JPH11172112A - Photocatalytic ligneous synthetic material composition and its production, photocatalytic ligneous synthetic foam and its production, photocatalytic ligneous synthetic molded product using the same material composition and molded product using the same foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a titanium oxide photocatalyst that shows not only antifungal or antimicrobial actions, the decomposition of bed smells and the oxidative decomposition of hazardous substances over a wide range of purposes such as package materials, construction materials but also is effective for air treatment, water treatment and soil treatment, further increases the photocatalytic activity of the titanium oxide itself. SOLUTION: A blend of 10-40 wt.% of titanium oxide, 10-60 wt.% of cellulose milled powder with an average particle size of 15-200 μm and 20-80 wt.% of a resin is mixed with a stirring impact blade and dried with the friction heat caused by the sheer force thereby reducing the moisture content of <=0.5 wt.%, and the objective photocatalyst synthetic material composition is obtained by sticking the titanium oxide to the milled wood powder. Further, the resultant formulated product is foamed to increase the surface are thereby giving a photocatalyst ligneous synthetic foamed product with increased photocatalyst effect.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalytic woody synthetic material composition having a photocatalytically active effect using a cellulosic crushed material such as wood flour as a main molding material, a method for producing the same, and the photocatalytic woody synthetic material composition. Regarding the photocatalyst woody synthetic molded body used, in more detail, titanium oxide is adsorbed on wood powder and mixed with a resin, and the photocatalytic properties of titanium oxide, that is, deodorization, antibacterial, etc., are activated by ultraviolet rays, organic substances, ammonia, A filter medium, an adhesive, which can improve or effectively exhibit the property of oxidatively decomposing NOx, SOx, and the like;
Or wood-based synthetic material that can be widely applied to various uses such as coating materials such as paints, packaging materials as films or sheets, other daily necessities, building materials for general or hospital interiors, appliances and fixtures in public facilities such as baths and parks Photocatalytic woody synthetic material composition as raw material of various molded articles including wood, method for producing the same, photocatalytic woody synthetic foam, method for producing the same, and photocatalytic woody synthetic molding using the photocatalytic woody synthetic material composition It provides the body.

[0002]

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.

[0003]

However, these conventional products are disadvantageous in that the coated product is limited in the area of application, the reaction speed is slow, and the termination of the reaction is extremely slow. Met. Further, there is a problem that the solvent used for coating is flammable and its use is limited.

[0004] The present invention solves the above-mentioned problems and provides antibacterial and antibacterial agents for a wide variety of uses such as packaging materials, paints, building materials, and filter media.
Photocatalytic woody synthetic material composition with antifungal, antifouling (dirty) and odor decomposition, deodorization treatment, oxidative decomposition of harmful substances and its production method, and also effective for air treatment, water treatment and soil treatment Photocatalytic woody synthetic material composition and method for producing the same, and a photocatalytic woody synthetic material composition capable of improving the photocatalytic activity itself of titanium oxide itself, a method for producing the same, and a photocatalytic woody synthetic foam It is an object of the present invention to provide a body and a method for producing the same, and a photocatalytic woody synthetic molded article using the photocatalytic woody synthetic material composition, and a photocatalytic wooden synthetic foamed article using the photocatalytic woody synthetic foam.

[0005]

Means for Solving the Problems In order to achieve the above object, the photocatalytic woody synthetic material composition of the present invention comprises titanium oxide 1
Cellulose-based crushed product 10 such as wood powder having an average particle size of 15 to 200 μm, with 0 to 40 wt% and water content within 0.5 wt%.
It is characterized in that the resin is blended at a ratio of 20 to 80 wt% to 60 wt% (claim 1).

[0006] The method for producing the above-mentioned photocatalytic wood-based synthetic material composition is as follows.
A mixture of 10 to 60% by weight of a cellulosic crushed product such as wood powder of 0 μm and a resin in a ratio of 20 to 80% by weight is mixed with a stirring impeller, and frictional heat generated by the shearing force of the stirring impeller is obtained. Drying the mixture to reduce the water content to within 0.5% by weight and adhering the titanium oxide to the cellulosic crushed product (claim 2).

[0007] Further, the photocatalytic woody synthetic foam comprises 10 to 40% by weight of titanium oxide, 10 to 60% by weight of crushed cellulosic material such as wood powder having an average particle size of 15 to 200 µm with a water content of 0.5% by weight or less. 20 to 80% by weight, and a foaming agent comprising a foamy adhesive in a ratio of 0.1 to 10% by weight (claim 3).

[0008] The method for producing the photocatalytic woody synthetic foam is as follows.
Titanium oxide 10-40 wt%, average particle size 15-200μ
m, a mixture of 10 to 60% by weight of a cellulosic crushed product such as wood flour and a foaming agent in a ratio of 0.1 to 10% by weight are mixed by a stirring impeller, and the shear force by the stirring impeller is used. Drying the composition with frictional heat generated by the above, reducing the water content to within 0.5 wt%, and adhering the titanium oxide and the foaming agent to the cellulosic crushed material by the shearing force of the stirring impeller. And 20 to 80% by weight of a resin in the compound, heating and melting to a melting temperature of the resin by frictional heat generated by shearing force of the stirring impact blade, and then granulating (claim 4). ).

If the amount of the foaming agent is less than 0.1% by weight, the foaming is insufficient. If the amount is more than 10% by weight, the molding becomes difficult due to excessive foaming.

