JP3275432B2 - Aqueous surface treatment composition for gas barrier, surface-treated resin molding using the composition, and gas barrier material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous surface treating composition capable of forming a film having excellent gas barrier properties, transparency and flexibility, and a gas barrier material surface-treated with the composition. .

[0002]

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

[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 in that the vapor-deposited layer is liable to be 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, studies have been made on surface treatment of plastic films using polysiloxane having a dense molecular structure and having excellent weather resistance, hardness and chemical resistance. . However, tetraalkoxysilane used as a raw material of polysiloxane has four hydrolysis-condensation reaction points and therefore has a large volume shrinkage at the time of condensation, and it has been difficult to obtain a coating film free of cracks and pinholes.

[0005] Therefore, it has been proposed to suppress the occurrence of cracks and pinholes by conducting hydrolysis-condensation condensation of an alkyltrialkoxysilane having only three hydrolysis-condensation reaction points alone or with tetraalkoxysilane. However, since alkyltrialkoxysilane has low reactivity, the monomer remaining without condensation by using alkyltrialkoxysilane alone increases, and when used in combination with tetraalkoxysilane, it is not possible to perform a uniform co-hydrolytic condensation. That was the current situation. Furthermore, since these silane-based surface treatment compositions have no affinity for plastic film materials and have poor wettability, there is also a problem that film forming properties are poor.

Japanese Patent Application Laid-Open No. 2-286331 discloses that
It has been shown that the alkoxysilane is hydrolyzed and condensed and coated on a plastic film. However, in this method, since only the alkoxysilane component is coated on the film, the flexibility of the film is significantly impaired.

In view of the above, for example, Japanese Patent Application Laid-Open No. 1-2785
No. 74 discloses that cracking of a surface treatment film is suppressed by combining an alkoxysilane hydrolyzate such as tetraalkoxysilane with a reactive urethane resin. However, since the reactive urethane resin reacts with alcohols used as a solvent, the alkoxysilane hydrolyzate and the reactive urethane resin are not sufficiently complexed to cause phase separation, and the coating may become opaque. there were.

As described above, in general, polar organic solvents such as alcohols are widely used as solvents for hydrolysis of alkoxysilanes. However, in view of pollution by organic solvents, work safety and health, and resource saving. Therefore, a shift to an aqueous system containing no organic solvent or minimizing the solvent is desired.

On the other hand, in recent years, facsimile and printer,
A heat-sensitive recording system in which a heat-sensitive coloring layer in which two components that develop color when heated are dispersed is provided on a substrate is often used. However, this method has disadvantages such as poor storage stability, easy falsification after recording, poor solvent resistance, and the like.
As a method for improving these disadvantages, a transfer-type thermal recording system is known.

The transfer type thermal recording system is a method in which printing is performed by a heat pulse of a heating head through a thermal transfer member on a receiving sheet (for example, plain paper), and the surface of the side in contact with the receiving sheet is thermally fused as a thermal transfer member. The one provided with a heat transferable ink layer such as a heat-sensitive ink layer and a layer containing a heat sublimable dye is generally known. In recent years, improvements in printing performance and printing speed have been desired, and various measures have been taken to reduce the thickness of the base film and to increase the amount of heat applied to the heating head. There is a problem that the load is increased and the base film is melted to hinder the running of the heating head. Such a phenomenon is generally called a heat stick.

Various attempts have been made to improve this heat stick. For example, Japanese Patent Application Laid-Open No. 55-746
No. 7 proposes a method in which a heat-resistant resin such as a silicone resin or an epoxy resin is applied to one surface of a base film.
In addition to requiring heat-curing treatment at 00 ° C or more for several hours, silicone resin has poor adhesion to the base film, and epoxy resin has poor lubricity on the film surface, and a satisfactory heat stick preventing effect can be obtained. It is not currently done.

[0012]

SUMMARY OF THE INVENTION In view of the above problems, the present inventors have developed a surface treatment film having excellent gas barrier properties, being transparent, and having flexibility so as not to impair the physical properties of the object to be treated. A second object of the present invention is to provide a water-based surface treatment composition that can be formed, and to provide a surface-treated resin molded article and a gas barrier material having such excellent characteristics.
The purpose of.

