JP2001049171A - Surface-coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-coating composition that can form surface- treating coating film having excellent gas barrier properties, transparency and such a grade of flexibility that does not damage of the physical properties of the coating treated body. SOLUTION: This surface-coating composition comprises (A) a polyethyleneimine bearing no Si(OR1) group (R1 may be the same or different, and represents H, a lower alkyl group or an acyl group), (B) a compound bearing functional groups reactive with the amino group in the polyethyleneimine in the molecule, (C) an organic silane and/or the hydrolyzate thereof and (D) a solvent that can dissolve (A) polyethyleneimine, (B) the compound reactive with the compound A and (C) an organic silane and/or the hydrolyzate and condensate of the organic silane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for surface coating capable of forming a film having excellent gas barrier properties, transparency and flexibility.

[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 molded material such as a plastic film or sheet, an ethylene-vinyl alcohol copolymer,
Forming molded objects with gas impermeable materials such as vinylidene chloride copolymers and aromatic nylons, laminating or coating these gas impermeable materials with other materials, laminating aluminum foil on film materials Do
Methods such as vapor deposition of metal oxides are known.

However, among the gas-impermeable materials, ethylene vinyl alcohol copolymers and aromatic nylons are inferior in moisture resistance, and have a problem that gas barrier properties are greatly reduced as the humidity of the atmosphere increases. Since the vinylidene chloride-based copolymer contains a chlorine atom, it may cause pollution. In addition, in the case of the aluminum foil laminated film, the packaged contents cannot be seen from the outside, and the metal vapor deposition film is inferior in flexibility, so that the vapor deposition layer is easily cracked, and the gas barrier property is lowered. was there.

[0004]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention forms a surface-treated film having excellent gas barrier properties, being transparent, and having flexibility so as not to impair the physical properties of an object to be processed. It is an object of the present invention to provide a surface coating composition that can be used.

[0005]

The surface coating composition of the present invention comprises 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). A polyethyleneimine (A) containing no compound, a compound (B) having a functional group capable of reacting with an amino group in polyethyleneimine in the molecule, and an organosilane compound (C) represented by the following general formula (I) and / or The hydrolysis condensate and R ² _m Si (OR ³ ) _n ... (I) (wherein R ² may be the same or different and include 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, and n is an integer of 1 or more. Or Where m + n coincides with the valency of Si) containing a polyethyleneimine (A), a compound (B) and a solvent (D) capable of dissolving the organosilane compound (C) and / or its hydrolytic condensate. Have a gist.

The compound (B) 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) together with a functional group capable of reacting with an amino group. Preferably, the compound has
Most preferably, it is a compound having an Si (OR ⁴ ) group and having an epoxy group as a functional group capable of reacting with an amino group. Further, a co-hydrolysis condensate of the compound (B) and the organosilane compound (C) may be contained in the composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As the polyethyleneimine (A) used in the present invention, 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) Is not particularly limited as long as it is not included. The polyethylene imine (A) mainly has a role of imparting flexibility to the formed film. In particular, when the formed film is used as a gas barrier material, the presence of polyethyleneimine (A) improves the film formability of the surface coating composition, and also improves the stability of the surface coating composition and the obtained film. Good gas barrier properties. Polyethyleneimine (A) is a polymer having the above-mentioned amino group as a reaction point with compound (B), and the poly (ethylimine) (A) contains a hydrolyzable Si (OR ¹ ) group. If so, the degree of cross-linking of the resulting coating film becomes too dense and the flexibility is reduced. Therefore, the polyethylene imine (A) used in the present invention is limited as described above.

[0008] As the polyethyleneimine (A), specifically, for example, Epomin series (Epomin SP-003, Epomin SP-006, Epomin SP
-012, Epomin SP-018, Epomin SP-10
3, epomin SP-110, epomin SP-200, epomin SP-300, epomin SP-1000, epomin SP-1020, etc.).

The preferred molecular weight of the polyethylene imine (A) is from 250 to 200,000. More preferably 250-1
It is in the range of 10,000. When the molecular weight is less than 250, the formed film is inferior in flexibility, and when the molecular weight 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 has a functional group in the molecule capable of reacting with the amino group in the polyethyleneimine (A). The functional group is an epoxy group, a carboxyl group,
Examples are an isocyanate group and an oxazolinyl group. It has been found that the compound (B) has an effect of enhancing the compatibility between the polyethylene imine (A) and the organic silane compound (C). Further, the compound (B) may further have a hydrolyzable condensed Si (OR ⁴ ) group (R ⁴ groups may be the same or different and represent a hydrogen atom, a lower alkyl group or an acyl group). For example, before or after the reaction with polyethyleneimine (A), hydrolytic condensation proceeds, and co-hydrolytic condensation with the hydrolyzable condensed group of the organosilane compound (C) described below occurs, and polycondensation proceeds. Therefore, a dense film can be formed quickly.