As the resin, as described later, a thermosetting resin such as phenol, urea, epoxy resin, etc.
As the thermoplastic resin, for example, polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (P
S) is used.

Here, as the foaming agent, a solvent having a low boiling point such as propane or butane (physical foaming), or a powdery azodicarbonamide which generates a gas upon thermal decomposition (chemical foaming) is used.

It should be noted that, depending on the raw material resin or the molding method, less than 40% by weight of a curing agent, less than 10% by weight of a foam stabilizer, 0.
A solvent of 1 to 10% by weight may be added.

When the mixture is mixed at a temperature not higher than the boiling point or the decomposition temperature of the blowing agent, the mixture is heated and foamed at the time of injection molding or extrusion molding or after sheet molding, whereby the surface area can be increased and the photocatalytic curing can be improved ( Claims 5 and 1
4).

The synthetic wood foam of photocatalyst is 10 to 40% by weight of titanium oxide and 10 to 60% by weight of crushed cellulosic material such as wood powder having an average particle size of 15 to 200 μm with a water content within 0.5% by weight. A) 100% by weight of a water-soluble adhesive; b-1) 100% by weight of a dilution water with a surfactant of 0.01%
A foamed adhesive as a foaming agent containing 50 to 100% by weight of a mixed solution of about 0.07% by weight or a foamed adhesive as a foaming agent composed of the above mixed solution; Gelatin and / or 100 wt% of the dilution water
Alternatively, a foam adhesive comprising 0.1% by weight or less of a protein such as an amino acid may be blended with 20 to 80% by weight of a foam adhesive (claim 6).

[0015] The method for producing the photocatalytic woody synthetic foam comprises:
A mixture of the titanium oxide and the cellulosic crushed material such as wood flour in the above ratio is mixed by a stirring impeller, and the composition is dried by frictional heat generated by the shearing force of the stirring impeller. Reducing the water content to within 0.5 wt%, and adhering the titanium oxide to the cellulosic crushed product; and applying the foamed adhesive in the above ratio to the composition obtained from the process. Stirring and mixing (claim 7).

The compounding of the foaming agent as the foamed adhesive according to the sixth and seventh aspects is the same as that of the third and fourth aspects.
By using a foam adhesive, it is possible to easily coat the same as a paint even outdoors, without the need for a special foam molding machine.

In order to form a plate-like molded product from the photocatalyst synthetic material composition or the photocatalytic woody synthetic foam, 0.1 to 1.0 wt%
Is preferable. (Claim 8).

By adding a resin as an adhesive raw material or a resin as a coating raw material together with a pigment as the resin, a coating material having high photocatalytic activity can be obtained.

If the content of titanium oxide is less than 10% by weight, the photocatalytic reaction is slowed down, and if it is more than 40% by weight, it becomes difficult to adsorb to the cellulosic crushed material, which is not appropriate.

In addition, cellulosic crushed material such as wood flour is 60 wt.
%, Wood powder burns during molding and molding becomes difficult. If it is less than 10% by weight, adsorption of the above-mentioned titanium oxide to wood powder becomes difficult, resulting in undesirable results.

In the photocatalytic woody synthetic foam, when the foaming agent is less than 20 wt%, the adhesive strength is weak, and when the foaming agent is more than 80 wt%, the photocatalytic effect is low.

Further, if a dispersion accelerator is added in an amount of 1.0% by weight or more, molding becomes difficult, and when a plate having a certain thickness or more is formed, an undesirable result such as a decrease in bending strength may be caused.

[0023] In the photocatalytic woody synthetic material composition of the present invention, titanium oxide is preferably 10 to 35 wt%.
In addition, the wood flour 25 to 45 wt.
%, And 35 to 45 wt% of polypropylene, polyethylene, polycarbonate, nylon, or PVC as a resin.

The photocatalyst woody synthetic material composition is not limited to this, but may be a film or sheet formed by forming a film by an extrusion method, or a photocatalytic woody synthetic material obtained by injection molding or extrusion into a plate. A molded article can be obtained (claim 10).

[0025] Obtaining an arbitrary photocatalyst woody synthetic molded article obtained by dry blending a blowing agent with the photocatalytic woody synthetic material composition to which the above-mentioned various foaming agents are not added, and then performing film forming processing, injection molding or extrusion molding into a plate shape. Is possible. (Claim 1
1).

This is because, depending on the resin, the foaming agent foams at the time of melting in the means of claim 4.

[0027] By sanding the surface of the formed plate-like synthetic synthetic body with the composition of the present invention, preferably by sand blasting, etc., the surface area can be increased and discoloration of the surface of the molded article can be prevented. ).

Further, the photocatalytic woody synthetic foamed article can be obtained by coating or spraying the above-mentioned photocatalytic woody synthetic foam on the surface of a substrate or release paper, or by casting, rotating, calendering or lining. (Claim 1
3).

Since wood powder and titanium oxide are weakly compatible with the resin, in the extrusion molding, the photocatalytic woody synthetic composition and the photocatalytic woody synthetic foam were heated and kneaded, and extruded with a screw into a forming die. By gradually cooling the extruded dough and applying a suppressing force to the extruded dough to increase the density of the extruded dough, a more uniform high-density photocatalytic woody synthetic molded article and a photocatalytic woody synthetic foaming molding are obtained. A body can be obtained (claim 15).

