JP3218765B2 - 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.

JP-A-2-286331 discloses that an alkoxysilane is hydrolyzed and condensed and coated on a plastic film. However, in this method, only the alkoxysilane component is coated on the film. Was significantly impaired in flexibility.

From the above viewpoint, for example, Japanese Patent Application Laid-Open No. 1-278574 discloses that cracking of a surface-treated film is suppressed by combining an alkoxysilane hydrolyzate such as tetraalkoxysilane with a reactive urethane resin. I have. 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 R ¹ and R ² may be the same or different and each represents a hydrogen atom, a lower alkyl group, an aryl group, an unsaturated aliphatic residue or a substituent having a functional group directly bonded to a carbon chain; R ³ may be the same or different and represents a hydrogen atom, a lower alkyl group, or an acyl group, and x and y each represent an integer of 0 to 3 (where x + y is an integer of 3 or less)] Reaction product with an organic compound (B) having two or more functional groups having reactivity with a functional group of R ¹ or R ² and / or a Si (OR ³ ) group in the molecule (A) (AB), (2) a reaction product (PAB) in which the silane compound (A) is hydrolyzed and condensed before or after the reaction with the organic compound (B), (3) with the silane compound (A) An organometallic compound represented by the following general formula (C), 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) , R ⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group or an acyl group, m is 0 or a positive integer, n is an integer of 1 or more, and m + n is the same as the valence of the metal element M. Do)

The reaction product (A) with the organic compound (B)
BC), (4) A reaction product (PAB) obtained by subjecting the silane compound (A) to (co) hydrolytic condensation before or after the reaction between 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), compounds containing a quaternary ammonium salt, and water. Further, the silane compound (A) is a silane compound represented by the following general formula (A ′),

[0017]

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

[0018]

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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 (w + z = 3)] and the organic compound (B)
Is an organic compound (B ′) having two or more functional groups in a molecule capable of reacting with an amino group and / or a functional group capable of reacting with —Si (OR ⁹ ) in a silane compound (A ′). It is an embodiment of a preferred water-based surface treatment composition for a gas barrier. Further, a surface-treated resin molded article and a gas barrier material treated with the above composition are also included in the present invention.

[0020]

The silane compound (A) used in the present invention
Is not limited as long as the following formula is satisfied, and one or more of them can be used.

[0021]

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(However, the meanings of R ¹ , R ² , R ³ , x and y in the formula are the same as described above.) Specific examples of these silane compounds (A) include a silane compound (A ′) described later.
In addition to those exemplified as, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, diphenyldimethoxysilane,
Diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri Ethoxysilane, γ-chloropropyltrimethoxysilane, γ
-Chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri Ethoxysilane and the like can be mentioned.

In particular, in the water-based surface treatment composition for a gas barrier of the present invention (hereinafter sometimes referred to as "water-based gas barrier"), the silane compound (A) is a silane compound represented by the following general formula (A '). Is a preferred embodiment.

[0024]

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(In the formula, the meanings of A ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , w and z are the same as described above.) As a specific example of the above (A ′), 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-aminopropylethyldibutoxysilane, γ-aminopropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,
γ-aminopropylmethyldiisopropoxysilane, γ
-Aminopropylmethyldibutoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldiisopropoxysilane, γ-aminopropylethyldibutoxysilane, γ-aminopropyltriacetoxy Examples include silane.

The organic compound (B) used in the composition for surface treatment of the present invention is a silane compound (A) [hereinafter, unless otherwise specified, (A) includes (A '). ] Is a compound (B) having two or more functional groups having reactivity with a functional group of R ¹ or R ² and / or a Si (OR ³ ) group in the molecule. Therefore, the functional group of the organic compound (B) is different from the silane compound (A) used.
Must be selected appropriately for the structure of For example, the functional group in the silane compound is glycidyl group and Si
When the organic compound (B) has an (OR ³ ) group, it is necessary that a hydroxyl group, an amino group, a carboxyl group and the like exist in the organic compound (B).

