JPS62233247A - Manufacture of aluminum metallic paper - 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] Industrial applications The present invention relates to a method for producing aluminum metal paper.

More specifically, a coating composition consisting of an electron beam curable resin composition having an ethylenic double bond and an aluminum pigment is applied to paper and then cured with electron beams to produce matte aluminum metal paper with excellent metallic luster. It is about the method.

BACKGROUND OF THE INVENTION Aluminum gold-aluminum pigments used in the production of paper include leafing and non-leafing types, and the latter lacks metallic luster.

Although the former has a metallic luster, it tends to cause chalking (peeling) when it is applied to paper or the like together with a curable resin and cured. Therefore, when a leafing type aluminum pigment is applied to paper or the like in combination with a curable resin and cured, it is necessary to further overcoat at the expense of some metallic luster. However, when an overcoat layer is provided on a cured resin containing aluminum (IP), there is a problem in that the adhesion is not good and the overcoat layer peels off.

Problems to be Solved by the Invention Stearic acid, which is usually added to leafing-type aluminum pigments, is adsorbed on aluminum and helps the leafing properties of the aluminum pigments.゛Therefore, the surface of the paint film (undercoat layer) obtained by applying a paint containing leafing-type aluminum pigment is covered with aluminum metal, but the surface tension decreases due to the stearic acid adsorbed to the aluminum, and this If a resin is overcoated on top of the paint film, wetting becomes extremely poor.

"Peeling" between the undercoat layer and overcoat layer
The phenomenon of "poor adhesion" occurs. Therefore, when providing a resin overcoat layer on a cured coating film (undercoat layer) containing aluminum pigment to prevent the aluminum pigment from peeling off, there is a method of providing an overcoat layer that has excellent adhesion to the undercoat layer and is difficult to peel off. development is desired.

Means for Solving the Problems In order to solve the above-mentioned problems, the composition of the resin for providing the undercoat layer and overcoat layer, the type of aluminum pigment and the amount added thereof.

As a result of various studies on the relationship between the amount of electron beam irradiation, etc., and the effect of improving adhesion, we discovered that there is a significant effect on improving adhesion by selecting an electron beam irradiation method other than that, and completed the present invention. Ta.

That is, the present invention involves irradiating an undercoat layer formed on paper with an electron beam curable resin composition having an ethylenic double bond and an electron beam curable coating composition containing a leafing type aluminum pigment with an electron beam. Provided is a method for producing aluminum gold-paper, which comprises partially curing the undercoat layer, then applying the above-mentioned sterilization beam curable resin composition to form an overcoat layer, and then irradiating the same with electron beams again.

The present invention will be described in detail.

First, the resin composition, aluminum pigment, and paper for the undercoat layer and overcoat layer used in the method of the present invention will be described.

14 for preparing undercoat layer and overcoat layer
The fat composition is composed of an electron beam curable resin (prepolymer) containing an ethylenic double bond and a bifunctional heptamer, and may contain an organic solvent if necessary. Specific examples of the prepolymer include polyester (meth)acrylate, glycidyl (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, etc., and two or more of these may be used as a mixture. The molecular weight of the polyester (meth)acrylate is preferably from 400 to 3,000, particularly preferably from 700 to 1,500.

The acid component that makes up the ester is adipic acid.

Alcohol components include terephthalic acid, succinic acid, sepacic acid, chlorendozougamata, hexanediol, butanediol, ethylene glycol, diethylene glycol, fluoropylene glycol, dipropylene glycol, tripropylene glycol, polytetramethylene glycol, trisic acid, etc. Diols such as clodicane dimethanol are used, and polyester diols obtained from these, Alu, are used in order to lower the viscosity in terms of molecular weight ratio, compared to diols.
Polyester (meth)acrylate made by reacting (meth)acrylic acid with a mono-branched polyester diol by adding a triol or tetraol such as trimethylolpropane or pentaerythritol within 5%, preferably within 2%. is given as a preferable example. Further, glycidyl (meth)acrylate was further reacted with polyester dicarboxylic acid prepared by reacting the polyester diol with amber anhydride, or polyester (meth)acrylate containing (meth)acrylic acid as a copolymerization component. Glycidyl (meth)acrylate adducts are also preferred. The molecular weight of this material is preferably 500 to 7,000.