Although the resin used is not particularly limited, PP (polypropylene), PVC (polyvinyl chloride), PET (polyester), PE (polyethylene), PC (polycarbonate), nylon, A
One of thermoplastic or thermosetting resins such as BS, epoxy and urethane, or a mixture of several of these resins can be used.

Titanium oxide also has an effect of preventing coloring of a molded article and burning of wood flour by the composition of the present invention and increasing a shearing force.

In addition, the titanium oxide has good fluidity and good dispersibility in a solution, and contributes to significantly reducing expansion and contraction due to a temperature change with respect to the photocatalytic woody synthetic molded article of the present invention.

With the above structure, the frictional resistance during the flow of the wood flour is reduced, the familiarity with the resin material is improved, and the structure of the wood flour in the formed woody synthetic molding is made dense and the density is made uniform. In addition, when the extruder is filled with wood powder and resin and heated, it is possible to prevent the surface of the formed synthetic wood body itself from being roughened, bubbles, nests, and the like.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Production Example of a Photocatalytic Wood Synthetic Material Composition
m to 10 to 60% by weight of a cellulosic crushed product such as wood flour, and 20 to 80% by weight of a resin.
The crushed cellulosic material such as wood flour is crushed by the stirring impeller and dried by frictional heat of the stirring impeller and the raw material itself, and the titanium oxide and the wood flour contain 0.5 wt%, preferably 0.5 wt%. , 0.1% by weight or less.

The average particle size of the wood flour means the particle size of 50% by weight in the cumulative weight percent distribution of the wood flour. The smaller the particle size of titanium oxide, the better the performance. An X-ray particle size of 7 to 50 nm can be used.

Further, the resin is kneaded with the wood flour by a stirring impact blade, and the resin is mixed for about 180 to 180 by the frictional heat of the raw material itself.
At 200 ° C., the water content is dried to 0.5% by weight or less,
Even during mixing and dispersing, it is kneaded and gelled without agglomeration, and in this step, around the fine wood flour or moisture evaporates, titanium oxide adheres to the hollowed pipe or temporary pipe,
Secure by infiltration.

Next, the kneading material in the jacket is set near the freezing point of the resin in the raw material, that is, near the melting point (melting point + 10
C), and dried to obtain granules having a particle size of about 25 mm or less and solidified by a stirring crushing blade.

Further, the granulated product is sized by a pulverizer such as a cutter mill having an 8 mm screen, for example.
The "photocatalytic woody synthetic material composition" of the first and second embodiments of the present invention having a particle diameter (short diameter) of 10 mm or less is obtained.

As described above, the state in which the resin is fixed to thermally and chemically stable wood powder particles (including titanium oxide) can be constantly maintained, and the wood powder and the resin are fixed. In order to constantly maintain the state of mixing and dispersing with the photocatalyst, a woody synthetic material composition giving good fluidity is formed, and the photocatalyst which does not rely on chemical reaction or adhesion is combined with condensation and shrinkage by cooling. A wood composite composition is formed.

This photocatalytic woody synthetic material composition is
Films can be formed into films and sheets by various film forming methods, but it is possible to obtain a photocatalytic wood-based synthetic molded article such as a film or sheet by forming a film by an extrusion method, preferably by inflation.
It is possible to obtain a photocatalytic woody synthetic molded article extruded into a plate shape.

In the following, a more detailed description will be given with reference to the drawings.

[Fluid Mixing and Kneading] In FIG. 1, reference numeral 80 denotes a mixer capable of mixing and kneading the raw materials to form a kneaded material. Reference numeral 81 denotes a mixer main body. Invisible motor 37KW (D
The shaft 83 which rotates at a high speed of 820 rpm / max by the rotation drive of C) is supported upward in the mixer 81, and this shaft 8
3 in order from the bottom to the top, the scraper 84 and the stirring impeller 8
5, 86 and 87 are attached, and the shaft 83 is fastened with a fastening nut 92 from the tip. In addition, each said stirring impeller 8
The shapes of 5, 86 and 87 are not particularly limited, but in the present embodiment, the blades are symmetrical two blades. As shown in FIG. 1, when three stirring impellers are stacked, the blades are composed of a total of six blades,
These six blades overlap each other so as to form an equal angle (60 degrees) obtained by dividing 360 degrees into six in a plane. In the case where a plurality of stirring impellers are provided, it is preferable that the stirring impellers intersect and overlap with each other at an angle equal to 360 degrees in terms of the total number of stirring impellers in terms of efficiently kneading the raw materials.

The raw materials to be introduced from the introduction port 94 with the top lid 82 opened are made of crushed cellulosic material such as titanium oxide and wood powder, resin, compatibilizing material and the like.

The resin is obtained by crushing discarded various resin molded articles as they are or a resin molded article having a surface resin coating film formed thereon into a plurality of small pieces. For each of the crushed individual small pieces, Grinding resin coating by adding compression grinding action,
Peeling, each of the ground individual pieces, crushing and crushing by applying a compressive impact force based on micro-vibration, and removing the resin coating peeled off by crushing and crushing as needed, thermoplastic resin One kind of resin such as polypropylene, polyethylene, polycarbonate, nylon, polyvinyl chloride, or a mixture of several kinds of these can be used.

