JP2001301305A - Print covering matter and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a beautiful print covering matter, in which an uneven feeling is remarkable and the contrast between the matting at dent parts and the gloss at smooth parts is sharp, and its manufacturing method. SOLUTION: In this manufacturing method of the print covering matter, first of all, a portion, in which the formation of a non-glossy region is wanted, is printed with a printing ink including a curing inhibitor and then dried so as to coat both the portion, in which the formation of the non-glossy region is wanted, and a portion, in which the formation of a glossy region (or a more glossier region is meant than the non-glossy region) is wanted, with an active energy beam curing type covering agent including no curing inhibitor and then irradiate both the portions with active energy beams having the output of 50 W/cm or more in order to make the gloss of the non-glossy region less by 80% or less of the gloss of the glossy region, resulting in obtaining the print covering matter and its manufacturing method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel printing method for easily providing a printed coating having a visually uneven and three-dimensional pattern by a combination of irradiation of ultraviolet rays and strong active energy rays.

[0002]

2. Description of the Related Art Ordinary printed matter is entirely glossy or entirely non-glossy. However, there are cases in which a printed material having unevenness and a three-dimensional effect is formed by forming a glossy print region and a glossless print region.

In order to respond to such a demand, Japanese Patent Laid-Open No.
According to JP-A-237344, as shown in FIG. 2, a solid printing layer 3 is formed on a thin paper 2 for building material printing by gravure printing using gravure ink, and the grain pattern portion 4A and the joint pattern portion 4B are formed thereon by gravure printing using gravure ink. Is formed, and then a matte OP layer 5 is formed thereon by gravure printing, and the register is further registered to the portion corresponding to the joint pattern portion 4B, and is made to correspond to the conduit groove portion of the wood pattern portion to some extent. A matte printing layer 6 is formed by gravure printing using matte ink, and a gloss printing layer 7 is formed on other parts by gravure printing using gloss ink at last. 1) A wood grain pattern is printed in a normal printing process. (2) Next, a matte printing layer using a matting ink is formed only at a desired position, and finally (3) a matte printing layer is formed. And is made of the step of forming a glossy print layer in a location other than the portion was required very large number of steps.

As measures to overcome such a situation, Japanese Patent Publication Nos. 50-19288, 50-33090 and 51
No.-5016, No.51-24371, No.51-392
No. 75, etc., after applying the ultraviolet absorber in synchronism with the grain pattern, apply an ultraviolet curable paint over the entire surface, and then irradiate ultraviolet rays to cure the surface layer. It is disclosed that the portion where is present becomes concave and a three-dimensional pattern is formed. However, as for gloss, Japanese Patent Publication Nos. 50-33090 and 51-24371 describe that there is no difference in gloss in the uneven portions, and other publications do not describe anything about gloss.

However, the mercury lamps used in these techniques have low irradiation energies, so that the three-dimensional pattern formed by them is not sufficiently satisfactory. Therefore, these technologies have been abandoned as they are, and have not been put into practical use until now.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the dose of active energy rays conventionally used in printing in which a region where a curing inhibitor such as an ultraviolet absorber exists and a region where a curing inhibitor does not exist exist. An object of the present invention is to provide a beautiful printed coating product in which the unevenness is remarkable by strengthening and the contrast between the matte of the concave portion and the gloss of the smooth portion is clear, and a method for producing the same.

[0007]

[Means for Solving the Problems] By the way, Japanese Patent Publication No. 50-
JP-A-19288, column 5, line 6 uses a 120 W ultraviolet chemical lamp for photopolymerization, and JP-B-51-5016, column 6, lines 11-12, which is an invention of the present inventor, uses a fluorescent lamp for photopolymerization. It is described that a high-pressure mercury lamp for photopolymerization (4 KW) was used.
Since a 0 cm mercury lamp is used, even when a 4KW mercury lamp with the highest output is used, its unit cm
Irradiation energy per

## EQU1 ## 4000 ÷ 140 = 28.57 W / cm 2, and the output was considerably small. As described above, the present inventors have investigated the cause of the insufficient unevenness and the insufficient difference between the matte part and the polished part, and as a result, it has been found that this is due to the insufficient amount of irradiation energy. Was.

