JP2017008434A - Blue color-based fluorescent colored paper and process for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a blue color-based fluorescent colored paper that has vivid color tone with no dullness.SOLUTION: Provided is a blue color-based fluorescent colored paper produced by continuously adding and mixing a predetermined amount of at least one of the following (A) and (B) as a coloring agent together with a pulp raw material into a mixing box 1 or a machine chest 2 in a pulp raw material adjustment step supplying the raw material to a paper-making machine, to fix the coloring agent to the pulp raw material, and by subjecting said dyed pulp raw material to paper-making, and in which the color L* value of said colored paper is 60 or more, the a* value is -10 or less, the b* value is -23 or less, and the fluorescence intensity is 0.10 or more. (A) fluorescent dye and dye. (B) fluorescent pigment.SELECTED DRAWING: Figure 1

Description

  TECHNICAL FIELD The present invention relates to a blue fluorescent colored paper and a method for producing the same, and more particularly to a blue fluorescent colored paper and a method for producing the same that enable a vivid hue without dullness. .

  Conventionally, as a method for producing colored paper that makes paper by adding dye to pulp material, a certain amount of dye is continuously added to the mixing box or chest of the pulp material adjustment process that supplies a certain amount of pulp slurry to the paper machine. A method for fixing a dye to pulp is known. However, in this method, since only the dye is added, the color texture is increased, but there is a drawback that the hue is not vivid.

  In addition, as a method of producing a colored paper having a rich and clear color tone and good water resistance, an anionic direct dye, a sulfuric acid band, a basic dye, a fixing agent, and a cationic direct dye are added in this order. A method for producing colored paper in which pulp is subjected to batch dyeing and paper making has been proposed (Patent Document 1: Japanese Patent Application Laid-Open No. 2006-183169).

  However, in the case of the production method in which the anionic direct dye, sulfate band, basic dye, fixing agent, and cationic direct dye of this Patent Document 1 are added in this order and the pulp is batch-dyed, it has a dense and clear color tone. In addition, although it is a batch dyeing method and a fixing time is high because of a long fixing time, and it is advantageous for producing a dark color, since the toning can be performed only for each batch, Fine adjustment is difficult, and it takes time to adjust to the target hue, and a paper machine with a large amount of production has a problem that a large amount of colored loss paper is generated.

  In addition, as a completely new fluorescent coloring paper which has not been heretofore, there has been proposed a fluorescent coloring paper characterized in that a fluorescent substance is dispersed in a paper sheet together with a water-soluble polymer substance and a filler (Patent Document 2: JP 2000-345495 A). However, in the case of the invention described in Patent Document 2, fluorescent aggregated particles emit light in a star shape on the entire paper surface, and an unprecedented fluorescent coloring paper can be obtained, but a vivid hue without dullness cannot be obtained. There was a problem.

  Furthermore, as a new and improved production method which is excellent in fixing dyes and pigments to paper, can be uniformly dyed, and can be easily dyed in various hues, the number average fiber length is 0.05 to 0.3 mm, After adding and mixing a facial cleansing carrier, in which a dye / pigment is supported on fine fibrillated cellulose having an axial ratio of 50 or more and a water retention value of 250% or more, to a stock prepared using paper pulp as a main material There is also a proposal of a method for producing a dyed paper, which is characterized in that the paper stock is made (Patent Document 3: Japanese Patent Laid-Open No. 7-324300).

  In the case of the method of Patent Document 3, excellent fixability to paper is possible, and uniform dyeing is possible. However, when using deinked waste paper pulp, high quality paper, medium quality paper, lower grade paper, newspaper, Since the selected waste paper such as leaflets and magazines and the unsorted waste paper in which these are mixed are used as raw materials, the average fiber length and the axial ratio are naturally various. In order to make this a specific fiber length, it must be refined by applying a mechanical shearing force or using a chemical treatment in combination with shearing, which requires new equipment and power. Therefore, there arises a problem that the miniaturization cannot be easily achieved.

