JPH0931335A - Resin composition with deodorizing function - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which exhibits an excellent deodorizing function for a long term and is applicable for a wide variety of products by compounding an org. resin with an inorg. deodoizer-adsorbent and a titanium oxide photocatalyst coated with an inorg. porous substance. SOLUTION: This resin compsn. is prepd. by compounding an org. resin with a component prepd. by protectively coating a mixture comprising an inorg. deodorizer-adsorbent and a titanium oxide photocatalyst with a porous inorg. substance or by compounding an org. resin with a mixture comprising an inorg. deodorizer-adsorbent and a titanium oxide photocatalyst protectively coated with a porous inorg. substance. The porous inorg. substance is required to have such a strength as not to be broken by an external force applied during coating the catalyst, during compounding into the resin, and during molding. Examples of such a substance are silica, alumina, and silica-alumina.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition having a deodorizing function, and more particularly to a resin composition exhibiting an excellent deodorizing function against a malodorous substance for a long period of time. The resin composition of the present invention is not only sensitive to odors such as wall materials, floor materials, and ceiling materials that make up living spaces, but also curtains, blinds, lighting device covers and reflectors, interior parts of automobiles, etc. It is preferably used in a wide range of fields including various food-related containers and packaging materials.

[0002]

2. Description of the Related Art Conventionally, an adsorption type deodorant represented by activated carbon has been widely used as a deodorant, but its deodorizing ability is limited because it physically removes malodorous substances.
Limited to short-term use. In addition, the deodorant of living spaces and the like is dealt with by using fragrances exclusively and masking offensive odors. However, in any of these methods, only short-term deodorizing and deodorizing effects can be expected,
There is a demand for a deodorant that exhibits deodorizing and deodorizing effects over a long period of time. In addition, in the case of food products, the odor of the container or the packaging material itself or the odor from the external environment is transferred to the contents, which causes a change or deterioration in the aroma or flavor of the food. As a method of preventing the deodorization of food containers and the transfer of odors from the external environment, research is being conducted to add a deodorant to the synthetic resin that makes up the food container. It is hard to say that it can sufficiently cope with long-term storage and poor storage environment. Furthermore, in recent years, deodorizing products using catalytic deodorizing agents and artificial enzymes (Fe-phthalocyanine) have been researched and developed for the purpose of maintaining the deodorizing function for a long period of time. The reality is that they are limited and therefore the form of the deodorant product is also limited.

Against the background described above, the present inventors have conducted research on the idea that if a catalyst type deodorant having a deodorizing function for a long period of time is blended with an organic resin, various applications as a deodorizing product can be expected. . However, an organic resin composition containing a catalytic deodorant is adversely affected by the catalytic action of the catalytic deodorant, such as the generation of decomposed odor and coloration during heat molding and subsequent aging. It has a problem that it cannot be used unless it is suppressed. In particular, the stronger the catalytic action and the greater the deodorizing effect, the more markedly the above adverse effects appear. In addition, many catalyst deodorants are colored and toxic, and their use is limited by themselves. However, some semiconductor-based photocatalysts are white and harmless, and titanium oxide having a large photocatalytic power is particularly preferable.

Regarding titanium oxide, Japanese Patent Publication No. 60-23
JP-A No. 5-294627 describes a technique in which a soluble silicate is used and the pH of the system is adjusted to a basic side for porous coating to improve the hiding power and durability. Described is the technology of contacting alkoxides of Si, Al and Zr with titanium oxide having an average particle size of 0.1 μm or less in an organic solvent and using it as a UV protection film for sunscreen cosmetics, automobiles, furniture, etc. In addition, JP-A-6
No. 227925 describes an antibacterial inorganic capsule by an interfacial reaction method using an aqueous solution of an alkali metal silicate as an antibacterial agent such as silver oxide and a hydrolysis method using a metal alkoxide, and further, Japanese Patent Publication No. 6-15407. Describes that polysiloxane having Si-H forms a uniform coating layer on titanium oxide and can be used for cosmetics, pharmaceuticals, packaging materials, sensors, etc. It is not described that the resin composition has a function.

[0005]

When added or blended to various organic materials or coated, the catalyst-based / adsorption-based deodorant is non-toxic and colorless to white. Is preferable because there is. But, for example,
It was confirmed that when a titanium oxide photocatalyst was used as a catalyst type deodorant and was added to an organic resin in an amount of 1.0% by weight or more, decomposition odor or coloring of the resin occurred during processing. Therefore, the compounding ratio of the titanium oxide photocatalyst that can exert the deodorizing effect is 0.01 at the most, without the problems of decomposition and coloring of the organic resin.
However, the deodorizing effect for a long period cannot be expected. Further, even if the mixing ratio of the titanium oxide photocatalyst is increased, it does not have immediate effect on a high-concentration odor substance. As described above, it is difficult to say that the conventional deodorizing agents and deodorizing methods have a sufficient deodorizing function for a long period of time, and it is necessary to further enhance the deodorizing power in order to apply them to various products. In view of such circumstances, the present invention provides a resin composition that exhibits an excellent deodorizing function for a long period of time and can be applied to a wide range of products.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that by coating a titanium oxide photocatalyst with a porous inorganic substance,
The present invention has been completed based on the finding that, when compounded with an organic resin, it can be compounded without adverse effects such as decomposition and coloring of the resin.

