JP2000063758A - Emulsion composition for coating glass vessel and glass vessel coated with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject glass coating emulsion composition that has high storage stability and coating properties, can form a coating layer having excellent resistances to water and weather, excellent injured part-shielding properties on the substrate material by using a specific carboxylic acid and amine base-containing compound or the like and water in a specific proportion. SOLUTION: The objective composition comprises (A) 100 pts.wt. of a carboxylic acid-amine base containing compound that is prepared by reaction of an acidulant containing carboxylic acid such as citric acid or the like with an amino group-containing silane of formula I (R1 is an amino group-containing group; R2 and X are each a 1-4C alkyl; 1<=a<=3; and a+b=3), (B) 0-1,000 pts.wt. of a carboxylic acid-amine base containing compound that is prepared by reaction of an acidulant containing carboxylic acid with an amino group-containing silane of formula II (R3 is a monovalent hydrocarbon, an alkoxy; R4 is R1; R5 is a monovalent hydrocarbon; and (m) and (n) are each an integer of 1-1,000), (C) 1,000-6,000 pts.wt. of an alkyl-modified silicone oil emulsion of formulas III-V (Z is a 10-90C alkyl; and (p) and (q) are each an arbitrary integer) having a viscosity of 20-50,000 cPs and (D) 1,000-30,000 pts.wt. of water.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an emulsion composition for coating glass containers such as glass bottles. More specifically, it has excellent storage stability and coatability, and after being applied to a substrate,
Water resistance on the substrate under short-time low temperature heating or room temperature,
The present invention relates to an emulsion composition for coating a glass bottle that forms a film having excellent weather resistance and scratch-shielding properties, and a glass container coated with the emulsion composition.

[0002]

2. Description of the Related Art Conventionally, glass containers used as filling containers for products such as beer, soft drinks, milk and coffee are collected from the market after use, washed and repeatedly used. Thus, the glass container repeatedly used, in the bottling process and the subsequent distribution process, due to contact between the glass or the glass container and the metal part of the mechanical device, scratches occur on the container surface, and as repeated use is repeated. The aesthetic appearance is significantly deteriorated and the exterior quality is impaired. As a result, the commercial value of the filled contents is also reduced. Therefore, it has been proposed to apply the coating composition for a glass container to a glass container in which scratches have occurred, and in this case, it is easy to apply and it is possible to form a film having the required physical properties at room temperature. Good property, good water resistance, no sticky or slippery feeling on the surface of the film, easy and complete peeling of the film by washing with an alkaline aqueous solution, no damage to the label attached to the glass container, transported over long distances At times, it is required to satisfy requirements such as no deterioration of the coating film.
In view of such a point, the inventor of the present invention has disclosed in
The prior art proposed in Japanese Patent Publication No. 8 consists of using a composition composed of a specific curable organopolysiloxane and volatile polydimethylsiloxane as a coating agent and satisfies the above requirements. is there. Further, the present inventor has improved this prior art, and disclosed in
In Japanese Patent Laid-Open No. 32341/1994 and Japanese Patent Application Laid-Open No. 6-32342, a glass container having good coating property and shielding effect against deep scratches and scratches of a colorless transparent glass container, and having excellent peelability with an alkaline aqueous solution is disclosed. A scratch-shielding agent and a glass container in which the scratches are shielded by the shielding agent have been proposed.

[0003]