  In addition, as a colored paperboard with reduced color fading when wetted with water, a dye, pigment, water-resistant agent and water-repellent agent are internally added to the first paper layer located on the surface of the plurality of paper layers. A characteristic colored paperboard has been proposed (Patent Document 4: Japanese Patent Laid-Open No. 2014-43653). However, in the case of the invention described in Patent Document 4, specifically, a dark color paperboard having a lightness of 60 or less is intended. According to this invention, a vivid hue without dullness cannot be obtained, In addition, since only the first paper layer on the surface is colored, the hue is different between the front and back of the paper, and there is a problem that a fluorescent colored paper having a vivid hue with no dullness cannot be obtained as a whole.

JP 2006-183169 A JP 2000-345495 A JP 7-324300 A JP 2014-43653 A

  As described above, in the case of the conventionally proposed colored paper or fluorescent color developing paper, the hue is not vivid, the hue is difficult to finely adjust, a large amount of colored loss paper is generated, or the raw material is used. There is a problem that the shearing process for making the unsorted used paper into a specific fiber length is expensive, and the miniaturization cannot be easily performed.

  The present invention has been made to solve such problems in the conventional production method, and there is no such problem, and a blue-type fluorescent colored paper capable of obtaining a vivid hue without dullness and a production method thereof It is a problem to provide.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have conceived that they contain fluorescent dyes and dyes or fluorescent pigments, and have completed the present invention. That is, the invention according to claim 1 for solving the above-mentioned problem is a fluorescent colored paper containing at least one of the following (A) and (B) as a pulp raw material and a colorant, and colored blue. A blue-based fluorescent colored paper having a color L * value of 60 or more, an a * value of −10 or less, a b * value of −23 or less, and a fluorescence intensity of 0.10 or more. It is.
(A) Fluorescent dye and dye (B) Fluorescent pigment

  In one embodiment, the colorant is internally added and colored, the pulp raw material is deinked waste paper pulp and / or bleached kraft pulp, a sulfuric acid band is internally added to the pulp raw material, and further fixing It is supposed to contain an agent.

  Moreover, the invention which concerns on Claim 6 for solving the said subject is said (A), (B) as a coloring agent with a pulp raw material in the mixing box or machine chest of the pulp raw material adjustment process which supplies a raw material to a paper machine. ) At least one of them is continuously added and mixed, or a certain amount of the colorant is continuously added together with the pulp raw material in a static mixer provided in the middle of the pulp raw material piping leading to the mixing box or machine chest. Then, the colorant is fixed by mixing, and the dyed pulp raw material is made into paper, which is a method for producing blue fluorescent colored paper.

  In one embodiment, the L * value, a * value, and b * value of the colored paper after paper making are measured with an online color meter installed after the paper machine dryer part, and the colorant is selected according to the measurement result. The amount added to the mixing box or the machine chest is adjusted. Further, a complementary color can be obtained by providing a size press step and adding one or more selected from dyes, fluorescent dyes and fluorescent pigments to the coating liquid applied in the size press.

  The fluorescent colored paper according to the present invention is colored blue by containing a colorant having fluorescence. The color L * value is 60 or more, the a * value is −10 or less, and the b * value is −. 23 or less and the fluorescence intensity is 0.10 or more, the brightness is high, the blue is strong, and a vivid hue without dullness is expressed. According to the method of the present invention, such a feature is obtained. This has the effect of efficiently producing a paper having blue-based fluorescent coloring.

It is a simplified diagram showing a machine white water system flow for carrying out the method for producing fluorescent colored paper according to the present invention.

  The paper having fluorescent coloring according to the present invention is a fluorescent colored paper containing at least a dye and a fluorescent dye as a pulp raw material and a colorant, or containing at least a fluorescent pigment as a pulp raw material and a colorant. It is characterized by this.

