JP3381866B2 - Photographic paper and method of manufacturing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is characterized by suppressing the generation of slime by adding an oxidizing agent to paper white water and a raw material for papermaking, and the generation of slime can be suppressed without adding a so-called slime control agent. The present invention relates to a photographic printing paper which is excellent in safety for the human body without impairing the paper quality and photographic properties, and a method for producing the same.

[0002]

2. Description of the Related Art Slime is a viscous substance that is generated in a stock material in a portion where the flow velocity is slow, such as a pipe and an inner wall of a chest in a papermaking process by the action of microorganisms. The slime is controlled by various methods because it not only adversely affects the quality of the appearance but also becomes a cause of impairing operability such as paper breakage and stains on the press blanket.

Of these methods, the most effective method is to add a chemical agent to the paper stock to suppress the growth of microorganisms or to sterilize it. With the improvement of the utilization rate and the neutralization of process pH, it is becoming difficult to select the effective chemical type (slime generation inhibitor), the addition position, and the like. In addition, since many conventional slime control agents are chemicals that adversely affect living organisms, it is becoming important to consider the safety of the photographic printing paper to which they are added to the human body.

Conventionally, 5-chloro-2-methyl has been used as a slime control agent (in the present text, the latter is particularly referred to as a slime control agent in order to distinguish the oxidizing agent of the present invention from the conventional toxic slime generation inhibitor). -4-
Organic nitrogen-sulfur compounds such as isothiazoline-3-thione, organic bromine compounds such as 2,2-dibromopropionamide, organic nitrogen compounds such as dichloroisocyanate, etc. are continuously or shockedly added to the paper stock and used. Has been done.

A method using chlorine dioxide as an oxidant instead of such a highly toxic slime control agent has become common in Europe and America. In this method, the effect of suppressing the generation of slime is enhanced by increasing the addition amount and the addition place. The amount of chlorine dioxide added effective for suppressing the generation of slime is 0.3 ppm or more, preferably 1.0 ppm or more, based on the total amount of white paper or raw materials for paper making. A problem that occurs with an increase in the amount of addition is an oxidative attack on internally added chemicals. In particular, 0.3 ppm is the upper limit in order to avoid decolorization of the dye. Further, when it is added in an amount of 1.0 ppm or more, the sizing property is adversely affected in the case of photographic printing paper which contains a large amount of the internally added size agent.

[0006]

In the conventional method of adding a slime control agent to paper stock, the generation of microorganisms can be suppressed by selecting an appropriate chemical and the addition amount, but the same slime control agent is used for a long time. Then, due to denaturation of microorganisms, a sufficient slime control effect was often not obtained. Further, even a slime control agent that can obtain a sufficient slime control effect, there are many problems such as the adverse effect on the paper quality such as size and the photographic property and the high risk to the human body when added, It was difficult to find a slime suppressor and a control method.

That is, an object of the present invention is to provide a slime generation / removal means which does not have these drawbacks. Instead of killing microorganisms and fungi by toxicity of chemicals, the microorganisms and fungi are killed by oxidative action. The purpose is to do. Further, the drug acting as an oxidizing agent becomes a harmless salt such as salt or water after oxidizing microorganisms and fungi.
Accordingly, it is an object of the present invention to provide a photographic printing paper which is excellent in safety for the human body without impairing the paper quality and photographic properties, and a manufacturing method thereof.

[0008]

Means for Solving the Problems The present invention adds hypochlorite or hydrogen peroxide as an oxidizing agent to a papermaking raw material system and a white water system to kill microorganisms and fungi which are internally generated and propagated, The oxidizing agent itself is achieved by oxidizing microorganisms and fungi and then converting them into harmless substances.

Since conventional slime control agents have a long-lasting toxicity after addition, they can be applied to the whole papermaking system by adding a small amount in a high concentration state such as a machine chest or a seed box. There was an advantage of crossing.
However, the oxidizing agent used in the present invention kills the microorganisms and fungi at the place where it is used, but the microorganisms and fungi are generated at other places, and it is not effective in suppressing the slime generation.

