JPH08295848A - Surface treating composition and molding of surface treated resin - Google Patents

Abstract

PURPOSE: To obtain a surface treating composition comprising an amino group- containing organic compound, a compound to be reacted with the compound, a hydrolyzable organometallic compound and a solvent, capable of forming a coating film excellent in gas barrier properties, transparency and flexibility. CONSTITUTION: This surface treating composition comprises (A) an organic compound (e.g. allylamine, a polyethyleneimine, etc.) containing a primary and/or a secondary amino group in the molecule and not containing a Si(OR<1> ) group (R<1> is H, a lower alkyl or an acyl), (B) a compound (e.g. phenyl glycidyl ether, γ-isocyanopropyltrimethoxysilane, etc.) containing a functional group to be reacted with the amino group of the component A, (C) an organometallic compound of the formula R<2> m M(OR<3> )n (M is a metal element; R<2> is H, a lower alkyl, an aryl, vinyl, etc.; R<3> is H, a lower alkyl or an acyl; (m) is 0 or a positive integer; (n) is an integer of >=1 and m+n is the valence of the metal element M) and/or its hydrolyzate condensate and (D) a solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treating composition capable of forming a film excellent in gas barrier property, transparency and flexibility, and a surface-treated resin molded product treated with the composition. .

[0002]

2. Description of the Related Art Demand for gas barrier materials having extremely low permeability to gases such as oxygen, nitrogen, carbon dioxide and water vapor is increasing in the field of packaging materials and the like. In order to impart a gas barrier property to a molding material such as a plastic film or sheet, an ethylene-vinyl alcohol copolymer,
Forming a molded body with gas impermeable material such as vinylidene chloride copolymer, aromatic nylon, etc., laminating or coating these gas impermeable materials on other materials, laminating aluminum foil on film material To do
Methods such as vapor deposition of metal oxides are known.

However, among the gas-impermeable materials, ethylene vinyl alcohol copolymer and aromatic nylon have poor moisture resistance, and there is a problem that the gas barrier property is significantly lowered as the humidity of the atmosphere increases. Since the vinylidene chloride-based copolymer contains chlorine atoms, it may cause pollution. Further, in the aluminum foil laminated film, the packaged contents cannot be seen from the outside, and the metal vapor-deposited film is inferior in flexibility, so that the vapor-deposited layer is apt to be cracked, which causes deterioration in gas barrier property. was there.

[0004]

In view of the above problems, the present invention forms a surface-treated film having excellent gas barrier properties, transparency, and flexibility that does not impair the physical properties of non-treated products. A second object of the present invention is to provide a surface-treating composition which can be obtained, and to provide a surface-treated resin molded article having such excellent properties.

[0005]

The surface treating composition of the present invention has a primary and / or secondary amino group in the molecule, and a Si (OR ¹ ) group (R ¹ is the same or different. Which may contain a hydrogen atom, a lower alkyl group or an acyl group), an organic compound (A), a compound (B) having a functional group capable of reacting with the amino group in the molecule, and the following general formula (I): An organometallic compound (C) and / or a hydrolyzed condensate thereof, R ² _m M (OR ³ ) _n ... (I) (wherein M is a metal element, R ² may be the same or different, Represents a hydrogen atom, a lower alkyl group, an aryl group, a vinyl group or a mercapto group directly bonded to a carbon chain, or a methacryloyl group, R ³ 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
Corresponds to the valence of the metal element M) and the solvent (D).

The organic compound (A) is preferably a high molecular weight organic compound, and most preferably a polyethyleneimine. The compound (B) has a functional group capable of reacting with an amino group and a Si (OR ⁴ ) group (R ⁴
Are preferably the same or different and each represent a hydrogen atom, a lower alkyl group or an acyl group), and epoxy as a functional group having a Si (OR ⁴ ) group and capable of reacting with an amino group. Most preferably, it is a compound having a group. Further, the composition may contain a cohydrolysis condensate of the compound (B) and the organometallic compound (C).

