JPS6174675A - Formation of multi-layer coated film - Google Patents

Abstract

PURPOSE:To form a coated film in extremely low cost in case of coating simultaneously coating soln. on a lapped layer by containing an electron beam curing compd. into the other coating soln. and irradiating electron beam after coating soln. CONSTITUTION:In case of forming a multi-layer coated film by coating simultaneously two or more kinds of nonaqueous coating soln. on a lapped layer, after an electron beam curing compd. is contained into at least one kind of nonaqueous coating soln. and the soln. is coated, the coated layer is cured or thickened by irradiating electron beam in <=50 Mrad/sec irradiation rate and thereafter it is dried. By this method, the nonaqueous multilayer coated film is formed at low cost.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to the 7J-method for forming multilayer coatings, and more specifically to the 7J-method for forming multilayer coatings. ”
It is called. ) is coated with 11 layers of two or more non-aqueous coating liquids, and the interlayer phase is expanded (11) (Relating to a method of forming a coating film so as not to cause mixing.

[Prior art]

Conventionally, in an aqueous solution system, gelatin is coated with a binder using an extrusion Ponova type coating device, etc. [Silver 1 Genide emulsion is simultaneously coated in multiple layers, and then cooled. Alternatively, using the sol-gel conversion property of Seratin with 41 cold air, the multi-layer 11-layer gel is made into an ultra-high viscosity state of tens of thousands to hundreds of thousands of CPS, making it difficult to mix between the layers, and then hot air is applied. A method of forming a coating film by drying or the like is known.

On the other hand, when an organic solvent system is simply applied in multiple layers and dried, spreading and mixing occurs not only in the drying section but also in the heating section and during drying due to the low surface tension of an aqueous system. Furthermore, since the sol-reel conversion step takes 4 hours, diffusion mixing occurs during drying, making it extremely difficult to obtain a coating film in which each layer is separated.

In addition, in solvent-based systems, there is no good blue gel converting substance that can be used in a wide range of solvents, and no other effective method has been invented, and multi-layer coatings in solvent-based systems are developed by sequentially applying one layer at a time. The method used is to apply and dry.

Sequential coating and drying methods include a method of winding up after each coating and drying, and a method of setting up multiple coating and drying sections and coating and drying continuously, but the former horn method requires a large amount of LSI manufacturing time. The latter method requires a coating section and a drying section for each layer, requiring extremely expensive production equipment and resulting in high production costs.

Incidentally, in recent years, several coating film forming methods have been proposed that utilize the phenomenon of curing of coating films by electron beam irradiation. Japanese Patent Publication No. 54-19894, Japanese Patent Publication No. 56-38] 6
(L Publication 8.4 is the -1- method for a single-layer coating film, and is disclosed in Japanese Patent Publication No. 53-16403, Japanese Unexamined Patent Application Publication No. 58-2
Publication No. 4384 describes the above-mentioned method for multi-layered coatings, but since the coatings are applied sequentially and actinic rays are sequentially irradiated even though the coating is multi-layered, the above-mentioned problems can be fundamentally solved. It's not a thing.

[LI aspect of the invention] An object of the present invention is to provide a coating film forming method that is extremely low cost compared to the conventional high cost non-aqueous multilayer coating film forming method.

Another object of the present invention is to provide a non-aqueous multilayer coating film forming method that can form a coating film using a coating liquid of any viscosity.

[Structure of the invention]

The above object of the present invention is to provide a continuously running flexible support with two
In the method of forming a multilayer coating film by simultaneous multilayer coating of two or more types of non-aqueous coating liquids, at least one of the two types of non-aqueous coating liquids J'J and l- contains an electron beam curable compound,
After simultaneous multilayer coating of the two or more non-aqueous coating solutions, 50 Mr.
This is achieved by a multilayer coating film forming method in which the coating layer is cured or swelled by ε:1 by irradiating electronic cotton at an irradiation rate of ad/second or less, and then dried.

