JP2002266234A - A processed vegetable fiber product carrying fine particles having the ability to decompose organic compounds - Google Patents

Abstract

(57) [Object] To provide a processed plant fiber product capable of binding fine particles having an organic compound decomposing ability in a state having an organic compound decomposing ability and stably maintaining such a state for a long period of time. provide. A processed plant fiber product having bonded thereto fine particles having an organic compound decomposing ability, wherein the fine particles are bonded to the processed product by a binder (binder) containing alkoxysilane as a main component. Solve the problem.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paper or cloth, such as paper or cloth, to which fine particles having the ability to decompose organic compounds such as titanium oxide and tourmaline are added for the purpose of adding the ability to decompose harmful substances in the atmosphere. The present invention relates to a processed plant fiber product, including a molded product.

[0002]

2. Description of the Related Art A method for decomposing harmful substances in the air using fine particles having a decomposing ability of organic compounds such as titanium oxide and tourmaline has been actively studied. Specifically, for example, by coating the surface of a building or the like with a paint mixed with titanium oxide fine particles, the particles are bonded to the surface, and are included in, for example, exhaust gas discharged from an automobile engine. Research has been actively conducted to decompose various harmful substances released into the atmosphere, such as fine particles, and to decompose harmful substances released into and out of buildings from building materials such as formaldehyde. is there.

[0003] When such fine particles having the ability to decompose organic compounds are mixed in a paint as described above, for example, and the particles are bonded by painting the surface of an object to be coated such as a wall or concrete, the particles are used as follows. Whether it can be bonded to the surface of the binding object in a state having the ability to decompose organic compounds, and further, whether such a state can be stably maintained over a long period of time, and the like The point is a very important point.

Taking the above-mentioned fine particles having the ability to decompose organic compounds as an example, for example, fine titanium oxide particles generate holes and electrons on the surface of the fine particles when irradiated with ultraviolet rays,
Thus, the organic compound is decomposed by the photocatalytic function of decomposing the organic compound attached to the surface of the fine particles. Therefore, as a matter of course, in order for the organic compound to be bonded to the surface of the object to be bonded such as a wall or concrete in a state having the ability to decompose the organic compound, the organic compound must be in a state where it can be directly attached to the fine particle surface. It doesn't. However, if the titanium oxide fine particles are mixed with the paint and bonded to the surface of the object to be bonded such as a wall or concrete, the surface of the titanium oxide fine particles will be covered with the paint. As a result, the organic compound to be decomposed cannot directly contact the surface of the titanium oxide fine particles, and the ability to decompose the organic compound is greatly reduced.

[0005] Furthermore, especially when coating outdoor walls and concrete parts, it is common to use an organic paint having excellent weather resistance. However, the ability to decompose organic compounds such as titanium oxide fine particles is required. When the fine particles having the fine particles are mixed into the organic paint, the fine particles act on the paint component itself, which is a binder for binding the fine particles to an object to be bonded, and are decomposed. As a result, in the long term, it is difficult to stably maintain the state in which titanium oxide fine particles and the like are bonded to the binding target, and if the decomposition of the organic paint progresses, the surface of the binding target is protected. It can even happen that the original purpose of the coating itself is lost.

Many attempts have been made to solve the above problems. For example, a method has been reported in which a fluorine-based paint is used instead of an organic paint as a paint in which fine particles having the ability to decompose organic compounds such as titanium oxide fine particles are mixed (see, for example, JP-A-171408). ). In addition, a method of coating an organic paint after forming an intermediate layer on a binding object (substrate) with a substance that is not decomposed by the photocatalysis of the fine particles, instead of simply mixing the organic paint with the organic paint (for example, industrial Material, Vol.48 (NO.6), p49,2
2000) have also been reported.

Further, the surface of the fine particles having the ability to decompose organic compounds is coated with porous silica having pores through which the organic compound to be decomposed passes, so as to form a so-called mask melon type catalyst. However, a method of preventing the surface of the fine particles from coming into direct contact with paint or the like (for example, photocatalyst, Vol.
2000).

[0008]

As described above, the method of using fine particles having the ability to decompose organic compounds has been conventionally improved in many ways and has achieved a certain effect. However, each of the improvement methods has a problem that requires further improvement.

For example, in the case of the above-mentioned method using a fluorine-based paint instead of an organic paint, the fluorine-based paint is more expensive than the organic paint, so that there is a new problem that the implementation is costly. I do. Further, in the case of a fluorine-based paint, an ozone hole depleting substance may be generated at the time of its decomposition, so that it cannot be widely used in general because of environmental problems, and there is a problem that its application range is naturally limited. In addition to these challenges,
In this method, the surface of the fine particles having an organic compound decomposing ability is covered with a paint, and as a result, the organic compound to be decomposed may not be able to directly contact the surface of the fine particles, and the organic compound decomposing ability is reduced. It does not bring about the solution of the problem.

In the above-described method using a so-called mask melon type catalyst, for example, when the surface of titanium oxide fine particles is covered with porous silica having no photocatalytic function, the surface is mixed with a coating material. The fine particles do not come into direct contact with the paint so that their decomposition does not occur, while the organic compounds to be decomposed can be brought into contact with the surface of titanium oxide fine particles through the pores of silica. It is.

