JP2000342668A - Deodorant sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive sheet as small as it is mountable within various devices in a manufacturing process by supporting a deodorant consisting of at least one compound selected from a water-insoluble or hardly soluble tetravalent metal phosphate represented by either one of two specified formulae and a specified material represented by a specified formula on a low dust generating material. SOLUTION: In this deodorant sheet, a deodorant consisting of at least one compound selected from a water-soluble or hardly soluble tetravalent metal phosphate represented by formula I or II, and aluminum silicate, a hydrotalcite compound or baked matter thereof, hydrated zirconium oxide, zirconium oxide and polyamine supported amorphous silicon dioxide, which are represented by formula III, is supported on a low dust generating material. In formula I, M is a tetravalent metal, (a)-(d) each are a positive number satisfying the equation (a+4b=2c+3d), and (n) is 0 or an integer. In formula II, A is a monovalent metal, B is a divalent metal, M is a 4-valent metal, (a')-(e') and (n) each are 0 or a positive number. In formula III, (n) is an integer of n>=6, and (m) is an integer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorizing sheet capable of removing harmful gases that adversely affect the function of a semiconductor product from an atmosphere in a facility related to semiconductor manufacturing.

[0002]

2. Description of the Related Art Conventionally, in a semiconductor manufacturing plant, development,
Various chemicals such as acids, alkalis, and oxidizing agents are used in large quantities in manufacturing processes such as etching, polishing, and cleaning, while processes that are extremely sensitive to chemical contamination, such as chemically sensitized resists, are also mixed. . For this reason, in a so-called clean room of a semiconductor manufacturing plant, in addition to dust removal equipment for removing particulate matter in the air, it is essential to remove chemical contamination in the air, and a chemical filter device called a chemical filter device is provided. Is common.

[0003] As a chemical filter, one obtained by impregnating activated carbon with potassium permanganate is generally used. However, since the processing capacity per volume is lower than that of a dust removing device, the size of a clean room is increased. As the filter device itself has become extremely large and the cost of installation and operation has become enormous, alternative technologies have been required.

[0004] In order to solve such a problem, covering the entire semiconductor factory with clean air is inefficient, so it is stopped, and only the internal atmosphere of each manufacturing apparatus and the transporting apparatus connecting them is cleaned to purify the air. Methods that try to lower the cost of employment are becoming more common. The problem at this time is
This is a method of purifying the air inside each device. The dust filter can be relatively easily miniaturized and attached to each device, but the chemical filter device takes up a large volume, making it impossible to install it inside the device without changing its size. And the equipment itself becomes unnecessarily large,
In order to avoid interference with the chemical filter device that has protruded out of the device, the transport path between the devices becomes longer, which is not only inefficient, but also has a risk of adversely affecting the product yield.

[0005]

In the semiconductor manufacturing process, a chemical filter device has conventionally been used in order to prevent chemical contamination by a chemical substance from adversely affecting a product, but it is large and expensive. Was in question. Therefore, there has been a need for a method of removing chemical contamination which is small enough to be installed inside each device in the manufacturing process and is inexpensive.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a specific inorganic deodorant is supported on a low-dusting material to avoid the influence of harmful gases. We have completed a deodorant sheet that can be attached to an arbitrary location, such as near a desired location, and can capture and remove harmful gases.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. ○ Deodorant In the present invention, a substance having a function of trapping harmful gases is essentially the same as a deodorant that traps malodorous substances for general use. Called odorant. As the deodorant used for the purpose, at least one is selected from those listed below,
Depending on the type of the harmful gas to be targeted, a plurality or a large number of them may be used at the same time. All of these deodorants are compounds having extremely low toxicity to the human body. A water-insoluble or hardly soluble tetravalent metal phosphate represented by the following general formula [1], or aluminum silicate represented by the general formula [3]

[0008]

Embedded image _{H a M b O c (PO} 4) d · nH 2 O (1) [M is a tetravalent metal, a, b, c and d are the formula (a + 4
b = 2c + 3d) is a positive number (however, c may be 0), and n is 0 or a positive number. ]

[0009]

Embedded image Al ₂ O ₃ .nSiO ₂ .mH ₂ O [3]

Where n is an integer of n ≧ 6, and m
Represents an integer.

