JP2942703B2 - Manufacturing method of dyed pattern paper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing dyed paper. More particularly, the present invention relates to a method for producing a dyed paper, which is partially dyed like a cloud pattern or a marble pattern, and the dyed portion is dyed with high contrast.

[0002]

2. Description of the Related Art It is known to produce a dyed paper such as a cloud pattern by dropping a dyeing solution onto a slurry or wet paper on a papermaking wire using a fourdrinier paper machine. This is done in the manner described. (1) Various kinds of dye liquids or pigment liquids or a mixture thereof are dropped on the slurry on the wire after the stock inlet, and these are diffused into the raw material by using the flow of the slurry generated by the shaking action of the paper machine. A method of producing various cloud-dyed papers. (2) Various kinds of dye liquids or pigment liquids or a mixture thereof are injected into the slurry on the wire immediately after the stock inlet through a thin tube in the opposite direction to the slurry and dropped, and diffused into the raw material by the shaking action of the paper machine to obtain multi-color. Method of producing Japanese ink-washed dyed pattern paper. For example, Japanese Patent Laid-Open No. 2-14
As proposed in US Pat. No. 5899, a colored liquid in which an arbitrary color is dissolved is dropped onto a slurry immediately after the stock inlet of a paper machine within a range of ± 90 ° toward the stock inlet with the wire traveling direction as a reference line. By doing so, a cloud-type color flow pattern is formed on the paper surface, and a color flow dyed pattern paper is manufactured. (3) A method of producing multicolor spot-colored dyed paper by spraying various kinds of dye liquids or pigment liquids or a mixture thereof onto a web on a wire.

[0003]

The above-mentioned method for producing a dyed patterned paper is a pattern developed by physical action. In other words, an aqueous dye solution or pigment solution or a mixture thereof is sprayed, dripped, and ejected onto the slurry and the web on the wire and the nozzle with a nozzle and a thin tube, and the colorant is diffused into the slurry or the web by the shaking action of the paper machine. The pattern is expressed. This method requires a flow of colorant that is so strong that you want a variety of color drifts,
For this reason, there is a disadvantage that the colorant is diffused and the color is blurred, resulting in a flat and low contrast pattern.

The present invention is different from the above-described dyed paper in which the dyed portion is blurred, flat and has low contrast.
It is an object of the present invention to obtain a method for producing a dyed paper such as a cloud pattern, a marble pattern, a sumi-shi pattern, a spot pattern, etc., which is characterized by a strong contrast and a rich design, accompanied by vivid color.

[0005]

Means for Solving the Problems In preparing a papermaking raw material, the present inventors have proposed a sizing agent for preventing bleeding of ink in the raw material, a paper strength enhancer for ensuring the processability of paper, Add other papermaking chemicals according to the purpose of use.
In order to fix them on the pulp fiber, attention was paid to adding a cationic substance such as aluminum sulfate to the paper raw material. The present inventors, a colorant containing a water-soluble polymer that thickens or gels by chemically reacting with the cationic substance,
The colored pattern paper containing the water-soluble polymer is thickened or gelled on a wire by dropping the slurry or web on a Fourdrinier paper machine, and if the diffusion of the colorant can be prevented, the dyed patterned paper of the present invention is intended. Various studies have been made based on the idea that can be obtained, and the present invention has been completed.

[0006] That is, the gist of the present invention is that when making a fourdrinier paper machine using a slurry mainly containing papermaking fibers and containing a cationic substance, the slurry or web on the wire after the stock inlet is treated with a cationic material. Spraying, dropping, squirting, flowing down, etc. of an aqueous solution of a chemical that thickens or gels due to a chemical reaction with a hydrophilic substance, or a mixture of both, prevents diffusion of the colorant and removes wet paper. This is a method for producing a dyed and patterned paper, which comprises papermaking, dehydration and drying.

