JP3190266B2 - Glass container coating composition and glass container coated with coating agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition for glass containers and a glass container coated with a coating agent.

[0002]

2. Description of the Related Art Glass containers conventionally used as filling containers for commodities such as beer, soft drinks, milk, yogurt, and coffee are collected from the market after use, washed, and repeatedly used. The glass container used repeatedly in this way causes abrasion on the container surface due to contact between the glass or the glass container and the metal part of the mechanical device in the bottling step and the subsequent distribution process, and the container is repeatedly used. As the aesthetic appearance declines remarkably,
Exterior quality is impaired. As a result, the commercial value of the filled contents is reduced. Therefore, it has been proposed to apply a coating composition for a glass container to a glass container in which a scratch has occurred. In this case, coating can be easily performed and a film having required physical properties can be formed at room temperature. Good water resistance Good water resistance No stickiness on the coating surface No toxic The coating film is easily and completely peeled off by washing with an alkaline aqueous solution.Do not damage the label attached to the glass container. It is required to meet the requirements such as no degradation of steel.
In view of such a point, Japanese Patent Application Laid-Open No.
The prior art described in Japanese Patent No. 31548 comprises the use of a composition composed of a specific curable organopolysiloxane and a volatile polydimethylsiloxane as a coating agent, which satisfies the above requirements. It is. The present inventor has also made improvements in this prior art, and has disclosed in Japanese Patent Application Laid-Open Nos. Hei 6-32341 and Hei 6-3234.
In JP-A No. 2, it shows good coating properties and shielding effect even for deep abrasions and abrasions of a colorless and transparent glass container, and is excellent in releasability with an alkaline aqueous solution. A shielded glass container was proposed.

[0003]

However, in recent years,
Along with the technology for reducing the weight of bottles, the use of a bottle having a tin oxide film formed on the surface of the bottle has been started as a technique for maintaining the strength of the bottle. In the bottle on which the tin oxide film is formed, the technology described in Japanese Patent Application Laid-Open No. 3-131548 and the technology described in Japanese Patent Application Laid-Open Nos. 6-32341 and 6-32342 are prior art. The cissing occurred on the surface of the bottle, and it had a disadvantage that it did not have sufficient properties as a coating agent. Further, there is a possibility that the composition may be used in a mixture of a normal glass bottle and a bottle having a tin oxide film formed thereon, and a stable film is formed on both bottles, and the composition has an effect and properties as a coating agent. The development was urgent. An object of the present invention is to solve the above-mentioned drawbacks, form a stable film on a normal glass bottle or / and a bottle on which a tin oxide film is formed, and satisfy the requirements required for a glass container coating agent. An object of the present invention is to provide a coating composition and a glass container to which the coating composition is applied.

[0004]

The present inventors have conducted intensive studies to obtain such a coating agent composition.
We have found a coating composition comprising a liquid silicone resin having a reactive group, a specific glycidoxy group-containing alkoxysilane or a partial hydrolyzate thereof, a volatile polydimethylsiloxane, and a curing catalyst optionally used, and have accomplished the present invention. . That is, the present invention, (A) the general formula _{R a SiX b O (4- (} a + b)) / 2 ( wherein, R is an alkyl group having 1 to 12 carbon atoms, alkenyl
Group, aryl group, aralkyl group, γ-aminopropyl
Group, γ- (β-aminoethyl) -γ-aminopropyl
Group, γ-methacryloxypropyl group, γ-mercaptop
Ropyl, cyanoethyl, chloromethyl, γ-chloro
Propyl and 3,3,3-trifluoropropyl groups
A substituted or unsubstituted monovalent hydrocarbon group selected, X represents a hydroxyl group and / or an alkoxy group, an acyloxy group;
Group, aminoxy group, ketoxime group, amide group,
A hydrolyzable group selected from a kenyloxy group and a halogen atom , and a and b are numbers that satisfy the following relationship. Curable liquid silicone resin represented by 0.8 ≦ a <2 0.3 ≦ b <2); 100 parts by weight (B) general formula

[0005]

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(Wherein, Y is a monovalent hydrocarbon group which may be substituted with a halogen atom (specifically, an alkyl group having 1 to 12 carbon atoms)
Alkyl, alkenyl, aryl, aralkyl,
γ-chloropropyl group and 3,3,3-trifluoropro
Substituted or unsubstituted monovalent hydrocarbon selected from pill groups
Group), R ¹ is an alkyl group having 1 to 4 carbon atoms, p is 0 or 1. 5) to 100 parts by weight; (C) volatile polydimethylsiloxane represented by the general formula (I) and / or (II); 50 to 2,000 parts by weight

