JP2015232196A - Fluorescent colored paper and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide fluorescent colored paper having a bright color phase without dullness.SOLUTION: Fluorescent colored paper contains at least a pulp raw material, a fluorescent pigment and a fixing agent and is produced by supplying continuously specified amounts of the fluorescent pigment and the fixing agent, together with the pulp raw material, to a mixing box 1 or a machine chest 2 for supplying a raw material to a paper-making machine in a pulp raw material adjustment step and mixing to fix the fluorescent pigment to the pulp raw material and paper-making the dyed pulp raw material. The color L* value, the a* value, the b* value and the range of the fluorescence intensity are set according to a coloring color.

Description

  The present invention relates to a fluorescent colored paper and a method for producing the same, and more specifically, a fluorescent colored paper that enables expression of a vivid hue without dullness by blending a fluorescent pigment and a fixing agent, and the same It relates to a manufacturing method.

  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.

JP 2006-183169 A JP 2000-345495 A JP 7-324300 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 unselected waste paper into a specific fiber length is expensive and cannot be easily performed.

  Therefore, the present invention has been made to solve such problems in the conventional production method, and there is no such problems as described above, and furthermore, a fluorescent colored paper capable of obtaining a vivid hue without dullness and its production It is an object to provide a method.

  As a result of intensive studies to solve the above problems, the present inventors have conceived that they contain a fluorescent pigment and a fixing agent, and have completed the present invention. That is, the invention according to claim 1 for solving the above problem is a fluorescent colored paper containing at least a pulp raw material, a fluorescent pigment, and a fixing agent and colored.

  In one embodiment, the fluorescent pigment and the fixing agent are internally added and colored, the pulp raw material is deinked waste paper pulp and / or bleached kraft pulp, and a sulfuric acid band is internally added to the pulp raw material. And further contains a dye. A color L * value, a * value, b * value and a range of fluorescence intensity are set according to the color to be colored.

  Further, the invention according to claim 11 for solving the above-mentioned problem is that a certain amount of fluorescent pigment and fixing agent are added 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. Continuously add and mix, or add and mix a certain amount of fluorescent pigment and fixing agent together with the pulp raw material in a static mixer placed in the middle of the pulp raw material piping leading to the mixing box or machine chest A method for producing fluorescent colored paper, wherein the fluorescent pigment is fixed by the above method and the dyed pulp raw material is paper-made.

  In one embodiment, the color tone of the colored paper after paper making is measured with an on-line color meter installed after the paper machine dryer part, and depending on the measurement result, the mixing box or the machine of the fixing agent and the fluorescent pigment Adjust the amount added to the chest. Further, a complementary color can be obtained by providing a size press step and adding the fluorescent pigment and / or dye to the coating liquid applied in the size press.

  Since the fluorescent colored paper according to the present invention is colored by containing a fluorescent pigment, it exhibits a vivid hue without dullness. According to the method of the present invention, such a feature is obtained. There is an effect that it is possible to efficiently produce paper having fluorescent coloring such as orange, green, pink, and yellow.

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 a pulp raw material, a fluorescent pigment and a fixing agent and colored.

  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 waste paper pulp affects the fluorescence intensity described later. 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 not particularly limited, it is desirable to mix 10% or more of waste paper pulp.

  In the present invention, the fluorescent pigment is characterized in that it has an effect of increasing vividness. By containing the fluorescent pigment, it is possible to obtain a vivid hue without dullness. The fluorescent pigment used in the present invention is for coloring, and is a powder that is insoluble or hardly soluble in water, oil, or an organic solvent and exists in a dispersed state. Fluorescent pigments include organic fluorescent pigments and inorganic fluorescent pigments, both of which can be used, but it is preferable to use organic fluorescent pigments from the viewpoint of excellent light resistance and vivid colors. In the present invention, a dye can be added for the purpose of complementary color. The dye has the effect of increasing the texture of the color. As the dye, a direct dye, a basic dye, or the like can be used, but a basic dye is preferably used.

  Hereinafter, orange, green, pink, and yellow colored paper will be described as an example of specific embodiments of the present invention. However, the present invention is not limited to these color systems, and various colors may be used. Fluorescent colored paper having a desired color can be obtained by using these fluorescent pigments alone or in combination, and further using dyes of various colors as necessary.

  In order to obtain orange-colored paper, an orange fluorescent pigment, a pink fluorescent pigment, and a yellow dye can be used alone or in combination. In particular, since a bright orange coloring is obtained, it is more preferable to use a pink fluorescent pigment and a yellow dye in combination. As an orange fluorescent pigment, for example, an aqueous dispersion type “SW-114 Orange” (manufactured by Sinloi Corporation), and as a pink fluorescent pigment, for example, an aqueous dispersion type “SW-117 Pink” (manufactured by Sinloi Corporation), yellow Examples of the dye include, but are not limited to, a methine-based cationic dye “TOA Basic Yellow G (L)” (manufactured by Toa Kasei Co., Ltd.) and the like.

