JPH01168448A - Vessel for sample or its component - Google Patents

Abstract

PURPOSE:To prevent a vessel for a sample from bleaching or discoloring by coating the surface printed in advance with paint mixed with solvent soluble copolymer containing fluorine, ultraviolet ray absorber and lubricant. CONSTITUTION:Solvent soluble copolymer containing fluorine preferably contains 10wt.% fluorine. Ultraviolet ray absorber is mixed at 20-35pts.wt. per 100pts.wt. copolymer containing fluorine. If the quantity of the absorber is excessively less, discoloring preventing effect of a sample vessel cannot be sufficiently obtained, while if it is excessively more, the weather resistance, solvent resis tance, acid resistance, alkaline property of the coating film are reduced unfovourably. This paint coats the printed surface in thickness of 20mum or less. It the thickness is excessively large, its coating work is not only compli cated, but its visibility of a printed image is reduced, and an expensive copoly mer containing fluorine is used in large quantity, thereby reducing its economy unfovourably.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sample container or its parts.

[Prior Art] Sample containers have traditionally been used for display purposes, and are printed with colorful colors, patterns, patterns, etc. to attract the attention of buyers. Pigments that produce colorful tones are used in such printing, and organic pigments that produce bright and glossy colors are often used.

In addition, sample containers are often exposed to high temperatures and strong light environments, such as inside vending machines installed outdoors.When exposed to such environments, sample containers may fade or change color. The vividness of printing was lost, causing people to lose their desire to purchase. Since such fading or discoloration progresses considerably in about -2 years, the work and cost required to replace the sample container is enormous. For this reason, sample containers are only replaced in a small number of cases, and the majority remain abandoned.

In order to prevent such fading and discoloration and shorten the replacement cycle, there is a method of applying clear coating such as acrylic resin.
Methods such as attaching a chlorinated polyethylene film are known, but none of these methods has a sufficient effect of preventing discoloration and discoloration, and has the problem of being susceptible to browning.

Attempts have also been made to layer clear acrylic paint with UV absorbers or chlorinated polyethylene film mixed with UV absorbers, but it is difficult to incorporate large amounts of UV absorbers. However, they did not provide a sufficient effect of preventing discoloration, and the problem of easy browning remained unresolved.

[Problems to be Solved by the Invention] The present invention aims to solve the problems of the prior art described above, and provides a sample container that does not fade, discolor, or lose its luster and can be used for a long period of time. or its parts.

[Means for Solving the Problems] The present invention was made to solve the above-mentioned problems, and contains 100 parts by weight of a solvent-soluble fluorine-containing copolymer, 20 to 30 parts by weight of an ultraviolet absorber, and a lubricant. To provide a sample container or its parts, characterized in that the blended paint is coated on a previously printed surface with a film thickness of 20 μm or less.

[Description of Structure] In the present invention, as the solvent-soluble fluorine-containing copolymer, a copolymer consisting of a fluoroolefin and a comonomer copolymerizable with the fluoroolefin is preferably employed.

Here, as the fluoroolefins, fluoroolefins having about 2 to 4 carbon atoms such as tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene, and pentafluoropropylene are preferable, and in particular, tetrafluoroethylene Ethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene are preferred, and
As the comonomer, an ethylenically unsaturated compound copolymerizable with a fluoroolefin or the like is employed. Examples of such ethylenically unsaturated compounds include olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters, and compounds containing acryloyl or methacryloyl groups. In particular, vinyl ethers, vinyl esters, and allyl ethers have excellent copolymerizability with fluoroolefins and excellent solvent solubility.
Allyl esters are preferably employed. As such vinyl ethers, vinyl esters, allyl ethers, and allyl esters, those having a linear, branched, or alicyclic alkyl group having about 1 to 15 carbon atoms are preferred. These ethylenically unsaturated compounds may have some or all of the hydrogens bonded to carbon replaced with fluorine.

Further, the fluoroolefin and the comonomer copolymerizable with the fluoroolefin may be used alone, or may be used alone.
More than one type of compound may be copolymerized.