[0007]

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(D) a viscosity at 25 ° C. of 100 to 10000000
Centistokes polydimethylsiloxane; 0.01-30
Parts by weight and a viscosity at 25 ° C. of 2 to 1000 centistokes, and a coating composition for a glass container, further comprising (E) 0.01 to 10 parts by weight of a curing catalyst. Agent composition,
And a glass container which is not coated with a film of a cured product of the coating composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The component (A) used in the present invention is: R _a SiX _b O _{(4- (a + b)) / 2} (where R is a substituted or unsubstituted monovalent hydrocarbon group, X
Is a hydroxyl group and / or a hydrolysable group,
a and b are numbers that satisfy the following relationship. A curable liquid silicone resin represented by 0.8 ≦ a <2 0.3 ≦ b <2), which is a base polymer of the present invention.

In the formula, R is a substituted or unsubstituted monovalent hydrocarbon, which may be the same or different. As such a substituted or unsubstituted monovalent hydrocarbon,
C1-C12 alkyl such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl; alkenyl such as vinyl and allyl; phenyl Aryl groups such as a group, tolyl group and xylyl group; β-phenylethyl group, β-
An aralkyl group such as a phenylpropyl group; and γ-
Aminopropyl group, γ- (β-aminoethyl) -γ-aminopropyl group, γ-methacryloxypropyl group, γ-
Examples thereof include monovalent substituted hydrocarbons such as a mercaptopropyl group, a cyanoethyl group, a chloromethyl group, a γ-chloropropyl group, and a 3,3,3-trifluoropropyl group.
Of these, it is most advantageous to use a methyl group from the viewpoints of availability of raw materials, hardness of the coating, curing speed, and alkaline water detergency, but when emphasis is placed on matching the refractive index with the container surface. Is a phenyl group, β-phenylethyl group, etc., or a group which functions as a catalyst and an adhesion improving material such as γ- (β-aminoethyl) -γ-aminopropyl group to impart self-curing property and adhesion. Is preferably used in combination with a methyl group. In the component (A), X is a hydroxyl group and / or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, an aminoxy group, a ketoxime group, an amide group, an alkenyloxy group, and a halogen atom. Among these, a hydroxyl group and an alkoxy group having 1 to 4 carbon atoms are preferred because of a low odor of by-products generated during the curing reaction and excellent curability and film properties. Particularly, a hydroxyl group, a methoxy group, and an ethoxy group are preferred. Particularly preferred is a group. Further, in the component (A), a and b need to satisfy the following relationship. When 0.8 ≦ a <2 0.3 ≦ b <2 a is less than 0.8, the cured coating becomes brittle, and when it is 2 or more, it becomes difficult to obtain a good coating, and the coating becomes slippery and sticky. Not suitable. On the other hand, b
If it is less than 0.3, the curing speed is too slow to be suitable for practical use, and if it is 2 or more, the cured film becomes brittle and is not suitable for the purpose of the present invention.
The component (A) preferably has a viscosity at 25 ° C. of from 10 to 100,000 cSt, particularly preferably from 10 to 1,000 cSt.
Is preferred. If the viscosity is less than 10 sSt, fixation to the surface of the glass container is insufficient, resulting in poor abrasion shielding. On the other hand, 100000cSt
When it exceeds, the high viscosity causes insufficient penetration or wettability into the abrasion, resulting in poor abrasion shielding. Such a curable liquid silicone resin (A) can be easily obtained by a known method. That is, alkoxysilanes such as methyltrialkoxysilane, dimethyldialkoxysilane, trimethylalkoxysilane, tetraalkoxysilane, phenyltrialkoxysilane, diphenyldialkoxysilane, triphenylalkoxysilane, methylphenyldialkoxysilane, and methyldiphenylalkoxysilane ,
Corresponding chlorosilanes in which these alkoxy groups are substituted with chlorine atoms, and carbons such as alkyl, propyl, butyl, amyl, hexyl, octyl, decyl, and dodecyl groups, Alkyl groups of the formulas 1 to 12; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group and xylyl group; β-phenylethyl group, β-
An aralkyl group such as a phenylpropyl group; and γ-
Aminopropyl group, γ- (β-aminoethyl) -γ-aminopropyl group, γ-methacryloxypropyl group, γ-
Selected from organosilicon compounds substituted with a monovalent substituted hydrocarbon such as a mercaptopropyl group, a cyanoethyl group, a chloromethyl group, a γ-chloropropyl group, and a 3,3,3-trifluoropropyl group. One or a mixture thereof can be appropriately selected and partially hydrolyzed in the presence of a catalyst. Examples of the catalyst used herein include organic acids such as acetic anhydride, glacial acetic acid, propionic acid, citric acid, benzoic acid, formic acid, acetic acid, and oxalic acid; aluminum chelate compounds such as aluminum alkyl acetate; and tetrabutyl titanate. Chlorosilanes such as methyltrichlorosilane and dimethyldichlorosilane; inorganic bases such as aqueous ammonia; organic bases such as ethylenediamine and triethanolamine; and N- (β-aminoethyl) -γ-amino Examples include aminoalkylsilanes such as propylmethyldimethoxysilane. In addition, as the component (A), a plurality of curable liquid silicone resins each having different properties and obtained as described above may be used by blending.

