JP2001131893A - Laminated photocatalyst pulp paper, its manufacturing method and defibrator used in the process, paper string comprising laminated photocatalyst pulp paper and its manufacturing method, and formed article comprising the paper string - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated photocatalyst pulp paper having an antibacterial effect, a decomposition effect on offensive odor and an oxidative decomposition effect on toxic substances, widely useful for filters, packaging materials, construction materials, or the like, and effective in using for atmospheric treatment, water treatment, soil treatment and capable of increasing the photocatalytic effect of titanium oxide itself. SOLUTION: The laminated photocatalyst pulp paper comprises a photocatalyst composition comprising 5-60 wt.% of titanium oxide compounded with 40-95 wt.% of pulp and/or paper having <=3 wt.% water content, 5-300 μm of an average fiber diameter and 0.1-70 mm of an average fiber length, laminated with waste paper pulp, and a paper string comprising the pulp paper is produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated photocatalytic pulp paper having a photocatalytic activity effect using pulp and / or paper and waste paper, preferably newspaper waste paper as a main molding material, and a method for producing the same. Considering the recycling of paper, after adsorbing titanium oxide on pulp and / or paper, it is preferable to laminate newspaper waste paper that has passed through the DIP process, for example, in the paper making process, or dry it separately to obtain recycled paper. Photocatalytic properties of titanium oxide when laminated via an adhesive, that is, activated by ultraviolet rays, such as deodorization and antibacterial, can improve or effectively exhibit the property of oxidatively decomposing organic substances, ammonia, NOx, SOx, etc. Deodorizing and antibacterial filter media, shoji, sliding paper, wallpaper, blinds, panels, lamp shades, sheets, curtains,
Furniture, building materials and general packaging materials such as carpets, sofas and seats, flexible composite packaging materials, special packaging materials such as fungicides, car interior materials, household electrical products surface materials, and other daily necessities And photo-catalytic activity that can be widely applied to various uses as films, sheets, adhesives or adhesive resin layers, various coating materials or coating resin films, or paint or coating resin films. And a laminated photocatalytic pulp paper having the same.

The present invention also relates to the development of a new use of the laminated photocatalytic pulp paper. The present invention relates to a packaging material having deodorizing and antibacterial properties and other daily necessities such as mats, baskets, screens, curtains, hats, and the like. Water-soluble pet sand that has an antibacterial and deodorizing function that is more efficient in treating odors generated from clothing and manure of pets and that can be poured into flush toilets, and paper made of the laminated photocatalytic pulp paper as various molded articles or materials It is intended to provide a cord and a molded article made of the paper cord.

[0003]

2. Description of the Related Art Conventionally, this kind of titanium oxide has been used as a deodorizing filter, and has been provided as a coating agent.
It is used to obtain antifouling and antibacterial effects on the surface. Further, a paper cord having a photocatalytic activity effect has not been provided so far.

[0004]

However, these conventional products have a slow reaction speed when coated or fixed in a space between fibers, and the completion of the reaction is extremely slow. It had a negative consequence.

[0005] The present invention solves the above problems and provides antibacterial, antifouling, and antifouling materials for a wide variety of uses such as packaging materials, building materials, and filter media.
It is an object of the present invention to provide a laminated photocatalytic pulp paper having an effect of decomposing (soil) and malodor, deodorizing treatment, and oxidative decomposition of harmful substances, and a method for producing the same.

Another object of the present invention is to provide a paper cord and a molded article which retain physical properties as a packaging material such as tensile strength and are suitable for the above-mentioned various uses or as a raw material of various molded articles. Is what you do.

[0007]

In order to achieve the above object, the laminated photocatalytic pulp paper of the present invention comprises titanium oxide 5 to 60 watts.
t%, moisture content within 3 wt% and average fiber diameter 5 ~ 300μ
m, pulp and / or paper 40-95wt with average fiber length 0.1-70mm
% Of a virgin pulp or a waste paper pulp on a photocatalytic pulp composition as a composition prepared by blending at a ratio of 0.1%.

In addition, the titanium oxide and 25 to 100% by weight of a thermoplastic resin based on the total weight of pulp and / or paper are blended, and virgin pulp or waste paper pulp is laminated on the blend. be able to.

The method for producing the laminated photocatalytic pulp paper is as follows: Pulp and / or paper defibrated and defibrated to 5 to 60% by weight of titanium oxide to an average fiber diameter of 5 to 300 μm and an average fiber length of 0.1 to 70 mm.
The photocatalytic pulp composition, which is blended at a ratio of t%, is stirred by applying a stirring impact force to generate shear heat by a shearing force based on the stirring impact force, and the shear heat is applied to the composition to generate the shear heat. Drying to reduce the water content to 3 wt% or less, swelling the pulp and / or paper with the drying to form a three-dimensional fiber entangled body, and stirring the titanium oxide by the stirring impact force. Virgin pulp or waste paper pulp is laminated in a papermaking process after the treatment process of pressing and fixing the pulp and / or paper on the fiber surface and the papermaking process after the treatment process of pressing and fixing the titanium oxide.

In the above-mentioned manufacturing process, the total weight of the titanium oxide, pulp and / or paper is 25 to 100 watts.
t% thermoplastic resin can be blended.

If the used paper pulp is made of used newspaper used in the DIP process, it is suitable for reuse of used newspaper. This used pulp can be used as a core material or a base material.

Further, the average fiber length is 1 to 100 m with respect to the titanium oxide of 5 to 60 wt% and the pulp and / or paper of 40 to 95 wt%.
m, average diameter 10 ~ 40μm, synthetic fiber with melting point 120 ° C or higher
It can be blended at a ratio of 1: 9.

