JPS5825370A - Film-forming agent and metallized paper for label prepared therefrom - Google Patents

Abstract

PURPOSE:To provide a film-forming agent consisting of a curable film-forming resin, a specified mixed hardener and a medium, and giving a metallized paper for label which shows excellent water resistance under normal conditions of use and excellent releasability in bottle washing. CONSTITUTION:A mixture. of an organic matal-based hardener[e.g., metal (e.g., Ti, Al or Sn) alcoholate, acylate or chelate compd.]and an amino hardener (e.g., known ethyleneimine, melamine or isocyanate hardener) is used as a hardener for the film-forming agent. When used as an undercoating, the agent gives a metallized paper for label to be attached to wine or beer bottles and other containers which shows an excellent resistace to water under normal conditions of use and an excellent releasability in bottle washing operation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metallized metallized paper for labels for adhesion to various containers such as liquor bottles and beer bottles, and a film-forming agent used in the production of the metallized paper.

Traditionally, various containers such as liquor bottles and beer bottles have been labeled with their contents,
Labels, etc. are attached with adhesive to indicate quality, brand, etc.Aluminum foil laminated paper was widely used as the base material for these labels, but recently metal-metalized paper with aluminum vapor-deposited has also been used. This metal-deposited paper has become widely used, with an undercoat layer on one side of the paper as a base material, a metal-deposition layer on top of that, and an overcoat layer if necessary. It is made up of the following.

Bottles with such labels attached thereto are required to have sufficient water resistance when placed in and out of refrigerators and the like. On the other hand, these two-pell affixed bottles are washed for reuse after use, but the label must be easily peeled off by the alkaline washing liquid used at that time. has been done. Peeling of the label during bottle washing is achieved by dissolving the sialuminium-deposited layer in the alkaline washing solution, destroying the undercoat layer, and allowing water to reach the adhesive layer.

Therefore, conventionally, in order to satisfy the above-mentioned requirements, it has been considered to provide an alkali-soluble undercoat agent, but in this case, the water resistance under normal conditions is impaired. As another method, a method has been proposed in which an alkali-soluble metal powder, such as aluminum powder, is contained in the undercoat layer (for example, Japanese Patent Laid-Open No. 56-9
However, since this method uses a significantly larger amount of aluminum powder than the aluminum vapor deposited layer, a large amount of hydrogen is generated during the bottle washing process, and a large amount of aluminum is also produced in the washing liquid. + Rum dissolves, causing serious problems in waste liquid treatment.

As a result of intensive research aimed at resolving the drawbacks of the prior art as described above, the present inventors have found that by using an undercoat agent containing a specific curing agent, it exhibits excellent water resistance under normal conditions; The present invention was completed based on the finding that metallized paper for labels that exhibits excellent releasability during bottle washing treatment can be obtained.

That is, the present invention consists of two inventions, and the first invention is a film-forming agent comprising a curable film-forming resin, a curing agent, and a medium, in which the curing agent is a combination of an organometallic curing agent and an amino-based curing agent. The present invention is a film-forming agent characterized in that it is a mixture, and the second invention is a metal-deposited paper for labels formed using the film-forming agent.

To explain the present invention in detail, the curable film-forming resin used in the film-forming agent of the present invention includes carboxyl groups, carbalkoxy groups, hydroxyl groups, amino groups, substituted amino groups, aldehyde groups, etc. Examples of the resin having a functional group include conventionally known resins such as acrylic, alkyd, butyral, Pvum, PVC, and cellulose resins.

Used in the present invention, mainly the present invention 1! ! The curing agent system designated f11 consists of two components, and each of these components alone is a known material. The organometallic curing agent, which is one of the components, includes metal alcoholades, metal acylates, and metal chelate compounds, and typical examples of these metals include Mg, Cm, B
aXBXAM81. sn, P, 8. Ti1Zr,
F@, Cm, ) Ji, Cu, Zn, etc., and the most useful ones are TI, MuAs, for example, for T1, T I (OR1)4, T I (OR1), (
OOCR2)4-+a, Tl(OR,)n(OR3CO
R4), -III, etc., and further includes nine substituents in which one or two of these substituents are substituted with hydrogen, or metal salts thereof. In the above, Rt,
R'2, R3, and R4 represent an alkyl group, a phenyl group, etc. which may have a substituent.

As such an organometallic curing agent, it is preferable to use a water-soluble curing agent when the medium of the film forming agent is also water-based, and to use an oil-soluble curing agent when the medium is oil-based.

The above organometallic curing agent is 1 part of film-forming resin (solid content).
It is used in a proportion of about 1 to 20 parts by weight per 00 parts by weight.

The amino-based curing agent, which is the other component of the curing agent of the present invention, includes conventional ethyleneimine-based, melamine-based, and isocyanate-based curing agents that are known per se, all of which are industrially available. It is something.

The amino curing agent is used in an amount of about 1 to 30 parts by weight per 100 parts by weight of the film-forming resin, and about 40 to 20 parts by weight per 100 parts by weight of the organometallic curing agent.
Preferably, it is used in a proportion of 0 parts by weight.

The medium used in the present invention is water, methanol, ethanol, inopropyl alcohol, ethyl acetate, methyl ethyl ketone, cellonorb acetate, ethyl cellosolve, toluene, and other solvents, singly or in mixtures, and consists of a film-forming resin and other components. Solid content is approximately 10-70
It is used at a ratio of weight IsK.

