JPH07216792A - Strong gloss print - Google Patents

Abstract

(57) [Summary] High-gloss printed matter [Purpose] Has high gloss equivalent to or better than press-coated paper or laminated paper, and possesses high abrasion resistance and water resistance, and has excellent crease resistance. It is excellent, and can be recovered and used as a raw material pulp, and provides a printed matter having strong gloss suitable for commercial art printed matter, publication printed matter, packaging material printed matter, paper container printed matter, and the like. [Structure] A pigment containing kaolin as a main component, a styrene-butadiene copolymer material having a glass transition temperature of 0 ° C. or less of a polymer as an adhesive, and a phosphate esterified starch on a base paper mainly made of wood pulp. And / or acetylated starch absolute dry coating weight 15-25g
/ M ² coating layer surface is printed to form a printing surface,
An overprint varnish coating layer is formed on the printed surface.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to high-gloss printed matter. More specifically, the present invention is mainly applied to commercial art printed matter, publication printed matter, packaging material printed matter, and paper container printed matter, and the gloss and luster (luster) of the printed surface are highly developed, and the abrasion resistance and water resistance are also high. The present invention also relates to a high-gloss printed matter which is resistant to folding and is fragile and can be easily disintegrated in water and reused as a raw material pulp when used or used.

[0002]

2. Description of the Related Art Recently, for commercial, publication printing and printed matter including cover covers for so-called magazines, books, comic magazines (so-called book covers), shopping bags, fashion bags, or paper containers for medicines, cosmetics, etc. As the paper to be used has been highly demanded by consumers, it is strongly demanded that it has abrasion resistance, water resistance, and crease resistance as suitability for use. Further, from the viewpoint of environment and resource protection, it is an important issue that these papers and paper boxes (containers) can be reused as raw materials by a recycling process using water after completing the purpose.

Conventionally, cast coated paper has been known as a paper exhibiting strong gloss. Cast coated papers are widely used in high-quality printed matter, cosmetic boxes, etc. because of their excellent gloss on the white surface. However, cast coated paper has relatively low gloss at the printed part after printing, and also has poor abrasion resistance and water resistance, so blocking due to rubbing stains after printing and contact between printing surfaces (meaning sticking phenomenon) Has the drawback that it is easy to occur.

In order to solve the disadvantages of the cast coated paper according to the prior art described above, measures have been taken to provide a varnishing treatment to provide an overlayer after printing on the cast coated paper. However, since there are countless minute voids in the coating layer of the cast coated paper, the varnished varnish does not remain on the surface of the coating layer and penetrates into the interior of the coating layer, so sufficient surface property is improved. The current situation is that there are none.

Further, in order to solve the drawbacks of the cast coated paper, as disclosed in JP-A-3-260192, the cast coated paper has an ethylenically unsaturated bond in the coating composition. Although a method of using a composite of a polymer obtained by polymerizing a monomer and colloidal silica has been proposed, it is still insufficient in terms of abrasion resistance and water resistance, and the drawbacks of cast coated paper are sufficiently It has not improved yet.

On the other hand, a press-coated paper obtained by applying a large amount of resin to the surface of an ordinary coated paper or a printed matter thereof and finishing the gloss is treated with the above-mentioned resin after printing, so that the glossiness is high. It achieves its objective in obtaining a marked improvement in abrasion resistance and water resistance. However, press coat processing is complicated and has a limited production speed,
It has a drawback that the manufacturing cost is increased due to low productivity.

Further, the laminated paper obtained by laminating and processing plastic films such as polyethylene and polypropylene is also subjected to the above-mentioned surface treatment after printing, and therefore has remarkable glossiness, abrasion resistance and water resistance. You can get improvement. However, the laminated paper laminated with these plastic films does not easily disintegrate in water, and therefore requires a great deal of energy, time, and labor to be recovered and regenerated. It is treated as non-recoverable.

In Japanese Patent Laid-Open No. 3-166, a low-viscosity UV-curable resin liquid is applied to the surface of paper or coated paper, and then the coating film is cured by irradiating it with UV light to achieve a gloss finish. A method is disclosed. However, in this method, since the UV-curable resin liquid used has a low viscosity, the above-mentioned UV-curable resin liquid is applied to the surface of a known coated paper or cast coated paper, and UV-cured. However, the ultraviolet curable resin penetrates inside the coating layer and is not retained on the surface of the coating layer, so that it is not possible to obtain sufficient strong gloss as obtained with press-coated paper or laminated paper. Of course, by increasing the amount of the ultraviolet curable resin to be coated, it is possible to eliminate the above-mentioned drawbacks, but then it becomes easier for the resin layer to break during binding, bag making and box making. Not suitable as it causes another problem.