Specific examples of the compound (B) include phenylglycidyl ether, 2-ethylhexyl glycidyl 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, and 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 Epoxy groups such as glycidoxypropyltriisopropoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and a Si (OR ⁴ ) group (R ⁴ is as defined above) ) (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 sometimes abbreviated as an isocyanate group-containing silane coupling agent); Isocyanates such as diisocyanate, 1,4-diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate, and the like. Two or more types can be used. Further, the compound (B) may be a high molecular organic compound having a functional group capable of reacting with an amino group, or a high molecular organic compound further having a Si (OR ⁴ ) group.

In the present invention, 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, the compound is subjected to hydrolysis and condensation before or after the reaction with the polyethyleneimine (A). Then, it is possible to carry out co-hydrolytic condensation with a hydrolyzable condensed group of the later-described organosilane compound (C).

The organic silane 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 Si (OR ³ ) _n ... (I) (wherein R ² may be the same or different and is a hydrogen atom, a lower alkyl group, an aryl group, a vinyl group, a mercapto group directly bonded to a carbon chain, or Represents 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 a valence of Si Matches)

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, and complex compounds thereof, methyltriacetoxysilane, trimethylsilanol, and the like, or these compounds. High molecular organic compounds, and one or more of these can be used. Among them, tetramethoxysilane and tetraethoxysilane are preferable because the formed film shows good moisture resistance.

In order to prevent the evaporation of the organic silane compound (C) during drying at the time of forming the film, it is preferable that the organic silane compound (C) is subjected to hydrolysis and condensation in advance. For this hydrolysis-condensation reaction, a known catalyst can be used, and it is advantageous to carry out the reaction in a solvent (D) described below. Compound (B)
As an epoxy group-containing silane coupling agent or an isocyanate-containing silane coupling agent such as Si (OR
⁴ ) When a group-containing compound is used, it is possible to carry out co-hydrolytic condensation with the organosilane compound (C) in advance.
The organic silane compound (C) has an effect of improving the moisture resistance of the formed film.

The surface coating composition of the present invention comprises polyethyleneimine (A), compound (B), organosilane compound (C) and a solvent (D) described below, and the total amount of each compound other than the solvent. A preferable amount of each compound when 100% by weight (that is, corresponding to the solid content of the composition) is described. Polyethylene imine (A)
40% by weight is preferred. Polyethyleneimine (A) is 1
When the amount is less than the weight%, the gas barrier property when the formed film is used as a gas barrier material is insufficient, and the flexibility of the film is reduced. If it is more than 40% by weight, the water resistance of the formed film may be poor. More preferred (A)
Is in the range of 5 to 30% by weight, more preferably 5 to 20% by weight. Compound (B) is 0.5 to 3
0% by weight is preferred. When the amount of the compound (B) is less than 0.5% by weight, the polyethyleneimine (A) and the organic silane compound (C) cannot be compatible with each other, so that the physical properties of the formed film are inferior. The stability of the composition for surface coating deteriorates. The more preferred amount of (B) used is in the range of 1 to 20% by weight, and more preferably 1 to 20% by weight.
-10% by weight.

5 to 90% by weight of the organic silane compound (C)
Is preferred. When the amount of the compound (C) is less than 5% by weight, the formed film has insufficient moisture resistance. However, use of more than 90% by weight is not preferable because the flexibility of the coating film is reduced. More preferably, the use amount of (C) is 10 to 90% by weight.
And more preferably 30 to 80% by weight.

The solvent (D) used in the present invention includes:
A solvent that can dissolve the polyethylene imine (A), the compound (B) and the organic silane compound (C) is preferable. For example, alcohols such as methanol, ethanol, 2-propanol, butanol, and ethylene glycol.
Further, these alcohols include 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, ethyl acetate, butyl acetate and the like. May be used alone or as a mixture of two or more of tetrahydrofuran, propyl ether, water and the like.

The method for preparing the composition of the present invention is not particularly limited, but the polyethyleneimine (A) and the compound (B) are previously prepared.
And then adding the organosilane compound (C), or the compound (B) in the presence of polyethyleneimine (A).
The method of hydrolyzing (C) (and (B) also has a hydrolyzable group, also (B)) while reacting the organic silane compound (C) with the silane compound (C) increases the stability of the surface coating composition. It is preferably adopted in terms of enhancing.

