JPS6351110B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a printing substrate, which is applied to offset printing and relief printing, and is made by applying a coating agent containing cyclized rubber as a main component to the surface of a non-oil-absorbing printing material such as a metal surface. It is something. Gravure printing is the main method used to print on metal surfaces such as aluminum foil due to issues such as drying and adhesion, but if printing is done using lithographic or letterpress methods, oxidation polymerization drying methods are preferred. Since resin-based ink is used, problems such as set-off, rubbing stains, or blocking are likely to occur before drying, which may require excessive spray powder, or a small number of " This requires a great deal of labor, expense, and storage space, such as being forced to "slat it out" and also requiring heat-drying. The present applicant has already proposed, in the specification of Patent No. 988923, a mixture of a cyclized rubber containing cyclized rubber as a main component and an ethylene/vinyl acetate copolymer, or a mixture of the above-mentioned rubber and the above-mentioned A printing substrate made by applying a coating agent containing a mixture of a copolymer and an alkyd resin as a binder component to a non-oil-absorbing printing material, which can be used with ordinary printing paper flat plate inks and letterpress inks. We have proposed a printing base material that can set and dry ink on non-oil-absorbing materials such as aluminum foil with performance equivalent to or better than paper, and that can also provide good adhesion to the materials. However, when applying the coating agent to a non-oil-absorbing substrate, the adhesion of this printing substrate may change depending on the state of the oxide film on the surface of the substrate, so the adhesion may change. In such cases, for example, any remaining rolling oil from rolling the printing material may be wiped off with a solvent, or a pretreatment process such as a commercially available isocyanate-based, organic titanium-based, polybutyral-based, or polyvinyl-based primer may be used. The agent was applied. In order to rationalize the manufacturing process and reduce manufacturing costs, it is absolutely necessary to eliminate the need for this type of pretreatment process. There has been a strong desire for a coating agent that can consistently provide high adhesion strength regardless of the weather conditions. As a result of intensive research to meet this demand, the present inventors discovered new knowledge that the addition of organic acid metal salts is extremely effective in achieving the above objective.
We have arrived at the present invention. That is, the present invention relates to a printing base material in which a coating agent formed by adding an organic acid metal salt to a film-forming component mainly composed of cyclized rubber is applied to an absorbent printing material. The "non-oil-absorbing printing material" used herein refers to materials made from aluminum, gold, silver, copper, brass, zinc, tin, steel, etc., such as aluminum foil, aluminum foil-laminated paper, or aluminum vapor-deposited paper. It refers to a printing material such as foil or rolled thin plate that is not permeable to oil-based substances such as printing ink. Therefore, the above-mentioned "printing substrate" refers to this non-oil-absorbing printing material. A paper obtained by applying the above-mentioned coating agent to a body, and which has the same printability as general printing paper that can be easily printed with ordinary flat plate ink or convex plate ink. means. In obtaining the printing substrate of the present invention, the coating agent to be applied to the non-oil-absorbing printing material is generally 0.01 to 1.0% by weight of the cyclized rubber based on 1 part of the cyclized rubber. A mixture of 70 to 95% by weight of cyclized rubber 1 and 30 to 5% by weight of ethylene/vinyl acetate copolymer 3 may be used.
of the above cyclized rubber for a mixture consisting of % by weight.
Add 0.01-1.0% by weight of organic acid metal salt or
Or 0.01 to 95% by weight of the cyclized rubber 1, 25 to 4% by weight of the ethylene/vinyl acetate copolymer 3, and 15 to 1% by weight of the alkyd resin 4, As a binder component, one of those to which 1.0% by weight of organic acid metal salt was added,
This is dissolved in an organic solvent, but if necessary, extender pigments such as fine calcium carbonate, non-colloidal silica, aluminum silicate, magnesium carbonate, clay, etc., or starch may also be mixed in. I can do it. Here, the above-mentioned "cyclized rubber" includes, for example, (1) a method of kneading sulfuric acid or sulfonic acid into rubber, (2) a method of removing hydrogen halide from halogenated rubber, (3) a method of solid rubber or It can be obtained by various methods such as heating a rubber solution to 250°C or higher under a catalyst, and (4) applying a cyclizing agent such as sulfuric acid to an acidic latex. Commercially available products have an average molecular weight of about 5,000 to about 100,000.
However, in the present invention, anything within this range can be used. Further, as the organic acid metal salt 2, for example, Co,
Transition metals such as Cr, Fe, Mn; aliphatic or aromatic carboxylates of rare earth metals such as Li and Zr can be used;
Particularly suitable are the above metal salts such as octylic acid, stearic acid, and abietic acid. The above-mentioned "ethylene/vinyl acetate copolymer" preferably has a vinyl acetate content of about 60% by weight or less, usually 10 to 50% by weight, preferably 20 to 40% by weight. Furthermore, in addition to the above components (1), (2), or (3), if necessary, rosin ester, rosin-modified phenolic resin, rosin-modified maleic acid resin, petroleum oil-based resin, rubber-based resin, cellulose resin, etc. Addition of resins with low oil resistance such as polyamide-based resins, and resins that can provide adhesion to metals such as polyamide-based resins, styrene/maleic acid-based resins, epoxy-based resins, vinyl-based resins, urethane-based resins, etc. I will not prevent you from forcing me. In addition, the above-mentioned organic solvents include aromatic hydrocarbons such as benzene, toluene, xylene, etc.; aliphatic hydrocarbons such as gasoline, kerosene, light oil, heavy oil, or n-hexane; alicyclic hydrocarbons such as cyclohexane, etc. Hydrocarbons: Chlorinated hydrocarbons such as carbon tetrachloride and trichloroethane; Ester systems such as ethylene acetate and butyl acetate; Ketone systems such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; or methanol, ethanol, isopropanol, etc. Alcohol-based materials can be used. A roll coater, a gravure roll coater, a bar coater, etc. can be used as a method for applying the coating agent to the printing material, and the coating amount is 5 to 5.
The appropriate amount is 10 g/m ² , which allows for a beautiful finish without impairing the metallic luster or color. On the other hand, in order to impart color or to obtain a faded effect, it is possible to do so appropriately by using colorants or the various extender pigments described above. Furthermore, during this coating, the adhesion to the printing material may vary depending on the drying ability, coating speed, coating amount, etc., so it is desirable to sufficiently dry the coating to reduce the amount of residual solvent. Thus, the printing substrate of the present invention has the effect of preventing oxidation or corrosion of the surface of the printing material, in addition to the effect of imparting printability as described above by applying such a coating agent. It also imparts an antifungal effect, an effect of imparting bacterial resistance, an effect of maintaining metallic luster, etc. On the other hand, the printing effects obtained using the printing substrate of the present invention are significantly improved, such as stacking of the substrate during printing, which was previously considered impossible, and multicolor printing using a multicolor printing machine. It is expected that process improvements and precision and sophisticated printing effects will be achieved. Next, the present invention will be specifically explained using examples. Example 1 "ALPEX-CK-514" (trade name of cyclized rubber manufactured by Hoechst in West Germany)
17 parts by weight "Ultracene UE750" (trade name of ethylene/vinyl acetate copolymer manufactured by Toyo Soda Kogyo Co., Ltd.) 6 Toluene 40 Cyclohexane 20 Ethyl acetate 15 Cobalt naphthenate solution (8% cobalt naphthenate (2.5% methyl ethyl ketone solution) 2 According to the above recipe, each component was dissolved in a solvent to obtain a coating agent. This coating agent was roller coated onto a printing material, a soft aluminum foil-high quality laminated paper, to obtain a printing substrate. Next, using this base material, "Super APEX Red K" (Dainippon Ink & Chemicals Co., Ltd.) was printed using an offset printing machine.
The results of printing using offset ink (trade name) for general paper were as follows. For comparison, Comparative Example 1 was prepared by repeating the same printing operation without using any of the above coating agents.

