JPS6235519B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an undercoat liquid composition for producing metal vacuum-deposited paper. More specifically, the present invention relates to a composition that can improve the production speed of vapor-deposited paper and improve the metallic feel and adhesion of vapor-deposited films. Furthermore, the present invention relates to a composition that enables vapor-deposited paper attached to a container or the like to be peeled off and removed using an alkaline solution. Generally, when vapor-deposited paper is produced by vacuum-depositing metal directly onto the paper itself, the purpose is to make the vapor-deposited surface of the paper uniform and smooth, and to prevent the appearance properties of the vapor-deposited film from deteriorating. In this case, the paper is coated with an undercoat in advance. By the way, since paper itself is highly flammable and is a material that is susceptible to warping and other deformations due to changes in moisture content, a liquid composition that dries naturally or cures at room temperature is generally used for undercoating. The use of such a composition not only prolongs the undercoating process by requiring a certain amount of time for drying and curing, but also when the undercoated paper is rolled up, the back side of the paper adjacent to the undercoated side is This causes so-called blocking, where
As a result, the production of metallized paper was subject to time and quantity constraints. Further, the metallic feel of the vapor-deposited surface was not fully satisfactory. Metallized paper is used for various purposes such as packaging for various products, labels, and stickers. By the way, since containers that are to be reused (for example, glass bottles for various alcoholic beverages) are generally washed with an alkaline solution during recycling, labels affixed to the containers are easily peeled off and removed during this washing. This is desirable. This naturally also applies when vapor-deposited paper is used as a label. The present invention has been devised based on the above-mentioned viewpoints, and provides an undercoat liquid composition for producing metal vacuum-deposited paper, which is characterized by containing an ultraviolet ray or electron beam curable component. As the ultraviolet ray or electron beam curable component in the above composition, (a) a compound having an acryloyl group, (b) a compound having a methacryloyl group,
(c) Styrenic compounds (e.g. styrene, vinyltoluene, α-methylstyrene, divinylbenzene), (d) Allyl compounds (e.g. diallyl phthalate, allyl glycidyl ether, triallyl isocyanurate), (e) Vinyl acetate, N - Those having a polymerizable double bond such as vinylpyrrolidone can be mentioned, and these components may be contained alone or in a mixture of two or more to contain 30 wt% or more or 100% in the composition. In the components (a) and (b) above, monomer (a1)
as acrylic acid and methacrylic acid itself,
and esters, acid chlorides (acrylic acid chloride, methacrylic acid chloride) and acid amides (eg, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide) which are acid derivatives thereof. Examples of the above ester include methyl ester, ethyl ester, propyl ester, butyl ester, lauryl ester, stearyl ester, 2-hydroxyethyl ester, n-butoxyethyl ester, dimethylaminoethyl ester, ethylene glycol diester, diethylene glycol diester, triethylene Examples include glycol diester, tetraethylene glycol diester, neopentyl glycol diester, trimethylolpropane triester, cyclohexyl ester, benzyl ester, glycidyl ester, tetrahydrofurfuryl ester, carbitol ester, sorbitol triester, and triethylene glycol monomethyl ether ester. . In the components (a) and (b) above, the resin intermediate and resin (a2) are exemplified by the following: a condensate of monohydric alcohol and polyhydric alcohol, or a condensate of polyhydric alcohol. A compound obtained by reacting a condensate with acrylic acid or methacrylic acid (ether acrylate or methacrylate),
A compound obtained by reacting acrylic acid or methacrylic acid with a hydroxyl group-containing compound obtained by reacting a monobasic acid or polybasic acid or its anhydride with an excess equivalent of polyhydric alcohol (polyester acrylate or methacrylate), glycidyl A compound obtained by adding a monobasic acid or a polybasic acid to an acrylate or methacrylate having a group, or an allyl compound having a glycidyl group, an isocyanate obtained by reacting a compound having a hydroxyl group with an excess equivalent of a polyvalent isocyanate compound. A compound obtained by reacting a group-containing compound with an acrylate or methacrylate having a monohydroxyl group (urethane acrylate or methacrylate), and a compound obtained by adding acrylic acid or methacrylic acid to a glycidyl compound (epoxy-modified acrylic or methacrylate) . Examples of raw materials used in the synthesis of the various compounds listed above include the following: monobasic acids such as acetic acid, propionic acid, benzoic acid, lauric acid, and stearic acid; polybasic acids and their anhydrides; Examples include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, hymic acid, hedic acid, succinic acid, succinic anhydride, maleic acid, Maleic anhydride, fumaric acid, adipic acid, sebacic acid, dodecenylsuccinic acid, trimellitic acid, pyromellitic acid, endo acid and azelaic acid, etc.