When the raw material pulp as the photocatalytic pulp composition is a paperboard dry pulp, the dry pulp is shattered into a plurality of small pieces to be subjected to impact milling. Fibrillation and disintegration step 3 which is substantially the same length as the fibrous raw material pulp which has been milled by applying force and flocculated into floc, and which has no cilia even after the above-mentioned milling.
03 is included.

Further, the above-mentioned dry pulp defibration and defibration apparatus comprises:
A plate-shaped dry pulp is to be processed, and is located on a fixed disk 131 having a central portion communicating with a supply inlet 132 for small pieces to be processed which are to be processed.
And a movable disk 1 provided so as to be rotatable and opposed to the fixed disk 131.
41, a movable-side impact grinding means in which the movable pins 144 are sequentially implanted on a plurality of rotation trajectories different from the fixed pins 134, and preferably, the fixed pins 134 for removing foreign matter. A screen 1 having a hole of a predetermined diameter in the outer peripheral portion of the combination of the movable pin 134 and the movable pin 144
A collecting means communicating with the discharge port through the discharge port 51; and removing the treated small pieces remaining in the screen 151 into the pulp fibers 84 in the form of the crushed and flocculent fibrous fibers. Means.

The pulp fibers 84 thus recovered
Is transferred to the next step of titanium oxide fixing.

Further, the paper string made of the laminated photocatalytic pulp paper according to the present invention is obtained by twisting the laminated photocatalytic pulp paper, preferably having a basis weight of about 20 to 80 g / m ^2, which is cut to an arbitrary width of 5 to 50 mm. It is characterized by comprising. In addition to its use as a packaging material, etc., it is cut to a diameter of about 2 to 5 mm and a length of about 5 to 30 mm to provide a more efficient antibacterial and deodorant function for the treatment of foul odors generated from pet manure as pet manure processing. Can be used as water-soluble pet sand that can be flushed into flush toilets.

The production method is characterized in that the laminated photocatalytic pulp paper is cut into a width of 5 to 50 mm, wound up in a roll shape, and then twisted, for example, for about 15 to 30 rotations.

In addition, the process of superposing a plurality of, for example, 10 to 40, of the paper cords on the same plane and immersing and drying the same in a water-soluble adhesive is repeated about three times, and the adhesive layer is removed by sanding. Thus, a belt-shaped flat cord can be formed.

Also, a woven fabric can be manufactured by using the paper cord as the weft yarn and the warp yarn as a yarn made of natural fiber such as cotton yarn or chemical fiber such as rayon. Further, the paper cord, flat cord or woven fabric can be combined to meet a wide range of applications. can do.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Photocatalytic pulp composition of material to be laminated: Example (1)] In this example, the pulp and / or paper used as a raw material is not only virgin pulp in the papermaking process but also waste paper pulp or For example, it contains pulp in which both are mixed at a ratio of 1: 1, and the paper includes waste paper such as plain paper or widely used newspaper. After crushing with a cutter mill having a 10 mm × 10 mm screen,
Used paper containing a large amount of printing ink is preferably bleached or colored by DIP treatment or the like in the paper making process similarly to used paper to be laminated later.

Then, 80% by weight of virgin pulp and / or paper having an average fiber diameter of 5 to 300 μmm, an average fiber length of 0.1 to 70 mm, a bulk specific gravity of 0.005 to 0.04, and 0.24 of virgin pulp and / or paper (the pulp and / or paper About 8 wt%) and 20 wt% titanium oxide
It is compounded.

The average fiber diameter of the pulp and / or paper of 5 to 300 μm and the average fiber length of 0.1 to 70 mm mean a particle diameter of 50% by weight in the cumulative weight percentage distribution of the pulp and / or paper.

In the case of paper, it is preferable to use a crusher or the like.
Use what has been crushed through a 10 mm mesh screen.

The printing ink on the used paper has no problem in processing, except that a slight color is attached to the product.

When the dry pulp in the form of paperboard is to be treated, the dry pulp is subjected to an impact milling force on each of the small pieces to be treated formed by chopping the dry pulp into a plurality of small pieces to be treated. In the same manner as described above, a pulp fiber which is substantially the same length as the fibrous raw material pulp which has been ground and flocculently flocculated and which has undergone the fibrillation / disintegration step 303 to be a pulp fiber having no cilia even after the grinding is used.

The impact grinding means used in this step is referred to as a "separator" in this embodiment for convenience.

3 to 6, the separator 130
A communication opening is formed at a central portion of the fixed disk 131 with a supply inlet 132 for inputting each of the small pieces to be processed.
The fixed end plate 133 is opposed to the processing space 155,
The outer peripheral edge of each fixed end plate 133 is fixed to the fixed disk 131 by a peripheral side plate 135. In the processing space 155, the movable disk 1 that is rotationally driven by the rotating horizontal shaft 142
41, and the rotating horizontal shaft 142 is pivotally supported by the bearings 143, 143. The rotation horizontal shaft 142 is rotationally driven by a rotation driving means such as a motor. On the fixed disk 131, a plurality of, in this embodiment, six concentric rotation trajectories a1 (relative to the movable disk 141)
A6 (FIG. 5). In this embodiment, each fixing pin 134 is moved from the center on the fixed disk 131 toward the outer peripheral edge on the concentric circle 16-16-32-36-. 40-4
On the other hand, two movable pins 144 are implanted on the movable disk 141 alternately on a plurality of rotation trajectories b1 to b6 in the present embodiment, which are different from the fixed pins 134. 4-4-4-4-4-6 pieces are sequentially planted from the center on the movable disk 141 toward the outer peripheral edge on the concentric circle, and these fixed and movable pins 134 and 144 are sequentially implanted. Are positioned so that the above-described defibrating and disintegrating action can be obtained by the impact grinding force.

