JPS6175376A - Metal evaporation paper for label - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to metallized paper for labels to be attached to various containers such as liquor bottles and beer bottles.

(Prior Art) Conventionally, various containers such as liquor bottles and beer bottles have labels attached to them to indicate the contents, quality, brand, etc. The base materials for these labels include: Aluminum foil-laminated paper was widely used, but recently metallized paper with aluminum vapor-deposited has also become widely used, and this metallized paper has an underlayer on one side of the paper as a base material. A coat layer is provided, a metal vapor deposition layer is further provided thereon, and an overcoat layer is further provided as necessary.

Bottles with such labels attached thereto are required to have sufficient water resistance in order to be taken out and put into refrigerators and the like. On the other hand, these labeled bottles are washed for reuse after use, but the label must be easily removed by the alkaline washing liquid used at that time. has been done.

Peeling of the label during bottle washing is performed by dissolving the aluminum deposited layer with the alkaline washing solution, then destroying the undercoat layer, and allowing water to reach the adhesive layer.

(Problem to be solved by the invention) Therefore, conventionally, in order to satisfy the above requirements, it has been considered to provide an alkali-soluble undercoat layer, but in this case, the water resistance under normal conditions is It has the disadvantage of being damaged.

Yet another 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 Application Laid-Open No. 56-9776). Since a significantly larger amount of aluminum powder is used compared to the aluminum vapor deposited layer, a large amount of hydrogen is generated during bottle washing, and a large amount of aluminum is dissolved in the washing liquid, causing serious problems in waste liquid treatment. It is something.

(Means for Solving the Problems) As a result of intensive research in order to solve the above-mentioned drawbacks of the prior art, the present inventor has discovered that by using an undercoating agent containing a specific curing agent, The present invention was completed based on the finding that a metallized paper for labels can be obtained which exhibits excellent water resistance and, on the other hand, exhibits excellent peelability during bottle washing.

That is, in Kizawa 1, an undercoat layer made of synthetic resin is provided on one side of the base material, and metal-deposited paper is provided on the layer.
In the metal-deposited paper for labels, which is further provided with an overcoat layer if necessary, the undercoat layer is composed of a curable film-forming resin, a curing agent of a metal alcoholate, a metal acylate, or a metal chelate compound, and an ethyleneimine-based, This metallized paper for labels is formed from an undercoat agent consisting of a mixed hardener with a melamine-based or isocyanate-based hardener and a medium.

To explain the present invention in detail, the curable film-forming resin used for forming the undercoat layer of the metallized paper for labels of the present invention has carboxyl groups, carbalkoxy groups, hydroxyl groups, and amino groups in its structure. , a substituted amine group, an aldehyde group, and other functional groups, such as acrylic, alkyd, butyral, PVA, and PVC resins.
These are conventionally known resins such as cellulose-based and cellulose-based.

The curing agent used in the present invention consists of 2s, and each of these components alone is a known material. A curing agent for one of the components, metal alcoholate, metal acylate, or metal chelate compound (
Typical examples of metals (hereinafter referred to as metal hardeners) are Mg
, Ca, Ba, B, A! L, S i, Sn, P, S, T
i, Zr, Fe, Co, Ni, Cu, Zn, etc., and the most useful ones are Ti, An, and Sn. For example, regarding Ti, Ti (ORI)4. Ti (OR
I) n(00CR2)4-n, Ti(ORI
)n (OR3COR4)4-n etc.,
Furthermore, among these substituents, those in which one or two of them are substituted with hydrogen, or metal salts thereof are also included. In the above, R1, R2, R3, and R4 represent an alkyl group or a phenyl group that may have a substituent.Such metal-based curing agents are water-soluble when the medium of the undercoat agent is water-based. When the medium is oil-based, it is preferable to use an oil-soluble hardening agent.

The above metallic curing agent is used in an amount of about 1 to 20 parts by weight per 100 parts by weight of the curable film-forming resin (solid content).

The other component of the curing agent used in the present invention is an ethyleneimine-based, melamine-based, or incyanate-based curing agent (
The amine curing agents (hereinafter referred to as amine curing agents) are known per se and are commercially available. Such an amine-based curing agent can be used in an amount of 100 weight 7 g of the above-mentioned curable film forming resin.
Preferably, from about 1 to 30 parts by weight per part and from about 40 to 200 parts by weight per ioo part of the metal-based curing agent.

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

The undercoat agent used to form the metallized paper for labels of the present invention can be prepared by mixing the above-mentioned essential components by any suitable means, but at that time, various additives etc. may be added as necessary. Anyone can join.

