JP2007126789A - Colored paper or colored paperboard - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored paper or colored paperboard free from discoloration by friction, not fouling other articles by contact. <P>SOLUTION: The invention relates to the colored paper or colored paperboard colored by a dye and/or a pigment wherein at least one surface is coated with a mixture of a chemical substantially comprising a polymeric compound of a sulfonate compound, with a water soluble resin. The preferable amount of the coating is 0.2-5.0 g/m<SP>2</SP>as a solid content and the ratio of the chemical substantially comprising the polymeric compound and the water soluble resin is 1:5-1:50. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to colored paper or colored paperboard, and more particularly to colored paper or colored paperboard that is dark and difficult to lose color.

  In addition, the fiber used below is a fiber used for clothing etc., and when saying the fiber used with paper and pulp, it says pulp fiber.

  Conventionally, colored paper or colored paperboard that is darkly colored is sometimes used to enhance the cosmetics of posters, flyers, wrapping papers, and packaging boxes so that they are more noticeable. In order to increase the color tone, the amount of dye or pigment added should be increased. However, when handling colored paper or colored paperboard or transporting or carrying the package in proportion to the increase in the added amount, There is a problem that the color of colored paper or colored paperboard adheres due to rubbing between the package and a person's clothes or packages.

  As a means for improving abrasion resistance and preventing such color fading in colored paper or colored paperboard, a method of printing OP varnish is generally known.

  Further, as a method for improving the fastness to friction of a textile product, a method in which a methyl hydrodiene polysiloxane emulsion is applied to the surface and then subjected to a low temperature plasma treatment is known (for example, see Patent Document 1).

  In addition, in a fibrous sheet-like material made of pulp, as a method for obtaining a strong color against water, a cationic direct dye is applied to the surface of a sheet made by adding a polyamidoamine / epoxy wetting strong agent, A method is also known in which, after drying, an aqueous solution of tannic acid is applied and dried by hot air to fix (see, for example, Patent Document 2).

In addition, it is advantageous to add a sulfonic acid ester of polycarboxylic acid as a wetting agent to the dyeing bath in the dyeing method of the fiber material by padding (see, for example, Patent Document 3), and a refined fiber of synthetic fiber. In the dyed paper made by adding and mixing the dye / pigment carrier carrying the dye / pigment to the paper stock, if acrylic fiber or polyester fiber is used as the refined fiber, the polymer accelerator acts as a molecular terminal. Techniques such as a sulfonic acid ester group entering, acidification, adsorption of a cationic dye, ionic bonding, and dyeing with a cationic dye in a clear color are known (for example, see Patent Document 4).
Japanese Patent Laid-Open No. 5-140874 JP-A-8-209551 Japanese Unexamined Patent Publication No. Sho 63-309585 Japanese Patent Laid-Open No. 9-158090

  However, the conventional method of printing OP varnish has a problem that the texture of the paper is impaired because a film is formed on the surface of colored paper or colored paperboard. In addition, there is a problem that surface cracks occur when bent.

  In addition, the method described in Patent Document 1 is a method that can be employed in textile products and the like, and requires low-temperature plasma treatment, or is not practically applicable to the manufacturing process of colored paper or colored paperboard with a high production rate. There is. Moreover, the technique disclosed in Patent Document 2 is a method for improving the water fastness, and does not improve the color abrasion resistance. The techniques described in Patent Document 3 and Patent Document 4 involve sulfonic acid esters, but they are used as wetting agents during fiber dyeing and dyeing acrylic synthetic fibers. It cannot be applied to prevent color fading on the surface of colored paper or colored paperboard using pulp fibers.

  In view of the above-described conventional problems, an object of the present invention is to provide colored paper or colored paperboard that is dark in color, does not lose color due to friction, and does not stain other articles by contact.

  The colored paper or colored paperboard of the present invention is colored with a dye and / or pigment, and at least one surface is coated with a mixture of a chemical compound mainly composed of a polymer compound composed of a sulfonate ester compound and a water-soluble resin. It is characterized by being.