Further, a screen 151 having a predetermined mesh formed by punching pores having a desired diameter is provided around the outer peripheral side of the movable disk 141 and the peripheral side plate 135 with a discharge space 156 therebetween. Outlet 15 below
2 is provided. A blower 157 is connected to the separator 130 as shown in FIG.

Then, the discharge port 152 is connected to the collection tank 250 via a discharge pipe 239 provided with a blower 157.

The screen 151 has a diameter of about 0.8 mm to 2.0 mm, depending on the number of rotations of a movable pin to be described later. Further, an outlet 153 is formed below the screen 151 in the processing space 155 (FIG. 3). By increasing the clearance between the fixed and movable pins 134 and 144, the grinding force applied to the small pieces to be processed is reduced,
By reducing the clearance, the grinding power is increased. As shown in FIG. 6, the blower 1 for sucking air in the separator 130 is provided in the outlet 153.
57 may be connected to the supply inlet 132 via the blower 157.

As shown in FIGS. 3 and 6, the outlet 153 and the processing space 155 communicate with each other through a communication pipe 235, and a compressed air supply source (not shown) circulating from the outlet 153 to the processing space 155. Is introduced into the communication pipe 235 through the pipe 236, and the milled pulp fibers and foreign matter discharged from the outlet 153 are again separated by the separator 130.
It can also be configured to recirculate in the processing space 155 in the inside.

A branch pipe 237 for branching the supply inlet side of the communication pipe 235 and communicating with the pulp fiber or the pulp fiber and foreign matter recovery tank 240 is provided. A two-way solenoid valve 238 that can be switched at appropriate intervals by a timer circuit is provided, the downstream side of the communication pipe 235 is closed with a solenoid valve and the branch pipe 237 side is opened, and the pulp fiber remaining in the screen 151 To the collection tank 24 via the branch pipe 237.
Collect within 0. Alternatively, an electromagnetic valve for opening and closing the branch pipe 237 and an electromagnetic valve for opening and closing the downstream side of the communication pipe 235 may be provided, and these two electromagnetic valves may be alternately opened and closed (FIG. 6).

The rotating horizontal shaft 1 is driven by a rotating drive means such as a motor.
When the movable disk 141 is rotated by rotating the movable disk 141 and each of the small pieces to be processed is supplied to the supply inlet 132, each small piece to be processed is located at the center of the processing space 155 and each of the fixed and movable pins
Due to the impact attrition force between the particles 34 and 144, the small pieces to be treated are more finely loosened into fibrous shapes, while the foreign substances are irregular in shape due to the impact attrition force but have a diameter of about 2 to 6 mm.
mm. That is, each piece to be treated is beaten by the impact of each of the fixed and movable pins 134 and 144 to be finely crushed or crushed, and the finely crushed paperboard is separated from the piece to be treated because the folding action is repeatedly applied to each piece to be treated. Is done. In this way, the pulp fibers and foreign substances constituting the small pieces to be treated are separated for each type,
The paperboard is unraveled into fibrous forms, and the foreign matter is ground into flakes. During this time, the centrifugal force due to the rotation of the movable disc 141,
The separated and fibrous paper layer and the pulp fiber or fibrous paper layer are gradually removed by suction by the blower 157 or an air current generated by compressed air supplied into the processing space 155 via the pipe 236. The separator 13 provided around the screen l51 in a state in which
0 approaching the outer circumference. Then, the screen 1 in which the fibrous pulp is formed into a mesh having a diameter of about 0.8 to 2 mm
After passing through the discharge space 156 and being discharged into the discharge space 156, the air is sucked from the discharge port 152 to the outside through the blower 157,
It is collected in the collection tank 250 via the discharge pipe 239. On the other hand, flaky foreign matter and pulp fibers in a slightly flocculated form cannot pass through the screen 151 and remain inside the processing chamber. When the collection of the pulp fiber is completed, the foreign matter remaining in the processing space 155 is discharged from the outlet 153 to the outside.

The discharged foreign matter is transferred downstream of the communication pipe 235 by a two-way solenoid valve 238 of a branch pipe 237 that communicates with a recovery tank 240 of the pulp fiber or the like branched from the supply inlet side of the communication pipe 23. Side is closed by a solenoid valve and the side of the branch pipe 237 is opened, foreign matter left in the screen 151 is sucked, and the collection tank 2 is sucked through the branch pipe 237.
Collected in 40.

In FIG. 3, the connection of the communication pipe 235 to the branch pipe 237 is performed on the upstream side of the communication pipe 235, at the outlet 1
This is through a flange 154 provided on a pipe branching off the 53 side (to the rear in FIG. 3).

The pulp fiber 84 thus recovered
Is transferred to the next step. The smaller the particle size of titanium oxide, the better the performance. For example, an X-ray particle size of 7 to 50 nm can be used.

The pulp and / or paper and titanium oxide,
Alternatively, synthetic fibers are charged together with them, and shear heat is generated by shearing force based on the stirring impact force of the stirring impact blade rotating at high speed in the mixer, the temperature is increased to about 120 ° C., and titanium oxide and pulp and / or paper 3wt% moisture content
Preferably, it is 1 wt% or less. In this step, moisture evaporates from the pulp and / or paper and dries, and in the case of paper, the pulp and / or paper becomes fibrous due to the pulverizing action by the impact force and further swells with the drying. Then, the fibers are fluffed, agglomerated in a defatted shape, and a three-dimensional fiber entangled body, and titanium oxide is also adhered to the fiber surface and inside the fiber by a pressing external force caused by the stirring impact force or the shearing force by the stirring impeller, Infiltrate and fix.