The present invention also includes a surface-treated resin molded product obtained by treating at least one surface of the resin molded product with the surface-treating composition within the scope of the present invention. A metal or metal oxide vapor deposition layer is laminated on the treated surface of the surface-treated resin molding,
On the treated surface of the surface-treated resin molded body or on the vapor deposition layer,
It may be a surface-treated resin molded product in which single or plural layers of thermoplastic resin are laminated. These surface-treated resin moldings are optimal as gas barrier materials.

[0008]

The organic compound (A) used in the present invention has a primary and / or secondary amino group in the molecule,
There is no particular limitation as long as the compound does not contain a Si (OR ¹ ) group (R ¹ may be the same or different and represents a hydrogen atom, a lower alkyl group or an acyl group). The organic compound (A) mainly plays a role of imparting flexibility to the formed film. Organic compound (A) is compound (B)
It must have the above-mentioned amino group as a reaction point with, but if a hydrolyzable Si (OR ¹ ) group is contained in the compound (A), the degree of cross-linking of the obtained coating will be close. The organic compound (A) is limited as described above because it becomes too much and the flexibility is lowered.

Specifically, allylamine, diallylamine, isopropylamine, diisopropylamine, iminobispropylamine, ethylamine, diethylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3-diethylaminopropylamine, di-2. -Ethylhexylamine, dibutylaminopropylamine, propylamine, dimethylaminopropylamine, methyliminobispropylamine,
3-methoxypropylamine, ethylenediamine, 1,
4-diaminobutane, 1,2-diaminopropane, 1,
Low molecular weight organic compounds such as 3-diaminopropane, hexamethylenediamine, ethanolamine, diethanolamine, polyethyleneimines such as Epomin series manufactured by Nippon Shokubai Co., Ltd. (Epomin SP-003, Epomin SP-0)
06, Epomin SP-012, Epomin SP-018,
Epomin SP-103, Epomin SP-110, Epomin SP-200, Epomin SP-300, Epomin SP
-1000, Epomin SP-1020, etc.), polyallylamines (for example, PAA-L, PAA-H manufactured by Nitto Boseki Co., Ltd.)
Etc.), homopolymers of amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, and these amino group-containing (meth) acrylates and other (meth) acrylates and ( Examples thereof include copolymers with (meth) acrylic acid and polymer organic compounds such as polyoxyethylene alkylamines.

When the formed coating film is used as a gas barrier material, it is preferable to select ethanolamine or the above high molecular weight organic compound as the organic compound (A). In order to improve the film forming property of the surface treatment composition, the organic compound (A) is preferably a high molecular weight organic compound, and further, the stability of the surface treatment composition and the gas barrier property of the obtained coating film are improved. The use of polyethyleneimines is particularly preferred in the present invention since they have been found to be good. Moreover, when using a high molecular organic compound as an organic compound (A), a preferable molecular weight is 250 to 200,000. More preferably, it is in the range of 250 to 100,000. If the molecular weight is less than 250, the formed film may be inferior in flexibility, and if it is more than 200,000, the formed film may be inferior in transparency.

The compound (B) used in the present invention is not particularly limited as long as it is a compound having a functional group capable of reacting with the amino group in the organic compound (A) in the molecule. The functional group is an epoxy group, a carboxyl group, an isocyanate group, an oxazolinyl group, or the like. Compound (B)
Was found to have the effect of enhancing the compatibilization of the organic compound (A) and the organometallic compound (C). Further, the compound (B) is a hydrolyzable condensed group Si (OR ⁴ ).
A group (R ⁴ may be the same or different, a hydrogen atom,
(Representing a lower alkyl group or an acyl group), hydrolysis and condensation proceeds before or after the reaction with the compound (A), and a hydrolyzable condensation group of the organometallic compound (C) described later. Since co-hydrolysis condensation occurs and polycondensation proceeds, a dense film can be quickly formed. When a low molecular weight compound is used as the compound (A), the compound (B) preferably has the above-mentioned hydrolyzable group, and is hydrolyzed and condensed before or after reacting the compound (A) with the compound (B). It is also preferable to carry out.