Next, the component (B) used in the present invention comprises:
General formula

[0012]

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Wherein Y is a monovalent hydrocarbon group which may be substituted by a halogen atom, R ¹ is an alkyl group having 1 to 4 carbon atoms, and p is 0 or 1. It is a glycidoxy group-containing alkoxysilane or its partial hydrolyzate. This component is an important component for forming a stable film on an ordinary glass bottle or / and a bottle on which a tin oxide film is formed, and is also an important component characterizing the present invention. In the formula, Y is an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, a decyl group or a dodecyl group; Alkenyl groups; aryl groups such as phenyl, tolyl, and xylyl groups;
aralkyl groups such as β-phenylethyl group and β-phenylpropyl group; monovalent substituted hydrocarbons such as γ-chloropropyl group and 3,3,3-trifluoropropyl group. Among these, those having a methyl group are particularly preferable because not only can a methyl group be easily obtained, but also the property balance to a glass bottle is advantageous. Examples of the glycidoxy group-containing alkoxysilane include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyltriethoxysilane. -Glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylethyltrimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropylethyltriethoxysilane, 3-glycidoxypropylmethyldi Examples thereof include propoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropylmethyldiisopropoxysilane, and 3-glycidoxypropyltriisopropoxysilane. Of these,

[0014]

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Is preferred because it not only can be easily obtained, but also makes the balance of curing and the adhesion of the coating film to tin oxide advantageous. These partial hydrolysates can be obtained by a known method, that is, by condensing an alkoxysilane or a mixture thereof under hydrolysis conditions (set appropriately according to the alkoxysilane used).
Preferred examples of the partially hydrolyzed condensate of alkoxysilane include siloxane and polysiloxane having a structure in which the above-mentioned alkoxysilane is partially hydrolyzed and condensed.

The amount of component (B) used is 5 to 100 parts by weight, preferably 20 to 100 parts by weight, per 100 parts by weight of component (A).
50 parts by weight. If the amount is less than 5 parts by weight, the cured film is not preferable because it causes a problem in adhesion to the tin oxide surface. On the other hand, if the amount exceeds 100 parts by weight, the cured film is not preferable because it causes problems in coatability and adhesion to the surface of a glass bottle which is usually used.

The component (C) used in the present invention is a volatile solvent. The component (C) is not particularly limited as long as it has a property of being volatile when heated at room temperature or low temperature and has a property of dissolving or dispersing the component (A) and the component (B). Volatile organopolysiloxanes are preferred because of their low activity (low irritation and sensitization) and no effect on the label. Penetrates well into deep abrasions,
Volatile organopolysiloxanes are preferred because they have a great effect of improving shielding properties and surface smoothness. Examples of such volatile organopolysiloxanes include, for example,
A linear polyorganopolysiloxane represented by the general formula (I) or a cyclic polydimethylsiloxane represented by the general formula (I) or (II) is disclosed. Advantageous and readily available industrially available cyclic polydimethylsiloxanes with a degree of polymerization of 4 or 5, ie octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane or a mixture of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane From the viewpoint that octamethylcyclotetrasiloxane solidifies at 17 ° C., a mixture of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane is particularly preferable.
These volatile solvents may be used as a mixture of two or more. The amount of the component (C) used is in the range of 50 to 2,000 parts by weight based on 105 to 200 parts by weight of the mixture of the components (A) and (B). If the amount is less than 50 parts by weight, the other components applied to the container, that is, the ratio of the active ingredient will be high, and the leveling property of the coating surface and the hardening and drying property within a predetermined time will be deteriorated, causing the stickiness of the yuzu skin and the surface. There is a risk. Also 2000
If the amount exceeds the weight part, the amount of the active ingredient applied to the surface of the container becomes insufficient, and it is difficult to obtain a sufficient shielding effect.