When the undercoat agent having the above structure is applied to any substrate surface and dried at an appropriate temperature (e.g. 100 to 200°C) for an appropriate time (e.g. within 1 minute), it normally forms a tough coating with a smooth surface. form. While this coating has excellent water resistance, it quickly deteriorates in alkaline media, becomes water permeable, and in some cases peels off.

The R vapor-deposited paper for labels of the present invention is characterized in that an undercoat layer is provided using the above-mentioned undercoat agent, gold B vapor-deposited paper is provided on the layer, and an overcoat layer is further provided as necessary. It is what it is. Hereinafter, the vapor-deposited paper of the present invention will be specifically explained with reference to the drawings.

The drawing is a partially enlarged sectional view schematically showing an example of the metallized paper for labels of the present invention, where l represents a base material such as paper or coated paper, 2 is an undercoat layer, and 3 is a metallized metallized paper. 4 is an overcoat layer provided as necessary. As the base material 1, a conventionally known base material for labels can be used as it is, and for the undercoat layer 2, the above-mentioned film forming agent is applied to about 1 to 20% by a method such as a gravure coating method, a roll coating method, an air knife method, etc. Apply to a thickness of microns (dry) and then apply at a temperature of about 100-200℃ for about 5 seconds to 5 minutes.
The layer 3 is easily formed by heat curing for minutes. Next, a metal such as aluminum, zinc, iron, chromium, etc. is vacuum-deposited using a conventional method to form a deposited layer 3.

Furthermore, if necessary, an overcoat layer 4 of acrylic, cyclized rubber, chlorinated rubber, cellulose derivative, maleic acid resin, alkyd resin, styrene-maleic acid resin, etc. may be provided to coat the metal for the label of the present invention. Metallized paper is obtained. When the metallized paper for labels of the present invention is attached to various types of bottles using an alkaline adhesive, the undercoat layer does not crack even in a humid atmosphere or even in water. without occurring,
It shows sufficient water resistance and does not allow water to pass through! lI
On the other hand, the alkaline washing liquid during the bottle washing process first dissolves the vapor deposited layer on the surface, and then the undercoat layer quickly deteriorates and becomes water permeable. The E layer is reached and label elaboration is easily accomplished.

The metal vapor-deposited paper for labels of the present invention as described above generates very little hydrogen gas during its bottle washing process, and the only metal such as aluminum that dissolves in the alkaline washing solution is the metal in the vapor-deposited layer. 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 in the text, parts or % are based on the fEffi standard.

Example Various undercoating agents used in the present invention were prepared by mixing the components listed in the following tjS1 table, and the obtained undercoating agent was applied onto a substrate (paper) at a rate of 5 g/m'' to 20 g/rr.
f(1) amount, applied at 110°C to 180°C, 5 to 120
After curing for seconds, aluminum was then vapor-deposited on the surface to obtain metal-deposited paper for labels, and various tests were conducted on this metal-deposited paper. The results are shown in Table 2, and the test conditions for the various tests are as follows.

1. Vapor deposition suitability test: Adhesiveness test was carried out by cellophane tape peeling test, gloss was visually checked, and heat resistance was judged by the presence or absence of burning at 120° C.

2. #Aqueous; immersed in water at room temperature for 24 hours, checking for whitening and surface cracking on the aluminum surface, and marking it as good or bad.

3. Alkali suitability: A metallized paper that had been adhered to a glass plate and dried was immersed in a 3% caustic soda aqueous solution heated to 60 to 70°C, and the time required for the label to peel off was measured.

In Tables 1 and 2 below, Nos. 1 to 13 are uninvented examples, and Nos. 14 to 17 are comparative examples. 1st
R1 of the metallic curing agent in the table is -CH3, -C2R5 or 103R7, and R2 is CH3CH= or CH
3CH=CH-, R3 is -CH3, -0CH3,
Or -〇〇2H5. Further, R1 of the ethyleneimine curing agent is -H1-CH3 or 102 R5,
R2 is -H1-Nl or -COOR, and R3 is -H1-N'11 or 0i.