According to this method, the fine particles having the ability to decompose organic compounds can be bonded to the surface of the object to be bound while having the ability to decompose organic compounds, and such a state can be stably maintained over a long period of time. Because it is possible, attention has been paid as a method that can solve the above problem, but it is still a method under study, for example, selection of a porous material used for coating fine particles, various organic compounds due to differences in the type of porous material Currently, there are many issues to be solved for practical use, such as the problem of selective passage.

What has been described above is a method of bonding fine particles having an organic compound decomposing ability by coating a bonding object such as a wall or concrete with the coating material, that is, an organic compound itself such as a coating material. This is a problem that has arisen when fine particles are mixed as a binder (binder) for bonding fine particles having a decomposability to the surface of a binding object. In addition to the above, when the object to be bound is paper, a method of forming fine particles having an organic compound decomposing ability such as titanium oxide fine particles into paper has been attempted (for example, Chemical, Vol. .54, N
o. 5, 33, 1999). However, paper made by this method has paper fibers and fine particles in direct contact with each other, and after a long time, it is broken down by photocatalytic functions such as titanium oxide, and the paper becomes brittle or broken. There is a problem that. For this reason, the paper has not been put to practical use so far.

As described above, if fine particles having a capability of decomposing organic compounds such as titanium oxide can be successfully bonded to various articles including processed vegetable fibers, harmful organic compounds present in the atmosphere can be decomposed. It has been proven at the experimental level that it can provide an article that is effective in doing so.
However, in order to actually put this into practical use, there was a problem to be solved in the basic part of how to bond the particles to an article.

Therefore, the present invention provides a processed plant fiber product which can combine fine particles having an organic compound decomposing ability in a state having an organic compound decomposing ability and stably maintain such a state for a long period of time. It is intended for.

[0015]

Means for Solving the Problems The present invention described in claim 1 for achieving the above object is a processed vegetable fiber product to which fine particles having an ability to decompose organic compounds are combined, wherein the fine particles are , And a bonded product containing the alkoxysilane or its hydrolyzate as a main component. Claim 2
The invention of the present application described in (1) is characterized in that the processed plant fiber product is a molded product obtained by processing and forming a plant fiber.
The present invention described in claim 3 relates to the invention described in claim 2, wherein the processed vegetable fiber product is made of paper or cloth containing cellulose. A fourth aspect of the present invention is the invention according to the first aspect, wherein titanium oxide or tourmaline is bonded as the fine particles having an organic compound decomposing ability. A fifth aspect of the present invention is the invention according to the first aspect, wherein titanium oxide and tourmaline are combined as the fine particles having an organic compound decomposing ability. The present invention described in claim 6 relates to the invention described in claim 1, wherein the binder (binder) contains an alkoxysilane compound represented by a chemical formula (1) as a main component. (In the formula 1, R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different, and each represents hydrogen or an alkyl group having 1 to 4 carbon atoms or a phenyl group. is there).

(Equation 1)

The present invention according to claim 7 is the invention according to claim 1, wherein the binder is an alkoxysilane compound represented by the chemical formula (1). It is characterized in that a compound represented by the chemical formula (2) is further added to the main component (in the formula 1, R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different. Good, hydrogen or carbon number 1
And R ₅ , R ₆ , R ₇ , and R ₈ in Formula 2 may be the same or different, and each may be hydrogen or an alkyl group having 1 to 4 carbon atoms or A phenyl group).

(Equation 1)

(Equation 2) Also, the present invention described in claim 8 is the invention according to claim 1,
The invention according to 6 or 7, wherein the binder (binder) contains a hydrolyzable organometallic compound. The present invention described in claim 9 relates to the invention described in claim 8, wherein the hydrolyzable organometallic compound is titanium,
It is characterized in that it is at least one organometallic compound selected from the group consisting of zircon, aluminum and tin. Hereinafter, the present invention will be described in detail.

The invention of the present application is obtained by binding fine particles having an ability to decompose organic compounds, using a plant fiber processed product obtained by processing plant fibers, such as paper or cloth containing cellulose, as an object to be bound. The processed plant fiber product to which the present invention can be applied is not limited to a product formed into a fixed shape, but also includes, for example, natural materials such as bark, paper, and cloth, and primary processed products thereof. In general, there is no limitation as long as the product is made of paper or cloth used indoors and outdoors.

More specifically, processed vegetable fiber products include:
For example, various products such as wallpaper, fusuma paper, shoji paper, ceiling paper, tablecloths, curtains, mats, bed sheets, and pet toilet mats (smell removal) can be exemplified.

In order to combine fine particles having an organic compound decomposing ability with a plant fiber processed product in a state having the organic compound decomposing ability and stably maintaining such a state over a long period of time, It is required that the fine particles be bound to the processed plant fiber using a binder that is not decomposed by the photocatalytic function of the particles. On the other hand, it is also required to reduce the amount of the binder covering the surface of the fine particles as much as possible. Further, in order to prevent the fine particles having the ability to decompose organic compounds from peeling from the processed plant fiber product, a binder is required.
However, it is also required that they be firmly bonded to the processed plant fiber product by directly bonding to the fine particles or enclosing the fine particles. In response to this requirement, in the present invention, plant fibers such as paper and cloth are produced by using a sol-gel method and using a binder (binder) that is not decomposed by the fine particles, using an sol-gel method. It employs a configuration of coupling to a processed product.