The synthetic fiber may have, for example, an average fiber length of 1 to 100 m.
m, an average diameter of 10 to 40 μm, and a melting point of 12 ° C. or higher are preferred.

The virgin pulp usually has a water content of about 10% by weight in the case of a plate-shaped dry pulp. However, even when the water content is higher than that, the above-mentioned mixer or a known dryer may be used before mixing the titanium oxide. As a result, predrying is performed or preferably performed to a water content of 10 wt% or less.

In this step, the attachment and fixation of titanium oxide are completed to form a photocatalytic pulp composition.

In this step, the pulp and / or paper in the raw material does not form a large lump, and the individual fibers agglomerate in the form of a loosened fiber without being entangled with each other hard,
In this sense, a three-dimensional fiber entangled body is formed, and the individual pulp and / or paper is formed with titanium oxide attached to the entire surface of the pulp and / or paper fiber alone, and these individual pulp and / or paper are formed. Since the lumps are paper-like lumps in which paper is gathered, there is no adhesion between pulp and / or paper alone, and the lumps themselves have a high bulk density. Therefore, the photocatalytic pulp composition formed by this process is a good material as a photocatalytic pulp paper that can be made in various known papermaking processes.

The above process is described in more detail. Since the pulp and / or paper has a water content of 3 wt% or less,
The interface between the titanium oxide and the pulp and / or paper is eliminated, and the titanium oxide is dispersed at a uniform density in the pulp and / or the paper, and the pulp and / or the paper is easily adsorbed or adhered to the pulp and / or the paper. The paper is mixed and dispersed so as to surround the outer periphery of the paper.

The photocatalytic pulp composition produced as described above can be used as a pulp raw material and formed into paper by various papermaking methods.

Further, photocatalytic pulp paper is obtained by mixing plastic fibers, glue, starch, wax, vinyl acetate, and an acrylic resin adhesive as a binder in a paper making process.

Using the pulp composition having photocatalytic activity, a photocatalytic pulp paper was produced.

As examples and comparative examples of the photocatalytic pulp paper using the photocatalytic pulp composition, titanium oxide was ST-01 (Ishihara Techno Co., Ltd.), X-ray particle diameter 7 nm, titanium oxide content 90 wt% or more, specific surface area. Treated by a stirring impact force of a stirring impeller that rotates at a high speed in the mixer (120 ° C.) using a m ² / g: 300.

[Photocatalytic Pulp Composition 1; Example 1] About 2.5 kg of a plate-like dry pulp was treated in the defibration and defibration step to obtain a defibrated pulp having a water content of 10 wt% and a water content of about 2.0 kg.

In the immobilization process, about 2.0 kg
Was immobilized to obtain about 3.90 kg of a photocatalytic pulp composition (water content: 0.5 wt%). [Photocatalyst pulp composition 2; Example 2] (FIGS. 1 and 2) Ground paper fiber 2 kg (80 wt%) water content 10 wt%: treated in the above defibration and defibration step Titanium oxide; 0.5 kg (20 wt%) Fix this Approximately 2.3 kg of a photocatalyst pulp composition was obtained through the hydrotreating process.

Photocatalyst pulp composition paper: Example 1 Using the photocatalyst pulp composition obtained in the above [Photocatalyst pulp composition 1; Example 1], a pulp concentration of 8 watts was measured by a beater.
The mixture was diluted to t% and beaten for 1 hour (hour).

On the other hand, a beaten pulp raw material such as virgin pulp containing Japanese paper, for example, used paper pulp made of used newspaper that has been subjected to a DIP (deinking treatment) process is diluted with water so as to have a pulp concentration of 8 wt% for 1 hour. A beating treatment is performed, and then, in a known papermaking process, a wet paper sheet of pulp composed of photocatalytic pulp and old newspaper is used using a papermaking machine. Photocatalytic pulp after beating (50 g
/ m ² ) and pulp (10 g / m ² ) consisting of used newspaper are respectively made by a circular net and a fourdrinier paper machine, overlapped, transported to a press part, and further dried and glued.

As described above, a translucent and air-permeable white base material layer made of used newspaper was laminated on the photocatalytic pulp layer (Example 1).

Photocatalyst pulp composition paper: Example 2 The photocatalyst pulp composition obtained in [Photocatalyst pulp composition 2; Example 2] was combined with used newspaper pulp in the same manner as in Example 1.

Beater treatment time 1 hour Photocatalytic pulp concentration 8 wt% Newspaper pulp concentration 8 wt% Basis weight Total 60 g / m ² Photocatalytic pulp layer 50 g / m ² Newspaper waste pulp layer 10 g / m ²

[Photocatalytic pulp + paper; Comparative example 1] The paper fiber; 2 kg (80 wt%) titanium oxide; 0.5 kg (20 wt%) was simply pulp-concentrated with a beater without using the mixer in the above embodiment and example. so as to be 8 wt%, paper and beating diluted basis weight total 50 g / m ^2.

