WO2015159910A1 - Desiccant composition - Google Patents
Desiccant composition Download PDFInfo
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- WO2015159910A1 WO2015159910A1 PCT/JP2015/061556 JP2015061556W WO2015159910A1 WO 2015159910 A1 WO2015159910 A1 WO 2015159910A1 JP 2015061556 W JP2015061556 W JP 2015061556W WO 2015159910 A1 WO2015159910 A1 WO 2015159910A1
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- Prior art keywords
- desiccant
- magnesium chloride
- desiccant composition
- hydrogen sulfide
- water
- Prior art date
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/28—Selection of materials for use as drying agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
Definitions
- the present invention relates to a desiccant composition.
- this invention relates to the desiccant composition which contains as a main component magnesium chloride which can be used for preservation
- Patent Document 1 proposes a desiccant containing 100 parts by weight of anhydrous magnesium chloride, 30 to 50 parts by weight of magnesium oxide and 50 to 70 parts by weight of magnesium hydroxide.
- Patent Document 2 proposes a desiccant comprising 100 parts by weight of magnesium chloride, 25 to 300 parts by weight of magnesium oxide and 3 to 30 parts by weight of calcium hydroxide.
- Deliquescent salts such as calcium chloride and magnesium chloride liquefy and become deliquescent when they absorb moisture. Leakage of deliquescent liquid may cause problems such as product contamination.
- Patent Document 3 contains a deliquescent inorganic compound such as calcium chloride and phosphorus pentoxide and a hydrophilic polymer such as polyvinyl alcohol, sodium polyacrylate, starch, and sodium alginate. A hygroscopic composition is proposed.
- Patent Document 1 or Patent Document 2 describes that a composition containing magnesium chloride and magnesium oxide forms an oxychloride cement upon water absorption and solidifies, and does not generate deliquescent liquid.
- a desiccant formed by packaging a desiccant composition containing magnesium chloride as a main component is stored in a storage bag, and the mouth of the storage bag is closed with a rubber band or the like and closed.
- the desiccant stored near the mouth of the storage bag sucks moisture preferentially, and the moisture absorption capacity of the desiccant varies depending on the storage location.
- An object of the present invention is to provide a desiccant composition containing magnesium chloride as a main component, which can be used for storage or packaging transportation of precision instruments, electronic parts, automobile parts, etc. under the background art as described above. is there.
- anhydrous magnesium chloride is excellent in hygroscopic capacity at low humidity, specifically 22% or less.
- a desiccant composition containing anhydrous magnesium chloride and a hydrogen sulfide absorbent containing anhydrous magnesium chloride and a hydrogen sulfide absorbent.
- the hydrogen sulfide absorbent is at least one selected from the group consisting of a heavy metal-containing compound, a metal simple substance, an alkali metal hydroxide, an oxidizing agent, and activated carbon.
- the hydrogen sulfide absorbent is at least one selected from the group consisting of a copper compound, a silver compound, and a zinc compound.
- the desiccant composition according to [4] further containing an inorganic water absorbing agent or a trivalent metal salt.
- a low-humidity packaging and packaging method characterized by enclosing a low-humidity desiccant containing anhydrous magnesium chloride in a sealed space.
- a desiccant formed by packaging a desiccant composition containing magnesium chloride is stacked and stored in a non-breathable resin storage bag, and a lidding resin film is placed on the stored desiccant.
- a method for storing a desiccant comprising covering and then closing the mouth of the storage bag.
- the desiccant composition according to an embodiment of the present invention contains anhydrous magnesium chloride as a main component, but does not cause black discoloration of a copper product that is considered to be caused by hydrogen sulfide gas. Moreover, the desiccant composition according to another embodiment of the present invention does not leak deliquescence even when the amount of moisture absorption increases. Since the desiccant containing magnesium chloride has a higher moisture absorption per weight than the desiccant containing calcium chloride, the desiccant containing magnesium chloride should be smaller and lighter than the desiccant containing calcium chloride. Can do.
- the packaging and packaging method in which the desiccant containing anhydrous magnesium chloride is enclosed in the sealed space, long-term storage and transportation in an environment having a low humidity, specifically, a relative humidity of 22% or less are possible.
- the method for storing a desiccant according to the present invention even if the mouth of the storage bag is simply squeezed and closed with a rubber band or the like, the decrease in the hygroscopic capacity of the desiccant stored near the mouth of the bag is suppressed, and the storage place Does not cause variation in moisture absorption capacity.
- the desiccant composition according to the first embodiment of the present invention contains anhydrous magnesium chloride and a hydrogen sulfide absorbent.
- Anhydrous magnesium chloride is a substance known as a moisture absorbent or desiccant component.
- the anhydrous magnesium chloride used in the present invention is preferably flakes, powders, or a mixture of flakes and powders. From the viewpoint of workability, a mixture of a powder having a particle size of 1 mm or less and flakes having a particle size of 1 to 10 mm is preferably used.
- the weight ratio of powder to flake is preferably 1: 9 to 9: 1, more preferably 3: 7 to 7: 3.
- the hydrogen sulfide absorbent is not particularly limited as long as it absorbs hydrogen sulfide gas in a mixed state with anhydrous magnesium chloride.
- Hydrogen sulfide absorbents include those that chemically absorb hydrogen sulfide gas and those that physically absorb hydrogen sulfide gas.
- the hydrogen sulfide absorbent examples include an absorbent made of a simple metal such as metal powder; an absorbent made of a heavy metal-containing compound such as a copper compound, a silver compound, a zinc compound, and a mercury compound; Absorbents composed of strongly basic substances such as alkali metal hydroxides; Absorbents composed of oxidizing agents such as permanganate, chromic acid, chromate and organic peroxides; Absorbents composed of activated carbon; SH inhibitors An absorbent consisting of These can be used alone or in combination of two or more.