In the present invention, the fine particles having the ability to decompose organic compounds are bound to the processed plant fiber product by
Specifically, for example, fine particles such as titanium oxide or tourmaline. For example, titanium oxide fine particles, which are sold as ordinary photocatalysts, can be expected to have a sufficient organic compound decomposing effect. is there. For example, tourmaline fine particles
In addition to the property that the organic compound can exert its photocatalytic function even when it does not come into contact with its surface, it has the property of being able to exert its photocatalytic function even in a room where the irradiation of visible light or ultraviolet light is weak or in a dark place, especially indoors It is preferable to provide the processed plant fiber product of the present invention for use in a tunnel, a dark room, or the like. Of course, in the present invention, there is no limitation on the use of fine particles other than these specific fine particles.

Two or more kinds of the above-mentioned fine particles having an organic compound decomposing ability can be used simultaneously, that is, two or more kinds can be simultaneously bound to the same processed plant fiber product. In particular, when two types of fine particles, titanium oxide fine particles and tourmaline fine particles, are simultaneously bonded to a plant fiber processed product, the properties of the titanium oxide fine particles are sufficient while sufficient light is irradiating the plant fiber processed product. Decomposition of compounds, and when light irradiation is small, decomposition by tourmaline microparticles occurs, and even under different or fluctuating light irradiation, plant fiber processing that can achieve a certain organic compound decomposition effect Goods can be provided. For example, in the case of processed plant fiber products used indoors, not only during the day when the amount of light irradiation is large, but also in the morning and evening when the amount of light is small, and even during the night when there is only light irradiation such as electric lights, a certain amount of indoor fiber Organic compounds can be decomposed.

The present invention is characterized in that the above-mentioned fine particles having the ability to decompose an organic compound and the above-mentioned processed vegetable fiber product are bound together with a binder mainly composed of alkoxysilane or a hydrolyzate thereof. Is what you do. More specifically, the fine particles are mixed in a solution of a binder (binder), and the mixture is applied to the surface of a processed plant fiber product, and the binder is condensed and cured to form a coating film. However, the fine particles are taken into a network formed during condensation and curing of the binder.

The alkoxysilane as a main component of the binder is, for example, one represented by the following chemical formula (1) (in the formula 1, R ₁ , R ₂ , R ₃ , R ₄
Is hydrogen or an alkyl group having 1 to 4 carbon atoms or a phenyl group, which may be the same or different.

[0024]

(Equation 1)

Specific examples of the compound represented by the above formula (1) include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane Propyl triethoxy silane, butyl triethoxy silane, methyl tripropoxy silane, ethyl tripropoxy silane, propyl tripropoxy silane, butyl tripropoxy silane, and the like, and condensates thereof. Monomer (n = 1)
However, in this case, it takes time for condensation and curing after application to the surface of the processed vegetable fiber product, so that n = 2 to 10, particularly preferably n = 2 to 8 It is preferable to use a condensate. The compound represented by the chemical formula (1) may be a compound obtained by condensing only one of the above-described monomers, or a compound obtained by condensing two or more of the above-described monomers. Is also good.

Binder in the present invention
Has the above-mentioned alkoxysilane as a main component, but a different alkoxysilane can be added to the main component. As the alkoxysilane to be added to the main component, for example, in Formula 2, which is an alkoxysilane represented by Chemical Formula (2), R ₅ , R ₆ , R ₇ , and R ₈
Is hydrogen or an alkyl group having 1 to 4 carbon atoms or a phenyl group, which may be the same or different.

[0027]

(Equation 2)

Specific examples of the compound represented by the chemical formula (2) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane,
Examples thereof include diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and the like, and condensates thereof. A monomer (n = 1) may be used, but in this case, it takes time for condensation and curing after application to the surface of the processed vegetable fiber, so that n = 2
To 10, particularly preferably n = 2 to about 8 condensates. The compound represented by the chemical formula (2) may be a compound obtained by condensing only one of the above-described monomers, or a compound obtained by condensing two or more of the above-described monomers. Is also good.

The condensates of the alkoxysilanes represented by the chemical formulas (1) and (2) exemplified above may be used alone or in combination of two or more. Is also good. Further, in the present invention, using an alkoxysilane other than the exemplified alkoxysilane condensate,
It is also possible to further strengthen the bond between the fine particles having the ability to decompose organic compounds and processed plant fiber products such as paper.

For the purpose of firmly binding the fine particles having the ability to decompose organic compounds to processed plant fiber products such as paper, it is preferable to use alkoxysilane called a silane coupling agent. As the silane coupling agent, specifically, for example, vinyltrimethoxysilane,
Phenyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane , Phenyltriethoxysilane, γ- (methacryloxypropyl) triethoxysilane, γ-glycidoxypropyltriethoxysilane, aminopropyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, and the like. May be used, or two or more kinds may be mixed and used. Further, these monomers may be used, or a condensate may be used.
In the case of condensates, not only condensates of the same thing,
It is also possible to use condensates of two or more different ones.

The alkoxysilane conventionally used in the sol-gel method is tetraalkoxysilane ((RO)
₄ Si) is common. Tetraalkoxysilane is
When completely hydrolyzed, as shown in FIG. 1, the structure has only a siloxane bond (—Si—O—Si—), resulting in a hard but brittle coating film. Therefore, as a binder for binding fine particles having an organic compound decomposing ability to the surface of a processed plant fiber product that is hard and not flexible or unnecessary, such as glass or metal. Can be used, but among the processed plant fiber products, if the fine particles are bonded to the surface using the binder, it may be peeled off when it expands or contracts or bends There is.