The above-mentioned titanium oxide and wood flour are introduced into the above-mentioned charging port 94.
And the temperature is increased to about 180 ° C. by the frictional heat generated by the shearing force of the stirring impact blades 85, 86, and 87 rotating at high speed in the mixer body 81.
Alternatively, the moisture content of titanium oxide and wood flour, which ranges from 100 to 200% by sapwood, is 0.5 wt%, preferably 0.1 wt%.
wt% or less. In this step, the titanium oxide is adhered to and penetrates and fixes in the surroundings of the fine wood flour or in the hollow or temporary conduit where the moisture evaporates.

Here, the resin and the compatibilizer are charged into the mixer body 81.

In this step, the kneading and melting are completed when the temperature in the mixer body 81 rises to about 200 ° C.

In this step, the resin does not form a large lump due to the wood powder in the raw material, and does not agglomerate during the mixing and dispersion, but gels into a clay-like form, forming a massive "kneading material" having a diameter of about 10 to 100 mm. It became.

That is, this lump is a lump in which the individual wood flour is formed with resin adhered to the entire surface of the single wood flour. And the lump itself is brittle. Therefore, the kneaded material formed in this step is a good material that can be kneaded more efficiently by an extruder in a subsequent step, and is a good material that reduces the frictional resistance of wood powder particularly during extrusion.

More specifically, the water content of the wood flour is 0.5% by weight, so that the function of the compatibilizer to improve the dispersibility is further promoted. Is dispersed at a uniform density in the resin as viewed from the wood powder, and is kneaded and melted in such a manner as to be easily impregnated into the wood powder and completely surround the outer periphery of the wood powder as viewed from the resin.

When the resin is PP, the mixing ratio with the wood flour is such that when the wood flour is less than 10 wt% of the total weight of the raw materials, the resin becomes a large lump in the mixer body 81. Must be greater than 10 wt%. Also, the raw material can be gelled up to 60 wt% of the wood flour, and when the wood flour increases, the wood flour burns.

[Cooling Granulation] In FIG. 2, reference numeral 100 denotes a “cooling mixer” that can form a “granulated material” by mixing and stirring the above-described kneading materials.

Reference numeral 101 denotes a mixer body, which covers the upper surface,
On the other hand, a discharge port 107 is provided at the lower end, and the discharge port 107 is provided to be freely opened and closed by a valve 106. Mixer body 1
A cooling water is constantly supplied from a water supply pipe 108 to a drain pipe 109 in the jacket 102 so as to cool the temperature of the raw material in the cooling mixer 100 to near the melting point of the resin. Will be retained.

At substantially the center of the upper wall of the mixer body 101, an arm 103 is rotatably supported in a substantially horizontal direction.
A stirring crushing blade 104 is supported at the tip of the arm 103, and the stirring crushing blade 104 has a screw shape in this embodiment.

An inlet 113 is provided on the upper wall of the mixer body 101, and the outlet 113 is connected to the outlet duct 93 of the mixer 80 described above.

The kneaded material formed in the mixer 80 described above is fed into the mixer main body 101 from the inlet 113 through the discharge duct 93. The charged kneading material is cooled with stirring and granulated to a diameter of about 25 mm or less to form a "granulated material". The granulated material is discharged from the discharge port 107 by opening the valve 106.

The kneaded material cooled by the cooling mixer 100 is desirably cooled to a temperature below the freezing point of the resin in the raw material, that is, the melting point. It is not necessary to cool the granulated material to a temperature at which the granulated material can be discharged from the discharge port 107, and may be cooled to a temperature about 10 ° C. higher than the melting point of the resin in the kneading material.

The cooling and granulating step is not limited to the above-described apparatus such as the cooling mixer. A stirring blade for stirring the kneaded material in the mixer main body is provided, and the above-described outer peripheral wall surface in the mixer main body is provided. Such a jacket may be provided as long as the kneading material in the mixer body is cooled by cooling water flowing through the jacket.

[Granulation] The granules formed in the cooling granulation step are preferably further sized using a “cutter mill” as shown in FIG. 3 to a particle size of 10 mm or less.

In FIG. 3, reference numeral 121 denotes a cutter mill body, which is a cylindrical casing having an upper surface opening.
The opening is covered with a lid 122 that can be opened and closed. The lid 12
2 is provided with an input port 123 for inputting granulated wood powder into the cutter mill main body 121.

In the cutter mill main body 121,
A cutter support 124 is provided on the bottom surface of the cutter mill body 121 and is horizontally rotated by a rotation driving means (not shown).
25, and the fixed blade 126 is connected to the rotary blade 1 through a slight gap with respect to the rotation locus of the blade edge of the rotary blade 125.
The cutter mill body 1 is located at a position substantially symmetrical with the rotation locus of the 25 blade edges.
21, the inside of the cutter mill main body 121 is divided into two by the fixed blade 126, the cutter support 124, and the rotary blade 125, and a charging chamber 127 and a sizing chamber 128 are formed. In addition, the sizing room 12
Reference numeral 8 denotes a screen 129 that separates the fixed blades 126 so as to surround the rotation locus of the rotary blade 125. The screen 129 is formed of a mesh through which the sized product can pass.

In the above-described cutter mill 120, when the granulated material formed by the cooling mixer 100 described above is charged from the charging port 123 and the cutter support 124 is rotated,
The granulated material is sized to a particle size of 10 mm or less by the rotating blade 125 and the fixed blade 126 to form a pellet-shaped "photocatalytic woody synthetic material composition", and the so-called resin is thermally and chemically stable oxidized. A photocatalyst that provides good fluidity to constantly maintain the state of being fixed to the wood flour containing titanium and constantly maintain the mixed and dispersed state of wood flour and titanium oxide with the resin. A woody synthetic material composition is formed, and the woody synthetic material composition having photocatalytic activity not due to chemical reaction or adhesion is formed in combination with the condensation and shrinkage effects by cooling.