The papermaking fibers used in the present invention include bleached softwood kraft pulp (NBKP), hardwood bleached kraft pulp (LBKP) and softwood bleached sulphite pulp (N
Chemical pulp such as BSP), mechanical pulp such as groundwood pulp (GP) and thermomechanical pulp (TMP), and non-wood fiber pulp such as cotton pulp and bast fiber pulp such as hemp, kozo, ganpi and mitsumata. used. In the present invention, firstly, the above-mentioned papermaking fiber alone or a mixture is usually 300 to
500 ml C.I. S. F, preferably 350-450 ml
C. S. F. And synthetic fibers such as polyolefin synthetic pulp, polyester, polyamide, etc., and regenerated cellulose fibers such as vinylon, etc. may be appropriately mixed.
Further, paper-making auxiliary materials such as a rosin-based sizing agent, a dry paper strength enhancer, a wet paper strength enhancer, a dye, a color pigment, and a white pigment can be appropriately used in combination. In the present invention, it is essential to add a cationic substance to the slurry thus prepared, and an inorganic or organic cationic substance is used. In the present invention, as the organic cationic substance, aluminum sulfate, aluminum chloride, potassium alum, ammonium alum, calcium chloride, ferrous sulfate, ferric sulfate, ferric chloride, sodium aluminate, cationic polyacrylamide, Cationic starch, cationic polyamine-polyamide-epichlorohydrin resin and the like are used. Using the slurry prepared in this manner, wet paper is usually formed at a basis weight of 50 to 400 g / m 2 (absolute dry basis weight, the same applies hereinafter), preferably 100 to 200 g / m 2 using a fourdrinier paper machine. .

[0008] The water-soluble polymer used in the present invention includes natural starches, rubbers, gums, plant proteins, sodium alginate produced from seaweeds and the like, and animal proteins such as casein and glue. , Semi-synthetic cellulose derivatives such as carboxymethylcellulose, processed starches, processed natural rubbers, synthetic vinyl derivatives, polyacrylic acid derivatives, etc. As a molecule, it is an essential condition that a chemical reaction with a cation (a positive ion, for example, trivalent aluminum ion is generated in aluminum sulfate) generated from a cationic substance contained in a slurry or a web on a papermaking wire to increase the viscosity or gel. It is. The water-soluble polymer is used after being dissolved in water, but the concentration of the aqueous solution is adjusted according to the viscosity. In the present invention, the upper limit of the viscosity of the aqueous solution is about 1000 CPS (centipoise). For example, when the viscosity is 1000 CPS with high-viscosity sodium alginate, the concentration corresponds to about 1%.

As the colorant used in the present invention, dyes such as direct dyes, acid dyes, reactive dyes and basic dyes, and coloring pigments of organic pigments and inorganic pigments are used. Used, the concentration is usually 0.01 to
Used at 1.00% by weight.

In the present invention, as described above, when making a fourdrinier paper machine using a slurry mainly containing papermaking fibers and containing a cationic substance, the slurry or web on the wire after the stock inlet is treated with an inorganic or organic material. Spraying, dropping, squirting, flowing down, etc. of an aqueous solution of a chemical that thickens or gels due to a chemical reaction with the cationic substance, or a mixture of the two, prevents diffusion of the colorant and prevents Paper is made, then dewatered and dried to produce a dyed paper with a strong contrast. An aqueous solution of a chemical that undergoes a chemical reaction with a cationic substance to thicken or gel, a colorant solution, or a mixture of both is supplied to a slurry or a web on a wire as follows. By supplying a different color of the colorant separately with a pipe, a thin tube, a sprayer, a sprinkler, or the like provided with a plurality of colorants, it is possible to obtain a highly designed dyed paper in which a different color pattern appears. 1) Make a hole in the pipe and drop or squirt. A hole is made in a pipe made of metal or plastic, and the above liquid is supplied to the pipe and dropped on a slurry on a wire or a web. Alternatively, it is ejected by applying pressure. 2) The above liquid is supplied to a thin tube made of metal or plastic and dropped onto a slurry or a web on a wire. Alternatively, it is ejected by applying pressure. 3) Spray the liquid onto a slurry or web on a wire using a nebulizer. 4) The liquid is caused to flow out to a slurry or a web on a wire by a sprinkler installed substantially perpendicular to the flow direction of the papermaking net.