A water-insoluble or sparingly soluble tetravalent metal phosphate represented by the following general formula [2]:

[0012]

Embedded image _{H a 'A b' B c} 'M d' O e '(PO 4) f' ・ NH ₂ O [2]

[A is a monovalent metal, B is a divalent metal, M is a tetravalent metal, and a ', b', c ', e', and n are 0 or a positive number; b and c are not both 0, d 'and f' are positive numbers, and a ', b', c ', d',
e ′ and f ′ are given by the formula (a ′ + b ′ + 2c ′ + 4d ′ = 2e ′ + 3
f ′). ]

At least one selected from a hydrotalcite compound or a calcined product thereof, hydrated zirconium oxide, and zirconium oxide. A material in which a polyamine compound or the like is supported on amorphous silicon dioxide.

The water-insoluble or hardly soluble tetravalent metal phosphate represented by the general formula [1] or the general formula [3]
Aluminum silicate represented by is the most problematic in the semiconductor manufacturing process, ammonia, trimethylamine,
It exhibits an excellent capturing effect on basic gases such as amine compounds such as triethylamine and pyridine. Preferred specific examples of M in the above formula [1] include zirconium, titanium, tin, cerium, hafnium and the like, with zirconium and titanium being more preferred. The preferred coefficients a, b, c and d are the following numbers. a = 1, b = 1, c = 1, d = 1 a = 1, b = 2, c = 0, d = 3 a = 2, b = 1, c = 0, d = 2

The tetravalent metal phosphate represented by a = 1, b = 1, c = 1, and d = 1 is a compound which is easily obtained as amorphous fine particles having an average particle diameter of 1 μm or less. , B = 2,
The tetravalent metal phosphate represented by c = 0 and d = 3 is a NASICON-type crystalline compound or an amorphous compound, and a = 2, b
= 1, c = 0, d = 2, a tetravalent metal phosphate represented by
It is a crystalline compound or an amorphous compound having a layered structure, such as an α-type crystal which is a monohydrate, a β-type crystal which is an anhydrous salt, and a γ-type crystal which is a dihydrate. Among them, a particularly preferable one is a γ-type crystal having coefficients of a = 2, b = 1, c = 0, and d = 2 since the interlayer distance between the crystals is the largest and the deodorizing speed is high.

The aluminum silicate may be crystalline or amorphous, but is preferably amorphous because it has a high deodorizing effect. The specific surface area of the aluminum silicate of the present invention is 20~800m ² / g, more preferably 200~800m ² / g. If the specific surface area is too small, the deodorizing performance of the offensive odor gas becomes small, which is not preferable. The specific surface area is calculated by BET calculated from the amount of adsorbed nitrogen.
It can be easily measured by the method.

Preferred specific examples of the deodorants represented by the formulas [1] and [3] include the following compounds. _{HTiO (PO 4) HZrO (PO} 4) HZr 2 (PO 4) 3 · H 2 O HTi 2 (PO 4) 3 · H 2 O HSn 2 (PO 4) 3 · 3H 2 O H 2 Zr (PO 4) _{2 H 2 Ti (PO 4)} 2 · 2H 2 O H 2 Sn (PO 4) 2 · H 2 O Al 2 0 3 · 9SiO 2 · 9H 2 O

