JP3228040B2 - Scratching agent for glass container and glass container - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is intended to prevent the occurrence of scratches on the surface of glass containers such as beer bottles and soft drink bottles which are collected and used repeatedly, and to shield the scratches generated. The present invention relates to an abrasion shielding agent for a glass container to be used and a glass container having a cured film formed by the shielding agent.

[0002]

2. Description of the Related Art Glass containers used for beer, soft drinks, milk and the like are usually collected and repeatedly used. The glass containers thus collected and used repeatedly have abrasions on the glass container surface due to contact between the glass containers or between the glass container and a metal such as a plastic case or a machine in a filling process or a distribution process, and as a result, The appearance is significantly impaired and the commercial value of the bottled beverage is reduced. Therefore,
Conventionally, attempts have been made to apply a shielding agent to the surface of a glass container to prevent the occurrence of scratches, or to shield the generated scratches.

In this case, the following properties are required as a material for preventing the occurrence of scratches on the glass container and shielding the scratches. (1) Good shielding of abrasions. (2) The strength of the coating is large enough to withstand the conditions under which abrasion occurs, and the surface has good slipperiness. (3) The surface does not have a foreign substance feeling such as stickiness (stickiness) or an abnormal sliding feeling, and the difference between the non-coated part and the coated part is not conspicuous. In addition, it is difficult to adsorb dust and dirt. (4) A film is formed at about room temperature to obtain required physical properties. (5) After coating, before the coating film is cured, dew condensation occurs on the coating surface, and the coating film is not easily affected even if immersed in water, and forms a coating film having required physical properties. (6) The shielding property is maintained even when immersed in water. Also,
When immersed in water, there should be no oil film on the water surface. (7) It can be easily and completely removed in the bottle washing process after collection. (8) The filling process should not affect label attachment or damage the label. (9) The shielding agent itself is not harmful and is safe to touch the human body and food. In addition, the diluent should not be harmful when used after dilution.

Conventionally, it has been known to use a silicone resin as a shielding agent for such a purpose.
No. 17863 proposes an organopolysiloxane resin containing a phenyl group. However, since a glass container coated with such a silicone-based shielding agent is difficult to apply a label, the glass container is filled with the contents and sealed, and after applying the label, the shielding agent is applied. It was used in a series of steps, and was applied using a solvent or a dispersion medium to keep the amount of adhesion constant.

Japanese Patent Publication No. 57-17863 discloses that when an organic solvent is used as a solvent or dispersion medium for such a silicone-based shielding agent, ethanol is preferred from the viewpoint of safety and health. Dissolves the ink on the label attached to the beer bottle, which is not preferable in terms of work.

Further, JP-A-3-131548 describes a volatile siloxane and a silicone resin containing a large amount of methyl groups in a side chain having good compatibility with the volatile siloxane. Although the cured film of this shielding agent has good characteristics, there is still room for improvement, particularly with respect to the characteristic (5). That is, for example, when the shielding agent is cured under high humidity after filling beer or the like at 5 to 15 ° C., dew condensation easily occurs. In addition, when the coating is submerged before being completely cured, there is a problem that the coating is easily whitened.

The present invention has been developed in order to improve the above-mentioned circumstances, and is capable of forming a coating film having good compatibility with a glass container, excellent adhesion, excellent abrasion shielding property, and good water repellency, An object of the present invention is to provide an abrasion-shielding agent for a glass container, which is excellent in bottle coatability and effectively prevents whitening of a film due to water penetration, and a glass container having a cured film formed on the surface thereof.

[0008]

Means for Solving the Problems and Actions The present inventors have made intensive studies to achieve the above object, and as a result, the silicone resin represented by the following general formula (1) was used as a main component of the abrasion shielding agent for glass containers. It has good compatibility with glass, good adhesion to glass, excellent abrasion shielding, coating removal, label damage prevention, water repellency, water resistance, and condensation bottle coating. The inventors have found that a shielding agent that is excellent and that prevents the whitening of the coating by water immersion can be obtained, and the present invention has been accomplished.