Methanol, ethanol as monohydric alcohols,
Polyhydric alcohols such as n-butanol, isobutal, isopropanol and phenol include ethylene glycol, diethylene glycol,
Propylene glycol, polyethylene glycol, 1,6-hexanediol, neopentyl glycol, hydrogenated bisphenol A, glycerin,
Polyvalent isocyanate compounds such as trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, and sorbitol include hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, and trimethyl. Hexamethylene diisocyanate, methylcyclohexane 2,6-diisocyanate, 4.
Glycidyl compounds such as 4-methylenebis(cyclohexyl isocyanate) and isophorone diisocyanate include ethylene oxide, propylene oxide, butyl glycidyl ether, epichlorohydrin, methyl epichlorohydrin,
Allyl glycidyl ether, phenyl glycidyl ether, styrene oxide, condensate of epichlorohydrin and bisphenol A (Epicote, manufactured by Shell Chemical), glycidyl versatate (Cardilla E, manufactured by Siel Chemical), condensate of methyl epichlorohydrin and bisphenol A ( Examples of acrylates or methacrylates with glycidyl groups include glycidyl acrylates such as ethylene glycol diglycidyl ether (Epolite 40E, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), and diglycidyl ether of polyethylene glycol (Epolite manufactured by the same company). Allyl compounds having a glycidyl group such as allyl glycidyl ether, such as methacrylate, and 2-hydroxyethyl acrylate or methacrylate as acrylates or methacrylates having a monohydroxyl group. The composition containing the above-mentioned curable component is a liquid material having an appropriate viscosity for convenient use. To adjust the viscosity, an organic solvent (for example, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, N-dimethylethanolamine) may be blended. In addition, in the case of ultraviolet curable compositions, ordinary photosensitizers (such as benzoin,
Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether,
Benzyl, benzophenone, α-methylanthraquinone, β-methylanthraquinone, α-ethylanthraquinone, β-ethylanthraquinone, acetophenone, 9-fluorenone, acetoin,
pp-(dimethyl)benzophenone, benzaldehyde, acetylphenanthrene, diethylaminoazobenzene, triphenyl phosphate,
Triphenylmethane, acetonaphthone, naphthoquinone, xanthone, thioxanthone, α-bromonaphthalin, L-ascorbic acid, p-aminoacetophenone, 1-(chloromethyl)naphthalene, o-anisaldehyde, β-tert-butylanthraquinone, phenanthrene , carbazole,
4-phenylbenzophenone, 4-methylbenzophenone, 4-nitro-benzophenone, 4-methoxybenzophenone, methyl o-benzoylbenzoate, allyl o-benzoylbenzoate, benzoin phenyl ether, lnitroanthraquinone , benzyldimethyl, ketal, α-
phenylbenzoin ethyl ether) or a mixture of two or more types, 0.1 to 10 wt% of the curable component.