A first aspect of the present invention relates to a print coating comprising a glossy region and a non-glossy region, wherein the gloss of the non-gloss region is 80% or less of the gloss of the gloss region. .

A second aspect of the present invention is that, after printing and drying a printing ink containing a curing inhibitor on a portion where a non-glossy region is to be formed, the portion where a non-glossy region is to be formed and a gloss (which is higher than the non-glossy region). An active energy ray-curable coating agent containing no curing inhibitor is applied to both the portions where the regions are desired to be formed, and 50 W / c is applied to both regions.
The present invention relates to a method for producing a printed coating, which comprises irradiating an active energy ray having an output of m or more and making the gloss in a non-glossy area 80% or less of the gloss in a glossy area.

In measuring the degree of gloss, a gloss checker IG-320 manufactured by Horiba, Ltd. was used.
Incident angle 60 degrees, reflection angle 60 degrees, measurement area 6 mm x 12 mm
Was measured.

According to the present invention, it is possible to obtain, for the first time, a printed coating having a desired high degree of unevenness and a clear contrast between a matte portion and a glossy portion by irradiating such a strong active energy ray. It was done. For this purpose, an active energy ray having an output of 50 W / cm or more is required. A typical output range is 5 W / cm.
0 to 200 W / cm, preferably 80 to 200 W / cm
It is. For example, in the case of a mercury lamp having a light emission length of 1400 mm, the product name H11-L21 is 80 W / cm (lamp output is 11,000 W) and the product name H17-L31X is 120 W in the case of a merchandise lamp having a light emission length of 1400 mm.
/ Cm (17,000 W as a lamp output), and 160 W / cm (trade name, 22,000 W) as a trade name of H22-L41. In addition, as an active energy ray, an electron beam, an X-ray, etc. other than ultraviolet rays like the above-mentioned mercury lamp can be mentioned.

Examples of the curing inhibitor which can be used in the present invention include a so-called ultraviolet absorber, a radical scavenger, a polymerization inhibitor, an antioxidant and the like. Examples of the ultraviolet absorber include benzotriazoles, benzophenones, triazines, salicylates, cyanoacrylates, hindered amines, and the like.Radical scavengers include hindered piperidines, hindered phenols, and semi-radicals. Hindered phenols can be mentioned, as polymerization inhibitors, quinones, catechols and the like can be mentioned, and as antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants and the like can be mentioned. it can. These amounts are used in such an amount that the curing reaction is delayed in the area where it is present, so that the part eventually becomes matte and looks concave. Since the amount varies depending on the difference in the curing inhibiting ability of each drug, it cannot be said unconditionally. However, among these, an ultraviolet absorber is particularly preferable, and the amount of the ultraviolet absorber used is 5 to 5% based on the total amount of the printing ink.
20% by weight, especially 10-15% by weight.

The printing ink for forming the non-glossy area is a lithographic ink, a relief printing ink, except that a curing inhibitor is added.
Formulation of ordinary printing inks such as letterpress rotary ink, rubber letterpress ink, tinplate ink, gravure printing ink (19)
Anything can be used as long as it is published by Gihodo Shuppan Co., Ltd. on Mar. 30, 1993, edited by The Printing Society of Japan, Handbook of Printing Engineering), but the one based on lithographic ink or gravure printing ink is particularly preferred.

As a printing method for forming the non-glossy area, any printing method such as lithographic printing, letterpress printing, gravure printing, silk screen printing, and roller type printing can be adopted.

The substrate for printing may be any paper, plastic sheet, plastic film, cellophane, wood, plywood, metal, various molded products and the like.

The use of the printed matter (painted matter) according to the present invention is arbitrary, for example, building materials, furniture, automobile interior materials,
Outer boxes, labels, sheets, nameplates, book covers, book covers, CD cases, product catalogs, posters, calendars, packaging materials and the like can be mentioned.

As the energy ray-curable coating material for forming the glossy region of the present invention, a coating material containing a prepolymer such as unsaturated polyester, acrylic, urethane acrylate or epoxy acrylate can be exemplified.