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 surface coating composition of the present invention as long as the effects of the present invention are not impaired. An agent can be added as needed.

The surface coating composition of the present invention can be used for coating various substrates. The substrate is not particularly limited, but a resin molded body is preferred. The type of the resin forming the molded body is not particularly limited, but, for example, polyethylene, a polyolefin resin such as polypropylene, polyethylene terephthalate, polyethylene isophthalate, polyethylene-
Polyester resins such as 2,6-naphthalate, polybutylene terephthalate and copolymers thereof, polyamides, polystyrene, poly (meth) acrylate,
Polyacrylonitrile, polyvinyl acetate, polycarbonate, cellophane, polyimide, polyetherimide,
Thermoplastic resins such as polysulfone, polyetherketone, ionomer resin, and fluororesin; and thermosetting resins such as melamine resin, polyurethane resin, epoxy resin, phenolic resin, unsaturated polyester resin, urea resin, alkyd resin, and silicon resin And the like. In addition to the resin molded body, for example, a metal plate such as aluminum, stainless steel, steel or the like or a plating material thereof may be used as a base material, or paper or a fiber product may be used as a base material. The shape of the molded article can be selected according to the intended use such as a film, a sheet, a bottle and the like. In particular, a thermoplastic film is preferable because of ease of processing.

The method of coating the substrate with the composition for surface coating 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 preferred because it increases the stability of the surface coating composition. Before coating, the resin molded body may be subjected to a surface activation treatment such as a corona treatment or a known anchor treatment such as a urethane resin. Moreover, after coating the resin composition with the surface coating composition, a lamination process or other known processes may be performed.

After the surface coating composition is coated, the coating is cured and dried. If it is desired to cure and dry the coating more quickly, it is preferable to heat the resin molded body at a temperature lower than the heat resistance temperature of the resin molded body. If humidification is performed in addition to heating, curing and drying are completed more quickly. The thickness of the film after drying is 0.0
A range of 1 to 20 μm is suitable. Preferably 0.1 to
It is 15 μm, more preferably 0.5 to 10 μm.
When the coating is thinner than 0.01 μm, pinholes are easily generated in the coating, and when the coating is thicker than 20 μm, the coating may crack.

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

Further, a single or plural layers of thermoplastic resin may be laminated on the treated surface of the surface-treated resin molded product or on the above-mentioned vapor deposition layer. The thermoplastic resin layer has an effect of improving steam resistance and imparting properties such as heat sealability, printability, and safety to the molded article. As specific examples of the thermoplastic resin, general-purpose polyolefin resins such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer are preferable because of their 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 laminate of these thermoplastic resins coated with polyvinylidene chloride can be used. Is also good.

The lamination of the surface-coated molded article of the present invention and a thermoplastic resin can be performed by dry lamination using a known adhesive,
Known methods such as extrusion lamination and hot melt lamination can be employed. The adhesive used at the time of lamination is not particularly limited, and examples thereof include polyurethane, polyester, epoxy, alkyl titanate, polyethyleneimine, polybutadiene, ethylene-vinyl acetate copolymer, low-molecular-weight polyethylene, and wax. You. In order to increase the adhesiveness, a surface coating such as a corona treatment may be performed.

[0028]

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 oxygen permeability is a result measured by using an oxygen permeability measuring device manufactured by MOCON under conditions of a temperature of 20 ° C. and a humidity of 90% Rh.

Example 1 Epomin SP-006 (trade name of Nippon Shokubai; polyethyleneimine (A) 6.98 g, γ-glycidoxypropyltrimethoxysilane compound (B); hereinafter referred to as GTMS 9.25 g) , 25.1 g of methanol,
The mixture was stirred at 65 ° C under a nitrogen atmosphere for 3 hours. To this reaction solution, a mixed solution of 72.0 g of tetramethoxysilane ｛organosilane compound (C); hereinafter abbreviated as MS and 11.1 g of methanol was added, and the mixture was stirred for 1 hour to obtain composition 1 for surface coating. This composition 1 was applied to 12 μm PET using a bar coater, and dried at 80 ° C. for 30 seconds. Processing layer thickness is 1.0μ
m. The oxygen permeability is 2.1 cc / m
It was ² · 24hrs · atm.