[0009]

Embedded image (Where R ¹ is a substituted or unsubstituted ethyl group, propyl group, alkenyl group, aryl group or aralkyl group, R ² is an alkyl group having 4 or more carbon atoms, and R ³ is
8 wherein a, b, c, d, e, and f are 0.
5 ≦ a + b + c ≦ 2, 1 <c / (a + b) <10, 0.
01 ≦ b <0.5, 0.4 ≦ d ≦ 2, e + f = 1, 0 ≦
A number that satisfies f <0.5. )

Hereinafter, the present invention will be described in more detail. The shielding agent for a glass container of the present invention has the following general formula (1)
It contains a silicone resin represented by

[0011]

Embedded image (Where R ¹ is a substituted or unsubstituted ethyl group, propyl group, alkenyl group, aryl group or aralkyl group, R ² is an alkyl group having 4 or more carbon atoms, and R ³ is
8 wherein a, b, c, d, e, and f are 0.
5 ≦ a + b + c ≦ 2, 1 <c / (a + b) <10, 0.
01 ≦ b <0.5, 0.4 ≦ d ≦ 2, e + f = 1, 0 ≦
A number that satisfies f <0.5. )

In this case, R ¹ is an ethyl group, a propyl group, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having an alkyl group having a carbon atom. It is preferred that the number 1 to 4, the aryl group portion has 6 to 10 carbon atoms, and specifically, R ¹ is an ethyl group, a propyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group, a tolyl group, and the like. Aralkyl groups such as aryl groups, β-phenylethyl groups, and β-phenylpropyl groups, and fluoropropyl groups in which part or all of the hydrogen atoms bonded to carbon atoms of these organic groups have been substituted with halogen atoms, cyano groups, etc. , Cyanomethyl group and the like.

R ¹ may be the same as or different from each other. However, R ¹ may be a phenyl group, a vinyl group, or the like for the purpose of improving the shielding property or imparting flexibility by bringing the refractive index close to that of glass. Or these groups can be used in combination with each other. In particular, when R ¹ is a phenyl group, the refractive index is close to that of glass, and a resin with improved transparency can be obtained. Further, in this case, a is 0.01 ≦ a
It is preferably in the range of <0.5, and if it is less than 0.01, there may be no effect on transparency, and if it is more than 0.5, it may cause deterioration of the cleaning property.

R ² is an alkyl group having 4 or more carbon atoms,
Examples thereof include an amyl group and an octyl group. R
Reference numeral ² denotes a group for imparting water repellency to the silicone resin, which is a feature of the present invention. These groups may be the same or different from each other. In this case, in order to impart water repellency, it is essential that b satisfies 0.01 ≦ b <0.5,
If it is less than 0.01, the effect cannot be obtained, and if it is more than 0.5, the curability and the cleaning property deteriorate.

In the silicone resin of the above formula (1), the methyl group is introduced in the range of 1 <c / (a + b) <10 from the viewpoint of hardness, controllability of curability and availability. However, there is a drawback that if the number of methyl groups is too large, the viscosity becomes low.

Further, R ³ O in R ³ showing the alkoxy group is an alkyl group having 1 to 8 carbon atoms, a methyl group, an ethyl group,
Propyl group, butyl group, amyl group, and octyl group and the like, R ³ is the effect on film formation during curing
O is preferably a methoxy group, and is preferably an ethoxy group from the viewpoint of by-products generated during curing with little odor and harmfulness.

A to f are as described above, but more preferably 0.7 ≦ a + b + c ≦ 1.8, 1 <c / (a +
b) <5, 0.02 ≦ b ≦ 0.2, 0.7 ≦ d ≦ 1.8
It is.

The amount of the silicone resin used is preferably 40% or less, particularly preferably 5 to 30% of the whole shielding agent.

The silicone resin is preferably used together with a volatile organosiloxane. This volatile organosiloxane is used for forming a uniform film on a glass container, and is not particularly limited as long as it has volatility. One or two or more selected from the chain polysiloxane (2) and the cyclic polysiloxane represented by the following general formula (3) are used.

[0020]

Embedded image (Wherein, R ⁴ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms, and each R ⁴ may be the same or different from each other; m is 1 to 10) Represents the number of

[0021]

Embedded image (Wherein, R ⁴ has the same meaning as described above, and n is 3 to
Represents the number 7. )

Specifically, the following can be exemplified as the polysiloxanes of the above formulas (2) and (3).

[0023]

Embedded image (In the formula, Me is a methyl group and Vi is a vinyl group.)

The amount of the volatile organosiloxane to be used is preferably 60% or more, more preferably 70 to 95%, of the entire shielding agent. If the content of the volatile organosiloxane is less than 60%, the amount of the silicone resin adhered becomes too large. Not only is the economy inferior, but also a problem may occur that the film thickness is too large to obtain a uniform coating film.

The shielding agent of the present invention contains the above-mentioned silicone resin and volatile organosiloxane as main components, but a catalyst may be used to further promote curing.