The test results of Examples 1 and 2 and Comparative Example 1 are shown below. Experimental conditions Added acetaldehyde concentration approx. 820 ppm Light intensity approx. 1 mW / cm ² reaction vessels 1 liter Photocatalytic pulp paper and other comparative examples Sample size: 8 × 8 cm Total grammage: Examples 1,2 60 g / m
² Comparative Example 1 50 g / m ²

[0056]

[Table 1] The initial generation rate of the photocatalyst CO ₂ is expressed by the following formula; (apparent CO ₂ initial generation rate)-(1ight control CO ₂ generation rate) The production rate (%) at 1h and 2h is the photocatalytic component in the production ratio to the theoretical value. The initial acetaldehyde extinction rate is the extinction rate at 30 min after light irradiation. The acetaldehyde extinction rate (%) at 1 h is: concentration at 1 h / initial concentration x 100 photocatalyst + pulp paper; The photocatalytic activity is extremely low, and the acetaldehyde disappearance rate is slow.

On the other hand, photocatalytic pulp paper;
Indicates 100% with the CO ₂ generation rate in 2h together with Example 2.
It turns out that sufficient reaction is performed after the concentration of acetaldehyde decreases.

The effect was not obtained only by mixing titanium oxide alone, and it was found that the present invention significantly improved the photocatalytic activity performance.

FIGS. 1 (A), 1 (B) and 2 (A)
In each of the photocatalyst pulp composition and the photocatalytic pulp paper (Example 2) in the photocatalytic pulp paper of the laminated photocatalytic pulp paper of the waste paper, the titanium oxide is fixedly bonded to the outer surface of the pulp raw material, In addition, it is required that the titanium oxide is maintained in a fixed state both on the outer surface of the pulp and inside the paper by the paper-making method using water. this is,
It is clear from the fact that almost no titanium oxide was eluted in the water added during stirring in the papermaking experiment in the test example.

[Photocatalytic pulp composition: Example (3), photocatalytic pulp paper: Example 3] In this example, the mixing ratio of titanium oxide, pulp and / or paper forming the photocatalytic pulp composition was determined according to the production example described above. This is the same as the case (1).

Further, the same titanium oxide, pulp and / or paper used as raw materials as in the above-mentioned production example (1) can be used.

In this example, titanium oxide and pulp and / or paper were mixed in the same manner as in Example (1), and the total weight of each titanium oxide and pulp and / or paper was 25 to 100 wt. % Of a thermoplastic resin was added to form a photocatalyst pulp composition (photocatalyst pulp composition: Example (3)), on which a recycled paper made of wastepaper pulp obtained by DIP-processing newspaper wastepaper was laminated. Photocatalytic pulp paper: Example 3).

As the thermoplastic resin, various types can be used, and the thermoplastic resin can be used in the form of a sheet, in addition to powders and granules. In the case of powder or granules, the particle size is preferably
1mm or less, preferably 1mm thick for sheet
The following are used by crushing each side to 10 mm or less.

When the formed photocatalyst composition is formed by heating to form a photocatalyst pulp molded body, the pulp in the photocatalyst pulp composition may be burned by this heat when heated at a high temperature, so that it has a relatively high melting point. polyester,
It is preferable to use a thermoplastic resin having a low melting point, such as PE (LLD: linear low density) or vinyl acetate, as compared with a thermoplastic resin such as polycarbonate.

The pulp constituting the photocatalytic pulp and / or
Or, the paper and the thermoplastic resin do not necessarily need to be charged into the mixer as independent raw materials, for example, used for milk packs and the like, a composite film having a paper layer laminated with a thermoplastic resin film. For example, after crushing into small pieces of about 10 mm on a side, it can be put into the above-mentioned mixer.In this case, the paper layer of the composite film forms pulp fibers constituting the photocatalytic pulp composition, and the thermoplastic resin layer is formed. It becomes a thermoplastic resin constituting the photocatalytic pulp composition. Therefore, the amount of titanium oxide is determined in consideration of the ratio between the pulp component and the thermoplastic resin component contained in the composite film, and the thermoplastic resin and / or pulp and / or paper are added as necessary. The blending of each raw material is adjusted so as to have the above-mentioned ratio.

The pulp and / or paper and titanium oxide,
After the thermoplastic resin is charged, the mixer is operated to generate shear heat by shearing force based on the stirring impact force of the stirring impeller rotating at high speed in the mixer, and the temperature is increased to about 120 ° C., and the pulp and / or paper Is 3 wt%, preferably 1 wt% or less. In this step, moisture evaporates from the pulp and / or paper and dries, and, in the case of paper, the pulp and / or paper is crushed by the impact force and becomes fibrous, and further swells with the drying. Then, the fibers are fluffed, agglomerated in a defatted shape, and a three-dimensional fiber entangled body, and titanium oxide is also adhered to the fiber surface and within the fiber by a pressing external force accompanying a stirring impact force or a shear force by the stirring impeller, Infiltrate and fix.

At the same time, at least a part of the thermoplastic resin charged into the mixer is also finely pulverized by the pulverizing action, and the stirring impact force by the stirring impeller on the fiber surface and in the fiber like the titanium oxide. Or, it is attached and penetrated and fixed by an external pressing force caused by a shearing force.

When a composite film such as a milk pack is used as the pulp and / or paper and the thermoplastic resin, small pieces of the composite film put into the mixer are mixed with the thermoplastic resin by the stirring impact force of the stirring impact blade. The paper layer is separated into a layer and a paper layer, and the separated paper layer is further pulverized by a stirring impact force and loosened into a fiber like the above-described paper.

Further, at least a part of the thermoplastic resin layer is also finely pulverized by the stirring impact force, and is pressed and adhered to the surface and inside of the pulp fiber similarly to the above-mentioned thermoplastic resin which is separately charged, and is fixed. .