  In the present invention, the pulp used as a raw material is not particularly limited. For example, bleached kraft pulp can be used to make fluorescent fine paper. As the bleached kraft pulp, the tree species is not particularly limited, and LBKP and NBKP can be used alone or in combination as appropriate. Moreover, in addition to bleached kraft pulp, waste paper pulp can also be used. The content of the used paper pulp affects the fluorescence intensity described later, and the used paper pulp has an effect of increasing the fluorescence intensity.

  As waste paper pulp, deinked pulp can be used, and as deinked pulp, selected waste paper such as high quality paper, medium quality paper, lower grade paper, newspaper, flyer, magazine, etc. and unselected waste paper mixed with these are used as raw materials. And deinked pulp can be used. Thus, in the present invention, a single type of pulp may be used, or a mixture of a plurality of types of pulp may be used. Although it does not specifically limit, it is desirable to mix | blend waste paper pulp 10weight% or more in the total pulp solid content.

  In the present invention, the dye used as the colorant has the effect of increasing the color and the texture of the color. The dye has a property of being dissolved in water, oil, or an organic solvent, and a direct dye, a basic dye, an amphoteric dye, or the like can be used. In particular, a blue dye is preferably used. For example, “Kayacel Turkis AGF Liq200” (manufactured by Nippon Kayaku Co., Ltd.), “Kayafect Turkis RN Liq150” (manufactured by Nippon Kayaku Co., Ltd.), “Kayafect Blue F Liq400” (Manufactured by Nippon Kayaku Co., Ltd.), “TOA Turkis MP Liq” (manufactured by Toa Kasei Co., Ltd.) and the like can be mentioned, but are not limited thereto.

  In addition, the fluorescent dye used as a colorant in the present invention has an effect of increasing vividness. The fluorescent dye is a dye having a function of selectively absorbing invisible short-wavelength ultraviolet rays in sunlight, and converting it into visible purple to blue light and emitting it. Examples thereof include, but are not limited to, “Kaya Hall TAC Liq” (manufactured by Nippon Kayaku Co., Ltd.) and “Lycopher FTS Liq” (manufactured by Arkroma Co., Ltd.).

  In addition, the fluorescent pigment used as a colorant in the present invention has the effect of coloring and increasing vividness. Fluorescent pigments are colored by photoluminescence (a process in which a substance absorbs light and then re-emits light). The pigment is a powder that is insoluble or hardly soluble in water, oil, or an organic solvent and exists in a dispersed state. The pigment includes an organic pigment and an inorganic pigment, and any of them can be used, but it is preferable to use an organic pigment from the viewpoint of excellent light resistance and vivid colors. In particular, it is preferable to use a blue fluorescent pigment, and examples thereof include an aqueous dispersion type “SW-128Blue” (manufactured by Sinloihi Co., Ltd.), but are not limited thereto.

  In the present invention, by using a combination of a dye and a fluorescent dye, a vivid color tone can be obtained as compared with the case of a dye alone. In addition to the dye and the fluorescent dye, a fluorescent pigment may be used in combination. Further, the fluorescent pigment may be used alone, or may be used in combination with one or both of the fluorescent dye and the dye.

  The addition amount may be adjusted so as to obtain a desired blue-based fluorescent coloring, and is not particularly limited. For example, the dye is 0.01% or more of pulp (preferably 1.3 to 1.3 of pulp). 2.5%), fluorescent dye is 0.01% or more of pulp (preferably 0.5 to 2.0% of pulp), and fluorescent pigment is 1% or more of pulp (preferably 20 to 40% of pulp). It is preferable to do. These addition amounts can be appropriately adjusted. In addition, the addition amount of the pigment, dye, and fluorescent dye here is addition in solid.

  As a blue hue, the color L * value of the colored paper is 60 or more, the a * value is −10 or less, the b * value is −23 or less, and the fluorescence intensity is 0.10 or more. When the color L * value is less than 60, the lightness is lowered and the color tone becomes dark. When the a * value exceeds -10, the red color becomes strong. When the b * value exceeds -23, the blue color becomes weak. It will be lacking. Furthermore, even when the fluorescence intensity is less than 0.10, the image is not vivid. In the present invention, since the color L * value, a * value, b * value, and fluorescence intensity are in the above-mentioned ranges, a more vivid blue-based fluorescent colored paper without dullness is obtained.

