JPH0688813B2 - Scratch coating agent for glass containers - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an agent for scratches on glass containers such as fruit juice bottles, soft drink bottles, beer bottles, etc., and particularly to a coating film formed by dew condensation on the surface of the glass container. The present invention relates to a scratch resistant coating agent for a glass container, which is not washed away and therefore has a good shielding property and in which a coating film is easily removed in a bottle washing process.

[Prior art and its problems]

Glass containers such as fruit juice drink bottles, soft drink bottles, beer bottles, etc. are currently collected after use and are used repeatedly, but in the process of bottling and distribution, the surface of the glass container is scratched and scratched. Occurs, which deteriorates the appearance and reduces the commercial value.

Therefore, in recent years, the various scratches are shielded by applying various coating agents to the surface of the glass container to protect the aesthetic appearance of the glass container.

As this type of coating agent, an emulsion or water dispersion containing liquid paraffin or silicone oil as a main component is conventionally known.

However, these not only have poor coating properties due to dew condensation, but also have a stickiness and slipperiness after application, which may result in poor tactile sensation and risk of slipping the container from the hands, and also dust. Not only is it easy to adhere, and the coating film peels off in cold water or in a showcase, the water resistance is poor, and the oil from the peeled product floats up on the water surface, or the oil is washed inside the container during the bottle washing process. There is also a risk of redepositing on and adversely affecting the contents.

As a coating agent for solving these problems, a cured product of an organopolysiloxane containing a phenyl group is known. (JP-A-55-56040). This kind of coating agent can be used successfully by improving the above-mentioned various drawbacks when it is applied to an empty container or when filling the contents above room temperature, but it can be used to fill the contents below room temperature. When applied after the coating, dew condensation occurs on the surface of the container due to temperature difference, and the dew condensation causes the coating film to be peeled off and washed away, thus losing the shielding effect.

Furthermore, this type of coating agent also has a drawback that the coating film is not always sufficiently removed in a normal bottle washing process.

[Object of the Invention]

The object of the present invention is to improve various drawbacks existing in the above-mentioned known technology, without stickiness and slipperiness, without attaching dust, and having good water resistance without causing oil to float when immersed in water, Therefore, the quality of the contents is not adversely affected, and even when the contents are filled in the container at a temperature equal to or lower than room temperature, the film is not washed away by dew condensation, and therefore the shielding property is good, and (EN) It is intended to provide a novel coating agent for scratch marks on a glass container, in which the coating film can be easily removed in the bottle washing process.

[Main points of the invention]

In order to achieve the above-mentioned object, according to the coating agent of the present invention,
It is characterized in that the main component is a reaction product produced by the reaction of the following components (A) and (B).

(A) Alkyl group-containing alkyl polysiloxane 100 parts by weight.

(B) Compounds 2 to 18 of the general formula RCOX [(R ') nH] m
Parts by weight. Where R is a C _{8 to} C ₂₂ alkyl group, X is O, N, or NH, R ′ is a C _{2 to} C ₈ polyalkylene oxide, n is an integer of 1 to 60, and m is an integer of 1 or 2. Is.

The above-mentioned component (A), that is, an alkoxy group-containing alkylpolysiloxane is, for example, methyltrialkoxysilane, dimethyldialkoxysilane, trimethylmonoalkoxysilane, ethyltrialkoxysilane, diethyldialkoxysilane, triethylmonoalkoxysilane, methylfluordisilane. 0.1 ~ 0.01N with alkoxysilane
It can be easily obtained by a known method using a dilute acid such as hydrochloric acid, sulfuric acid, sulfonic acid or chloroacetic acid. of course,
It goes without saying that it can be obtained from a halogen silane corresponding to the above alkylalkoxysilane or other methods. Alkoxy groups are methoxy, ethoxy, n-, i-propoxy, n-, sec- and tert-butoxy groups.