- the SH inhibitor is an inorganic compound or an organic compound that inhibits the action of the SH group of the protein and exhibits a bactericidal effect.
- the amount of the hydrogen sulfide absorbent contained in the desiccant composition according to the first embodiment is preferably 0.001 to 50 parts by mass, more preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of anhydrous magnesium chloride. Part. If the amount of the hydrogen sulfide absorbent is too small, the effect of preventing the black discoloration of the copper product by the hydrogen sulfide gas tends to decrease. When the amount of the hydrogen sulfide absorbent is too large, the moisture absorption amount per weight of the desiccant composition tends to decrease.
- the method for preparing the desiccant composition according to the first embodiment is not particularly limited.
- the desiccant composition according to the first embodiment can be obtained, for example, by mixing a hydrogen sulfide absorbent powder and an anhydrous magnesium chloride powder. Also, by dissolving the hydrogen sulfide absorbent in water or an organic solvent, impregnating the solution into an inorganic porous material or an organic porous material, drying as necessary, and mixing the impregnated product with anhydrous magnesium chloride Obtainable.
- the porous material include silica gel powder, zeolite powder, sepiolite powder, diatomaceous earth powder, kaolin powder, bentonite powder, activated carbon powder, and cellulose powder.
- the contact area between the hydrogen sulfide absorbent and the hydrogen sulfide gas is greatly increased compared to the case where the hydrogen sulfide absorbent is added as a powder. Even if the addition amount of the agent is significantly smaller than when added as a powder, a sufficient effect can be exhibited.
- the amount of water used in the impregnation of the hydrogen sulfide absorbent into the porous body is preferably 3 parts by mass or less, more preferably 1 part by mass or less with respect to 100 parts by mass of anhydrous magnesium chloride.
- the impregnated product and anhydrous magnesium chloride are mixed with each other by using a very small amount of water with respect to the water absorption amount of anhydrous magnesium chloride, the water is absorbed by anhydrous magnesium chloride and becomes dry in a short time. Does not affect the performance.
- the hydrogen sulfide absorbent is an acidic substance, hydrogen chloride gas is generated, so it is preferable to add a basic substance.
- a basic substance a substance whose pH of a 1% aqueous solution is 9.0 or more can be used.
- Specific examples of basic substances include oxides and hydroxides of alkaline earth metals, alkali metal salts of weakly acidic substances, preferably magnesium oxide, magnesium hydroxide, calcium hydroxide and the like. Can do.
- the addition method of a basic substance is not specifically limited.
- a basic substance and a hydrogen sulfide absorbent may be mixed uniformly, and the mixture may be added to anhydrous magnesium chloride and mixed.
- the basic substance, the hydrogen sulfide absorbent and other additives may be added separately. It may be added to anhydrous magnesium chloride and mixed.
- the desiccant composition according to the second embodiment of the present invention contains magnesium chloride and carboxymethylcellulose sodium salt and / or polyacrylamide.
- Magnesium chloride is a substance known as a moisture absorbent or desiccant component. Magnesium chloride has an anhydride and hexahydrate at room temperature. In the present invention, anhydrous magnesium chloride is preferably used.
- the magnesium chloride used in the present invention is preferably flakes, powders or granules. In the second embodiment, magnesium chloride can be used singly or in combination of two or more kinds of flakes, powders, or granules.
- the water-soluble polymer is known as a substance that suppresses leakage of calcium chloride deliquescent solution.
- carboxymethyl cellulose sodium salt and / or polyacrylamide which is a kind of water-soluble polymer, is contained.
- carboxymethyl cellulose sodium salt and / or polyacrylamide is contained, the liquid produced by deliquescence of magnesium chloride can be solidified into a gel and the leakage of the deliquescence liquid can be reliably prevented.
- Polyvinyl alcohol and sodium polyacrylate proposed in Patent Document 3 and others have a weak effect of solidifying the deliquescent solution of magnesium chloride in a gel form, and therefore it is not possible to sufficiently suppress leakage of the deliquescent solution.
- the amount of carboxymethylcellulose sodium salt and / or polyacrylamide contained in the desiccant composition according to the second embodiment is preferably 10 to 80 parts by mass, more preferably 20 to 70 parts by mass with respect to 100 parts by mass of magnesium chloride. Part.
- the amount of carboxymethylcellulose sodium salt and / or polyacrylamide is too small, the effect of preventing the leakage of deliquescence tends to decrease.
- the amount of carboxymethylcellulose sodium salt and / or polyacrylamide is too large, the moisture absorption per weight of the desiccant composition tends to decrease.
- the desiccant composition according to the second embodiment of the present invention preferably further contains an inorganic water absorbing agent or a trivalent metal salt. Addition of an inorganic water-absorbing agent or a trivalent metal salt increases the hardness of the gel composed of sodium carboxymethylcellulose and / or polyacrylamide, and increases the effect of preventing leakage of the deliquescent solution.
- the inorganic water-absorbing agent used in the present invention examples include silica gel powder, sepiolite powder, apatal gite powder, zeolite powder, and diatomaceous earth powder. Of these, sepiolite powder and apatalite powder are preferred.
- the trivalent metal salt used in the present invention is preferably a water-soluble aluminum salt such as aluminum sulfate or alum; a water-soluble iron (III) salt such as ferric sulfate or ferric chloride.
- the amount of the inorganic water-absorbing agent or trivalent metal salt that can be included in the desiccant composition according to the second embodiment is not particularly limited.