That is, the present invention relates to a titanium oxide photocatalyst that is protectively coated with a porous inorganic material, is blended with an organic resin a mixture of a titanium oxide photocatalyst and an inorganic deodorant adsorbent, or is a protective coating with a porous inorganic material. A resin composition having a deodorizing function, characterized in that a mixture with an inorganic deodorizing adsorbent is blended in an organic resin, and a resin composition having a deodorizing function, wherein the porous inorganic material is silica and / or alumina. Furthermore, a resin composition having a deodorizing function using each sol or a reaction product of each sol and each monomer as silica or alumina,
Each is a content.

[0008]

[Function] When the titanium oxide photocatalyst is coated with a porous inorganic substance, the function of the porous inorganic coating layer is to prevent contact between the titanium oxide photocatalyst and the organic resin, and the organic resin is decomposed to give off a strange odor. It suppresses adverse effects such as coloring, and also decomposes and deodorizes a malodorous substance by passing it through the pores of the porous inorganic coating layer and bringing it into contact with the titanium oxide photocatalyst. When the mixture of titanium oxide photocatalyst and inorganic deodorant adsorbent is coated with a porous inorganic substance, the malodorous substance is adsorbed on the deodorant adsorbent coexisting with the titanium oxide photocatalyst through the pores of the porous inorganic substance coating layer, and It is decomposed by a titanium oxide photocatalyst activated by light.

[0009]

EXAMPLES The titanium oxide photocatalyst used in the present invention is
It is designed so that the catalytic action is activated by light energy of sunlight or fluorescent light and has a stronger redox power than ordinary titanium oxide, and both rutile type and anatase type can be used. Examples of commercially available products include "Taipeque ST series", a trade name manufactured by Ishihara Sangyo Co., Ltd. The titanium oxide photocatalyst may be loaded with a metal such as gold, platinum, palladium, copper, nickel oxide, or a metal oxide to promote the photocatalytic function.

The porous inorganic material in the present invention is required to have a protective coating on the titanium oxide photocatalyst and have a strength such that it is not destroyed by an external force during compounding with an organic resin or during molding. Examples of such a porous inorganic material include silica, alumina, and silica-alumina. These may be used alone or in combination of two or more.

The pore size of the porous inorganic coating layer is 5.0.
Approximately 1000 Å is preferable, and 100 to 300 Å is particularly preferable. If the pore size is too large, the organic resin will come into contact with the titanium oxide photocatalyst to be decomposed, causing offensive odor and coloring. Conversely, if the pore size is less than the order of the offensive odor molecular size, the odorous substance will reach the titanium oxide photocatalyst. In addition, the catalyst does not decompose odorous substances.

The inorganic deodorant adsorbent used in the present invention refers to a physical adsorbent, a chemical adsorbent, a physicochemical adsorbent or the like that adsorbs a malodorous substance and exerts a deodorizing effect, and is colorless or White and non-toxic ones are preferred. As such an inorganic deodorant adsorbent, zeolite (hydrophilic / hydrophobic), activated clay, acid clay, hydrotalcite, sepiolite, silica-alumina, silica-magnesia,
Examples include a composition of silica and zinc oxide, activated carbon, and the like. Absents (trade name manufactured by Union Showa Co., Ltd.) and the like as physical adsorbents, and Shukleens (trade name manufactured by Lhasa Co., Ltd.) as chemical adsorbents. ) And Kyoward (trade name of Kyowa Chemical Industry Co., Ltd.) are commercially available.
These may be used alone or in combination of two or more. In addition, since inorganic deodorant adsorbents have different adsorption capacities for malodorous substances, common malodors (acetic acid, ammonia,
When all trimethylamine, acetaldehyde, hydrogen sulfide, methyl mercaptan, etc.) are deodorized, it is particularly preferable to use two or more kinds in combination.

The inorganic deodorizing adsorbent is mixed with a titanium oxide photocatalyst and protectively coated with a porous inorganic material, and then blended in an organic resin, or in combination with a titanium oxide photocatalyst protectively coated with a porous inorganic material. It is used by being blended with an organic resin (hereinafter referred to as post-addition). Inorganic deodorant adsorbents have an immediate effect and quickly adsorb and deodorize high-concentration malodorous substances, but their deodorizing ability is limited and unsustainable.
Therefore, if a titanium oxide photocatalyst and an inorganic deodorant adsorbent are used together as described above, the titanium oxide photocatalyst has the ability to eliminate and odorize malodorous substances for a long period of time, and thus it will be adsorbed by the nearby inorganic deodorant adsorbent. It also decomposes malodorous substances, and as a result, the deodorizing ability of the inorganic deodorant adsorbent is restored, and it has both immediate and long-term effects.