The water-insoluble or sparingly soluble tetravalent metal phosphate represented by the general formula [2] can be used to remove lower organic acid gas generated in washing, etching, resist stripping steps, etc. in the semiconductor manufacturing process. It exhibits excellent deodorizing properties against sulfur-containing gases such as hydrogen sulfide and methyl mercaptan. The above equation [2]
Specific examples of M in the above include zirconium, titanium, tin, cerium, hafnium, and the like, and zirconium and titanium are more preferable. Preferred specific examples of the monovalent or divalent metal include lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, copper, iron, zinc, nickel, manganese, and cobalt. Among these, sodium, potassium, copper, zinc and manganese are preferred. The preferable coefficients of a ′, b ′, c ′, d ′, e ′ and f ′ in the formula [2] are numbers satisfying the following formulas (provided that a ′, b ′ and c ′ are 0). And b ′ and c ′ are not both 0). a ′ + b ′ + 2c ′ = 1, d ′ = 1, e ′ = 1, f ′ = 1 a ′ + b ′ + 2c ′ = 1, d ′ = 2, e ′ = 0, f ′ = 3 a ′ + b ′ + 2c ′ = 2, d ′ = 1, e ′ = 0, f ′ = 2 The tetravalent metal phosphate represented by the formula [2] is a part of the hydrogen of the compound represented by the formula [1] or Compounds having a structure in which all are substituted with a monovalent or divalent metal are particularly preferable. The compounds having the formula (a ′ + b ′ + 2c ′ = 2, d ′ = 1, e ′ =
0, f ′ = 2) (where a, b and c are 0)
And both of b and c are not 0) is a crystalline compound having a γ-type layered structure.

The hydrotalcite compound is a compound having a hydrotalcite structure represented by the following general formula [4].
There is aluminum hydrotalcite.

[0021]

Embedded image _{^{M 1 (1-x) M}} 2 x (OH) 2 A n- (x / n) · mH 2 O [4]

(M ¹ is a divalent metal, M ² is a trivalent metal, x is a number greater than 0 and 0.5 or less,
An- is an n-valent anion such as a carbonate ion or a sulfate ion, and m is a positive number. The calcined product of hydrotalcite is a compound obtained by calcining a hydrotalcite compound at about 500 ° C. or higher and eliminating carbonate groups and hydroxyl groups. The hydrated zirconium oxide may be either crystalline or amorphous,
It is a compound having the same meaning as zirconium oxyhydroxide, zirconium hydroxide, hydrous zirconium oxide and zirconium oxide hydrate.

The zirconium oxide may be either crystalline or amorphous, but is preferably amorphous in order to exhibit high deodorizing properties. As the zirconium oxide in the present invention, a commercially available product may be used as it is, or an anhydride obtained by calcining the above hydrated zirconium oxide may be used. The preferred firing temperature for firing amorphous hydrated zirconium oxide to obtain amorphous zirconium oxide is 150 ° C to 350 ° C.

Hydrotalcite, calcined hydrotalcite, hydrated zirconium oxide, zirconium oxide and the like have a high effect of trapping acidic gases such as hydrofluoric acid and phenol generated in the semiconductor manufacturing process.

An amorphous silicon dioxide (hereinafter simply referred to as silicon dioxide) having a polyamine supported thereon has a high heat resistance and is generated from an interior paint, an adhesive or the like in a semiconductor manufacturing plant and adversely affects the semiconductor manufacturing process. It is highly effective in trapping aldehyde gas such as formaldehyde, which causes aldehyde gas. As its composition, first, as preferred silicon dioxide, the specific surface area is
50 to 900 m ² / g, average pore size of 0.1 to 10 nm
And the average particle size is 0.1 mm to 100 mm. A particularly preferred specific surface area is 100 to 800 m ² / g, and an average pore diameter is 1 to 8 nm.

If the specific surface area is too small, the contact area between the amine compound and the aldehyde gas decreases, and the gas adsorption amount is impaired. On the other hand, if the specific surface area is too large, the pore diameter becomes too small, and aldehyde gas cannot enter the pores under normal pressure. The specific surface area can be easily measured by the BET method calculated from the nitrogen adsorption amount. On the other hand, when the average pore diameter is too large, the specific surface area decreases, the amount of the polyamine compound supported decreases, and the gas adsorption performance of aldehydes decreases. If an attempt is made to make the specific surface area sufficiently large despite the fact that the average pore diameter is too large, the porosity of the porous body becomes too large, the mechanical strength becomes small, or the ability to support the polyamine compound becomes weak. However, there is a problem that the amine compound is released by a slight heat, which is not preferable.

