JPH0777972B2 - Scratch coating agent for glass containers - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an agent for scratches and scratches on glass containers such as fruit juice beverage bottles, soft drink bottles, beer bottles, etc., and in particular, a coating film is formed by dew condensation on the surface of the glass container. The present invention relates to a coating agent for scratch marks on a glass container, which is not washed away and therefore has a good shielding property and 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 used repeatedly, but during the bottling process and distribution process, 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 a poor coating property because the coating film is washed away due to dew condensation, but also have stickiness and slipperiness after application, which makes the feel uncomfortable and the risk of the container slipping out of the hand, and also dusting. Not only does it have a tendency to adhere, and the coating film peels off in cold water or in a showcase, causing not only poor water resistance, but the oil from the peeled product floats 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 The coating film is easily removed during the washing process. It is intended to provide a novel scratch coating agent for glass containers.

[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 by comprising two or more blends selected from the group of the following components (A), (B) and (C).

(A) Polymer of the general formula RSi (OR ') n.

(B) Polymer of the general formula Si (OR ′) ₄ .

(C) A reaction product produced by the reaction of the compounds represented by the general formulas (A) and (B).

However, in the above formula (A), R is a methyl, ethyl, dimethyl, or methylethyl group, and R'is C ₁
To C ₄ alkyl groups, and n is an integer of 2 to 3. In the formula (B), R ′ is a C _{1 to} C ₄ alkyl group.

[Specific Description of the Invention]

 Hereinafter, the present invention will be described in detail.

The above-mentioned general formula RSi (OR ') n is specifically methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, Ethyltributoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldipropoxysilane,
Methylethyldibutoxysilane, methyltriisopropoxysilane, methyltriisobutoxysilane, ethyltriisopropoxysilane, ethyltriisobutoxysilane, dimethyldiisopropoxysilane, dimethyldiisobutoxysilane, dimethyldiisobutoxysilane, methylethylisopropoxy Silane, methylethylisobutoxysilane, etc., which are components (A) according to the present invention, which are easily polymerized in the presence of a dilute acid such as 0.1 to 0.01 N hydrochloric acid, sulfuric acid, sulfonic acid, chloroacetic acid. To generate. Specifically, these components (A) are alkoxy group-containing alkylpolysiloxanes such as methoxy group-containing methylpolysiloxane, ethylpolysiloxane,
Dimethylpolysiloxane, methylethylpolysiloxane, ethoxy group-containing methylpolysiloxane, ethylpolysiloxane, dimethylpolysiloxane, methylethylpolysiloxane, propoxy-containing methylpolysiloxane, ethylpolysiloxane, dimethylpolysiloxane,
Ethylpolysiloxane, dimethylpolysiloxane, methylethylpolysiloxane, butoxy group-containing methylpolysiloxane, ethylpolysiloxane, dimethylpolysiloxane, methylethylsiloxane, isopropoxy group-containing methylpolysiloxane, ethylpolysiloxane, dimethylpolysiloxane, Methyl ethyl polysiloxane,
Examples thereof include isobutoxy group-containing methyl polysiloxane, ethyl polysiloxane, dimethyl polysiloxane, and methyl ethyl polysiloxane.

The above-mentioned general formula Si (OR ') ₄ is, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraisopropoxysilane, tetraisobutoxysilane, etc., and these compounds are the components (A Polymerization in the same manner as in ()) to produce the component (B) according to the present invention.

These components (B) are specifically alkoxy group-containing polysiloxanes such as methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group, and isobutoxy group.

The component (C) according to the present invention is a reaction product produced by reacting the compound represented by the general formula of the above-mentioned components (A) and (B) under the same conditions as the above-mentioned component (A). Specifically, it is an orthosilicate-bonded alkylpolysiloxane, and examples thereof include an orthosilicate-bonded methylpolysiloxane, ethylpolysiloxane, dimethylpolysiloxane, and methylethylpolysiloxane.