Specific examples of the compound (B) include phenylglycidyl ether, 2-ethylhexylglycidyl ether, glycerol diglycidyl ether, trimethylolpropane diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-. Hexanediol diglycidyl ether, ethylene glycol diglycidyl ether,
Glycidyl such as diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hydroquinone diglycidyl ether, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, pentaerythritol tetraglycidyl ether Ethers; glycidyl esters such as adipic acid diglycidyl ester and phthalic acid diglycidyl ester; β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriisopropoxysilane, β-
(3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ -Glycidoxypropyltriisopropoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and other epoxy groups and Si (OR ⁴ ) groups (R ⁴ has the same meaning as described above. ) Having a) (hereinafter sometimes abbreviated as an epoxy group-containing silane coupling agent); γ-isocyanopropyltrimethoxysilane, γ-isocyanopropyltriethoxysilane,
γ-isocyanopropylmethyldimethoxysilane, γ-
A silane coupling agent containing an isocyanate group such as isocyanopropylmethyldiethoxysilane and a Si (OR ⁴ ) group (R ⁴ has the same meaning as described above) (hereinafter may be abbreviated as an isocyanate group-containing silane coupling agent);
Isocyanates such as tolylene diisocyanate, 1,4-diphenyl methane diisocyanate, 1,5-naphthalene diisocyanate, triphenyl methane triisocyanate, tolidine diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate and the like, and one of these Alternatively, two or more kinds can be used. Further, the compound (B) may be a polymer organic compound having a functional group capable of reacting with an amino group, or a polymer organic compound further having a Si (OR ⁴ ) group.

In the present invention, since the reactivity with the amino group is good and the formed film has excellent moisture resistance,
It is preferable to use an epoxy group-containing silane coupling agent as the compound (B).

When an epoxy group-containing silane coupling agent or an isocyanate group-containing silane coupling agent is used as the compound (B) in the present invention, hydrolysis condensation is carried out before or after the reaction with the organic compound (A). Then, it is possible to carry out cohydrolysis condensation with the hydrolyzable condensation group of the organometallic compound (C) described later.

Organometallic compound (C) used in the present invention
Is not particularly limited as long as it is represented by the following general formula (I). R ² _m M (OR ³ ) _n (I) (wherein M is a metal element, R ² may be the same or different, and is directly bonded to a hydrogen atom, a lower alkyl group, an aryl group, a vinyl group or a carbon chain. Represents a mercapto group or a methacryloyl group, R ³ 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 the valence of the metal element M)

Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane. , Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane,
Diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, γ-mercaptopropyltrimethoxysilane, γ -Alkoxysilanes such as mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, titanium tetraethoxide,
Titanium tetraisopropoxide, titanium alkoxides such as titanium tetrabutoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium alkoxides such as zirconium tetrabutoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum tributoxide, etc. The aluminum alkoxides, the complex compounds thereof, methyltriacetoxysilane, trimethylsilanol, and the like, or high molecular weight organic compounds containing these compounds can be used, and one or more of these can be used. Among them, tetramethoxysilane and tetraethoxysilane are preferable from the viewpoint that the formed coating film has good moisture resistance.

In order to prevent evaporation of the organometallic compound (C) during drying during film formation, the organometallic compound (C) is preferably hydrolyzed and condensed beforehand. A known catalyst can be used for this hydrolysis condensation reaction, and it is advantageous to carry out the reaction in a solvent (D) described later. As the compound (B), Si (OR) such as epoxy group-containing silane coupling agent or isocyanate-containing silane coupling agent
⁴ ) When a group-containing compound is used, it is also possible to carry out co-hydrolysis condensation with the organometallic compound (C) in advance.
The organometallic compound (C) has an effect of improving the moisture resistance of the formed film.