  In order to solve the problem that color fading occurs due to friction in dark colored paper or colored paperboard, the present inventors have conducted extensive research on various means, and as a result, sulfonic acid used in antiwear chemicals. It has been found that this problem can be solved by applying a mixture of a chemical compound mainly composed of an ester compound and a water-soluble resin to the surface. In particular, by mixing and using a water-soluble resin that is not used for dyeing textile products, the wear resistance of the polymer compound when applied to the surface is improved, and a polymer compound comprising a sulfonate compound is provided. It has been found that the wear resistance effect can be prevented from being reduced by aging or thermal deterioration. As a result, for example, even when heat is applied when color paperboard is laminated with a corrugator, the wear resistance effect of the polymer compound composed of the sulfonic acid ester compound is not lost, so that the effect is particularly remarkable (dyeing fastness level 3 or higher). ). In addition, by applying a mixture containing a chemical compound mainly composed of a polymer compound composed of a sulfonic acid ester compound and a water-soluble resin on the surface, the chemical yield is better than the method of internally adding the mixture. Further, since the solidification of the surface does not occur as in the case of using OP varnish, the surface crack or the like when the colored paper or colored paperboard is folded does not occur.

Moreover, the coating amount of the mixed solution of the chemical comprising the polymer compound composed of the sulfonic acid ester compound as a main component and the water-soluble resin is 0.2 to 5.0 g / m ² in terms of solid content, more preferably 0.00. It is preferable that 5 to 2.0 g / m ^{2 is} applied. If it is less than 0.2 g / m ² , the color fading prevention effect is reduced, and if it exceeds 5.0 g / m ² , drying in the production process becomes worse and costs increase, which is not preferable. It is preferable that the mixture of the chemical mainly composed of a polymer compound composed of a sulfonic acid ester compound and the water-soluble resin is mixed at a solid content ratio of 1: 5 to 1:50. More preferably, it is 1: 8 to 1:15. Even if the mixing ratio of the water-soluble resin is smaller or larger than this range, the dyeing fastness is lowered and the color fading easily occurs.

  In addition, it is preferable that the result of the dyeing fastness test specified in JIS-L0849 is grade 3 or higher using a contamination gray scale specified in JIS-L0805.

  In particular, in the case of dark colored paper or colored paperboard having a lightness L value of 60 or less based on JIS-Z8722 and JIS-Z8730, the effect of the present invention is more effective because the color is easily lost due to the dark color. Demonstrated.

  According to the present invention, at least one surface of colored paper or colored paperboard is coated with a mixture of a chemical compound mainly composed of a polymer compound composed of a sulfonic acid ester compound and a water-soluble resin. However, it is possible to obtain colored paper or colored paperboard that does not discolor due to friction and does not contaminate other articles by contact.

  Hereinafter, embodiments of the colored paper or colored paperboard of the present invention will be described in detail.

  The colored paper or colored paperboard of the present invention is formed by combining a single layer or a plurality of paper layers. The raw material is made of virgin pulp such as bleached kraft pulp and unbleached kraft pulp and various waste paper pulp such as high-quality waste paper as appropriate.

Such colored paper or colored paperboard is made by a known paper machine such as a long paper machine or a circular paper machine.

  As a dye for coloring, a basic dye having a beautiful color and a large color density can be used together with an anionic direct dye or a cationic direct dye. The order of addition of these dyes is that the anionic direct dye is added at the initial stage, the pH is adjusted by adding a sulfuric acid band, and then the basic dye and the necessary fixing agent are added. In addition, it is preferable to add a cationic direct dye having high dyeing property, high exhaustibility, and good fastness to water and fastness to sunlight. Further, by adding a pigment, it is possible to realize coloring with a deeper color and higher weather resistance.