The component (D) used in the present invention functions to adjust the hardness of the coating and to assist in easy peeling by an aqueous alkali solution. The viscosity of the polydimethyl silicone oil (D) is 100 to 100,000
0 cSt, preferably 1,000 to 100,000 cSt. 100c
If it is less than St, it is not preferable because interference islands are generated when the coating is formed, and if it exceeds 1,000,000 cSt, the solubility in the base resin becomes poor and the coating becomes cloudy, which is not preferable.
The amount of component (D) used is in the range of 0.01 to 30 parts by weight per 105 to 200 parts by weight of the mixture of component (A) and component (B). If the amount is less than 0.01 part by weight, a problem occurs in the easy peeling property by the aqueous alkali solution, which is not preferable. On the other hand, if it exceeds 30 parts by weight, it is not preferable because the coating is slick and sticky.

The coating composition of the present invention generally uses a curing catalyst as the component (E). However,
As the R of the component (A), a γ-aminopropyl group or γ- (β
-Aminoethyl) -γ-aminopropyl group is not particularly required in the case of containing a group having a curing catalytic action. As such a catalyst, a catalyst known as a curing catalyst for polyorganosiloxane can be used. Specifically, for example, organic amines such as triethanolamine; aminoalkylsilanes such as N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; carboxylic acids such as iron octylate and zinc octylate Metal salts; organotin compounds such as tin dioctylate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate; titanates such as tetraisopropoxy titanate, tetrabutyl titanate; and organosilicon quaternary ammonium salts Examples thereof include quaternary ammonium salts. Among them, dioctyltin dilaurate, dibutyltin dilaurate, and tetrabutyl titanate are particularly preferable from the viewpoint of effectiveness and safety and health. (E) The amount of the curing catalyst used is the amount of the components 105 to 2 comprising (A) and (B).
0.01 to 10 parts by weight, more preferably 0.02 parts by weight based on 00 parts by weight
-5 parts by weight. If the amount is less than 0.01 part by weight, the curing and drying of the film is slow, which is not suitable for practical use. On the other hand, if it exceeds 10 parts by weight, there is no particular effect on the film formation, and the storage stability of the abrasion shielding agent (coating agent composition) is rather poor. There is inconvenience to do.

The coating composition of the present invention is obtained by dissolving the above-mentioned component (A), component (B), component (D) and optionally component (E), which is a catalyst component, in component (C). It is obtained. The viscosity at 25 ° C. of the coating composition thus obtained is 2 to 1000.
cSt, preferably in the range of 5-200 cSt. If the viscosity at 25 ° C. is less than 2 cSt, the adhesion to the container surface is small, and a single treatment cannot provide a sufficient shielding effect.
If it exceeds 1000 cSt, the amount of adhesion increases and the film becomes thicker, and on the contrary, disadvantages such as stickiness occur, which is not preferable. The coating composition of the present invention comprises the component (A) described above,
It comprises the component (B), the component (D), the component (E) and the component (C). In addition to the component consisting only of these five components, various auxiliary components can be blended. Examples thereof include plasticizers such as surfactants, pigments and ultraviolet adsorbents for preventing the deterioration of contents and odoration due to visible light and ultraviolet light, coloring agents such as dyes, leveling agents, and inorganic powders.

As a method of applying the coating composition of the present invention to a container, commonly used techniques such as spray coating, brush coating, puff coating, dipping, flow coater, and transfer can be used. . Also, large volumes of glass containers, usually such glass containers,
Although the opening is a bottle with a narrow mouth, when these are to be treated, for example, a roller-type coating apparatus described in Japanese Patent Application Laid-Open No. 58-21365 or a coating belt-type coating described in Japanese Patent Publication No. 1-59221. The device is operational. The thickness of the coating is arbitrary, but is preferably about 0.5 to 30 μm from the viewpoints of the abrasion shielding effect, the appropriate coating strength, and the releasability with an alkaline aqueous solution. Needless to say, the portion to be applied is not limited to the abraded portion, but for the purpose of cost reduction, it is also effective to coat only the abraded portion to the above-mentioned film thickness.
Further, the coating agent of the present invention does not damage the label even when applied on the label attached to the glass container. The coating composition of the present invention does not require any special heating during curing, and after application, if left at room temperature for about 0.5 to 48 hours, a cured film having no surface tackiness can be easily obtained. Heating may be performed to shorten the time.

