JP3095698B2 - Composition for surface treatment and molded article of surface treated resin - Google Patents

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, 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.

On the other hand, in recent years, facsimile machines and printers
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 drawbacks such as poor storage stability, susceptibility to falsification after recording, and poor solvent resistance. Therefore, a transfer type thermal recording method is known as a method for improving these drawbacks. I have.

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 thermal transfer ink layer such as a hydrophilic ink layer or 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.

[0011]

SUMMARY OF THE INVENTION In view of the above problems, the present inventors have developed a surface treatment film which has excellent gas barrier properties, is transparent, and has flexibility so as not to impair the properties of non-processed materials. It is a second object to provide a surface coating composition that can be formed, and to provide a surface-treated resin molded article having such excellent properties. It is a third object of the present invention to provide a high-performance heat-sensitive thermal transfer heat stick inhibitor paint using the composition.

[0012]

According to the present invention, a composition for surface coating comprises a silane compound (A) represented by the following general formula (I):
When,

[0013]

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

[0015]

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Wherein A ² represents an alkylene group, R ⁵ and R ⁶ represent a hydrogen atom or a lower alkyl group,
R ² represents a hydrogen atom or a lower alkyl group, R ³ represents the same or different lower alkyl group, aryl group or unsaturated aliphatic residue, and R ⁴ represents a hydrogen atom, a lower alkyl group or an acyl group (provided that R ¹ , At least one of R ² , R ³ and R ⁴
One is a hydrogen atom), w is any of 0, 1, or 2, z
Represents an integer of 1 to 3 (where w + z = 3)]
An organometallic compound (C ₁ ) represented by the following general formula (II), R ⁷ _mM (OR ⁸ ) _n ... (II) (wherein M represents titanium, zirconium or aluminum, and R ⁷ is the same or different; May represent a hydrogen atom, a lower alkyl group, an aryl group or an unsaturated aliphatic residue, R ⁸ represents a hydrogen atom, a lower alkyl group or an acyl group, m is 0 or a positive integer, and n is 1 or more. And m + n is the same as the valence of the element M) or an organometallic compound which is a mixture of the organometallic compound (C ₁ ) and an organosilane compound (C ₂ ) represented by the following general formula (III): (C ₁ + C ₂ ) [Hereinafter, the organometallic compound (C ₁ ) and the organometallic compound (C ₁ + C ₂ ) are referred to as “organometallic compound (C)”] R ⁹ _o Si (OR ¹⁰ ) _p ... (III (Wherein R ⁹ may be the same or different and a hydrogen atom Represents a lower alkyl group, an aryl group or an unsaturated aliphatic residue, R ¹⁰ represents a hydrogen atom, a lower alkyl group or an acyl group, o is 0 or a positive integer, p is an integer of 1 or more, and o + p is Co-hydrolysis condensate (D) with a valence of Si), a compound (E) having two or more functional groups capable of reacting with an amino group in the molecule, and a solvent (F)
Or the silane compound (A) and / or the hydrolyzed condensate (B) of the silane compound (A) and the organometallic compound (C) and / or the organometallic compound (C). The gist of the present invention is to contain the hydrolysis condensate (G), the compound (E) and the solvent (F).

The present invention also includes a surface-treated resin molded product obtained by treating at least one surface of the surface of the resin molded product with the surface coating composition. In the following description, the surface coating composition of the present invention may be referred to as a surface treatment composition.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION A silane compound (A) represented by the following general formula (I) used in the present invention:

[0019]

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(Where A ¹ , R ¹ , R ² , R ³ , R ⁴ , w,
z has the same meaning as described above).
The silane compound having an amino group and a hydrolytic condensable group in the molecule represented by (I) is not particularly limited.

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-
Aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldiisopropoxysilane, γ-aminopropylethyldibutoxysilane, γ-aminopropyltriacetoxysilane, etc. Alternatively, two or more kinds can be used.