[0013]

The present invention provides an aqueous surface treating composition for a gas barrier, comprising: (1) a silane compound represented by the following general formula (A):

[0014]

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Wherein A ¹ is an alkylene group, R ⁶ is a hydrogen atom, a lower alkyl group, or

[0016]

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Wherein A ² is a direct bond or an alkylene group, R ¹⁰ and R ¹¹ are a hydrogen atom or a lower alkyl group, R ⁷ is a hydrogen atom or a lower alkyl group, and R ⁸ is the same Or a different lower alkyl group, aryl group or unsaturated aliphatic residue, R ⁹ represents a hydrogen atom, a lower alkyl group or an acyl group (provided that R ⁶ , R ⁷ , R
¹⁰ and at least one of R ¹¹ is a hydrogen atom), w
Represents any one of 0, 1, and 2 and z represents an integer of 1 to 3 (where w + z = 3)] The functional group capable of reacting with the amino group in the silane compound (A) and / or the silane compound ( -Si (OR) in A)
⁹ ) a reaction product (AB) with an organic compound (B) having at least two functional groups in the molecule capable of reacting with the organic compound (B); A reaction product (PAB) hydrolyzed and condensed before or after the reaction, (3) the silane compound (A), an organometallic compound represented by the following general formula (C), and R ⁴ _mM (OR ⁵ ) _n ... (C) (wherein M is a metal element, R ⁴ may be the same or different and represents a hydrogen atom, a lower alkyl group, an aryl group or an unsaturated aliphatic residue, and R ⁵ is the same or different May be 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 the metal element M. Reaction product (ABC) with B), (4) the above silane compound A reaction product (PABC) in which (A) is (co) hydrolyzed and condensed before or after the reaction of the organometallic compound (C) and the organic compound (B);
The gist of the present invention is that it contains one or more reactive compounds selected from the group consisting of (1) to (4), an anionic surfactant, and water.

Further, a surface-treated resin molded article and a gas barrier material treated with the above composition are also included in the present invention.

[0019]

The silane compound (A) used in the gas barrier aqueous surface treating composition of the present invention (hereinafter sometimes referred to as "gas barrier aqueous system") may be limited as long as it satisfies the following formula. And at least one of them can be used.

[0020]

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(Where A ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , w, z
Has the same meaning as described above).

Specific examples of the above (A) include N-β (aminoethyl) γ-aminopropyltrimethoxysilane,
N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriisopropoxysilane, N-β (aminoethyl) γ
-Aminopropyltributoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropylmethyldibutoxysilane, N
-Β (aminoethyl) γ-aminopropylethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylethyldiethoxysilane, N-β (aminoethyl) γ
-Aminopropylethyldiisopropoxysilane, N-
β (aminoethyl) γ-aminopropylethyl dibutoxysilane, γ-aminopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiisopropoxysilane , Γ-aminopropylmethyldibutoxysilane, γ-
Examples include aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldiisopropoxysilane, γ-aminopropylethyldibutoxysilane, γ-aminopropyltriacetoxysilane, and the like.

The organic compound (B) used in the composition for surface treatment of the present invention may be a functional group capable of reacting with an amino group in the silane compound (A) and / or -Si (-) in the silane compound (A). OR ⁹ ) has a functional group capable of reacting with 2
Compounds. 2 of organic compound (B)
The at least two functional groups are an epoxy group, a carboxyl group, an isocyanate group, an oxazoline group and the like, and these functional groups may be the same or different in the compound (B). Specific examples of such an organic compound (B) include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, and propylene glycol diglycidyl. Ether, dipropylene glycol diglycidyl ether,
Tripropylene glycol diglycidyl ether, 1,
Diglycidyl ethers such as 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether, glycerol diglycidyl ether; glycerol triglycidyl ether;
Diglycerol triglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate,
Triglycidyl ethers such as trimethylolpropane triglycidyl ether; tetraglycidyl ethers such as pentaerythritol tetraglycidyl ether;
Other polyglycidyl ethers or polymers having a glycidyl group as a functional group; dicarboxylic acids such as tartaric acid and adipic acid; carboxyl-containing polymers such as polyacrylic acid; isocyanates such as hexamethylene diisocyanate and xylylene diisocyanate; oxazoline Containing polymer; alicyclic epoxy compound, etc., and one or more of these can be used. From the viewpoint of reactivity, a compound having two or more glycidyl groups is preferably used. .