  In the present invention, it is preferable to contain a fixing agent in order to obtain a clear hue. By virtue of the optimum blending of the colorant and the fixing agent, a vivid hue without dullness can be obtained. Examples of the fixing agent include dimethylamine / ammonia / epichlorohydrin polycondensate. The addition ratio is preferably 0.01 to 3.5% added to pulp, but can be adjusted as appropriate. The addition of the fixing agent here is a solid addition.

  In the case of the present invention, a sulfuric acid band can be added in order to further improve the fixing effect of the colorant to the pulp fiber. The addition ratio is preferably 0.5 to 2% to pulp, but can be adjusted as appropriate. The addition of the sulfuric acid band here is a solid addition.

  A preferred method for producing the fluorescent colored paper of the present invention is to add and mix a certain amount of colorant together with the pulp raw material in the mixing box or machine chest of the pulp raw material adjusting step for supplying the raw material to the paper machine. Alternatively, the colorant is added to the pulp raw material by continuously adding and mixing a certain amount of colorant together with the pulp raw material in a static mixer provided in the middle of the pulp raw material piping leading to the mixing box or machine chest. Is made, and the dyed pulp raw material is made into paper. The fixing agent is desirably added at the same timing as the colorant. Moreover, when using a coloring agent together, it is desirable to add these at the same timing.

  FIG. 1 shows a paper machine raw material flow used in the present invention. For example, as shown therein, a pulp raw material, which is a mixed slurry of waste paper pulp and bleached kraft pulp, is charged into a mixing box 1 and the mixing is performed. In the box, the pulp raw material and the colorant are mixed to dye the pulp raw material.

  Or although not shown in figure, a static mixer is arranged in the middle of the pulp raw material piping which enters the mixing box 1 or the machine chest 2, and the pulp raw material and a coloring agent are mixed in the static mixer, and the said pulp raw material dyes | stains. Is done. When mixing with a mixing box or a static mixer in this way, the pulp raw material and the colorant are mixed better, and a dyed mixture without unevenness is generated.

  The dyed pulp raw material is sent to the machine chest 2 where a paper strength enhancer is added as appropriate, and a sizing agent is added as appropriate in the seed box 3. Then, a filler is added while being sent to the cleaner 5 via the fan pump 4, dust is removed from the cleaner 5 via the screen 6, and then sent to the inlet 7 of the paper machine.

  In one embodiment, the color adjustment is performed by measuring the L * value, a * value, and b * value of the colored paper after paper making using an on-line color meter installed after the paper machine dryer part. Fine adjustment of the amount of the colorant added to the mixing box 1 and the machine chest 2 is performed. Furthermore, it is possible to adjust the L * value, the a * value, and the b * value with higher accuracy by adjusting the humidity of the product rolled up on the reel part and measuring it with a color difference meter.

  Further, by providing a size press step and adding one or more selected from dyes, fluorescent dyes and fluorescent pigments to the coating liquid applied in the size press, complementary colors can be obtained. The coating solution may be water alone, or may contain water-soluble polymers such as starch, polyvinyl alcohol, polyacrylamide, and cellulose, and various copolymers (latex) such as styrene / butadiene. . These are used individually or in mixture of 2 or more types. In the present invention, water or starch is preferred. The addition rate of the dye, fluorescent dye, and fluorescent pigment in this case is not particularly limited, but a concentration of about 0.01 to 10% with respect to water is preferable. Furthermore, the product rolled up on the reel part can be conditioned and measured with a color difference meter to adjust the hue and color tone with higher accuracy.