Further, the solvent-soluble fluorine-containing copolymer preferably has a fluorine content of 10% by weight or more. If the fluorine content is too low, sufficient weather resistance cannot be obtained, which is not preferable. Preferably, the fluoroolefin is 30 to 70 mol%
It is a fluorine-containing copolymer copolymerized at a ratio of . If the copolymerization ratio of fluoroolefin is too high, the solubility in the solvent will be poor, and if it is too low, the weather resistance will be deteriorated, which is not preferable.

Further, it is preferable that the solvent-soluble fluorine-containing copolymer has a curing-reactive site because this further improves the solvent resistance, acid resistance, alkalinity, etc. of the coating film. Such curing reactive sites include active hydrogen-containing groups such as hydroxyl groups, carboxylic acid groups, acid amide groups, and amino groups, epoxy groups, and unsaturated groups.

Examples include active halogen-containing groups. Among these, active hydrogen-containing groups and epoxy groups are preferred from the viewpoint of excellent reactivity with isocyanate curing agents, aminoplast curing agents, etc. that are commonly used as curing agents, and hydroxyl groups are particularly preferred. As a method for introducing such a curing reactive site, a monomer having a curing reactive site such as hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxyalkyl vinyl ester, glycidyl vinyl ether, acrylic acid, methacrylic acid, allyl vinyl ether, etc. may be introduced. Polymerization or addition of acid anhydride, incyanate alkyl (meth)acrylate, etc. to a fluorine-containing copolymer through a polymer reaction, or hydrolysis of ester bonds in the polymer to convert them into carboxylic acid groups or hydroxyl groups. Methods such as these are adopted.

Moreover, the solvent-soluble fluorine-containing copolymer has a viscosity of 0.01 to 2.0 as measured in tetrahydrofuran at 30°C. On
/H range means paintability.

It is preferable because the physical properties of the coating film are excellent.

In the present invention, the ultraviolet absorber is blended in an amount of 20 to 30 parts by weight per 100 parts by weight of the solvent-soluble fluorine-containing copolymer. If the amount of the ultraviolet absorber is less than the above range, the effect of preventing discoloration and fading of the sample container will not be sufficiently obtained, which is undesirable.If it is too much, the weather resistance, solvent resistance, acid resistance, and alkalinity of the coating film will decrease. And it's not desirable.

As such ultraviolet absorbers, organic types such as benzophenone, benzotriazole, phenyl salicylate, and inorganic oxide types are used. Specifically, 2,4-dihydroxybenzophenone, 2.2', 4.4'-tetrahydroxybenzophenone, 2-hydroxy-4-
Octoxybenzophenone, 2-hydroxy-4-tridecyloxybenzophenone, 2 (2'-hydroxy-
4'-octoxyphenyl)benzotriazole, p-
Examples include t-butylphenyl salicylate and fine particle titanium oxide. In addition, by using a UV absorber with a crosslinking part that can react with the curing agent, the UV absorber is fixed in the coating film formation network, resulting in a more durable coating that will not migrate or elute over a long period of time. It is also possible to form a film, and examples of such ultraviolet absorbers include 2-hydroxy-4-hydroxyethoxybenzophenone and 2-hydroxy-4-(2'-hydroxy)propoxybenzophenone. In particular, it is preferable to use an organic ultraviolet absorber because the clarity is excellent.

In the present invention, a silicone-based lubricant is preferably employed as the lubricant. Such silicone lubricants include:
Examples include dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, higher fatty acid-modified silicone oil, and polyether-modified silicone oil. The lubricant is preferably used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the solvent-soluble fluorine-containing copolymer.

In addition, in the present invention, the paint used for painting is the one described above.
In addition to the components, the composition may also contain a curing agent, a solvent, a matting agent, a curing catalyst, etc. It is particularly preferable that the curing agent and solvent are included. As such a curing agent, a compound which reacts with the curing reactive site of the above-mentioned solvent-soluble fluorine-containing copolymer and/or the crosslinked part of the ultraviolet absorber to form a good hardened product is employed, and is usually used in the paint field. Curing agents can be used.

Examples include polyisocyanate curing agents, metal alkoxides, aminoplasts, and the like. As the polyisocyanate curing agent, a polyisocyanate compound such as hexamethylene diisocyanate: a polymer thereof, or a blocked isocyanate compound in which the isocyanate group is blocked with a blocking agent such as phenol, etc. are employed. In particular, non-yellowing types are preferred.

