JPS60199999A - Imparting of surface gloss to 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] In recent years, it has become common practice to apply a resin solution over the printed surface of cosmetic boxes, book and mat covers, calendars, etc. and then dry it to give it a glossy, deluxe feel. It is. Previously, vinyl chloride-vinyl acetate copolymer was mainly used as a resin for such gloss varnish paints, but since this resin is soft, it is usually difficult to use the mirror plate required after drying in the above operation. Although it is suitable for the patch method in the hot pressing process, continuous pressing using a stainless steel endless belt has the disadvantage that it does not peel off smoothly from the belt surface, so recently methacrylic resin, a resin with a high glass transition point, has been Acrylic copolymers containing acid methyl and styrene are used.

However, with recent advances in printing technology, especially color printing technology, it has become possible to produce printing paper that uses various colors in even the smallest detail. The adhesion of the resin to the printed surface varies depending on the type, and partial cracks may occur over time.Also, even if the coating appears to be evenly coated, rubbing the coating with your finger or nail may cause certain problems. Adhesion is so poor that colors, especially dark colors, can easily peel off, and a solution to this problem is desired.

However, the inventors of the present invention solved these problems and continued intensive research with the aim of improving adhesion to the printed surface and further improving other performances such as gloss and abrasion resistance. As a result, (a) Copolymerize (b) a basic monomer with 0.5 to 15 parts by weight and (C) an acidic monomer in a ratio of 0 to 10 parts by weight with respect to 100 parts by weight of styrene and/or (meth)acrylic acid ester. , and the glass transition temperature (hereinafter referred to as Tf) is 8
When applying a copolymer with a temperature of 0 to 110°C to the printing surface,
It was discovered that a uniform coating film with excellent adhesion to printed paper of any color could be obtained, and that processed paper with beautiful gloss could be obtained, and the workability of completing the present invention was poor. There is a tendency for the gloss of the coated surface to decrease.
Undesirable. (Meth)acrylic acid esters are preferably alcohol esters having 1 to 8 carbon atoms, typically methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, Examples include ethyl methacrylate, propinope methacrylate, butyl methacrylate, e2-ethylhexyl methacrylate, and methyl methacrylate is particularly frequently used.

In the copolymer, it is essential to copolymerize 0.5 to 15 parts by weight of component (b) with respect to 100 parts by weight of component (a). The presence of component (b) can be expected to have a significant effect, particularly in terms of adhesion. (The bl component is 0.
If the amount is less than 5 parts by weight, the effect of improving adhesion cannot be obtained;
If the amount is more than 5 parts by weight, the copolymer will be colored, making it impossible to obtain a transparent coated surface. Basic monomer 7 is dimethylaminoethyl acrylate, diethylaminoethyl acrylate, butylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, butylaminoethyl methacrylate, 2-
Vinylpyridine, 4-vinylpyridine, N-vinylimidazole, 2-methyl-N-vinylimidazole, 2-
Ethyl-5-vinylpyridine, dimethylallylamine,
Examples include diallylamine.

Among these, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate are particularly preferable because they more significantly exhibit the effects of the method of the present invention.

In the copolymer used in the present invention, if necessary, (
c) It is also possible to use acidic monomers as copolymerization components. The use of such a component is particularly useful when the copolymer of the present invention is used in an aqueous system. is copolymerized with (a) and (b) to obtain a water-based paint. Even a copolymer using the Gagaruru salt type component (c) can be used in an organic solvent system. Such acidic additives usually contain 100% of component (a). Preferably I'i is in the range of '-7''n to 15 folds for the hanging part.
Weight used for 0 to 10 heavy scenes. If the amount exceeds 15 parts by weight, coating properties will deteriorate. As the acidic acid, acrylic acid,
Examples include methacrylic acid, crotonic acid, maleic acid, maleic anhydride or its monoester, fumaric acid, itaconic acid, acotinic acid, vinyl sulfonic acid, and the like.

In addition to the components (a), (bl, and (c)), other copolymer components such as vinyl acetate, vinyl toluene, and versatic acid may be used if the amount is less than the 20th doublet based on the entire resin. Vinyl, acrylonitrile, methacrylate trile,
There is no problem in using acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl methacrylate, hydroxylethyl acrylate, hydroxylpropyl acrylate, etc. to form a multi-component copolymer.

The above copolymers can be produced by bulk polymerization, solution polymerization, emulsion polymerization,
It can be produced by any method such as suspension method.