- the amount of the inorganic water-absorbing agent is preferably 1 to 30 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of magnesium chloride.
- the amount of the trivalent metal salt is preferably 0.0001 to 0.03 mol, more preferably 0.001 to 0.01 mol, relative to 100 g of magnesium chloride.
- the desiccant according to the present invention is obtained by packaging the desiccant composition with a packaging material having at least one surface made of a breathable water-impermeable film.
- the packaging material made of a breathable water-impermeable film is not particularly limited as long as it allows water vapor to pass through but does not allow liquid to pass through. Since the liquid produced by deliquescence of magnesium chloride promotes rust generation of metal products, it is preferable that the packaging material does not leak the liquid.
- An example of such a packaging material is a microporous film.
- the film constituting the packaging material is preferably a microporous film made of polyolefin such as polyethylene or polypropylene.
- the moisture permeability of the film is preferably 1000 to 20000 g ⁇ m ⁇ 2 24 Hr ⁇ 1 , more preferably 3000 to 10000 g ⁇ m ⁇ 2 24 Hr ⁇ 1 at a temperature of 40 ° C. and a relative humidity of 90%.
- the moisture permeability is measured by a method according to JIS-Z-0208.
- the film constituting the packaging material various commercially available microporous films can be used. Specifically, there is a film in which fine calcium carbonate powder is kneaded into polyethylene or polypropylene, formed into a film, and then stretched to form fine pores in the film. Furthermore, from the viewpoint of improving the strength of the packaging material, it is preferable to use a composite film in which a nonwoven fabric is bonded to one side or both sides of the film. Further, a hydrogen sulfide gas adsorption film (manufactured by Kyodo Printing Co., Ltd.) can be used as a part of the packaging material.
- a hydrogen sulfide gas adsorption film manufactured by Kyodo Printing Co., Ltd.
- the desiccant according to the present invention is stored so as not to be deteriorated by unnecessary moisture absorption before it is used for drying the object.
- the storage method is not particularly limited, in the present invention, the desiccant formed by packaging the desiccant composition containing magnesium chloride is stacked and stored in a non-breathable resin storage bag. It is preferable to store by a method including covering the desiccant with a lid resin film and then closing the mouth of the storage bag.
- the non-breathable resin storage bag and the lid resin film are not particularly limited as long as water vapor is not substantially allowed to pass therethrough.
- a polyethylene film, a multilayer resin film, a resin film laminated with an aluminum film, a resin film laminated with a silicon nitride film, and the like can be mentioned.
- the mouth of the bag for storage may be closed by heat sealing, etc., but in consideration of frequently opening and closing the bag when using a desiccant, it may be closed by squeezing the mouth of the bag with a rubber band, A zipper may be attached to the bag mouth and closed with it. Since the lidding resin film diffuses water vapor entering from a slight gap in the bag mouth throughout the bag, it is possible to eliminate variations in the moisture absorption capacity of the stored desiccant.
- the resin film for the lid covers up to the middle stage of the stacked desiccant.
- the volume of a plurality of stacked desiccant is large, it is possible to take measures such as providing an appropriate pinhole in the lid resin film in order to avoid concentration of moisture in the desiccant below the middle stage. .
- Reference example (measurement of hydrogen sulfide gas) 10 g of anhydrous magnesium chloride powder was put into a 100 ml beaker.
- the beaker was placed in a polyethylene film bag having a width of 250 mm, a length of 500 mm, and a thickness of 0.08 mm. 2 g of water was poured into the beaker.
- the bag mouth was squeezed with a rubber band to close the bag. Left for 5 minutes.
- the hydrogen sulfide gas concentration inside was measured with a hydrogen sulfide gas detector tube.
- the hydrogen sulfide gas concentration was 1.2 ppm.
- After measuring the hydrogen sulfide gas concentration the amount of air in the bag was measured. The amount of air was 3500 ml.
- Comparative Example 1 [Copper plate discoloration test] A copper plate of 50 mm ⁇ 50 mm ⁇ thickness 1 mm washed with methanol and dried was prepared. A plastic frame having a length of 340 mm, a width of 270 mm, and a height of 180 mm and having a bottom plate was prepared. The copper plate was vertically installed on the bottom plate at a position 20 mm inward from the short side of the bottom plate. Anhydrous calcium chloride granules (drying agent) 10 g was put in a petri dish having a diameter of 60 mm. The petri dish was placed on the bottom plate at a position 20 mm inward from the short side opposite to the copper plate placement position.
- the whole was stored in a polyethylene film bag (500 mm ⁇ 750 mm) having a thickness of 100 ⁇ m, the bag was fixed with an adhesive tape so as to follow the shape of the frame, and the mouth of the bag was closed with a rubber band. It was put in a constant temperature and humidity chamber.
- the temperature and humidity in the constant temperature and humidity chamber were set as follows in a 24-hour cycle. (1) Changed to 40 ° C and 90% relative humidity over 1 hour. (2) Hold for 11 hours at a temperature of 40 ° C. and a relative humidity of 90%. (3) Change to a temperature of 20 ° C and a relative humidity of 90% over 1 hour. (4) Hold at a temperature of 20 ° C and a relative humidity of 90% for 11 hours.
- Comparative Examples 2-3 A copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that anhydrous calcium chloride granules were changed to anhydrous magnesium chloride powder and anhydrous magnesium chloride flakes. The results are shown in Table 1.
- Comparative Example 4 10 g of anhydrous magnesium chloride powder and 10 g of magnesium oxide were mixed to obtain a powdery desiccant composition.
- a copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that 10 g of anhydrous calcium chloride granules were changed to the desiccant composition. The results are shown in Table 1.