Examples of the unsaturated polyester resin include ethylenically unsaturated dibasic acids such as maleic acid, fumaric acid, itaconic acid and anhydrides thereof and ethylene glycol, diethylene glycol, triethylene glycol, butylene glycol, propylene glycol, The main component is a product obtained by blending a reaction product with a glycol such as pentyl glycol and a photoinitiator or a photosensitizer.
Further, these compounds include saturated dibasic acids such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, adipic acid, sebacic acid, tung oil, linseed oil,
A combination of higher fatty acids such as dehydrated castor oil and soybean oil, and polyhydric alcohols such as pentaerythritol, trimethylolpropane, trimethylolethane, glycerin and dihydroxypentadiene is also used. Also,
Various modified resins such as a urethane-modified polyester resin or an epoxy-modified polyester resin in which a part of the unsaturated polyester is substituted with tolylene diisocyanate, methylene diisocyanate or the like can also be used. Styrene or the like can be used as a crosslinking monomer.

Examples of the acrylic resin, urethane acrylate resin and epoxy acrylate resin include alkyd acrylate, polyester acrylate, polyol acrylate, polyether acrylate, polyurethane acrylate, oligo acrylate and epoxy acrylate [July 1985]. Published by CMC Co., Ltd., “Special Function Inks”, pp. 34-40; CMC Co., Ltd., Nov. 21, 1980, “Synthesis and Application of Photosensitive Resins (Continued)”, No. 404
417 pages; December 10, 1983, published by Sogo Gijutsu Publishing Co., Ltd., "Handbook for Painting and Printing Plastics", No. 70-83
See page.

Since the viscosity cannot be controlled with the prepolymer alone, various crosslinkable monomers are usually used in combination as a reactive diluent. Examples of these include 2-ethylhexyl (meth) acrylate, isoamyl acrylate, uralyl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxy. Dipropylene glycol (meth) acrylate,
Phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol di (meth) acrylate,
Cyclohexyl (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, bisphenol A Ethylene oxide adduct di (meth) acrylate, bisphenol A propylenoxide adduct di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylenoxide modified trimethylolpropane tri (meth) acrylate, ditrimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ( Data) acryloyl morpholine, N- vinylformamide, N- vinyl pyrrolidone,
Dodecyl vinyl ether, hydroxybutyl vinyl ether, cyclohexane dimethanol divinyl ether,
Triethylene glycol divinyl ether and the like can be mentioned.

In the present invention, a photoinitiator (photosensitizer) can be added to the coating. These are also described in the cited references in the preceding section, but typical photoinitiators include 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone, and diethoxyacetophenone. , 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-
1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin,
Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate,
4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 '
-Methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-
Chlorothioxanthone, 2-methylthioxanthone,
2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2.4-
Diisopropylthioxanthone, α-acyloxime ester, acylphosphinoxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, dibenzosperone, triethanol as a photoinitiator Amine, methyldiethanolamine, triisopropanolamine, 4,4-dimethylaminobenzophenone, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminoethylbenzoic acid, isoamyl 4-dimethylaminoethylbenzoate And 2-dimethylhexyl 4-dimethylaminoethylbenzoate, and a polymerizable tertiary amine.

[0022]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto. In addition, all the following "parts" are parts by weight.

Example 1 Chemi Soap # 72 (Ultraviolet absorber: manufactured by Chemipro Kasei) 1
Gravure ink containing 5% by weight of wood grain pipe
(Corresponding to the curing inhibitor-containing printing ink layer 12 in FIG. 1) On a printed resin-reinforced paper (corresponding to the base material 11 in FIG. 1), 50 parts of a urethane acrylate oligomer, 50 parts of an acrylate monomer, and 5 parts of benzyldimethyl ketal The resulting coating agent was applied at 5 g / m ² with a bar coater (coating layer 13 containing no curing inhibitor in FIG. 1), and a high-pressure mercury lamp (eye graphics Co., Ltd., trade name H11-L21, unit output 80 W / cm, emission length 1400mm, lamp output 1
(1,000 W) was irradiated at 1.0 J / cm ² . The resulting print-coated paper had a beautiful finish with a three-dimensional appearance in which only the printed portion of the conduit had no gloss. In order to measure the difference in gloss between the glossy part and the non-glossy part, the area of the measurement part must satisfy the measurement conditions of the measuring instrument. To measure the gloss of solid printing paper coated only with the coating agent used in the non-glossy area and separately measure the gloss of the non-glossy area, apply the curing inhibitor-containing printing ink and coating agent used in the non-glossy area The gloss of the printed solid printing paper was measured, and the gloss of the glossy part (A) was obtained from the measured data.
Of the gloss (B) of the non-gloss part to the [[A ÷ B) × 1
00], the value was 50%.