The surface treating composition of the present invention comprises an organic compound (A), a compound (B), an organometallic compound (C) and a solvent (D) described below, and the total amount of each compound other than the solvent. (That is, corresponding to the solid content of the composition) is 100
The preferred amount of each compound used will be described in terms of% by weight. The organic compound (A) is preferably 1 to 40% by weight.
When the amount of the organic compound (A) is less than 1% by weight, the gas barrier property when the formed coating film is used as a gas barrier material is insufficient, and the flexibility of the coating film is lowered. If it exceeds 40% by weight, the water resistance of the formed film may be poor. The more preferable amount of (A) used is in the range of 5 to 30% by weight, and further preferably 5 to 20% by weight. The compound (B) is preferably 0.5 to 30% by weight. When the compound (B) is less than 0.5% by weight, the organic compound (A)
Since the organometallic compound (C) cannot be compatibilized with each other, the physical properties of the formed coating film are inferior, and when it is more than 30% by weight, the stability of the surface treatment composition is deteriorated. The more preferable amount of (B) used is in the range of 1 to 20% by weight, and further preferably 1 to 10% by weight.

The organometallic compound (C) is preferably 5 to 90% by weight. When the amount of the compound (C) is less than 5% by weight, the formed film has insufficient moisture resistance. However, if it is used in an amount of more than 90% by weight, the flexibility of the coating film decreases, which is not preferable. The more preferable amount of (C) used is in the range of 10 to 90% by weight, and further preferably 30 to 80% by weight.

The solvent (D) used in the present invention is not particularly limited, but includes organic compound (A), compound (B),
A solvent capable of dissolving or dispersing the organometallic compound (C) is preferable. For example, methanol, ethanol,
Alcohols such as 2-propanol, butanol and 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, acetic acid. Examples thereof include esters such as ethyl and butyl acetate, tetrahydrofuran, propyl ether, water and the like, and one kind or a mixture of two or more kinds thereof can be used.

The method of preparing the composition of the present invention is not particularly limited, but a method of previously reacting the organic compound (A) with the compound (B) and then adding the organometallic compound (C), or a method of adding the organic compound (A) A method of hydrolyzing (C) [when [(B) has a hydrolyzable group, (B) also]] while reacting compound (B) with organometallic compound (C) in the presence,
It is preferably used in order to enhance the stability of the surface treatment composition.

To the surface-treating composition of the present invention, various inorganic or organic additives such as a curing catalyst, a wettability improving agent, a plasticizer, a defoaming agent and a thickening agent are added within a range that does not impair the effects of the present invention. Agents can be added as needed.

The substrate coated with the surface treatment composition of the present invention is not particularly limited, but a resin molded product is preferable. The type of resin forming the molded body is not particularly limited, and examples thereof include polyolefin resins such as polyethylene and polypropylene, polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate and copolymers thereof. Thermoplastics such as polyester resin, polyamides, polystyrene, poly (meth) acrylic acid ester, polyacrylonitrile, polyvinyl acetate, polycarbonate, cellophane, polyimide, polyetherimide, polysulfone, polyetherketone, ionomer resin, fluororesin Examples thereof include resins and thermosetting resins such as melamine resins, polyurethane resins, epoxy resins, phenol resins, unsaturated polyester resins, urea resins, alkyd resins, and silicon resins. In addition to the resin molded body, it is also possible to use, for example, a metal plate of aluminum, stainless steel, steel or the like or a plated material thereof, or paper or a textile product as a base material. The shape of the molded body can be selected according to the application such as a film shape, a sheet shape, and a bottle shape. A thermoplastic film is particularly preferable because it is easy to process.

The method for coating the above-mentioned substrate with the composition for surface treatment is not particularly limited, and for example, a roll coating method, a dip coating method, a bar coating method, a die coating method, or a combination thereof can be employed. Among them, the die coating method is preferable because it increases the stability of the surface treatment composition. Before coating, the resin molding may be subjected to surface activation treatment such as corona treatment, or known anchor treatment such as urethane resin. Further, after coating the resin composition with the surface treatment composition, laminating treatment or other known treatment may be performed.