- Comparative Examples 5-6 and Examples 1-12 A powdery desiccant composition was obtained in the same manner as in Comparative Example 4 except that 10 g of magnesium oxide was changed to the amount of compound powder shown in Tables 1 and 2, and a copper plate discoloration test was performed. The results are shown in Tables 1 and 2.
- the desiccant compositions according to the present invention contain anhydrous magnesium chloride as a main component, but the copper products considered to be caused by hydrogen sulfide gas. Does not cause black discoloration.
- Example 13 An aqueous solution was obtained by dissolving 1 part by mass of anhydrous cupric chloride in 9 parts by mass of water. 5 parts by mass of the aqueous solution was impregnated into 5 parts by mass of silica gel powder to obtain a powder.
- the powdery desiccant composition having the composition shown in Table 3 was obtained by mixing 0.2 g of the powder and 10 g of anhydrous magnesium chloride powder.
- a copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that anhydrous calcium chloride granules were changed to the desiccant composition. The results are shown in Table 3.
- Examples 14-20 A powdery desiccant composition was obtained in the same manner as in Example 13 except that the type and amount of the hydrogen sulfide absorbent were changed so as to obtain the composition shown in Table 3, and a copper plate discoloration test was conducted. The results are shown in Table 3.
- Examples 21-26 A powdery desiccant composition was obtained in the same manner as in Example 13 except that the silica gel powder was changed to the porous body shown in Table 4, and a copper plate discoloration test was conducted. The results are shown in Table 4.
- Example 27 An aqueous solution was obtained by dissolving 1 part by mass of anhydrous cupric chloride in 9 parts by mass of water. 5 parts by mass of the aqueous solution was added to and mixed with 5 parts by mass of silica gel powder, and then heated and dried to obtain a powder. A powdery desiccant composition was obtained by mixing 0.11 g of the powder and 10 g of anhydrous magnesium chloride powder. A copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that anhydrous calcium chloride granules were changed to the desiccant composition. The results are shown in Table 5.
- Example 28 1 part by mass of anhydrous cupric chloride was dissolved in 19 parts by mass of glycerin to obtain a solution. 10 parts by mass of the solution was added to and mixed with 10 parts by mass of silica gel powder to obtain a powder. 0.4 g of the powder and 10 g of anhydrous magnesium chloride powder were mixed to obtain a powdery desiccant composition. A copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that anhydrous calcium chloride granules were changed to the desiccant composition. The results are shown in Table 5.
- Example 29 An aqueous solution was obtained by dissolving 1 part by mass of anhydrous cupric chloride in 9 parts by mass of water. 5 parts by mass of the aqueous solution was added to and mixed with 5 parts by mass of silica gel powder to obtain a powder. 0.2 g of the powder, 0.5 g of magnesium hydroxide powder, and 10 g of anhydrous magnesium chloride powder were mixed to obtain a powdery desiccant composition. A copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that anhydrous calcium chloride granules were changed to the desiccant composition. The results are shown in Table 5.
- Example 30 An aqueous solution was obtained by dissolving 1 part by mass of anhydrous cupric chloride in 2 parts by mass of water. 3 parts by mass of the aqueous solution was added to and mixed with 3 parts by mass of silica gel powder to obtain a powder. 0.06 g of the powder, 0.5 g of magnesium hydroxide powder and 10 g of anhydrous magnesium chloride powder were mixed to obtain a powdery desiccant composition. The test was performed in the same manner as the copper plate discoloration test performed in Comparative Example 1 except that the temperature and humidity in the thermo-hygrostat were changed as follows. The results are shown in Table 6. (1) Changed to 50 ° C and 90% relative humidity over 1 hour. (2) Hold for 11 hours at a temperature of 50 ° C.
- Examples 31-32 A powdery desiccant composition was obtained in the same manner as in Example 30 except that the types and amounts of the hydrogen sulfide absorbent and the basic substance were changed so that the composition shown in Table 6 was obtained. A copper plate discoloration test was conducted. The results are shown in Table 6.
- Examples 33-34 An anhydrous magnesium chloride powder, a hydrogen sulfide absorbent, and a basic substance were mixed so as to have the composition shown in Table 6 to obtain a powdery desiccant composition, and a copper plate discoloration test was performed in the same manner as in Example 30. The results are shown in Table 6.
- the desiccant composition of the present invention containing both the hydrogen sulfide absorbent and the basic substance under the severe conditions in which moisture absorption progresses in a short period of time and high concentration hydrogen sulfide gas is easily generated. Does not cause discoloration.
- Example 35 27 g of anhydrous magnesium chloride and 8 g of carboxymethylcellulose sodium salt were mixed to obtain a powdery desiccant composition.
- the desiccant composition was put into a bag made of a breathable water-impermeable film of 115 mm ⁇ 113 mm. The bag mouth was heat sealed to obtain a desiccant. The weight of the desiccant was measured.
- a plastic frame having a bottom plate of 340 mm ⁇ 270 mm ⁇ height 180 mm was prepared. The desiccant was placed on the bottom plate in the frame.
- a 0.9 mm thick filter paper box (inner dimensions: 345 mm ⁇ 275 mm ⁇ height 185 mm) was placed on the frame.
- the weight of the desiccant was measured at the elapse of 24 hours, 48 hours, 120 hours, and 240 hours from the start of standing, and the water absorption [g / g] per weight of the desiccant was calculated.
- Examples 36 to 46 and Comparative Examples 7 to 13 A desiccant composition was obtained in the same manner as in Example 35 except that the compositions shown in Tables 7 and 8 were changed, and the composition was evaluated. The results are shown in Tables 7 and 8.