[Problems to be Solved by the Invention]

As described above, abrasion resistance, water resistance,
Appearance of strong gloss prints that are useful as commercial art prints, publication prints, packaging material prints, and paper container prints by solving all of the problems such as resistance to bending, possibility of recovery and use, and glossiness without complicated processes. Was strongly requested,
At present, there has not been developed anything that can fully satisfy this demand.

In view of the present situation, the present inventors have a high gloss equivalent to or better than that of press-coated paper or laminated paper, have high abrasion resistance and water resistance, and are resistant to folding cracks. As a result of earnest research to obtain a printed matter having excellent glossiness and strong gloss that can be collected and used as spoiled paper without going through complicated steps, the main reason is that the coating layer formed on the base paper has a dense structure. In order to obtain strong gloss and excellent resistance to bending, while suppressing the penetration of the pigment consisting of kaolin as a component and the overprint varnish applied to the printing ink and the printing surface into the coating layer as much as possible,
A coating layer composed of a styrene-butadiene copolymer material having a low glass transition temperature as an adhesive and phosphoric esterified starch and / or acetylated starch is provided on a base paper, and printing is performed on the coated layer. After applying the coating, the coating layer of the overprint varnish is further provided, so that the coating layer is held on the surface of the printing surface, so that the glossiness is further increased and at the same time, the function of the overprint varnish is extremely excellent. Abrasion resistance and water resistance can be imparted, and the coating layer and coating layer used can be easily disintegrated in water by mechanical stirring, so used deinking treatment can be performed on used printed materials. Thus, the raw material pulp can be easily recovered and reused, and finally, it has been found that a strong gloss printed matter that can satisfy the above-mentioned demand can be obtained, and the present invention has been completed. It came to that.

The object of the present invention is that the gloss and shine (gloss) of the printed surface are highly developed, and the print surface has abrasion resistance, water resistance, and crease resistance. It is to provide a strong gloss printed matter that can be easily disintegrated and reused as a raw material pulp.

[0012]

The present invention is directed to a pigment containing kaolin as a main component on a base paper containing wood pulp as a main raw material.
15-25 g / m ² of absolutely dry coating composed of a styrene-butadiene copolymer material having a glass transition temperature of 0 ° C. or less of a polymer as an adhesive, and a phosphate esterified starch and / or an acetylated starch. It is a strong-gloss printed matter characterized in that a layer surface is printed to form a printing surface, and an overprint varnish coating layer is formed on the printing surface.

The base paper used in the present invention is a chemical pulp such as bleached hardwood kraft pulp and bleached softwood kraft pulp,
Using fine pulp, RGP, TMP, and other mechanical pulp as a raw material, a well-known long-mesh multi-cylinder paper machine, long-mesh Yankee paper machine, round-net paper machine, etc. It includes acidic paper such as kraft paper, medium quality paper, and alkaline paper. The base paper contains paper-making auxiliary agents such as paper-strengthening agents, sizing agents, fillers, retention aids, etc., and if necessary, chemicals such as starch, polyvinyl alcohol, polyacrylonitrile, etc. with a size press or gate roll coater. Is applied.

The composition of the coating layer provided on the base paper of the present invention comprises a pigment and an adhesive, of which the pigment plays a particularly important role. That is, in order to develop strong gloss, it is strongly recommended to suppress the penetration of the solvent-based ink used for printing and the overprint varnish applied thereon onto the inside of the coating layer as much as possible and keep it on the surface of the coating layer. Since it is an important requirement for obtaining gloss, it is necessary to use plate-like kaolin as a main component so that the pigments have a dense structure in the coating layer. As the kaolin, for example, special grade kaolin for paper coating, primary and secondary kaolin commercially available from Engelhard Co., ECC Co., Georgia Kaolin Co., Australia, Comarco Co., Australia, etc., alone or appropriately mixed with other pigments. Can be used. Further, as other kaolin, delaminated kaolin obtained by mechanically flaking kaolin particles having a laminated structure can be blended.