Some of the inorganic deodorant adsorbents have a catalytic function, and when such an inorganic deodorant adsorbent is brought into direct contact with an organic resin, decomposition odor or coloring occurs. Since it cannot be added later, it is preferable to carry out protective coating with a porous inorganic material together with the titanium oxide photocatalyst as described above. For example, when "Absentu # 3000" (hydrophobic zeolite; manufactured by Union Showa Co., Ltd.) is used as the inorganic deodorant adsorbent, the adsorptive power of basic malodor such as ammonia is weak. Therefore, it is preferable to use "Absentu # 1000" (hydrophobic zeolite; manufactured by Union Showa Co., Ltd.), which is well adsorbed with a basic odor,
Since "Absentu # 1000" has a catalytic function, if it is added later, it decomposes the organic resin at the time of compounding or molding, and causes decomposition odor or coloring. This "Absent # 1000"
It is advisable to coat them with a porous inorganic material together with the titanium oxide photocatalyst.

The proportions of the titanium oxide photocatalyst and the inorganic deodorant adsorbent to be mixed with the organic resin are appropriately determined depending on the required deodorizing ability (determined depending on the place of use of the product) and the processing method. Generally, the titanium oxide photocatalyst is about 0.1 to 5.0 with respect to 100 parts by weight of the organic resin.
It is preferable that the parts by weight and the inorganic deodorizing adsorbent are blended so as to be approximately 0.5 to 10.0 parts by weight.

As a method of coating both the titanium oxide photocatalyst and the inorganic deodorizing adsorbent with a porous inorganic material, for example, after adding an alkali solution of a soluble silicate or a soluble aluminum salt to a slurry containing titanium oxide,
A method of precipitating silica or alumina on titanium oxide by adding an acid, a method of contacting an alkoxide of Si, Al, or Zr diluted with an organic solvent with titanium oxide in a floating state, a starting material of alkali silicate After forming an emulsion, a silica microcapsule method utilizing an interfacial reaction is used.

As the porous inorganic substance coating method, various methods can be used as described above. In the present invention, silica or alumina is selected as the inorganic substance, and a porous membrane having an appropriate pore size can be easily formed as the starting material. Therefore, a silica sol, an alumina sol or a mixture thereof is used, and the silica content or the alumina content is 0.1% by weight or more by weight% 2
By adding 0% by weight or less of a silica monomer or an alumina monomer, an inorganic coating material suitable for the purpose of the present invention can be obtained. When an aqueous silica sol is used, the solution can coat titanium oxide at any pH, but the isoelectric point of titanium oxide (5.5-6.0)
It is preferable to react at pH = 3-5, which is between the isoelectric point (2.0-2.5) of silica, because a good coating due to adsorption by static electricity of both can be expected. Also, acidifying the pH of the system can be expected to have a catalytic effect when the monomers are polymerized. Further, when the acidic silica sol is used, coated titanium oxide having a smaller particle size than that of the basic silica sol is obtained, and as a result, it is possible to uniformly mix it with the organic resin.

The type of silica sol is not limited to an aqueous system and may be an organic solvent system. In the latter case, for example, when a commercially available organo silica sol is used, the pH of the solution is preferably acidic for the same reason as the aqueous silica sol. In this case, the water required for the hydrolysis of the monomer used in combination is supplied from the adsorbed water on the surface of the titanium oxide particles, and as a result, the reaction occurs selectively on the surface of titanium oxide, and more efficient coating is expected. it can. Regarding the effect of addition of the monomer, in the case of silica, not only the function of connecting the silica particles to each other but also the bond between silica and titanium oxide can be expected, and a stronger and more strongly adhered silica coating layer can be formed on the titanium oxide surface. When the amount of the monomer added is less than 0.1% by weight, the effect is not recognized, and when it exceeds 20% by weight, fusion and aggregation of particles become remarkable, which is not preferable for the purpose of obtaining fine particles, and economically. Is also a disadvantage. Any silica monomer may be used as long as it is polymerized to (SiO ₂ ), but tetramethoxysilane (TMOS), tetraethoxysilane (TE) which has a high reaction rate.
OS) are preferable, and these are used alone or in combination. Although aluminum alkoxide is used as the alumina monomer, aluminum tri-sec-butoxide and aluminum tri-tert-butoxide are preferable, and these are used alone or in combination.

In the case of alumina, it is preferable to treat the alumina sol between the isoelectric points (9.0) of titanium and alumina just like silica, and an alkoxide of A1 can be used as a monomer. When reacting titanium oxide with silica sol or alumina sol and their monomers, it is effective to add a small amount of a dispersant such as polycarboxylic acid to improve the dispersion of titanium oxide in order to obtain a uniform coating.

The titanium oxide fine particle powder coated with the porous inorganic material is obtained by drying the obtained reaction-completed liquid. However, the drying method obtains the fine particles directly without a crushing step, so that freezing with as little heat as possible is performed. Drying, vacuum drying with a rotary evaporator, spray drying and the like are desirable. It is also an effective method to directly obtain fine particles by subjecting the powder surface to butyl esterification by heating using t-butyl alcohol or n-butyl alcohol. Regarding the heat treatment after drying, it was confirmed that the particle size of the powder increased due to the treatment and fusion of the particles occurred, but the heat treatment did not give a strong and adhesive force to titanium oxide and the inorganic deodorant adsorbent. It is necessary to obtain a large coating layer.