The amount of the organic compound (B) used is 0.1 to 300% by weight, preferably 1 to 200% by weight, based on the total amount of the silane compound (A). The organic compound (B) reacts with a functional group in the silane compound (A) and functions as a crosslinking agent component. When the amount of the organic compound (B) is less than 0.1% by weight, the flexibility of the coating film becomes insufficient, and 300% by weight.
If used in excess of this, the gas barrier properties may be undesirably reduced.

The organometallic compound (C) used in the present invention
Is not particularly limited as long as it can be represented by the following general formula (C).

R ⁴ _mm (OR ⁵ ) _n (C) (where M, R ⁴ , R ⁵ , m, and n have the same meaning as described above).

Specific examples include tetramethoxysilane,
Tetraethoxysilane, tetraisopropoxysilane,
Alkoxysilanes such as tetrabutoxysilane; titanium alkoxides such as titanium tetraethoxide, titanium tetraisopropoxide and titanium tetrabutoxide; zirconium alkoxides such as zirconium tetraethoxide, zirconium tetraisopropoxide and zirconium tetrabutoxide; aluminum Triethoxide, aluminum triisopropoxide,
Aluminum alkoxides such as aluminum tributoxide; acetoxysilanes such as tetraacetoxysilane and methyltriacetoxysilane; and silanols such as trimethylsilanol. One or more of these can be used.

The organometallic compound (C) has the chemical resistance of the film,
It is effective for improving heat resistance, but it is desired to use about 0 to 200 mol%, preferably 0 to 100 mol%, based on the silane compound (A). If it is used more than 200%, it may gel rapidly.

The reactive compound used in the composition for surface treatment of the present invention is obtained by reacting a silane compound (A) with an organic compound (B) and an organometallic compound (C) as follows. It is. (1) Reaction product (AB) of a silane compound (A) and an organic compound (B) (2) A product obtained by hydrolytic condensation of the silane compound (A) before or after the reaction with the organic compound (B) ( PAB) (3) Reaction product (ABC) of silane compound (A) with organic compound (B) and organometallic compound (C) (4) Silane compound (A) is composed of organic compound (B) and organic metal Compounds (PABC) hydrolyzed and condensed before or after the reaction with compound (C).

Of the above (1) to (4), (2) and (4) can be further divided as follows. (5) A product obtained by reacting a hydrolysis condensate of a silane compound (A) with an organic compound (B) (PAB-1). (6) A product obtained by reacting a silane compound (A) with an organic compound (B). Obtained by hydrolysis and condensation of the reaction product (AB) (PAB-
2) those belonging to (4) (7) those obtained by reacting the hydrolysis condensate of the silane compound (A) with the organic compound (B) and the organometallic compound (C) (PABC-1) (8) the silane compound ( A) The compound (PABC-2) obtained by reacting A) with an organic compound (B) and an organometallic compound (C) and then co-hydrolyzing and condensing (PABC-2).

The composition for surface treatment of the present invention essentially contains at least one of the above reactive compounds (1) to (8), together with an anionic surfactant and water. The anionic surfactant is not particularly limited, but specifically, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium dialkyl succinate, sodium alkyl diphenyl ether disulfonate, Examples thereof include sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene alkyl phenyl ether sulfate. These are contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the reactive compound. If the amount is less than 0.001 part by weight, storage stability is poor, and a precipitate or the like may be generated. If the amount is more than 5 parts by weight, water resistance may be poor. These anionic surfactants control the crosslinking point due to their ionic affinity with alkoxysilanes, prevent gelation, and provide an aqueous surface treatment composition with excellent storage stability and film formability. You can give it.