The present invention provides two or more blends selected from the groups (A), (B) and (C) described above, that is, (A) (B),
(A) (C), (B) (C) or (A) (B) (C)
It is a blend of. These compounding amounts are arbitrary, but (A)
In the case of blending (B), (A) and (C), 0.5 to 1 of the components (B) and (C) are added to 100 parts by weight of the component (A).
00 parts by weight is preferable, and 1.0 to 60 parts by weight is more preferable. In the case of the components (B) and (C), the amount of the component (B) is preferably 0.5 to 100 parts by weight, and more preferably 1.0 to 60, relative to 100 parts by weight of the component (C). Further component (A),
In the case of (B) and (C), the total amount of the components (B) and (C) is preferably 0.5 to 100 parts by weight, and more preferably 1.0 to 60 parts by weight, relative to 100 parts by weight of the component (A).

The above-mentioned coating agent of the present invention is a stock solution or water or alcohol,
It is mixed and diluted with an organic solvent such as hydrocarbons and then applied with a cloth, sponge, felt, brush, belt or the like, or by any method such as dipping or spraying.

Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1 Components (A) (B) and components (C) used in this example
Is as follows.

Component (A) (1) Ethoxy group-containing methylpolysiloxane.

(2) Ethoxy group-containing ethyl polysiloxane.

(3) Ethoxy group-containing methylethyl polysiloxane.

Component (B) ethoxy group-containing polysiloxane.

Component (C) Orthosilicate-bonded dimethylpolysiloxane.

The component (A) was synthesized as follows. That is,
Distilled water (1 mol) was added dropwise to alkylethoxysilane (1 mol) in the presence of hydrochloric acid to make the mixture homogeneous and transparent, and the temperature was raised to 81 ° C. and refluxed for 1 hour. 130 ℃ while distilling off low-boiling substances
The temperature was raised to 130 ° C., and the mixture was aged under reduced pressure (400 mm / Hg) at 130 ° C. for 1 hour to obtain an ethoxy group-containing alkylpolysiloxane component (A).

The synthesis of the component (B) is carried out in the same manner as the component (A) by adding 1.4 mol of distilled water to 1 mol of tetraethoxysilane in the presence of hydrochloric acid to obtain an ethoxy group-containing polysiloxane component (B). It was

In addition, the synthesis of component (C) is carried out by using dimethylethoxysilane 0.5
1 mole of distilled water in the presence of hydrochloric acid, and the components (A) and (B) are mixed.
In the same manner as in (1), an orthosilicate-bonded dimethylpolysiloxane was obtained. The above-mentioned components (A), (B) and (C) were mixed in the respective amounts shown in Table 1 to prepare sample No. 1 to
Thirty examples were obtained.

Among them, the samples according to the present invention are Nos. 1 to 25, and the reference samples for comparison are Nos. 26 to 30.

Then, each sample in Table-1 was diluted 10 times with ethanol,
Each of these samples was subjected to various performance tests shown in Table-2, 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 leaving it in a constant temperature and humidity chamber (Yamato IG41) for 24 hours, the shielding property of scratches was observed. In addition, a beer bottle (633 ml)
Water of 10 ° C. was poured into the test piece, 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.

(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.
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.

In Table 2, the ⊚ mark indicates "very good", the O mark indicates "good", the Δ mark indicates "a little bad", and the X mark indicates "bad".

From Table-2, the coating agent according to the present invention (Sample No. 1 to
25) is “very good” or “good” in all of the 5 items such as the scratch shielding property and the comparative example (Sample No. 2).
It can be seen that it is remarkably superior to that of 6 to 30).

It should be noted that the components (A) and (B) in the above-mentioned examples both used blended products, but it was found that the same results as described above were obtained even if these were reaction products.

〔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 (56) References JP 61-26636 (JP, A) JP 60-188476 (JP, A)

Claims (1)

[Claims] 1. A scratch resistant coating agent for glass containers, which comprises a mixture of two or more selected from the group consisting of the following components (A), (B) and (C): (A) Polymer of the general formula RSi (OR ') _n . (B) Polymer of the general formula Si (OR ′) ₄ . (C) A reaction product produced by the reaction of the compounds represented by the general formulas (A) and (B). However, in the above formula (A), R is a methyl, ethyl, dimethyl, or methylethyl group, and R'is C ₁
To C ₄ alkyl groups, and n is an integer of 2 to 3. In the formula (B), R ′ is a C _{1 to} C ₄ alkyl group.