Generally, a solution polymerization method is used in which KIIu is heated in a solvent such as toluene, xylene, or ethyl acetate under the introduction of an inert gas and in the presence of a polymerization UB initiator. Polymerization initiators include azo polymerization initiators, such as peroxide polymerization initiators such as azobisinbutyronitrile and azobismethylvaleronitrile;
For example, acetyl peroxide, butyl peroxide, benzoyl peroxide, etc. can be used arbitrarily.

The copolymers of the present invention are those obtained as described above, and only those having Tp in the range of 80 to +10'C are used. When Tp is below 80'C, dry Bl
The film is too soft and tends to adhere to the belt surface, which poses a problem in terms of workability. At temperatures above 110°C, the dried film becomes brittle and cracks occur over time, reducing gloss. Therefore, there is a practical problem.

Then, the above copolymer having such composition and physical properties is applied to printed paper and dried. As the application means, any means such as roll coating, brush coating, curtain 70-coating, spray coating, doctor coating, etc. can be employed. The amount of coating is usually adjusted appropriately so that the thickness after drying is 5 to 20 μm, but there is no particular limitation as long as the printed surface is beautifully and completely protected. As the solvent used for coating, the solvent used during copolymerization may be used as is, or if necessary, the solvent may be replaced with a solvent having a faster volatilization rate.

Further, as described above, when the acidic monomer (c) is used as a copolymerization component, it is also possible to apply the coating in an aqueous system. The concentration of the coating liquid used is usually in the range of 10 to 60% by weight. After coating, drying is performed at a temperature of 50 to 100°C. As the drying means, a known method is appropriately employed.

According to method 1 of the present invention, a transparent coating film with excellent adhesion and optical pK can be obtained at this stage, but if you want to obtain a coating film with even better elasticity, hot press on the coating surface after drying. administer. For hot pressing, mirror plates made of stainless steel, aluminum, etc. are layered on the resin surface obtained by applying the resin to the surface of the printing paper, and an appropriate number of these plates are stacked alternately and hot pressed at about 70 to 150 degrees Celsius, or The mirror-finished plate is made into an endless belt and passed between hot rollers to perform continuous processing.

According to the method of the present invention, there is also the operational advantage that peeling of the paper from the mirror plate, which has been a problem during such hot pressing, can be done extremely smoothly.

In addition, when employing the method of the present invention, the copolymer used in the present invention may be blended with other resins as long as the excellent physical properties such as adhesion, gloss, and abrasion resistance are not deteriorated. There is no problem in doing so. Such resins include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin,
Acrylic resin or the like is blended in an amount of about 0 to 50% by weight based on the copolymer.

゛1 Next, the method of the present invention will be further explained with reference to Examples.Example 1: 70 parts of styrene, 60 parts of methyl methacrylate, and 5 parts of diethylaminoethyl methacrylate.0 gloss: Appearance was visually inspected and evaluated on a 5-grade scale.

O Gloss: Based on gloss meter 60°-60° reflection.

0 wear resistance: Taper wear tester, load 500g x 1
The results are shown as the wear weight (Me x 1000) under the condition of 00 rotations.

・E O Blocking Resistance'After being left at a temperature of 50°C and a relative humidity of 90% under a load of 400p for 6 hours, the coated surfaces were overlapped and rapidly peeled off by hand.The degree of blocking was 5: Very Good peeling; 4: Easy peeling; 3: Slight blocking; 2: Lots of blocking; 1: Fully blocking.

Next, the coated paper was layered on a stainless steel mirror plate, and then
1, hot pressing was carried out for 1 minute at a temperature of 80° C. and a pressure of 200 vJ. Peeling paper from mirror plate after hot pressing
The process went extremely smoothly, and there was not a single problem during the continuous hot pressing of 100 sheets.

The decorative paper thus obtained was prepared by mixing a copolymer (TF, t=95°C) with a composition that was even brighter than that before pressing, using toluene as a solvent, to obtain a resin solution with a concentration of 30 g6, and hand-mixing this. Using an applicator, apply the film to a thickness of 10μ on gastric fin printed cardboard (concentrically printed in six colors of red, yellow, and black), and apply it to a film thickness of 10μ at 80℃.
Dry with hot air for 0 seconds.

The following tests were conducted on the resulting coating to evaluate its performance.

The results are shown in Table 1.

0 Scratch adhesion: Degree of peeling of the paint film when rubbing the coated surface with a clip 5 = No change at all, 4: Almost no change, 3: Slight peeling, 2: Noticeable peeling, 1: Full surface It was shown at the time of peeling off.