In the present invention, the amount of water as a solvent can be arbitrarily determined according to the coating conditions, viscosity, etc., but is preferably at least 5 times, more preferably at least 10 times, the molar ratio to the silane compound. It is desirable to use an amount of If the amount of water is less than 5 times, the solid content concentration may be too high and the film formability may deteriorate. From the viewpoint of improving the wettability at the time of film formation, a water-soluble organic solvent such as alcohols is used in all solvents.
It may be used in an amount of less than 5% by weight. Examples of the water-soluble organic solvent used include methanol, ethanol, isopropanol and the like.

In the surface treatment composition of the present invention, various inorganic or organic additives such as a curing catalyst, a wettability improver, a plasticizer, an antifoaming agent and a thickener are added as long as the effects of the present invention are not impaired. Agents can be added as needed.

As the substrate coated with the composition for surface treatment of the present invention, a resin molded product is used. The resin forming the molded article is not particularly limited, but is, for example, a polyolefin resin such as polyethylene and polypropylene; polyester such as polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate and a copolymer thereof. Polyamide resin such as polyoxymethylene; polystyrene, poly (meth) acrylate, polyacrylonitrile, polyvinyl acetate, polycarbonate,
Thermoplastic resins such as cellophane, polyimide, polyetherimide, polyphenylene sulfone, polysulfone, polyetherketone, ionomer resin, and fluororesin;
Melamine resin, polyurethane resin, epoxy resin, phenol resin, unsaturated polyester resin, alkyd resin,
Thermosetting resins such as urea resin and silicon resin are exemplified. 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 for coating the surface molding composition with the resin molding is not particularly limited, and a roll coating method, a dip coating method, a bar coating method, a nozzle coating method, or a combination thereof is employed. 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. After the surface treatment composition is coated on the resin molded body, a laminating treatment or other known treatment may be performed. The surface-treated resin molded product thus obtained is also useful as a gas barrier material.

After coating, the coating is cured and dried, but the composition for surface treatment of the present invention is cured and dried even at room temperature. In the case of curing and drying faster, it is preferable to heat the resin molded body at a temperature equal to or lower than the allowable temperature limit. The thickness of the film after drying is 0.001 to 20 μm, more preferably 0.01 to 1 μm.
0 μm is suitable. When the thickness is less than 0.001 μm, the coating is not uniform and pinholes are easily generated.
When the thickness is more than m, cracks are easily generated in the coating film, which is not preferable.

In the composition for surface treatment of the present invention, the reactive compounds (PAB-1 to 3) and (PABC-1 to 4) of the reactive compounds having a small volume shrinkage upon curing as a silane compound component.
If 3) is used in a large amount, it is possible to reliably prevent the occurrence of cracks in the coating. Use of the organometallic compound (C) is effective for improving the heat resistance and chemical resistance of the coating.

The composition for surface treatment of the present invention can also be applied as a heat stick inhibitor for a thermal transfer material. One application example is shown in FIG. By providing a heat transferable ink layer 2 on one surface of the base film 1 and a heat stick prevention layer 3 comprising the heat stick prevention agent of the present invention on the other surface of the base film 1, a heat-sensitive heat transfer material is formed. I have. The thermal transferable ink layer 2 is a conventionally used hot-melt ink layer or a thermally sublimable dye-containing layer, and is formed by coating or printing by a conventionally known method. The heat stick preventing layer 3 of the present invention has heat resistance, good slipperiness, and a large heat stick preventing ability, and is prepared by using the above-mentioned composition for surface treatment with a normal coating machine or printing machine. It can be obtained simply by applying it to a film.