Other examples include ethylene glycol, diethylene glycol, triethylene glycol,
Tetraethylene glycol, nonaethylene glycol,
Glycols such as propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; diamines such as hexamethylene diamine; dicarboxylic acids such as tartaric acid and adipic acid; and carboxyl group-containing water-soluble polymers such as polyacrylic acid. One or more of these can be used, but diamines are preferred from the viewpoint of hydrolysis resistance and reactivity.

When the silane compound (A ') is particularly used in the present invention, the organic compound (B') has at least two functional groups such as epoxy group, carboxyl group, isocyanate group,
These functional groups in the form of an oxazoline group and the like 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. Glycidyl ether,
Dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether, glycerol diglycidyl ether, etc. Diglycidyl ethers; triglycidyl ethers such as glycerol triglycidyl ether, diglycerol triglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, and trimethylolpropane triglycidyl ether; tetra such as pentaerythritol tetraglycidyl ether Glycidyl ethers; other polyglycidyl ethers or polymerization having glycidyl groups as functional groups 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 polymers; and alicyclic epoxy compounds. Of these, one or more kinds can be used, but a compound having two or more glycidyl groups is preferably used from the viewpoint of reactivity.

The amount of the organic compound (B) used (hereinafter, unless otherwise specified, (B) includes (B ′)) is 0.1 to the total amount of the silane compound (A). ~ 3
It is good to be 00% by weight, preferably 1 to 200% by weight. 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 when the amount exceeds 300% by weight, the gas barrier property may be reduced, which is not preferable.

When the composition for surface treatment of the present invention is used as a paint for a heat-sensitive thermal transfer heat stick inhibitor,
A functional group in which the organic compound (B ') can react with an amino group or an imino group and / or-
It is preferable to have two or more functional groups capable of reacting with Si (OR ¹³ ) in the molecule.

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)

As specific examples, 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; acyloxylanes such as tetraacetoxysilane and methyltriacetoxysilane; and silanols such as trimethylsilanol. One or more of these can be used.

The organometallic compound (C) has a chemical resistance of the coating,
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 comprises a silane compound (A), an organic compound (B) (including B ') and an organometallic compound (C).
The types were reacted as follows. (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 Compound (C) hydrolyzed and condensed before or after reaction with compound (C) (PABC)

Of the above (1) to (4), (2) and (4) can be further divided as follows. (5) A product obtained by reacting a hydrolyzed condensate of a silane compound (A) with an organic compound (B) (PAB-1). (6) A silane compound (A) and an organic compound (B) (PAB-2) which is obtained by hydrolyzing and condensing the reaction product (AB) of (4) (7) The hydrolyzing and condensing product of the silane compound (A) is converted into an organic compound (B) and an organometallic compound (C) ) (PABC-1) (8) A product obtained by reacting a silane compound (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 one or more of the above reactive compounds (1) to (8), a compound containing a quaternary ammonium salt, and water. The compound containing a quaternary ammonium salt is not particularly limited, but specifically, an alkyltrimethylammonium salt,
Examples thereof include dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, and alkylpyridium salts, which are contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the reactive compound. It has been clarified that these quaternary ammonium salts have a function of controlling the cross-linking point and preventing gelation due to ionic affinity with silanol. Therefore, even when a highly reactive silane compound is used in an aqueous system, an aqueous surface treatment composition excellent in storage stability and film formability can be provided.

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.

Various inorganic and organic additives such as a curing catalyst, a wettability improver, a plasticizer, a defoaming agent and a thickener are added to the composition for surface treatment of the present invention 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 body 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, cellophane, polyimide, polyetherimide, polyphenylene sulfone, polysulfone, polyether ketone,
Thermoplastic resins such as ionomer resins and fluororesins; thermosetting resins such as melamine resins, polyurethane resins, epoxy resins, phenolic resins, unsaturated polyester resins, alkyd resins, urea resins and silicon resins. 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 thermal 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.