  The addition amount may be adjusted so as to obtain a desired orange-based fluorescent coloring, and is not particularly limited. For example, when a pink fluorescent pigment and a yellow dye are used in combination, a pink fluorescent pigment is used. Is preferably 3 to 7% (preferably 5% or more), and the yellow dye is preferably 0.48 to 1.28% (preferably 0.5% or more). When an orange fluorescent pigment and a yellow dye are used in combination, it is preferable to add 10% or more of the orange fluorescent pigment and 0.01% or more of the yellow dye to the pulp. These addition amounts can be appropriately adjusted. In addition, the addition amount of the fluorescent pigment and dye here, and the addition amount of the fluorescent pigment and dye described below are addition in solid form.

  As the orange hue, it is preferable that the color L * value of the colored paper is 77 or more, the a * value is 21 or more, the b * value is 47 or more, and the fluorescence intensity is 0.07 or more. When the color L * value is less than 77, the lightness is lowered and the color tone becomes dark. When the a * value is less than 21, the red color becomes weak. When the b * value is less than 47, the yellow color becomes weak. It will be lacking. Further, even when the fluorescence intensity is less than 0.07, 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 orange fluorescent colored paper without dullness is obtained.

  In order to obtain green colored paper, a green fluorescent pigment, a yellow fluorescent pigment, and a blue fluorescent pigment can be used alone or in combination. In particular, it is more preferable to use yellow and blue fluorescent pigments together because vivid green-based coloring is obtained. Examples of the green fluorescent pigment include water dispersion type “SW-112Geen” (manufactured by Sinloihi), and examples of the yellow fluorescent pigment include water dispersion type “SW-115 Lemon Yellow” (manufactured by Sinloihi), blue fluorescence. Examples of the pigment include, but are not limited to, an aqueous dispersion type “SW-128Blue” (manufactured by Sinloihi Co., Ltd.).

  The addition amount is not particularly limited as long as it is adjusted so that a desired green fluorescent coloring can be obtained, but the green fluorescent pigment is 1% or more of the pulp, the yellow fluorescent pigment is 3 to 8% of the pulp, blue The fluorescent pigment is preferably 1 to 2% of pulp. In addition, a dye can be used in combination, and since a dull green is obtained when the blue becomes strong, it is preferable to add a yellow dye. The addition amount of the yellow dye is preferably 0.3 to 0.8% with respect to the pulp. These addition amounts can be appropriately adjusted.

  As the green hue, it is preferable that the color L * value of the colored paper is 87 or more, the a * value is −30 or less, the b * value is 58 or more, and the fluorescence intensity is 0.24 or more. When the color L * value is less than 87, the lightness is lowered and the color tone becomes dark. When the a * value exceeds -30, the green color becomes weak. When the b * value is less than 58, the yellow color becomes weak. It will be lacking. Further, even when the fluorescence intensity is less than 0.24, 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-described ranges, a more vivid green-based fluorescent colored paper can be obtained.

  In order to obtain pink colored paper, a pink fluorescent pigment can be used because vivid pink coloring is obtained. Examples of the pink fluorescent pigment include, but are not limited to, an aqueous dispersion type “SW-117 Pink” (manufactured by Sinloihi Co., Ltd.).

  The addition amount may be adjusted so as to obtain the desired pink fluorescent coloring, and is not particularly limited, but the pink fluorescent pigment is preferably 5 to 15% of the pulp. In addition, a dye can be used in combination. However, in the case of a yellow dye, a yellowish color becomes dull pink. Therefore, the addition amount is preferably 0.01% or less with respect to pulp. These addition amounts can be appropriately adjusted.

  As the pink hue, it is preferable that the color L * value of the colored paper is 70 or more, the a * value is 44 or more, the b * value is -10 to 0, and the fluorescence intensity is 0.25 or more. When the color L * value is less than 70, the lightness is lowered and the color tone becomes dark. When the a * value is less than 44, the red color becomes weak. When the b * value exceeds 0, the yellow color becomes strong. Will be lacking. Furthermore, even when the fluorescence intensity is less than 0.25, the image is not vivid. In the present invention, since the color L * value, a * value, b * value, and fluorescence intensity are within the above ranges, a more vivid pink fluorescent colored paper without dullness is obtained.

  In order to obtain yellow colored paper, a yellow fluorescent pigment can be used because vivid yellowish coloring is obtained. Examples of the yellow fluorescent pigment include, but are not limited to, the above-described water dispersion type “SW-115 Lemon Yellow” (manufactured by Sinloihi Co., Ltd.).

  The addition amount is not particularly limited as long as it is adjusted so as to obtain a desired yellow fluorescent coloring, but the yellow fluorescent pigment is preferably 3 to 8% of pulp. Moreover, dye can be used together, and in the case of a yellow dye, it is preferable to set it as 0.25 to 0.5% with respect to pulp as addition amount. These addition amounts can be appropriately adjusted.