The photocatalytic woody synthetic composition of the present invention produced by the above steps can be formed into films, sheets, etc. by various film-forming methods, or formed into a plate-like shape by an extruder to form a photocatalytic woody synthetic molded article. Can be obtained.

However, since wood powder and titanium oxide are weakly compatible with the resin, at the time of extrusion molding, the extruded dough extruded with a screw into a forming die is gradually cooled, and the extruded dough is resistant to the extruding force. By applying such a suppressing force, the density of the extruded dough can be increased.

Such a molded article is a material for a wide range of uses as various building materials, daily necessities, furniture materials, equipment parts, etc. having functions such as antibacterial and deodorizing. For example, the photocatalytic woody synthetic molded article of the above molded article is used as a building material such as a decorative molded article for interior decoration of a house, or processed into a size of about 300 mm square and used as a floor material such as a floor link block. used.

Further, as another application, it is used as an interior material inside a car, for example, as a decorative molded body around a meter panel in a driver's seat, a decorative molded body around a transmission, or a decorative molded body around a wall inside a vehicle. , NOx can be reduced, and a sense of quality can be obtained. As an equipment part, it is used as a box panel of an electric equipment or the like or a decorative molded body of another equipment.

Accordingly, the photocatalytic woody synthetic material composition of the present invention can mold a wide range of thick woody synthetic molded articles ranging from thin-film molded articles to thick molded articles. Molded.

It is to be noted that since the woody synthetic molded article formed from the photocatalytic woody synthetic material composition of the present invention has a high density, a large amount of wood flour can be mixed therein. An inexpensive synthetic wood article is formed. Further, a synthetic wood compact in which a large amount of wood powder is mixed is an excellent compact having properties close to those of a natural wood panel.

Production Example of Photocatalytic Wood Synthetic Foam 10 to 40% by weight of titanium oxide was added to an average particle size of 15 to 200 μm.
A mixture of 10 to 60 wt% of a cellulosic crushed product such as wood flour and a foaming agent in a ratio of 0.1 to 10 wt% is stirred and mixed in the same manner as in the fluid mixing and kneading step. After drying and adhering the titanium oxide, the resin is
Add wt%, knead and granulate similarly.

When a powdery foaming agent such as azodicarbonamide is used as the foaming agent, the foaming agent can also adhere to the wood powder by stirring and mixing with the titanium oxide before charging the resin.

Further, a compound (photocatalyst woody synthetic material composition) and a blowing agent were dry-blended by stirring, mixing and kneading the components other than the blowing agent, and pelletizing in the same manner as in the cooling granulation step.
Injection or extrusion molding is also possible.

Depending on the raw material resin or the molding method, less than 40% by weight of a curing agent,
A foam stabilizer of less than 0% by weight, a solvent of 0.1 to 10% by weight, or the like may be added.

In the mixture mixed as described above, the foaming agent is vaporized or decomposed by heating to form a foam. By performing the fluid mixing and kneading step at a temperature not higher than the boiling point or decomposition temperature, injection molding and extrusion molding can be carried out. Alternatively, the sheet can be heated and foamed into a predetermined shape after the sheet is formed.

For example, an example using a composition having the following composition is shown: Resin (phenol resin): 100% by weight Blowing agent (low boiling point solvent): 2% by weight Foam stabilizer: 2% by weight Wood powder and titanium oxide: 25 to 100% by weight The above composition is stirred and mixed, and placed in a constant temperature room (20 to 30 ° C.) together with 5% by weight of a curing agent in a separate container to make it equal temperature.
When they are stirred and mixed, the foaming agent is vaporized by the heat of reaction of the curing of the phenol resin, and foams.

As an example of using a powdery foaming agent, resin (low-density polyethylene): 59 wt% foaming agent (azodicarbonamide ADCA (decomposed at 200 ° C. or more)): 1 wt% wood powder: 20 wt% titanium oxide: Wood flour and titanium oxide are mixed and stirred at 180 ° C for 20 wt% and dried. Titanium oxide is adhered to the wood flour, and then the resin is charged, melted and mixed at about 150 ° C, and cooled and granulated. Dry blend the foaming agent to the pelletized one. When this mixture is injection-molded at 200 ° C. or higher, it is foamed about twice in the mold to obtain a photocatalytic woody synthetic foamed article.

Further, titanium oxide, wood flour and a foaming agent were mixed with stirring at 170 ° C. and dried to make the titanium oxide and the foaming agent adhere to the wood flour. When injection-molded at a temperature of 200 ° C. or higher by melt-mixing at about 150 ° C., the wood powder is exposed at the time of foaming and the photocatalytic effect is increased by the amount of the foaming agent attached to the wood powder.

The melt-blended material is formed into a sheet at about 170 ° C., and when the sheet is heated to 200 ° C. or higher, the sheet foams and becomes about twice as thick.

As a method for producing a photocatalytic woody synthetic foam, a step of using a foam adhesive as a foaming agent will be described.