- the desiccant composition of the present invention maintains the gel state even when it absorbs water, the deliquescent liquid does not leak out.
- a desiccant composition using an inorganic water absorbing agent or a trivalent metal salt has a strong gel and does not leak from the film surface even if the amount of water absorption increases.
- anhydrous magnesium chloride has more water absorption per weight or water absorption per mole than anhydrous calcium chloride, and is excellent in moisture absorption capacity in a low humidity environment.
- Relative humidity must be kept at 50-60% or less to prevent rust of machine parts that use desiccant containing calcium chloride.
- the moisture absorption capacity in this humidity range is anhydrous calcium chloride and anhydrous magnesium chloride. There is no big difference. However, it is required to maintain a lower humidity in precision machines and electronic parts that generate rust even with a slight humidity.
- a desiccant containing anhydrous magnesium chloride By enclosing a desiccant containing anhydrous magnesium chloride in the sealed space, it becomes possible to package and keep it at low humidity for a long time, and it is effective for storage and transportation of precision machines and electronic parts that are extremely sensitive to moisture.
- Various known methods can be used for forming the sealed space, such as sealing and packaging with a resin film, and storing in a sealed container made of resin or metal.
- the mouth of the storage bag was twisted and closed with a folded rubber band, and left in a constant temperature and humidity chamber at a temperature of 25 ° C. and a relative humidity of 90% for 17 weeks.
- the rubber band was removed, the desiccant was taken out from the storage bag, and the weight was measured.
- Table 10 shows the relationship between the storage position of the desiccant and the moisture absorption rate.
- Comparative Example B Fill a bag (packaging material) made of a breathable and water-impermeable film of 115 mm ⁇ 113 mm with a magnesium chloride-based desiccant (24 g of a mixture of anhydrous magnesium chloride, sodium carboxymethylcellulose, and an inorganic water-absorbing agent (sepiolite)). The mouth was heat sealed to obtain a desiccant. Twelve desiccants were vertically stacked and stored in a polyethylene film storage bag having a width of 230 mm, a length of 550 mm, and a thickness of 0.08 mm.
- a magnesium chloride-based desiccant 24 g of a mixture of anhydrous magnesium chloride, sodium carboxymethylcellulose, and an inorganic water-absorbing agent (sepiolite)
- the mouth of the storage bag was twisted and closed with a folded rubber band, and left in a constant temperature and humidity chamber at a temperature of 25 ° C. and a relative humidity of 90% for 17 weeks.
- the rubber band was removed, the desiccant was taken out from the storage bag, the weight was measured, and the moisture absorption rate for each storage position [number of steps] was calculated.
- Table 10 shows the relationship between the storage position of the desiccant and the moisture absorption rate.
- Example C A magnesium chloride desiccant was obtained by the same composition and method as Comparative Example B. Twelve desiccants were vertically stacked and stored in a polyethylene film storage bag having a width of 230 mm, a length of 550 mm, and a thickness of 0.08 mm. The polyethylene film of 180 mm ⁇ 180 mm ⁇ thickness 0.08 mm was placed on the stacked desiccant, and the end of the polyethylene film was sandwiched between the bag and the desiccant. The edge of the polyethylene film reached around the 5th stage of the accumulated desiccant. The mouth of the storage bag was twisted and closed with a folded rubber band, and left in a constant temperature and humidity chamber at a temperature of 25 ° C.
- the magnesium chloride-based desiccant stored by the method of Comparative Example B has a larger variation in water absorption depending on the storage position than the calcium chloride-based desiccant stored by the method of Comparative Example A.
- the magnesium chloride desiccant stored by the method of Example C suppresses the decrease in the hygroscopic capacity of the desiccant stored near the mouth of the bag, and the variation in the hygroscopic capacity depending on the storage location is the method of Comparative Example A Reduced to the same level as the calcium chloride desiccant stored in
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Abstract
Description
また塩化マグネシウムと酸化マグネシウムを含有する組成物は吸水時にオキシクロライドセメントを形成して固化し、潮解液を発生しないことが、特許文献1または特許文献2に記載されている。 Deliquescent salts such as calcium chloride and magnesium chloride liquefy and become deliquescent when they absorb moisture. Leakage of deliquescent liquid may cause problems such as product contamination. As a technique for preventing leakage of deliquescent liquid, Patent Document 3 contains a deliquescent inorganic compound such as calcium chloride and phosphorus pentoxide and a hydrophilic polymer such as polyvinyl alcohol, sodium polyacrylate, starch, and sodium alginate. A hygroscopic composition is proposed.
Patent Document 1 or Patent Document 2 describes that a composition containing magnesium chloride and magnesium oxide forms an oxychloride cement upon water absorption and solidifies, and does not generate deliquescent liquid.
本発明は、これらの知見に基づいて完成するに至ったものである。 As a result of intensive studies to solve the above problems, it was found that (1) hydrogen sulfide gas was generated from a desiccant containing anhydrous magnesium chloride as a main component, and that the hydrogen sulfide gas caused black discoloration of the copper product. This phenomenon has not occurred in desiccants containing calcium chloride as a main component. And it discovered that the black discoloration of copper products could be suppressed by adding a hydrogen sulfide absorber to the desiccant which contains anhydrous magnesium chloride as a main component. (2) It has been found that a desiccant containing magnesium chloride as a main component can effectively contain the deliquescent solution by using sodium carboxymethyl cellulose and / or polyacrylamide. (3) It has been found that anhydrous magnesium chloride is excellent in hygroscopic capacity at low humidity, specifically 22% or less. (4) In the desiccant formed by packaging a desiccant composition containing magnesium chloride as a main component, when a film is placed on a plurality of desiccants stored in a storage bag and the mouth of the storage bag is closed It has been found that the desiccant can be stored for a long time without causing variations in the hygroscopic ability.