Therefore, among the processed plant fiber products, when fine particles having the ability to decompose organic compounds are bonded to the surface of paper or cloth that requires flexibility, even after condensation and curing, the flexibility is high. It is required to use a binder (binder) capable of exhibiting the following formula. From such a viewpoint, in the present invention, for example, the alkoxysilane represented by the chemical formula (1) is used as a main component of the binder (binder). It is particularly preferred to use them. Chemical formula (1)
In the alkoxysilane represented by the formula, one of the four substituents of the silicon atom is not hydrolyzed. Therefore, when compared with the tetraalkoxysilane, the number of strong siloxane bonds between the adjacent silicon atom and Has one missing structure. Ultimately, the unreacted substituents remain in the form of “dangling”, which results in condensation and curing that retains flexibility even after binding the plant fiber processed product to the fine particles, Does not peel off when it expands or contracts.

The alkoxysilane represented by the chemical formula (2) can be used for the purpose of imparting more flexibility to the alkoxysilane used as a main component.
In the alkoxysilane represented by the chemical formula (2), two of the four substituents of the silicon atom are not hydrolyzed, and therefore, compared to the alkoxysilane represented by the chemical formula (1). , To form a more flexible connection. Therefore, when, for example, the alkoxysilane represented by the chemical formula (1) is condensed to form a network, it enters into the main chain structure, and finally, the binder is condensed and cured. Even more flexibility is maintained after binding the processed plant fiber and the microparticles.

As described above, in the present invention, for example, an alkoxysilane represented by the chemical formula (1) is used as a main component,
The above-mentioned configuration is adopted in which a processed plant fiber product and fine particles having an organic compound decomposing ability are combined with a binder (binder) to which an alkoxysilane represented by the chemical formula (2) is added as necessary. While achieving the above object, it is possible to bond the fine particles to a flexible processed plant fiber product such as paper or cloth without causing separation or the like. In general, it is preferable to use the alkoxysilane represented by the chemical formula (2) in a range that does not exceed 50% of the main component alkoxysilane. If it exceeds this range, it will not be condensed well with the alkoxysilane as the main component, and the strength of the coating film will decrease, and the bonding of the fine particles having the ability to decompose organic compounds to the processed plant fiber product may be weakened. Therefore, when using the alkoxysilane represented by the chemical formula (2), it is preferable to conduct a preliminary experiment to determine an appropriate amount to be used.

By the way, the unreacted substituent R4 in the alkoxysilane represented by the chemical formula (1) is
Unreacted substituent R6 in the alkoxysilane represented by
When R8 and R8 are organic substituents, it is possible to impart flexibility to the condensed and cured binder (binder) and also to impart water repellency to the cured binder (binder). In general, organic substituents have more carbon atoms,
Organic, ie, water repellent, increases, but too high a carbon number causes steric hindrance, causing distortion inside the film formed by the cured binder, resulting in reduced strength Might be. Therefore, for the purpose of imparting water repellency to processed plant fiber products by utilizing the water repellency of the cured binder (binder),
When any or all of R4, R6 or R8 is an organic substituent, the type and the amount used as a binder are adjusted depending on the purpose, and are preferably determined after conducting preliminary experiments. good.

A catalyst is used to condense and harden (solidify) the binder, and a commonly used catalyst may be used as the catalyst. Examples of such a catalyst include an acid catalyst and a base catalyst. As the acid catalyst, specifically, for example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid,
Formic acid, acetic acid and the like can be exemplified. Specific examples of the base catalyst include ammonia, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, ethanolamine, diethanolamine, and triethanolamine.

If the binder is to be cured using an acid catalyst or a base catalyst, it is necessary to supply reaction water. Here, the alkoxysilane, which is the main component of the binder, easily gels when reaction water and a catalyst coexist, making long-term storage difficult. Therefore, if the solution of the binder is to be stored for a long period of time without causing gelation, it is preferable to add a hydrolyzable organometallic compound without using the above-mentioned catalyst. When a binder to which an organometallic compound is added is applied to, for example, a surface of paper or the like, it absorbs moisture (humidity) in paper and air and hydrolyzes itself without a catalyst such as acid or alkali. At the same time, it condenses with the alkoxysilane as the main component to form a network and cure. Therefore, when a hydrolyzable organometallic compound is used as a catalyst, there is no need to allow reaction water to coexist, and the solution can be stably stored in a solution state for a long period of time.

Specific examples of the organometallic compound usable for the above purpose include titanium, zircon, aluminum, and the like.
A material containing tin can be exemplified. More specifically, tetrapropoxy titanate, tetrabutoxy titanate,
Examples include tetrapropoxyzirconate, tetrabutoxyzirconate, tripropoxyaluminate, aluminum acetylacetonate, dibutyltin diacetate, dibutyltin dilaurate and the like.

A reaction solution comprising fine particles having an organic compound decomposing ability, alkoxysilane as a main component of a binder, a catalyst or an organometallic compound, and, if necessary, reaction water is applied to the surface of a processed plant fiber product. The fine particles can be bound to the processed vegetable fiber product only by application. The reaction solution may be sufficiently mixed with each component using a mixer, a paint shaker, or the like.

It is preferable to add an organic solvent to the solution in order to uniformly mix the components. As the organic solvent used for this purpose, alcohol can be exemplified. Specific examples of the alcohol include methanol, ethanol, propanol, isopropanol, butanol, pentanol, and hexanol. Incidentally, the organic solvent exemplified above,
In addition to the purpose of uniform mixing of each component, it may be added for the purpose of adjusting the viscosity of the reaction solution or the drying speed of the reaction solution.