In addition, the aforementioned component (B), that is, the general formula RCOX
The compound having [(R ') nH] m is, for example, a derivative of fatty acid obtained from natural coconut oil, rice bran oil or the like. In the formula, R is a C _{8 to} C ₂₂ alkyl group, and examples of fatty acids corresponding thereto include saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Etc.,
Unsaturated fatty acids include oleic acid, ricinolenic acid and others, and preferably lauric acid, myristic acid, palmitic acid, stearic acid or oleic acid. These have an even number of carbons because they are all derived from nature,
It may be an odd number of carbons. X is any one of O, N and NH, and R ′ is a C _{2 to} C ₈ polyalkylene oxide, such as oxyethylene group, oxypropylene group, oxybutylene group, oxypentylene group, oxyhexylene group, An oxyheptylene group, an oxyoctylene group and the like are preferable, and an oxyethylene group and an oxypropylene group are preferable, but an arbitrary combination of these various groups may be used. The degree of polymerization n is in the range of 1-60. m is an integer of 1 or 2.

Specific examples of the compound represented by the general formula include propylene glycol monolaurate, propylene glycol monostearate, polyoxyethylene glycol monooleate, polyoxyethylene polyoxypropylene glycol monostearate and monoethanol laurate. Amide, monoethanol amide palmitate, diethanol amide mytistic acid and the like.

When the above components (A) and (B) are mixed and heated in the presence of a curing catalyst described below at a temperature of 130 ° C. or higher under normal pressure or reduced pressure, the alkoxy group of the component (A) and the component (B) are mixed.
A transesterification reaction occurs with the terminal functional group of the fatty acid derivative of to obtain a reaction product.

The blending amounts of the above (A) and (B) are the same as those of the component (A), that is, 100 parts by weight of the alkoxy group-containing alkyl polysiloxane, the component (B), that is, the general formula RCOX [(R ')].
The compound of [nH] m is 2 to 18 parts by weight, preferably 5
To 12 parts by weight. When the amount is less than this range, defects such as cracks in the coating film, poor shielding performance, and poor removability in a bottle can occur. On the other hand, if the amount is more than this range, there are drawbacks such as softening of the coating film, easy peeling, and loss of the coating film to impair the appearance.

As the above-mentioned curing catalyst, for example, there are amine salts such as titanic acid ester, organic tin, zinc, cobalt, fatty acid salts such as iron, triethanolamine, and choline hexoate.
From the viewpoint of hygiene, harmless titanic acid esters are preferable. This addition amount is 0.1 to 10 relative to 100 parts by weight of component (A), that is, alkoxy group-containing alkyl polysiloxane.
It is about part by weight.

The obtained reaction product can be used as a mixture with an organic silicic acid compound such as orthosilicic acid alkyl ester or polysilicate, and may be used after being mixed and diluted with a solvent such as water or alcohol. When diluting with water,
Before mixing, mix with a mixer and use. If mixing is not successful, an appropriate amount of a surfactant such as glycerol fatty acid ester or sorbitan fatty acid ester can be added.

The above-mentioned coating agent of the present invention is applied manually by a cloth, sponge, felt, brush or the like, or by a belt or the like,
Alternatively, it is applied by any method such as dipping or spraying. The applied coating is cured by leaving it at room temperature for 2 to 4 days to obtain a hard coating having a glossy aesthetic appearance.

Example of Invention

 (1) Synthesis of component (A).

178 g of methyltriethoxysilane is collected in a 3,000 ml four-necked flask, and 198 g of 0.03N hydrochloric acid is added dropwise with stirring. After becoming homogeneous and transparent, the temperature is raised to 81 ° C. and refluxed for 1 hour.
While distilling off low-boiling substances, the temperature was raised to 130 ° C and the pressure was reduced (400
mm / Hg) and aging at a temperature of 130 ° C. for 1 hour to obtain 1000 g of ethoxy group-containing methylpolysiloxane.

(2) Synthesis of reaction product from components (A) and (B).