The present invention has been completed based on these findings.
〔1〕無水塩化マグネシウムと硫化水素吸収剤とを含有する乾燥剤組成物。
〔2〕硫化水素吸収剤が、重金属含有化合物、金属単体、アルカリ金属水酸化物、酸化剤、および活性炭からなる群より選ばれる少なくとも一つである、〔1〕に記載の乾燥剤組成物。
〔3〕硫化水素吸収剤が、銅化合物、銀化合物、および亜鉛化合物からなる群より選ばれる少なくとも一つである、〔1〕に記載の乾燥剤組成物。 That is, the present invention includes the following forms.
[1] A desiccant composition containing anhydrous magnesium chloride and a hydrogen sulfide absorbent.
[2] The desiccant composition according to [1], wherein the hydrogen sulfide absorbent is at least one selected from the group consisting of a heavy metal-containing compound, a metal simple substance, an alkali metal hydroxide, an oxidizing agent, and activated carbon.
[3] The desiccant composition according to [1], wherein the hydrogen sulfide absorbent is at least one selected from the group consisting of a copper compound, a silver compound, and a zinc compound.
〔5〕無機吸水剤または3価の金属塩をさらに含有する〔4〕に記載の乾燥剤組成物。
〔6〕セピオライトまたはアパタルジャイトをさらに含有する〔4〕に記載の乾燥剤組成物。
〔7〕水溶性アルミニウム塩および/または水溶性鉄(III)塩をさらに含有する〔4〕に記載の乾燥剤組成物。 [4] A desiccant composition containing magnesium chloride and carboxymethylcellulose sodium salt and / or polyacrylamide.
[5] The desiccant composition according to [4], further containing an inorganic water absorbing agent or a trivalent metal salt.
[6] The desiccant composition according to [4], further containing sepiolite or apatal gite.
[7] The desiccant composition according to [4], further comprising a water-soluble aluminum salt and / or a water-soluble iron (III) salt.
〔10〕塩化マグネシウムを含有する乾燥剤組成物を包装してなる乾燥剤を非透湿性樹脂製保管用袋の中に積み重ねて収納し、 収納された乾燥剤の上に蓋い用樹脂フィルムを被せ、 次いで前記保管用袋の口を閉じることを含む乾燥剤の保管方法。 [9] A low-humidity packaging and packaging method characterized by enclosing a low-humidity desiccant containing anhydrous magnesium chloride in a sealed space.
[10] A desiccant formed by packaging a desiccant composition containing magnesium chloride is stacked and stored in a non-breathable resin storage bag, and a lidding resin film is placed on the stored desiccant. A method for storing a desiccant comprising covering and then closing the mouth of the storage bag.
また、本発明の別の一実施形態に係る乾燥剤組成物は、吸湿量が多くなっても、潮解液の漏出が無い。
塩化マグネシウムを含有する乾燥剤は、塩化カルシウムを含有する乾燥剤に比べて重量当たりの吸湿量が多いので、塩化マグネシウムを含有する乾燥剤は塩化カルシウムを含有する乾燥剤よりも小型軽量化することができる。
密封空間内に無水塩化マグネシウムを含有する乾燥剤を同封する梱包包装方法によれば、低湿度、具体的に相対湿度22%以下、の環境下での長期保管、輸送が可能になる。
本発明に係る乾燥剤の保管方法によれば、保管用袋の口をゴムバンドなどで絞って閉じるだけでも、袋の口付近に収納された乾燥剤の吸湿能の低下が抑制され、収納場所による吸湿能のばらつきを生じさせない。 The desiccant composition according to an embodiment of the present invention contains anhydrous magnesium chloride as a main component, but does not cause black discoloration of a copper product that is considered to be caused by hydrogen sulfide gas.
Moreover, the desiccant composition according to another embodiment of the present invention does not leak deliquescence even when the amount of moisture absorption increases.
Since the desiccant containing magnesium chloride has a higher moisture absorption per weight than the desiccant containing calcium chloride, the desiccant containing magnesium chloride should be smaller and lighter than the desiccant containing calcium chloride. Can do.
According to the packaging and packaging method in which the desiccant containing anhydrous magnesium chloride is enclosed in the sealed space, long-term storage and transportation in an environment having a low humidity, specifically, a relative humidity of 22% or less are possible.
According to the method for storing a desiccant according to the present invention, even if the mouth of the storage bag is simply squeezed and closed with a rubber band or the like, the decrease in the hygroscopic capacity of the desiccant stored near the mouth of the bag is suppressed, and the storage place Does not cause variation in moisture absorption capacity.
塩基性物質の添加方法は特に限定されない。例えば、塩基性物質と硫化水素吸収剤とを均一混合して、該混合物を無水塩化マグネシウムに添加し、混合してもよいし、塩基性物質、硫化水素吸収剤およびその他の添加剤を別々に無水塩化マグネシウムに添加し、混合してもよい。 When the hydrogen sulfide absorbent is an acidic substance, hydrogen chloride gas is generated, so it is preferable to add a basic substance. As the basic substance, a substance whose pH of a 1% aqueous solution is 9.0 or more can be used. Specific examples of basic substances include oxides and hydroxides of alkaline earth metals, alkali metal salts of weakly acidic substances, preferably magnesium oxide, magnesium hydroxide, calcium hydroxide and the like. Can do.