Blend in the following proportions. In the case of compositions, in order to modify the properties of the paint or coating film as with ordinary paints, non-curing components (e.g. acrylic resin, polyester resin, petroleum resin, nitrified cotton, urethane resin) may be added as necessary. , epoxy resin, vinyl acetate resin, vinyl chloride resin,
(vinyl chloride-vinyl acetate copolymer) and other additives (for example, dyes, leveling agents, antifoaming agents) may be blended. Furthermore, although the composition of the present invention has the property of being cured by ultraviolet rays or electron beams, the vapor-deposited paper obtained using the same can be easily peeled off with an alkaline solution once it has been applied to containers. It is characterized in a certain way. In order to provide such characteristics, it is necessary to use chemical substances defined below as curable or non-curable components. As a curable component, (i) one having a tertiary amino group, a hydroxyl group and/or an ether bond together with a polymerizable double bond, and (ii) an acid value of 30 to 800 and a molecular weight of 140 to 20,000 in addition to a polymerizable double bond. A quaternary ammonium salt of a compound having As a non-curable component, (iii) a quaternary ammonium salt of a compound having an acid value of 30 to 800 and a molecular weight of 300 to 100,000. Among these specific ingredients, the above purpose can be achieved by using each of (i) and (iii) separately, but (ii) needs to be used in combination with (i) or (iii). There is. Of course, a combination of (i) and (iii), and
A combination of (i), (ii) and (iii) may also be employed. Moreover, each of the above-mentioned specific components may be used alone or in combination of two or more. Furthermore, such specific components may be used in combination with the other curable components and non-curable components mentioned above. The amount of each of the above-mentioned specific components to be used cannot be uniformly prescribed, and may be appropriately selected depending on the composition of the composition and the relationship with the alkaline solution for peeling and removal. Specific examples of the above-mentioned specific components are shown in the reference examples below, but the present invention is not limited thereto. For example, the following are exemplified. (i)A As a compound having a tertiary amino group and a hydroxyl group together with a polymerizable double bond, and a compound having a tertiary amino group, a hydroxyl group, and an ether bond together with a polymerizable double bond: Partial amine addition of a glycidyl compound reaction products of substances with acrylic acid and methacrylic acid,
A compound in which an amine is partially added to a reaction product of a glycidyl compound and acrylic acid or methacrylic acid, an acrylate or methacrylate with a glycidyl group, or a partial amine adduct of an allyl compound with a glycidyl group, an excess equivalent of polyhydric alcohol and acrylic acid or methacrylic acid, some amine adducts, excess equivalents of reaction products of polyhydric alcohols with tertiary amino groups and acrylic acid or methacrylic acid, polyesters with terminal carboxyl groups, and excess A compound obtained by partially adding an amine to the reaction product with a polyfunctional glycidyl compound, a reaction product of acrylic acid or methacrylic acid, a polyester having a terminal carboxyl group, and an excess of the polyfunctional glycidyl compound are reacted, Compounds reacted with acid or methacrylic acid and further added with some amines, polyesters containing a monohydric or polyhydric alcohol having a tertiary amino group as one component and having terminal carboxyl groups, and excess polyfunctional glycidyl compounds. and acrylic acid or methacrylic acid, and a compound obtained by reacting a portion of the remaining glycidyl group of the compound which was reacted with an excess equivalent of glycidyl group with an acid. B As a compound having a polymerizable double bond, a tertiary amino group, and an ether bond: A partial amine adduct of an equivalent reaction product of a polyhydric alcohol having an ether bond and acrylic acid or methacrylic acid. (ii) Equivalent reaction product of each of the following compounds and tertiary amino: Reaction of an acrylate or methacrylate with a hydroxyl group, or an allyl compound with a hydroxyl group, and an excess equivalent of a polyfunctional carboxylic acid or its acid anhydride. reaction of an excess equivalent of an unsaturated polyfunctional carboxylic acid with a monohydric or polyhydric alcohol or a mixture of both, a reaction product of a glycidyl compound with acrylic acid or methacrylic acid, and an excess equivalent of a polyfunctional carboxylic acid anhydride. A reaction product of an acrylate or methacrylate having a glycidyl group, or an allyl compound having a glycidyl group, and an excess equivalent of a polyfunctional carboxylic acid or its anhydride, an acrylic polymer containing acrylic acid or methacrylic acid as one component, A compound in which a part of the carboxyl group is reacted with an acrylate or methacrylate having a glycidyl group, or an allyl compound having a glycidyl group, an acrylic polymer containing acrylic acid or methacrylic acid as one component,
Acrylate or methacrylate having a hydroxyl group or an allyl compound having a hydroxyl group, a polyester having a terminal carboxyl group, an acrylate having a glycidyl group as a part of its carboxyl group Or a compound made by reacting with methacrylate or an allyl compound having a glycidyl group, and a compound made by reacting a polyester having a terminal carboxyl group with a part of the carboxyl group with an acrylate or methacrylate having a hydroxyl group. (iii) Equivalent reaction product of the following or with a tertiary amino group: a polymer of styrene or a vinyl compound and an unsaturated polyfunctional carboxylic acid or its anhydride or its half ester compound, and an ethylenically unsaturated carboxylic acid An acrylic polymer consisting of Examples of raw materials used in the synthesis of the various compounds listed above include the following: acids include benzoic acid, acetic acid, acrylic acid, and methacrylic acid; acrylates or methacrylates include methyl acrylate, methyl methacrylate, Butyl acrylate, carbitol acrylate and ethoxyethyl acrylate, etc.