The reaction solution contains fine particles capable of decomposing organic compounds such as titanium oxide and tourmaline.
These fine particles need to be particularly uniformly dispersed.
For this reason, adjusting the viscosity of the reaction solution is important. As described above, alcohol can be used to adjust the viscosity of the reaction solution. For the purpose of adjusting the viscosity, a substance having a high viscosity or a high boiling point can be used in addition to alcohol.
Specifically, for example, glycols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, dipropylene glycol, and polypropylene glycol, and methoxyethanol, propoxyethanol, butoxyethanol, methoxypropanol, ethoxypropanol, propoxypropanol, and butoxy Cellsolves such as propanol can be exemplified. Further, the viscosity can be adjusted by using a surfactant.

The above glycols and cellosolves are
It has a hydroxyl group in its molecule. Therefore, when the alkoxysilane, which is the main component of the binder, reacts and condenses with these hydroxyl groups to form a network and cures, such organic molecules are introduced into the siloxane bond network. The flexibility is further increased. To increase the viscosity of the reaction solution,
A so-called thickener may be added. Specific examples of the thickener include colloidal silica and diatomaceous earth.

When the above reaction solution is applied to the surface of a processed vegetable fiber such as paper or cloth, for example, alkoxysilane, which is the main component of the binder, is condensed and cured to form a coating film. At this time, fine particles having the ability to decompose organic compounds are taken into the network and bonded to the surface of the processed plant fiber product, but at the same time, the physical properties such as the water resistance and abrasion resistance of the processed plant fiber product are maintained without loss of flexibility. The characteristics are improved. This is presumed to be due to the following reasons.

Generally, when an alkoxysilane is hydrolyzed, it undergoes a reaction shown in the following reaction formulas (1) to (3),
A siloxane bond (-Si-O-Si- in the reaction formula) is generated. -In the siloxane bond thus formed
The bond energy of Si-O is 106 kcal / mol, while the CC bond energy, which is a typical bond of an organic compound, is 82.6 kcal / mol. Accordingly, a siloxane bond network in which alkoxysilane represented by the chemical formula (1), which is the main component of the binder (binder), and alkoxysilane represented by the chemical formula (2) are hydrolyzed, condensed, and cured, that is, Vitreous coatings are thermally much more stable bonds than organic compounds, and as a result, the formation of such a coating results in physical properties such as water and abrasion resistance of the processed plant fiber. Is improved.

[0045]

[Reaction formula 1]

[0046]

[Reaction formula 2]

[0047]

[Reaction formula 3]

When the reaction solution contains an organometallic compound such as tetrabutoxytitanium instead of a catalyst such as an acid or an alkali, as described above,
Although it has already been mentioned that the reaction similar to the above-mentioned reaction formulas (1) to (3) proceeds even if the reaction solution does not contain reaction water, the reaction occurring in this case is described in detail in the following reaction formula ( A siloxane bond is generated as in 4) and (5). By introducing the thus-formed -Ti-O bond into the siloxane bond network, physical properties such as heat resistance and abrasion resistance of the processed plant fiber product can be further improved as compared with the case of only the siloxane bond. The properties are improved. Thus, when an organometallic compound is used, in addition to the above, a binder (binder) is condensed,
This also contributes to the improvement of the physical properties of the coating film formed by curing and, in effect, to the improvement of the physical properties of the processed plant fiber product.

[0049]

[Reaction formula 4]

[0050]

[Reaction formula 5]

In order to apply the reaction solution to a processed plant fiber such as paper or cloth, a general method such as a so-called dipping method, a spray method, or a brush coating method may be used. Those skilled in the art can easily carry out these methods. After applying the reaction solution, just dry it.
Condensation and curing occur, but as a drying method, it is generally sufficient to leave the coating at room temperature for about 10 minutes and then dry it at 120 ° C. for about 10 minutes. However, this is only an example, the composition of the reaction solution, the amount of the applied reaction solution,
That is, the thickness of the film formed on the surface of the processed plant fiber product,
Since it can vary depending on the temperature, the properties of the surface of the processed vegetable fiber, and the like, preferably, appropriate drying conditions are determined by conducting preliminary experiments according to the conditions actually performed. Should.

Fine particles having an ability to decompose organic compounds such as titanium oxide and tourmaline contained in the reaction solution are applied to the surface of a processed vegetable fiber product together with a binder (binder) containing alkoxysilane as a main component. Then, at the stage where the solvent is dried and the binder is condensed and cured to be bonded to the surface of the processed plant fiber product, it is taken into the alkoxysilane network and is strongly fixed.

In the present invention, when the reaction solution is applied to the surface of a processed vegetable fiber such as paper or cloth, the binder becomes entangled with the fibrous material, and is cured in this state. The particles are firmly bound to the fine particles having the ability to decompose organic compounds. In addition, the binder (binder) that has not evaporated due to drying is maintained in a state of being absorbed between fibers by capillary action. FIG. 2 schematically shows this state, as shown in FIG. 2, in a state where the fine particles 1 are not covered with a binder, that is, in a state where the fine particle surfaces are exposed to the outside, the surface of the processed plant fiber product. The bonding portion 2 between the fine particles and the fibers is bonded via a binder (binder).