The organic resin used in the present invention may be a thermoplastic resin, a thermosetting resin, a synthetic resin or a natural resin, but the titanium oxide photocatalyst to be incorporated is decomposed by a catalytic function, and an inorganic deodorant adsorbent is also used. In order to deodorize a malodorous substance by adsorbing the malodorous substance, it is necessary to select an organic resin that can pass the malodorous substance that needs to be deodorized.

Specifically, ethylene monomer homopolymer resins such as low density polyethylene resin, high density polyethylene resin, linear low density polyethylene resin, ethylene-methacrylic acid copolymer resin, ethylene-maleic anhydride copolymer Polyolefin resin including polymer resin, ethylene copolymer resin such as ethylene-vinyl acetate copolymer resin, polypropylene resin, polystyrene resin, methacrylic acid resin, acrylic acid resin, low saponification polyvinyl alcohol resin Resin, polyvinyl chloride resin, polyvinyl acetate resin, fluorine resin, polyurethane resin, diene resin, maleic acid resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, alkyd Resin, phthalic acid resin, styrene-butadiene resin , Butyl resins, polychloroprene resins, petroleum resins, drying oils (linseed oil, perilla oil, etc. tung oil) and the like, which may be used either alone or in combination of two or more.

In the present invention, as a method for compounding / molding a titanium oxide photocatalyst coated with a porous inorganic material into an organic resin, a known compounding / molding method can be adopted as long as the porous inorganic material coating is not destroyed by an external force. . For example, when the organic resin is a thermoplastic resin, it is added and mixed by a melt-kneading method, and the desired form is obtained by a known molding method (inflation processing, extrusion laminating processing, injection processing, hot melt coating processing, fiber spinning processing, etc.). Mold into In addition, when the organic resin is a thermosetting resin and is in a liquid state such as a monomer liquid / oligomer liquid before molding, or when the resin is an emulsion / dispersion solution, polymerization, crosslinking, heating, drying, etc. It may be added and mixed before the curing by means of, and known molding, coating and printing methods such as roll coating, spray coating, dipping, gravure printing, screen printing and flexo printing can be applied.

Further, an organic acid-based or flavonoid-based organic deodorant may be added by post-addition to the resin composition having a deodorizing function of the present invention for the purpose of supplementing the deodorizing ability, but it is heat resistant. It is necessary to consider the processing method because there is a problem. In addition, an antistatic agent, a plasticizer, a filler, a coloring agent, an antibacterial agent, an antifouling agent, etc. may be added depending on the purpose. The compounding ratio of the titanium oxide photocatalyst coated with the porous inorganic material to the organic resin is appropriately determined depending on the required deodorizing ability, the processing method and the like.

As described above, since the resin composition having a deodorizing function according to the present invention contains the titanium oxide photocatalyst coated with a porous inorganic material, it has an excellent deodorizing function for a long period of time and has various properties. It can be applied to various processing methods and various forms, and can be applied in a wide variety of ways.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1-1 "Taipaque ST-01" (anatase type, particle size = 70 nm; manufactured by Ishihara Sangyo Co., Ltd.) 2 as a titanium oxide photocatalyst 2
By weight, as an inorganic deodorant adsorbent, "Absentsu # 300
0 ”Hydrophobic zeolite, average particle size = 3.3 μm; Union Showa Co., Ltd.) To 2 parts by weight, 6.4 parts by weight (as silica) of“ Snowtex ”(manufactured by Nissan Chemical Industries, Ltd.) as silica sol was added and pot milled. At 100 rpm for 1 hour to react. The reaction solution was dried with a spray dryer and then heat-treated at 550 ° C. for 1 hour to obtain a silica-coated mixture of titanium oxide and a deodorant adsorbent. Next, with respect to 10.4 parts by weight of this protective coating, "Mirason-206P" (low density polyethylene resin, density = 0.923 g / cm ³ , MI as organic resin)
= 3.7 g / 10 minutes; manufactured by Mitsui Petrochemical Industry Co., Ltd.) 9
After dry blending with 0 part by weight, a continuous kneading extruder (KCK 120X2-65VEX; KCK Co., Ltd.
Manufactured by K.K.) while depressurizing and degassing the vent part, and kneading and extruding at an outlet temperature of 180 ° C. to pelletize, to obtain a resin composition having a deodorizing function. Next, pellets of this resin composition were T-die extrusion laminating machine (screw diameter = 40 mm
φ, L / D = 22, T die temperature = 330 ° C.),
It is composed of a low-density polyethylene resin (20 μm) having a deodorizing function / high-quality paper, which is extruded into a film shape with a thickness of 20 μm on high-quality paper (basis weight = 52.3 g / m ² ) and laminated by a laminating machine. A laminated paper was prepared.