As the electron beam curable compound that can be contained in the non-aqueous coating solution in the present invention, various known compounds that can be cured by electron beam irradiation and are soluble in solvents even after electron beam irradiation can be used. Of these compounds: U, special C, =
Preferred compounds are those having an unsaturated bond or an epoxy group that can be polymerized by electron beams, such as a compound having a vinyl or vinylidene carbon-carbon double bond or an epoxy group.
1, preferably 2, an acryloyl group, an acrylamide group, an allyl group, a vinyl ether group,
These include compounds containing vinyl thioether groups, unsaturated polyesters, epoxy resins, and the like.

Particularly preferred compounds are those having the above-mentioned unsaturated bond, and which have an acryloyl or methacrylic 1-coil group.
It is a compound having at both ends of one chain, and these are 8, Vr
uncken Patipec CongressI
'11 19 (] 972). For example, CIIz=CILCO□CIICIIO+cocuz
c++zcozcnzcnc++zo+n1
]n II
OII-COC11=[':11□, and the polyester skeleton of the exemplified compound may be a polyurethane skeleton, an epoxy resin skeleton, a polyether skeleton, a polycarbonate skeleton, or a mixture thereof. Moreover, the terminal of the illustrated compound may be a methacryloyl group. The number of molecular stars is preferably about 500 to 20,000.

The other side of these compounds is that they are commercially available.
There are Aronix M6100 and M7100 made by Toagosei.

Furthermore, 1,000 carbon atoms having a carbon-carbon unsaturated bond in the molecule
is also preferable. Such monomers include, for example, acrylic acid, methacrylic acid, itaconic acid, methyl acrylate and its homologues, acrylic acid alkyl esters, methyl methacrylate and its homologs, methacrylic acid alkyl esters, styrene and its homologs. Some α-methylstyrene, β-chlorostyrene, etc., acrylonitrile, methacrylic acid, tolylamide, vinyl acid, dipropionate, etc.
′ and ゛ are mentioned. There may be two or more unsaturated bonds in the molecule. An example of such a tr compound is 6.1 [Photosensitive Resin Data Collection 1 (Kikugou Chemical Research Institute 1968
Compounds listed in February publication 235-236 are listed. In particular, unsaturated esters of polyols, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate-1, ethylene glycol 1-dimethylacrylate-1, 4-butanethiol diacrylate-1., 1.6-hexanediol acrylate, stearyl acrylate, 2-ethylhexyl acrylate-1, tetrahydrofurfuryl methacrylate, diethylene glycol dimethacrylate-1., te].
Diethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, glycerol I-reacrylate acrylate, pentaerythryl triacrylate, J Nichi [/nglycol cymethacrylate 1 no 1~, pentaerythri 1~-luna 1 Preferred examples include glycidyl methacrylate 1., dipentaerythryl 1--ruhexaacrylate, and glycidyl methacrylate 1/-1-4ζ having an epoxy ring.

No., t as the iiJ flexible 1-1 support used in the present invention
, paper, plastic film, metal, silica, synthetic paper, etc. The material of the Zolast film is, for example, polyolefin such as polyethylene, polypropylene, polyacid-resistant polyhinyl, polyhinyl chloride, polyhinyl polymer such as polystyrene, 6,6-nyl, etc.
Polyamide 1 such as nylon, 6-nylon, polyconylene terephthalate 1, polypropylene 2.

Polyesters such as 6-naphthalene-1, polycarbonate, cells such as cellulose triacetate diacetate I-1, etc. are also used as resins used in resin-coated paper. Polio[/Fin] is representative, but it is not necessarily limited to this.

Among the non-aqueous coating liquids of non-invention number, 1゛, and 2 types 1-1-,
Contains at least one electron beam curable compound! ,
The method is characterized in that after coating the coating liquid in multiple layers, an electron beam is irradiated at an irradiation rate of 50 Mrad/sec or less.