On the other hand, when the kaolin particles are calcined at 900 ° C., the particles whose surfaces are melted are re-aggregated, and when incorporated into the coating layer, calcined kaolin, which tends to have a structure rich in porosity, has a dense structure in the present invention. It is not suitable for use because it is important to form a coating layer. Also, Japanese Patent Laid-Open No. 62-2673
No. 71 and Japanese Patent Application Laid-Open No. 63-278986, and the polyelectrolyte kaolin selected from quaternary ammonium polymer salt, diallyl ammonium chloride and polyamine is used in an amount of 0.03 to 0. 15%
Amount of 0.77 added to kaolin and processed
For the same reason as described above, kaolin having a sedimentation volume of ˜0.95 ml / g and having a bulky structure such as calcined clay by such a chemical treatment (eg, Exilon manufactured by Engelhard) is also printed. It is not suitable because it is not possible to suppress the penetration of the ink and overprint varnish into the coating layer.

On the other hand, the pigment which can be used in combination with kaolin for the present invention is not particularly limited, and general pigments such as common heavy calcium carbonate, light calcium carbonate, aluminum hydroxide, satin white, titanium dioxide and plastic pigments can be used. Mention may be made of inorganic pigments and organic pigments,
It can be appropriately used as necessary, but as described above, it is necessary to limit it to such an extent that it does not hinder the formation of a dense coating layer, that is, 10% by weight or less, preferably 7% by weight or less of the total pigment.

The water-insoluble styrene-butadiene copolymer material having a glass transition temperature point of the polymer as an adhesive used in the present invention in the range of 0 ° C. or lower is, for example, an aromatic vinyl monomer or an aliphatic conjugate. Aliphatic conjugated diene-based when copolymerizing a monomer composed of a diene-based monomer, methacrylic acid, an ethylenically unsaturated acid monomer and another copolymerizable monomer by a known method It is obtained by appropriately adjusting the usage ratio of the monomers. The lower limit of the glass transition temperature is determined by the content of butadiene, and is about −55 ° C. although not within the estimated range, and if it is lower than this temperature, roll stain or blocking during coating tends to occur, which is preferable. Absent. Examples of the aliphatic conjugated diene-based monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like. It is produced at 30 to 55% by weight based on the absolute dry weight of all monomers, and the composition itself is not strictly limited as long as the glass transition temperature of the polymer satisfies the above conditions. Such a copolymer substance is emulsified and dispersed by a known method and used as a latex or an emulsion.

The glass transition temperature of the styrene-butadiene copolymer material has a great influence on the film-forming property in the coating layer, that is, the number of voids in the coating layer, and it rapidly increases when the glass transition temperature exceeds 0 ° C. It becomes impossible to suppress the permeation of printing ink and overprint varnish into the inside of the coating layer by increasing voids. On the other hand, the glass transition temperature is 0
When a styrene-butadiene copolymer substance having a temperature of ℃ or less is used as an adhesive, the pigment, the polymer, and the polymer are continuously and firmly bonded to each other due to the excellent film-forming property of the polymer. Can be sufficiently suppressed from penetrating into the coating layer.

Further, the glass transition temperature of the styrene-butadiene copolymer material is greatly involved in the resistance to folding, which is one of the important qualities of the present invention, and the styrene-butadiene copolymer weight exceeding 0 ° C. When the coalescing substance is blended, the coating layer is brittle and cracks are likely to occur at the folded portion, whereas when a styrene-butadiene copolymer substance having a glass transition temperature of 0 ° C. or less is used as an adhesive in the present invention. Since the coating layer is flexible, it is possible to impart extremely excellent folding crack resistance to the coated paper.

Examples of the styrene-butadiene copolymer material satisfying the requirements for the present invention include JSR0596 (gas transition temperature: -51 ° C) and JSR0692 (glass transition temperature: commercially available from Nippon Synthetic Rubber Industry Co., Ltd.). −
12 ° C), JSR0619 (glass transition temperature: -4 ° C)
The amount of such a styrene-butadiene-based copolymer substance added to the coating layer makes the printability of the coating layer good, and the penetration of printing ink and overprint varnish into the coating layer is sufficient. In order to suppress the above, it is preferable to add 10 to 30% by weight based on the absolute dry weight of the pigment.