If necessary, an adhesive layer may be provided between the base film 1 and the heat stick preventing layer 3. The thickness of the heat stick prevention layer 3 is preferably from 0.1 to 5 μm. The heat stick prevention layer can be formed by coating or printing using the heat stick prevention agent of the present invention by a conventionally known method. In the formation, a curing catalyst may be used if necessary. As the base film, those conventionally used can be used, and examples thereof include a polyester film, a polycarbonate film, a cellulose acetate film, a polypropylene film, and cellophane.

[0040]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. The evaluation of the property test was performed by the following method. <Oxygen permeability> Measured with a gas permeability measuring device manufactured by Toyo Seiki Seisakusho in accordance with JIS K 7126. <Flexibility> The composition for surface treatment was applied to 25 μm polyethylene terephthalate (hereinafter abbreviated as PET) to a predetermined thickness by dipping, and then the dried coated film was bent at 180 °.
も の indicates that no crack occurred, and X indicates that crack occurred. <Transparency> A PET film coated and treated in the same manner as in the flexibility evaluation test was visually compared with an untreated PET film, and those having no difference in transparency were evaluated as ○, and those having cloudiness such as white turbidity were evaluated as ×. . <Storage Stability> After the surface treatment composition was stored at 23 ° C. for one month, it was evaluated as を when it was visually transparent, and as X when precipitation occurred.

Reference Example 1 (Pretreatment of Resin Molded Product) 10 g of urethane coating agent Takenate A-3 (manufactured by Takeda Pharmaceutical Co., Ltd.), 60 g of Takerac A-310 (manufactured by the company), and 600 g of ethyl acetate were mixed, and urethane under was mixed. A coating agent was obtained. This undercoat agent was applied to a 25 μm PET film to a thickness of 2.0 μm by dipping,
A minute drying was performed. The obtained film was transparent, the flexibility was good, and the oxygen permeability was 71.19 cc / m ² · 24 hrs · atm.

Example 1 To a mixture of 100 g of water and 0.2 g of sodium polyoxyethylene alkylphenyl ether sulfate (hereinafter abbreviated as POESNa), 20 g of γ-aminopropyltrimethoxysilane (hereinafter abbreviated as APTMS) was added, and the mixture was heated at 21 ° C. For 24 hours to obtain an APTMS hydrolysis-condensation product. This APTMS
2 g of ethylene glycol diglycidyl ether (hereinafter abbreviated as 1EDGE) is added to the hydrolysis condensate solution, and the mixture is heated at 21 ° C.
For 5 hours to obtain a composition for surface treatment. This composition was applied to the resin molded product obtained in Reference Example 1 by a dipping method, and left to dry at 21 ° C. for 24 hours. The obtained surface-treated film was transparent and flexible, and the oxygen permeability was 3.
It was 54 cc / m ² · 24 hrs · atm. Further, the composition for surface treatment was transparent without precipitation after storage at 23 ° C. for one month.

Examples 2 to 13 Example 2 was repeated except that various conditions were changed as shown in Table 1.
A surface-treated film was prepared in the same manner as described above, and a characteristic test was performed. The results are shown in Table 1.

Example 14 An APTM was added to a mixture of 100 g of water and 0.2 g of POESNa.
After adding 20 g of S, the mixture was stirred at 21 ° C. for 24 hours to obtain an APTMS hydrolyzed condensate. 2 g of 1EDGE was added to this APTMS hydrolyzed condensate solution, and the mixture was stirred at 21 ° C. for 5 hours, and then 5 g of tetramethoxysilane (hereinafter abbreviated as TMOS) was added to obtain a composition for surface treatment. This composition was applied and dried in the same manner as in Example 1, and a characteristic test was conducted. The results are shown in Table 1.

Example 15 To a mixture of 130 g of water, 0.2 g of POESNa and 0.4 g of concentrated hydrochloric acid was added 10 g of TMOS, followed by stirring at 21 ° C. for 24 hours.
A hydrolysis condensate was obtained. 15 g of APTMS and 2 g of 1EDGE were added to this TMOS hydrolysis condensate solution,
After stirring for an hour, a composition for surface treatment was obtained. This composition was applied and dried in the same manner as in Example 1, and a characteristic test was conducted. The results are shown in Table 1.