The compound (B) is represented by one or two selected from the silane compounds (A) exemplified above.
It is a compound obtained by preliminarily hydrolyzing and condensing (poly) combining compounds. For example, when γ-aminopropyltrimethoxysilane is used as the silane compound (A), the hydrolysis condensation reaction is represented by the following formula. H ₂ NC ₃ H ₆ -Si (OCH ₃ ) ₃ + 3H ₂ O → H ₂ NC ₃ H ₆ -Si (OH) ₃ + 3CH ₃ OH H ₂ NC ₃ H ₆ -Si (OH) ₃ → H ₂ NC ₃ H ₆ -SiO _3/2 +3/2 H ₂ O

The hydrolysis-condensation polymerization proceeds in the presence of the silane compound (A) and water, but the reaction in a solvent (F) described below is more advantageous as a composition for surface treatment. The molar ratio A / W of the silane compound (A) and water is preferably 0.1 to 3. If it is less than 0.1, gelation tends to occur during the polycondensation, and if it is more than 3, the reaction takes too much time, and the unreacted silane compound may remain. The reaction time is not particularly limited, but it is preferable that the hydrolysis-condensation polymerization reaction is completed. This is because, when a silane compound (B) which has been prepolymerized is used, the volume shrinkage is reduced when the hydrolytic polycondensation is sufficiently performed, so that the occurrence of cracks in the surface treatment film can be suppressed. .

As the composition for surface treatment of the present invention, a composition obtained by previously co-hydrolyzing and condensing the silane compound (A) and the organometallic compound (C) is used. As the organometallic compound (C), an organometallic compound (C) represented by the following general formula (II)
₁ ) or an organometallic compound (C ₁ + C ₂ ) which is a mixture of the organometallic compound (C ₁ ) and an organosilane compound (C ₂ ) represented by the following general formula (III) is used.

The organometallic compound (C ₁ ) is not particularly limited as long as it can be represented by the following general formula (II). R ⁷ _mm (OR ⁸ ) _n (II) (where M, R ⁷ , R ⁸ , m, and n have the same meaning as described above)

Specific examples include titanium alkoxides such as titanium tetraethoxide, titanium tetraisopropoxide and titanium tetrabutoxide; zirconium alkoxides such as zirconium tetraethoxide, zirconium tetraisopropoxide and zirconium tetrabutoxide; Aluminum alkoxides such as ethoxide, aluminum tetraisopropoxide, and aluminum tetrabutoxide are exemplified.

The organic silane compound (C ₂ ) is not particularly limited as long as it can be represented by the following general formula (III). R ⁹ _o Si (OR ¹⁰ ) _p (III) (where R ⁹ , R ¹⁰ , o, and p have the same meaning as described above)

Specific examples include tetramethoxysilane,
Tetraethoxysilane, tetraisopropoxysilane,
Tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, Dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycid Xypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane,
alkoxysilanes such as γ-chloropropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane; acyloxysilanes such as tetraacetoxysilane and methyltriacetoxysilane; and silanols such as trimethylsilanol.

The organic metal compound (C ₁ ) and the organic metal compound (C ₁ + C ₂ ) are collectively referred to as “organic metal compound (C)”. One or two of the organometallic compounds (C)
The co-hydrolyzed condensate (D) is produced by hydrolyzing and condensing the silane compound (A) with the silane compound (A) using more than one kind. The reaction may be carried out under the same conditions as described above for the case where the silane compound (A) is subjected to hydrolytic condensation polymerization.

The composition for surface treatment of the present invention comprises, as a main component, a co-hydrolysis condensate (D) of an organometallic compound (C) and a silane compound (A) as a main component. (A) and either or both of the hydrolysis condensate (B) of the silane compound (A), the hydrolysis condensate (G) of the organometallic compound (C) and the organometallic compound (C)
A combination of any one or both may be used as a main component. The metal compound (C) or its hydrolyzed condensate (G) is effective for improving the chemical resistance and heat resistance of the coating. Also, if a large amount of hydrolysis condensate is used,
The generation of cracks in the coating can be reliably prevented.

In this case, the organometallic compound (C) and / or
Alternatively, the hydrolysis condensate (G) is about 0 to 200 mol%, preferably 0 to 100 mol%, based on the silane compound (A) and / or the hydrolysis condensate (B).
It is desired to be used. If it is used more than 200%, the amine in the silane compound component may be used as a catalyst to form particles and rapidly gel. Hereinafter, (1) a cohydrolysis condensate (D) of an organometallic compound (C) and a silane compound (A), and (2) a hydrolysis condensate of the silane compound (A) and the silane compound (A) (B) a hydrolysis condensate (G) of one or both of the above and the organometallic compound (C)
And a combination of either or both of the organometallic compound (C) and the organometallic compound (C) are referred to as a silane compound component.