[0022]

EFFECT OF THE INVENTION The coating composition of the present invention is not only excellent in abrasion-shielding effect, but also can be applied not only to a glass bottle which is usually used but also to a light-weight bottle using a tin oxide film. The coating that can be stably applied and formed has more excellent characteristics with respect to the requirements of 8 items described in the section of the related art. Therefore, the coating agent composition of the present invention has an advantage that it can be used without classifying various containers to be mixed and used.

[0023]

The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. The scope of the present invention is not limited only to the following examples. In addition, the compounding amount in a synthesis example, an example, and a comparative example shows a weight part at 25 degreeC unless otherwise indicated, and shows the value in 25 degreeC. Synthesis Example 1 In a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a heating jacket, 136.0 g (1.0 mol) of methyltrimethoxysilane, 20.0 g of methanol and methyltrichlorosilane were added so that the hydrogen chloride content was 50 ppm. And 17.1 g (0.95 mol) of water was gradually dropped using a dropping funnel while stirring. 4 at reflux temperature (about 68-72 ° C)
After holding for a time, hydrolysis and condensation reactions were performed. Then, after evaporating the volatile components under the conditions of normal pressure and a liquid temperature of 100 ° C., gradually reducing the pressure, gradually evaporating the volatile components under the conditions of a reduced pressure of 40 Torr and a liquid temperature of 150 ° C. Back to
63.0 g of the curable liquid silicone resin shown in Table 1 (A-
1) was obtained. However, the content a of the organic group and the content b of the hydrolyzable group (including the hydroxyl group) in the table are values calculated based on the charged amounts of the silane compound and water (the same applies to the following synthesis examples). .).

Synthesis Example 2 A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a heating jacket was charged with the silane compound and the hydrolysis catalyst in the amounts shown in Table 1 and gradually heated with stirring. The solution was held at a liquid temperature of 80 ° C. for 6 hours to carry out hydrolysis and condensation reactions. Then, after evaporating volatile components under conditions of normal pressure and a liquid temperature of 130 ° C., the pressure was gradually reduced, and the pressure was reduced to 30 Torr. After further evaporating volatile components under the condition of a liquid temperature of 130 ° C., the pressure was returned to normal pressure, and curable liquid silicone resins (A-2, A-3, A-4) shown in Table 1 were obtained.

Synthesis Example 3 A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and heating jacket was charged with 95.2 g (0.7 mol) of methyltrimethoxysilane and 19.8 g of phenyltrimethoxysilane.
g (0.1 mol), 51.6 g (0.4 mol) of dimethyldichlorosilane, and 120.0 g of toluene.
23.4 g (1.3 mol) was gradually added dropwise. After dropping, liquid temperature
The mixture was heated and refluxed at 110 ° C. for 1 hour. The reaction solution was cooled to room temperature, transferred to a separating funnel, allowed to stand and separated into an organic layer and an aqueous layer, and then the lower aqueous layer was removed to obtain a toluene solution of polyorganosiloxane. A saturated saline solution was added to the toluene solution, and the mixture was stirred well, and allowed to stand still to separate an aqueous layer. This salting-out operation was repeated twice. The organic layer thus obtained was put into a flask equipped with a stirrer, heating jacket and Dean-Stark separation tube, and volatile components were distilled off under the conditions of a reduced pressure of 30 Torr and a liquid temperature of 80 ° C. A liquid silicone resin (A-5) was obtained.

Synthesis Example 4 A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and heating jacket was charged with 236.3 g (1.0 mol) of 3-glycidoxypropyltrimethoxysilane, methanol
20.0 g and methyltrichlorosilane with hydrogen chloride content of 50
ppm, and 17.1 g of water (0.95 g
Mol) was gradually added dropwise using a dropping funnel. The mixture was kept at a reflux temperature (about 68 to 72 ° C.) for 4 hours to carry out hydrolysis and condensation reactions. Then, after evaporating the volatile components under the conditions of normal pressure and a liquid temperature of 100 ° C., the pressure was gradually reduced, and the pressure was reduced to 40 To.
After evaporating further volatile components under the conditions of rr and a liquid temperature of 150 ° C., the pressure was returned to normal pressure to obtain 153.0 g (B-1) of a partial hydrolyzate of a glycidoxy group-containing alkoxysilane shown in Table 1. .