  As the yellow hue, it is preferable that the color L * value of the colored paper is 90 or more, the a * value is −20 or less, the b * value is 68 or more, and the fluorescence intensity is 0.2 or more. When the color L * value is less than 90, the lightness is lowered and the color tone becomes dark. When the a * value exceeds -20, the green color becomes weak. When the b * value is less than 68, the yellow color becomes weak. It will be lacking. Furthermore, even when the fluorescence intensity is less than 0.2, 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 yellowish 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. An optimal blend of the fluorescent pigment and the fixing agent makes it possible to obtain a vivid hue without dullness. 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. Among these, in the case of orange, green, and yellow, it is preferably 0.5 to 3%. The present invention is not limited to these examples, and the amount of the fixing agent may be adjusted according to the desired hue. Further, the addition of the fixing agent here is an addition in a solid form.

  In the case of the present invention, a sulfuric acid band can be added in order to further enhance the effect of fixing the fluorescent pigment to the pulp fiber. The addition ratio is preferably 0.5 to 2% to pulp, but can be adjusted as appropriate. Especially, in the case of green type and pink type, it is preferable to set it as 0.5 to 1.5%. In addition, this invention is not limited to these examples, What is necessary is just to adjust the quantity of a sulfuric acid band according to a desired hue. Moreover, the addition of the sulfate band here is addition in the form.

  A preferred method for producing the fluorescent colored paper of the present invention is that a certain amount of a fluorescent pigment and a fixing agent are continuously added together with a pulp raw material in a mixing box or a machine chest in a pulp raw material adjusting step for supplying the raw material to a paper machine. By adding and mixing, or by continuously adding a certain amount of fluorescent pigment and fixing agent together with the pulp raw material into a static mixer provided in the middle of the pulp raw material piping leading to the mixing box or machine chest. The fluorescent pigment is fixed to the pulp raw material, and the dyed pulp raw material is made into paper. When adding a dye, it adds with a fluorescent pigment.

  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, the fluorescent pigment, and the fixing agent 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, the fluorescent pigment, and the fixing agent are mixed in the static mixer, and the pulp The raw material is dyed. When mixing is performed with a mixing box or a static mixer in this way, the pulp raw material, the fluorescent pigment, and the fixing agent are better mixed, and a uniform dyeing mixture 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 color tone of the colored paper after paper making using an on-line color meter installed after the paper machine dryer part, and depending on the result, the fluorescence to the mixing box 1 and the machine chest 2 is measured. Fine adjustment of the addition amount of the pigment and the fixing agent is performed. Furthermore, it is possible to adjust the hue 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, complementary color can be obtained by providing a size press step and adding a fluorescent pigment and / or dye to the coating liquid applied in the size press. 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 fluorescent pigment and / or dye in this case is not particularly limited, but a concentration of about 0.01 to 10% with respect to water is preferable. Further, the product rolled up on the reel part can be conditioned and measured with a color difference meter to adjust the color tone with higher accuracy.

  As described above, the case where the fluorescent pigment and the fixing agent are internally added has been described as a preferred embodiment in obtaining the fluorescent colored paper of the present invention. However, the present invention is not limited to the internal addition, and the fluorescent pigment and the fixing agent. And may be added as an external additive. 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 fluorescent pigment and a fixing agent in a size press process, or a separate coating process is provided to contain a fluorescent pigment and a fixing agent. The method etc. of apply | coating a coating liquid are mentioned. The coating liquid can contain organic or inorganic pigments and additives.

  Moreover, when there is a difference between the front and the back of the hue, a fluorescent pigment and / or a dye can be externally added to the surface side where the hue is 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.

Orange-based fluorescent colored paper (Orange)
[Example OR1]
In the mixing box, together with pulp raw materials (LBKP 60%: freeness 350 cc, waste paper 40%: freeness 280 cc, pulp concentration 3%), a fixing agent (trade name “Jetfix PA-401” manufactured by Satoda Chemical Co., Ltd. 2.5% Pulp), methine-based cationic dye (trade name “TOA Basic Yellow G (L)” manufactured by Toa Kasei Co., Ltd. 0.8% pulp), pink fluorescent pigment (trade name “SW-117 Pink” manufactured by Sinroihi Co., Ltd. 5% Pulp), and a pulp material dyed by continuously adding and mixing a sulfuric acid band (1.5% to pulp) to a paper machine, and a colored paper for printing having a basis weight of 76.7 g / m ² Paper was made and the surface was measured.

[Example OR2]
A pulp material dyed in the same manner as in Example OR1 except that the ratio of waste paper pulp was set to 10% was supplied to a paper machine, and a colored paper for printing having a basis weight of 76.7 g / m ² was made. It was measured.
[Example OR3]
A pulp raw material dyed in the same manner as in Example OR1 except that the ratio of waste paper pulp was changed to 0% was supplied to a paper machine, and a colored paper for printing having a basis weight of 76.7 g / m ² was made. It was measured.
[Example OR4]
A pulp material dyed in the same manner as in Example OR1 except that the ratio of waste paper pulp was 72% was supplied to a paper machine, a colored paper for printing having a basis weight of 76.7 g / m ² was made, and the surface was measured. did.