Example 16 15 g of APTMS, 15 g of methanol and 2 g of 1EDGE were mixed and stirred at 21 ° C. for 5 hours, and then 5 g of TMOS, 100 g of water,
0.2 g of OESNa was added, and the mixture was stirred at 21 ° C. for 24 hours to obtain a composition for surface treatment. This composition was applied and dried in the same manner as in Example 1 and then subjected to a characteristic test. The results are shown in Table 1.

Example 17 10 g of APTMS, 15 g of methanol and 2 g of 1EDGE were mixed and stirred at 21 ° C. for 5 hours. 100 g of water and POE
0.2 g of SNa was added and the mixture was stirred at 21 ° C. for 24 hours to obtain a composition for surface treatment. This composition was applied and dried in the same manner as in Example 1 and then subjected to a characteristic test. The results are shown in Table 1.

Comparative Example 1 APTM was added to a mixture of 100 g of water and 0.2 g of POESNa.
S20g was added and the mixture was stirred at 21 ° C for 24 hours to obtain a composition for surface treatment. This composition was applied to the resin molded article obtained in Reference Example 1, and left at 21 ° C. for 24 hours to dry. The thickness of the obtained surface-treated film was 0.8 μm and was transparent. The flexibility was ×, the oxygen permeability was 6.31 cc / m ² · 24 hrs · atm, and the storage stability of the surface treatment composition was で.

Comparative Examples 2 to 5 Comparative Examples 1 to 5 except that various conditions were changed as shown in Table 2.
A surface-treated film was prepared in the same manner as described above, and a characteristic test was performed. The results are shown in Table 2.

Comparative Example 6 APTMS20 was added to a liquid obtained by mixing 8 g of water and 0.2 g of POESNa.
g was added and stirred at 21 ° C. for 24 hours to obtain an APTMS hydrolyzed condensate. 2 g of 1EDGE was added to this APTMS hydrolyzed condensate solution and stirred at 21 ° C. for 5 hours to obtain a composition for surface treatment. This composition was applied and dried in the same manner as in Comparative Example 1 and then subjected to a characteristic test. The results are shown in Table 2.

Comparative Example 7 APTMS (20 g), water (100 g), and POESNa (0.2 g) were mixed and stirred at 21 ° C. for 24 hours to obtain an APTMS hydrolyzed condensate. TMOS is introduced into this APTMS hydrolysis condensate solution.
5g was added to obtain a surface treatment composition. This composition was subjected to a coating and drying test in the same manner as in Comparative Example 1, and the results are shown in Table 2.

Comparative Example 8 5 g of TMOS, 130 g of water, 0.2 g of POESNa, 0.4 g of concentrated hydrochloric acid
And stirred at 21 ° C. for 24 hours to obtain a TMOS hydrolyzed condensate. A is introduced into this TMOS hydrolysis condensate solution.
15 g of PTMS was added to obtain a composition for surface treatment. After applying and drying this composition in the same manner as in Comparative Example 1, a property test was carried out, and the results are shown in Table 2.

Comparative Example 9 20 g of APTMS and 100 g of water were mixed and stirred at 21 ° C. for 24 hours to obtain a composition for surface treatment. After applying and drying this composition in the same manner as in Comparative Example 1, a property test was performed.
It was also described in.

Comparative Example 10 20 g of APTMS and 100 g of water were mixed and stirred at 21 ° C. for 24 hours to obtain an APTMS hydrolyzed condensate. 1
2 g of EDGE was added, and the mixture was stirred at 21 ° C. for 5 hours to obtain a composition for surface treatment. This composition was subjected to coating, drying and characteristic tests in the same manner as in Comparative Example 1, and the results are shown in Table 2.

[0055]

[Table 1]

* 1 The unit of oxygen permeability is [cc / m ² · 24 hrs · atm]. * 2 Only in Example 7, the drying conditions were 80 ° C. for 30 minutes, and all other conditions were drying at 21 ° C. for 24 hours. * 3 In Example 10, sodium dodecylbenzenesulfonate was used as the anionic surfactant. In all other cases, POESNa was used. * 4 After the reaction of APTMS of Example 17 with 1EDGE, water was added to carry out a hydrolysis reaction.