One molecular weight of epoxy (meth)acrylate is 30
0 to 3000 is preferable, and Epicoat 82B, 1
Preferably, 001, 1002, and 1003 (epoxy 4 fat, manufactured by Yuka Zoel Epokin Co., Ltd.) are reacted with (meth)acrylic acid.

As urethane (meth)acrylate, the molecular weight is 500.
5,000 is preferable, and an oligomer obtained by reacting polyester diol with toluylene diisocyanate or inphorone diisocyanate and further reacting with hydroxyethyl (meth)acrylate is preferable.

The viscosity (25°C) of the bifunctional 7-mer is 5ooc,
Bifunctional monomers with p (centipoise) or less are preferred, and specific examples include hydroxyhybalic acid ester neopentyl glycol (caprolactone modified) diacrylate, tricyclodecane dimetatool (caprolactone modified) diacrylate, neopentyl glycol adipate diacrylate. Examples include acrylate.

The ratio of difunctional monomer to prepolymer is usually 5 to 5 parts per 100 parts of prepolymer.
It is used in a proportion of 500 parts, preferably 10 to 150 parts.

The viscosity of the mixture of prepolymer and bifunctional monomer (electron beam curable resin composition, vehicle) is preferably from 10 to 300, because if it becomes extremely small, it will easily soak into the paper, and if it is too large, it will be difficult to coat. is 40-15
One with 0 poise is used. The viscosity is controlled by the type and mixing ratio of the grepolymer used, the bifunctional monomer, and may be adjusted by using an organic solvent in some cases.

In the present invention, a leafing type aluminum pigment is used. The thinner the leafing aluminum boat is, the larger the water surface diffusion area becomes. Water surface diffusion area is 30,000c
If it exceeds m/f', a grayish metallic luster will be obtained, and if it is less than 10,000 cm/1, the coating surface will become rough, the hiding property will be reduced, and the moisture resistance will be reduced. The lustrous metallic luster of aluminum metal paper, which is the object of the present invention, refers to the whitish metallic luster of, for example, aluminum foil for shoemaking, but the glossy metallic luster of aluminum metal paper, which is the object of the present invention, refers to the whitish metallic luster of aluminum foil for shoemaking.
/? When using an aluminum pigment having a particle size in the range from 30,000 mm2/f to 30,000 mm2/f, it is easy to obtain the metallic luster of brushed aluminum foil, and it is also easy to obtain a coating film with excellent moisture resistance. The aluminum pigment is 1 to 40%, preferably 10% to 50%, based on the electron beam curable resin composition (vehicle).
Particularly preferably, it is added in an amount of 15 to 25%. If it exceeds 40%, the technotropy will increase and it will be difficult to apply.
This causes poor adhesion between the undercoat layer and overcoat layer. Moreover, if it is less than 1%, metallic luster tends to decrease.

As the paper used in the present invention, any paper having a strength above a certain level can be used as a support, but clay coated paper or paper coated with resin to prevent paint from seeping in is particularly preferred.

The resin composition for providing the overcoat layer may contain silicone additives (for example, 5H28PA, 5H29 manufactured by Toshi Silicon Co., Ltd.) as necessary to prevent "repelling".
PA, 8H30PA) etc. to the resin composition.
It may be added in an amount of 1 to 2.0% (weight ratio).

The production method of the present invention is carried out by the method described below using the above-mentioned fat-supporting composition, aluminum pigment, and paper.

A difunctional monomer is mixed with an electron beam curable resin (prepolymer) having a predetermined amount of ethylenic double bonds, and an organic solvent is added if necessary to obtain an electron beam curable resin composition (vehicle).

A predetermined amount of leafing type aluminum pigment is added to this to form an electron beam curable coating composition.
Coating is performed using a bar coater or the like to a thickness of ~50 μm, preferably 3 to 10 μm.