Such an attempt has been confirmed by ultraviolet (UV) irradiation, and when the white water flowing into the white water tray under the wire is irradiated with UV, the tray outlet (silo inlet) is used.
Confirmed the effect of killing microorganisms and fungi, but did not kill the microorganisms and fungi in the headbox raw material.

According to the present invention, 1 to 30 ppm of an oxidizing agent is added to a papermaking raw material before adding chemicals for papermaking to sterilize the pulp, and 1 to 30 ppm of an oxidizing agent is added to white papermaking paper. It is achieved by killing the microorganisms and fungi that cause slime generation by adding at least two places. These additions are at the minimum necessary addition place, and more preferably, by adding to a seal pit such as a suction box for establishing a vacuum and a white water recovery system, a further effect can be exhibited.

The papermaking raw material of the present invention is a material obtained by dispersing pulp or an internally added chemical in water, and a recovered raw material. The recovered raw materials are wet brooke, white water recovered raw material, and co-paper. Therefore, it goes without saying that it is effective to reduce the number of microorganisms and fungi in advance by adding the oxidizing agent used in the present invention to water for disintegrating pulp and water for adjusting various chemicals. Further, the stock material of the present invention is a raw material obtained by mixing the above-mentioned papermaking raw material pulp, recovered raw material and chemicals.

Further, when an oxidizing agent which suppresses the generation of slime does not cause a problem in the characteristics required for photographic printing paper, a hypochlorite or hydrogen peroxide is used. It turned out to be effective. Further, it has been found that hydrogen peroxide can be added to the stock after the addition of internal additives in the raw material for photographic printing paper, and it can be more effective by combining both. understood.

The photographic printing paper of the present invention contains an antifoggant, a dye, a filler, a sizing agent, a fixing agent, a dry paper strengthening agent,
A wet paper strength enhancer, a yield improver, etc. may be added as necessary. Various starches, polyvinyl alcohol,
It is also possible to apply a surface treatment with gelatin or the like, and an antistatic treatment with Glauber's salt, sodium chloride, an organic conductive agent or the like to the surface, if necessary. Furthermore, it is possible to coat the paper surface with a waterproof resin such as a polyolefin resin.

The photographic printing paper of the present invention can be used as color printing paper, black-and-white printing paper, copy printing paper, plate-making printing paper, and the like.

[0016]

[Function] Stimulation of slime is suppressed by adding one or both of hypochlorite and hydrogen peroxide as an oxidizing agent to a papermaking raw material to kill microorganisms and fungi causing slime generation. Therefore, it is possible to obtain a photographic printing paper sheet that does not affect the paper quality and photographic property and is excellent in safety for the human body.

[0017]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples. The present invention is not limited to the examples. All parts and% in the following are by weight. In the examples described below, sodium salt was selected as the hypochlorite salt, but calcium salt can be used without any problem.

Production Example 1 LBKP beaten to a freeness of 350 ml and freeness of 450
To 100 parts of beaten pulp obtained by mixing NBSP beaten to a volume of 7: 3 in a weight ratio, 2.0 parts of cationic starch (Kate F, manufactured by Oji National Co., Ltd.), alkyl ketene dimer size agent (SPK903, Arakawa Chemical Co., Ltd.) 0.4)
Part, 0.3 part of polyamide-polyamine-epichlorohydrin resin (WS-525, manufactured by Japan PMC Co., Ltd.) is added. The stock thus blended was manufactured with a Fourdrinier paper machine to produce a photographic printing paper having a basis weight of 180 g / m ² . here,
The water-making temperature was 35 ° C. The composition is not limited to the above.