[Example OR5]
A pulp raw material dyed in the same manner as in Example OR1 except that the pink fluorescent pigment was 8.0% pulp and the yellow dye was 1.28% pulp was supplied to the paper machine and the basis weight was 76.7 g / m ^2. The printed colored paper was made and the surface was measured.
[Example OR6]
A pulp raw material dyed in the same manner as in Example OR1 except that the fixing agent was 2% to pulp and the mixing ratio of waste paper pulp was 0% was supplied to a paper machine and used for printing with a basis weight of 76.7 g / m ² . Colored paper was made and the surface was measured.

[Example OR7]
The pulp material dyed in the same manner as in Example OR1 except that the fixing agent was 2% to pulp, the yellow dye was 0.6% to pulp, and the ratio of waste paper pulp was 0%. 76.7 g / m ² of colored paper for printing was made and the surface was measured.
[Example OR8]
The pulp material dyed in the same manner as in Example OR1 except that the fixing agent was 2% pulp, the yellow dye 0.5% pulp, and the waste paper pulp content was 0%. 76.7 g / m ² of colored paper for printing was made and the surface was measured.

[Example OR9]
Pulp raw material dyed in the same manner as in Example OR1, except that the fixing agent was 2% pulp, the pink fluorescent pigment 7% pulp, the yellow dye 0.6% pulp, and the waste paper pulp content 0%. Was supplied to a paper machine, a colored paper for printing having a basis weight of 76.7 g / m ² was made, and the surface was measured.
[Example OR10]
Fixing agent 0.5% pulp, pink fluorescent pigment 3.9% pulp, yellow dye 0.71% pulp, sulfuric acid band 0.5% pulp, wastepaper pulp 72% The dyed pulp raw material was supplied to a paper machine, a colored paper for printing having a basis weight of 76.7 g / m ² was made, and the surface was measured.

[Example OR11]
1% fixing agent for pulp, orange fluorescent pigment (trade name “SW-114 Orange” manufactured by Sinroihi Co., Ltd. for 10% pulp), yellow dye (trade name “TOA Basic Yellow G (L)” manufactured by Toa Kasei Co., Ltd. 0.01% to pulp), and pulp material dyed in the same manner as Example Or1 except that the ratio of waste paper pulp was 10% was supplied to the paper machine, and the basis weight was 76.7 g / m ² for printing. Colored paper was made and the surface was measured.

[Reference Example OR1]
A pulp raw material dyed in the same manner as in Example OR1 except that the fixing agent was not added was supplied to a paper machine, a colored paper for printing having a basis weight of 76.7 g / m ² was made, and the surface was measured.
[Reference Example OR2]
A pulp raw material dyed in the same manner as in Example OR5 except that the fixing agent was not added was supplied to a paper machine, a colored paper for printing having a basis weight of 76.7 g / m 2 was made, and the surface was measured.
[Reference Example OR3]
A pulp raw material dyed in the same manner as in Example OR1 except that the fixing agent was not added, the pink fluorescent pigment was 3% pulp, and the yellow dye was 0.48% pulp was supplied to the paper machine. A colored paper for printing of .7 g / m 2 was made and the surface was measured.

[Reference Example OR4]
A pulp raw material dyed in the same manner as in Example OR1 except that 3% of the pink fluorescent pigment is pulp and 0.48% of the yellow dye is pulp is supplied to the paper machine and printed at a basis weight of 76.7 g / m ² . A colored paper for printing was made and the surface was measured.
[Reference Example OR5]
A pulp material dyed in the same manner as in Example OR1 except that the fixing agent was 4% pulp was supplied to a paper machine, a colored paper for printing having a basis weight of 76.7 g / m ² was made, and the surface was measured. did.

[Example OR12]
In the mixing box, pulp material (LBKP28%: freeness 350cc, recycled paper 72%: freeness 280cc, pulp concentration 3%) and fixing agent (trade name Jetfix PA-401 0.5% vs. pulp manufactured by Satorita Chemical Co., Ltd.) , A methine-based cationic dye (trade name “TOA Basic Yellow G (L)” manufactured by Toa Kasei Co., Ltd. 0.71% vs. pulp), a pink fluorescent pigment (trade name “SW-117 Pink” manufactured by Singloi Co., Ltd. 3.9% Pulp), and a pulp material dyed by continuously adding and mixing a sulfuric acid band (0.5% to pulp) to a paper machine, and a colored paper for printing having a basis weight of 76.7 g / m ² Paper was made and the front and back sides were measured.

[Example OR13]
The pulp raw material dyed in the same manner as in Example OR12 was supplied to a paper machine, and after making colored paper for printing, an anionic direct dye having a concentration of 0.35% against water (trade name “Kayafect” was added as an external additive. “Orange NR Liq” (manufactured by Nippon Kayaku Co., Ltd.) was applied to the back side of the colored paper to obtain a colored paper for printing having a basis weight of 76.7 g / m ² , and the back side was measured.
[Example OR14]
The pulp raw material dyed in the same manner as in Example OR12 was supplied to a paper machine, and after printing colored paper for printing, an anionic direct dye (trade name “Cardazole” with a concentration of 0.2% against water was added as an external additive. “Red 2GFN Liq” (manufactured by Arkroma Japan Co., Ltd.) was applied to the back side of the colored paper to obtain a colored paper for printing having a basis weight of 76.7 g / m 2, and the back side was measured.