[0045]

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 is applied to 25 μm polyethylene terephthalate (hereinafter abbreviated as PET) to a predetermined thickness by a dipping method, and then the dried coating film is coated at 180 °.
When no crack was formed, the case where no crack occurred was evaluated as ○, and when the crack occurred, it was evaluated as x.

<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. X. <Storage Stability> After the surface treatment composition was stored at 23 ° C. for one month, it was evaluated as ○ 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 A coating agent was obtained. This undercoat agent is applied to a 25 μm PET film by dipping at a thickness of 2.0 μm,
For 10 minutes. The obtained film was transparent, the flexibility was good, and the oxygen permeability was 71.19 cc / m ² · 24 hrs · atm.

Example 1 20 g of γ-aminopropyltrimethoxysilane (hereinafter abbreviated as APTMS) was added to a mixture of 100 g of water and 0.2 g of lauryltrimethylammonium chloride (hereinafter abbreviated as LTMAC), and the mixture was added at 21 ° C. for 24 hours. After stirring, an APTMS hydrolysis-condensation product was obtained. Ethylene glycol diglycidyl ether (hereinafter referred to as 1) is added into the APTMS hydrolysis condensate solution.
2 g), and the mixture was stirred 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,
It was left to dry for 24 hours and dried. The resulting surface-treated film is
Transparent flexible ○, oxygen permeability is 3.95cc / m ² · 24hrs · at
m. 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 APTMS was added to a mixture of 100 g of water and 0.2 g of LTMAC.
After adding 20 g, the mixture was stirred at 21 ° C. for 24 hours to obtain an APTMS hydrolyzed condensate. 2 g of 1EDGE was added to the APTMS hydrolyzed condensate solution, and the mixture was stirred at 21 ° C. for 5 hours. Then, 5 g of tetramethoxysilane (hereinafter abbreviated to 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 LTMAC and 0.4 g of concentrated hydrochloric acid was added 10 g of TMOS, followed by stirring at 21 ° C. for 24 hours to obtain a TMOS hydrolyzed condensate. 15 g of APTMS and 2 g of 1EDGE were added to this TMOS hydrolyzed 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, stirred at 21 ° C. for 5 hours, and then mixed with 5 g of TMOS and 100 g of water.
g, and LTMAC 0.2 g, 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 20 g of methyltrimethoxysilane (hereinafter abbreviated as MTMOS) was added to a mixture of 100 g of water, 0.4 g of LTMAC and 0.4 g of concentrated hydrochloric acid.
And stirred at 21 ° C. for 24 hours to obtain an MTMOS hydrolyzed condensate. 2 g of diethylene glycol was added to the MTMOS hydrolyzed condensate solution and stirred at 21 ° C. for 7 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 18 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 L
0.2 g of TMAC 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 liquid obtained by mixing 100 g of water and 0.2 g of LTMAC.
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 6.22 cc / m ² · 24 hrs · atm, and the storage stability of the surface treatment composition was ○.

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 mixture of 8 g of water and 0.2 g of LTMAC.
g was added and stirred at 21 ° C. for 24 hours to obtain an APTMS hydrolyzed condensate. 2 g of 1EDGE was added to the APTMS hydrolyzed condensate solution and stirred at 21 ° C. for 5 hours to obtain a composition for surface treatment. This composition was applied in the same manner as in Comparative Example 1.
After drying, a property test was performed, and the results are shown in Table 2.

Comparative Example 7 APTMS (20 g), water (100 g) and LTMAC (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.
5 g 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 LTMAC, 0.4 of concentrated hydrochloric acid
g was mixed 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 APTMS (20 g) and water (100 g) 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 applied in the same manner as in Comparative Example 1.
After drying and a property test, the results are shown in Table 2.