Acrylates or methacrylates with hydroxyl groups include hydroxyethyl acrylate, hydroxylethyl acrylate, and hydroxypropyl acrylate; allyl compounds with hydroxyl groups include allyl alcohol, trihydroxyethyl isocyanurate (THEIC manufactured by Nippon Kasei Co., Ltd.), and diallyl phthalate; Monohydric alcohols include ethylhexyl alcohol, normal octyl alcohol, butyl alcohol, and lauryl alcohol; polyhydric alcohols include trimethylolpropane, pentaerythritol, ethylene glycol, glycerin, neopentyl glycol, polyethylene glycol, and polypropylene glycol; Examples of polyhydric alcohols with tertiary amino groups include diethylene glycol and polyethylene glycol; examples of monohydric alcohols with tertiary amino groups include dimethylethanolamine (Amino Alcohol 2Maby, manufactured by Nippon Nyukazai Co., Ltd.); Diethanolamine, triethanolamine, methyldiethanolamine (amino alcohol manufactured by Nippon Nyukazai Co., Ltd.)
Examples of polyfunctional glycidyl compounds such as MDA) and tris(hydroxymethyl)aminomethane include a condensate of epichlorohydrin and bisphenol A (Epicote manufactured by Ciel Chemical Co., Ltd.), hexahydrophthalic acid diglycidyl ester (Araldide CY 183 manufactured by Ciba Geiki Co., Ltd.) ), ethylene glycol diglycidyl ether (Epolite 40E manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and polyethylene glycol diglycidyl ether (Epolite manufactured by the same company)
Examples of glycidyl compounds include the above-mentioned polyfunctional glycidyl compounds, ethylene oxide, propylene oxide, butyl glycidyl ether, and phenyl glycidyl ether; examples of acrylates or methacrylates with a glycidyl group include glycidyl acrylate and glycidyl methacrylate; allyl compounds with a glycidyl group; (i), such as allyl glycidyl ether,
Examples of amines that can be used for amine addition in (ii) and (iii) include diethylamine, dibutylamine, propylamine, morpholine, diethanolamine, and methylethanolamine (amino alcohol MMA manufactured by Nippon Nyukazai Co., Ltd.). Tertiary amines that can be used include triethylamine, tributylamine, N-methylmorpholine, dimethylethanolamine, and triethanolamine, and polyfunctional carboxylic acids that can be used include phthalic acid, trimellitic acid, pyromellitic acid, succinic acid, maleic acid, and fumaric acid. , tetrahydrophthalic acid and adipic acid; unsaturated polyfunctional carboxylic acids such as maleic acid, itaconic acid and fumaric acid; vinyl compounds such as vinyl acetate,
Ethylenically unsaturated carboxylic acids such as vinyl chloride and vinyl propionate include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and monoethyl maleate; polyfunctional carboxylic acid anhydrides include phthalic anhydride. , maleic anhydride, succinic anhydride, pyromellitic anhydride, trimellitic anhydride, etc., and half esters of unsaturated polyfunctional carboxylic acids such as monoethyl maleate, monobutyl maleate, and monomethyl itaconate. To apply the composition of the invention to paper for vapor deposition, conventional coating methods may be employed, such as reverse roll coating, natural roll coating, offset coating, gravure coating, spraying, knife coating, electrostatic coating. can be mentioned. The coating amount is 1 as a cured film.