However, 1) safety in handling (no use of raw materials having a low flash point) 2) simplification of work (the coating machine can be easily washed with water) 3) environmental hygiene Problem 4) An emulsion-type treatment agent containing water as a dispersant is desired due to further requirements such as the ability to apply a label after coating depending on the production line. As a prior art of an emulsion type coating agent, a method using carnauba wax or dimethyl silicone oil as a main component is known (JP-A-59-102973, JP-A-59-1).
11947, JP 55-56040 A, JP 5
7-17863). However, glass bottles that have undergone such treatment are difficult to handle because they are easily slipped, and dust and dirt in the air tend to adhere to them easily to stain. There are problems such as floating, and further, because water is used as a dispersion medium, when applied to a substrate, a phenomenon such as cissing occurs. As a technique for improving these, the present inventor has disclosed in JP-A-6-9873 a specific silicone resin and a volatile polyorganosiloxane,
We have proposed an emulsion composition that uses a surfactant, but since a volatile silicone is used as a dispersant for the base resin, the product has a flash point even when it is made into an emulsion, and further coating is performed. There was a problem that the label was peeled off in the step of applying the label later. The present invention solves the above problems and is a one-pack type emulsion composition using water as a dispersion medium, which has excellent storage stability and coatability, and after being applied to a substrate, is heated under low temperature for a short time. Another object of the present invention is to provide an emulsion composition for glass bottle coating which forms a film having excellent water resistance, weather resistance and scratch-shielding property on a substrate at room temperature, and a glass container coated with the emulsion composition.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventor has obtained an acid group having a carboxylic acid by reacting a silane having an amino group and a hydrolyzate thereof. It was found that a useful emulsion composition can be obtained by using such a carboxylic acid / amino base-containing compound and an emulsion of an alkyl-modified silicone oil having a specified viscosity, and completed the present invention. That is, the glass bottle coating emulsion composition of the present invention, (A) the acidulant having a carboxylic acid, the general formula R ¹ -Si (OR ² ) _a X _b (wherein, R ¹ is an amino group-containing group, R ² is an alkyl group having 1 to 4 carbon atoms, X is an alkyl group having 1 to 4 carbon atoms, and a and b are numbers satisfying the relations 1≤a≤3 and a + b = 3, respectively.). Carboxylic acid / amino base-containing compound obtained by reacting amino group-containing silane 100 parts by weight (B) An acidulant having a carboxylic acid has the general formula

[0005]

[Chemical 3]

(In the formula, R ³ is a monovalent hydrocarbon group or an alkoxy group, R ⁴ is an amino group-containing group, R ⁵ is a monovalent hydrocarbon group, m is 1 to 1000, and n is 1 to 1000. Carboxylic acid / amino base-containing compound obtained by reacting amino group-containing polyorganosiloxane represented by
Parts by weight (C) 1000 to 6000 parts by weight of an emulsion of an alkyl-modified silicone oil having a viscosity of 20 to 50,000 cP at 25 ° C. (D) 1000 to 30,000 parts by weight of water.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) used in the present invention is
A component of the present invention, which is a component having a carboxylic acid, has a general formula R ¹ —Si (OR ² ) _a X _b (in the formula, R ¹ is an amino group-containing group, and R ² is a carbon number of 1 to 1). A C4 alkyl group, X is a C1-4 alkyl group, a and b
Are numbers satisfying the relations of 1 ≦ a ≦ 3 and a + b = 3, respectively. ) A carboxylic acid / amino base-containing compound obtained by reacting an amino group-containing silane. Here, as the acidulant having a carboxylic acid, citric acid, gluconic acid, succinic acid, lactic acid, fumaric acid, DL-malic acid and the like are exemplified, among these, to form a stable film, synthetic Citric acid and DL-malic acid are preferred because of their ease. In the amino group-containing silane represented by the general formula R ¹ -Si (OR ² ) _a X _b , R ¹ is an amino group-containing group,

[0008]

[Chemical 4]

Examples of the compounds represented by the formula: wherein R ⁶ and R ⁷ are divalent hydrocarbon groups having 1 to 6 carbon atoms, R ⁸ is hydrogen atom or monovalent hydrocarbon group having 1 to 6 carbon atoms, r represents an integer of 0 to 3. Such amino group-containing groups include aminomethyl group, β-aminoethyl group, γ-aminopropyl group, δ-
Aminobutyl group, N- (β-aminoethyl) aminomethyl group, γ- (N- (β-aminoethyl) amino) aminopropyl group and the like are exemplified.

The component (B) of the present invention is a component which improves the adhesiveness of the label, and is added to the acidulant having a carboxylic acid by the following general formula:

[0011]

[Chemical 5]