The functional group of the compound (E) having at least two functional groups capable of reacting with an amino group in the molecule used in the present invention includes an epoxy group, a carboxyl group, an isocyanate group and an oxazoline group. These functional groups may be the same or different in compound (E). Specific examples of the compound (E) include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and dipropylene. Diglycidyls such as glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl adipate, diglycidyl o-phthalate, and glycerol diglycidyl ester Glycerol triglycidyl ether, diglycerol triglycidyl ether, trig Triglycidyl ethers such as sidyl tris (2-hydroxyethyl) isocyanurate and trimethylolpropane triglycidyl ether; tetraglycidyl ethers such as pentaerythritol tetraglycidyl ether; and 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 polymers; 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 compound (E) used is 0.1 to 300% by weight, preferably 1 to 200% by weight, based on the total amount of the silane compound components. Compound (E)
Reacts with the amino group in the silane compound component to act as a crosslinking agent component. When the compound (E) is less than 0.1% by weight,
If the coating is insufficient in flexibility and used in excess of 300% by weight, the gas barrier properties may be undesirably reduced.

The solvent (F) used in the present invention includes:
The solvent is not particularly limited as long as the solvent dissolves the silane compound component and the compound (E). Specific examples include methanol, ethanol, isopropanol, butanol, pentanol, ethylene glycol, diethylene glycol, triethylene glycol, and ethylene glycol monomethyl. Alcohols such as ether, diethylene glycol monomethyl ether and triethylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, benzene and xylene; hexane, heptane and octane Hydrocarbons; acetates such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; other ethyl phenol ethers, Pills ether, tetrahydrofuran and the like, can be used as a mixture of one or more of these. Of these, alcohols are preferably used. It is desirable to carry out the above-mentioned hydrolysis-condensation reaction using these solvents.

Various inorganic and organic additives such as a curing catalyst, a wettability improver, a plasticizer, an antifoaming agent and a thickener are added to the composition 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, polyetherketone, ionomer Thermoplastic resin such as resin and fluorine resin;
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 of coating the surface treatment composition on the resin molded article 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.

After coating, the coating is cured and dried, and 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.

The composition for surface treatment of the present invention can also be applied to a thermal stick inhibitor for a thermal transfer material. An example of the application is shown in FIG. By providing a thermal transfer ink layer 2 on one surface of the base film 1 and a thermal stick prevention layer 3 made of the thermal stick inhibitor of the present invention on the other surface, a thermal transfer material is constructed. The thermal transferable ink layer 2 is a conventionally used hot-melt ink layer, a thermally sublimable dye-containing layer, or the like, and is formed by coating or printing by a conventionally known method. The heat stick prevention layer 3 of the present invention has heat resistance, good slipperiness, high heat stick prevention ability, and can be easily applied to a base film by a usual coating machine or printing machine. Things.

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 is preferably from 0.1 to 5 μm. The heat stick preventing layer 3 can be formed by coating or printing using the composition for surface treatment of the present invention by a conventionally known method, and a curing catalyst may be used as needed in the formation.

As the base film, those conventionally used can be used, for example, polyester film, polycarbonate film, cellulose acetate film, polypropylene film, cellophane and the like.

[0042]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In addition, the evaluation method of the characteristic test was performed as follows. <Oxygen permeability> Measured with a gas permeability measuring device manufactured by Toyo Seiki Seisakusho in accordance with JIS K 7126. <Flexibility> After applying the surface treatment composition to a 25 μm polyethylene terephthalate (hereinafter abbreviated as PET) film to a predetermined thickness by dipping, the dried coated film was bent at 180 ° and no crack was generated. ○, and those with cracks were evaluated as ×. <Transparency> P coated in the same manner as in the flexibility evaluation test
The untreated ET film was visually compared with the untreated ET film, and those having no difference in transparency were evaluated as ○, and those having turbidity such as white turbidity were evaluated as ×.

Reference Example 1 (Pretreatment of Resin Molded Product ) Urethane coating agent Takenate A-3 (manufactured by Takeda Pharmaceutical Co., Ltd.) 25
g, Takerac A-310 (manufactured by the company) 150 g, and ethyl acetate phenol 500 g were mixed to obtain a urethane undercoat agent. This undercoat agent was applied to a 25 μm PET film by dipping to a thickness of 2.0 μm.
Drying was performed at 20 ° C. for 30 minutes. The obtained film was transparent and flexible, and the oxygen permeability was 70.01 cc / m ² · 24 hrs · atm.