Example 2 Chemi Soap # 74 (Ultraviolet absorber: manufactured by Chemipro Kasei) 1
50 parts of epoxy acrylate, 50 parts of acrylate monomer, and 1 part of cardboard (base material 11) on which characters of a medicine outer box (hardening inhibitor-containing printing ink layer 12) are printed with offset ink containing 2% by weight. A coating agent consisting of 5 parts of hydroxycyclohexyl phenyl ketone was applied with a bar coater at 5 g / m ² (coating layer 13 containing no curing inhibitor), and a high-pressure mercury lamp (Eigraphics Co., Ltd., trade name H17-L31X, unit) Output 120W / c
m, emission length 1400mm, lamp output 17,000W)
At 1.0 J / cm ² . The obtained print-coated cardboard paper had a beautiful finish with a three-dimensional appearance in which only the character printing portion had no gloss. The ratio of the gloss (B) of the non-glossy portion to the gloss (A) of the gloss portion ((A ÷ B) × 100) was determined, and the value was 25%.

Example 3 Joints of tile pattern with gravian ink containing 10% by weight of 2,6-di-t-butyl-4-methylphenol (antioxidant) (printing ink layer 12 containing curing inhibitor) On a resin-reinforced paper (base material 11) printed with
0-70 (unsaturated polyester resin: manufactured by Nippon Synthetic Chemical)
5 g of a coating agent comprising 70 parts, 30 parts of styrene monomer and 5 parts of benzoin isopropyl ether was coated with a bar coater.
/ M ² applied (coating layer 13 containing no curing inhibitor),
High pressure mercury lamp (eye graphics Co., Ltd., trade name H1
7-L31X, unit output 120W / cm, emission length 140
1.0mm / 0mm, lamp output 17,000W)
^Two irradiations were performed. The obtained print-coated paper had a beautiful finish with a three-dimensional appearance in which only the joints of the tile pattern disappeared. Gloss of non-glossy part (B) relative to gloss of glossy part (A)
The ratio [(A ÷ B) × 100] was found to be 38%.

Example 4 Chemi Soap # 72 (ultraviolet absorber: manufactured by Chemipro Kasei) 1
Gravure ink containing 5% by weight of wood grain pipe
(Curing inhibitor-containing printing ink layer 12) On a printed resin-reinforced paper (base material 11), 60 parts of Gothrac 750-70 (unsaturated polyester resin: manufactured by Nippon Synthetic Chemical), 40 parts of styrene monomer, 5 parts of benzoin isopropyl ether ,
Acemat OK500 (silica-based matting agent: manufactured by Degussa Japan) 10 g of a coating agent consisting of 1 part with a bar coater
/ M ² and a high-pressure mercury lamp (Eye Graphics Co., Ltd., trade name H22-L41, unit output 160 W / cm,
Irradiation was performed at a light emission length of 1400 mm and a lamp output of 22,000 W) at 1.0 J / cm ² . The resulting printed coated paper had no gloss on the entire surface, and the printed part of the conduit had a beautiful finish with a deeper gloss and a three-dimensional appearance. The ratio of the gloss (B) of the non-glossy portion to the gloss (A) of the gloss portion [(A ÷
B) × 100], the value was 33%.