The thermoplastic resin does not need to be melted by the heat at the time of stirring by the mixer, but may be any one as long as it adheres to the pulp fiber and penetrates and fixes it.

The photocatalyst pulp composition can be easily formed into a photocatalyst pulp molded article such as a fleece sheet by, for example, pressing the composition under heating, and the molded article formed by the method is pulp. Since the thermoplastic resin adhered to and infiltrated on the surface and inside of the fiber serves as a binder to firmly bond between the pulp fibers, a molded article such as a tough press sheet is formed.

A photocatalytic pulp molded article (press sheet) was produced using the pulp composition having photocatalytic activity obtained in the above Production Example.

Examples and Comparative Examples of Photocatalytic Pulp Paper Using Photocatalytic Pulp Composition As examples, the thermoplastic resin was PE [Uldzex 40
30P (powder: Mitsui Petrochemical Industry Co., Ltd.), and the other raw materials are the same as in Example 2 above. Used paper made of used newspaper obtained through the DIP (deinking treatment) process on the pressed sheet compact The dried pulp was laminated on one side by hot pressing via an adhesive.

Photocatalytic pulp paper; Example 3 Ground paper fiber; 2 kg (80 wt%) Water content 10 wt% Titanium oxide; 0.5 kg (20 wt%) Thermoplastic resin: PE 1.5 kg (based on the total weight of paper fiber + titanium oxide (60 wt%) Water content after treatment: 0.5 wt% The above raw materials are put into a mixer and stirred, the temperature is raised to about 120 ° C, and the water content of the paper fiber is 3 wt%, preferably
Reduce to 1 wt% or less.

The photocatalytic pulp composition obtained as described above was used.
Spread 51g to 8 × 8 cm, sandwiched by Teflon sheets, 2 hours at 0.99 ° C. while applying a load of 1 kg, and heated in a thermostatic chamber, the photocatalytic pulp molded article having a basis weight of 50 g / m ² (Press to form a sheet), the molded body in DIP (deinking process of the pressed sheet) was also dried from the used paper pulp consisting of waste newspaper through the steps a basis weight 10 g / m ² by a hot press via an adhesive This was laminated on one side and used as a sample (Example 3).

Beater treatment time 1 hour Photocatalytic pulp concentration 8 wt% Photocatalytic pulp, no beater treatment Basis weight Total 60 g / m ² Photocatalytic pulp layer 50 g / m ² Newspaper pulp layer 10 g / m ²

Comparative Example 2 (Photocatalytic pulp paper described above; Example 2) Ground paper fiber; 2 kg (80 wt%) Water content 10 wt% Titanium oxide; 0.5 kg (20 wt%) Water content after treatment; 0.6 wt% Using the photocatalytic pulp composition obtained in Example (2), papermaking was performed in the same manner as in the process of Comparative Example 1 (basis weight: 50 g / g).
m ² ), a molded article of this photocatalyst pulp, a waste paper pulp made of waste newspaper that has been subjected to a DIP (deinking treatment) process, made and dried (total basis weight: 10 g / m ² ) is hot-pressed via an adhesive. Was laminated on one side.

Beater treatment time 1 hour Photocatalytic pulp concentration 8 wt% Newspaper wastepaper concentration 8 wt% Basis weight Total 60 g / m ² Photocatalytic pulp layer 50 g / m ² Newspaper wastepaper pulp layer 10 g / m ²

Table 2 shows the results of comparison between the photocatalyst pulp compact of Example 3 and Comparative Example 2 under the following conditions. Experimental conditions Added acetaldehyde concentration about 820 ppm Light intensity about 1 mmW / cm ² reaction vessel 1 liter Photocatalytic pulp paper and other comparative examples Sample size: 8 × 8 cm Basis weight Total 60 g / m ²

[0080]

[Table 2] It was confirmed that the photocatalyst pulp molded article (press sheet + waste paper) formed from the photocatalyst pulp composition produced in Example 3 had substantially the same characteristics as the photocatalyst pulp paper (Comparative Example 2) described above.

Accordingly, it was clarified that the photocatalytic pulp molded article of Example 3 had an effect of improving photocatalytic activity, which could not be obtained by simply mixing titanium oxide.

Further, since the CO ₂ generation rate in 2 hours is 100%, it can be seen that a sufficient reaction can be performed even after the concentration of acetaldehyde is reduced.

Recycled paper having the photocatalytic activity function obtained by laminating the above-mentioned waste paper is a paper on the photocatalyst side as an inner layer, an outer layer, or an intermediate layer. Film, nonwoven fabric can be laminated in two or three layers and the like, in this case, having a light-transmitting core or base material, or
The use of plain paper, synthetic paper, non-woven fabric, woven fabric, non-woven fabric with low fiber density, coarse-woven woven fabric, transparent film, etc., which have excellent light transmission, has a large number of apertures. In the case where the photocatalytic pulp is not directly located on the light source side, such as when the photocatalytic pulp is sandwiched between the core material or the base material, the core material or The photocatalyst pulp is irradiated with light that has passed through the base material, whereby the photocatalytic property of titanium oxide is suitably exhibited, and the core material or the base material is made to have air permeability with openings and the like, whereby It becomes easy to use the pulp molded article as a filter or the like.

Example 1 of Paper String as Molded Article Made of the Laminated Photocatalytic Pulp Paper In the same defibration and defibration step as in Example 1, a milk pack was treated to obtain pulp. In the immobilization step, about 23 wt% of titanium oxide was immobilized to obtain a photocatalytic pulp composition. Next, the obtained photocatalytic pulp composition was diluted with a beater so as to have a pulp concentration of 8% by weight and beaten for 1 hour (hour).