[0062]

[Table 1]

* 1 The unit of oxygen permeability is [cc / m ² · 24 hrs · a
tm]. * 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, distearyl dimethyl ammonium chloride was used as the compound containing a quaternary ammonium salt. In all other cases, LTMAC was used. * 4 After the reaction of APTMS of Example 18 with 1EDGE, water was added to carry out a hydrolysis reaction.

[0064]

[Table 2]

* 1 The unit of oxygen permeability is [cc / m ² · 24 hrs · a
tm]. * 2 No compound containing a quaternary ammonium salt 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 TEOS: Tetraethoxysilane MTMOS: Methyltrimethoxysilane TBOT: titanium tetrabutoxide 1EDGE: ethylene glycol diglycidyl ether 2EDGE: diethylene glycol diglycidyl ether 4EDGE: tetraethylene glycol diglycidyl ether PE4GE: pentaerythritol tetraglycidyl ether EG: ethylene glycol 2EG: diethylene glycol 1EDEE L ether: ethylene glycol Ann Chloride

Example 19 Lauryl trimethyl ammonium chloride was added to 100 g of water.
After adding 0.2 g and stirring, 20 g of γ-aminopropyltrimethoxysilane was added dropwise to this liquid at 30 ° C. over 30 minutes. After stirring at 30 ° C. for 30 minutes, 3 g of diethylene glycol diglycidyl ether was added, and stirring was further continued for 1 hour to obtain a polymer solution 1. This polymer solution 1 was applied to one surface of a polyethylene terephthalate base film having a thickness of 6 μm with a bar coater and then dried by heating.
A 1.5 μm heat stick prevention layer was formed. Next, a thermal transferable ink layer having a thickness of 2 μm was provided on the other surface of the base film to obtain a thermal transfer material (1).

Example 20 20 g of γ-aminopropyltriethoxysilane and 4 g of ethylene glycol diglycidyl ether were mixed and stirred at 30 ° C. for 3 hours. To this solution, 100 g of water and 0.2 g of lauryltrimethylammonium chloride were added dropwise over 1 hour.
Stirring was further continued for 2 hours to obtain a polymer solution 2. This polymer solution 2 was applied to one surface of a polyethylene terephthalate base film having a thickness of 6 μm with a bar coater and then dried by heating to form a heat stick preventing layer having a thickness of 1.5 μm. Next, a thermal transfer ink layer having a thickness of 2 μm was provided on the other surface of the base film to obtain a thermal transfer material (2).

Example 21 0.2 g of distearyldimethylammonium chloride was added to 100 g of water and stirred, and then 20 g of methyltrimethoxysilane was added dropwise at 30 ° C. over 30 minutes. 3 at 30 ° C
After stirring for 2 hours, 2 g of triethylene glycol was added, and stirring was further continued for 1 hour to obtain a polymer solution 3. This polymer solution 3 was applied to one surface of a polyethylene terephthalate base film having a thickness of 6 μm with a bar coater and then dried by heating to form a heat stick prevention layer having a thickness of 1.5 μm. Next, a thermal transferable ink layer having a thickness of 2 μm was provided on the other surface of the base film to obtain a thermal transfer material (3).

Comparative Example 11 A comparative heat stick inhibitor for a heat-sensitive thermal transfer material was prepared in the same manner as in Example 19 except that diethylene glycol diglycidyl ether was not used. Using this, a heat stick preventing layer was formed in the same manner as in Example 19, and then a heat transferable ink layer was provided.
A comparative thermal transfer material (1) was obtained.

Comparative Example 12 A polymer solution was prepared in the same manner as in Example 20, except that lauryltrimethylammonium chloride was not used. However, a precipitate formed in the polymer solution after one month.

Comparative Example 13 A comparative thermosensitive thermal transfer material was prepared in the same manner as in Example 19 except that the heat stick preventing layer was not formed.
(3) was obtained.