Accordingly, this allows the organic compound such as odor to come into direct contact with the surface of the fine particles, and the fine particles can exert their ability to decompose the organic compound without any problems. Since the bonding state is maintained via the binder, the fibers themselves are not decomposed by light or temperature conditions. According to the knowledge of the inventor of the present application, such a phenomenon can only be observed so far with a binding object having a fiber component such as paper or cloth. In addition, in FIG.
Are fine particles of titanium oxide (TiO ₂ ) or the like, 2 is a bonding portion between the fine particles and cellulose fiber, 3 is a fiber,
Fig. 1 schematically shows a portion where a binder component is absorbed in the fiber.

As described above, the binder absorbed between the fibers by the capillary action is:
Due to surface tension, it gathers at the contact point between fiber and fine particles (Fig. 2
reference). The binder gathered at the contact point then condenses and cures. In this way, a large number of networks are formed between the fibrous material and the fine particles, and the fine particles are
It will be very strongly bonded to the processed plant fiber product.

Generally, processed plant fiber products such as paper and cloth are
Is mainly composed of cellulose. Cellulo
The base has a hydroxyl group, and the hydroxyl group is used as a binder (biase).
And alkoxysilane, which is the main component of
As a result of this reaction, cellulose-silicon-fine particles are chemically
Strongly bind to. This bonding state is referred to as titanium oxide (Ti
O ₂) As an example, it binds with fibers such as cellulose.
It is estimated that the state shown in FIG.
(TiO₂) Is bonded through silicon,
As in the present invention, as a plant fiber processed product,
In particular, use paper or cloth that contains cellulose.
Then, the binder becomes fine particles through silicon
And the plant fiber product are chemically bonded and fine particles are
Form a network while embedding
Tightly bind. In other words, plant fiber processing containing cellulose
For products, it is more than simply taking particles into the network
Above, a stronger bond between the two by chemical bonding
It is.

Further, the binder gathers at the contact point between the fibrous material on the surface of the processed vegetable fiber and the fine particles having the ability to decompose organic compounds due to surface tension or capillary action. Degradation of the fibrous material is prevented. This is because the binder gathers at the contact point between the fibrous material and the fine particles and hardens between them, thereby preventing the fine particles and the fibrous material from coming into direct contact with each other, so to say, acts as a cushioning material. It is considered to be.

In order to maximize the effect of the buffering agent, the concentration of the binder (binder) for the fine particles, that is, the concentration of the alkoxysilane (the total amount of the main component and the subcomponent) is important. Since the concentration varies depending on the particle diameter of the fine particles used, the type and thickness of the fiber present on the surface of the processed plant fiber product, the thickness thereof, and the weaving method of the fiber, a preliminary experiment is preferably performed. It is better to determine the optimum concentration as needed. According to the findings of the present inventor, generally, when a binder is used in an amount of 10 to 100% by weight, particularly preferably 30 to 60% by weight, based on the weight of the fine particles having the ability to decompose organic compounds, the fiber It has been found that the self-destructive action of the compound can be prevented, and that a successful odorant decomposition efficiency can be achieved.

Needless to say, if it is out of this range, the present invention cannot be carried out. However, if a large amount of the binder (binder) is used, not only does not participate in the binding of the fine particles, waste increases, but also the binder ( binder)
May cover the surface of the fine particles and the activity of the fine particles may be reduced. Conversely, if the amount of the binder (binder) used is too small, not only the chemical bond between the fibrous material and the fine particles having the ability to decompose organic compounds, but also the network formed by condensation of the binder (binder) is formed. It becomes difficult to incorporate the fine particles into the processed vegetable fiber product, and the fine particles easily come into contact with the processed vegetable fiber product, and the fiber itself may be decomposed. No, you need to be careful.

[0060]

Industrial Applicability The present invention relates to a method of producing fine particles of titanium oxide and tourmaline, which are capable of decomposing organic compounds, using a binder (binder) mainly composed of alkoxysilane or a hydrolyzate thereof which is not decomposed into the fine particles. Since the fine particles are firmly bonded to the surface of the processed product, there is no fear that the binder is decomposed by the photocatalytic function of the fine particles and peeled off.

In particular, when the processed vegetable fiber product has a functional group capable of reacting with alkoxysilane, such as paper or cloth containing cellulose fiber as a main component, as described above, the binder is used. By controlling the usage of
There is no problem that the surface of the fine particles having the ability to decompose organic compounds is excessively covered with the binder, and as a result, the photocatalytic function is reduced. Further, in this case, the effect that the plant fiber processed product and the fine particles can be more firmly bonded by both the chemical bond and the mechanical bond of incorporation into the network, and the effect of the binding agent (binder) on the plant fiber processed product Since the product and the fine particles are prevented from coming into contact with each other, even when the titanium oxide fine particles are used, the effect that the processed plant fiber itself can be prevented from being decomposed by the photocatalytic function of the fine particles can also be achieved.

As described above, the present invention is characterized in that the fine particles having the ability to decompose organic compounds are bonded to the processed plant fiber product by using a binder containing an alkoxysilane as a main component. Are provided in a state of having an organic compound decomposing ability, and the state is stably maintained over a long period of time.

The alkoxysilane, which is the main component of the binder, forms a vitreous coating film on the surface of the processed plant fiber product by condensation and curing. Therefore, as described above, not only the fine particles having the ability to decompose organic compounds are bonded to the plant fiber processed product, but at the same time, the plant fiber processed product can be imparted with water resistance and abrasion resistance, as well as imparting heat resistance and the like. it can. As a result, the processed plant fiber product becomes glossy, and is not only valuable as an indoor interior, but also can withstand outdoor use exposed to wind and snow.