[Example OR15]
The pulp raw material dyed in the same manner as in Example OR12 was supplied to a paper machine, and after making colored paper for printing, an anionic direct dye (trade name “Direct Paper” with a concentration of 0.12% against water was added as an external additive. Red 4BL "(manufactured by Nippon Chemical Industry Co., Ltd.) was applied to the back side of the colored paper to obtain a colored paper for printing having a basis weight of 76.7 g / m ² , and the back side was measured.

Tables 1 and 2 show L * values, a * values, b * values, and measured values of fluorescence intensity measured using a Murakami color whiteness meter for each colored paper made under the above conditions. The evaluation of clarity in the table is by visual inspection,
(Poor) 1 <4 (Excellent)
Light orange Orange is strongly dull Based on vivid standards. The hue L * value, a * value, and b * value were measured according to Murakami Color Whiteness Meter, Color Difference Value (UV-IN) JISP8150, and the fluorescence intensity was based on Murakami Color Whiteness Meter, JISP8148. And measured.

<Table 1>

<Table 2>

  The results of the measurement are as shown in Table 1. As is clear from the results, in the cases of Examples OR1 to 11 in which the fixing agent, the fluorescent pigment and the dye are combined and combined, all of the reference examples OR1 to 3 lacking the fixing agent. It can be seen that although the lightness of the L * value is low, the red value of the a * value is strong and the yellow value of the b * value is small. In the case of Reference Examples OR1 to OR3, the lightness of the L * value is high, the green of the a * value is strong, and the yellow value of the b * value is slightly large. In the case of Reference Examples OR4 to 5, the lightness of the L * value is high, the red of the a * value is weak, and the yellow value of the b * value is slightly large. The bright orange emission color as in Examples OR1 to 11 is not exhibited.

  Further, from Example OR1 and Reference Example OR5, the a * value tends to decrease in the range where the fixing agent addition rate exceeds 2.5%, and the b * value indicating yellow is increased. I understand. From this, it is understood that a good fixing effect of the fluorescent pigment on the pulp raw material can be obtained particularly when the addition ratio of the fixing agent is 2.5% or less.

  Further, from the measurement results of Examples OR12 to 15 shown in Table 2, when color adjustment is performed by externally adding a red dye, L * value is obtained in the case of Examples OR13 to 15 compared to Example OR12. It can be seen that the brightness of decreases, the a * value increases and red becomes stronger. In addition, it can be seen that the b * value indicating yellow decreases, yellow becomes weaker, and a bright orange emission color is developed, and the front and back surfaces have a unchanged hue.

Green fluorescent colored paper (Green)
[Example G1]
In the mixing box, together with pulp raw materials (LBKP 60%: freeness 350 cc, waste paper pulp 40%: freeness 280 cc, pulp concentration 3%), fixing agent (trade name “Jetfix PA-401” manufactured by Satoda Chemical Co., Ltd. 1.0% Pulp), methine cationic dye (trade name “TOA Basic Yellow G (L)” manufactured by Toa Kasei Co., Ltd. 0.5% pulp), fluorescent pigment (trade name “SW-115 Lemon Yellow” manufactured by Shinrohi Co., Ltd. 5% Pulp and fluorescent pigment “SW-128Blue” Sinloihi Co., Ltd. 1% pulp) and sulfuric acid band (1.5% pulp) are added continuously and mixed to supply pulp material dyed to the paper machine A colored paper for printing having a basis weight of 76.7 g / m ² was made.

[Example G2]
A pulp material dyed in the same manner as in Example G1 except that the ratio of waste paper pulp was changed to 10% was supplied to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .
[Example G3]
A pulp raw material dyed in the same manner as in Example G1 except that the yellow fluorescent pigment was 8% pulp and the blue fluorescent pigment was 1.6% pulp was supplied to the paper machine, and the basis weight was 76.7 g / m ² . Colored paper for printing was made.

[Example G4]
A pulp raw material dyed in the same manner as in Example G1 except that the fixing agent was changed to 2% pulp was supplied to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .
[Example G5]
A pulp raw material dyed in the same manner as in Example G1 except that the fixing agent was 2.5% pulp was supplied to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .

[Example G6]
A pulp material dyed in the same manner as in Example G1 except that the fixing agent was 2.5% pulp and the yellow fluorescent pigment was 4.5% pulp was supplied to the paper machine, and the basis weight was 76.7 g / A colored paper for printing m ² was made.
[Example G7]
A pulp material dyed in the same manner as in Example G1 except that the fixing agent is 2.5% pulp and the yellow fluorescent pigment is 4% pulp is supplied to the paper machine and printed with a basis weight of 76.7 g / m ² . Paper for coloring was made.

[Example G8]
A pulp raw material dyed in the same manner as in Example G1 except that the fixing agent was changed to 3.0% was supplied to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .
[Example G9]
The pulp material dyed in the same manner as in Example G1 except that the fixing agent was 2.5% pulp, the yellow fluorescent pigment was 4% pulp, and the ratio of waste paper pulp was 72% was supplied to the paper machine. A colored paper for printing having an amount of 76.7 g / m ² was made.