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

Example 3 Epomin SP-300 (trade name of Nippon Shokubai; polyethyleneimine (A)) 7.22 g, γ-glycidoxypropyltriethoxysilane (compound (B)) 3.25 g, ethanol 36.1 g And 72.0 g of tetraethoxysilane {organosilane compound (C)} were mixed and stirred at 65 ° C. under a nitrogen atmosphere for 4 hours to obtain composition 3 for surface coating. 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 transparent. The oxygen permeability is 1.
It was 1 cc / m ² · 24 hrs · atm.

Example 4 7.18 g of Epomin SP-300 {polyethyleneimine (A)} and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane {compound (B)} 4.7
2 g and 21.1 g of methanol were mixed and stirred at 55 ° C. under a nitrogen atmosphere for 2 hours. 55.0 g of MS (organic silane compound (C)) and 15.
4 g of the mixture was added, and the mixture was stirred at room temperature for 1 hour to obtain Composition 4 for surface coating. This composition 4 was 12 μm thick with a bar coater.
And dried at 100 ° C. and 20% Rh for 10 seconds. The thickness of the treated layer was 2.7 μm and transparent. The oxygen permeability is 3.50 cc / m ² · 24 hrs · a
tm.

Example 5 6.89 g of Epomin SP-006 {polyethyleneimine (A)}, 1.25 g of ethylene glycol diglycidyl ether {compound (B)} and methanol.
Then, the mixture was stirred at 65 ° C. for 3 hours under a nitrogen atmosphere. In this reaction solution, MS {organosilane compound (C)} 6
0.0 g was added and stirred for 1 hour to obtain a composition 5 for surface coating. This composition 5 was applied to a 20 μm OPP with a bar coater and dried at 80 ° C. for 30 seconds. The thickness of the processing layer is 1.
It was transparent at 5 μm. The oxygen permeability is 5.3cc
/ M ² · 24 hrs · atm.

Example 6 1.25 g of hexamethylene diisocyanate {compound (B)} was added to a mixture of 7.18 g of epomin SP-018 {polyethyleneimine (A)} and 30.1 g of tetrahydrofuran with vigorous stirring. Then, the mixture was stirred at 65 ° C. for 3 hours under a nitrogen atmosphere. A mixed solution of 49.0 g of MS (organosilane compound (C)) and 15.4 g of tetrahydrofuran was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour to obtain Surface Coating Composition 6. This composition 6 was applied to 12 μm PET using a bar coater,
Dried at 0% Rh for 10 seconds. The thickness of the processing layer is 4.5 μm
And was transparent. The oxygen permeability is 1.1 cc / m ^2.
・ 24 hrs ・ atm.

Example 7 7.22 g of Epomin SP-018 {polyethyleneimine (A)}, 3.56 g of GTMS {compound (B)}, and 51.1 g of methanol were mixed, and the mixture was mixed at 65 ° C. under a nitrogen atmosphere for 3 hours. Stirred. To this reaction solution was added a mixed solution of M silicate 51 (organosilane compound (C '); oligomer of MS; product name of Tama Chemical Industry Co., Ltd., 52.0 g, and methanol (15.4 g)), and the mixture was stirred at room temperature for 1 hour to form a surface coating. Composition 7 was obtained. This composition 7 was treated with a bar coater to form 12 μm PET.
And dried at 100 ° C. and 20% Rh for 10 seconds. The thickness of the treated layer was 2.7 μm and transparent. The oxygen permeability was 1.3 cc / m ² · 24 hrs · atm.

Example 8 On the treated surface of the surface-coated film obtained in Example 1, an adhesive obtained by mixing the urethane coating agents A310 and A3 manufactured by Takeda Pharmaceutical Co. at a ratio of 10: 1 (weight ratio) was used. Apply so that the thickness after drying is 0.5 μm, and after drying, the thickness is 50 μm
Were bonded together. The oxygen permeability of this laminate was 1.8 cc / m ² · 24 hrs · at
m.

Example 9 352 g of Epomin SP-018 {polyethyleneimine (A)}, 200 g of GTMS {compound (B)} and 1000 g of methanol were mixed and stirred at 65 ° C. for 3 hours in a nitrogen atmosphere. To this reaction solution, a mixed solution of 2500 g of MS {organosilane compound (C)} and 750 g of methanol was added.
The mixture was added dropwise at 60 ° C. over 0 minutes and stirred for 1 hour to obtain a composition 10 for surface coating. This composition 10 was treated with 12 μm PET.
To a thickness of 3 μm after drying, and at 100 ° C.
Dry for 5 seconds at 20% Rh. The obtained surface-coated film was set in a high-frequency induction heating type vapor deposition machine for a film, and silicon monoxide was evaporated at 80 m / m under a vacuum of 10 ^-4 Torr.
Vapor deposition was performed on the treated surface at a speed of minutes. The thickness of the deposited layer of the obtained deposited film was 500 °. The oxygen permeability was 0.4 cc / m ² · 24 hrs · atm.