Synthesis Example 5 In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and heating jacket, 118.2 g (0.50 mol) of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy 131.3 g of silane (0.5
Mol), methanol 20.0 g and methyltrichlorosilane were charged so that the hydrogen chloride content was 50 ppm, and 17.1 g (0.95 mol) of water was gradually added dropwise using a dropping funnel while stirring. Hold at reflux temperature (about 68-72 ° C) for 4 hours,
Hydrolysis and condensation reactions were performed. Then, normal pressure, liquid temperature
After the volatile components were distilled off at 100 ° C., the pressure was gradually reduced, and the volatile components were further distilled off under the conditions of a reduced pressure of 40 Torr and a liquid temperature of 150 ° C., and the pressure was returned to normal pressure. The partial hydrolysis product of the glycidoxy group-containing alkoxysilane shown 134.
0 g (B-2) was obtained.

Examples 1 to 14 and Comparative Examples 1 to 14 The curable liquid silicone resins (A-1 to 5) synthesized in the above Synthesis Examples and glycidoxy group-containing alkoxysilanes and glycidoxy group-containing alkoxysilanes were partially hydrolyzed. Table 2 based on the decomposition products (B-1, B-2)
-The coating composition of Examples 1-14 and Comparative Examples 1-14 was obtained by mix | blending each component in the ratio shown in Table 5, respectively. Comparative Examples 1 to 14 are the coating compositions of Examples according to the present invention.
This is the case where the component or the component (B) is not used.

Using these coating agent compositions,
The following evaluation was performed. The conditions for preparing the evaluation bottle, the shaking test conditions, and the method for evaluating the film properties are as follows. [Conditions for making bottles for evaluation] <Brown large bottle for beer bottles> Brown large bottle for beer bottles that is returnable and has scratches on all sides
l) was prepared, and each coating agent composition was applied thereto such that the coating amount per one was 0.3 g. After application,
Immediately, these bottles were filled with an amount of ice water equivalent to 20% of the contents, and a part of the surface of the bottles (to a height of about 7 cm from the bottom of the bottle) was allowed to condense. Furthermore, in an environment of 25 ° C and 60% RH, 7
It was left for a period of days to make a bottle for evaluation. <Brown large bottle for beer bottles treated with tin oxide> A large brown bottle for beer bottles (633 ml), which is returnable and has scratches on the entire side, is prepared, and one of each coating agent composition is added to it. Application amount per
It applied so that it might become 0.3 g. Immediately after the application, the bottles were filled with an amount of ice water equivalent to 20% of the content, and a part of the surface of the bottles (to a height of about 7 cm from the bottom of the bottle) was dewed. Furthermore, it is left under the environment of 25 ° C and 60% RH for 7 days,
The bottle was used for evaluation. -Method for evaluating coating properties [Evaluation of applicability] The applicability of the coating composition at the time of preparing the evaluation bottle was visually observed and evaluated according to the following criteria. A: A uniform film is formed on the surface of the bottle, and no repelling or unevenness occurs. ×: A uniform film was not formed, and repelling and unevenness occurred. <Shaking test> A predetermined plastic case (usually a P box) containing an evaluation bottle was fixed to a vibration tester manufactured by Emic Corporation, vibration frequency 5 to 40 Hz, vibration acceleration 1 G, amplitude
Shake at 10 cm for 120 minutes. This condition corresponds to a transport distance of 1800 mm or more in actual truck transport. [Abrasion shielding property] The appearance of the abrasion site before and after the shaking test was visually observed and evaluated on a 4-point scale based on the following criteria. A: The abrasion site is completely shielded. ：: A part of the abrasion site is exposed. Δ: Half of the abrasion site is exposed. X: The abrasion shielding effect is insufficient. [Oil floating property] After the evaluation medium was immersed in water at 20 ° C for 3 days, the surface of the water bath was visually observed, and evaluated on a three-point scale according to the following criteria. ：: No oil film is observed at all. Δ: An oil film is slightly observed.