Example 1 γ-aminopropyltrimethoxysilane (hereinafter referred to as APTM
15g, titanium tetrabutoxide (hereinafter TB)
1 g of OT) and 120 g of methanol were mixed and stirred at 21 ° C. for 24 hours to obtain a cohydrolysis condensate of APTM and TBOT. Tetraethylene glycol diglycidyl ether (hereinafter abbreviated as 4EDGE) is introduced into this co-hydrolysis condensate solution.
2 g was added and the mixture was stirred at 21 ° C. for 5 hours to obtain composition 1 for surface treatment. This composition 1 was applied to the resin molded product obtained in Reference Example 1 to a thickness of 0.2 μm by dipping,
It was left for a while and dried. The obtained surface-treated film was transparent and flexible, and the oxygen permeability was 9.97 cc / m ² · 24 hrs · atm.

Comparative Example 1 APTM (15 g) and methanol (120 g) were mixed, applied directly to the resin molded product obtained in Reference Example 1, and dried. The thickness of the obtained surface-treated film was 0.1 μm and was transparent. The flexibility ×, oxygen permeability is 5.98cc / m ² · 24hrs · at
m.

Comparative Example 2 15 g of APTM, 60 g of methanol and 1.5 g of water were mixed, and
The mixture was stirred at 24 ° C for 24 hours to obtain an APTM hydrolyzed condensate. This APTM hydrolyzed condensate was directly applied to the resin molded product obtained in Reference Example 1 and dried. The obtained surface-treated film had a thickness of 0.3 μm and was transparent. The flexibility was × and the oxygen permeability was 2.70 cc / m ² · 24 hrs · atm.

Comparative Examples 3 to 10 Comparative Examples 1 to 10 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.

Comparative Example 11 15 g of APTM, 5 g of methanol and 1.5 g of water were mixed,
For 24 hours to obtain an APTM hydrolyzed condensate. This A
Add 2 g of 1EDGE to the PTM hydrolyzed condensate, and add 5 g at 21 ° C.
After stirring for an hour, a composition for surface treatment was obtained. This composition was thickly applied to the resin molded product obtained in Reference Example 1 and dried.
Although the thickness of the obtained surface-treated film was 21.0 μm and transparent, the flexibility was poor and the oxygen permeability was 69.21 cc / m ² · 24 h.
It was rs · atm.

Comparative Example 12 A mixture of 15 g of APTM, 120 g of methanol and 1.5 g of water was prepared by mixing
The mixture was stirred at 24 ° C for 24 hours to obtain an APTM hydrolyzed condensate. 5 g of TMOS was added to the APTM hydrolyzed condensate solution to obtain a composition for surface treatment. This composition was coated 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 13 TMOS 15.8 g, methanol 124.8 g, water 3.0 g, concentrated hydrochloric acid 0.1 g
4 g were mixed and stirred at 21 ° C. for 24 hours to obtain a TMOS hydrolyzed condensate. Into this TMOS hydrolysis condensate solution, A
15 g of PTM was added to obtain a composition for surface treatment. This composition was coated 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 14 A mixture of 15 g of APTM and 120 g of methanol was mixed with TMOS.
5 g was added to obtain a composition for surface treatment. After applying and drying this composition in the same manner as in Example 1, a characteristic test was conducted. The results are shown in Table 1.

[0052]

[Table 1]

The abbreviations of the compounds in Table 1 are as follows. APTM: γ-aminopropyltrimethoxysilane TMOS: tetramethoxysilane TEOS: tetraethoxysilane TBOT: titanium tetrabutoxide GPTM: γ-glycidopropyltrimethoxysilane VTM: vinyltrimethoxysilane 1EDGE: ethylene glycol diglycidyl ether 4EDGE: tetra Ethylene glycol diglycidyl ether EG: Ethylene glycol HMDA: Hexamethylene diamine

[0054]

By using the composition for surface treatment of the present invention, a transparent film having excellent gas barrier properties and flexibility can be formed. The surface-treated resin molded article of the present invention is useful as a gas barrier material in the field of packaging materials and the like. Further, when the composition for surface treatment of the present invention is used as a paint for a heat-sensitive thermal transfer heat stick inhibitor, it provides a coating film having excellent heat resistance and slipperiness and having high heat stick preventing ability.