The preferred water content of silicon dioxide in the present invention is at least 0.01% by weight (hereinafter simply referred to as%).
More preferably, it is 0.1 to 10%. When the water content is less than 0.01%, since the surface has few silanol groups, the supporting force for the amine compound in the present invention is small.

The polyamine compound constituting the deodorant of the present invention together with silicon dioxide has two primary amino groups in the molecule.
And a polyamine compound represented by the following formula [5] is preferable.

[0029]

Embedded image H ₂ N— (CH ₂ —CH ₂ —NH) _n —H [5] (n is an integer of 0 or more)

In order to simultaneously deodorize gases having different properties such as a basic gas, a sulfur-containing gas, an aldehyde gas, and a lower fatty acid gas, two or more of the above-mentioned deodorants can be used in combination. For example, a plurality of low-dusting materials loaded with various deodorants are compounded by bringing their ends or the center into contact with a line or surface and sharing them via a binder, or a plurality of deodorizing materials. The odorant can be carried on one low dusting material. When two or more deodorants are used in combination, there is no particular limitation on the combination ratio of each deodorant, and the mixing ratio may be appropriately adjusted depending on the type of gas to be deodorized.

The deodorant in the present invention is usually obtained in powder form, and preferably has an average particle size of 0.01 to 20 μm.
And more preferably 0.01 to 10 μm, and still more preferably 0.01 to 5 μm. The average particle size is 0.
If the average particle size is less than 01 μm, it is likely to be re-agglomerated and difficult to handle.
The deodorant particles may easily fall off from the low dust-producing material.

In the present invention, the deodorant is 200 to 300.
It is stable when heated at ℃ or exposed to ultraviolet light without any change in structure and composition, and no discoloration. Therefore, processing and storage when producing the deodorant sheet of the present invention,
Further, at the time of use, there are no restrictions such as temperature control and light shielding for preventing deterioration of the deodorant.

○ Supporting Material In the present invention, the material for supporting the deodorant is not particularly limited in terms of its material and the like, and metals, woods, resins, papers, fibers and the like, or composites thereof can be used. Considering the use in a clean room, etc., it is better that the dust emission from the material itself is low, while the contact area between the deodorant and the harmful gas should be as large as possible. There are paper, non-woven fabric, cloth, resin film, etc., and particularly preferable one is thin, flexible, and has a large surface area.
Nonwoven fabrics, papers, and the like, particularly those having a long fiber length and those subjected to a binder treatment to suppress dust generation, are particularly preferable.

More specifically, wood pulp, bast fiber,
There are reed pulp, bagasse pulp, straw pulp, bamboo pulp, polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, polystyrene, alumina fiber, carbon fiber, glass fiber, zirconia fiber, synthetic fiber composed of alumina / silica fiber, and the like.

In the case of natural pulp, it is preferable to apply a dust-proofing treatment with a dust-proof binder or the like because of its high dust-generating property. At this time, a deodorant can be simultaneously adhered and fixed to the fiber surface. When using synthetic fibers, in addition to the method of fixing the deodorant using a binder, deodorant powder is attached to the surface and a part of the fiber is melted, The adhesive force can be increased, or a deodorant can be previously kneaded into the fiber material. As the dustproof binder, an appropriate binder can be used from commercially available binders according to the material. Specific examples include SBR and N as water systems.
Rubber-based latex such as BR and polyurethane, resin-based latex such as polyacrylate, polyvinyl acetate and ethylene-vinyl acetate copolymer, etc.
R, NBR, alkyd resin, amino alkyd resin,
Examples thereof include polyvinyl acetate, urethane, and polyacrylate.