As a component (A), 100 parts by weight of the ethoxy group-containing methylpolysiloxane synthesized according to the above (1) was sampled in a 200 ml four-necked flask, and as a component (B), Table 1
0 to 22 parts by weight of the various compounds shown in Table 1 and 0.1 parts by weight of tetraisopropoxy titanate as a curing catalyst were added, and the temperature was raised to 180 ° C. under reduced pressure with stirring (400 mm / Hg), and the sample No. Got 1-18. In Table 1, the "number of n" is "n" in the general formula of the component (B) and means the degree of polymerization of R '.

Then, each sample in Table-1 was diluted 4-fold with ethanol,
Furthermore, 2 parts by weight each of tetraisopropoxy titanate as a curing catalyst was added to 100 parts by weight of these ethanol diluted solutions to prepare each sample in Table-2. Various performance tests shown below were conducted, and the results are shown in Table-2.

The performance test was conducted as follows.

(Scratch scratch shielding test) Water at 2 ° C was poured into a soft drink bottle (200 ml), and after 5 minutes, each sample was applied to the surface of the dewed bottle with a sponge.
After being left in a thermo-hygrostat at ℃ (Yamato IG41) for 24 hours, the shielding property against scratches was observed. In addition, a beer bottle (633m
Water was injected into l) at 10 ° C., and the test was conducted in the same manner as described above.

The sponge used had a width of 1.5 cm and was applied in a strip shape on the faint portion of the bottle. (The following applies to this.) (Stickiness and slipperiness test) Each sample was applied to a soft drink bottle (200 ml) and a beer bottle (633 ml) using a sponge, and allowed to stand at room temperature for 3 days, and then the stickiness was felt by touch. , And the slip property were investigated.

(Dust adhesion test) Each sample was applied to a soft drink bottle (200 ml) and a beer bottle (633 ml) using a sponge, left at room temperature for 3 days, and then left outdoors for 14 days to observe the dust adhesion state. .

(Water resistance test) Each sample was applied to a soft drink bottle (200 ml) and a beer bottle (633 ml) using a sponge, allowed to stand at room temperature for 5 days, then immersed in water for 7 days, and the coating film lost or peeled off. Was observed.

(Floating property test of coating film) The floating state of the coating film was observed according to the above water resistance test.

(Appearance of coating film) Each sample was applied to a soft drink bottle (200 ml) and a beer bottle (633 ml) using a sponge, and after leaving for 7 days, the appearance state of the coating film was observed.

(Removal test for washing bottle) Each sample was applied to a soft drink bottle (200 ml) and a beer bottle (633 ml) using a sponge and left at room temperature for 100 days, and then washed with a washing liquid (caustic soda 3.5%, sodium gluconate).
It was soaked in 0.35%, 70 ° C) for 15 minutes, rinsed with warm water, and the removal property of the coating film on the bottle was observed.

From Table-2, the coating agents according to the present invention (Sample Nos. 3 to 7 and 10 to 18) were all very good in the test of the scratch shielding property and the other 6 items, and Comparative Examples (Sample No. 1,
It can be seen that the entry is significantly better than that of 2, 8, and 9).

〔The invention's effect〕

As described above, the coating agent according to the present invention is not sticky or slippery, does not adhere to dust, has good water resistance, and does not cause oil floating when immersed in water, and thus has a quality of contents. There is no adverse effect, and the film does not flow away due to dew condensation when applied after filling the contents of the room temperature or below, and therefore the shielding property is good, and the film is coated in the bottle washing process. Is an invention that is easily removed and is extremely useful in practice.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshinori Chiba 27-15 Enokigaoka, Midori-ku, Yokohama-shi, Kanagawa (56) References JP-A-56-23444 (JP, A) JP-A-59-121138 ( JP, A)

Claims (1)

[Claims] 1. A scratch-applying agent for glass containers, which comprises a reaction product produced by the reaction of the following components (A) and (B) as a main component. (A) Alkyl group-containing alkyl polysiloxane 100 parts by weight. (B) Compounds 2 to 18 of the general formula RCOX [(R ') nH] m
Parts by weight. Where R is a C _{8 to} C ₂₂ alkyl group, X is O, N, or NH, R ′ is a C _{2 to} C ₈ polyalkylene oxide, n is an integer of 1 to 60, and m is an integer of 1 or 2. Is.