  As described above, in the case of obtaining the fluorescent colored paper of the present invention, the case where a colorant is internally added has been described as a preferred embodiment, but the present invention is not limited to the internal addition, and these may be added and added. Also good. However, the internal addition is preferable because the cut end of the colored paper cut surface can be uniformly dyed. The method of external addition is not particularly limited, for example, a method of applying a coating liquid containing a colorant in a size press process, a method of applying a coating liquid containing a colorant by providing a separate coating process, etc. Is mentioned. In addition, when a fluorescent dye or a dye is used, there is a method in which either one of the fluorescent dye or the dye is internally added to the base paper and the other is externally added. The coating liquid can contain organic or inorganic pigments and additives.

  Further, when there is a difference between the front and back in hue and color tone, one or more selected from dyes, fluorescent dyes and fluorescent pigments can be externally added to the surface to be adjusted. The addition rate is preferably 0.1 to 0.4% with respect to water, but can be adjusted as appropriate.

  In addition to the above, the fluorescent colored paper of the present invention can be subjected to various treatments according to a conventionally known method for producing paper such as calendar finishing.

In the fluorescent colored paper of the present invention, the basis weight may be set according to the intended use and is not particularly limited, but is preferably about 30 to 205 g / m ² . Uses include printing paper, envelopes, sticky notes, POP advertisements, and the like, but are not limited to these, and can be used in a wide range of applications by taking advantage of vivid hues without dullness.

[Example]
Hereinafter, the present invention will be described more specifically with reference to examples, but it goes without saying that the present invention is not limited to the following examples. In the present specification, the numerical range is described as including the end points.

[Example 1]
In the mixing box, together with pulp raw materials (LBKP 90% by weight: freeness 350 cc, waste paper pulp 10% by weight: freeness 280 cc, pulp concentration 3%), a blue dye (trade name “Kayacel Turkis AGF Liq200” manufactured by Nippon Kayaku Co., Ltd. 5% pulp), fluorescent dye (trade name “Kayahol TAC Liq” manufactured by Nippon Kayaku Co., Ltd. 1.0% pulp), and sulfuric acid band (1.5% pulp) are continuously added and mixed. The pulp raw material dye | stained by (1) was supplied to the paper machine, and the fluorescent colored paper was manufactured so that it might become basic weight 100.0g / m < ² >.

[Example 2]
The blue dye is replaced by the trade name “Kayafect Turkis RN Liq150” manufactured by Nippon Kayaku Co., Ltd. (1.6% of pulp), and a fixing agent (trade name “Jetfix PA-401” manufactured by Satita Chemical Co., Ltd.) A fluorescent colored paper was produced in the same manner as in Example 1 except that 3% of pulp was added.

[Example 3]
A fluorescent colored paper was produced in the same manner as in Example 1 except that the blue dye was changed to the trade name “TOA Turkis MP Liq” manufactured by Toa Kasei Co., Ltd. (1.3% pulp).

[Example 4]
The blue dye is replaced by the trade name “TOA Turkis MP Liq” manufactured by Toa Kasei Co., Ltd. (1.3% pulp), and the fluorescent dye is replaced by the trade name “Lyco Far FTS Liq” manufactured by Arkroma Co., Ltd. (1.0% pulp) ) Was used in the same manner as in Example 1 except that it was replaced with ().

[Example 5]
Instead of blue dyes and fluorescent dyes, a blue fluorescent pigment (trade name “SW-128Blue” manufactured by Sinloihi Co., Ltd., 30% of pulp) is added, and a fixing agent (trade name “Jetfix PA-401” Satoda Chemical Co., Ltd.) A fluorescent colored paper was produced in the same manner as in Example 1 except that 1.0% of pulp manufactured by the company was added.

[Comparative Example 1]
A fluorescent colored paper was produced in the same manner as in Example 1 except that no fluorescent dye was added.
[Comparative Example 2]
Fluorescent colored paper was produced in the same manner as in Example 2 except that no fluorescent dye was added.
[Comparative Example 3]
A fluorescent colored paper was produced in the same manner as in Example 3 except that no fluorescent dye was added.
[Comparative Example 4]
In the mixing box, together with pulp raw materials (LBKP 85 wt%: freeness 350 cc, waste paper pulp 15 wt%: freeness 280 cc, pulp concentration 3%), a blue dye (trade name “Kayacel Turkis AGF Liq200” manufactured by Nippon Kayaku Co., Ltd. 5% pulp), blue dye (trade name “Kayafect Blue F Liq400” made by Nippon Kayaku Co., Ltd. 7.5% pulp) and sulfuric acid band (2.0% pulp) Thus, the dyed pulp raw material was supplied to a paper machine to produce fluorescent colored paper so that the basis weight was 76.7 g / m ² .