The addition method of a basic substance is not specifically limited. For example, a basic substance and a hydrogen sulfide absorbent may be mixed uniformly, and the mixture may be added to anhydrous magnesium chloride and mixed. Alternatively, the basic substance, the hydrogen sulfide absorbent and other additives may be added separately. It may be added to anhydrous magnesium chloride and mixed.
本発明に用いられる3価の金属塩としては、硫酸アルミニウム、ミョウバンなどの水溶性アルミニウム塩;硫酸第二鉄、塩化第二鉄などの水溶性鉄(III)塩が好ましい。 Examples of the inorganic water-absorbing agent used in the present invention include silica gel powder, sepiolite powder, apatal gite powder, zeolite powder, and diatomaceous earth powder. Of these, sepiolite powder and apatalite powder are preferred.
The trivalent metal salt used in the present invention is preferably a water-soluble aluminum salt such as aluminum sulfate or alum; a water-soluble iron (III) salt such as ferric sulfate or ferric chloride.
〔硫化水素ガスの測定〕
100mlビーカーに無水塩化マグネシウム粉末10gを入れた。幅250mm×長さ500mm×厚さ0.08mmのポリエチレンフィルム製の袋の中に、前記ビーカーを入れた。水2gをビーカー内に注入した。注入後直ちに袋口を輪ゴムで絞って袋を閉じた。5分間放置した。硫化水素用ガス検知管にて内部の硫化水素ガス濃度を測定した。硫化水素ガス濃度は1.2ppmであった。硫化水素ガス濃度測定後に袋内の空気量を測定した。空気量は3500mlであった。 Reference example (measurement of hydrogen sulfide gas)
10 g of anhydrous magnesium chloride powder was put into a 100 ml beaker. The beaker was placed in a polyethylene film bag having a width of 250 mm, a length of 500 mm, and a thickness of 0.08 mm. 2 g of water was poured into the beaker. Immediately after the injection, the bag mouth was squeezed with a rubber band to close the bag. Left for 5 minutes. The hydrogen sulfide gas concentration inside was measured with a hydrogen sulfide gas detector tube. The hydrogen sulfide gas concentration was 1.2 ppm. After measuring the hydrogen sulfide gas concentration, the amount of air in the bag was measured. The amount of air was 3500 ml.
〔銅板変色試験〕
メタノールで洗浄し、乾燥させた50mm×50mm×厚さ1mmの銅板を用意した。長さ340mm×幅270mm×高さ180mmで底板を有するプラスチック製の枠を用意した。前記底板の短辺から内側に20mmの位置の底板上に前記銅板を垂直に立てて設置した。直径60mmのシャーレに無水塩化カルシウム顆粒(乾燥剤)10gを入れた。銅板設置位置に対して反対側の短辺から内側に20mmの位置の底板上に前記シャーレを設置した。これら全体を100μm厚さのポリエチレンフィルム製の袋(500mm×750mm)に収納し、袋を枠の形状に沿うように粘着テープで固定し、袋の口をゴムバンドで閉じた。それを恒温恒湿器に入れた。恒温恒湿器内の温度および湿度を24時間サイクルで下記のとおりにした。
(1)1時間かけて温度40℃、相対湿度90%に変更。
(2)温度40℃、相対湿度90%で11時間保持。
(3)1時間かけて温度20℃、相対湿度90%に変更
(4)温度20℃、相対湿度90%で11時間保持。 Comparative Example 1
[Copper plate discoloration test]
A copper plate of 50 mm × 50 mm × thickness 1 mm washed with methanol and dried was prepared. A plastic frame having a length of 340 mm, a width of 270 mm, and a height of 180 mm and having a bottom plate was prepared. The copper plate was vertically installed on the bottom plate at a position 20 mm inward from the short side of the bottom plate. Anhydrous calcium chloride granules (drying agent) 10 g was put in a petri dish having a diameter of 60 mm. The petri dish was placed on the bottom plate at a position 20 mm inward from the short side opposite to the copper plate placement position. The whole was stored in a polyethylene film bag (500 mm × 750 mm) having a thickness of 100 μm, the bag was fixed with an adhesive tape so as to follow the shape of the frame, and the mouth of the bag was closed with a rubber band. It was put in a constant temperature and humidity chamber. The temperature and humidity in the constant temperature and humidity chamber were set as follows in a 24-hour cycle.
(1) Changed to 40 ° C and 90% relative humidity over 1 hour.
(2) Hold for 11 hours at a temperature of 40 ° C. and a relative humidity of 90%.
(3) Change to a temperature of 20 ° C and a relative humidity of 90% over 1 hour. (4) Hold at a temperature of 20 ° C and a relative humidity of 90% for 11 hours.
A:変色なし
B:微小変色
C:変色小
D:変色
E:変色大
結果を表1に示す。 The copper plate was visually observed through the film when 4 days, 7 days, and 14 days passed, and evaluated by the following indices.
A: No discoloration B: Small discoloration C: Small discoloration D: Discoloration E: Large discoloration The results are shown in Table 1.
無水塩化カルシウム顆粒を無水塩化マグネシウム粉末および無水塩化マグネシウムフレークに変えた以外は比較例1と同じ方法で、銅板変色試験を行った。結果を表1に示す。 Comparative Examples 2-3
A copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that anhydrous calcium chloride granules were changed to anhydrous magnesium chloride powder and anhydrous magnesium chloride flakes. The results are shown in Table 1.
無水塩化マグネシウム粉末10gと酸化マグネシウム10gとを混合して粉末状乾燥剤組成物を得た。無水塩化カルシウム顆粒10gを前記乾燥剤組成物に変えた以外は比較例1と同じ方法で、銅板変色試験を行った。結果を表1に示す。 Comparative Example 4
10 g of anhydrous magnesium chloride powder and 10 g of magnesium oxide were mixed to obtain a powdery desiccant composition. A copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that 10 g of anhydrous calcium chloride granules were changed to the desiccant composition. The results are shown in Table 1.