X: An oil film is remarkably observed on the surface of the water bath. [Bottle washing property] The evaluation medium was a solution temperature of 60 ° C and sodium hydroxide 3
%, And an aqueous solution containing 5% of sodium aluminate was immersed, and the degree of film removal after 15 minutes was visually observed. ：: The coating was almost completely removed. Δ: About half of the film remains. ×: Most of the coating remains. [Generation of White Powder] The state of white powder generation on the surface of the bottle after the shaking test was visually observed, and evaluated on a 4-point scale based on the following criteria. A: There is no generation of white powder. ：: White powder is slightly generated. Δ: White powder is slightly generated. X: White powder is considerably generated, which is out of practical use.

The evaluation results of Examples 1 to 14 and Comparative Examples 1 to 14 are summarized in Tables 6 to 9. As is clear from these tables, all of the coating compositions of Examples 1 to 14 according to the present invention have good general properties as a coating agent such as abrasion shielding property, oil floating property, and bottle washing property. It was confirmed that there was. Furthermore, the coating agent composition and the formed film of the present invention are not only excellent in abrasion shielding effect, but also can be applied not only to a commonly used glass bottle, but also to a lightweight bottle using a tin oxide film. It was also confirmed that the composition could be stably applied.
On the other hand, the coating compositions of Comparative Examples 1 to 14 can be applied to a commonly used glass bottle, but cannot be applied to a lightweight bottle using a tin oxide film, and also have a shielding property and an oil floating property. However, no satisfactory results were obtained.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

[0037]

[Table 6]

[0038]

[Table 7]

[0039]

[Table 8]

[0040]

[Table 9]

Continuation of the front page (56) References JP-A-3-157453 (JP, A) JP-A-6-32341 (JP, A) JP-A-6-32342 (JP, A) JP-A-8-2940 (JP) , A) JP-A-61-6152 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 1/00-201/10

Claims (6)

(57) [Claims] 1. A (A) the general formula _{R a SiX b O (4- (} a + b)) / 2 ( wherein, R is an alkyl group having 1 to 12 carbon atoms, alkenyl
Group, an aryl group, Ara alkyl group, .gamma.-aminopropyl
Group, γ- (β-aminoethyl) -γ- aminopropyl
Group, γ-methacryloxypropyl group, γ-mercaptop
Ropyl, cyanoethyl, chloromethyl, γ-chloro
Ropuropiru group and 3,3,3 - door Li-fluoro-propyl group
A substituted or unsubstituted monovalent hydrocarbon group selected, X represents a hydroxyl group and / or an alkoxy group, an acyloxy group;
Shi group, Aminoki sheet group, ketoxime group, an amido group, Al
A hydrolyzable group selected from a kenyloxy group and a halogen atom , and a and b are numbers that satisfy the following relationship. Curable liquid silicone resin represented by 0.8 ≦ a <2 0.3 ≦ b <2); 100 parts by weight (B) general formula ( Wherein , Y is an alkyl group having 1 to 12 carbon atoms, alkenyl
Group, an aryl group, Ara alkyl group, .gamma.-chloropropyl group
And 3,3,3 - location chosen Ri by trifluoropropyl group
A substituted or unsubstituted monovalent hydrocarbon group, R ¹ has 1 to 4 carbon atoms
And p is 0 or 1. 5) to 100 parts by weight; (C) volatile polydimethylsiloxane represented by the general formula (I) and / or (II); 50 to 2,000 parts by weight Embedded image (D) a polydimethylsiloxane having a viscosity of 100 to 100,000,000 centistokes at 25 ° C; a coating composition for glass containers comprising 0.01 to 30 parts by weight and having a viscosity at 25 ° C of 2 to 1000 centistokes. . 2. The coating composition for a glass container according to claim 1, further comprising (E) 0.01 to 10 parts by weight of a curing catalyst. (E) a curing catalyst comprising an organic amine, a metal carboxylate, an organic tin compound, a titanate,
At least one selected from the group consisting of quaternary ammonium salts
The coating composition for a glass container according to claim 2, which is a seed. 4. The method according to claim 1, which is treated with the coating composition for glass containers according to any one of claims 1 to 3, wherein
A glass container characterized in that a coating of a cured product of an organopolysiloxane comprising a mixture of (B) and (B) is formed on the surface of a glass container. 5. The glass container according to claim 4, wherein the glass container has a tin oxide film formed on a surface thereof in advance. 6. The glass container according to claim 4, wherein the glass container is a bottle.
The glass container as described.