It is sufficient if the amount is at least g/m ² , and if it is less than this, a smooth and continuous film will not be formed due to the absorption of the composition into the paper, and the appearance of the metal film after vapor deposition will be poor. In addition, if it exceeds 20 g/m ² , it becomes economically disadvantageous. For curing the applied composition, ultraviolet rays or electron beams may be selected depending on the composition. For ultraviolet curing, use a low-pressure mercury lamp, high-pressure mercury lamp, or xenon lamp, for example, at a wavelength of 2000 to 8000.
A light beam of 2000 to 4000 Å may be irradiated in air or in a nitrogen atmosphere. On the other hand, in the case of electron beam curing, an electron beam at a dose rate of 0.1 to 20 Mrad/sec may be extracted and irradiated using an electron beam accelerator of 0.1 to 2.0 MeV. In the case of ultraviolet curing, the irradiation time of these active energy rays is, for example, 0.1 to 1 second when irradiated with a high-pressure mercury lamp concentrating ozone type (80 W/cm) from a distance of 10 cm. In the case of electron beam curing, this is the time at which the absorbed dose is 0.1 to 10 Mrad.
If irradiation is insufficient, the composition will not be sufficiently cured, resulting in the above-mentioned blocking problem. On the other hand, if it is in excess, the cured film will crack due to warpage and bending of the paper. According to the above-mentioned undercoating process, the paper can be processed in a short time, so that continuous undercoating can be performed using wrapping paper. Moreover, there is no fear that the rolled up undercoat paper will cause blocking. Vacuum deposition of metal onto the thus obtained undercoated paper may be carried out according to a conventional method, and specifically, the metal film thickness is 400 to 600 Å at 10 ^-4 to ^{10 -5} Torr.
All you have to do is make it look like this. Examples of the metals used include aluminum, tin, nickel, gold, and silver; however, when removing the pasted vapor-deposited paper with an alkaline solution as described above, alkali-soluble aluminum, tin, zinc, antimony, Lead or an alloy thereof may be used. According to the present invention having the above configuration, it is possible to perform the undercoating process on paper in a short time, and the problem of blocking of the undercoated paper can be solved, so that the manufacturing speed of metallized paper can be greatly improved. Furthermore, the resulting vapor-deposited film has excellent metallic feel and adhesion. Further, according to the present invention, the pasted vapor-deposited paper can be easily peeled and removed using an alkaline solution, thereby further enhancing the usefulness of the vapor-deposited paper. Note that the vapor-deposited paper obtained by the present invention may be coated with a top coat to protect the vapor-deposited surface and improve printing suitability. The composition used for this is dipentaerythritol pentaacrylate (NK ester ADP-
5) 80 parts (parts by weight, the same applies hereinafter), 20 parts of carbitol acrylate, 5 parts of benzophenone and 3 parts of dimethylethanolamine, Dianal BR
-107 (manufactured by Mitsubishi Rayon Co., Ltd.) 20 parts, carbitol acrylate 40 parts, dipentaerythritol pentaacrylate 40 parts, benzophenone 5 parts and dimethylethanolamine 3 parts. This may be cured with ultraviolet light. Next, the present invention will be specifically explained with reference to Reference Examples, Examples, and Comparative Examples. Reference Example 1 Production of a quaternary ammonium salt of a compound having a polymerizable double bond, an acid value of 30 to 800, and a molecular weight of 140 to 20,000, which can be used as a curable component: (1) Place oligoester acrylate in a flask equipped with a stirrer. (Manufactured by Toagosei Kagaku Co., Ltd. “Aronix M-
5500'') and 40 g of butyl acetate were added, and 89.1 g (1 mol) of diethylethanolamine was gradually added dropwise over about 2 hours while stirring at room temperature. The reaction was allowed to proceed for 2 hours while suppressing the temperature rise within the flask to within 70°C, and then the butyl acetate was removed to obtain reaction product 1. (2) Pyromellitic anhydride in a flask with a stirrer
218 g (1 mol), 232 g (2 mol) 2-hydroxyethyl acrylate, 450 g carbitol acrylate (diluent) and 1.8 g hydroquinone
g and while blowing air into the flask.