After coating the surface treating composition, the coating is cured and dried, but if it is desired to cure and dry it more quickly, it is preferable to heat it at a temperature not higher than the heat resistant temperature of the resin molding. Further, if humidification is performed in addition to heating, curing and drying are completed more quickly. The thickness of the coating is 0.0 after drying.
A range of 1 to 20 μm is suitable. Preferably 0.1-
It is 15 μm, more preferably 0.5 to 10 μm.
If the coating is thinner than 0.01 μm, pinholes are likely to occur in the coating, and if it is thicker than 20 μm, cracks may occur in the coating.

On the treated surface of the surface-treated resin molding of the present invention,
Further, a metal or metal oxide vapor deposition layer may be laminated.
By stacking these vapor-deposited layers, a higher gas barrier property can be imparted to the resin molded body. It has been found that the treated surface treated with the surface treatment composition of the present invention has excellent adhesion to the vapor deposition layer and has high flexibility even when the vapor deposition layer is laminated. Aluminum is preferable as the metal constituting the vapor deposition layer, and silica and alumina are preferable as the metal oxide. As the vapor deposition method, a known method such as a vacuum vapor deposition method, a sputtering method, a physical vapor deposition method (PVD) such as an ion plating method, or a chemical vapor deposition method (CVD) can be adopted.

Further, a single or a plurality of layers of thermoplastic resin may be laminated on the treated surface of the surface-treated resin molded product or on the vapor deposition layer. The thermoplastic resin layer has the effects of improving steam resistance and imparting properties such as heat sealability, printability, and safety to the molded body. As a specific example of the thermoplastic resin, a general-purpose polyolefin resin such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer is preferable because it has excellent heat sealability and steam resistance. In addition, polystyrene, polyvinylidene chloride, polyethylene terephthalate, polyacrylonitrile, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, cellophane, nylon and the like can be used, and a film coated with polyvinylidene chloride is laminated on these thermoplastic resins. Good.

The surface-treated molded article of the present invention and the thermoplastic resin may be laminated by dry lamination using a known adhesive,
Known methods such as extrusion laminating and hot melt laminating can be adopted. The adhesive used during lamination is not particularly limited, and examples thereof include polyurethane-based, polyester-based, epoxy-based, alkyl titanate-based, polyethyleneimine-based, polybutadiene-based, ethylene-vinyl acetate copolymer-based, low molecular weight polyethylene, wax and the like. It Surface treatment such as corona treatment may be performed to improve the adhesiveness.

[0029]

The present invention will be described in more detail with reference to the following examples, but the following examples do not limit the present invention.
All modifications and implementations that do not depart from the spirit of the description below are included in the technical scope of the present invention. The oxygen permeability is a result measured by an oxygen permeability measuring device manufactured by MOCON under the conditions of a temperature of 20 ° C. and a humidity of 90% Rh.

Example 1 Epomine SP-006 {polyethyleneimine; trade name of Nippon Shokubai; organic compound (A)} 6.98 g, γ-glycidoxypropyltrimethoxysilane {compound (B); hereinafter abbreviated as GTMS} 9.25 g, methanol 25.1 g
Were mixed and stirred at 65 ° C. under a nitrogen atmosphere for 3 hours. 72.0 g of tetramethoxysilane {organometallic compound (C); hereinafter abbreviated as MS} and methanol 1 were added to the reaction solution.
1.1 g of the mixed liquid was added and stirred for 1 hour to obtain a surface treating composition 1. This composition 1 was applied to 12 μm PET with a bar coater and dried at 80 ° C. for 30 seconds. The treatment layer had a thickness of 1.0 μm and was transparent. The oxygen permeability was 2.1 cc / m ² · 24 hrs · atm.