(In the formula, R ³ is a monovalent hydrocarbon group or an alkoxy group, R ⁴ is an amino group-containing group, R ⁵ is a monovalent hydrocarbon group, m is 1 to 1000, and n is 1 to 1000. A carboxylic acid / amino base-containing compound obtained by reacting an amino group-containing polyorganosiloxane represented by (indicated by an integer), and the acidulant having a carboxylic acid is the same as the one exemplified in the component (A). Is exemplified. In the amino group-containing polyorganosiloxane represented by the above general formula, R ³ is a monovalent hydrocarbon group or an alkoxy group, and as the monovalent hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, Examples include alkyl groups such as octyl group, decyl group and dodecyl group, cycloalkyl groups such as cyclohexyl group and cyclooctyl group, aryl groups such as phenyl group and tolyl group, alkenyl groups such as vinyl group, allyl group and propenyl group. Among them, an alkyl group is preferable,
Particularly, a methyl group, an ethyl group, a propyl group and a hexyl group are preferable. Examples of the alkoxy group are methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t
An alkoxy group having 1 to 4 carbon atoms such as -butoxy group is preferable, and a methoxy group is particularly preferable because it is easily available. Moreover, as the amino group-containing group for R ^4, the same groups as those for R ¹ are exemplified. Also, m is 1-1000, n is 1-1000.
Is an integer of 5, preferably m is 5 to 500 and n is an integer of 11 to 50. As the amino group-containing polyorganosiloxane, it is preferable to use one having a viscosity of 5 to 2000 cP. If the viscosity of the amino group-containing polyorganosiloxane is less than 5 cP, oil floating is likely to occur when a coating film is formed, which is preferable. If it exceeds 2000 cP, the adhesiveness of the label will be unsatisfactory when the label is applied after coating, which is not preferable. In addition, the blending amount of component (B) is the same as component (A)
0 to 1000 parts by weight, particularly preferably 5 to 100 parts by weight
It is 200 parts by weight. When the amount of the component (B) exceeds 1000 parts by weight, the film becomes sticky and the adhesiveness of the label is deteriorated, which is not preferable.

The component (C) used in the present invention is a component for imparting toughness to the coating film and allowing the coating film to be stably adhered to the substrate, and to specify the viscosity of the alkyl-modified silicone oil. Thus, in the case where there is a step of applying a label after coating, the component imparts one of the features of the present invention that the label can be used without peeling.
25 of the alkyl-modified silicone oils used in the present invention
The viscosity at 0 ° C. is preferably 20 to 50,000 cP, and particularly preferably 100 to 500 cP. When the viscosity of the alkyl-modified silicone oil in the component (C) is 20 cP or less, volatile components are mixed, the components incorporated in the coating are reduced, and a low flash point is caused, which is not preferable. Further, when it is applied to a glass surface, it is not preferable because it moves remarkably in the direction of gravity and the shielding property is deteriorated. If the viscosity exceeds 50,000 cP, the problem of stickiness and slipperiness on the surface of the bottle body and the label being peeled off when the label is applied after coating is not preferable.

The alkyl-modified silicone oil used in the component (C) of the present invention has the following average composition formulas (1) and (2).
Those represented by and (3) are preferable, and the average composition formula (1)
The alkyl-modified silicone oils represented by (2) and (3) are obtained by adding a hydrocarbon having at least one double bond to polydimethylhydrogensiloxane or polymethylhydrogendimethylsiloxane copolymer. These can be synthesized by adding α-olefin to polymethyl hydrogen siloxane or polymethyl hydrogen dimethyl silicone copolymer by an addition reaction using a platinum catalyst.

[0015]

[Chemical 6]

(In the formula, Z is an alkyl group having 10 to 90 carbon atoms, p and q are 25 of an alkyl-modified silicone oil.
Viscosity at 20 ° C is an arbitrary integer of 20 to 50000 cP) The surfactant for emulsifying the alkyl-modified silicone oil is not particularly limited as long as it forms a uniform emulsion as the component (C). Any of nonionic, cationic, anionic, and mixed systems thereof may be used. As the nonionic surfactant, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester,
Examples thereof include polyoxyethylene sorbitan fatty acid ester. Examples of cationic surfactants include alkyl trimethyl ammonium salts such as hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride; dialkyl dimethyl ammonium salts such as didodecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride and dioctadecyl dimethyl ammonium chloride. Examples of salts include benzylammonium salts such as hexadecyldimethylbenzylammonium chloride and octadecyldimethylbenzylammonium chloride. Examples of the anionic surfactant include alkyl sulfate, alkyl phosphate, sodium polyoxyethylene alkylphenyl ether sulfate, and the like. The ratio of the silicone component in the emulsion of the alkyl-modified silicone oil in the component (C) is not particularly limited, but is preferably 5 to 50% because of easy preparation as a composition and good emulsion stability. , Particularly preferably 30 to 35%. In the present invention, the compounding amount of the component (C) is (A) component 1
The amount is preferably 1000 to 6000 parts by weight, particularly preferably 500 to 2000 parts by weight, relative to 00 parts by weight. If the amount is less than 1000 parts by weight, the durability of the coating may be deteriorated, which is not preferable.
If the amount is more than parts by weight, the compatibility with the film-forming component becomes poor, the film becomes cloudy, and a clear surface is not formed, which is not preferable.