Furthermore, the phosphoric acid esterified starch and / or the acetylated starch used as the adhesive in the present invention is excellent in suppressing the penetration of the solvent-based printing ink and overprint varnish into the coating layer. It exhibits a barrier effect. For example, as a phosphoric acid esterified starch, Neil gum A85 commercially available from Matsutani Chemical Co., Ltd., and as an acetylated starch, National Starch and Chemical Co. National 78-commercially available. 0338 etc. can be mentioned. These may be used alone or as a mixture, but they function together with the pigment and the styrene-butadiene copolymer material to improve printability, and to the inside of the coating layer of the printing ink and overprint varnish. In order to achieve this, it is preferable to add 0.5 to 10% by weight based on the weight of the pigment. Furthermore, a dispersant, a water resistance agent, a lubricant,
An auxiliary chemical such as an antifoaming agent, a coloring agent, an antiseptic agent, etc. may be optionally mixed to obtain a coating material by a known preparation method.

The coating composition obtained as described above is applied to the base paper in a known coating equipment arbitrarily selected from a size press, a gate roll coater, a bar coater, a roll coater, an air knife coater, a blade coater and the like. It is coated on one or both sides.

In the present invention, the coating amount of the coating layer is extremely important for obtaining the desired quality, and the coating amount on one side should be 15-25 g / m ² in terms of absolute dry weight. is necessary. If the coating amount is less than 15 g / m ² , the coating layer cannot sufficiently cover the surface of the base paper and the gloss of the printed matter becomes insufficient. On the other hand, when the coating amount exceeds 25 g / m ² and increases, no matter how flexible the coating layer is formed, it may result in a decrease in the folding property, which is an important quality. .

The coated paper coated in this manner is dried by a known drier, directly printed, and then overprint varnished. This gives a high gloss, but in order to make the high gloss effect even more noticeable, the surface of the coated paper before printing is smoothed by surface finishing equipment such as soft calender and super calender. Is good. The glossiness of the coated paper for the present invention is such that the gloss and crease resistance developed after printing and applying the overprint varnish are properly adjusted,
The value measured by a specular gloss meter having an incident light flux / reflected light flux of 75 ° / 75 ° is finished in a range of 20 to 70%. The higher the glossiness of the coated paper, the higher the glossiness after applying the overprint varnish, but if the glossiness value is less than 20%, the glossiness of the product will be insufficient, and the glossiness will exceed 70% and become excessive. If it is increased, the folding crack resistance may be deteriorated. Therefore, the surface of the coated paper before printing is maintained within the above-mentioned range of glossiness.

As described above, the coated paper whose glossiness is adjusted is printed, but at the time of printing, the original (characters / design), printing method, ink and printing conditions (printing pressure, speed, etc.) There is no limitation to the above, and normally, lithographic, intaglio and letterpress printing such as offset printing, gravure printing and flexo printing, which are used for commercial art printed matter, publication printed matter, packaging material printed matter and paper container printed matter, can be freely applied according to the purpose. It

After the surface of the coated paper is printed in this way, an overprint varnish is further applied to the printed surface by a known method known as a glossing treatment. Of course, it is important that the overprint varnish does not penetrate into the coating layer and stays on the surface. In the present invention, kaolin as a pigment constituting the coating composition and low glass as an adhesive are used. This is achieved by the interaction of the styrene-butadiene based copolymer material at the transition temperature with the phosphorylated and / or acetylated starch. This makes it possible to further enhance the glossiness and at the same time impart extremely excellent abrasion resistance and water resistance to the product by the function of the overprint varnish.

For the overprint varnish, a thermosetting varnish,
Many known varnishes, such as UV curable varnishes, can be used in the strong gloss prints of this invention. However, since the types of such overprint varnishes are too wide, a UV curable varnish that is widely used for drawing overprint varnishes will be described below as an example. The UV-curable varnish contains, as essential components, at least one monomer or prepolymer having a radical-polymerizable unsaturated double bond and a sensitizer, and various additives such as a resin colorant and wax are required as the essential components. It is compounded according to.