The reaction was carried out at 120°C for 8 hours. After cooling to room temperature,
238.4 g (2 mol) of N-methyldiethanolamine was gradually added dropwise over about 2 hours. Reaction product 2 was obtained by further reacting for 2 hours while suppressing the temperature rise in the flask to within 70°C. Reference Example 2 Production of a component that can be used as a curable component and has a polymerizable double bond, a tertiary amino group, a hydroxyl group, and/or an ether bond: (1) 174 g of ethylene glycol diglycidyl ether in a flask equipped with a stirrer. (1 mol) and 10 g of toluene, and while stirring, 34.8 g of morpholine.
(0.4 mol) was gradually added dropwise over 40 minutes. During the dropping, the temperature was kept below 60°C. While stirring after dropping,
Acrylic acid while keeping the temperature between 100 and 110℃.
A mixture of 115.2 g (1.6 mol) and 0.05 g of hydroquinone was gradually added dropwise over 3 hours, and the mixture was reacted with stirring at 110° C. for 2 hours. Then, toluene was removed to obtain reaction product 3. (2) Into a flask equipped with a water separation and reflux device and a stirrer, charge 134 g (1 mol) of trimethylolpropane, 216 g (3 mol) of acrylic acid, 5 g of sulfuric acid, 0.5 g of hydroquinone, and 100 g of toluene.
The reaction was carried out at 0.degree. C. until 45 g of water was produced in a water separator. The reaction was then washed several times with 600 ml of water and then the toluene was removed to obtain reaction product 4. 269 g of reaction product 4 in a stirred flask
was added, and 34.8 g (0.4 mol) of morpholine was gradually added over 1 hour and 30 minutes while stirring and maintaining the temperature at 50 to 60°C. Thereafter, the mixture was reacted at 50° C. for 1 hour with stirring to obtain reaction product 5. Reference example 3 Acid value 30-800 that can be used as a non-curing component
Production of a quaternary ammonium salt of a compound having a molecular weight of 300 to 100,000: (1) Place a styrene-maleic acid copolymer (Tamanol manufactured by Arakawa Chemical Co., Ltd.) with an acid value of 175 to 200 and a molecular weight of 5,000 to 20,000 in a flask equipped with a stirrer. KG613”) 100
g and 32 g of butyl acetate were added thereto, and 53 g of toluethanolamine was added dropwise over 2 hours while stirring at room temperature, and the mixture was reacted for 2 hours to obtain reaction product 6. (2) Put 98g of xylene in a flask with a stirrer,
A mixture of 20 g of methyl methacrylate, 18 g of styrene, 39 g of n-butyl methacrylate, 11 g of n-butyl acrylate, 12 g of acrylic acid, 5 g of lauryl mercaptan and 2 g of azobisisobutyronitrile was heated at 140 to 150°C over about 3 hours. Gradually dripping, then t after 1 hour
-Butyl peroxy (2-ethylhexanoate) (0.5 g of "Perbutyl O" manufactured by NOF Corporation) and 2 g of xylene were added and aged for 2 hours. Then, the xylene was removed and the acid value was 94 and the average molecular weight was approximately 2000-4000 of reaction product 7 was obtained. 100 g of reaction product 7 was placed in a flask with a stirrer.
and then 27 g of triethylene glycol monomethyl monoacrylate (“Light Ester M-TGA” manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.).