In the present invention, the water of the component (D) is the water of the component (A).
The carboxylic acid / amino base-containing compound is used in an amount of 1000 to 30,000 parts by weight per 100 parts by weight. If it is less than 1000 parts by weight, the characteristics such as stickiness will be inferior, and if it exceeds 30,000 parts by weight, the content of the film-forming component will be small, and defects in shielding scratches will be undesired.

The emulsion composition of the present invention comprises the above-mentioned component (A), component (B), component (C) and component (D), and various additives may be added if necessary. However, the compounding amount of this additive is not particularly limited as long as the object of the present invention is not impaired. As this additive,
For example, a film modifier such as a higher fatty acid ester, an ultraviolet absorber, a thickener, an antioxidant and the like are exemplified.

As a method for applying the emulsion composition for glass bottle coating of the present invention to a container, a commonly used method such as spray coating, brush coating, puff coating, dipping method or the like can be used. Further, a large amount of glass containers, usually such glass containers are bottle bodies having a narrow mouth, but when processing these, for example, a roller type coating device described in Japanese Patent Laid-Open No. 58-213654 or The coating belt type coating device described in JP-B-1-59221 can be used. The thickness of the coating is arbitrary, but from the viewpoint of scratch-shielding effect, balance of tactile sensation, and releasability with an alkaline aqueous solution, it is 0.5-40
About μm is appropriate. Needless to say, the part to be applied is not limited to the scratched portion, but for the purpose of cost reduction, it is possible to coat only the scratched portion to the above-mentioned film thickness. Moreover, the emulsion composition for coating a glass bottle of the present invention does not damage the label even when applied on a label attached to a glass container.

The emulsion composition for coating a glass bottle of the present invention does not need to be particularly heated during curing, and if left at room temperature for 0.5 to 48 hours after coating, a coating having no surface tackiness can be easily obtained. Accordingly, heating may be performed to shorten the curing time.

[0021]

INDUSTRIAL APPLICABILITY The emulsion composition for coating a glass container of the present invention is not only excellent in scratch-shielding effect but is also excellent in water repellency and water resistance when applied to a glass substrate and heated at room temperature or for a short time at low temperature. It forms a coating film that has good properties and weather resistance and does not have a sticky feeling, and the formed coating film and emulsion composition can adhere to the label surface without damaging the label surface or even when the label is applied after coating. It does not cause a problem in sex. The emulsion composition for coating a glass container of the present invention is an emulsion type in which water is used as a dispersion medium, so that there is no problem with safety and environmental hygiene due to an organic solvent, and even though it is an emulsion, it has excellent stability. And further to the substrate,
It shows good coatability without cissing, does not cause slipperiness, stains, oil floating during flooding, etc. and shows good properties as a shielding agent.

[0022]

EXAMPLES The present invention will be described in more detail below with reference to synthesis examples, examples and comparative examples. The scope of the invention is not limited to the following examples. In addition, unless otherwise specified, the compounding amounts in the synthesis examples, examples and comparative examples are all parts by weight, and the viscosity is a value at 25 ° C.