The electron beam irradiation rate is the amount of electron beam irradiation that the irradiated object receives per unit time! = j amount, also called irradiation intensity or dose rate.

When the electron beam irradiation rate is greater than 50 Mrad/sec,
Curing or thickening of the electron beam curable compound-containing layer slows down or does not occur, and diffusion mixing occurs between the multiple coating layers, making it impossible to form the desired coating film.

The method of the present invention can be carried out using an apparatus as shown in FIG. However, the present invention is not limited to such extrusion bead coating, but can also be carried out by slide bead coating, homper slide coating, curtain coating, etc.

From a liquid tank not shown in Fig. 1, 2
A non-aqueous coating liquid of type 1 is supplied to the coating section 11, and is coated on the continuously running web 3 in the extrusion bee 1 section 2. 5 c; + application section backing roller, 6, 7, 8, 9, I O 4; I pass roll. In addition, 4 is a decompression chamber, and by reducing the pressure with a vacuum pump (not shown), etc., the beat is stabilized [21
Ru. l I L; l electron 8sr+ +! <! Miscellaneous equipment, 1
2 is a drying device.

In the present invention, at least one of the above non-aqueous coating liquids contains an electron beam-curable 1'l compound. There is no particular restriction on the content of the layer ij1, but it is suitably about 2 to 3 ou<t%, based on the solid content of the coating l&. Further, the viscosity of the coating liquid used in the present invention is not particularly limited.

+1. When the multi-layer coating layer coated with one layer is subjected to electron beam irradiation in the electron beam irradiation II device 11, the layer containing the electron beam curing compound is hardened or +J thickened, and the multi-layer coating layer is Diffusion mixing between the coated layers is suppressed, and then dried in the drying device 12 to form a multilayer coating film.

Method L:1 of the invention is used for the production of multilayer coatings+A Il having at least two non-aqueous coating layers on a DC-capable support. , - as a multilayer coating +A diagonal, various multilayer photographic materials including, but not limited to,
These include multilayer analysis materials. For example, as a specific example of a photosensitive material H for lithographic printing plates having at least two non-aqueous coating layers, at least one of which is a photosensitive layer, which is suitable for production by the method of the present invention, 50-11022
No. 1, which has an O-quinonediazide photosensitive layer and a resin layer as described in Japanese Patent Publication No. 56-34858, and has two O-quinonediazide photosensitive layers described in JP-A-56-126836. Thing, Japanese Unexamined Patent Publication No. 51-4
3125, which has an O-quinone diazide 1 photosensitive layer and an acid compound photosensitive layer; 1. +fThose having a photosensitive material layer and an organic resin layer described in Japanese Patent Application Laid-open No. 37-11558, and those having a 0-quinonediazide-1 photosensitive layer and an electrophotographic photosensitive layer described in JP-A No. 57-90648+ Examples include those that have.

Example 1 Using the apparatus shown in FIG. 1, a coating solution having the composition and physical properties shown in Table 1 was applied to one film of polyethylene terephthalate having a thickness of 500 mm 1 l/fQp m and 25 cc/m of IW.
2. Multi-layer coating with a lower coating layer of 15 cc/m2, coating 4j
After 1 second, the acceleration voltage was 250kV and the irradiation amount was 4Mr.
ad, 1 (θ) After electron beam irradiation was performed in the electron beam irradiation device 11 with an injection rate of 30 Mrad/sec, the product was heated and dried at 90° C. in the drying device 12.

Comparative Example 1 The same operation as in Example 1 was performed except that the electron beam irradiation rate was changed to 75 Mrad/sec.