The foamed adhesive used here is 10 to 40% by weight of titanium oxide, water content is within 0.5% by weight, and cellulose crushed material such as wood powder having an average particle size of 15 to 200 μm. A foaming adhesive having the following composition is blended as a foaming agent with the above-mentioned woody synthetic material composition blended at a ratio of 20 to 80% by weight. 100% by weight of adhesive
Surfactant 0.01-0.0 with respect to 100 wt% of dilution water
7wt% Mixed solution containing 50 to 00wt%. Alternatively, the above-mentioned mixed solution is further mixed with a protein such as amino acid and / or gelatin at 0.1 wt% or less.

The surfactant is not limited thereto, but nonionic surfactants such as polyoxyethylene lauryl ether having a degreasing effect and anionic surfactants such as lauryl alcohol sulfate are used.

The gelatin particles are obtained by, for example, using a polypeptide obtained by hydrolyzing a protein derived from collagen such as commercially available gelatin or the like with an enzymatic acid or alkali as a raw material, and drying the polypeptide using a dry mill such as a jet mill. Pulverization is preferably performed by a pulverization method. For example, gelatin having an average molecular weight in a range smaller than 8,500 is used as a raw material.

Amino acids (coarse powder) are positioned on the extension of gelatin grains, and are very similar to gelatin grains.
Without limitation, for example, defatted soy, wheat protein,
The average molecular weight obtained by hydrolyzing keratin and the like contained in milk and the like with enzymes, acids and alkalis is 100 to 200.
Is an amino acid having no polypeptide bond.

Thus, it can be used together with the above-mentioned gelatin particles or in place of the above-mentioned gelatin particles. The amino acid particles used here are produced by crushing the coarse powder of the amino acid.

The above-mentioned water-soluble adhesive is formed of a resin usually used for an adhesive, and is a layer containing additives such as a tackifier, a softener, a filler, an antioxidant, and a crosslinking agent, if desired. possible.

Examples of the resin include an acrylic resin such as methyl acrylate, an olefin resin such as polyethylene, and a phenol resin.

A mixture comprising the above-mentioned dilution water, surfactant, water-soluble adhesive and amino acid or gelatin was mixed with titanium oxide 1
0 to 40 wt%, wood flour 10 to 60 wt%, 20 to 80
wt%, and preferably mixed with the titanium oxide and wood flour by stirring. This stirring and mixing is performed in order to mix air bubbles into the liquid mixture to form a fluid foam having a predetermined granular shape.

Then, the aqueous solution containing the foam layer scum mixed and stirred is immediately poured into a foaming device comprising a pressure vessel having a gauge pressure of 8 kg / cm ³ . 0.5 diameter at the outlet of the tank
The foamed portion contains ceramic beads of 1 mm in a compacted state, and a foam having a suitable viscosity and a substantially uniform particle size of 9 μm is generated from the discharge port by pressurizing for about 30 seconds to obtain a photocatalytic woody synthetic foam.

When this photocatalytic woody synthetic foam is applied to a wooden board or the like by a spray gun and dried, the sheet-like foamed molded article is coated or sprayed on a release paper, or is subjected to cast molding or rotational molding. A photocatalytic woody synthetic foamed molded article can be molded by a known molding method such as calendering, lining, or the like.

The photocatalytic woody synthetic foam thus obtained has better dispersibility and is easier to coat than non-foamed foam, and also increases the surface area to increase the exposure of wood flour and increase the photocatalytic effect.

EXAMPLES Examples and Comparative Examples of Photocatalytic Woody Synthetic Molded Articles Using the Photocatalytic Woody Synthetic Material Composition As an example, 30 wt% of the raw material has an average particle size of 15 to 200 μm and a bulk density of 0.2 wood powder. (At this time, the wood flour contains about 8 wt% of water), the titanium oxide is ST-101 (Ishihara Techno Co., Ltd.), the X-ray particle size is 7 nm, the titanium oxide content is 90 wt% or more, and the specific surface area is m ² / g: 30% by weight of 300 and 39.5% by weight of the remaining 39.5% are made of polypropylene resin and 0.5% by weight of a compatibilizer as a dispersion promoter.

In this embodiment, the form of the resin is 3 mm in diameter.
Pellet composed of granular material of about mm size is used. As a compatibilizer, Sanyo Chemical Industries, Ltd. Umex 1010 was used. Examples 1 and 2 and Comparative Example 1 are formed by extrusion using a single-screw extruder having a diameter of 65 mm.

Comparative Example 1 used titanium oxide coated with R930 aluminum coating (Ishihara Techno Co., Ltd.) for pigments having a particle size of 0.25 μm (electron microscope) and a coating thickness of 0.01 μm.

In Comparative Example 2, the photocatalytic woody synthetic material composition had a particle size of 2 × 2 mm and was hot-pressed at 200 ° C.

In Comparative Example 3, 10% by weight of a silica-based binder was used.
A glass plate was immersed in a solution in which a solvent was added to 10 wt% of titanium oxide to obtain a dried silica-based binder 50 wt% and titanium oxide 50 wt% sample.

Comparative Example 4 is an example in which the kneading step was replaced with a ball mill, and after the mixing treatment, press working was performed.

[0096]

[Table 1]

[0097]

[Table 2]

The test results of the above Examples and Comparative Examples are shown below.

Experimental conditions Added acetaldehyde concentration Approx. 820 ppm Light intensity Approx. 1 mW / cm ² Reaction vessel 1.0 l (liter) Photocatalytic wood-based synthetic molded body and other comparative examples Sample size: 8 × 8 cm Thickness: 4 mm Comparative example 4 After the ball mill treatment, the particles were melt-kneaded in the same manner as in the example, sized to a particle size of 4 mm or less, and pressed into a 4 mm thick sheet.