Example 2 Epomin SP-018 {polyethyleneimine; trade name of Nippon Shokubai; compound (A)} 7.18 g, GTMS {compound (B)} 3.25 g, and methanol 21.1 g were mixed to obtain 65. After stirring at ℃ for 3 hours under a nitrogen atmosphere, a mixture of 5 g of methanol and 0.1 g of water was added dropwise at room temperature over 15 minutes, and the mixture was stirred for 1 hour. Further, a mixed solution of 52.0 g of MS {compound (C)} and 15.4 g of methanol was added to this reaction solution, and the mixture was stirred at room temperature for 3 hours to obtain a composition 2 for surface treatment. This composition 2 was applied to 12 μm PET with a die coater and dried at 100 ° C. and 20% Rh. The length of the drying oven of the die coater was 3 m, and the coating speed was 10 m / min. The thickness of the treated layer was 2.5 μm and was transparent. The oxygen permeability was 2.0 cc / m ² · 24 hrs · atm.

Example 3 Epomine SP-300 {polyethyleneimine; trade name of Nippon Shokubai; compound (A)} 7.22 g, γ-glycidoxypropyltriethoxysilane {compound (B)} 3.2
5 g, ethanol 36.1 g, and tetraethoxysilane {compound (C)} 72.0 g were mixed and stirred at 65 ° C. under a nitrogen atmosphere for 4 hours to obtain a surface treating composition 3. This composition 3 was applied to 12 μm PET with a bar coater,
It was dried at 100 ° C. and 20% Rh for 30 seconds. The thickness of the treated layer was 2.4 μm and was transparent. The oxygen permeability is 1.
It was 1 cc / m ² · 24 hrs · atm.

Example 4 7.18 g of Epomin SP-300 {Compound (A)}
Was mixed with 4.72 g of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane {compound (B)} and 21.1 g of methanol, and the mixture was stirred at 55 ° C. under a nitrogen atmosphere for 2 hours. A mixed solution of 55.0 g of MS {compound (C)} and 15.4 g of methanol was added to this reaction solution, and the mixture was stirred at room temperature for 1 hour to obtain a composition 4 for surface treatment.
This composition 4 was applied to 12 μm PET with a bar coater and dried at 100 ° C. and 20% Rh for 10 seconds. The treatment layer had a thickness of 2.7 μm and was transparent. The oxygen permeability was 3.50 cc / m ² · 24 hrs · atm.

Example 5 6.89 g of Epomine SP-006 {Compound (A)}
And ethylene glycol diglycidyl ether {compound
(B)} 1.25 g and methanol 80.0 g are mixed
Then, the mixture was stirred at 65 ° C. under a nitrogen atmosphere for 3 hours. This reaction
60.0 g of MS {compound (C)} was added to the solution and stirred for 1 hour.
By stirring, a surface treating composition 5 was obtained. This composition 5
Coat with 20μm OPP with a coater, and 30 seconds at 80 ℃
Dried. The treatment layer had a thickness of 1.5 μm and was transparent.
Also, the oxygen permeability is 5.3 cc / m ² ・ 24 hours ・ a
It was tm.

Example 6 1.25 g of hexamethylene diisocyanate {Compound (B)} was stirred for 10 minutes while vigorously stirring a mixed solution of 7.18 g of Epomin SP-018 {Compound (A)} and 30.1 g of tetrahydrofuran. Then, the mixture was stirred at 65 ° C. under a nitrogen atmosphere for 3 hours. MS {compound (C)} 49.0 g, tetrahydrofuran 15.4 was added to this reaction solution.
g of the mixed solution was added, and the mixture was stirred at room temperature for 1 hour to obtain a composition 6 for surface treatment. This composition 6 was applied to 12 μm PET with a bar coater and dried at 100 ° C. and 20% Rh for 10 seconds. The treatment layer had a thickness of 4.5 μm and was transparent. Also,
The oxygen permeability was 1.1 cc / m ² · 24 hrs · atm.