Example 10 To the vapor-deposited layer of the vapor-deposited film obtained in Example 9, 10 urethane coating agents A310 and A3 for adhesion manufactured by Takeda Pharmaceutical Co. were added.
The adhesive mixed at 1 (weight ratio) has a thickness after drying of 0.1.
It was applied so as to have a thickness of 5 μm, and after drying, a 50 μm-thick polypropylene film was bonded. The oxygen permeability of the laminate 11 is 0.3 cc / m ² · 24 hrs · atm
Met.

Comparative Example 1 7.18 g of Epomin SP-018 {polyethyleneimine (A)}, 3.73 g of GTMS {compound (B)}, and 51.1 g of methanol were mixed and mixed at 65 ° C. under a nitrogen atmosphere for 3 hours. After stirring, a composition 1 for comparative surface coating was obtained. This comparative composition 1 was applied to 12 μm PET using a bar coater, and dried at 100 ° C. and 20% Rh for 30 seconds. The thickness of the treated layer was 2.5 μm and transparent. The oxygen permeability was 67.0 cc / m ² · 24 hrs · atm. Since the organic silane compound (C) was not added, the oxygen permeability was poor.

Comparative Example 2 7.18 g of Epomin SP-012 (trade name of Nippon Shokubai; polyethyleneimine (A)), 52.0 g of MS (organosilane compound (C)), and 55.4 g of methanol were mixed, and nitrogen was added. The mixture was stirred at 65 ° C. for 3 hours in an atmosphere to obtain a composition 2 for comparative surface coating. This comparative composition 2 was applied to 12 μm PET using a bar coater, and was applied at 100 ° C. and 20% Rh for 1 hour.
Dry for 0 seconds. The thickness of the treated layer was 2.8 μm and was cloudy. The oxygen permeability is 69.0 cc / m ² · 24 hr.
s · atm. Since the compound (B) was not added, the compatibility was poor, and only a film having cloudiness and poor oxygen permeability was obtained.

Comparative Example 3 GTMS {Compound (B)} 5.25 g, MS {organosila
Compound (C) (52.0 g) and methanol (30.4 g)
Mix and stir at 65 ° C. for 1 hour, composition for comparative surface coating
3 was obtained. This comparative composition 3 was 12 μm thick with a bar coater.
And dried at 100 ° C and 20% Rh for 5 minutes
did. Although the thickness of the treated layer was 2.5 μm and transparent,
There was a part crack. The oxygen permeability is 72.0
cc / m ^Two・ 24 hrs ・ atm. Polyethylene
Since no imine (A) is present, it is flexible and oxygen-permeable.
Too poor.

[0042]

The composition for surface coating of the present invention combines polyethyleneimine (A), a compound (B) capable of reacting with an amino group in polyethyleneimine, and a hydrolyzable organosilane compound (C). This makes it possible to form a transparent and flexible film having excellent gas barrier properties. Therefore, the surface-treated resin molded article treated with this composition exhibits excellent gas barrier properties and is useful in the field of packaging and various fields.

Claims (5)

[Claims] 1. A polyethyleneimine (A) containing no 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), and an amino in the polyethyleneimine. compound having a functional group capable of reacting with group in the molecule (B), and an organic silane compound (C) and / or a hydrolysis condensate represented by the following general formula _{^{(I), R 2 m Si}} (oR 3 ) _n ... (I) (wherein, R ² represents identical or different and have good hydrogen atom, a lower alkyl group, an aryl group, a mercapto group directly bonded to a vinyl group or a carbon chain or a methacryloyl group,, R ³ 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 coincides with the valence of Si. Ren'imin (A), compound (B) and the organosilane compound (C) and / or a hydrolysis condensate, solvent capable of dissolving (D) and the surface coating composition characterized by containing. 2. The compound (B) 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 together with a functional group capable of reacting with an amino group. The surface coating composition according to claim 1, which is a compound having: 3. The surface coating composition according to claim 1, wherein the compound (B) is a compound having an epoxy group as a functional group capable of reacting with an amino group. 4. The surface coating composition according to claim 2, which has a co-hydrolysis condensate of the compound (B) and the organosilane compound (C). 5. The organic silane compound (C) is tetramethoxysilane or tetraethoxysilane.
5. The composition for surface coating according to any one of items 4 to 4.