In addition, polyethylene, polypropylene, polyvinyl chloride, polystyrene, alkyd resin, polyamide resin, polyvinyl chloride, acrylic resin, vinyl chloride
A vinyl acetate copolymer resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, chlorinated polypropylene, styrene resin, epoxy resin, kneading a deodorant in a synthetic resin such as a polyurethane and a cellulose derivative, or in the same manner as described above They can be carried to form sheets, films, foams, molded products, and the like. In addition, by mixing a deodorant in a coating material, a coating film can be formed on the surface of an appropriate material, not limited to the above materials, and used.

The amount of the deodorant carried on these low dusting materials can be generally increased by increasing the amount of the deodorant, and the deodorant can be more strongly exerted and maintained for a longer period of time. Even if carried on the above, there is no significant difference in the effect of the deodorant, so the preferred amount of the deodorant carried is 0.1 to 100 parts by weight per 100 parts by weight when kneaded into the carried material.
Parts by weight, and 0.05 to 50 g / m2 when a deodorant is carried on the surface of the material such as by application.

The deodorizing sheet of the present invention can be used as an effective well at a place where it is desired to remove the influence of a harmful gas in a semiconductor manufacturing facility or the like. An adhesive is applied to the deodorizing sheet, and if necessary, the adhesive surface is protected with a release paper or the like to form a seal shape, but any general adhesive or release paper is used. The steps such as application of the adhesive, drying, and bonding of release paper can be performed by combining appropriate methods from general ones. Further, the pressure-sensitive adhesive is not essential in the present invention, and any common simple mounting method such as a commercially available double-sided tape or a single-sided pressure-sensitive adhesive tape, a magnet, a hook, and a button can be used for the deodorant sheet.

Hereinafter, the present invention will be described more specifically with reference to examples.

EXAMPLES (Examples 1 to 9 and Comparative Example 1) A specific deodorant shown in Table 1 below was added in an amount of 10 wt% based on the solid content of a polyacrylate aqueous binder. This was applied to a long-fiber polyester cloth so that the deodorant became 1.0 g / m 2, and dried at 150 ° C. to obtain a deodorant coated cloth. As a comparison, a coated cloth not carrying a deodorant was also prepared (Comparative Example 1). Then, an acrylic pressure-sensitive adhesive was applied to one surface of each, a pressure-sensitive adhesive layer having a thickness of 20 μm was formed, a pressure-sensitive adhesive sheet sticker was cut, and one piece cut into an A6 plate was subjected to a deodorizing test.

O Deodorizing Test Each sample obtained in Examples and Comparative Examples was evaluated for deodorizing properties against the five harmful gases shown in Table 2 as follows. That is, the sample was placed in a Tedlar bag (1 liter), sealed, and then gas was injected. After 24 hours from the completion of the gas injection, the gas concentration in the Tedlar bag was measured using a detector tube (manufactured by Gastech Co., Ltd.) or a gas chromatograph. It was measured by graphy (manufactured by Shimadzu Corporation). Table 2 shows the initial gas concentration when the gas was injected into the Tedlar bag. However, when the gas generation source was a liquid, the sample was allowed to stand for about 2 hours to completely gasify, and then the sample was brought into contact with the gas. The measurement method of the gas concentration was appropriately selected according to the type of gas, gas chromatography was used for the sulfur-based malodorous gas, and the detection tube was used for the other gases. In the case of a high concentration exceeding 100 ppm, gas chromatography was performed by appropriately diluting the concentration to a measurable concentration due to the limitation of the measuring instrument, and the measured value was converted to the original concentration according to the dilution ratio. The results of the deodorizing test obtained as described above are shown in Table 2 below (ND in the table indicates that the value is below the detection limit).