Synthesis Example 1 Water: 100 g, citric acid monohydrate 2 in a flask equipped with a stirrer, heating jacket, reflux condenser and dropping funnel.
Dissolve 1.0 g (0.1 mol). At this time, it is confirmed by pH test paper that it is on the acidic side. 23.4 g (0.1 mol) of γ- (N- (β-aminoethyl) amino) aminopropylmethyldimethoxysilane was added thereto from the dropping funnel, and the mixture was stirred at a liquid temperature of 50 to 60 ° C. for 1 hour. afterwards
The mixture was cooled to 30 ° C., the pH of the aqueous solution was confirmed to be neutral, and a carboxylic acid / amine base-containing compound (A-1) was obtained. Synthesis Example 2 Water: 100 g, citric acid monohydrate 2 in a flask equipped with a stirrer, heating jacket, reflux condenser and dropping funnel.
Dissolve 1.0 g (0.1 mol). At this time, it is confirmed by pH test paper that it is on the acidic side. 25.9 g (0.1 mol) of γ- (N- (β-aminoethyl) amino) aminopropyltrimethoxysilane was added thereto from the dropping funnel, and the mixture was stirred at a liquid temperature of 50 to 60 ° C. for 1 hour. Then 30 ° C
Until the pH of the aqueous solution is neutral, and the carboxylic acid / amine base-containing compound (A-
2) was obtained. Synthesis Example 3 Water: 100 g, DL-malic acid 13.4 in a flask equipped with a stirrer, heating jacket, reflux condenser and dropping funnel.
Dissolve g (0.1 mol). At this time, it is confirmed by pH test paper that it is on the acidic side. From the dropping funnel, aminopropyltrimethoxysilane; 22.1g (0.1mo
l) was added, and the mixture was stirred at a liquid temperature of 50 to 60 ° C. for 1 hour.
Then, the mixture was cooled to 30 ° C., the pH of the aqueous solution was confirmed to be neutral, and a carboxylic acid / amine base-containing compound (A-3) was obtained. Synthesis Example 4 1 mol of an amino group-containing polyorganosiloxane having the structure shown below was dispersed in an acetone solvent, and 12 times mol thereof was added thereto.
Citric acid was added and reacted at 60 ° C. for 3 hours, acetone was dissolved under reduced pressure, and a carboxylic acid / amine base-containing compound (B-
1) was obtained.

[0024]

[Chemical 7]

Synthesis Example 5 1 mol of an amino group-containing polyorganosiloxane having the structure shown below was dispersed in an acetone solvent, and 5 times mol thereof was added thereto.
Citric acid was added and reacted at 60 ° C. for 3 hours, acetone was dissolved under reduced pressure, and a carboxylic acid / amine base-containing compound (B-
2) was obtained.

[0026]

[Chemical 8]

Synthesis Example 6 1 mol of an amino group-containing polyorganosiloxane having the structure shown below was dispersed in an acetone solvent, and 3 times mol thereof was added thereto.
Citric acid was added and reacted at 60 ° C. for 3 hours, acetone was dissolved under reduced pressure, and a carboxylic acid / amine base-containing compound (B-
3) was obtained.

[0028]

[Chemical 9]

In the preparation example, the following were used as the alkyl-modified silicone oil as the component (C).

[0030]

[Chemical 10]

Preparation Example 1 In a flask equipped with a stirrer, a heating jacket, a reflux condenser and a dropping funnel, 92 g of an alkyl-modified silicone oil (1) having a viscosity of 200 cP, NIKKOL OP-5 (emulsifier manufactured by NOF Corporation); 3.3 g, NIKKOL 18TX (Emulsifier made by NOF Corporation);
3.3 g, baukinin P; 0.1 g, baukinin M; 0.2 g are charged and mixed with stirring at 50 to 55 ° C. 20 g of water was added thereto. The mixture was subjected to mill reversal at a mill pressure of 40 mil pressure, and the reversal product was dispersed in water so that dimethyl silicone oil was 30% to obtain an emulsion (C-1).

Preparation Example 2 In a flask equipped with a stirrer, a heating jacket, a reflux condenser and a dropping funnel, 92 g of an alkyl-modified silicone oil having a viscosity of 1000 cP (2), NIKKOL OP-5 (an emulsifier made by NOF Corporation); 3.3 g, NIKKOL 18TX (Nippon Yushi Emulsifier); 3.
Charge 3g, baukinin P; 0.1g, baukinin M; 0.2g
Stir and mix at 50-55 ° C. 20 g of water was added thereto. The mixture was subjected to mill inversion at a mill pressure of 40 mil pressure, and the inversion product was dispersed in water so that dimethyl silicone oil was 30% to obtain an emulsion (C-2).

Preparation Example 3 A flask equipped with a stirrer, a heating jacket, a reflux condenser and a dropping funnel is charged with 200 g of alkyl-modified silicone oil (3) and 7.5 g of dodecylbenzenesulfonic acid, and mixed by stirring. Then, 907 g of water was added thereto to carry out rough emulsification. Pressurized homogenizer (primary pressure 50 kg)
/ Cm ² : Emulsified at a secondary pressure of 400 kg / cm ² ) and a viscosity of 3
An emulsion (C-3) having 00cP and a component concentration of 32% was obtained.