That is, as the above-mentioned monomer having a radical-polymerizable unsaturated double bond, one obtained by esterifying (meth) acrylic acid with an alcohol such as ethylene glycol, polyethylene glycol, trimethylolpropane, pentaerythritol, Examples thereof include those obtained by esterifying allyl alcohol with phthalic acid, maleic acid, isocyanuric acid, etc., and those obtained by esterifying glycidyl (meth) acrylate. As the prepolymer, an epoxy resin esterified with (meth) acrylic acid, a hydroxyl group-containing resin esterified with (meth) acrylic acid, a hydroxyl group-containing alkyd, a polyester resin or an acrylic resin (meth) is used. ) Acrylic acid-polyol esterified product is crosslinked with a diisocyanate compound.

Further, as the sensitizer, benzoin, benzoin methyl ether, benzoin ethyl ether,
Benzoin butyl ether, 2-allylbenzoin, 2
-Benzoin sensitizers such as chlorobenzoin, benzophenone, p-methylbenzoin, Michler's ketone, ketone sensitizers such as acetophenone, azo sensitizers such as azobisisobutyronitrile, anthraquinone, 2-chloroanthraquinone, Examples thereof include quinone-based sensitizers such as phenanthrene and sulfide-based sensitizers such as tetramethylthiuram monosulfide. These sensitizers can be appropriately selected and used in combination. The blending amount of the sensitizer is adjusted within the range of 0.1 to 2.5% by weight based on the total solid content of the resin liquid used.

The UV-curable varnish can be adjusted to a desired viscosity by adding a known organic solvent, and water or a mixture of water and an organic solvent may be appropriately used instead of the organic solvent. can do. Further, as the ultraviolet irradiation, a high pressure, medium pressure or low pressure of an ordinary mercury lamp and a metal halide lamp is used, and the type, size, number, etc. thereof are appropriately adjusted depending on the coating amount of the ultraviolet curable varnish, the curing speed, etc. To be done. In this way, for the purpose of the present invention, it is possible to appropriately select and use the ultraviolet-curable varnish composed of the respective components according to various uses.

The UV-curable varnish is applied by a known offset printing machine, roll coater, gravure coater,
It can be performed using a flexo coater, a screen coater, or the like. These coating devices are used by being directly connected to the printing machine or installed separately from the printing machine for sheet or web processing. In that case, the coating amount is
In the present invention, the absolute dry weight is adjusted within the range of 0.3 to 10 g / m ² . If the coating amount is less than 0.3 g / m ² ,
It is difficult to obtain the strong gloss desired by the present invention.
A coating amount of more than 0 g / m ² is not suitable because there is a concern that the folding crack resistance may decrease.

As described above, a pigment containing kaolin as a main component, a styrene-butadiene copolymer material having a low glass transition temperature of a polymer as an adhesive, and a phosphoric acid esterified ester on a base paper mainly made of wood pulp. By providing a dense and highly continuous coating layer composed of starch and / or acetylated starch, the penetration of printing ink and overprint varnish into the coating layer is suppressed,
It can be retained on the surface, which makes it possible to obtain a high gloss. Furthermore, the styrene-butadiene copolymer material having a low glass transition temperature of the polymer forms a flexible coating layer, and thus has a remarkable effect on the crease resistance. In addition, by providing the coating layer of the overprint varnish on the printing surface formed on the surface of the coating layer, the present invention has high gloss and desired abrasion resistance and water resistance, and re-disaggregation in water. Thus, it is possible to provide an unprecedented strong gloss printed matter that can be collected and reused.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the following,% means% by weight.

Example 1 Content of talc (trademark: SPE, manufactured by Arakawa Chemical Industry Co., Ltd.) per dry weight of pulp material consisting of 20% freeness 470 mlcsf softwood bleached kraft pulp and 80% freeness 470 mlcsf hardwood bleached kraft pulp Of reinforced rosin size 0.3% and sulfuric acid band 2%, and a base paper having a rice basis weight of 100 g / m ^{2 was made} by a fourdrinier multi-cylinder paper machine. The Oken smoothness of the base paper was 45 seconds. Next, 100% of kaolin (trademark: HT clay, manufactured by Engelhard, USA) for paper coating was used as a pigment, and 2.5% of an acrylic dispersant (trademark: Poise 520, manufactured by Kao) was used per weight of the dry pigment. Add and disperse at a solid content concentration of 50% by using a high-speed deleter, and then use a styrene-butadiene copolymer latex (trademark: JSR-0619, glass transition temperature -4 ° C, made by Japan Synthetic Rubber) as an adhesive agent in terms of solid content. In the same manner, 10% based on the weight of the absolutely dry pigment and 3% of phosphoric esterified starch (trademark: Neil gum A85, manufactured by Matsutani Chemical Co., Ltd.) were similarly added and mixed, and a wetting agent (trademark: Nopcoat C-108, manufactured by San Nopco) was further added. 1.0%, antifoaming agent (trademark: DEF122N
S, San Nopco) 0.03%, fluorescent dye (trademark: F
oL, manufactured by Nippon Kayaku Co., Ltd.) was added and mixed, and the pH was adjusted to 8.5 with a caustic soda solution having a concentration of 5% to 60.
A coating liquid with a% solids concentration was produced.