[0064]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail based on embodiments, but these embodiments are merely examples and do not limit the present invention.

Example 1 Methyltrimethoxysilane oligomer (average degree of polymerization: 3 to tetramer) (19.0 g), dibutyltin diacetate (0.8 g) and isopropyl alcohol (20 g) were sufficiently mixed to obtain fine particles having an ability to decompose an organic compound. 32 g of titanium oxide for photocatalyst (AMT-100, trade name, manufactured by Teika Co., Ltd., anatase type, average particle size: 6 nm), and further sufficiently mixed and dispersed with a homogenizer,
A reaction solution was prepared.

Next, on both sides of the A4 size cut Japanese paper,
The above reaction solution was applied using a brush. The Japanese paper coated with the reaction solution was dried at room temperature for 10 minutes, and further dried at 130 ° C. for 10 minutes. It should be noted that the weight of the titanium oxide-bonded Japanese paper manufactured in this manner increased by 19.0 g after drying as compared with the Japanese paper used as the material.

Example 2 Except for using 17 g of an oligomer of methyltrimethoxysilane (average degree of polymerization of 3 to tetramer) and 2 g of an oligomer of dimethyldimethoxysilane (average degree of polymerization of 4 to pentamer) as alkoxysilane Produced titanium oxide-bonded Japanese paper in the same manner as in Example 1. In addition, the weight of the titanium oxide-bonded Japanese paper manufactured in this example was increased by 17.3 g after drying as compared with the Japanese paper used as the material.

Example 3 The same procedure as in Example 2 was carried out except that 32 g of tourmaline (short tourmaline powder, average particle size: 3 μm) manufactured by Eco Academy was used instead of titanium oxide as the fine particles having the ability to decompose organic compounds. To produce tourmaline-bonded Japanese paper. In addition, the tourmaline-bonded Japanese paper manufactured in this example weighs 1 after drying compared to the Japanese paper used as the material.
It had increased by 4.7 g.

Example 4 The procedure of Example 2 was repeated except that 16 g of titanium oxide used in Example 1 and 16 g of tourmaline used in Example 2 were used as fine particles having the ability to decompose organic compounds, for a total of 32 g. Thus, titanium oxide and tourmaline-bound Japanese paper were produced. In addition, the weight of the titanium oxide and tourmaline-bonded Japanese paper manufactured in this example was increased by 18.7 g after drying as compared with the Japanese paper used as the material.

Example 5 The amount of the oligomer of methyltrimethoxysilane (average degree of polymerization from 3 to 4) was 9.5 g, and the amount of dibutyltin diacetate was 0.4 g.
In the same manner as in Example 1, titanium oxide-bonded Japanese paper was manufactured. The titanium oxide-bonded Japanese paper manufactured in this example is
Weight is 18.9 after drying compared to Japanese paper used as material
g.

Example 6 The amount of the oligomer of methyltrimethoxysilane (average polymerization degree 3 to tetramer) was changed to 4.8 g, and the amount of dibutyltin diacetate was changed to 0.2 g.
In the same manner as in Example 1, titanium oxide-bonded Japanese paper was manufactured. The titanium oxide-bonded Japanese paper manufactured in this example is
The weight after drying is 19.2 compared to the Japanese paper used as the material.
g.

Example 7 Titanium oxide-bonded Japanese paper was produced in the same manner as in Example 1, except that the amount of titanium oxide used was changed to 4 g. In addition, the weight of the titanium oxide-bonded Japanese paper manufactured in this example was increased by 17.3 g after drying as compared with the Japanese paper used as the material.

Example 8 As alkoxysilane, oligomer of tetramethoxysilane (commonly known as MS-51, average degree of polymerization of 3 to 4)
Except having used 19.0g, it carried out similarly to Example 1, and
Titanium oxide bonded Japanese paper was manufactured. In addition, the weight of the titanium oxide-bonded Japanese paper manufactured in this example was increased by 17.3 g after drying as compared with the Japanese paper used as the material.

Example 9 Test of Binding Property of Fine Particles to Paper A test of the binding property of fine particles to paper was performed as follows.

First, the surface of the fine particle-bonded Japanese paper having the ability to decompose organic compounds produced in Examples 1 to 8 was strongly rubbed five times with the finger of a hand wearing a glove, and the degree of peeling of the fine particles was measured. The binding to the paper was observed.

Table 1 shows the results. In the measurement results in the table, the double circle indicates that the fine particles did not peel off at all in the above test, the circle indicates that the fine particles were slightly but peeled off in the above test, and the square indicates that the fine particles were slightly peeled off in the above test. However, it indicates that the particles peeled off, and the crosses indicate that significant particles were peeled off in the above test.

As is apparent from Table 1, tetramethoxysilane, that is, a siloxane bond (-S
In the washi paper of Example 8 manufactured using only a binder (i.e., i-O-Si-) which forms a hard coating film and containing alkoxysilane as a main component, considerable fine particles were peeled off. However, in the case of Japanese paper manufactured using a binder (binder) containing an alkoxysilane represented by the chemical formula (1) as a main component, peeling of fine particles was slight. Above all, Japanese paper manufactured using two types of alkoxysilanes as a binder (Examples 2 to 4) and Japanese paper estimated to be manufactured using an appropriate amount of a binder (Binder) (Example 7) No peeling of the fine particles was observed.