Examples of such catalysts include those known as condensation catalysts for organopolysiloxanes. For example, (1) organic amines such as triethanolamine; (2) zinc octylate; Carboxylic acid metal salts such as tin octylate (3) Organotin compounds such as dibutyltin dilaurate and dibutyltin dioctoate (4) Titanate esters such as tetrabutyl titanate and tetrapropyl titanate (5) Aluminum organic such as aluminum acetylacetone Compound (6) Boron fluoride complex such as boron trifluoride triethylamine complex and the like can be mentioned. Among them, from the viewpoint of safety and health, titanates such as tetrabutyl titanate and dibutyltin dilaurate are preferred.

The amount of the catalyst used is appropriately selected.
About 0.05 to 100 parts by weight of the silicone resin
20 parts by weight, preferably 0.1 to 10 parts by weight, is suitable.

The shielding agent of the present invention may further contain various auxiliary components such as a solvent or a dispersion medium other than the volatile organosiloxane, a stabilizer, a thixotropic agent, a coloring agent, and a filler. In addition, when other solvents or dispersion media are used in addition to the volatile organosiloxane, ethanol and isoparaffinic fatty acid hydrocarbons are preferable from the viewpoint of safety and health, but if necessary, for example, methanol, propanol, butanol. And other organic solvents having the required solubility.

The glass container to which the abrasion shielding agent of the present invention is applied is not particularly limited, but those which are collected and reused from the market, such as beer, soft drink, milk and sake containers, are effectively used.

As a method of applying the shielding agent of the present invention to a glass container, a commonly used method such as brush printing, a spray method, a dipping method, a flow coater method, a transfer method, or any other method is employed. be able to. Further, the place to be applied is a part where a scratch is generated or a part where a scratch is easily generated, but it is needless to say that only such a part is not limited.

Since the labeling agent of the present invention does not dissolve the label ink and does not damage the label, it can be applied after the label is applied. Further, a component having a particularly high volatility may be used as the volatile siloxane, and the volatile siloxane may be applied at the end of the washing step, and may be dried promptly in the next drying step.

The shielding agent of the present invention cures at room temperature with moisture in the air to form a film. Therefore, after coating, by leaving the coating at room temperature for about 1 to 96 hours, it is possible to obtain a film having no surface sticking property. However, it is necessary to shorten the curing time, remove volatile organosiloxane, and perform other necessary operations. Accordingly, heat treatment may be performed to such an extent that the quality of the contents in the glass container is not impaired.

Although the thickness of the cured film is arbitrary, it is preferably 0.5 to 10 μm, and more preferably about 1 to 3 μm, because the effect of shielding the abrasion, the strength of the film and the fact that it can be easily removed in the washing step. Appropriate. If the thickness is less than 0.1 μm, the abrasion shielding properties may be insufficient, and
If the thickness is more than m, it may be difficult to remove the cleaning step.

[0034]

According to the abrasion-shielding agent for glass containers of the present invention, a coating film having good adhesion to glass, excellent adhesion to glass, abrasion-shielding property, removability of a coating film, and anti-label damage property is formed. In addition, it is possible to form a film that is excellent in water repellency, excellent in dew condensation resistance, excellent in dew condensation bottle coating property, and excellent in water resistance and hardly whitens without oil film floating.

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. All parts in each example are parts by weight.

EXAMPLES, COMPARATIVE EXAMPLES Abrasion shielding agents for glass containers having the composition shown in Table 1 were prepared, and their performance was evaluated by the following methods. The results are also shown in Table 1. The components shown in Table 1 are as follows. Organosiloxane A (C ₆ H ₁₃ ) _0.05 (C ₆ H ₅ ) _0.1 (CH ₃ ) _0.85 (CH
₃ O) _1.2 SiO _0.9 having a viscosity represented by the average composition formula of 15
Centistokes organopolysiloxane Organosiloxane B (C ₄ H ₉ ) _0.2 (C ₆ H ₅ ) _0.2 (CH ₃ ) _0.6 (CH ₃ O)
_1.2 Organopolysiloxane having a viscosity of 18 centistokes represented by the average composition formula of SiO _0.9 organosiloxane C (C ₁₀ H ₂₁ ) _0.02 (C ₆ H ₅ ) _0.28 (CH ₃ ) _0.7 (C ₂ H ₅₎
O) An organopolysiloxane having a viscosity of 15 centistokes represented by an average compositional formula of _1.2 SiO _0.9 and a organosiloxane D (comparative example) (C ₆ H ₅ ) _0.1 (CH ₃ ) _0.9 (CH ₃ O) _1.2 SiO _0.9 Organopolysiloxane having a viscosity represented by the average composition formula of 17 centistokes Organosiloxane E (Comparative Example) The viscosity represented by the average composition formula of (CH ₃ ) _1.0 (C ₂ H ₅ O) _1.2 SiO _0.9 is 13 centistokes Organopolysiloxane titanosiloxane A (C ₆ H ₁₃ ) _0.2 (C ₆ H ₅ ) _0.1 (CH ₃ ) _0.7 (C ₂ H
₅ O) An organopolysiloxane having a viscosity of 14 centistokes expressed by _1.2 Si _0.9 Ti _0.1 O _0.9