(Undercoat layer) Next o, 1 to G, 7 Mrad
<D Electron beam irradiation (primary irradiation) to partially cure the undercoat layer.

In this case, it is preferable to adjust the reaction rate of ethylenic double bonds in the undercoat layer to 10 to 90% before curing, and if the reaction rate of ethylenic double bonds in the undercoat layer is less than 10%, the overcoat layer should be cured. Sometimes, the aluminum on the surface of the coating film tends to move and the metallic luster decreases, while when the reaction rate exceeds 90%, curing tends to progress too much and adhesion tends to be poor. The reaction rate of ethylenic double bonds was measured using infrared absorption spectroscopy at 1640crIL-
It is determined from the rate of decrease in absorbance based on the ethylenic double bond appearing in 1 (KBr method).

After the electron beam irradiation for partial curing is completed, calendar treatment may be performed as necessary to compensate for the metallic luster. The partially cured undercoat layer is calendered, for example, at a drum rotation speed of 600-800 rpm for 10-60 seconds.

Next, the electron beam curable resin composition (vehicle) to which silicone additives and the like were added as necessary was applied to a film thickness of 1 to 7'.
soPm, preferably 6 to 1 (ljm), is overcoated. Next, an electron beam of 1 to 5 Mraa is irradiated (secondary irradiation) to obtain a striped aluminum metal paper with excellent metallic luster. This secondary irradiation The ethylenic double bonds in the coat layer and overcoat layer are almost completely eliminated, and the resins in both layers are almost completely cured.

By the production method of the present invention, a glossy real aluminum metal paper having excellent adhesion between the undercoat layer and the overcoat layer and high glossiness can be obtained.

Example The present invention will be specifically explained by examples.

Example 1 Ebominoku R301 (Mitsui Petrochemical Epoxy Co., Ltd. Pear,
Epoxy methacrylate 401° HX-220 (manufactured by Nippon Kayaku Co., Ltd., described below) 60 S' was stirred to obtain a uniform 1. I named it item A.

The above composition A301 was added little by little to leafing type aluminum paste 700M (manufactured by Toyo Aluminum Co., Ltd.) 151, and 'C! This was designated as a child beam curable coating composition B. Also composition A50? Composition C was prepared by adding 0.6 PHR of 5H28PA (manufactured by Higashi Shinricon Co., Ltd., 7licon resin).

Coating composition B was applied to paper with a bar coater to a thickness of 8 μm, and coated with a curtain-type electron beam irradiator (K, S. 1 Co., Ltd.).
An electron beam of 0.3 Mrad was irradiated. Further, the paper was overcoated with Composition C to a thickness of 7 μm using a bar coater, and further irradiated with an electron beam of 3 Mrad to obtain a polished aluminum metal paper with excellent metallic luster.

As a result of testing by peeling off cellophane tape on the overcoat layer, the adhesion between the undercoat layer and the overcoat layer was good. 0.3M for undercoat layer
The reaction rate of olefinic double bonds when irradiated with rad electron beam was 55%.

Comparative Example 1 In Example 1, an electron beam was applied to the undercoat layer at 0.
Matte aluminum metal paper was obtained in the same manner as in Example 1 except that 3 Mrad irradiation was performed instead of 5 Mrad irradiation. After applying cellophane tape to the overcoat layer and peeling it off, it was found that the adhesion between the undercoat layer and the overcoat layer was poor.

When the undercoat layer was irradiated with an electron beam of 5 Mrad, the reaction rate of ethylenic double bonds was 98%.

Example 2 Epicoat 828 (manufactured by Yuka Shell Epoxy C Co., Ltd.).

Made by reacting epoxy resin with acrylic acid; tl
-shi7ri1JL/-to45S', HX-220551
The mixture was stirred to obtain a uniform electron beam curable resin composition.

The above composition D502 was added little by little to leafing type aluminum paste 700T (manufactured by Toyo Aluminum Co., Ltd.) 151 to prepare electron beam curable coating composition E.