This coating liquid was coated on the above-mentioned base paper with a blade coater at a coating speed of 600 m / min so that the dry weight on one side was 20.0 g / m ² , and the moisture was dried with a known dryer. It was dried until the content was 5.5%. The coated paper thus obtained is passed through a super calender and subjected to pressure contact treatment to finish the surface of the coated paper to 42% with a specular gloss value of incident light flux / reflected light flux = 75 ° / 75 °. Manufactured. Next, this coated paper was printed using a Heidelberg KOR type offset printing machine (ink: Super Apex (Indigo), manufactured by Dainippon Ink & Chemicals, Inc.), and after 24 hours, the acrylic UV curable varnish ( Product name: Seika Beam K-4085, manufactured by Dainichi Seika) was applied with an isopropyl alcohol solution by a gravure coater and then immediately irradiated with ultraviolet rays to obtain a strongly glossy printed matter.
The coating amount at this time was 2 g / m ² in terms of absolute dry weight. In addition, the acrylic UV curable varnish was directly applied in the same manner without printing on the surface of the coated paper to obtain a strong gloss paper.

The white paper surface gloss of the obtained high-gloss paper and the print surface gloss of high-gloss printing, abrasion resistance (rubbing suitability), water resistance, crease resistance, and disintegration property of paper were tested by the following methods, evaluated. Test method (1) White paper gloss About obtained strong gloss paper (without printing) Incident luminous flux / reflected luminous flux / reflected luminous flux by a gloss meter manufactured by Murakami Color Research Laboratory =
The specular gloss of 75 ° / 75 ° was measured. (2) Printed surface gloss The specular glossiness of the incident light flux / reflected light flux / reflected light flux = 75 ° / 75 ° was measured with a gloss meter manufactured by Murakami Color Research Laboratory for the obtained strongly glossy printed matter (printed). (3) Abrasion resistance (rubbing suitability) The printed portion of a high-gloss printed matter is 50 g / in using a friction tester.
The scratches and stains on the printed surface after rubbing 20 times with a load of cm ² were visually observed and judged according to the following criteria. ⊚: No scratches or stains are seen on the rubbed surfaces. ◯: Scratches and dirt are generated on the rubbed surface at a level that is not noticeable, but there is no problem in practical use Δ: Scratches or dirt are clearly visible on the rubbed surface, but can be used for practical purposes . X: Scratches and stains are remarkably generated on the rubbed surfaces, and the surfaces cannot be used. ∘∘, ∘∘, and ∘x indicate the middle of each.

(4) Water-resistant strong-gloss printed matter was immersed in water for 10 minutes, then surface water was wiped off with a filter paper, two gloss-finished surfaces were superposed on each other, and a load of 100 g / cm ² was applied to the surface. The state of the paper surface after being left for a period of time was visually observed and judged according to the following criteria. ◯: Paper surfaces do not stick to each other at all Δ: Paper surfaces stick to each other partially and partially block ×: Paper surfaces stick to each other and blocking occurs on all surfaces ○ △ and △ × are respectively Shows the middle of. (5) Folding and cracking resistance The product was folded with the printed surface of the strong glossy printed product on the outside, and a metal roll having a weight of 2 kg was rolled to make a crease, and the crease portion was visually observed and judged according to the following criteria. ◯: The coating layer at the creases was not cracked at all Δ: The coating layer was partially cracked, but there was no problem in practical use ×: Marked creases were not practically acceptable ○ △ and △ × are in between Indicates.