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

From the results of Examples 1 and 2 in Table 3 above, it can be seen that the deodorant sheet containing the deodorant made of zirconium phosphate has excellent deodorizing properties against basic gases such as ammonia. From the results of Examples 3 to 5 in Table 3 above, 2
A deodorant sheet containing a deodorant composed of a tetravalent metal phosphate containing a valent metal is particularly excellent in deodorizing properties against sulfur-containing gases such as hydrogen sulfide and methyl mercaptan, and is suitable for a basic gas such as ammonia. It can be seen that they also have excellent deodorizing properties. From the results of Examples 6 to 8 in Table 4 above, it can be seen that the deodorizing sheet containing the deodorant composed of hydrotalcite or its calcined product and hydrated zirconium oxide is suitable for aldehyde gas such as acetaldehyde and lower grade such as acetic acid. It turns out that the deodorizing property with respect to the fatty acid gas is excellent. Also,
Example 9 shows that the deodorant composed of polyamine-supported amorphous silicon dioxide has particularly excellent trapping performance for aldehyde.

○ Dust generation test Four A5 size test specimens of the fabric samples prepared in Example 1 and Comparative Example 1 were prepared, and two sheets were stuck together with the adhesive surface inside so that the influence of the adhesive was not exerted. To do. Then, two sets of cloths are rubbed once every two seconds in a glove box type clean bench under conditions where dust does not enter from the outside, and light scattering of 0.3 μm or less particles generated in the clean bench is performed. The cleanliness was measured by a particle counter (particle counter), and the total number of the particles in one cubic foot was expressed. In addition, the same dust generation test was performed by applying the same pressure-sensitive adhesive as the non-treated cloth which was not subjected to the binder treatment to the cloth used in the examples. The results are shown in Table 4.

[0046]

[Table 4]

The results in Table 4 show that the dust generated from the deodorizing sheet is very small and has a negligible effect on the cleanliness of the environment.

[0048]

The deodorant sheet of the present invention has an excellent trapping effect on various harmful gases even with small pieces, can be used without special equipment, and poses a problem in semiconductor manufacturing equipment. Dust generation is also kept low. Since it is possible to remove the harmful gas at a necessary place at a low cost and eliminate the influence of chemical contamination, it is extremely useful in a semiconductor manufacturing site for stabilizing the physical properties of the semiconductor and improving the yield.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C002 AA03 BB05 CC04 DD12 HH10 4C080 AA03 BB02 BB10 CC12 HH05 HH09 JJ06 KK08 LL10 MM01 MM02 MM03 MM06 NN24 QQ03

Claims (3)

[Claims] 1. A water-insoluble or hardly soluble tetravalent metal phosphate represented by the following general formula [1] or [2], an aluminum silicate represented by the general formula [3], a hydrotalcite compound or A deodorant comprising at least one compound selected from the calcined product, hydrated zirconium oxide, zirconium oxide, and polyamine-supported amorphous silicon dioxide on a low-dusting material. Odor sheet. ## STR1 ## _{H a M b O c (PO} 4) d · nH 2 O (1) [M is a tetravalent metal, a, b, c and d are the formula (a + 4
b = 2c + 3d) is a positive number (however, c may be 0), and n is 0 or a positive number. ] ## STR2 ## _{H a 'A b' B c} 'M d' O e '(PO 4) f' NH ₂ O [2] [A is a monovalent metal, B is a divalent metal, M is a tetravalent metal, and a ′, b ′, c ′, e ′ and n are 0 or a positive number Where b and c are not both 0 and d ′ and f ′
Is a positive number, and a ′, b ′, c ′, d ′, e ′, and f ′ satisfy the expression (a ′ + b ′ + 2c ′ + 4d ′ = 2e ′ + 3f ′). ] Embedded image _{Al 2 0 3 · nSiO 2 ·} mH 2 O (3) In the formula, n is an integer of n ≧ 6, m is an integer. 2. The deodorizing sheet according to claim 1, wherein the material having low dust generation is a fiber or paper which has been subjected to a dust prevention treatment with a dust prevention binder. 3. A deodorizable sheet according to claim 1 or 2, wherein one side of the deodorant sheet is coated with an adhesive.