[Example G10]
Other than setting the compounding ratio of fixing agent 1.3% to pulp, yellow fluorescent pigment 3% to pulp, yellow dye 0.32% to pulp, sulfuric acid band 0.5% to pulp and waste paper pulp Supplied a pulp material dyed in the same manner as in Example G1 to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .

[Reference Example G1]
A pulp raw material dyed in the same manner as in Example G1 except that no fixing agent was added was fed to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .
[Reference Example G2]
A pulp raw material dyed in the same manner as in Example G3 except that no fixing agent was added was fed to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .

[Reference Example G3]
A pulp raw material dyed in the same manner as in Example G1 except that no fixing agent was added, yellow fluorescent pigment was 3% pulp, and blue fluorescent pigment was 0.6% pulp was supplied to the paper machine, and the basis weight was 76. A colored paper for printing of 0.7 g / m ² was made.
[Reference Example G4]
A pulp material dyed in the same manner as in Example G1 except that the fixing agent was changed to 4.0% was supplied to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .

Table 3 shows the measured values of L * value, a * value, b * value, and fluorescence intensity measured with a Murakami color whiteness meter for each colored paper made under the above conditions. The evaluation of clarity in the table is by visual inspection,
(Poor) 1 <4 (Excellent)
Yellow Green Green is dull. Based on vivid standards. The hue L * value, a * value, and b * value were measured according to Murakami Color Whiteness Meter, Color Difference Value (UV-IN) JISP8150, and the fluorescence intensity was based on Murakami Color Whiteness Meter, JISP8148. And measured.

<Table 3>

  The results of the measurement are as shown in Table 3. As is clear from the results, in Examples G1 to 10 in which the fixing agent and the fluorescent pigment were combined and combined, all of the cases in Reference Examples G1 to G3 lacking the fixing agent were used. In addition, although the lightness of the L * value is low, it can be seen that the green value of the a * value is small and the yellow value of the b * value is slightly large. In the case of Reference Examples G1 to G3, the lightness of the L * value is high, and the b * value indicating yellow is slightly large, so that a yellow fluorescent color is expressed. It does not express a bright green light emission color. Further, from Reference Example G4, even when a fixing agent and a fluorescent pigment are combined and combined, any one of the L * value, the a * value, the b * value, and the fluorescence intensity value defined in the present invention is not satisfied. It can be seen that the desired vivid green color cannot be obtained.

  Further, from Examples G1, 5, 8 and Reference Example G4, the value of a * value indicating green is almost unchanged when the addition rate of the fixing agent is in the range of 1.0 to 3.0%. In a range exceeding%, it can be seen that the value of the a * value tends to increase, and green is weak. From this, it is understood that a good fixing effect of the fluorescent pigment on the pulp raw material can be obtained particularly when the addition ratio of the fixing agent is 3.0% or less.

Pink fluorescent colored paper (Pink)
[Example P1]
In the mixing box, together with the pulp raw material (LBKP 60%: freeness 350 cc, waste paper pulp 40%: freeness 280 cc, pulp concentration 3%), a fixing agent (trade name “Jetfix PA-401” manufactured by Satoda Chemical Co., Ltd., 1.0 % Vs. pulp), methine cationic dye (trade name “TOA Basic Yellow G (L)” manufactured by Toa Kasei Co., Ltd., 0.01% vs. pulp), fluorescent pigment (trade name “SW-117 Pink” manufactured by Sinloihi Co., Ltd., 10% pulp) and a pulp material dyed by continuously adding and mixing a sulfuric acid band (1.5% pulp) to a paper machine, and for printing with a basis weight of 76.7 g / m ² Colored paper was made.

[Example P2]
A pulp material dyed in the same manner as in Example P1 except that the fluorescent pigment was changed to 15% to pulp was fed to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .
[Example P3]
A pulp material dyed in the same manner as in Example P1 except that the pulp material (LBKP 90%: freeness 350 cc, waste paper pulp 10%: freeness 280 cc, pulp concentration 3%) was changed to 10% fluorescent pulp. A colored paper for printing having a basis weight of 76.7 g / m ² was made.

[Example P4]
A pulp material dyed in the same manner as in Example P3 except that the fluorescent pigment is 5.0% to pulp and the yellow dye is 0% to pulp is supplied to a paper machine, and after printing colored paper for printing, the outside In addition, a fluorescent pigment having a concentration of 1% with respect to water was applied to colored paper to obtain a colored paper for printing having a basis weight of 76.7 g / m ² .
[Example P5]
As an external addition, a colored paper for printing having a basis weight of 76.7 g / m ^{2 was made under} the same conditions as in Example P4 except that a fluorescent pigment having a concentration of 3% to water was applied to the colored paper.

