coating on a resin molded product. Since the solvent volatilizes after coating, the solvent does not exist in the surface treatment layer of the surface-treated resin molded article.

The solvent is not particularly limited, but a solvent capable of dissolving or dispersing the essential components (A) and (B) is preferable. For example, methanol, ethanol,
2-propanol, butanol, alcohols such as ethylene glycol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene, benzene and xylene, hydrocarbons such as hexane, heptane and octane, and acetic acid Examples thereof include esters such as ethyl and butyl acetate, tetrahydrofuran, propyl ether, and water, and one or more of these can be used as a mixture.

The amount of the solvent may be appropriately set so that it is easy to handle at the time of coating and that curing and drying easily proceed at the time of forming a film.
Preferably, it is 50% by weight. If the amount is less than 5% by weight, thick coloring is difficult, and it is too thin to take a long time to dry.
If it exceeds 50% by weight, storage stability may be deteriorated.

The method for preparing the composition for surface treatment is not particularly limited. In addition, various inorganic and organic additives such as a curing catalyst, a wettability improver, a plasticizer, an antifoaming agent, and a thickener are added to the composition as needed, as long as the effects of the present invention are not impaired. May be.

The surface-treated resin molded article of the present invention is obtained by coating the surface-treating composition described above into a layered form on the resin molded article by means of coating or the like directly or via another layer, and then drying the composition. This is one in which a treatment layer is formed. The shape of the resin molded body is not particularly limited, such as a film or sheet or a container formed by a known method. The surface treatment layer is
What is necessary is just to form on at least any one surface of a resin molding.

Examples of the material resin for producing the resin molded product include ethylene-vinyl alcohol copolymer;
Polyvinylidene chloride resin; Polyolefin resin such as polyethylene and polypropylene; Polyethylene terephthalate, Polyethylene isophthalate, Polyethylene
Polyester resins such as 2,6-naphthalate, polybutylene terephthalate and copolymers thereof; polyoxymethylene; polyamide resins; polystyrene, poly (meth) acrylate, polyacrylonitrile, polyvinyl acetate, polycarbonate, cellophane, Polyimide, polyetherimide, polyphenylene sulfone,
Thermoplastic resins such as polysulfone, polyetherketone, ionomer resin, polyvinyl alcohol, and fluororesin; melamine resin, polyurethane resin, epoxy resin,
Thermosetting resins such as phenolic resins, unsaturated polyester resins, alkyd resins, urea resins, and silicon resins; rubbers, and the like; known additives such as antistatic agents, lubricants, ultraviolet absorbers, and coloring agents; May be included.

Further, a molded article in which two or more kinds of resins are composited and laminated may be used. For example, an anchor coat layer used for improving the adhesion between the surface treatment layer and the resin molded product is applied on the resin molded product, or a film obtained by laminating two or more films of different materials. As a lamination means, a dry lamination using a known adhesive, an extrusion lamination method, a hot melt lamination method, a coating method, or the like can be employed.

When the surface treatment layer is formed directly on the resin molding, a surface activation treatment such as a corona treatment or a glow discharge treatment may be performed in order to improve the adhesion between the resin molding and the surface treatment layer. Good.

On the other hand, an embodiment in which a surface treatment layer is formed via another layer without directly forming a surface treatment layer on the resin molding is also included in the surface treatment resin molding of the present invention. At this time, as the `` other layer '', an anchor coat layer used to improve the adhesion between the surface treatment layer and the resin molded body, a metal vapor deposition layer to further improve the gas barrier properties,
Paper and the like for giving a design property are included.

The method for coating the composition for surface treatment is not particularly limited, and may be a roll coating method, a dip coating method, a bar coating method, a die coating method, a spray coating method, a curtain flow coating method, or a combination thereof. It is good to adopt a method. The drying method is not particularly limited.

The thickness of the surface treatment layer after drying is 0.01 to
It is preferably about 20 μm. When the thickness is less than 0.01 μm, the film is not uniform and pinholes are easily generated. 20 μm
A larger thickness is not preferred because cracks are likely to occur. The thickness is preferably 10 μm or less, and more preferably 5 μm or less.

The surface-treated resin molded product of the present invention has a temperature of 20 ° C.
Oxygen permeability at ^{90% RH, 20cc / m 2} · 24h
It must be less than rs · atm. This is because if it exceeds this value, it cannot be said that the oxygen permeability under a high humidity atmosphere is low. Further, the oxygen permeability at 20 ° C. and 90% RH is preferably 3.0 times or less the oxygen permeability at 20 ° C. and 0% RH. That is, 20 ° C., 0% R
When the oxygen permeability OP1 at H and the oxygen permeability at 20 ° C. and 90% RH are defined as OP2, and “OP2 / OP1” is defined as “the degree of increase in oxygen permeability”, the degree of increase is 3.0 times. The following is preferred. This is an indication that the oxygen permeability under a low humidity atmosphere does not extremely increase even under a high humidity atmosphere.