Further, in the making of colored paper or colored paperboard, the water absorption measured according to JIS-P8140 is adjusted so as to be 15 to 150 g / m ² at a contact time of 120 seconds. More preferably, it is 30-100 g / m < ² >. That is, if it is less than 15 g / m ² , it is not possible to uniformly apply a mixed solution of a chemical mainly composed of a polymer compound composed of a sulfonic acid ester compound and a water-soluble resin in a subsequent coating step, and color fading The prevention effect is uneven. On the other hand, if it exceeds 150 g / m ² , the mixed solution of the chemical compound mainly composed of a polymer compound composed of a sulfonic acid ester compound and a water-soluble resin will permeate into the inside of the paper and the effect of coating will be reduced. become. The water absorption is adjusted with a known sizing agent such as an acidic rosin sizing agent, a neutral rosin sizing agent, or an alkyl ketene dimer.

  In the coating process after the pre-dryer of the paper machine on the surface of the colored paper or colored paperboard that has been dark-colored and made as described above, a chemical mainly composed of a polymer compound composed of a sulfonate compound Apply a mixture of water-soluble resin. Specifically, as a chemical mainly composed of a polymer compound composed of a sulfonate ester compound, the product name “Vortex RF” (manufactured by Meisei Chemical Industry Co., Ltd.), developed as a friction fastness improver for textile products. Are preferably used. This antiwear chemical is composed of a special polymer compound composed of a sulfonate compound and an aqueous emulsion of polyethylene wax.

  In addition, polyvinyl alcohol (PVA), polyacrylamide resin (PAA), and starch can be suitably used as the water-soluble resin used in combination with the above-mentioned antiwear chemical.

The coating amount of the mixture of the antiwear chemical and the water-soluble resin is preferably 0.2 to 5.0 g / m ² in terms of solid content. If it is less than 0.2 g / m ² , the effect is not sufficiently obtained, and when the paper surface is rubbed, there is a possibility that other articles that come into contact with the color will be stained and soiled. On the other hand, if it exceeds 5.0 g / m ² , the drying property in the production process is deteriorated or the cost is increased. Further, the mixture of the antiwear chemical and the water-soluble resin is preferably mixed at a solid content ratio of 1: 5 to 1:50. More preferably, it is 1: 8 to 1:15. Even if the mixing ratio of the water-soluble resin is smaller or larger than this range, the dyeing fastness is lowered and the color fading easily occurs.

  After applying the mixture of the wear-resistant chemical and the water-soluble resin as described above, drying with a dryer and imparting paper smoothness with a calendar part completes colored paper or colored paperboard.

  Next, some examples and comparative examples of the present invention will be described.

Example 1
A raw material slurry for the surface layer (first layer) was prepared by blending 40% by weight of hardwood bleached kraft pulp (LBKP, freeness 450 ml CSF) and 60% by weight of high-quality waste paper pulp (freeness 350 ml CSF). The following colorants, fixing agents and sizing agents were added. The amount of the colorant added was adjusted so that the hue of the surface layer based on JIS-Z8722 was (L, a, b) = (58.0, 34.0, 0.6).
In addition, when there is no description in particular, addition amount represents the solid content addition amount per pulp ton.
Anionic direct dye: “TOA Red 2BP” (manufactured by Toa Kasei)
"Carta Violet 3B70"
(Manufactured by Clariant Japan Co., Ltd.)
Fixing agent: Sulfuric acid band 4.0%
Sizing agent: Acidic rosin sizing agent 0.4%

Further, a raw material slurry for the back layer (second layer to fifth layer) was prepared using 100% of the old paper waste paper pulp, and the following sizing agent and fixing agent were added to the raw material slurry for the back layer.
Sizing agent: 0.25% acidic rosin sizing agent
Fixing agent: Sulfuric acid band 4.0%

Using these raw material slurries, the paper layers of the surface layer and the back layer of 4 layers are made together by a circular net five-layer paper machine, and the basis weight is 170 g / m ² and the water absorption is 100 g / m ² with a contact time of 120 seconds. A paperboard with a five-layer structure was made, and then the coating part after the pre-dryer was subjected to wear resistance chemical: “Vortex RF” (manufactured by Meisei Chemical Co., Ltd.) and water-soluble resin: polyvinyl alcohol 1: 9. The coating solution mixed at the ratio was applied at a solid content of 1.0 g / m ² and dried with an after drier. Thereafter, a calendar process was performed with a machine calendar at a linear pressure of 30 kgf / cm to produce a colored paperboard.