Comparative Preparation Example 1 In a flask equipped with a stirrer, a heating jacket, a reflux condenser and a dropping funnel, 92 g of dimethyl silicone oil having a viscosity of 20000 cP, NIKKOL OP-5 (emulsifier manufactured by NOF CORPORATION); 3.3 g, NIKKOL 18TX ( Nippon Oil & Fats Emulsifier); 3.3
Charge g, baukinin P; 0.1 g, baukinin M; 0.2 g 5
Stir-mix at 0-55 ° C. 20 g of water was added thereto. The mixture was subjected to mill inversion at a mill pressure of 40 mil pressure, and the inversion product was dispersed in water so that dimethyl silicone oil was 30% to obtain an emulsion (S-1).

Comparative Preparation Example 2 A flask equipped with a stirrer, a heating jacket, a reflux condenser and a dropping funnel was charged with 402 g of octamethylcyclotetrasiloxane, 2.6 g of hexamethyldisiloxane; 2.6 g of dodecylbenzenesulfonic acid; 7.5 g, and mixed by stirring. I do.
Then, 907 g of water was added thereto to carry out rough emulsification. Pressurized homogenizer (primary pressure 50kg / cm ² : secondary pressure 400kg)
/ Cm ² ) and emulsified. Subsequently, the emulsion is emulsion polymerized at 80 to 90 ° C to obtain a dimethyl silicone oil viscosity of 300
An emulsion (S-2) having 00 cP and a component concentration of 32% was obtained.

Comparative Preparation Example 3 Carnauba wax 50 parts, liquid paraffin 25 parts, polyoxyethylene (10) stearate 9 was placed in a flask equipped with a stirrer, a heating jacket, a reflux condenser and a dropping funnel.
Parts, polyoxyethylene (40) stearate 9 parts, and polyoxyethylene (10) octyl phenyl ether 12 parts were charged, gradually heated to dissolve, and heated and stirred while maintaining at 90 ° C, and then heated to 90 ° C. Stir for 1 hour while gradually adding 380 parts of water, then cool and stir to cool to 25 ° C.
An emulsion composition (S-3) was obtained.

Examples 1 to 6 and Comparative Examples 1 to 12 Compositions shown in Tables 1 to 3 (units of numerical values in the table are parts)
Then, the emulsion composition of the present invention and the emulsion composition for comparative examples were prepared, and as a coating agent for scratches shielding, shielding property, water resistance, weather resistance, aesthetics, oil floating property,
The effects on stability and label were evaluated as follows. The results are shown in Tables 1 to 3.・ Preparation of test sample <Brown large bottle for beer bottle> A brown large bottle for beer bottle (content volume 633 ml) that is used returnable and has scratches on the entire side surface.
Was prepared, and each coating agent composition was applied thereto such that the coating amount per one was 0.4 g. Immediately after the application, these bottles were filled with 20% of the content of ice water, and a part of the bottle surface (from the bottle bottom to a height of about 7 cm) was condensed. Furthermore, under the environment of 25 ℃ and 60% RH, 3
The bottle was left for one day for evaluation.