【table】

[Table] Example 2 "Thermolite" (trade name of cyclized rubber manufactured by Seiko Kagaku Co., Ltd.) 18.5 parts by weight "Evaflex 250" (trade name of ethylene/vinyl acetate copolymer manufactured by Mitsui Polychemical Co., Ltd.)
4.0 〃 “Soritstobetsucozone No. 18” (trade name of alkyd resin manufactured by Dainippon Ink and Chemicals Co., Ltd.) 2.5 〃 Toluene 40.0 〃 Acetate ethyl ester 20.0 〃 Methyl ethyl ketone 15.0 〃 Manganese octenoate solution (2.5%) Methyl ethyl ketone solution) 5.0 According to the above recipe, prepare a coating agent by sufficiently dissolving the cyclized rubber, ethylene, vinyl acetate copolymer, and alkyd resin in a solvent, and apply this coating agent to aluminum vapor-deposited paper using a gravure roll coater. A substrate for printing was obtained by coating using the following method. Next, printing was carried out in the same manner as in Example 1 using this printing substrate, and the results are shown in Table 2. For comparison, similar printing was carried out on art paper and high-quality paper that were not coated with any of the above coating agents, and the results are also shown together.

[Table] Example 3 "Thermolite" (trade name of cyclized rubber manufactured by Seiko Kagaku Co., Ltd.) 19.0 parts by weight "Elvax 250" (trade name of ethylene-vinyl acetate copolymer manufactured by DuPont, USA) 3.0 " Solid Vetsucosol No. 1” (trade name of alkyd resin manufactured by Dainippon Ink and Chemicals Co., Ltd.)
1.5 Toluene 26.0 n-hexane 25.0 Ethyl acetate 20.0 Rare earth octenoate/cobalt octenoate solution (rare earth octenoate/cobalt octenoate/toluene = 8.0/2.0/90.0 (%)) 5.0 According to the above recipe, a coating agent was prepared in the same manner as in Example 2, and this coating agent was further added with oil-soluble dyes such as "Neozabone" (product of BASF, West Germany) or Orazol (Switzerland) as a coloring agent. A gold-tone printing base material was obtained by coating aluminum foil with the additive (product of Kuni Ciba Co., Ltd.), and then printing was performed on these base materials in the same manner as in Example 1. Beautiful prints could be obtained from the materials, and all of them also had excellent printability. In addition, "Aerosil" is used as a matuto effect giver.
In the same way, various types of As a result of producing a printing substrate, it was possible to process the metal surface to have a semi-matte or matte luster depending on the amount of these matte effect imparting substances added.

Claims (1)

[Claims] 1. A printing base material in which a coating agent containing cyclized rubber as the main film-forming component and an organic acid metal salt added thereto is applied to a non-oil-absorbing printing material.