FIG. 1 shows an example of the flow of the paper machine of Production Example 1, but it is a typical Fourdrinier paper machine and is not particularly limited. Next, regarding the flow of the paper machine of FIG.
explain. The beaten pulp is stored in the pulp chest 1. The wet broke recovered in the press part 17 is defibrated in the wet broke defibration pit 16 and then stored in the wet broke chest 2 and mixed in the machine chest 3 with pulp and various chemicals. The raw materials mixed in the machine chest 3 are raised to the seed box 4, and after adjusting the concentration, the necessary amount is measured by the seed mouth valve 5. This raw material is diluted with white water in the white water silo 6, and dust is removed by the cleaner 7 and the screen 9. Deaccuration tank 8
Is for deaeration of raw materials. This raw material is jetted from the head box 10 to the wire 11. Wire 11
The white water dehydrated below is collected in the white water tray 13 and returns to the white water silo 6. The white water dewatered by the suction box 12 of the wire part and the white water squeezed by the press part 17 are collected in the seal pit 14. The white water in the seal pit 14 returns to the white water silo 6, and the white water silo 6
Then, in order to keep the liquid level, white water is overrun by the silo over 15, and this is returned to the seal pit.

EXAMPLE 1 Sodium hypochlorite as a slime generation inhibitor was added as a slime generation inhibitor at each of the pulp chest 1, wet broke chest 2, white water silo 6, white water tray 13 and seal pit 14 1 for the total amount of
ppm was added to produce a photographic printing paper.

Example 2 A photographic printing paper sheet was produced in the same manner as in Example 1 except that the amount of sodium hypochlorite added was 3 ppm with respect to the total amount of white water or papermaking raw material.

Example 3 Photographic paper was produced in the same manner as in Example 1 except that the amount of sodium hypochlorite added was 10 ppm with respect to the total amount of white water or papermaking raw material.

Example 4 A photographic printing paper sheet was produced in the same manner as in Example 1 except that the amount of sodium hypochlorite added was 30 ppm with respect to the total amount of white paper or papermaking raw material.

Example 5 Sodium hypochlorite was added to the pulp chest 1 and the white water silo 6 at 1 ppm with respect to the total amount of white water for paper making or paper making raw materials to produce photographic printing paper.

Example 6 A photographic printing paper was produced in the same manner as in Example 5 except that the amount of sodium hypochlorite added was 3 ppm with respect to the total amount of white paper or the raw material for papermaking.

Example 7 A photographic printing paper sheet was produced in the same manner as in Example 5 except that the amount of sodium hypochlorite added was 10 ppm with respect to the total amount of white paper or papermaking raw material.

Example 8 A photographic printing paper sheet was produced in the same manner as in Example 5 except that the amount of sodium hypochlorite added was 30 ppm with respect to the total amount of white paper or papermaking raw material.

Example 9 Pulp chest 1, white water silo 6 and seal pit 1
Sodium hypochlorite was added at 1 ppm in each place of 4 to the total amount of white paper or the raw material for paper making to produce photographic printing paper.

Example 10 A photographic printing paper sheet was produced in the same manner as in Example 9 except that the amount of sodium hypochlorite added was 3 ppm with respect to the total amount of white paper or papermaking raw material.

Example 11 A photographic printing paper sheet was produced in the same manner as in Example 9 except that the amount of sodium hypochlorite added was 10 ppm with respect to the total amount of white paper or papermaking raw material.

Example 12 A photographic printing paper sheet was produced in the same manner as in Example 9 except that the amount of sodium hypochlorite added was 30 ppm with respect to the total amount of white paper or papermaking raw material.

Example 13 Sodium hypochlorite was added to the pulp chest 1, the wet broke chest 2, the white water silo 6, the white water tray 13 and the seal pit 14 at 3 ppm with respect to the total amount of the papermaking whitewater or the papermaking raw material. Further, hydrogen peroxide was added in the seed box 4 to the total amount of the raw materials for paper making in the seed box 4 to produce a photographic printing paper.