Example 5 Chemi Soap # 72 (ultraviolet absorbent: manufactured by Chemipro Kasei) 1
Goserac 750-70 (unsaturated polyester resin: Nippon Gohsei) on a resin-reinforced paper (base material 11) printed with a grid pattern (hardening inhibitor-containing printing ink layer 12) having a width of 10 mm with gravure ink containing 5% by weight. Co., Ltd.) 60 parts, styrene monomer 40 parts, benzoin isopropyl ether 5 parts, Acemat OK500 (silica-based matting agent: Degussa Japan) 1 part coated with a bar coater at 10 g / m ² with a high pressure mercury lamp ( Eye Graphics Co., Ltd., product name H17-L31, unit output 120W /
cm, emission length 1400mm, lamp output 17,000
W) at 1.0 J / cm ² . In the obtained printed coated paper, the glossiness of the lattice pattern portion was 20 (incident angle of 60 degrees), the glossiness of the other portions was 40 (same), and the glossiness of the glossy portion (A)
Of the gloss (B) of the non-gloss part to the [[A ÷ B) × 1
00], the value was 50%.

Comparative Example 1 The procedure of Example 1 was repeated except that Chemi Soap # 72 (ultraviolet absorber) was not used in the ink. The resulting printed coated paper had a glossy finish without a three-dimensional effect, including the printed portion of the conduit.

Comparative Example 2 The high-pressure mercury lamp of Example 1 (Eye Graphics Co., Ltd.
Product name H11-L21, unit output 80W / cm, emission length
1400mm, lamp output 11,000W)
High pressure mercury lamp (Matsushita Electric Industrial Co., Ltd., trade name: HTQ40
00, unit output 28W / cm, emission length 1400mm,
1.0 J / cm with a pump output of 4000 W) ²Irradiated. Profit
The printed coated paper has a shiny overall surface, including the conduit printing section.
The finish was unfeeling.

Comparative Example 3 A high-pressure mercury lamp used in Example 5 (eye graphics, trade name H17-L31, unit output: 120 W / c)
m, emission length 1400mm, lamp output 17,000W)
Is a low-power high-pressure mercury lamp (Matsushita Electric Industrial Co., Ltd., trade name: HTQ4000, unit output: 28 W / cm, emission length: 140
1.0 J / c instead of 0 mm, lamp output 4000 W)
m ² was irradiated. The glossiness of the lattice pattern portion of the obtained print-coated paper was 60 (incident angle 60 degrees), and the glossiness of the other portions was 4
The result was 0 (same), the gloss appearance was opposite to that of the present invention, and a result lacking in reproducibility was obtained.

[0031]

(1) According to the present invention, it is possible to form a robust print having a matte portion and a glossy portion rather than a matte portion by a relatively simple process, and it is possible to form a glossy portion and a non-glossy portion. By making the difference in gloss from the part 20% or more, an optical illusion was caused. The matte part was concave, and the glossy part was convex, giving a three-dimensional pattern. . (2) Since the glossy region can be formed to any thickness by painting, the printed matter is more robust than the conventional method using only printing means.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a printed material that gives a sense of unevenness according to the present invention.

FIG. 2 is a cross-sectional view of a conventional printed matter giving a sense of unevenness.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Thin paper (base material) for printing building materials 3 Solid printing layer 4 Picture layer 4A Wood pattern part 4B Joint pattern part 5 Matt OP layer 6 Matte printing layer 7 Glossy printing layer 11 Base material 12 Printing ink containing curing inhibitor Layer 13 Coating layer not containing curing inhibitor 14 Non-glossy 15 Gloss

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H113 AA01 AA06 BA03 BB01 CA08 DA15 DA26 DA53 EA17 FA10 FA36 FA42

Claims (2)

[Claims] 1. A print coating comprising a glossy area and a non-glossy area, wherein the gloss of the non-glossy area is 80 times the gloss of the glossy area.
% Or less. 2. After printing and drying with a printing ink containing a curing inhibitor in a portion where a non-glossy region is to be formed,
An active energy ray-curable coating agent containing no curing inhibitor is applied to both a part where a non-glossy area is to be formed and a part where a glossy (meaning glossier than the non-glossy area) is to be formed. A method for producing a print coating, comprising irradiating an active energy ray having an output of 50 W / cm or more with a gloss in a non-glossy area being 80% or less of a gloss in a glossy area.