(6) Re-disintegration property A pulp disintegrator manufactured by Kumagai Riki Kogyo (according to JIS 8209) was used. A sample of strong gloss printed matter cut into 1 cm squares was taken in an absolute dry weight of 24 g, put in a container of a disintegrator together with 2000 g of water (20 ° C.), and stirred for 3 minutes for disaggregation treatment. Then, the pulp slurry after re-deagglomeration in this way was diluted to a concentration of 0.6%, and a deinking agent (trademark: DI-610, manufactured by Kao) was added to the pulp in an absolute dry weight of 0.3%. , Model Floatator (Trademark: F
Deinking treatment was performed at a temperature of 20 ° C. for about 15 minutes using a W-1K type manufactured by Kyoshin Sangyo. The pulp slurry after the deinking treatment was handmade, and it was visually observed whether or not there were undisaggregated substances (film pieces, paper pieces, etc.) on the handmade paper, and it was judged according to the following criteria. ◯: The handmade paper does not contain any undisintegrated matter at all, and is a uniform paper (good redisintegration property). Δ: The handmade paper contains a very small amount of undisintegrated matter,
It is a practically usable level. X: The handmade paper contains a considerable amount of undisintegrated matter and cannot be put to practical use (no redisintegration). ○ △ and △ × show the middle of each.

Example 2 The surface of the coated paper for printing has an incident light flux / reflected light flux = 75 ° / 7.
A coated paper for printing was prepared in the same manner as in Example 1 except that it was finished with a super calendar so that the specular gloss value at 5 ° was 65%. A glossy print was produced and its quality was evaluated.

Example 3 A coated paper for printing was prepared in the same manner as in Example 1 except that the coated amount of the coated paper for printing was set to 16 g / m ^2. Paper and strong gloss prints were produced and their quality was evaluated.

Example 4 A coated paper for printing was prepared in the same manner as in Example 1 except that the coated amount of the coated paper for printing was 23 g / m ² , and printing and varnishing treatment were performed to obtain a strong gloss paper. And a high-gloss printed matter were manufactured and their quality was evaluated.

Example 5 Instead of the phosphate esterified starch in the coating composition of Example 1, acetylated starch (trademark: National 70) was used.
(0338, manufactured by National Starch and Chemical Co., Ltd.) was used to prepare a coated paper for printing in the same manner as in Example 1, followed by printing and varnishing treatment to produce a high-gloss paper and a high-gloss printed matter. Evaluated the quality.

Example 6 Instead of the styrene-butadiene copolymer latex (trademark: JSR-0619, -4 ° C) in the coating composition of Example 1, a styrene-butadiene copolymer latex (trademark: JSR-) was used. 0596, glass transition temperature: −51 ° C., manufactured by Japan Synthetic Rubber), except that a coated paper for printing was prepared in the same manner as in Example 1 and subjected to printing and varnish processing to obtain a strong gloss paper and a strong gloss. Prints were produced and their quality was evaluated.

Example 7 Pigment Kaolin (trademark: HT in the coating composition of Example 1)
A coated paper for printing was prepared in the same manner as in Example 1 except that kaolin (trademark: HT clay) / ground calcium carbonate (trademark: Softon 2200, manufactured by Shiraishi Calcium) = 93/7 was used instead of clay. The high-gloss paper and the high-gloss print paper were manufactured, printed, and varnished, and their quality was evaluated.

Comparative Example 1 Example 1 was repeated except that a commercially available cast coated paper (Mirror Coat K Platinum, basis weight 127.9 g / m ² , manufactured by Shin Oji Paper Co., Ltd.) was used as the coated paper for printing. Printing and varnish processing were performed to produce high-gloss paper and high-gloss printed matter, and the quality was evaluated.

Comparative Example 2 A commercially available coated paper (New OK coat,
Printing and varnishing treatments were carried out in the same manner as in Example 1 except that a rice basis weight of 127.9 g / m ² (made by Shin Oji Paper Co., Ltd.) was used to produce strong gloss paper and strong gloss printed matter, evaluated.

Comparative Example 3 A coated paper for printing was prepared in the same manner as in Example 1 except that the coated amount of the coated paper for printing was set to 13 g / m ^2. Paper and strong gloss prints were produced and their quality was evaluated.

Comparative Example 4 A coated paper for printing was prepared in the same manner as in Example 1 except that the coated amount of the coated paper for printing was 27 g / m ^2, and printing and varnishing treatment were performed to obtain a strong gloss. Paper and strong gloss prints were produced and their quality was evaluated.