According to such a method, the cationic substance contained in the slurry or the web on the wire and the chemical substance which reacts chemically with the cationic substance to increase the viscosity or gel cause a chemical reaction to increase the viscosity or gel. As a result, the diffusion of the colorant is prevented, and a dyed pattern having a strong design and rich in design, which cannot be obtained with a conventional dyed pattern paper, is developed. Drain into slurry or web.

According to the results of studies by the present inventors, in a combination of a cationic substance and a water-soluble polymer, aluminum sulfate was used as a cationic substance under general papermaking conditions, and a water-soluble polymer was used as a cationic substance. It has been found that sodium alginate is the most suitable combination for developing the desired dyed pattern. This combination is fast-acting and sharp, so that the sodium alginate thickens or gels instantaneously and the colorant does not excessively diffuse even by shaking the paper machine. Because.

[0013] The dyed pattern can be variously changed by changing physical conditions and chemical conditions.
The aspect is the concentration of the cationic substance contained in the slurry, the concentration of the water-soluble polymer, the molecular weight, and the colorant liquid containing the same, the dropping of the mixture to the pulp slurry and the web, the jetting, the spraying method, the slurry. Although it largely depends on the density and the shaking method of the paper machine, it is appropriately adjusted depending on the intended dyed pattern.

The wet paper thus formed is pressed and dried in a conventional manner to produce the dyed paper of the present invention. Embossing of wet paper during papermaking, application of a chemical by a size press, and improvement of smoothness by performing a calendering treatment are appropriately performed.

[0015]

【Example】

Example 1 Pulp composed of 30 parts by weight of softwood bleached kraft pulp (NBKP) and 70 parts by weight of hardwood bleached kraft pulp (LBKP) (dry weight part, the same applies hereinafter) was beaten with a refiner, and the freeness was reduced to 400 mlC.P. S. F. (Measured by Canadian Freeness Tester). This is followed by a yellow direct dye (CI Direct Yellow)
w 50) with respect to 0.01 parts by weight of pulp and 0.002 of red direct dye (CI Direct Red 23).
Parts by weight, black direct dye (CI Direct Bl)
ack 19), and 0.0021 parts of a black pigment (C.I.
Pigment Black 1)) vs. pulp 0.0
Dyeing was performed by adding 02 parts by weight. Then, a sizing agent (trade name “Size Pine” manufactured by Arakawa Chemical Industry Co., Ltd.) was added to 2.5
A slurry was prepared by adding 4.0 parts by weight of a dry paper strength agent (trade name "Polystron" manufactured by Arakawa Chemical Industries, Ltd.) and 5.0 parts by weight of liquid aluminum sulfate. This raw material was paper-made using a fourdrinier paper machine with a basis weight of 120 g / m2 and a papermaking width of 1000 mm. At the time of this papermaking, a thin pipe having an inner diameter of 1 mm and a length of 5 cm was attached to a metal pipe having an inner diameter of 1 inch by 5 c
At a distance of 20 cm after slicing, three tubes (pipes A, B, and C) were placed at 10 cm intervals in the width direction at a height of 10 cm on the wire. And a dye solution containing sodium alginate (a solution to be supplied to the pipe C) with respect to the slurry on the wire of the paper machine.
It was ejected at a pressure of 0 kg / cm 2 and diffused into the slurry by the shaking action of the paper machine to produce a patterned paper. This patterned paper was a colored paper having a marble-colored pattern with a strong contrast that could not be obtained by known techniques. B. Liquid to be supplied to pipe A (the following aqueous solution) I. Direct Yellow 50 ... 0.02 parts by weight C.I. I. Direct Red 218 ... 0.003 parts by weight C.I. I. Direct Black 19: 0.005 parts by weight Water: 100 parts by weight Liquid to be supplied to pipe B (the following aqueous solution) I. Direct Yellow 50 ... 0.02 parts by weight C.I. I. Direct Red 224... 0.004 parts by weight C.I. I. Direct Black: 0.01 parts by weight Water: 100 parts by weight Liquid to be supplied to pipe C (the following aqueous solution) I. Direct Yellow 50 ... 0.03 parts by weight C.I. I. Direct Red 218 ... 0.007 parts by weight C.I. I. Direct Black: 0.01 parts by weight Sodium alginate 0.3 parts by weight Water: 100 parts by weight