The dry films obtained in Example 1 and Comparative Example 1 were subjected to ESCA (formerly e
ctron 5pectroscopy for
Using chemical analysis),
Chlorine in the cresol resin detected in the upper layer while scraping the membrane was analyzed. The distribution of the detected symptoms is shown in FIG. In FIG. 2, the solid line indicates the sample measurement result of Example 1, and the 11th winding indicates the sample measurement result of Comparative Example 1. From this result, in Example 1, the electron beam irradiation rate was 50 Mra.
d/sec or less, it was found that the cresol resin remained unevenly distributed in the obtained sample as shown by the solid line in Figure 2. In Comparative Example 1, the electron beam irradiation rate was 50 Mr.
ad/sec, it was found that the cresol resin was distributed over the entire layer of the obtained sample due to diffusion mixing, as shown by the dotted line.

Table 1 Example 2 A coating solution having the composition and physical properties shown in Table 2 was applied to a polyethylene terephthalate film having a width of 1200 mm and a thickness of 180 pm using the apparatus shown in FIG. 15cc/m2.15cc/m2.5cc
/m'', and at 3 seconds after coating, the acceleration voltage was set to 200 ν, the irradiation amount was 3 Mrad, and the irradiation speed was 20 M.
After electron beam irradiation was carried out in the electron beam irradiation device 11 so that the radiation rate was rad/sec, it was heated and dried in the drying device I2.

Comparative Example 2 The same operation as in Example 2 was performed except that the electron beam irradiation rate was changed to 60 Mrad/sec.

The distribution of the cresol resin and pigment in the buffy coat layer obtained in Example 2 and Comparative Example 2 was detected using ESCA for chlorine and copper in each molecule. The analysis results of the sample obtained in Example 2 are shown by the solid line in Figure 3, and the results of the analysis of the sample obtained in Example 2 are shown by the solid line.
The analysis results of the samples obtained are shown by dotted lines in Figure 3.

As is clear from Table 2 and Figure 3, when the electron beam irradiation rate exceeds 50 Mrad/sec as in Comparative Example 2, the distribution of the cresol resin or pigment in the buffy coat becomes almost uniform over the entire layer. , in the method of the present invention, both are unevenly distributed in the original layer.

This clearly shows the effects of the present invention.

〔Effect of the invention〕

According to the present invention, as confirmed in Example 2, in multilayer coating of non-aqueous coating liquids, diffusion mixing between layers is suppressed and a multilayer coating film is formed, thereby simplifying the process.
Costs are reduced. Further, according to the present invention, there is no restriction on the viscosity of the coating solution, and a multilayer coating film can be formed using a non-aqueous coating solution of any viscosity.

[Brief explanation of the drawing]

FIG. 1 is a side sectional view of an apparatus for implementing the coating film forming method according to the present invention, and FIGS. 2 and 3 are characteristic diagrams showing the effects of the present invention. ■... Coating head, 2... Extrusion bee 1 part, 3... Web, ] 1... Electron beam irradiation device,
12...Drying device. Procedural amendments Director General of the Patent Office Michibu Uga 3. Person making the amendment Relationship to the case Applicant name (520) Fuji Photo Film Co., Ltd. 4. Agent 5. Date of amendment order Voluntary 6. Subject of amendment Details. The formula in Column 1, Detailed Description of the Invention, Line 1, Page 6 of the Specification is corrected as follows. [C11□=Cll-Co 2C112CIICI!
2O-(COC11□C112CO□clhcllcI
l□0) T-I-COC11= CII□” 2. “Fatipec” in the 2nd line from the bottom of page 5 of the specification
is corrected as [“Fatipecl.

Claims (1)

[Claims] In a method of forming a multilayer coating film by simultaneously applying two or more types of non-aqueous coating liquids on a continuously running flexible support,
At least one of the two or more types of non-aqueous coating liquids contains an electron beam curable compound, and after simultaneous multilayer coating of the two or more types of non-aqueous coating liquids, irradiation with an electron beam at an irradiation rate of 50 Mrad/second or less is performed. A method for forming a multilayer coating film, which comprises curing or thickening the coating layer using a method of coating, and then drying the coating layer.