Comparative Example 5 Same as Example 1 except that oxidation modified starch (trademark: Oji Ace, Oji Corn Starch) was used in place of the phosphate esterified starch in the coating composition of Example 1. Then, a coated paper for printing was prepared, and printing and varnishing treatments were carried out to produce a high-gloss paper and a high-gloss printed matter, and the quality thereof was evaluated.

Comparative Example 6 Instead of the styrene-butadiene copolymer latex (trademark: JSR-0619, -4 ° C.) in the coating composition of Example 1, a styrene-butadiene copolymer latex (trademark: JSR-) was used. 0687, glass transition temperature: + 2 ° C., made by Japan Synthetic Rubber), except that a coated paper for printing was prepared in the same manner as in Example 1 and subjected to printing and varnishing treatment to obtain a strong gloss paper and a strong gloss print. Was manufactured and its quality was evaluated.

Comparative Example 7 Pigment Kaolin (trademark: HT in the coating composition of Example 1)
A coated paper for printing was prepared in the same manner as in Example 1 except that kaolin (trademark: HT clay) / heavy calcium carbonate (trademark: Softon 2200, manufactured by Shiraishi Calcium) = 87/13 was used instead of clay. It was produced, printed and varnished to produce high-gloss paper and high-gloss printed matter, and the quality was evaluated.

Comparative Example 8 Laminated paper was manufactured by melting melted low-density polyethylene manufactured by Sumitomo Chemical without using a varnishing treatment on the coated paper and the printed matter of Comparative Example 2 and evaluated their quality. When the cross section of this laminated paper was observed with a scanning electron microscope, the thickness of the polyethylene film layer was 23 microns.

Comparative Example 9 The coated paper and the printed material of Comparative Example 2 were not varnished, but were coated with a vinylene acetate adhesive, a polypropylene film having a thickness of 15 μm was applied, and two rolls having a flat surface were used. By press-bonding, so-called dry laminated paper was manufactured and its quality was evaluated.

The results obtained in Examples 1 to 7 and Comparative Examples 1 to 9 are shown in Table 1.

[0055]

[Table 1]

As is clear from Table 1, the high-gloss printed matter according to the present invention has a high gloss comparable to that of polyethylene-laminated paper on both the white paper and the printing surface, and has important qualities such as abrasion resistance, water resistance and folding. Since it has excellent cracking suitability and can be easily disintegrated in water, it can be reused as a raw material pulp (Examples 1 to 7). On the other hand, when cast coated paper or ordinary coated paper, which is called high-gloss paper, is used, the abrasion resistance, water resistance and re-disintegration property are excellent, but the permeation of printing ink and varnish into the coating layer is significantly desired. In addition to the lack of glossiness, the coating layer was so hard that creases occurred (Comparative Examples 1 and 2). When the coating amount is small, the gloss is inferior (Comparative Example 3), and when the coating amount is large, the bending cracking property is inferior, which is not suitable (Comparative Example 4). Furthermore, when the composition of the coating layer does not meet the requirements of the present invention, problems arise in gloss, abrasion resistance and water resistance, and it cannot be put to practical use (Comparative Examples 5 to 7). In addition, as a matter of course, the conventional laminated paper, which is laminated with a film to express gloss, cannot be disintegrated in water at all and cannot be practically reused as a raw material pulp (Comparative Examples 8 to 8). 9).

[0056]

INDUSTRIAL APPLICABILITY The present invention exhibits extremely high gloss and is excellent in important properties such as abrasion resistance, water resistance and cracking resistance, and can be easily disintegrated in water so that it can be reused as a raw material pulp. , Commercial art print, publication print,
An effect of providing a strong gloss printed matter that can be suitably used for a packaging material printed matter, a paper container printed matter, and the like.

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Claims (1)

[Claims] 1. A pigment containing kaolin as a main component, a styrene-butadiene copolymer material having a glass transition temperature of 0 ° C. or less of a polymer as an adhesive, and a phosphoric acid ester on a base paper mainly made of wood pulp. 15-25 g of absolute dryness composed of modified starch and / or acetylated starch
/ M ² coating layer surface is printed to form a printing surface,
A strong-gloss printed matter having an overprint varnish coating layer formed on the printed surface.