[0038]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention.
Modifications and alterations that do not depart from the spirit described below are all included in the technical scope of the present invention. The evaluation method of the characteristics used in the examples is as follows.

<Storage stability> When the composition for surface treatment was prepared and stored at 23 ° C., it did not gel for 4 days or more, and it was evaluated as ○. .

<Transparency> The laminated films were compared visually, and those having no difference in transparency compared with those before lamination were evaluated as ○,
Those which produced cloudiness such as white turbidity were evaluated as x.

<Oxygen Permeability> The oxygen permeability was measured at 20 ° C. using 0% RH and 90% RH using an oxygen permeability measuring apparatus manufactured by MOCON. The unit of the measured value in the table is cc / m ² · 24 hrs · atm.

Example 1 While stirring at room temperature, polyacrylamide (molecular weight: 70,000 to 100,000, hereinafter abbreviated as PAAm) was dissolved in water, and
A weight% PAAm aqueous solution was prepared. To this aqueous solution, tetramethoxysilane (hereinafter abbreviated as MS) is added to SiO ₂ / P
AAm was added so as to be 0.67 (weight ratio). Acetic acid was added as a catalyst so as to be 0.1 mol% of MS. Stirring was continued until a transparent homogeneous solution was obtained, to obtain a composition 1 for surface treatment. This composition was coated on a polyethylene terephthalate film having a thickness of 12 μm so that the thickness after drying was 3 μm, dried at 100 ° C. for 5 minutes, and then aged at 60 ° C. for 3 days to obtain a surface-treated resin molded article 1. Obtained. The characteristics evaluation results are shown in Table 1.

Examples 2 to 11 and Comparative Examples 1 to 5 Surface treated resin moldings were obtained in the same manner as in Example 1 except that various conditions were changed as shown in Table 1. Table 1 shows the results of the property test evaluation.

[0044]

[Table 1]

In Table 1, the following abbreviations were used to express the surface treatment composition. MS: Tetramethoxysilane M51: "M-silicate 51" (manufactured by Tama Chemical; oligomer of tetramethoxysilane) ES: Tetraethoxysilane E40: "Silicate 40" (manufactured by Tama Chemical; oligomer of tetraethoxysilane) MS-GPS: Co-hydrolysis condensate of tetramethoxysilane and γ-glycidoxypropyltrimethoxysilane (MS: GPS = 8: 2 (weight ratio)) ES-TBO: Co-hydrolysis condensate of tetraethoxysilane and titanium tetrabutoxide (ES: TBO =
9: 1 (weight ratio) MS-MTS: Co-hydrolysis condensate of tetramethoxysilane and methyltrimethoxysilane (MS: MTS =
8: 2 (weight ratio)) PAAm: polyacrylamide HEA-MMA: copolymer of 2-hydroxyethyl acrylate and methyl methacrylate (HEA: MMA =
9: 1 (weight ratio) PA: polyacrylic acid PVA: polyvinyl alcohol

[0046]

The surface-treated resin molded article of the present invention can be prepared under a high humidity atmosphere by combining an organometallic compound and / or a hydrolytic condensate thereof with a (meth) acrylic polymer having a polar functional group. In this case, a surface treatment layer having sufficient oxygen permeability is formed on the resin molded body. The surface-treated resin molded article of the present invention exhibits the same degree of gas barrier properties under a low-humidity atmosphere and a high-humidity atmosphere, so that it is necessary to block oxygen in a high-humidity atmosphere as a packaging material, or as another material. It can be suitably used in various fields.

Claims (4)

[Claims] And 1. A solvent, the organometallic compound and / or a hydrolysis-condensation product represented by the following essential components (A) represented by the following general formula _{^{(I), R 1 m M}} (OR 2) n ... (I) [ wherein medium M represents a metal element, R ¹ may be identical or different, represent a hydrogen atom, a lower alkyl group, an aryl group, a mercapto group directly bonded to a vinyl group or a carbon chain, or a (meth) acryloyl group, R ² is May be the same or different and represent a hydrogen atom, a lower alkyl group or an acyl group, m is 0 or a positive integer, n is an integer of 1 or more,
And m + n is equal to the valence of the metal element M], and (B) a (meth) acrylic polymer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an amide group, (Equation 1) Characterized by having a surface treatment layer formed from a composition for surface treatment containing so as to have an oxygen permeability at 20 ° C. and 90% RH of 20 cc / m ² · 24 hrs · atm or less. Surface-treated resin moldings. 2. The surface-treated resin molded product according to claim 1, wherein the (meth) acrylic polymer (B) is polyacrylamide. 3. The surface-treated resin molded article according to claim 1, wherein m in the general formula (I) representing an organometallic compound is 0. 4. The oxygen permeability at 20 ° C. and 90% RH is as follows:
The surface-treated resin molded product according to any one of claims 1 to 3, which has an oxygen permeability at 20 ° C and 0% RH of 3.0 times or less.