Example 1-2 2 parts by weight of "Taipaque ST-01" as a titanium oxide photocatalyst and "Absent # 300" as an inorganic deodorizing adsorbent
0 "2 parts by weight as silica sol" Snowtex "
Add 6.4 parts by weight (as silica) and add 1 in a pot mill.
After stirring at 00 rpm for 15 minutes, tetramethoxysilane 0.
016 parts by weight (as silica) was added, and the mixture was further stirred for 1 hour for reaction. The reaction solution was dried with a spray dryer and then heat-treated at 550 ° C. for 1 hour to obtain a silica-coated mixture of titanium oxide and a deodorant adsorbent. Next, after 10.46 parts by weight of this protective coating was dry blended with 90 parts by weight of "Mirason 206P", a resin composition having a deodorizing function was similarly prepared by using the above continuous kneading extruder. Obtained. Next, using this resin-blended composition in the same manner as in Example 1, a laminated paper was prepared using a T-die extrusion laminator.

Example 1-3 2 parts by weight of "Taipaque ST-01" as a titanium oxide photocatalyst and "Absent # 300" as an inorganic deodorant adsorbent
0 "2 parts by weight as silica sol" Snowtex "
Add 6.4 parts by weight (as silica) and add 1 in a pot mill.
After stirring at 00 rpm for 15 minutes, tetramethoxysilane 0.
16 parts by weight (as silica) was added, and the mixture was reacted for 1 hour with stirring. The reaction solution was dried with a spray dryer and then heat-treated at 550 ° C. for 1 hour to obtain a silica-coated mixture of titanium oxide and a deodorant adsorbent. next,
After 10.56 parts by weight of this protective coating was dry blended with 90 parts by weight of "Mirason 206P", a resin composition having a deodorizing function was obtained in the same manner by using the above continuous kneading extruder. Next, using this resin-blended composition in the same manner as in Example 1, a laminated paper was prepared using a T-die extrusion laminator. However, when the laminate thickness was 20 μm, film cracking occurred, so a laminate paper was prepared with a laminate thickness of 40 μm.

Examples 1-4 2 parts by weight of "Taipaque ST-01" as a titanium oxide photocatalyst and "Absent # 300" as an inorganic deodorant adsorbent
0 "2 parts by weight as silica sol" Snowtex "
Add 6.4 parts by weight (as silica) and add 1 in a pot mill.
After stirring at 00 rpm for 15 minutes, tetramethoxysilane 0.
8 parts by weight (as silica) was added, and the mixture was further stirred for 2 hours for reaction. The reaction solution was dried with a spray dryer and then heat-treated at 550 ° C. for 1 hour to obtain a silica-coated mixture of titanium oxide and a deodorant adsorbent. next,
11.4 parts by weight of this protective coating and "Idemitsu Styrol ET-60" as an organic resin (high impact polystyrene resin, density = 1.05 g / cm ³ , MI = 2
5 g / 10 min; 90 parts by weight of Idemitsu Petrochemical Co., Ltd.) was dry-blended, and then kneaded into pellets by the continuous kneading extruder (exit temperature = 200 ° C.) to obtain a resin composition having a deodorizing function. It was The pellets were put into a T-die extruder (screw diameter = 40 mmφ, L / D = 22, T-die temperature = 250 ° C.), and extruded into a sheet form with a T-die to produce a sheet having a thickness of 100 μm.

Example 1-5 2 parts by weight of "Taipaque ST-01" as a titanium oxide photocatalyst and "Absent # 300" as an inorganic deodorant adsorbent
0 "2 parts by weight as silica sol" Snowtex "
Add 6.4 parts by weight (as silica) and add 1 in a pot mill.
After stirring at 00 rpm for 15 minutes, tetramethoxysilane 1.
6 parts by weight (as silica) was added, and the mixture was further stirred for 2 hours for reaction. The reaction solution was dried with a spray dryer and then heat-treated at 550 ° C. for 1 hour to obtain a silica-coated mixture of titanium oxide and a deodorant adsorbent. next,
After dry blending 12 parts by weight of this protective coating and 90 parts by weight of "Idemitsu Styrol ET-60",
The sheet was molded into a sheet having a thickness of 100 μm by the same operation as in Example 1-4.

Example 2 "Taipaque ST-01" as a titanium oxide photocatalyst
According to Example 1-1, 0 part by weight was silica-coated with 3.2 parts by weight of silica sol. 5.2 parts by weight of this protective coating and 2.0 parts by weight of "Absent # 3000" as an inorganic deodorant adsorbent that was added later were mixed, and "Mirason-68" (low density polyethylene resin, density = 0.916 g / cm ³ , MI = 23
g / 10 minutes, molding brand; 90 parts by weight of Mitsui Petrochemical Co., Ltd.) is dry blended, and then kneaded into pellets by the above-mentioned continuous kneading extruder (exit temperature = 170 ° C.) to have a deodorizing function. A resin composition was obtained. Next, an injection molding machine (mold clamping pressure = 80 t, nozzle temperature =
150 ° C., mold temperature = 30 ° C .; manufactured by Meiki Seisakusho Co., Ltd.), and molded into a plate shape having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm.