[Brief description of the drawings]

FIG. 1 is an enlarged explanatory cross-sectional view 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) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 1/00-201/10

Claims (5)

(57) [Claims] (1) A silane compound (A) represented by the following general formula (I): Wherein A ¹ is an alkylene group, R ¹ is a hydrogen atom, a lower alkyl group, or Wherein A ² represents an alkylene group, R ⁵ and R ⁶ represent a hydrogen atom or a lower alkyl group, R ² represents a hydrogen atom or a lower alkyl group, R ³ represents the same or different lower alkyl group, Aryl group or unsaturated aliphatic residue, R ⁴
Represents a hydrogen atom, a lower alkyl group or an acyl group (provided that at least one of R ¹ , R ² , R ³ and R ⁴ is a hydrogen atom), w is any one of 0, 1, and 2, and z is 1-3
(Where w + z = 3)] an organometallic compound (C ₁ ) represented by the following general formula (II): R ⁷ _mm (OR ⁸ ) _n ... (II) (where M is titanium, Represents zirconium or aluminum, R ⁷ 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 ⁸ represents a hydrogen atom, a lower alkyl group or an acyl group. , M is 0 or a positive integer, n is an integer of 1 or more, and m + n is equal to the valence of the element M) or the organometallic compound (C ₁ ) and an organosilane represented by the following general formula (III). compound (C ₂₎ and the organometallic compound is a mixture of (C ₁ + C ₂₎ and co-hydrolytic condensate (D), in _{^{R 9 o Si (OR 10)}} p ... (III) ( wherein, R ⁹ is May be the same or different, a hydrogen atom, a lower alkyl group, an aryl R ¹⁰ represents a hydrogen atom, a lower alkyl group or an acyl group, o is 0 or a positive integer, p is an integer of 1 or more, and o + p is a valence of Si. (2) A composition for surface coating comprising (2) a compound (E) having two or more functional groups capable of reacting with an amino group in a molecule, and (3) a solvent (F). (1) a silane compound (A) represented by the following general formula (I) and / or a hydrolyzed condensate (B) of the silane compound (A): Wherein A ¹ is an alkylene group, R ¹ is a hydrogen atom, a lower alkyl group, or Wherein A ² represents an alkylene group, R ⁵ and R ⁶ represent a hydrogen atom or a lower alkyl group, R ² represents a hydrogen atom or a lower alkyl group, R ³ represents the same or different lower alkyl group, Aryl group or unsaturated aliphatic residue, R ⁴
Represents a hydrogen atom, a lower alkyl group or an acyl group (provided that at least one of R ¹ , R ² , R ³ and R ⁴ is a hydrogen atom), w is any one of 0, 1, and 2, and z is 1-3
(Where w + z = 3)] (2) An organometallic compound (C ₁ ) represented by the following general formula (II): R ⁷ _mM (OR ⁸ ) _n ... (II) Represents titanium, zirconium or aluminum, R ⁷ may be the same or different and represents a hydrogen atom, a lower alkyl group, an aryl group or an unsaturated aliphatic residue; R ⁸ represents a hydrogen atom, a lower alkyl group or an acyl 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 element M) or the organometallic compound (C ₁ ) and the following general formula (III): organosilane compound (C ₂₎ and which is a mixture an organic metal compound (C ₁ + C ₂₎ [hereinafter, the organometallic compound (C ₁₎ with an organometallic compound (C ₁ + C ₂₎ "organometallic compound (C) and _{^{"] R 9 o Si (OR 10}} ) p ... (III) ( Among, R ⁹ may be the same or different, represent a hydrogen atom, a lower alkyl group, an aryl group or an unsaturated aliphatic residue, R ¹⁰ represents a hydrogen atom, a lower alkyl group or an acyl group, o is 0 or a positive integer, p is 1 or more integer and o + p is consistent with the valence of Si) and / or organic hydrolytic condensation product of a metal compound (C) (G), amino and (3) in the molecule A composition for surface coating, comprising: a compound (E) having two or more functional groups capable of reacting with a group; and (4) a solvent (F). 3. The compound according to claim 1, wherein the functional group capable of reacting with an amino group in the compound (E) is an epoxy group.
The composition for surface coating according to the above. 4. A surface-treated resin molded article obtained by treating at least one surface of the surface of the resin molded article with the composition for surface coating according to claim 1. 5. The surface-treated resin molded product according to claim 4, wherein the molded product is used as a gas barrier material.