Examples of metal alkoxides include aluminum propoxide, titanium butoxide, zirconium butoxide,
Silane alkoxide etc. are used. Further, as the aminoplast, melamine resin, guanamine resin, urea resin, etc. are employed. In particular, among melamine resins, melamine that is at least partially etherified with one or more lower alcohols such as methanol, ethanol, propatool, and butanol is preferably employed.

Examples of solvents include aromatic hydrocarbons such as xylene and toluene, alcohols such as n-butanol, esters such as butyl acetate, ketones such as methyl isobutyl ketone, and glycol ethers such as ethyl cellosolve. Various commercially available thinners can also be used.

In the present invention, the above-mentioned paint is applied onto the printed surface in a film thickness of 201 parts m or less. If the film thickness is too large, not only will the painting process be complicated, but the clarity of the printed image will decrease, and a large amount of expensive fluorine-containing copolymer will be used, reducing economic efficiency. , undesirable.

In the present invention, existing coating methods such as brush coating, dip coating, roll coating, and spray coating can be employed as a method for coating the above-mentioned paint sample container or its parts.

In addition, sample containers of the present invention or their parts include metal cans such as beer cans, paper containers such as milk cartons, glass containers such as beer bottles, plastic containers, and parts such as beer bottle lids and sealing films. Examples include.

[Examples] The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples in any way.

In the Examples and Comparative Examples below, unless otherwise specified, the amounts are in parts by weight.

Example 1゜Chlorotrifluoroethylene/as a fluorine-containing copolymer
Cyclohexyl vinyl ether/ethyl vinyl ether/hydroxybutyl ether in a weight ratio of 80/1B/1
Fluorine-containing copolymer polymerized in a ratio of 41/12 (intrinsic viscosity measured at 30°C in tetrahydrofuran is 0.2)
A 50% by weight xylene solution containing 18 parts of hexamethylene diisocyanate cyclic trimer (trade name: Coronate EH1 manufactured by Nippon Polyurethane) was used as a curing agent, and xylene, methyl isobutyl ketone, and methyl ethyl ketone were used as solvents. 30, 15, and 15 parts of each were blended for 100 parts of the combined material.

Further, 25 parts of 2-hydroxy-4-octoxybenzophenone was blended as an ultraviolet absorber with respect to 100 parts of the fluorine-containing copolymer.

As a catalyst, 7 pp of dibutyltin dilaurate was added to the fluorine-containing copolymer.

As a lubricant, 1 part of polyether-modified silicone oil (trade name KP-323, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts of the above paint. This paint was evenly applied to a sample can by spraying, air-dried for 15 minutes, and then dried at 130° C. for 10 minutes to obtain a sample can having a coating film with a thickness of 15 p−.

This was subjected to a weather meter test. The results are shown in Table 3.

Example 2 As a fluorine-containing copolymer, chlorotrifluoroethylene/cyclohexyl vinyl ether/ethyl vinyl ether/hydroxybutyl ether was used in a weight ratio of 80/151.
Fluorine-containing copolymer polymerized at a ratio of 5/20 (intrinsic viscosity measured at 30°C in tetrahydrofuran is 0.07)
12 parts of hexamethoxymethyl melamine (trade name Cynull 303, manufactured by Mitsui Toatsu Chemical Co., Ltd.) was used as a curing agent in a 50% by weight xylene solution of db/g), and as a solvent, tripropylene glycol monomethyl ether, n-butanol,
30 and 20.10 parts of Nrubetsuso 150 were respectively blended with 100 parts of the fluorine-containing copolymer.

Further, 25 parts of 2-hydroxy-4-tridesiloxyhenzophenone (trade name G-SORB 103, manufactured by Sanbe Kasei Co., Ltd.) as a UV absorber was blended with respect to 100 parts of the fluorine-containing copolymer.

As a catalyst, a sulfonic acid derivative (trade name Cateoo,
(manufactured by Mitsui Toatsu Chemical Co., Ltd.) was added in an amount of 0.5 part to the fluorine-containing copolymer.