While stirring at room temperature, 7.3 g of morpholine was gradually added dropwise over about 2 hours. The temperature rise inside the flask
Reaction was carried out for 2 hours while keeping the temperature within 70°C, and reaction product 8 was obtained. Examples and Comparative Examples (1) Preparation of undercoat composition: Each component was mixed according to the formulation (unit: parts by weight) shown in Table 1. In the table: ``NK Ester ADP-5'' manufactured by Shin-Nakamura Chemical Co., Ltd. ``Dynal BR-107'' manufactured by Mitsubishi Rayon Co., Ltd. ``Esletsuku AL'' manufactured by Sekisui Chemical Co., Ltd. ``HiResin NX'' manufactured by Toho Petroleum Resin Co., Ltd.: Toto Chemical Co., Ltd. ``Epototo YD011'' manufactured by Nippon Paint Co., Ltd. ``Nitspe 2000 Class Clear'' manufactured by Nippon Paint Co., Ltd. ``Labarac 3000 Sealer'' manufactured by Nippon Paint Co., Ltd.

【table】

[Table] (2) Undercoating treatment: Use art paper for labels, and cure each composition with a roll coater or dry film amount 3 to 6.
It was applied continuously at g/m ² . Next, for experiment numbers 13 and 14, the acceleration voltage was 300 KV, the current density was 30 mV, and the dose rate was set using an electron beam accelerator.
Irradiation was performed for 1.7 seconds at 3 Mrad/sec. In other experiment numbers, irradiation was performed for 0.3 seconds from a distance of 10 cm using a condensing ozone type high-pressure mercury lamp of 80 W/cm. In the comparative example, the coating was applied using a roll coater and then left at room temperature for 10 minutes. (3) Vacuum deposition: using aluminum as the metal,
The metal film was deposited to a thickness of 500 Å under 10 ^-5 Torr. (4) Performance test of vacuum-deposited paper: The following tests were conducted on each of the obtained vacuum-deposited papers. The results are shown in Table 2. (a) Alkali solubility test A glass plate with casein coated with vapor-deposited paper was
The paper was placed in a flow of 3wt% caustic soda aqueous solution at 70°C, and the time required for the vapor-deposited paper to peel off was judged. ◎: Less than 5 minutes ○: Less than 15 minutes ×: More than 15 minutes (b) Metallic sensitivity test of vapor-deposited surface A three-level evaluation was performed by visual inspection. 〇: Good image clarity and shine similar to a well-polished metal surface △: Between 〇 and × ×: No metallic feel at all, whitish and matte (c) Vapor-deposited film adhesion Test Judgment was made by attaching an adhesive tape to the vapor-deposited surface and peeling it off. 〇: Peeling between paper ×: Peeling between paper and undercoat or between undercoat and vapor deposited film Immediately after the completion of undercoating, the papers were stacked one on top of the other, and a load of 10 kg/cm ² was applied to this, and the paper was left at 20°C for 4 hours. The blocking properties of the paper were determined, and the results are also listed in Table 2. In addition, 〇: No abnormality ×: The undercoat surface and the adjacent back side of the paper are partially or completely adhered Reaction products 3 and 5 are chemical substances as component (i), and reaction products 1 and 2 are chemical substances as component (i). Chemicals as ii), reaction products 6 and 8, correspond to chemicals as component (iii). Experiment numbers 4, 5, 7, 8, 10, 11, and 12 are examples of the present invention, and other experiment numbers are comparative examples.

【table】

Claims (1)

[Scope of Claims] 1. Ultraviolet or electron beam curable, characterized by containing at least two chemical substances selected from the following three chemical substances (i), (ii) and (iii): Undercoating liquid composition for manufacturing metal vacuum-deposited paper: (i) A compound having a polymerizable double bond, a tertiary amino group, a hydroxyl group, and/or an ether bond; (ii) A compound having an acid value of 30 to 30, as well as a polymerizable double bond. 800 and a molecular weight of 140 to 20,000; (iii) a quaternary ammonium salt of a compound having an acid value of 30 to 800 and a molecular weight of 300 to 100,000; 2. The composition according to claim 1, which contains a photosensitizer.