[Example P6]
As an external addition, a colored paper for printing having a basis weight of 76.7 g / m ^{2 was made under} the same conditions as in Example P4, except that a fluorescent pigment having a concentration of 5% water was applied to the colored paper.
[Example P7]
Fixing agent 2.5% pulp, fluorescent pigment 8.4% pulp, yellow dye 0% pulp, LBKP 28%, waste paper pulp 72%, sulfuric acid band 1.5% pulp The obtained pulp raw material was supplied to a paper machine, and a colored paper for printing having a basis weight of 76.7 g / m ² was made.

[Example P8]
Pulp dyed as fixing agent 3.5% pulp, fluorescent pigment 13% pulp, yellow dye 0% pulp, LBKP 28%, waste paper pulp 72%, sulfate band 0.5% pulp The raw material was supplied to a paper machine, and a colored paper for printing having a basis weight of 76.7 g / m ² was made.
[Example P9]
A pulp raw material dyed in the same manner as in Example P8 except that the fixing agent was changed to 2.0% pulp was supplied to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .

[Example P10]
A pulp raw material dyed in the same manner as in Example P8 except that the fixing agent was changed to 1.0% pulp was supplied to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .

[Reference Example P1]
A pulp raw material dyed in the same manner as in Example P1 except that the fixing agent was not added was supplied to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .
[Reference Example P2]
A pulp raw material dyed in the same manner as in Example P1 except that the fixing agent was not added and the fluorescent pigment was changed to 15% pulp was supplied to a paper machine, and a colored paper for printing having a basis weight of 76.7 g / m ^2. Was made.

[Reference Example P3]
A pulp raw material dyed in the same manner as in Example P1 except that no fixing agent was added and the fluorescent pigment was changed to 5% pulp was supplied to a paper machine, and a colored paper for printing having a basis weight of 76.7 g / m ^2. Was made.
[Reference Example P4]
A pulp material dyed in the same manner as in Example P1 except that the fixing agent is 1.0% pulp and the fluorescent pigment is 5% pulp is supplied to the paper machine for printing with a basis weight of 76.7 g / m ² . The colored paper was made.

[Reference Example P5]
A pulp material dyed in the same manner as in Example P1 except that the fixing agent was 4.0% pulp, the fluorescent pigment was 10% pulp, and LBKP was 100% was supplied to the paper machine, and the basis weight was 76.7 g / A colored paper for printing m ² was made.
[Reference Example P6]
A pulp material dyed in the same manner as in Example P8, except that the fixing agent is set to 3.0% pulp and the fluorescent pigment is set to 5% pulp, is supplied to the paper machine and is used for printing with a basis weight of 76.7 g / m ² . The colored paper was made.

[Reference Example P7]
A pulp material dyed in the same manner as in Example P8 except that the fixing agent is 3.5% pulp and the fluorescent pigment is 10% pulp is supplied to the paper machine for printing with a basis weight of 76.7 g / m ² . The colored paper was made.

Table 4 shows the measured values of L * value, a * value, b * value, and fluorescence intensity measured using a Murakami color whiteness meter for each colored paper made under the above conditions. The evaluation of clarity in the table is by visual inspection,
(Poor) 1 <6 (Excellent)
Light pink Red strong red Dull Based on vivid standards. The L * value, a * value, and b * value are measured according to Murakami Color Whiteness Meter, Color Difference Value (UV-IN) JISP8150, and the fluorescence intensity is based on Murakami Color Whiteness Meter, JISP8148. Measured.

<Table 4>

  The results of the measurement are as shown in Table 4. As is clear from this, in Examples P1 to 6 in which the fixing agent and the fluorescent pigment were combined and combined, all of the examples P1 to P3 lacking the fixing agent were used. It can be seen that although the brightness of the L * value is low, the red value of the a * value is strong and the yellow value of the b * value is small. In the case of Reference Examples P1 to P3, the brightness of the L * value is high and the a * value is low, so the color is dull and light pink, and the bright pink fluorescent color as in Examples P1 to P6 is exhibited. Not done. Further, from Reference Example P4, even when a fixing agent and a fluorescent pigment are combined and combined, any one of the L * value, the a * value, the b * value, and the fluorescence intensity value defined in the present invention is not satisfied. It can be seen that the desired bright pink color cannot be obtained.

  Further, from Examples P7 to 10 and Reference Examples P6 and P7, the b * value indicating yellow is almost unchanged when the addition rate of the fixing agent is in the range of 1.0 to 2.5%. It can be seen that in the range exceeding%, the a * value tends to decrease, and red is weakened. From this, it is understood that a good fixing effect of the fluorescent pigment on the pulp raw material can be obtained particularly when the addition ratio of the fixing agent is 2.5% or less. Further, it can be seen from the reference example P5 that the b * value indicating yellow increases when the fixing agent addition rate is 4%, and yellow becomes stronger. Also, as a matter of course, in Examples P4 to 10 in which the yellow dye was 0%, the b * value indicating yellow was lower than in Examples P1 to P3 containing the yellow dye. I understand that. From these results, the effectiveness of the present invention could be fully confirmed.