Evaluation Method of Coating Properties [Evaluation of Coating Property] The coating property of the coating composition at the time of preparing the bottle for evaluation was visually observed and evaluated according to the following criteria. ⊚: A uniform film is formed on the surface of the bottle body, and repelling and unevenness do not occur. X: A uniform film is not formed and repelling and unevenness occur. <Vibration test> A predetermined plastic case (usually a P box) containing a bottle for evaluation is fixed to a vibration tester manufactured by Emic Co., Ltd., and the vibration frequency is 5 to 40 Hz, the vibration acceleration is 1 G, and the amplitude is.
Vibrated at 10 cm for 120 minutes. This condition corresponds to a transportation distance of 1800 km or more in actual truck transportation. <Made of Scratch Shielding> The appearance of the scratched portion before and after the vibration test was visually observed, and evaluated according to the following criteria on a 4-point scale. ⊚: The abrasion site is completely shielded. ○: A part of the scratched portion is exposed. Δ: Half of the scratches are exposed. X: The scratch shielding effect is insufficient. <Oil Floatability> After the evaluation bottle was immersed in water at 20 ° C. for 3 days, the surface of the water bath was visually observed and evaluated according to the following criteria in three grades. ○: No oil film is observed. Δ: An oil film is slightly observed. X: An oil film is remarkably observed on the surface of the water bath. <Washability> Use a bottle for evaluation with a liquid temperature of 60 ° C and sodium hydroxide 3
% And sodium aluminate 5%, the degree of removal of the coating film after 15 minutes was visually observed, and evaluated according to the following criteria in 3 grades. ○: The coating is almost completely removed. Δ: About half of the film remains. X: Most of the coating remains. <Generation of White Powder> The state of white powder generation on the surface of the bottle body after the vibration test was visually observed and evaluated according to the following criteria in four levels. ◎: No white powder is generated. ○: White powder was slightly generated. Δ: White powder is slightly generated. X: White powder is considerably generated, which is outside the range of practical use. <Water resistance> After running tap water on the evaluation bottle for 14 hours,
The appearance was visually observed and evaluated according to the following criteria in four levels. ⊚: The scratched area is completely shielded and the transparency of the film is good. ○: A part of the scratched part is exposed, but the transparency is good. Δ: A part of the scratched portion was exposed and the transparency was slightly poor. X: The scratch-shielding effect is insufficient and the film has no transparency. <Weather resistance> 500 using a sunshine weatherometer
After exposure for 4 hours, visually inspect the appearance and
Graded. ⊚: The scratched area is completely shielded and the transparency of the film is good. ○: A part of the scratched part is exposed, but the transparency is good. Δ: A part of the scratched portion was exposed and the transparency was slightly poor. X: The scratch-shielding effect is insufficient and the film has no transparency. <Stability> After the coating agent composition was allowed to stand at room temperature for 4 months, the uniformity of the liquid was observed and evaluated. ○: The uniformity of the liquid is good. Δ: A slight separation of the liquid is observed, but there is no problem with the film properties. X: Separation of liquid is observed, and a problem occurs in the film characteristics. <Label Adhesion> A label coated with casein glue is attached to a test body, left for 4 hours, and then immersed in water,
The peeling of the label was visually observed and evaluated according to the following criteria. ◎: There is no peeling of the label. X: Peeling of the label is seen.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // B05D 7/00 B05D 7/00 E (72) Inventor Yoshiaki Takezawa 6-2 Roppongi, Minato-ku, Tokyo No. 31 F term in Toshiba Silicon Co., Ltd. (reference) 4D075 CA02 DA20 DB13 DC43 EA06 EA13 EB42 4H017 AA04 AB15 AD06 AE04 4J002 CP091 EX076 GH00 HA07 4J038 DL031 DL032 DL051 DL052 HA156 JC35 MA08 MA10 NA03 NA04 NA11 PC03 NA03 NA03 NA03

Claims (3)

[Claims] 1. An acidulant having (A) a carboxylic acid, a compound of the general formula R ¹ -Si (OR ² ) _a X _b (wherein R ¹ is an amino group-containing group, R ² is a group having 1 to 4 carbon atoms). Alkyl group, X is an alkyl group having 1 to 4 carbon atoms, and a and b are numbers satisfying the relations of 1≤a≤3 and a + b = 3, respectively). 100 parts by weight of the resulting carboxylic acid / amino base-containing compound (B) A sour agent having a carboxylic acid is added with a compound of the general formula (In the formula, R ³ is a monovalent hydrocarbon group or an alkoxy group, R ⁴
Is an amino group-containing group, R ⁵ is a monovalent hydrocarbon group, m is 1 to 10
00, n represents an integer of 1 to 1000) a carboxylic acid / amino base-containing compound obtained by reacting an amino group-containing polyorganosiloxane represented by 0 to 1000 parts by weight (C) with a viscosity of 20 to 50000 cP at 25 ° C. An emulsion composition for coating glass containers, which comprises 1000 to 6000 parts by weight of an alkyl-modified silicone oil (D) and 1000 to 30,000 parts by weight of water. 2. The glass container coating according to claim 1, wherein the alkyl-modified silicone oil used as the component (C) is represented by the average composition formula (1) and / or (2) and / or (3). Emulsion composition. [Chemical 2] (In the formula, Z is an alkyl group having 10 to 90 carbon atoms, p
, Q is an arbitrary integer that makes the viscosity of the alkyl-modified silicone oil at 25 ° C 20 to 50,000 cP) 3. A composition treated with the emulsion composition for coating a glass container according to claim 1 or 2,
A glass container, wherein a film of the film-forming material comprising the mixture of (B) and (C) is formed on the surface of the glass container.