[0078]

[Table 1]

Example 10 Light Resistance Test and Strong Elongation Test The Japanese paper produced in Examples 2 and 3 was subjected to a light resistance test according to the following procedure. For comparison, a light resistance test and a strong elongation test were also performed on Japanese paper (blank) used as a material.

Test method: JIS L08432 carbon arc light test Black panel temperature 63 ± 3 ° C Irradiation for 100 hours

The elongation test was performed on Japanese paper after the light test.
This was performed according to the following procedure.

Test method: JIS P8113 Paper and paperboard tensile property test Tensilon tensile tester, sample width 15 mm, gripping distance 1
00mm, Tensile speed 10mm / min

Table 2 shows the results. As is clear from Table 2, the light fastness of the fine particle-bonded Japanese paper manufactured in Examples 2 and 3 is improved because the coating film is formed on the surface of the Japanese paper by the condensation and curing of the binder. You can see that it is. Further, it can be seen that in the Japanese paper manufactured in Examples 2 and 3, the strong elongation resistance is remarkably improved.

[0084]

[Table 2]

Example 11 Formaldehyde Decomposition Ability Test Using the fine particle-bound Japanese paper produced in Examples 2, 3 and 7, a formaldehyde decomposition capability test, which has recently become a problem as a causative substance of sick house disease, was carried out. For comparison, a similar test was performed on Japanese paper (blank) used as a material.

In the test, first, Japanese paper cut into a square having a side of 10 cm was sealed in a 1 L Tedlar bag. This bag was filled with a formaldehyde gas adjusted to 24 ppm, and the time-dependent change in the gas concentration was measured by a detector tube method to evaluate formaldehyde decomposition ability.

Table 3 shows the results. As is clear from Table 3, it can be seen that all of the Japanese paper manufactured in the examples have formaldehyde resolution.

[0088]

[Table 3]

[Brief description of the drawings]

FIG. 1 is a diagram for explaining a state in which tetraalkoxysilane ((RO) ₄ Si) conventionally used in a sol-gel method is completely hydrolyzed.

FIG. 2 is a diagram illustrating a state in which fine particles are not covered with a binder (binder) by a binder (binder) absorbed between fibers by capillary action, and the fine particles are bound to the surface of a processed plant fiber product. FIG.

FIG. 3 shows an example of titanium oxide (TiO ₂ ).
It is the schematic diagram which showed typically the state which couple | bonds with fibers, such as cellulose.

[Explanation of symbols]

1 ... fine particles of titanium oxide (TiO ₂ ), etc. 2 ... bonded part between fine particles and cellulose fiber 3 ... fiber 4 ... binder component was absorbed in the fiber part

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B01J 35/06 D21H 19/38 D06M 11/77 19/62 13/513 21/14 Z D21H 19/38 D06M 101: 04 19/62 11/12 21/14 B01D 53/36 ZABG // D06M 101: 04 F-term (reference) 4D048 AA17 AA19 AB03 BA03X BA07X BA09X BA14X BA15X BA21X BA36X BB08 CD05 EA01 4G069 AA03 AA08 A02A02BA02B BA16A BA16B BA27C BA48A BC22A BC22B BC22C CA01 CA10 CA11 DA06 EA09 FA02 FB23 4L031 AA02 AB31 BA09 BA24 BA33 DA12 DA13 4L033 AA02 AB04 AC10 AC15 BA96 DA06 4L055 AG04 AG19 AG25 AG34 AG86 AH02 AH37 AGA20 GA

Claims (9)

[Claims] 1. A processed vegetable fiber product to which fine particles having an ability to decompose organic compounds are bonded, wherein the fine particles are bonded to the processed product by a binder (binder) containing alkoxysilane as a main component. The processed plant fiber product. 2. The processed vegetable fiber product according to claim 1, wherein the processed vegetable fiber product is a molded product obtained by processing and molding a vegetable fiber. . 3. The processed plant fiber product according to claim 2, wherein the processed plant fiber product is made of paper or cloth containing cellulose. 4. The processed vegetable fiber product as claimed in claim 1, wherein said fine particles having an organic compound decomposing ability are bonded with titanium oxide or tourmaline. 5. The processed vegetable fiber product according to claim 1, wherein titanium oxide and tourmaline are combined as the fine particles having the ability to decompose organic compounds. 6. The organic compound decomposing ability according to claim 1, wherein the binder is mainly composed of an alkoxysilane compound represented by the chemical formula (1). A processed vegetable fiber product that combines fine particles. (Equation 1) (In the formula 1, R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different, and each of R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different.
To 4 alkyl groups or phenyl groups). 7. The binder according to claim 1, wherein the binder is a main component which is an alkoxysilane compound represented by the chemical formula (1) and a compound represented by the chemical formula (2) added thereto. A processed plant fiber product to which the fine particles having an ability to decompose an organic compound according to claim 1 are bonded. (Equation 1) (Equation 2) (In the formula 1, R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different, and each of R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different.
And R ₅ , R ₆ , R ₇ , and R ₈ in Formula 2 may be the same or different, and may be hydrogen or an alkyl group having 1 to 4 carbon atoms or A phenyl group) 8. The plant to which the fine particles capable of decomposing organic compounds according to claim 1, 6 or 7, wherein the binder contains a hydrolyzable organometallic compound. Textile products. 9. The method according to claim 8, wherein said hydrolyzable organometallic compound is at least one organometallic compound selected from the group consisting of titanium, zircon, aluminum and tin. A processed vegetable fiber product combined with fine particles having the ability to decompose organic compounds.