As a lubricant, 1 part of polyether-modified silicone oil (trade name KP-323, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts of the above paint.

This paint was applied uniformly to each sample using a roll coater, air-dried for 15 minutes, and then dried at 190°C for 2 minutes to obtain a 15-thick coating film for each sample.This was tested in a weather meter test. provided. The results are shown in Table 3.

Examples 3 to 7 To 100 parts of the copolymer having the composition shown in Table 1, 200 parts of xylene/methyl isobutyl ketone mixed solvent was added as a solvent.
A curing agent, a catalyst, and an ultraviolet absorber in the types and amounts shown in Table 2 were blended, and 1 part of polyether-modified silicone oil (trade name KP-323, manufactured by Shin-Etsu Chemical Co., Ltd.) was further blended as a lubricant.

This paint was applied to each sample using a roll coater, air-dried for 15 minutes, and then dried at 190°C for 2 minutes (Example 4.6 was dried at 130°C for 10 minutes) to form a coating film with a thickness of 15 l. Each sample was obtained. These were subjected to a weather meter test. The results are shown in Table 3.

The fluorine-containing copolymer used in Example 6 was prepared by reacting anhydrous amber at 60°C for 30 minutes using triethylamine as a catalyst to modify 10% of the hydroxyl groups in the fluorine-containing copolymer into carboxylic acid groups. It is something that

Table 1 In Table 1, TFE is tetrafluoroethylene CTFIJi chlorotrifluoroethylene HEAE is hydroxyethyl allyl ether CHVE is cyclohexyl vinyl ether EVE is ethyl vinyl ether HBVE is hydroxybutyl vinyl ether GVE is glycidyl vinyl ether.

Table 2 Coronet in Table 2) EH is hexamethylene isocyanate cyclic trimer manufactured by Nippon Polyurethane Cymel 303 is manufactured by Mitsui Toatsu Chemical Co., Ltd. Hexamethoxymelamine DBTDL is dibutyltin dilaurate Cat, E1000 is manufactured by Mitsui Toatsu Chemical Co., Ltd. The sulfonic acid derivative Di-Sorb 103 is 2-hydroxy-4 manufactured by Sanbe Kasei Co., Ltd.
-Tridecyloxybenzophenone Tinuvin P is 2(2'-hydroxy-4'-octoxyphenyl)penztriazole manufactured by Ciba Geigy, Japan.

Comparative Examples 1 and 2 Comparative Example 1 is one that is not coated with fluororesin, and Comparative Example 2 is one that is coated with acrylic clear paint instead of the fluororesin paint, and the results of the weather meter test are as follows. It is shown in Table 3.

Table 3 [Weather Meter Test] [Weather Meter Test] The degree of discoloration is determined by measuring the color difference (4E) before and after the Sunshine Weather Meter 800 hour test using a colorimeter (Suga Test Instruments HA-
C) Measured by. Gloss retention is after 800 hours of Sunshine Weather Meter testing.

Gold, orange, and blue were all colored using organic pigments.

Comparative Example 3 A sample can was laminated with a chlorinated polyethylene film into which 3 parts of 2(2°-hydroxy-4°-octoxyphenyl)benzotriazole was kneaded as an ultraviolet absorber.

This sample can had a gap in the squeezed area and had a poor appearance. Furthermore, after 800 hours using the Sunshine Weather Meter, all of the colors gold, orange, and blue had significantly faded.

[Effects of the Invention] Compared to conventional containers, the sample container or its parts of the present invention has the advantage that fading, discoloration, and loss of color occur much less frequently, and can be used for a long period of time. Therefore, even when used in a vending machine, etc., the replacement cycle is extremely long, and the amount of work and cost can be reduced.

Claims (1)

[Scope of Claims] 1. A coating containing 100 parts by weight of a solvent-soluble fluorine-containing copolymer, 20 to 30 parts by weight of an ultraviolet absorber, and a lubricant is coated on a pre-printed surface with a film thickness of 20 μm or less. A sample container or its parts characterized by being painted with. 2. The sample container or parts thereof according to claim 1, wherein the solvent-soluble fluorine-containing copolymer is a fluorine-containing copolymer having a curing reactive site.