Example 3 2 parts by weight of "Taipaque ST-01" as a titanium oxide photocatalyst and "Absent # 300" as an inorganic deodorant adsorbent
0 "2 parts by weight as alumina sol" Alumina sol-5 "
20 "(manufactured by Nissan Chemical Industries, Ltd.), 6.4 parts by weight (as alumina) are added, and a pot mill is operated at 100 rpm for 15 minutes.
After stirring for a minute, aluminum tri-sec-butoxide 0.16
By weight (as alumina) was added, and the mixture was further stirred for 2 hours for reaction. The reaction solution was dried with a spray dryer and then heat-treated at 550 ° C. for 1 hour to obtain an alumina-coated mixture of titanium oxide and a deodorant adsorbent. 10.416 parts by weight of this protective coating and "Evaflex P-1207" as an organic resin (ethylene-vinyl acetate copolymer resin, vinyl acetate content = 12% by weight, MI = 12 g / 10 min; Mitsui DuPont Poly 90 parts by weight of Chemical Co., Ltd.) was kneaded and pelletized using the above-mentioned continuous kneading extruder (exit temperature = 170 ° C.) to obtain a resin composition having a deodorizing function. The obtained pellets and “Mitsubishi Polypro PY-240B” (polypropylene resin, homopolymer type, density = 0.90 g / cm ³ , M
I = 5.0 g / 10 minutes; pellets of Mitsubishi Petrochemical Co., Ltd.) were respectively charged into a melt extrusion spinning machine, and an ethylene-vinyl acetate copolymer resin (sheath) / polypropylene resin (core) having a deodorizing function was introduced. A fiber having a core-sheath structure and a thickness of 20 denier was produced.

Example 4 "Taipaque ST-01" as a titanium oxide photocatalyst
5 parts by weight, "Absent # 30
00 "1.5 parts by weight and" Absent # 1000 "1.5
Parts by weight, 9.6 parts by weight of "Snowtex" as silica sol (as silica), and 100 rp in a pot mill
After stirring for 15 minutes at m, 0.24 parts by weight of tetramethoxysilane (as silica) was added, and the mixture was further stirred for 2 hours for reaction. After drying the reaction solution with a spray dryer, 55
Heat treatment was performed at 0 ° C. for 1 hour to obtain a silica-coated mixture of titanium oxide and a deodorant adsorbent. Next, 14.34 parts by weight of this protective coating is added to "Ester D11
7B "(unsaturated polyester resin for decorative plywood, solid content =
35% by weight; manufactured by Mitsui Toatsu Chemicals, Inc.) and mixed by stirring, and then 1.0 part by weight of 2-methylethylketone peroxide as a curing agent was added and further mixed by stirring. This solution was cast on a plywood sheet having a thickness of 10 mm, and a polyvinyl alcohol film was applied thereto, which was then pressed with a roll so as to obtain a uniform coating film thickness and left to stand overnight for curing to give an unsaturated polyester surface treatment layer ( A surface-treated plywood having a deodorizing function having a constitution of 60 g / m ² ) / plywood was obtained.

Example 5 In the same manner as in Example 4, the titanium oxide photocatalyst and the inorganic deodorant adsorbent were protectively coated with porous silica. 14.34 parts by weight of this protective coating and "Vinicron 4
000M "(polyvinyl chloride resin, average degree of polymerization = 105
0: Mitsui Toatsu Chemicals, Inc.) 100 parts by weight and 45 parts by weight of dioctyl phthalate as a plasticizer were put into a high speed mixer, mixed for 5 minutes, and the temperature was raised to 100 ° C. to obtain a mixture. This mixture was put into a kneading roll (temperature of 160 ° C.) to homogenize the kneading, transferred to a calender roll and molded into a sheet (thickness: 2 mm) to obtain a polyvinyl chloride resin sheet molded product having a deodorizing function. .

Example 6 As in Example 4, "Taipaque ST-01", "Abscent # 3000" and "Abscent # 1000" were protectively coated with porous silica, and 14.34 parts by weight of this protective coating was applied. 100 parts by weight of "Asahipen / water-based enamel (white)" (household paint, main component: acrylic resin, solid content concentration = 50% by weight; manufactured by Asahipen Corporation) were mixed with stirring, and then plywood (thickness = 5 mm). ), And a deodorizing paint film (40 g / m ² )
A film of a resin composition having a deodorizing function, having a composition of a veneer plate (5 mm) was formed.

Example 7 1.5 parts by weight of "Taipaque ST-01" and 1.5 parts by weight of "Absent # 3000" and "Kyoward 700"
(Silica-alumina compound, chemical adsorbent, average particle size =
Porous silica coating was carried out in accordance with Example 1-1 by using 4.8 parts by weight of silica sol and 10 parts by weight of 10 μm; manufactured by Kyowa Chemical Industry Co., Ltd.). 9.3 parts by weight of this protective coating was added to 100 parts by weight of "Asahipen / water-based enamel (white)", and a film of the resin composition having a deodorizing function was formed on the plywood plate by the same operation as in Example 6.