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

``Maiyu'' 1 Hoshiboshi Sanzuki JLLfl Acrylic Resin 50
Part i and Sumire 11 HOT i Mi Ko0CH2CH2 Buttocks N 5 part 7E7,1
Shin 1 Methylolated melamine 8-part smallpox wound
Wed 20ilff! IPA I7
10 parts of hydroxypropyl cellulose Adan (ORI) 2 (OR2COR3) 5 parts -
y2y, rb [[;N-cRtR2Ra 5g
Symptoms --- Cloth Water 40 parts Methanol 40 parts ■ 11 Nami 1 Sumire 1 Polyvinyl alcohol 24 parts 1 T f (ORI) 3 (OR2COR3) 3
part 737, 1pN-cu1n2na 3 part 1
-ml Water 50 parts Methanol 20 parts
'Hie A Mourning Parallel' Wataru 1 Acrylic polyol resin 50 parts Shuo and Rinshin 1 T i (ORI) 3 (OR2COR3) 3
Part 4 L-1-1 Ethyl acetate 20 parts Toluene
17 parts ■ `` 1 crotch average imaginary blue moon acrylic polyol resin 50 parts association and presentation l Ti (ORI) 3 (OR2COR3) 5
Part y; 7, 1pN-cRt R2R35 Part U Ethyl acetate 20 parts Toluene
20 parts Aimu J 1 Ying' 111 Soybean fat Nitrocellulose resin 30 parts
5 parts LLjldJ and 3 parts of N-CR1R2R!
Ethyl acetate 40 parts Toluene ・
24 parts Hieru 1 1 Ibaraboshi Kazuki Sumire 1 Alkyd resin 50 parts Gold Ij
(ORI) 3 (OR2COR3) 5 parts melamine urea butylated 8 parts 1-1 ethyl acetate 20 parts toluene
20 parts■Work 1 1Yoshidarayum Alkyd resin 50 partsi凰线presentationl HOT f-EimOCH2CH2de=N 5 parts 7;
yst, ray-CRIR2R35-m-1
#Ethyl acid 20 parts Toluene 20
50 parts of acrylic polyol resin 50 parts of acrylic polyol resin S n (ORI)2 (OR2COR3)2 5
Triazine cocondensation resin 8 parts 1-
11 cloth Ethyl acetate 20 parts Toluene
17 parts No, 10
, :DB IQN-CRIR2R35 part U
Ethyl acetate 25 parts Toluene 2
0 Part No, ll (Yoshiarashi Utsuki 11 Epoxy Resin 40 Part Kai and l Shin) A9. (ORI) 2 (OR2COR3) 5 Part y=
y, Bl, r-cRt R2R35-
m-1 ethyl acetate 20 parts toluene
17 Part No. 12 1 male average and negative Sumire J Acrylic polyol resin 50 parts -J Water 20 parts IPA 20 parts No.
13 1 male return 1 acrylic resin 50 parts 11 and 11 parts T i (ORI) (OR2COR3) 3 5 parts y
;yt pN-cRIR2R35sU Water 20 parts IPA 20 parts No., 14 11 parts U Shellac resin 50 parts 1--J
Water 50 parts (pH 3~to) No. 15 1 Male average Kozuki Sumire J Acrylic resin 50 parts 1--
J Water 25 parts IPA 25 parts No, 16 11 凰 mi Acrylic resin 50 parts i to 1 None y=y, 5 pN-cRx R2R35 parts U
Water 25 parts IPA 20 parts No, 17 1 ward return 瀘■Wata] Acrylic resin 50 parts
25 parts of water, 20 parts of IPA (margin below), 2 - eggplant, 7 liquids, equipment 5, engineer, Wataru Salmono, 1 water, 1-15 liters
Good Good Good Good Within 1 part 2
Good Good Good Good Within 10 minutes 3 Good Good Good 10
Within minutes 4 Good Good Good
Within 1 part 5 Good Good Good Good
Within 10 minutes 6 Good Good Good
Good Within 10 minutes7 Good Good Good
Good Within 1 minute 8 Good Good Good Good Within io minute 9 Good Good
Good Good Within 10 minutes10 Good
Good Good Good Within 1 part 11
Good Good Good Within 10 minutes
2 Good Good Good Good Within 10 minutes 3 Good Good Good Good
Within 1 part 14 Good Good Bad Bad 3
Within 0 minutes15 Good Good Bad Bad Within 10 minutes 6 Good Good Good Good
Within 30 minutes17 Good Good Good Bad 3
Within 0 minutes

[Brief explanation of the drawing]

The drawing is a partially enlarged sectional view showing an example of metallized paper for labels according to the present invention, in which 1t± base material, 2 an undercoat layer, 3 a metallized layer, and 4 an overcoat layer. shows. Attorney Attorney 1 Katsu Hiro-J Furnace Figure 1

Claims (1)

[Claims] (1) In metal-metalized paper for labels, which has an undercoat layer made of synthetic resin on one side of a base material, a metal-deposited layer on the layer, and an overcoat layer if necessary, the undercoat layer is formed from an undercoat agent consisting of a curable film-forming resin, a mixed curing agent of a metal alcoholate, metal acylate, or metal chelate compound curing agent and an ethyleneimine-based, melamine-based or isocyanate-based curing agent, and a medium. Metallic metallized paper for labels, characterized in that it is made of