[0057]

[Table 2]

* 1 The unit of oxygen permeability is [cc / m ² · 24 hrs · atm]. * 2 No anionic surfactant was added to Comparative Examples 9 and 10. In addition, the symbol of the compound in Table 1 and Table 2 is as follows. APTMS: γ-aminopropyltrimethoxysilane APTES: γ-aminopropyltriethoxysilane NAEAPTMS: N-β (aminoethyl) γ-aminopropyltrimethoxysilane TMOS: Tetramethoxysilane MTMOS: Methyltrimethoxysilane TBOT: Titanium tetrabutoxide 1EDGE: ethylene glycol diglycidyl ether 2EDGE: diethylene glycol diglycidyl ether 4EDGE: tetraethylene glycol diglycidyl ether PE4GE: pentaerythritol tetraglycidyl ether 1EDEE: ethylene glycol diethyl ether POESNa: sodium polyoxyethylene alkyl phenyl ether sulfate.

[0059]

By using the composition for aqueous surface treatment for gas barrier of the present invention, a transparent film excellent in gas barrier properties and flexibility can be formed. The resin molded article treated with the surface treatment composition of the present invention is useful as a gas barrier material in the field of packaging materials and the like. Moreover, the paint for heat-sensitive thermal transfer heat stick preventive obtained by using the composition for surface treatment of the present invention was able to give a coating film having excellent heat resistance and slipperiness and having high heat stick preventing ability.

[Brief description of the drawings]

FIG. 1 is a diagram showing an application example of a thermal stick inhibitor for a thermal transfer material.

[Explanation of symbols]

 1 base film 2 heat transferable ink layer 3 heat stick prevention layer

────────────────────────────────────────────────── ─── Continued on the front page (56) References Patent 3218765 (JP, B2) Patent 2647293 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 183/04

Claims (3)

(57) [Claims] (1) A silane compound represented by the following general formula (A): Wherein A ¹ is an alkylene group, R ⁶ is a hydrogen atom, lower alkyl
Group, or ( Where A ² represents a direct bond or an alkylene group, R ¹⁰ , R
¹¹ is represented by a hydrogen atom or a lower alkyl group)
R ⁷ is a hydrogen atom or a lower alkyl group, and R ⁸ is the same
Or different lower alkyl, aryl or unsaturated
An aliphatic residue, R ⁹ is a hydrogen atom, a lower alkyl group or
Means a sill group (provided little of ^{R 6, R 7, R 10} , R 11
At least one is a hydrogen atom), w is 0, 1 , 2
Or z represents an integer of 1 to 3 (w + z = 3
The functional group capable of reacting with the amino group in the silane compound (A)
-Si (OR) in the group and / or the silane compound (A)
⁹ ) a reaction product (AB) with an organic compound (B) having at least two functional groups in the molecule capable of reacting with the organic compound (B); A reaction product (PAB) hydrolyzed and condensed before or after the reaction, (3) the silane compound (A), an organometallic compound represented by the following general formula (C), and R ⁴ _mM (OR ⁵ ) _n ... (C) (wherein M is a metal element, R ⁴ may be the same or different and represents a hydrogen atom, a lower alkyl group, an aryl group or an unsaturated aliphatic residue, and R ⁵ is the same or different May be 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 the metal element M. Reaction product (ABC) with B), (4) the above silane compound (A) is a reaction product (PABC) which is (co) hydrolyzed and condensed before or after the reaction of the organometallic compound (C) and the organic compound (B), from (1) to (4). A water-based surface treatment composition for a gas barrier , comprising one or more reactive compounds selected from the group consisting of an anionic surfactant and water. 2. A surface-treated resin molded product obtained by treating at least one surface of the surface of the resin molded product with the aqueous barrier composition for gas barrier according to claim 1. 3. A gas barrier material treated with the water-based surface treatment composition for gas barrier according to claim 1.