The film-forming agent of the present invention can be produced by mixing the above-mentioned essential components by any suitable means, and at this time various additives can be added as necessary.

The above-mentioned film forming agent of the present invention is applied to any substrate surface and kept at an appropriate temperature (for example, 1 minute or less) for an appropriate time (for example, within 1 minute).
When dried at a temperature of 00 to 2 QOC), a tough film with a smooth surface is formed under normal conditions. While this coating has excellent water resistance, it quickly deteriorates in alkaline media, becomes water permeable, and in some cases peels off.

Therefore, the film-forming agent of the present invention is very useful for applications that require water resistance under normal conditions and deterioration resistance in an alkaline atmosphere, for example, as a constituent material of metal-deposited paper for labels.

The metal-deposited paper for labels, which is the second invention of the present invention, is characterized in that the undercoat layer is provided with a film-forming agent. The vapor-deposited paper of the present invention will be specifically described with reference to the drawings under DJ.

The drawing shows the label stand 1 of the present invention! ! 4 is a partially enlarged sectional view showing an example of metallized paper, 1 represents a base material such as paper or coated paper, 2 is an undercoat layer, 3 is metallized paper, and 4Fi is provided as necessary. This is an overcoat layer. As the base material 1, a conventionally known base material for labels can be used as is, and the undercoat layer 2Fi, the above-mentioned film forming agent,
It is applied to a thickness of about 1 to 202 chrome (when dry) by a method such as a gravure coating method, a roll coating method, an air knife method, etc., and then coated at a temperature of about 100 to 200 r for about 5 seconds to
It is easily formed when heated for 5 minutes. Next, metals such as aluminum, zinc, iron, and chromium are deposited using a conventional method to form a deposited layer 3.

Even more necessary! The label of the present invention may be provided with an overcoat layer 4 of acrylic, cyclized rubber, chlorinated rubber, cellulose derivative, maleic acid resin, alkyd resin, styrene-maleic acid resin, etc. Metal-deposited paper for use is obtained. When the metallized metallized paper for labels of the present invention is attached to various types of paper using an alkaline adhesive, the undercoat layer does not crack even in a humid atmosphere or even in water. It exhibits sufficient external water resistance without causing water damage, and exhibits sufficient peeling resistance because water does not pass through.On the other hand, the alkaline washing liquid during the bottle washing process first dissolves the vapor deposited layer on the surface and then removes the underlayer. Since the coating layer also quickly deteriorates and becomes water permeable, the alkaline cleaning solution quickly reaches the adhesive layer and the label can be easily peeled off.

The metal-deposited paper for labels of the present invention as described above generates very little hydrogen gas during its bottle-washing process, and only the metal in the metal-deposited layer dissolves in the alkaline washing solution. It is also very useful from this point of view.

Next, the present invention will be explained in more detail with reference to Examples. Note that the text in the middle of the sentence or ``chi'' is based on weight.

Examples Various film-forming agents were prepared by mixing the components listed in Table 1 below, and the resulting film-forming agents were applied to a base material (paper) for 5 f.
/vl~20t/+wF, ll0
Cure for 5-120 seconds at C-180r. Next, aluminum was vapor-deposited on the surface to obtain vapor-deposited paper for labels, and various tests were conducted on this vapor-deposited paper. The second result is
Shown in the table. The test conditions for the various tests are as follows.

1. Vapor deposition suitability test: Adhesiveness test was performed using cellophane tape peeling test, gloss was determined visually, heat resistance was 120tZ'X1
The presence or absence of burning was determined in G seconds, and it was indicated as good or bad.

2. Water resistance: It was immersed in water at room temperature for 24 hours, and the presence or absence of whitening and surface cracking on the surface of the aluminum alloy was examined, and the results were rated as good or bad.

3. Alkali suitability: The vapor deposited paper that had been stuck on a glass plate and dried was immersed in the caustic soda aqueous solution of 3- heated for 60 to 70 CK, and the time required for the label to peel off was measured.

Flats 1 to 1 and 3 in Tables 1 and 2 below are examples of the present invention, and A14 to 17 are comparative examples.

The Ro of the organometallic curing agent in Table 1 is -CH3, "C
2H5 or -CaH7 and B2 is Cll3CH=
The number 9 is CH3CH:CH-, and the number 3 is -CH3, -
0CH3maroku is -OC2Hs. In addition, R1 of the ethyleneimine curing agent is -H1-CH3 or a part z
Hs, R2 is on, -N(11 or -COOR
and R3 is H, -N<1 or 0i.

As is clear from Table 2 below, the metallized paper for labels of the present invention has excellent water resistance and excellent alkali suitability.

No. 1, Table 1.

[Brief explanation of the drawing]

The drawing is a partially enlarged sectional view showing an example of the metallized paper for labels of the present invention, in which 1 is a base material, 2 is an undercoat layer, 3 is a metallized layer, and 4L is an overcoat layer. Applicant Dainichiseika Kagyo Co., Ltd.

Claims (2)

[Claims] (1) A film-forming agent comprising a curable film-forming resin, a curing agent, and a medium, wherein the curing agent is a mixture of an organometallic curing agent and an amino-based curing agent. (2) In label metallized paper, in which an undercoat layer made of synthetic resin is provided on one side of a base material, a metallized layer is provided on the layer, and an overcoat layer is further provided as necessary, the undercoat layer is a metal-deposited paper for labels, which is formed from a curable film-forming resin, a mixed curing agent consisting of an organometallic curing agent and an amino-based curing agent, and a film-forming agent exposed from a medium.