[0037]

Embedded image

Performance evaluation (1) Appearance of liquid (whether turbid or separated, uniform solubility) 均一: Uniform, transparent Δ: Slightly turbid ×: Non-uniform, turbid liquid (2) Scratching and coating Uniformity Evaluate visually. ：: No scratches are observed at all. △: Scratches are slightly observed. ×: Scratches are considerably observed. (3) Condensation bottle shielding property After filling a scratched bottle with 5 ° C water and applying a shielding agent, 30 ° C is applied. After leaving for 5 hours in a dew condensation state in an atmosphere of 80% RH, it is dried at room temperature for 4 days, and the appearance is visually evaluated in the same manner as “abrasion shielding property”. ：: transparent △: slightly non-uniform ×: non-uniform with uneven surface (4) Water resistance-1
After immersion in water for a day, take out and visually evaluate the appearance. ：: transparent △: slightly cloudy ×: whitening (5) Water resistance-2 One beer bottle coated with a shielding agent and dried at room temperature for 4 days.
After being immersed in water for a week, it is taken out and its appearance is visually evaluated. ：: Transparent ：: Slightly cloudy ×: Whitening (6) Removability Evaluate the ease of film removal when washed with 3.5% sodium hydroxide solution at 70 ° C. for 10 minutes. ○: Completely removed △: Slight residual ×: Coating film remaining unevenly (7) Label damageability The label of a commercial beer bottle was treated vertically 5 times with a sponge containing a shielding agent, and the label surface was treated. And to evaluate the printing ink for damage. ○: No damage at all △: Damaged ×: The entire surface is damaged by solvent

[0039]

[Table 1]

From the results shown in Table 1, it can be seen that the shielding agent of the present invention is particularly excellent in dew condensation bottle shielding property and water immersion whitening prevention property.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-213631 (JP, A) JP-A-4-55343 (JP, A) JP-A-3-131548 (JP, A) JP-A-4-134 139036 (JP, A) JP-A-3-16934 (JP, A) JP-A-63-117932 (JP, A) JP-A-56-23444 (JP, A) (58) Fields investigated (Int. ⁷ , DB name) C03C 17/30 C09D 183/00-183/16

Claims (4)

(57) [Claims] [Claim 1] The following general formula (1) (Where R ¹ is a substituted or unsubstituted ethyl group, propyl group, alkenyl group, aryl group or aralkyl group, R ² is an alkyl group having 4 or more carbon atoms, and R ³ is
8 wherein a, b, c, d, e, and f are 0.
5 ≦ a + b + c ≦ 2, 1 <c / (a + b) <10, 0.
01 ≦ b <0.5, 0.4 ≦ d ≦ 2, e + f = 1, 0 ≦
A number that satisfies f <0.5. Abrasion shielding agent for glass containers, characterized by containing a silicone resin represented by the formula (1): 2. The composition according to claim 1, which comprises a water-repellent silane-containing silicone resin represented by the general formula (1) and a volatile organosiloxane, wherein the volatile organosiloxane is represented by the following general formula (2). (Wherein, R ⁴ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms, and each R ⁴ may be the same or different from each other; m is 1 to 10) And a linear polysiloxane represented by the following general formula (3): (Wherein, R ⁴ has the same meaning as described above, and n is 3 to
Represents the number 7. A) a scuff-protecting agent for glass containers, which is at least one member selected from the group consisting of cyclic polysiloxanes represented by the formula (1), and the content of the volatile organosiloxane is 60% by weight or more. 3. The glass container according to claim 1, wherein R ^{1 in} the general formula (1) is a phenyl group and a contains a silicone resin in which a satisfies 0.01 ≦ a <0.5. Abrasion shield. 4. A glass container having a cured film of the abrasion barrier agent according to claim 1 formed on a surface thereof.