(Examples 2, 3, 4, 5)
Example 1 except that the coating amount of the solid content of the coating solution was changed to 0.2 g / m ² , 0.5 g / m ² , 2.0 g / m ² , and 5.0 g / m ² , respectively. Similarly, a colored paperboard was prepared.

(Examples 6 and 7)
The coating amount of the solid content of the coating solution, respectively 0.1 g / m ^2, except for changing the 10.0 g / m ^2, was prepared in the same manner as in color paperboard Example 1.

(Examples 8, 9, 10, 11)
A colored paperboard was prepared in the same manner as in Example 1 except that the ratio of the antiwear chemical in the coating solution to the water-soluble resin was changed to 1: 5, 1: 8, 1:15, 1:50.

(Examples 12 and 13)
A colored paperboard was prepared in the same manner as in Example 1 except that the ratio of the abrasion-resistant chemical of the coating liquid to the water-soluble resin was changed to 1: 1 and 1:60.

(Examples 14 and 15)
A colored paperboard was prepared in the same manner as in Example 1 except that the L value (brightness) of the colored paperboard was changed to 55 and 70.

(Examples 16 and 17)
The sizing agent addition amount of the surface layer is 0.6%, the water absorption is 15 g / m ² at a contact time of 120 seconds, the sizing agent addition amount of the surface layer is 0.5%, and the water absorption is 120 hours of contact time. A colored paperboard was produced in the same manner as in Example 1 except that the second set was 30 g / m ² .

(Example 18)
Example 1 except that the sizing agent addition amount of the surface layer was 0.2%, the sizing agent addition amount of the back layer was 0.15%, and the water absorption was 150 g / m ² at a contact time of 120 seconds. Similarly, a colored paperboard was prepared.

Example 19
A colored paperboard was prepared in the same manner as in Example 1 except that the amount of sizing agent added to the surface layer was 0.7% and the water absorption was 10 g / m ² at a contact time of 120 seconds.

(Example 20) Except that the sizing agent addition amount of the surface layer was 0.15%, the sizing agent addition amount of the back layer was 0.15%, and the water absorption was 200 g / m ² at a contact time of 120 seconds. Produced a colored paperboard in the same manner as in Example 1.

(Example 21)
A colored paperboard was prepared in the same manner as in Example 1 except that the water-soluble resin was polyacrylamide (PAA).

(Example 22)
A colored paperboard was produced in the same manner as in Example 1 except that starch was used as the water-soluble resin.

(Example 23)
A colored paperboard was prepared in the same manner as in Example 21 except that the solid content was 0.2 g / m ² .

(Example 24)
A colored paperboard was prepared in the same manner as in Example 22 except that the solid content was 0.2 g / m ² .

(Example 25)
A colored paperboard was prepared in the same manner as in Example 21 except that the solid content was 5.0 g / m ² .

(Example 26)
A colored paperboard was prepared in the same manner as in Example 22 except that the solid content was 5.0 g / m ² .

(Comparative Example 1)
A colored paperboard was prepared in the same manner as in Example 1 except that the mixture of antiwear chemical and water-soluble resin was not applied.

(Comparative Example 2)
A colored paperboard was prepared in the same manner as in Example 1 except that only the antiwear chemical was applied so that the coating amount of the solid content was 1.0 g / m ² .

(Comparative Example 3)
A colored paperboard was prepared in the same manner as in Example 1 except that only the water-soluble resin was used so that the solid content was 1.0 g / m ² .

  For the color paperboards of Examples 1 to 21 and Comparative Examples 1 to 3 described above, in order to see color fading due to frictional contact with the surface, a dyeing fastness test against friction was performed in accordance with JIS-L0849. The color grade was measured using a based soiling gray scale.