Example 8 Protective coating 1 produced in the same manner as in Example 3
0.56 parts by weight of "Rox orange" (flexo ink, solid content = 35%; manufactured by Toyo Ink Mfg. Co., Ltd.) was mixed with 40 parts by weight, and the viscosity was adjusted by adding water, and then the flexographic printing machine. (Manufactured by Sobu Machinery Co., Ltd.), a dry solid content of 1 g / on ^high -quality paper (basis weight = 50 g / m ² ).
Printing was performed so as to be m ^2, and after drying, a printing paper having a deodorizing function was obtained. Next, the protective coating 10.56
Part by weight is "New Dicure-OL Beni" (for offset printing, UV curable ink, main component: acrylic resin) 75
Pour into the parts by weight, stir and mix, and then use a roll coater so that the coated amount is 1 g / m ²
m ² ), and the ink was cured by irradiating it with ultraviolet rays to obtain a printing paper having a deodorizing function.

Example 9 "Taipaque ST-01" as a titanium oxide photocatalyst
5 parts by weight, "Absent # 30
00 "1.5 parts by weight and" Absent # 1000 "1.5
Parts by weight, 4.8 parts by weight of "Snowtex" as silica sol (as silica) and 4.8 parts by weight of "alumina sol 520" as alumina sol (as alumina) were added, and the mixture was stirred at 100 rpm for 15 minutes in a pot mill, and then tetramethoxysilane was added. 24 parts by weight (as silica) is added, and the mixture is stirred for another 2 hours to react. The reaction solution was dried with a spray dryer and then heat-treated at 550 ° C. for 1 hour to obtain a silica-alumina-coated mixture of titanium oxide and a deodorant adsorbent. After dry blending 14.34 parts by weight of this protective coating and 90 parts by weight of "Mirason 206P", a biaxially stretched polyethylene terephthalate resin film (PET film and PET film was used as the base material in the extrusion laminating process of Example 1-1. (Thickness = 38 μm)
In the laminator process, the urethane anchor coating agent is applied, dried with a dryer, and then extrusion laminated with a T-die (thickness 20 μm) to obtain a resin layer having a deodorizing function 20 μm / anchor coating agent / PET A laminated product of a resin film having a deodorizing function and having a structure of a film of 38 μm was obtained.

Example 10 Porous silica protective coating 1 prepared in Example 9
4.34 parts by weight and "LEXRON F-3" as an organic resin
1 "(low density polyethylene resin, density = 0.923 g /
cm ³ , MI = 2.0 g / 10 min, dry-blending with 100 parts by weight of a general packaging film brand (manufactured by Nippon Petrochemical Co., Ltd.), and then the continuous kneading extruder (exit temperature = 2)
The mixture was kneaded into pellets at 00 ° C. to obtain a resin composition having a deodorizing function. Next, the pellets were put into an inflation film molding machine (screw diameter 65 m / mφ; die-slot gold diameter = 400 m / m; manufactured by Tommy Kikai Co., Ltd.) and extruded at a die mouthpiece temperature of 155 ° C. to obtain a thickness of 40 μm.
m was prepared. Further, 14.34 parts by weight of this porous silica protective coating and "HIZEX 7000F" as an organic resin (high-density polyethylene resin, density = 0.956 g / cm ³ , MI = 0.05 g / 1
0 minutes, industrial film brand; manufactured by Mitsui Petrochemical Co., Ltd.)
100 parts by weight was kneaded and pelletized by the same operation as in Example 6 to obtain a resin composition having a deodorizing function in the present invention, and then the thickness was measured using an inflation film molding machine (die die temperature = 190 ° C.). A 40 μm film was made.

Example 11 Porous silica protective coating 1 prepared in Example 9
4.34 parts by weight and as an organic resin, "HIPOL LA-
221 "(polypropylene resin, homopolymer type,
Density = 0.91 g / cm ³ , MI = 25 g / 10 minutes; dry blended with 90 parts by weight of Mitsui Petrochemical Co., Ltd., and then the above continuous kneading extruder (exit temperature = 200
K) and kneaded and extruded into pellets to obtain a resin composition having a deodorizing function. Next, the pellets of this resin composition were mixed with the above-mentioned T-die extrusion laminating machine (T-die temperature = 300).
(° C), and the same operation as in Example 1 was performed to produce a laminated paper.

Example 12 10.4 parts by weight of the protective coating prepared in Example 1-1 and 400 parts by weight of "Cybinol EK-1005" (acrylic resin emulsion, solid content = 39%; manufactured by Saiden Chemical Co., Ltd.) And are mixed by stirring, and coated on a biaxially oriented polypropylene film (abbreviated as OPP, thickness = 25 μm) using a Meyer bar so that the coating amount after drying is 10 g / m ^2, and then a gear oven dryer. O which is made into a dry film with an acrylic resin film having a deodorizing function
A PP film was obtained.

Example 13 10.4 parts by weight of the protective coating prepared in Example 1-1 was added to 400 parts of "Chris Bonn 3355" (urethane resin for synthetic leather, solid content = 22%; manufactured by Dainippon Ink and Chemicals, Inc.). Pour into 1 part by weight, stir and mix, add 2 parts by weight of "Crisbon NX" (isocyanate-based cross-linking agent, manufactured by Dainippon Ink and Chemicals, Inc.) to this, coat with a coater and dry. A film of a resin composition having a deodorizing function, which was composed of cured urethane synthetic leather (50 g / m ² ) having a deodorizing function / fabric, was formed.