Examples 22 to 24 and Comparative Examples 14 to 15 The thermal transfer materials (1) to (3) obtained in Examples 19 to 21 and Comparative Examples 11 and 13, and the thermal transfer materials (1) and (3) )
Was subjected to a thermal transfer test on recording paper using a thermal head print test apparatus (Matsushita Electronic Parts Co., Ltd.). The test conditions were as follows: applied voltage: 20 V, printing speed: 2 mm /
Seconds. The presence or absence of the heat stick phenomenon during the thermal transfer test was evaluated by observing the running state of the thermal head. Further, the state of contamination of the thermal head after the thermal transfer test was also examined. Table 3 shows the results.

[0073]

[Table 3]

[0074]

By using the aqueous surface treating composition of the present invention, a transparent film having excellent 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 2812120 (JP, B2) Patent 3095699 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 183/04

Claims (4)

(57) [Claims] (1) A silane compound represented by the following general formula (A): [Wherein R ¹ and R ² may be the same or different, and a substituent having a hydrogen atom, a lower alkyl group, an aryl group, an unsaturated aliphatic residue or a functional group directly bonded to a carbon chain is represented by R ³
May be the same or different and represent a hydrogen atom, a lower alkyl group or an acyl group, and x and y are from 0 to 3
(Where x + y is an integer of 3 or less)], a functional group having reactivity with a functional group and / or a Si (OR ³ ) group of R ¹ or R ^{2 in} the silane compound (A). Organic compound (B) having two or more groups in the molecule
(2) a reaction product (PAB) obtained by hydrolytic condensation of the silane compound (A) before or after the reaction with the organic compound (B); Compound (A), an organometallic compound represented by the following general formula (C), and R ⁴ _mM (OR ⁵ ) _n ... (C) (where M is a metal element, and R ⁴ is the same or different. ^May represent a hydrogen atom, a lower alkyl group, an aryl group or an unsaturated aliphatic residue; R ⁵ may be the same or different; and represents a hydrogen atom, a lower alkyl group or an acyl group, and m is 0 or A positive integer, n is an integer of 1 or more, and m + n is equal to the valency of the metal element M) (ABC) a reaction product with the organic compound (B), (4) the silane compound (A) Reaction between the organometallic compound (C) and the organic compound (B) A reaction product (PABC) which has been (co) hydrolyzed and condensed before or after the reaction, at least one reactive compound selected from the group consisting of (1) to (4), a compound containing a quaternary ammonium salt, And a water-based surface treatment composition for a gas barrier , characterized by containing water. 2. The silane compound (A) according to claim 1.
Is a silane compound represented by the following general formula (A ′); Wherein A ¹ is an alkylene group, R ⁵ is a hydrogen atom, a lower alkyl group, or (Where A ² represents a direct bond or an alkylene group, R ¹⁰ , R
¹¹ represents a hydrogen atom or a lower alkyl group), R ⁷ is a hydrogen atom or a lower alkyl group, R ⁸ is the same or different lower alkyl group, aryl group or unsaturated aliphatic residue, R ⁹ is hydrogen Atom, lower alkyl group, or acyl group (provided that at least one of R ⁶ , R ⁷ , R ¹⁰ , and R ¹¹ is a hydrogen atom); w is any of 0, 1, and 2; Represents an integer of 3 (where w + z = 3
)] And the organic compound (B) according to claim 1 has a functional group capable of reacting with an amino group and / or a functional group capable of reacting with -Si (OR ⁹ ) in the silane compound (A ′). ,
The water-based surface treatment composition for a gas barrier according to claim 1, which is an organic compound (B ') having two or more in the molecule. 3. A surface-treated resin molded article characterized in that at least one surface of the resin molded article is treated with the composition for surface treatment for gas barrier according to claim 1 or 2. 4. A gas barrier material treated with the water-based surface treatment composition for a gas barrier according to claim 1 or 2.