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[Table 3]

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[Table 4]

Light control CO2 generation rate indicates the amount of CO2 that is emitted only by irradiating a sample with light. -The apparent initial CO2 generation rate is the generation rate at 45 minutes after light irradiation. The initial photocatalytic CO2 generation rate is given by the following formula: (apparent CO2 initial generation rate) (Light control CO2)
(Production rate) The production rates (%) at 1h and 2h are calculated based on the photocatalyst content only at the production ratio with respect to the theoretical value.・ The initial disappearance rate of acetaldehyde is 30 min after light irradiation.
Extinction rate at -The acetaldehyde extinction rate (%) at lh was: concentration at lh / initial concentration x 100. * 50 became 100% after 20 hours. 99 * indicates that trace acetaldehyde remains.

Since the wood chip of Comparative Example 1 did not show photocatalytic activity, it is considered that acetaldehyde was adsorbed rather than disappeared.

On the other hand, in Example 1, the CO2 production rate at 2 hours was 100% together with Example 2, indicating that the reaction was sufficient after the concentration of acetaldehyde was reduced.

In Example 2, the content of titanium oxide was half that of Comparative Example 2, but the acetaldehyde disappearance rate in 2 hours was 100 with respect to 91 of the latter. In 1h
The CO2 production rate is reversed at 2h, and the reaction end time is short and under acetaldehyde atmosphere at normal concentration,
Compared to Comparative Example 2, it is expected that Example 2 will surpass, and the effect is not obtained simply by increasing the amount of titanium oxide, and that the addition of the cellulosic crushed product of the present invention significantly improves the photocatalytic activity performance. Do you get it.

In Comparative Example 4, since the kneaded material obtained using a ball mill was round without fluffing, the surface area was small and the adhesion of titanium oxide was poor. Extrusion could not be performed because it contained about 1.6% by weight of water. That is, the photocatalytic activity performance could be obtained by the production method of the present invention.

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[Table 5]

The types of resins in Table 5 are one or several of the following types, respectively.

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[Table 6]

The above-mentioned film or sheet can be sanded, and becomes woody with paints and adhesives, and can be printed, bonded and painted.

Further, due to the mixed wood powder, the heat radiation is excellent.

[0112]

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, and the photocatalytic activity effect of titanium oxide itself can be improved. Building materials such as packaging materials, paints and wallpapers, concentrated materials, and interior materials for automobiles A photocatalytic woody synthetic material composition having antibacterial, antifungal, antifouling (dirty) and deodorizing treatment, deodorizing treatment, oxidative decomposition of harmful substances, and a method for producing the same, and a photocatalyst wood applicable to a wide variety of uses such as Provided are a photocatalytic woody synthetic material composition which is effective by using a photocatalyst woody synthetic molded article comprising a synthetic material composition for air treatment, water treatment, and soil treatment, a method for producing the same, and the photocatalytic woody synthetic molded article. I was able to.

Further, the surface area is increased by using the photocatalytic woody synthetic material composition and forming it into a foam,
The photocatalytic effect can be enhanced, and furthermore, as an application example, a synthetic wooden photocatalyst foam can be floated on, for example, a sewage treatment layer or the sea to purify sewage by the photocatalytic effect.

[Brief description of the drawings]

FIG. 1 is an overall front view showing a cross section of a main part of a mixer (flow mixing and kneading) used in an embodiment of the present invention.

FIG. 2 is an overall front view showing a cross section of a main part of a cooling mixer (cooling granulation) used in an example of the present invention.

FIG. 3 shows a cutter mill (grain size) used in an embodiment of the present invention.
1 is an overall front view showing a cross section of a main part of FIG.

[Explanation of symbols]

 Reference Signs List 80 mixer (fluid mixing and kneading) 81 mixer body 82 top lid 83 shaft 84 scraper 85, 86, 87 stirring impact blade 92 nut 93 discharge duct 94 inlet 100 cleaning mixer (cooling granulation) 101 mixer body 102 jacket 103 arm 104 stirring and crushing Wing 106 Valve 107 Discharge port 108 Water supply pipe 109 Drain pipe 113 Input port 120 Cutter mill (grain sizing) 121 Cutter mill body 122 Lid 123 Input port 124 Cutter support 125 Rotary blade 126 Fixed blade 127 Input chamber 128 Sizing chamber 129 Screen

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23/06 C08L 23/06 23/12 23/12 27/06 27/06 69/00 69/00 77/00 77/00 101/00 101/00 C09D 189/00 C09D 189/00 197/00 197/00 C09J 189/00 C09J 189/00 197/00 197/00 // B29K 103: 00 105: 04 (54) [Title of the Invention] A photocatalytic woody synthetic material composition, a method for producing the same, a photocatalytic woody synthetic foam, a method for producing the same, a photocatalytic woody synthetic molded article using the photocatalytic woody synthetic composition, and a photocatalyst using the photocatalytic woody synthetic foam Wooden synthetic foam

Claims (16)