Add 0.6 PHR of 5H28PA to Composition D502 and prepare 1
It was designated as composition F. Composition E was coated on paper with a bar coater to a viscosity of 8 pm, and irradiated with an electron beam of 0.3 Mrad using a Subaya<g,s, Kosha curtain type '4' beam irradiator. This coating film was calendered for 50 seconds at a drum rotational speed of 80 (l rpm), and then overcoated with a coating of the composition De to a film thickness of 7 μm, and then exposed to an electron beam of 5 M.
Polished aluminum metal paper with excellent metallic luster was obtained by rad irradiation. This product had good adhesion between the undercoat layer and overcoat layer. 0.3 for undercoat layer
The reaction rate of ethylenic double bonds when irradiated with Mrad's electron beam was 70%.

Example 5 Kbecryl 44 Q (polyester acrylate).

[Manufactured by JCBC Co., Ltd.] 80 2. A uniform electron beam curable resin composition was prepared by stirring HX-2202oy.

f'L f700T (Leafing type aluminum paste, Toyo Aluminum Co., Ltd. t15)
Add the prepared electron beam curable coating composition (undercoating agent) little by little to 30 ii' on paper using a bar coater.
It was coated to a thickness of μm and irradiated with 0.5 Mraa using a Subaya<g-s, Kosha curtain type electron beam irradiator. Next, F
ibecry1440 50f, tricyclodecane dimethanol diacrylate) 50fS 5H28PA (silicon additive, manufactured by Toshi Silicon Co., Ltd.) and 11 were stirred to prepare a uniform electron beam curable resin composition (overcoat agent). , and apply this to the aluminum coating.

Coat with a percoater to a thickness of 7 μm, and then apply an electron beam for 3 times.
Matte aluminum metal paper was obtained by Mrad irradiation. After applying cellophane tape to the overcoat layer and peeling it off, the adhesion was good. The reaction rate of ethylenic double introduction at 0.3 Mrad of the undercoat layer during electron beam irradiation was 50%.

Example V-Examples 4 to 19 According to Example 1, real aluminum metal paper with excellent metallic luster was coated using an electron beam curable paint having the composition shown in the table. All of them had excellent adhesion between the undercoat layer and the overcoat layer.

In the table, PK-5-IG is an adduct of drinklodecane dimethanol amphate (1 molecular weight: 48B) and glycidyl methacrylate (molecular weight: 772).
and glycidyl methacrylate (molecule-31
114) EA-11F is Epomic R301 (Mitsui Petrochemical Epokin Co., Ltd.) epoxy methacrylate, E
ltA-18F is epoxy acrylate of Epomisoku R301, Kbecryl a 40 is polyester acrylate of 008 company KA-15 is epoxy acrylate of Epicoat 828, EA-17 is epoxy acrylate of Epicoat 828
epoxy methacrylate, EX-220 is Nippon Kayaku Co., Ltd.'s caprolact/modified diacrylate of hydroxypiparic acid ester neopentyl glycol, R68.
4 is tricyclodecane dimetatool diacrylate, M
ANDA is Nippon Kayaku Co., Ltd.'s hydroquine pivalate neopentyl glycol diacrylate, HDDA
is hexanediol diacrylate, and R6.76 is caprolactone-modified shea 1 of trine clodecane dimethanol.
') V-1', HX-6201dHX-220 is a diacrylate with a large number of caprolactones.

Effects of the Invention: A glossy aluminum metal paper with excellent adhesion between the undercoat layer (aluminum pigment-containing layer) and overcoat layer and high metallic luster was obtained.

Claims (1)

[Claims] (1) An undercoat layer made of an electron beam curable resin composition having an ethylenic double bond and an electron beam curable coating composition containing a leafing amount aluminum pigment provided on paper is irradiated with an electron beam to 1. A method for producing aluminum metal paper, which comprises partially curing an undercoat layer, applying the electron beam curable resin composition to form an overcoat layer, and then irradiating the paper with an electron beam again.