On the other hand, the pulp obtained by treating the same milk pack as described above was diluted with water so as to have a pulp concentration of 43 g / m ^{2 at a} concentration of 8 wt%, beaten for 1 hour, and then subjected to laminating paper making in a known paper making process. The photocatalyst layer (20 g / m ² ) containing 15 wt% of the photocatalytic pulp and the pulp layer (43 g / m ² ) composed of milk packs are made with a circular net and fourdrinier paper machine, respectively, using a paper machine. Then, it was transferred to a press part, and further dried and laced to obtain a two-layer photocatalytic pulp paper of 63 g / m ² .

The following table, Test Example 1, is an evaluation of the physical properties of the photocatalytic pulp paper. After standing in a constant temperature and constant temperature room for 24 hours, JI
It was measured according to S P8124, JIS P8113 and JIS P8135.

This photocatalytic pulp paper was slit with a slitter.
It was cut into 48 mm, wound up into a roll of about 500 m, and twisted by a known ring twisting machine so that the photocatalytic pulp layer became the outer surface, thereby producing a paper cord of about φ3 mm.

The following Table, Test Example 2, is an evaluation of the physical properties of a paper string made of the photocatalytic pulp paper. The paper string was conditioned at 20 ± 5 ° C. and 65 ± 2% relative humidity for 48 hours or more so as not to dry at 105 ° C., and then measured according to JIS Z1518-1976.

[0089]

[Table 3] Test Examples 1 and 2

[Example 2 of paper string made of the laminated photocatalytic pulp paper] As in Example 1 of the above-described paper string, a photocatalytic pulp composition: a photocatalyst layer (12 g / A two-layer photocatalytic pulp having a pulp layer (26 g / m ² ) obtained by treating a milk pack with respect to m ² ) and having a clearance of 38 g / m ² was obtained. Then, the photocatalyst pulp layer was twisted so as to be on the outer surface to produce a paper cord of about φ1 mm.

[Embodiment 3 of the band-shaped cord as a molded product made of the laminated photocatalytic pulp pulp cord] The 16 paper cords produced in the embodiment 2 of the paper cord are overlapped on the same plane, and a water-soluble adhesive is used. Concentration in polyvinyl alcohol (30wt% for the first time, 1
The immersion and drying were repeated three times while changing 5 wt% and a third 3 wt% aqueous solution to produce a 20-mm-wide strip. Then, at least one side of the strip was sanded (NS-15D, manufactured by Amitec Co., Ltd .; abrasive paper No. 400) to expose the photocatalyst layer.

In Table 5 and Test Example 3 below, before and after sanding of Examples 1 and 2 of the above-mentioned paper string and Example 3 of the strip-like string, and as Comparative Example 1, strip-like cords containing no photocatalyst were used as samples. Experimental conditions Gas / concentration: added acetaldehyde gas / 20 ppm (concentration after adsorption on paper) Irradiation intensity About 1 mW / cm ² reaction vessel 3 liter Sample: Cut to total area of 5 cm x 10 cm. Light source: 40 W black light Measurement: Measured with 92 L of gas tech detection tube Pretreatment: Irradiated with ultraviolet rays of 1 mW / cm ² for 15 hours and dried in a desiccator for one day.

[0093]

[Table 4]

[0094]

Since the present invention is configured as described above, it has the following effects.

The reaction speed and termination of the reaction can be remarkably accelerated, the photocatalytic activity of titanium oxide can be improved, and antibacterial and antimicrobial properties can be applied to a wide variety of applications such as packaging materials, wallpaper, building materials, and filter materials. Mold, antifouling (dirty) and odor decomposition, deodorizing treatment, photocatalytic pulp paper including waste paper laminated photocatalyst recycled paper having an oxidative decomposition effect of harmful substances, and paper string comprising the laminated photocatalytic pulp paper and the paper string The resulting molded article could be provided.

[Brief description of the drawings]

FIG. 1 shows the surface of a photocatalytic pulp composition in a working example of the present application, as measured by a scanning microscope. (A) is magnification × 200, (B)
Is the magnification × 750

FIG. 2 shows a surface and a cross section of a photocatalytic pulp paper in a working example of the present application by a scanning microscope. (A) shows the surface, magnification × 750

FIG. 3 is a partial vertical cross-sectional view schematically showing a schematic configuration of an impact milling apparatus used in the paperboard dry pulp defibration and defibration step of the present invention.

FIG. 4 is a plan view of FIG. 3;

FIG. 5 is a schematic front view for explaining an impact grinding operation in the defibration and defibration step of FIG. 3;

FIG. 6 is a schematic view showing an example of use of an impact grinding means used in the defibration and defibration step of the present invention.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) D21H 17/74 D21H 17/74 21/14 21/14 B 21/36 21/36 23/04 23/04 F-term ( 4F100 AA21A AJ04A AJ04B AK01A BA02 DG03A DG10A EH41 GB07 GB15 GB56 GB90 JA04A JL08A JL16B YY00A 4L036 MA34 MA37 PA21 UA26 4L055 AA01 AA11 AF09 AF44 AG19 AH50 AJ20 BB30 GA17

Claims (15)