Yellow fluorescent colored paper (Yellow)
[Example Y1]
In the mixing box, pulp material (LBKP 60%: freeness 350 cc, waste paper 40%: freeness 280 cc, pulp concentration 3%) and fixing agent (trade name Jetfix PA-401 0.5% by Satoda Chemical Co., Ltd. pulp) , A methine-based cationic dye (trade name “TOA Basic Yellow G (L)” manufactured by Toa Kasei Co., Ltd., 0.5% pulp), fluorescent pigment (trade name “SW-115 Lemon Yellow” manufactured by Shinhiro Corporation, 3% pulp) And a pulp raw material dyed by continuously adding and mixing a sulfuric acid band (1.5% to pulp) to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² . .

[Example Y2]
A pulp raw material dyed in the same manner as in Example Y1 except that the fluorescent pigment was changed to 5% pulp was fed to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .
[Example Y3]
A pulp material dyed in the same manner as in Example Y1 except that the fluorescent pigment was changed to 8% pulp was supplied to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .

[Reference Example Y1]
A pulp raw material dyed in the same manner as in Example Y1 except that no fixing agent was added was fed to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .
[Reference Example Y2]
A pulp raw material dyed in the same manner as in Example Y2 except that no fixing agent was added was supplied to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .

[Reference Example Y3]
A pulp raw material dyed in the same manner as in Example Y3 except that no fixing agent was added was fed to a paper machine to produce a colored paper for printing having a basis weight of 76.7 g / m ² .
[Reference Example Y4]
A pulp material dyed in the same manner as in Example Y1 except that the fixing agent was not added and the fluorescent pigment was not added was supplied to a paper machine, and a colored paper for printing having a basis weight of 76.7 g / m ² was produced. did.

Table 5 shows the measured values of L * value, a * value, b * value, and fluorescence intensity measured using a Murakami color whiteness meter for each colored paper made under the above conditions. The evaluation of clarity in the table is by visual inspection,
(Poor) 1 <4 (Excellent)
Pale yellow Yellow is dull and strong. Based on vivid standards. The hue was measured according to Murakami Color Whiteness Meter, Color Difference Value (UV-IN) JISP8150, and the fluorescence intensity was measured according to Murakami Color Whiteness Meter, JISP8148.

<Table 5>

  The results of the measurement are as shown in Table 5. As is clear from the results, in Examples Y1 to Y3 in which a fixing agent, a fluorescent pigment and a dye were combined and combined, all of Reference Examples Y1 to Y4 lacking the fixing agent. It can be seen that the lightness of the L * value is high, the green value of the a * value is strong, and the yellow value of the b * value is large. In addition, the fluorescence intensity is 0.21 in Example Y1, which is the lowest of the Examples, and in Examples Y1 to Y3, all express a bright yellow fluorescent color with no dullness when visually observed. From this result, the effectiveness of the present invention could be fully confirmed.

  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 (13)

  Fluorescent colored paper containing at least a pulp raw material, a fluorescent pigment, and a fixing agent.   The fluorescent colored paper according to claim 1, wherein the fluorescent pigment and the fixing agent are internally added and colored.   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 dye.   The fluorescent colored paper according to any one of claims 1 to 5, wherein a range of color L * value, a * value, b * value and fluorescence intensity is set according to a color to be colored.   Fluorescent colored paper colored orange, wherein the color L * value of the colored paper is 77 or more, the a * value is 21 or more, the b * value is 47 or more, and the fluorescence intensity is 0.07 or more. The fluorescent colored paper according to claim 6.   Fluorescent colored paper colored green, wherein the color L * value of the colored paper is 87 or more, the a * value is −30 or less, the b * value is 58 or more, and the fluorescence intensity is 0.24 or more. The fluorescent colored paper according to claim 6.   Fluorescent colored paper colored pink, and the color L * value of the colored paper is 70 or more, the a * value is 44 or more, the b * value is -10 to 0, and the fluorescence intensity is 0.25 or more. The fluorescent colored paper according to claim 6.   Fluorescent colored paper colored yellow, wherein the color L * value of the colored paper is 90 or more, the a * value is −20 or less, the b * value is 68 or more, and the fluorescence intensity is 0.20 or more. The fluorescent colored paper according to claim 6.   A certain amount of fluorescent pigment and fixing agent are continuously added and mixed with the pulp raw material in the mixing box or machine chest of the pulp raw material adjustment process for supplying the raw material to the paper machine, or it is passed to the mixing box or machine chest. The pulp obtained by fixing the fluorescent pigment to the pulp raw material by continuously adding and mixing a certain amount of the fluorescent pigment and the fixing agent together with the pulp raw material in a static mixer provided in the middle of the pulp raw material pipe A method for producing fluorescent colored paper, characterized in that the raw material is made of paper.   Measure the color tone of the colored paper after paper making with an on-line color meter installed after the paper machine dryer part, and according to the measurement result, add the amount of the fluorescent pigment and fixing agent to the mixing box or the machine chest. The method for producing the system fluorescent colored paper according to claim 11, wherein adjustment is performed.   The method for producing fluorescent colored paper according to claim 11 or 12, wherein the method comprises a size press step, and the color is complemented by adding the fluorescent pigment and / or dye to a coating liquid applied in the size press. .

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