Example 14 Pulp chest 1, white water silo 6 and seal pit 1
In each place of 4, 3ppm of sodium hypochlorite is added to the total amount of white paper or raw materials for papermaking, and
10 pp of hydrogen peroxide in seed box 4 for the total amount of papermaking raw materials
m was added to produce a photographic printing paper.

Example 15 In each place of the pulp chest 1 and the white water silo 6,
Sodium hypochlorite was added in an amount of 3 ppm with respect to the total amount of white paper or raw materials for making paper, and hydrogen peroxide was added in seed box 4 in an amount of 10 ppm with respect to the total amount of raw materials for making paper to produce a photographic printing paper.

Example 16 In each of the pulp chest 1, the wet broke chest 2, the white water silo 6, the white water tray 13, the seal pit 14 and the seed box 4, hydrogen peroxide was added to the papermaking whitewater or the total amount of the papermaking raw material. 3 ppm was added to produce a photographic printing paper.

Example 17 In each of the pulp chest 1, the wet broke chest 2, the white water silo 6, the white water tray 13, the seal pit 14 and the seed box 4, hydrogen peroxide was added to the total amount of papermaking whitewater or papermaking raw materials. 10 ppm was added to produce photographic printing paper.

Comparative Example 1 A photographic printing paper sheet was produced without using an oxidizing agent, using the same raw materials and the same papermaking conditions as in the above Production Example.

Comparative Example 2 A photographic printing paper was produced in the same manner as in Example 1 except that the amount of sodium hypochlorite added was 40 ppm with respect to the total amount of white paper or the raw material for papermaking.

Comparative Example 3 A photographic printing paper was manufactured in the same manner as in Example 1 except that the amount of sodium hypochlorite added was 0.5 ppm with respect to the total amount of white paper or papermaking raw material.

Comparative Example 4 Machine Chest 3 was prepared by adding 5-chloro-2methyl-4-isothiazoline-3-thione as a slime control agent.
In this place, 60 ppm was added to the solid content to produce a photographic printing paper.

Table 1 shows the above examples and comparative examples.
The location and amount of addition of the oxidizer are shown in. The numbers in Table 1 represent the addition rate in ppm with respect to the pulp slurry flow rate. Also, * attached to the left of the numbers in Table 1 is the one to which hydrogen peroxide is added, and when * is not attached, sodium hypochlorite is added.

Subsequently, Table 2 shows the results of the number of bacteria measured as described below, the size property (paper quality) and the photographic property of the base paper according to the following evaluation method.

[Number of bacteria] The number of bacteria that causes slime is
The headbox raw material was sampled every day after the papermaking was measured. The number of bacteria was shown per 1 ml of the headbox material by the colony counting method using Waxman agar medium. When the number of bacteria per ml is 10 ³ or less, there is no problem at all, and when it is 10 ⁷ or more, slime is generated and papermaking cannot be performed.

[Size Property] The size property is a value of the permeability of a photographic developer at 120 ° C. for 120 seconds at 30 ° C., which is measured according to the Cobb size test method of T-441m-60, which is a standard test method of TAPPI. g / m ² ), and assuming that other chemicals do not adversely affect, a value of 25 g / m ² or less should be obtained when the addition amount of the alkyl ketene dimer sizing agent is 0.4%.

[Photographic Property] The photographic property was evaluated by coating a color photographic paper obtained by coating a color photographic emulsion on the surface of a photographic photographic paper at 50 ° C. and 65% RH. H. After aging for 10 days under the conditions of temperature and humidity, the image was developed by a usual method, and the background color was measured as fog with a Macbeth densitometer (RD519). Here, if the density is 0.3 or less, it can be determined that there is no problem in photographic properties. As for the problematic ones, it is impossible to use all of them, so it is indicated by x. Those with no problems are marked with a circle.