Example 7 7.22 g of Epomin SP-018 {Compound (A)},
GTMS {compound (B)} 3.56 g, methanol 5
1.1 g was mixed and stirred at 65 ° C. under a nitrogen atmosphere for 3 hours. M silicate 51 {compound (C '); MS oligomer; product name of Tama Chemical Industry} in this reaction solution
A mixed solution of 52.0 g and methanol 15.4 g was added, and the mixture was stirred at room temperature for 1 hour to obtain a surface treatment composition 7. This composition 7 was applied to 12 μm PET with a bar coater, and 10
It was dried at 0 ° C. and 20% Rh for 10 seconds. The treatment layer had a thickness of 2.7 μm and was transparent. The oxygen permeability is 1.3.
It was cc / m ² · 24 hrs · atm.

Example 8 A mixed solution of 5.1 g of 2-aminoethanol {compound (A)}, 10 g of methanol, 2.1 g of GTMS {compound (B)} and 20 g of toluene was heated at 65 ° C. for 2 hours. 27.0 g of MS {compound (C)} was added thereto and stirred at room temperature for 2 hours to obtain a composition 8 for surface treatment. This composition was applied to 12 μm PET with a bar coater, and the temperature was kept at 80 ° C. and 40 ° C.
Dry for 10 seconds at% Rh. The treatment layer had a thickness of 2.3 μm and was transparent. Also, the oxygen permeability is 1.8 cc / m ² ·
It was 24 hrs.atm.

Example 9 On the treated surface of the surface-treated film obtained in Example 1, an adhesive obtained by mixing the urethane coating agents A310 and A3 for adhesion manufactured by Takeda Pharmaceutical Co., Ltd. in a ratio of 10: 1 (weight ratio) was used. It is applied so that the thickness after drying becomes 0.5 μm, and after drying, the thickness is 50 μm.
The polypropylene film of was pasted together. The oxygen permeability of this laminate is 1.8 cc / m ² · 24 hrs · at
It was m.

Example 10 352 g of Epomin SP-018 {Compound (A)},
GTMS {compound (B)} 200 g, methanol 100
0 g was mixed and stirred at 65 ° C. under a nitrogen atmosphere for 3 hours.
A mixed solution of 2500 g of MS {compound (C)} and 750 g of methanol was added dropwise to this reaction solution at 60 ° C. over 30 minutes, and stirred for 1 hour to obtain a composition for surface treatment 10. This composition 10 was applied to 12 μm PET and the thickness after drying was 3 μm.
And was dried at 100 ° C. and 20% Rh for 5 seconds. The obtained surface-treated film was set in a high-frequency induction heating type vapor deposition machine for film, and silicon monoxide was vapor-deposited on the treated surface at a rate of 80 m / min under a vacuum of 10 ⁻⁴ Torr. The thickness of the vapor deposition layer of the obtained vapor deposition film is 500.
Was Å. The oxygen permeability is 0.4cc / m ² · 2
It was 4 hrs atm.

Example 11 On the vapor-deposited layer of the vapor-deposited film obtained in Example 10, 1 layer of urethane coating agents A310 and A3 for adhesion manufactured by Takeda Pharmaceutical Co., Ltd. was used.
The adhesive mixed at 0: 1 (weight ratio) was applied so that the thickness after drying would be 0.5 μm, and after drying, a polypropylene film having a thickness of 50 μm was laminated. This stack 1
The oxygen permeability of 1 is 0.3 cc / m ² · 24 hrs · a
It was tm.

Comparative Example 1 7.18 g of Epomin SP-018 {Compound (A)},
GTMS {Compound (B)} 3.73 g, methanol 5
1.1 g was mixed and stirred at 65 ° C. under a nitrogen atmosphere for 3 hours to obtain a comparative surface treatment composition 1. This comparative composition 1
Is coated on 12 μm PET with a bar coater, and 100
It was dried at 20 ° C. and 20% Rh for 30 seconds. The thickness of the treatment layer is 2.
It was transparent at 5 μm. The oxygen permeability is 67.0c.
It was c / m ² · 24 hrs · atm. Compound (C)
Since oxygen was not added, the oxygen permeability was poor.