Example 2 Pulp composed of 30 parts of softwood bleached kraft pulp (NBKP) and 70 parts of hardwood bleached kraft pulp (LBKP) was beaten with a refiner, and the freeness was reduced to 400 ml.
C. S. F. And This was followed by a yellow direct dye (CI.
Direct Yellow 50) was 0.021 parts,
Orange direct dye (CI Direct Ora)
nge 39) 0,018 parts, blue direct dye (C.I.
I. Direct Blue 78) and 0.004 parts by weight of a black direct dye (CI Direct Black).
The dyeing was carried out by adding 0.004 parts of k19). To this, 2.0 parts by weight of a sizing agent (trade name “Size Pine” manufactured by Arakawa Chemical Industry Co., Ltd.) and 5 parts of a dry paper strength enhancer (trade name “Polystron” manufactured by Arakawa Chemical Industry Co., Ltd.) 0 parts by weight and 6.0 parts by weight of liquid aluminum sulfate were added to prepare a slurry. Using a fourdrinier paper machine, this raw material
Papermaking was performed at 10 g / m2 and a papermaking width of 1000 mm. At the time of this paper making, a 1-inch metal pipe with spray nozzles attached at 10 cm intervals was sliced to 100 cm.
From the position, two pipes (pipes A and B) are passed in the width direction at a height of 70 cm above the wire at intervals of 30 cm, and the following two types of pigment liquid containing sodium alginate are applied to the web on the wire of the paper machine. The dyed paper was jetted at a pressure of 2.0 kg / cm 2 to produce a dyed paper having a characteristic spot-like dyed pattern with a strong contrast. B. Liquid to be supplied to pipe A (the following aqueous dispersion) I. Pigment Yellow 3 ... 0.28 parts by weight C.I. I. Pigment Red 21 ... 0.02 parts by weight C.I. I. Pigment Blue 15 0.005 parts by weight Sodium alginate 0.3 parts by weight Water 100 parts by weight Liquid to be supplied to pipe B (the following aqueous dispersion) C.I. I. Pigment Yellow 3 ... 0.11 parts by weight C.I. I. Pigment Red 21 ... 0.02 parts by weight C.I. I. Pigment Black 1 0.005 parts by weight Sodium alginate 0.3 parts by weight Water 100 parts by weight

[0017]

Heretofore, dyed pattern paper having a high contrast as obtained by the present invention cannot be obtained by a papermaking method, but a similar pattern paper can be produced only by a printing technique. For the first time in the present invention, an unprecedented dyed and patterned paper can be obtained by a papermaking method, and a dyed and patterned paper having a color that cannot be obtained by a printing technique can be provided to the market at low cost. Taking advantage of such features, the dyed patterned paper of the present invention is suitably used for calendars, book bindings, packages, stationery and the like.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D21H 27/02-27/04 D21H 23/28

Claims (2)

(57) [Claims] Claims: 1. When making a fourdrinier paper machine using a slurry mainly containing papermaking fibers and containing a cationic substance, a slurry or a web on a wire after a stock inlet is used.
Spraying an aqueous solution and colorant solution of a chemical that thickens or gels by chemically reacting with a cationic substance, or a mixture of both,
A method for producing a dyed pattern paper, comprising forming a wet paper by dropping, jetting, flowing down, or the like to prevent diffusion of a colorant, and then dehydrating and drying the wet paper. 2. The method according to claim 1, wherein the cationic substance is aluminum sulfate.
2. The method according to claim 1, wherein the chemical which thickens or gels by a chemical reaction with the cationic substance is sodium alginate.