[0046]

[Table 1]

[0047]

[Table 2]

From the results shown in Table 2, by comparing Comparative Example 1 with Examples, it is possible to add one or both of hypochlorite and hydrogen peroxide, which are oxidants, to the white paper and the papermaking raw material. The effect of suppressing the number of fungi causing slime generation in the headbox was confirmed. Further, as shown in the examples, it can be confirmed that the larger the amount of the oxidizing agent added and the more the places where the oxidizing agent is added, the more the growth of fungi can be suppressed.

Regarding the quality, it can be confirmed that there is no problem with respect to the size and the photographic property as long as it is within the range of 1 to 30 ppm, which is the addition amount of this embodiment. However, when the addition amount is 40 ppm as in Comparative Example 2,
Although the effect of suppressing the growth of fungi is very excellent, it results in a decrease in size. Further, when the addition amount is reduced to 0.5 ppm as in Comparative Example 3, the effect of suppressing the growth of fungi is completely lost.

Regarding the slime control agent used conventionally, it is a mistake that the addition amount of the slime control agent is 60 ppm with respect to the solid content of the raw material, and that the addition of a very small amount has an effect of suppressing the growth of fungi. Although it does not exist, there are problems with size and photographic characteristics. When a displacement progenitor test was carried out on the examples of the present invention, there was no problem at all with regard to the white water for papermaking and the headbox raw material obtained by adding at least one of hypochlorite and hydrogen peroxide to the raw material for papermaking.

[0051]

As described above, in the present invention, the addition of an oxidizing agent as a slime generation inhibitor, particularly hypochlorite or hydrogen peroxide, to papermaking white water and papermaking raw materials in an amount of 1 to 30 ppm causes slime formation. It is clear that a photographic printing paper which is suppressed and is excellent in sizing property, photographic property and human safety can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing a flow of a paper machine used in a production example, which is an example of an embodiment.

[Explanation of symbols]

1 pulp chest 2 Wet Broke Chest 3 machine chest 4 kinds box 5 kinds mouth valve 6 white water silo 7 cleaner 8 deaccuration tank 9 screen 10 head box 11 wires 12 suction box 13 White water tray 14 seal pit 15 silo over 16 Wet Broke Disaggregation Pit 17 Press Part

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kazuo Kodama Kazuo Kodama 3-4-3 Marunouchi, Chiyoda-ku, Tokyo Sanryo Paper Co., Ltd. (72) Ken Yamazaki 3-4-2-3 Marunouchi, Chiyoda-ku, Tokyo Within Ryo Paper Co., Ltd. (56) Reference JP-A-56-77845 (JP, A) JP-A-2-96132 (JP, A) JP-A 61-89396 (JP, A) (58) Fields investigated ( Int.Cl. ⁷ , DB name) G03C 1/775

Claims (5)

(57) [Claims] 1. A photographic printing paper, wherein the paper contains an oxidizing agent as a slime generation inhibitor and a raw material for papermaking.
Add 1 to 30ppm to the total amount, and in papermaking white water
A photographic printing paper, which is the paper produced by adding 1 to 30 ppm to the total amount of the white water . 2. The photographic printing paper according to claim 1, wherein the oxidizing agent is at least one of hypochlorite and hydrogen peroxide. 3. A method of manufacturing a photographic printing paper sheet, comprising:
An oxidizing agent is used as a slime generation inhibitor and is used as a raw material for papermaking.
1 to 30 ppm with respect to the total amount of
As paper stock, and for papermaking white water based on the total amount of the white water
A method for producing a photographic printing paper , comprising adding 1 to 30 ppm and making a paper using the paper stock. 4. The method for producing a photographic printing paper sheet according to claim 3 , wherein the oxidizing agent is at least one of hypochlorite and hydrogen peroxide. 5. A method for producing a photographic printing paper, wherein an oxidizing agent is added, and hydrogen peroxide is added to the stock after addition of internal additives in an amount of 1 to 30 ppm with respect to the total amount of the papermaking raw material.
A method for producing a photographic printing paper sheet according to claim 3 or 4 , which comprises making a paper.