上記実施例１〜２６及び比較例１〜３について、塗工液における耐摩耗薬品と水溶性樹脂の混合比率と、塗工液（固形分）の塗工量と、明度と、吸水度と、染色堅牢度の測定等級の測定結果を表１に示した。

About the said Examples 1-26 and Comparative Examples 1-3, the mixing ratio of the antiwear chemical | medical agent and water-soluble resin in a coating liquid, the coating amount of a coating liquid (solid content), the brightness, and a water absorption degree, Table 1 shows the measurement results of the measurement grade of dyeing fastness.

In Example 1, the coating amount of the wear resistant chemical is 1.0 g / m ² , and the fastness is 5th grade. In Example 2, the coating amount is 0.2 g / m ² , which is the lower limit of the specified range of the present invention, and the fastness is the fourth grade. Examples 3 and 4, the coated amount each was 0.5 g / m ² and 2.0 g / m ^2, fastness has a preferred value 4-5. In Example 5, the coating amount is 5.0 g / m ² , which is the upper limit of the specified range of the present invention, and the fastness is grade 5. In Example 6, the coating amount is as low as 0.1 g / m ² , the ability to prevent discoloration is low, and the fastness is third grade. In Example 7, the coating amount was as high as 10.0 g / m ² and the fastness was as good as grade 5. However, the dry state in the manufacturing process was deteriorated and the cost was increased.

  In Example 8, the ratio of the wear-resistant chemicals to the water-soluble resin was 1: 5, and the concentration of the wear-resistant chemicals was increased, so the fastness was grade 5. In Examples 9 and 10, the ratios are 1: 8 and 1:15, respectively, and the fastness is 5 and a preferable value. In Example 11, since the ratio was 1:50 and the concentration of antiwear chemicals was low, the fastness was grade 3. In Example 12, since the ratio between the wear-resistant chemical and the water-soluble resin was 1: 1, there was little water-soluble resin and the fastness was grade 4, while conversely, Example 13 was set to 1:60, so the wear-resistant chemical. There are few, and the fastness is the second grade.

  In Examples 14 and 15 in which the lightness (L value) is changed to 55 and 70, the same effect is obtained.

In Example 16 in which the water absorption was as low as 15 g / m ² , the fastness was grade 4, and in Example 17 in which the water absorption was raised to 30 g / m ² , it was in grade 5. In Example 18 in which the water absorption was increased to 150 g / m ² and in Example 19 in which the water absorption was further decreased to 10 g / m ² , the fastness was tertiary, and in Example 20 in which the water absorption was further increased to 200 g / m ^2. Degree has fallen to 3rd grade.

In Examples 21 to 26, in which polyacrylamide and starch were used as the water-soluble resin and the coating amount was changed to 0.2 g / m ² and 5.0 g / m ² , the same effect was obtained. Yes.

On the other hand, in Comparative Example 1, neither the wear-resistant chemical nor the water-soluble resin is applied, and the fastness is lower than the first grade and the fourth grade of Example 2. In Comparative Example 2, 1.0 g / m ^{2 of} only the wear-resistant chemical is applied, and the fastness is only in the second grade. In Comparative Example 3, only 1.0 g / m ^{2 of} water-soluble resin was applied, and the fastness was as low as second grade.

Claims (4)

  In paper or paperboard colored with dyes and / or pigments, at least one surface is coated with a mixture of a chemical compound mainly composed of a polymer compound composed of a sulfonate compound and a water-soluble resin. Colored paper or colored paperboard. 2. A mixture of a chemical comprising a polymer compound comprising a sulfonic acid ester compound as a main component and a water-soluble resin is applied in a solid content of 0.2 to 5.0 g / m ^2. Colored paper or colored paperboard.   The colored paper or color according to claim 1, wherein the abrasion resistance according to the dyeing fastness test specified in JIS-L0849 is grade 3 or more using a gray scale for contamination specified in JIS-L0805. Paperboard.   The colored paper according to any one of claims 1 to 3, wherein the lightness L value based on JIS-Z8722 and JIS-Z8730 of colored paper or colored paperboard colored with a dye and / or pigment is 60 or less Colored paperboard.