For each colored paper produced in the above examples and comparative examples, the surface L * value, a * value, b * value, and fluorescence intensity measurement values measured using a whiteness meter manufactured by Murakami Color Research Laboratory Co., Ltd. Table 1 shows. The evaluation of clarity in the table is by visual inspection,
(Poor) 1 <4 (Excellent)
Light blue Blue is strong and dull Based on vivid standards. The hue L * value, a * value, and b * value were measured with a whiteness meter CMS-35SPX manufactured by Murakami Color Research Laboratory Co., Ltd., and the color difference value (UV-IN) was measured according to JISP8150. The strength was measured according to JISP8148 with the same whiteness meter manufactured by Murakami Color Research Laboratory.

[Table 1]

  The results of the measurement are as shown in Table 1. As is clear from the results, in Examples 1 to 5 in which a dye and a fluorescent dye as a colorant, or a fluorescent pigment as a colorant are blended, both are fluorescent dyes or fluorescent pigments. It can be seen that the intensity of fluorescence is higher than that of Comparative Examples 1 to 3 lacking, and a bright blue color tone is obtained. Further, in the case of Comparative Example 4 in which two types of dyes are used in combination, the b * value indicating yellow is slightly large, so the yellowish color is strong, and the bright blue color of Examples 1 to 5 is bright. The hue of the system is not expressed.

  Although the present invention has been described in some detail with its most preferred embodiments, it will be apparent that a wide variety of different embodiments can be constructed without departing from the spirit and scope of the invention. Accordingly, the invention is not limited to that particular embodiment, except as limited in the appended claims.

1 Mixing box 2 Machine chest 3 Seed box 4 Fan pump 5 Cleaner 6 Screen 7 Inlet

Claims (8)

Fluorescent colored paper containing a pulp raw material and at least one of the following (A) and (B) as a colorant and colored blue: the colored paper has a color L * value of 60 or more and an a * value Is a blue-based fluorescent colored paper characterized by having a b * value of -23 or less and a fluorescence intensity of 0.10 or more.
(A) Dye and fluorescent dye (B) Fluorescent pigment   The fluorescent colored paper according to claim 1, which is colored by internally adding the colorant.   The fluorescent colored paper according to claim 1 or 2, wherein the pulp raw material is deinked waste paper pulp and / or bleached kraft pulp.   The fluorescent colored paper according to any one of claims 1 to 3, wherein a sulfuric acid band is internally added to the pulp raw material.   The fluorescent colored paper according to any one of claims 1 to 4, further comprising a fixing agent. In the mixing box or machine chest of the pulp material adjustment process for supplying the raw material to the paper machine, the pulp material and the following (A), (B) as a colorant are continuously added and mixed, or The colorant is fixed to the pulp raw material by continuously adding and mixing a certain amount of the colorant together with the pulp raw material in a static mixer provided in the middle of the pulp raw material piping leading to the mixing box or machine chest, A process for producing a blue-based fluorescent colored paper, wherein the dyed pulp raw material is made.
(A) Dye and fluorescent dye (B) Fluorescent pigment   The L * value, a * value, and b * value of the colored paper after paper making are measured by an on-line color meter installed after the paper machine dryer part, and depending on the measurement result, the mixing box of the colorant or the The method for producing fluorescently colored paper according to claim 6, wherein the amount of addition to the machine chest is adjusted.   8. The method according to claim 6, wherein the method includes a size press step and complements the coating liquid applied in the size press by adding one or more selected from the dye, fluorescent dye, and fluorescent pigment. Method for producing fluorescent colored paper.