[Claims] Claims: 1. A titanium oxide of 5 to 60% by weight and a water content of 3% by weight.
Virgin pulp or waste paper pulp laminated on a photocatalytic pulp composition blended in a ratio of pulp and / or paper of 40 to 95 wt% with an average fiber diameter of 5 to 300 μm and an average fiber length of 0.1 to 70 mm. A laminated photocatalytic pulp paper characterized by the following. 2. A titanium oxide of 5 to 60 wt% and a water content of 3 wt%.
Pulp and / or paper having an average fiber diameter of 5 to 300 μm and an average fiber length of 0.1 to 70 mm, and a thermoplastic resin of 25 to 100 wt% based on the total weight of the titanium oxide, pulp and / or paper. A laminated photocatalytic pulp paper characterized by laminating a virgin pulp or a waste paper pulp with a photocatalytic pulp composition comprising the following. 3. An average fiber diameter of 5 to 300 wt% of titanium oxide.
pulp defibrated and disintegrated to an average fiber length of 0.1 to 70 mm
Alternatively, a composition formed by mixing 40 to 95% by weight of paper is stirred by applying a stirring impact force to generate shear heat by shearing force based on the stirring impact force. Drying the material to reduce the water content to 3 wt% or less; swelling the pulp and / or paper with the drying to form a three-dimensional fiber entangled body; A virgin pulp or a waste paper pulp after pressing and fixing the titanium oxide to the fiber surface of the pulp and / or paper, and fixing the titanium oxide. Production method. 4. A titanium oxide of 5 to 60% by weight and a water content of 3% by weight.
The average fiber diameter is 5 to 300 μm, the average fiber length is 0.1 to 70 mm, pulp and / or paper is 40 to 95 wt%, and the titanium oxide, the thermoplastic resin is 25 to 100 wt% based on the total weight of the pulp and / or paper. Stirring is performed by applying a stirring impact force to the blended composition to generate shear heat by the shearing force based on the stirring impact force, and the shear heat is used to dry the blend to reduce the water content to 3 wt. %, A step of swelling the pulp and / or paper with the drying to form a three-dimensional fiber entangled body, and a step of stirring the titanium oxide and the thermoplastic resin into the pulp and / or Or a step of pressing and fixing to the fiber surface of paper, a step of pressing and fixing titanium to the surface of the pulp and / or paper fiber, and a step of pressing and fixing the titanium oxide to virgin pulp or virgin pulp. Method for manufacturing a laminated photocatalytic pulp paper which is characterized by formed by laminating pulp. 5. The method for producing a laminated photocatalytic pulp paper according to claim 3, wherein virgin pulp or waste paper pulp is laminated by lamination in a papermaking step after the step of pressing and fixing the titanium oxide. 6. The method for producing a laminated photocatalytic pulp paper according to claim 1 or 2, or the laminated photocatalytic pulp paper according to claim 3 or 4, wherein the waste paper pulp is composed of waste newspaper subjected to a DIP process. 7. The laminated photocatalytic pulp paper or the laminated photocatalytic pulp paper according to any one of claims 1 to 5, wherein the waste paper pulp is made of waste newspaper, and the waste paper pulp is laminated as a core material or a base material. Method. 8. An average fiber length of 1 to 100 mm and an average diameter of 10 to 4 with respect to 5 to 60% by weight of titanium oxide and 40 to 95% by weight of pulp and / or paper.
The laminated photocatalytic pulp paper or the method for producing a laminated photocatalytic pulp paper according to any one of claims 1 to 6, wherein synthetic fibers having 0 µm and a melting point of 120 ° C or higher are mixed at a maximum of 1: 9. 9. The dry pulp as a paperboard-like pulp, wherein the dry pulp is to be processed, and the dry pulp is shredded into a plurality of pieces to be processed. And a fibrillation and disintegration step of obtaining a pulp fiber having substantially the same length as the fibrous raw material pulp that has been subjected to impact grinding power to be ground and flocculated and flocculently flocculated, and has no cilia even after the grinding. Item 5. The method for producing a laminated photocatalytic pulp paper according to item 3 or 4. 10. An apparatus for use in the method for producing a laminated photocatalytic pulp paper according to claim 9, wherein the apparatus is provided on a fixed disk having a central portion communicating with a supply inlet of a plurality of small pieces to be processed, A fixed-side impact grinding means in which each fixed pin is sequentially implanted on a plurality of rotation trajectories; and a plurality of fixed disks different from each of the fixed pins on a movable disk provided rotatably opposite to the fixed disk. A defibrating and disintegrating apparatus comprising: a movable impact milling means in which respective movable pins are sequentially implanted on the rotation trajectory; and a takeout means for taking out a crushed and flocculent fiber-like small piece to be processed into an outlet. 11. A titanium oxide having a water content of 3w to 5-60wt%.
within 5%, average fiber diameter 5 ~ 300μm, average fiber length 0.1 ~ 70mm
A virgin pulp or waste paper pulp is laminated on a photocatalytic pulp composition blended at a ratio of 40 to 95 wt% of pulp and / or paper, and the laminated photocatalytic pulp paper obtained by cutting to an arbitrary width is twisted. A paper string characterized by the following. 12. The method according to claim 11, wherein the laminated photocatalytic pulp paper is cut into a width of 5 to 50 mm, wound into a roll, and then twisted. 13. A molded article made of a paper cord according to claim 11, wherein said molded article is a flat cord formed by superposing a plurality of said paper cords on the same plane. 14. A molded article comprising the paper cord according to claim 1, wherein the paper cord according to claim 11 is a woven fabric comprising a weft yarn and the warp yarn a yarn comprising a natural or chemical fiber. 15. A molded article according to claim 11, 13 or 14 comprising a combination of two or three kinds.
A molded article comprising the paper cord according to any one of the preceding claims.