O-tape adhesion: The degree of peeling of the coating film when cellophane tape is applied to the coated surface and rapidly peeled off: 5: completely peeled off from the base material (paper layer), 4: most of it peeled off from the base material, 6: Partially peeled off from the base material; 2: peeled off from most of the coated surface; 1: peeled off entirely from the coated surface.

In the adhesive tape peel test, in which adhesive tape was applied from the surface and then vigorously removed, the adhesion was so strong that the paper layer, which was the base material, broke.

Comparative Example 1 An experiment similar to Example 1 was conducted using acrylic acid instead of diethylaminoethyl methacrylate.

The results are shown in Table 1.

Example 2 Performance evaluation was performed in the same manner as in Example 1 except that the copolymerization ratios of styrene, methyl methacrylate, and diethylaminoethyl methacrylate were changed to 20 parts, 80 parts, and 5 parts, respectively. (Tp of copolymer: 100°C) The results are shown in Table 1.

Example 6 Performance was evaluated in the same manner as in Example 1, except that a copolymer (Tf: 97°C) having a composition of 50 parts of styrene, 50 parts of methyl methacrylate, 5 parts of dimethylaminoethyl methacrylate, and 5 parts of acrylic acid was used. We conducted an evaluation.

The results are shown in Table 1.

Example 4 A copolymer having a composition of 65 parts of styrene, 35 parts of methyl methacrylate, 5 parts of diethylaminoethyl methacrylate, and 10 parts of acrylic acid (TI: 95°C) was added to an aqueous ammonia solution and dissolved, resulting in a resin concentration of 6596. Prepared as follows.

This aqueous solution was applied to the printed surface according to Example 1, and the performance of the coating film was evaluated.

The results are shown in Table 1.

Examples 5 to 8 In place of the jetylaminoethino-tafrylate used in Example 1, N-vinylimidazo was used. 6, Tf of copolymer: 95°C), 2
-Methyl-N-vinylimidazole (Example 7, Tf of copolymer: 95°C), dimethylallylamine (Example 8)
, copolymer Tf: 95° C.) was used, but the experiment was conducted in the same manner as on the same side.

The results of the above performance evaluation are summarized in Table 1.

Example 9 A copolymer (Tf
: 90°C), and the performance was evaluated in the same manner as in Example 1.

The results are shown in Table @1.

Example 10 A copolymer (TV:
Performance evaluation was performed in the same manner as in Example 1 using a temperature of 100°C.

The results are shown in Table 1.

Example 11 Copolymer CT9 with a composition consisting of 70 parts of styrene, 60 parts of methyl methacrylate, 3 parts of diethylaminoethyl methacrylate, and 10 parts of hydroxyethyl methacrylate:
Performance evaluation was performed in the same manner as in Example 1 using a temperature of 95°C.

The results are shown in Table 1.

Example 12 Performance evaluation was performed using a copolymer (Tg: 100° C.) having a composition of 20 parts of styrene, 80 parts of methyl methacrylate, 10 parts of acrylonitrile, and 5 parts of diethylaminoethyl methacrylate.

The results are shown in Table 1.

Example 16 The resins used in Example 1.2 were mixed (1/1) and their performance was evaluated.

The results are shown in Table 1.

Table 1 Note that when coated papers using the copolymers of Examples 2 to 13 were hot pressed in accordance with Example 1, the operation proceeded very smoothly.

The thus obtained decorative paper also became more glossy than before pressing, and the paper layer serving as the base material broke in the peel test.

Patent applicant: Nippon Gosei Chemical Industry Co., Ltd. 1 Handbook continued by Yuu Masho (self-published) February 5, 1985 ,・Ij l'l's entry Patent Application No. 51397 (1939) □1 Name of invention 81] (Table 1 River I R4/IJ) Method, lottery market [Run name °Ii l’l related patent applicant 11 Location: 9-6 Nozakicho, Kita-ku, Osaka City.

, extraction pressure λ, j (IJ deficiency Specification, 1: Detailed description of the invention

Claims (1)

[Claims] (b) 0.5 parts of basic monomer per 100 wk parts of (a) styrene and/or (meth)acrylic acid ester
-15 parts by weight, copolymerized with (C) acidic monomer at a ratio of 0 to 15 parts by weight, and has a glass transition temperature of 80 to 80 parts by weight.
A method for imparting surface gloss to paper, which comprises applying a copolymer at 110° C. to a printing surface and then drying it.