[Claims] 1. A resin is added to 10 to 40% by weight of titanium oxide, 10 to 60% by weight of a crushed cellulosic material such as wood powder having an average particle size of 15 to 200 μm with a water content of 0.5% by weight or less.
A photocatalytic woody synthetic material composition characterized by being blended at 0 wt%. 2. An average particle diameter of 1 to 40% by weight of titanium oxide.
Cellulose crushed material such as wood powder of 5 to 200 μm
A composition comprising 20% to 80% by weight of a resin and 20% by weight of a resin is mixed by a stirring impeller, and the composition is dried by frictional heat generated by a shearing force of the stirring impeller. Is reduced to within 0.5% by weight, the titanium oxide is adhered to the crushed cellulosic material, and then granulation is performed. 3. Titanium oxide: 10 to 40% by weight; water content: within 0.5% by weight; 10 to 60% by weight of cellulosic crushed material such as wood powder having an average particle size of 15 to 200 μm;
0% by weight, and 0.1 to 0.1%
A synthetic wood photocatalyst foam characterized in that it is blended at a ratio of 10 wt%. 4. An average particle diameter of 1 to 40% by weight of titanium oxide.
Cellulose crushed material such as wood powder of 5 to 200 μm
wt.%, and a composition comprising 0.1 to 10% by weight of a foaming agent is mixed by a stirring impeller, and the composition is dried by frictional heat generated by the shearing force of the stirring impeller. Reducing the water content to within 0.5% by weight, and adhering the titanium oxide and the foaming agent to the crushed cellulosic material by the shearing force of the stirring impeller, and then adding 20 to 50% of the resin to the compound. 80 wt%, and heating and melting to the melting temperature of the resin by frictional heat generated by the shearing force of the stirring impeller, followed by granulation. 5. The method according to claim 4, wherein the mixing is performed at a temperature not higher than the boiling point or the decomposition temperature of the blowing agent. 6. A composition comprising 10 to 40% by weight of titanium oxide and 10 to 60% by weight of crushed cellulosic material such as wood powder having an average particle size of 15 to 200 μm with a water content of 0.5% by weight or less. On the other hand, a photocatalytic wood-based synthetic foam comprising 20 to 80% by weight of a foamed adhesive having the following composition as a foaming agent: a) 100% by weight of a water-soluble adhesive; b-1) 100% by weight of dilution water Surfactant 0.01
A foam adhesive comprising 50 to 100% by weight of a mixed solution of 0.07% by weight. Or, b-2) gelatin and / or
Or a foam adhesive containing 0.1% by weight or less of a protein such as an amino acid. 7. An average particle size of 10 to 40% by weight of titanium oxide.
Cellulose crushed material such as wood powder of 5 to 200 μm
The composition, which is blended at a ratio of wt%, is mixed by a stirring impeller, and the composition is dried by frictional heat generated by the shearing force of the stirring impeller, and the water content is reduced to within 0.5 wt%. Lowering and adhering the titanium oxide to the cellulosic crushed product; and a foam adhesive having the following composition with respect to the composition obtained from the process: 20 to 80 wt.
% A) Water-soluble adhesive 100 wt% b-1) Dilution water 100 wt% surfactant 0.01
A foam adhesive comprising 50 to 100% by weight of a mixed solution of 0.07% by weight. Or b-2) gelatin and / or 100% by weight of the dilution water with respect to the foaming agent comprising the mixed solution.
Or a foam adhesive containing 0.1% by weight or less of a protein such as an amino acid. 8. The photocatalyst wood synthetic material composition according to claim 1, wherein 0.1 to 1.0% by weight of a dispersing agent is added to the mixture of the titanium oxide and the cellulose crushed product. A method for producing a woody synthetic material composition, the photocatalyst woody synthetic foam according to claim 3, and the method for producing a photocatalytic woody synthetic foam according to claim 4 or 5. 9. Titanium oxide 10-35 wt%, said wood flour 25-45 wt% as a cellulosic crushed product, and polypropylene, polyethylene, polycarbonate as a resin,
3. The photocatalytic wood synthetic material composition according to claim 1, wherein 35 to 45% by weight of nylon or polyvinyl chloride is blended.
A method for producing the photocatalytic woody synthetic material composition according to the above. 10. A photocatalytic woody synthetic molded article obtained by subjecting the photocatalytic woody synthetic material composition according to any one of claims 1, 2, 8 and 9 to film forming processing, injection molding or extruding into a plate shape. 11. A photocatalytic wood-based synthetic material composition according to any one of claims 1, 2, 8 and 9, which is obtained by dry blending a foaming agent, followed by film forming, injection molding or extrusion molding into a plate shape. Photocatalytic wood-based synthetic molding. 12. A synthetic photocatalytic wood product which is obtained by sanding the surface of the synthetic photocatalytic wood product according to claim 11. 13. A photocatalytic woody synthetic foam according to claim 6 or 7, which is coated or sprayed on a substrate surface or release paper;
Alternatively, a photocatalytic woody synthetic foamed article obtained by casting, rotation molding, calendering, and lining. 14. A photocatalytic woody synthetic foam or a photocatalytic woody synthetic foam obtained by heating and foaming the photocatalytic woody synthetic foam according to claim 3, 4 or 5 during injection molding or extrusion molding, or after sheet molding. Manufacturing method. 15. The extruded dough that has been extruded with a screw into a forming die by heating and kneading the photocatalytic woody synthetic material composition according to claim 1 or 2 and resisting the extruding force of the extruded dough. A synthetic photocatalytic wood product formed by increasing the density of the extruded fabric by adding a suppressing force. 16. A method for producing a photocatalytic woody synthetic molded article according to claim 14, wherein 0.1 to 1.0% by weight of a dispersion accelerator is blended with the blend of titanium oxide and the cellulosic crushed product.