Comparative Example 2 7.18 g of Epomin SP-012 {Compound (A); Polyethyleneimine; Trade name of Nippon Shokubai}, MS {Compound (C)} of 52.0 g, and 55.4 g of methanol were mixed,
The mixture was stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to obtain a comparative surface treatment composition 2. This comparative composition 2 was applied with a bar coater 12
It was applied to PET having a thickness of μm and dried at 100 ° C. and 20% Rh for 10 seconds. The thickness of the treated layer was 2.8 μm and was cloudy.
Also, the oxygen permeability is 69.0 cc / m ² · 24 hrs ·
It was atm. Since the compound (B) is not added, the compatibility is poor, and only a coating film having white turbidity and poor oxygen permeability is obtained.

Comparative Example 3 GTMS {Compound (B)} 5.25 g, MS {Compound (C)} 52.0 g, and methanol 30.4 g were mixed,
It stirred at 65 degreeC for 1 hour, and obtained the composition 3 for comparative surface treatments. This comparative composition 3 was treated with a bar coater to obtain PE of 12 μm.
It was applied to T and dried at 100 ° C. and 20% Rh for 5 minutes.
The treatment layer had a thickness of 2.5 μm and was transparent, but had some cracks. The oxygen permeability is 72.0 cc /
It was m ² · 24 hrs · atm. Since the compound (A) does not exist, it is inferior in flexibility and oxygen permeability.

[0044]

The surface treating composition of the present invention comprises an amino group-containing organic compound (A), a compound (B) capable of reacting with the compound (A) and a hydrolyzable organometallic compound (C). By combining them, it was possible to provide a composition for surface treatment which was excellent in gas barrier properties, was transparent, and was capable of forming a flexible coating film. Therefore, the surface-treated resin molded product of the present invention treated with this composition exhibits excellent gas barrier properties and is useful in the packaging field and various fields.

Claims (10)

[Claims] 1. A molecule having a primary and / or secondary amino group and having a Si (OR ¹ ) group (R ¹ may be the same or different, a hydrogen atom, a lower alkyl group or an acyl group). (Not represented), an organic compound (A), a compound (B) having a functional group capable of reacting with the amino group in the molecule, an organometallic compound (C) represented by the following general formula (I), and / or its hydrate. Decomposition condensate, R ² _m M (OR ³ ) _n ... (I) (wherein M is a metal element, R ² may be the same or different, and is a hydrogen atom, a lower alkyl group, an aryl group, a vinyl group or a carbon group). Represents a mercapto group directly linked to the chain, or a methacryloyl group, R ³ 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 the same as the valence of the metal element M) and a solvent (D). 2. The surface treatment composition according to claim 1, wherein the organic compound (A) is a high molecular weight organic compound. 3. The composition for surface treatment according to claim 1, wherein the organic compound (A) is a polyethyleneimine. 4. The compound (B), together with a functional group capable of reacting with an amino group, has a Si (OR ⁴ ) group (R ⁴ may be the same or different and represents a hydrogen atom, a lower alkyl group or an acyl group. The surface treating composition according to any one of claims 1 to 3, which is a compound having 5. The surface treating composition according to claim 4, wherein the compound (B) is a compound having an epoxy group as a functional group capable of reacting with an amino group. 6. The surface treating composition according to claim 4, which comprises a cohydrolysis condensate of the compound (B) and the organometallic compound (C). 7. The resin molded body according to claim 1, wherein at least one surface is formed.
7. A surface-treated resin molded article, which is treated with the surface-treating composition according to any one of to 6. 8. The surface-treated resin molded body according to claim 7, wherein a metal or metal oxide vapor deposition layer is laminated on the treated surface of the surface-treated resin molded body. 9. A thermoplastic resin of a single layer or a plurality of layers is laminated on the treated surface of the surface-treated resin molding according to claim 7 or on the vapor-deposited layer according to claim 8. 7. The surface-treated resin molded product according to 7 or 8. 10. The use according to claim 7, which is a gas barrier material.
9. The surface-treated resin molded product according to any one of 9 above.