Comparative Example 1 In Example 1-1, the porous inorganic substance coating of the titanium oxide photocatalyst was not performed, and "Absentu # 300" was used.
Without adding "0", it was directly mixed with the organic resin, and a laminated paper was prepared by the same operation.

Comparative Example 2 In Example 1-1, the operation of the porous inorganic material coating was not carried out, and the titanium oxide photocatalyst “Taipaque ST-0” was used.
1 "and an inorganic deodorant adsorbent" Absent # 3000 "were directly mixed with an organic resin, and a laminated paper was produced by the same operation.

Comparative Example 3 In the same manner as in Example 1-2, a titanium oxide photocatalyst "Taipaque ST-01" and an inorganic deodorant adsorbent "Absent # 3" were used.
000 "was protectively coated with porous silica. After dry blending 10.416 parts by weight of this protective coating and 1.5 parts by weight of "Absent # 1000" (post-addition), kneading into pellets by the same operation as in Example 1-1, and T-die extrusion laminator. Was used to produce a laminated paper.

Comparative Example 4 In the same manner as in Example 2, 2.0 parts by weight of titanium oxide photocatalyst "Taipaque ST-01" was used as a protective coating with 3.2 parts by weight of silica sol, and inorganic deodorant adsorption after addition was carried out. An injection process was performed in the same manner as in Example 2 without using the agent "Absentu # 3000" to obtain a size 1
A plate having a size of 0 cm × 10 cm and a thickness of 1 mm was prepared.

The deodorizing ability of each of the samples prepared in Examples 1 to 13 and Comparative Examples 1 to 4 was evaluated by the following method. 1. Preparation of Samples Samples are prepared in the proportions shown in Table 1 for each sample and malodorous odorous substance, and the samples are enclosed in a weighing bottle having a body diameter of 6 cm and a height of 8 cm.

2. Deodorization immediate effect performance evaluation method 1. Check the odor of each sample prepared by the method 1) on the 1st day after the inclusion of the malodorous odorous substance, and confirm that there is no odor. After that, light is applied for 7 days (daytime uses sunlight and nighttime uses black light). After 7 days, each sample is filled with the malodorous odor substances shown in Table 1, and one day later, an odor check is performed to confirm whether or not there is no odor and there is immediate deodorizing effect. If the odor remains, extend the light irradiation time and check. Further, each sample is repeated for 6 months by the same method, and after 6 months, it is confirmed whether or not it has the deodorant immediate effect performance.

3. Long-term deodorizing performance evaluation method 1. Each sample prepared by the above method is irradiated with light for 7 days (using daytime sunlight and night black night). 7
Check the odor after a day to see if there is any odor. If there is no odor, the amount of malodorous substance shown in Table 1 is further added and sealed, and after irradiating with light for 7 days (using daytime sunlight and black light at night), odor check is performed to confirm deodorizing performance. This operation is repeated for 6 months to confirm the long-term deodorizing performance. The above deodorization performance evaluation results are shown in Tables 2 to 4.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

As described above, the resin composition of the present invention exerts an excellent deodorizing function over a long period of time, and is used for building materials such as wall materials, floor materials and ceiling materials, and curtains, blinds, and lighting equipment covers. It is useful in a wide range of fields such as interior products such as reflectors, interior materials for automobiles, containers for foods, packaging materials and the like.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C08K 9/02 (72) Inventor Masahiro Nakajima 4-13-18 Anritsu, Suminoe-ku, Osaka-shi, Osaka Inside the paper manufacturing company (72) Inventor Yoshinori Tanigami 2-21 Hamamatsubara-cho, Nishinomiya-shi, Hyogo Yamamura Glass Co., Ltd. (72) Inventor Zhang Zhou 2-21 Hamamatsubara-cho, Nishinomiya-shi, Hyogo Yamamura Glass Co., Ltd. In the company

Claims (9)

[Claims] 1. A resin composition having a deodorizing function, characterized in that a mixture of a titanium oxide photocatalyst and an inorganic deodorizing adsorbent coated with a porous inorganic material is mixed with an organic resin. 2. A resin composition having a deodorizing function, characterized in that a mixture of a titanium oxide photocatalyst coated with a porous inorganic material and an inorganic deodorizing adsorbent is mixed with an organic resin. 3. The resin composition according to claim 1, wherein the porous inorganic substance is silica and / or alumina. 4. The resin composition according to claim 3, wherein the silica is silica sol. 5. The resin composition according to claim 4, wherein silica is a reaction product of silica sol and a silica monomer. 6. The silica monomer is 1 to the amount of silica.
The resin composition according to claim 5, which is 20% by weight. 7. The alumina is an alumina sol according to claim 3.
The resin composition as described in the above. 8. The resin composition according to claim 7, wherein the alumina is a reaction product of an aluminum sol and an alumina monomer. 9. The resin composition according to claim 8, wherein the amount of the alumina monomer is 1 to 20% by weight based on the amount of alumina.