酸化マグネシウム10gを、表1および表2に示す量の化合物の粉末に変えた以外は比較例4と同じ方法で粉末状乾燥剤組成物を得、銅板変色試験を行った。結果を表1および表2に示す。 Comparative Examples 5-6 and Examples 1-12
A powdery desiccant composition was obtained in the same manner as in Comparative Example 4 except that 10 g of magnesium oxide was changed to the amount of compound powder shown in Tables 1 and 2, and a copper plate discoloration test was performed. The results are shown in Tables 1 and 2.
無水塩化第二銅1質量部を水9質量部に溶解させて水溶液を得た。該水溶液5質量部をシリカゲル粉末5質量部に含浸させて粉末を得た。該粉末0.2gと無水塩化マグネシウム粉末10gとを混合して、表3に示す組成の粉末状の乾燥剤組成物を得た。無水塩化カルシウム顆粒を前記乾燥剤組成物に変えた以外は比較例1と同じ方法で、銅板変色試験を行った。結果を表3に示す。 Example 13
An aqueous solution was obtained by dissolving 1 part by mass of anhydrous cupric chloride in 9 parts by mass of water. 5 parts by mass of the aqueous solution was impregnated into 5 parts by mass of silica gel powder to obtain a powder. The powdery desiccant composition having the composition shown in Table 3 was obtained by mixing 0.2 g of the powder and 10 g of anhydrous magnesium chloride powder. A copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that anhydrous calcium chloride granules were changed to the desiccant composition. The results are shown in Table 3.
表3に示す組成となるように硫化水素吸収剤の種類と量を変えた以外は実施例13と同じ方法で粉末状の乾燥剤組成物を得、銅板変色試験を行った。結果を表3に示す。 Examples 14-20
A powdery desiccant composition was obtained in the same manner as in Example 13 except that the type and amount of the hydrogen sulfide absorbent were changed so as to obtain the composition shown in Table 3, and a copper plate discoloration test was conducted. The results are shown in Table 3.
シリカゲル粉末を表4に示す多孔質体に変えた以外は実施例13と同じ方法で粉末状の乾燥剤組成物を得、銅板変色試験を行った。結果を表4に示す。 Examples 21-26
A powdery desiccant composition was obtained in the same manner as in Example 13 except that the silica gel powder was changed to the porous body shown in Table 4, and a copper plate discoloration test was conducted. The results are shown in Table 4.
無水塩化第二銅1質量部を水9質量部に溶解させて水溶液を得た。該水溶液5質量部をシリカゲル粉末5質量部に添加混合し、次いで加熱乾燥させて粉末を得た。該粉末0.11gと無水塩化マグネシウム粉末10gを混合して粉末状の乾燥剤組成物を得た。無水塩化カルシウム顆粒を前記乾燥剤組成物に変えた以外は比較例1と同じ方法で、銅板変色試験を行った。結果を表5に示す。 Example 27
An aqueous solution was obtained by dissolving 1 part by mass of anhydrous cupric chloride in 9 parts by mass of water. 5 parts by mass of the aqueous solution was added to and mixed with 5 parts by mass of silica gel powder, and then heated and dried to obtain a powder. A powdery desiccant composition was obtained by mixing 0.11 g of the powder and 10 g of anhydrous magnesium chloride powder. A copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that anhydrous calcium chloride granules were changed to the desiccant composition. The results are shown in Table 5.
無水塩化第二銅1質量部をグリセリン19質量部に溶解させて溶液を得た。該溶液10質量部をシリカゲル粉末10質量部に添加混合して粉末を得た。該粉末0.4gと無水塩化マグネシウム粉末10gとを混合して粉末状の乾燥剤組成物を得た。無水塩化カルシウム顆粒を前記乾燥剤組成物に変えた以外は比較例1と同じ方法で、銅板変色試験を行った。結果を表5に示す。 Example 28
1 part by mass of anhydrous cupric chloride was dissolved in 19 parts by mass of glycerin to obtain a solution. 10 parts by mass of the solution was added to and mixed with 10 parts by mass of silica gel powder to obtain a powder. 0.4 g of the powder and 10 g of anhydrous magnesium chloride powder were mixed to obtain a powdery desiccant composition. A copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that anhydrous calcium chloride granules were changed to the desiccant composition. The results are shown in Table 5.
無水塩化第二銅1質量部を水9質量部に溶解させて水溶液を得た。該水溶液5質量部をシリカゲル粉末5質量部に添加混合して粉末を得た。該粉末0.2gと水酸化マグネシウム粉末0.5gと無水塩化マグネシウム粉末10gとを混合し粉末状の乾燥剤組成物を得た。無水塩化カルシウム顆粒を前記乾燥剤組成物に変えた以外は比較例1と同じ方法で、銅板変色試験を行った。結果を表5に示す。 Example 29
An aqueous solution was obtained by dissolving 1 part by mass of anhydrous cupric chloride in 9 parts by mass of water. 5 parts by mass of the aqueous solution was added to and mixed with 5 parts by mass of silica gel powder to obtain a powder. 0.2 g of the powder, 0.5 g of magnesium hydroxide powder, and 10 g of anhydrous magnesium chloride powder were mixed to obtain a powdery desiccant composition. A copper plate discoloration test was performed in the same manner as in Comparative Example 1 except that anhydrous calcium chloride granules were changed to the desiccant composition. The results are shown in Table 5.
無水塩化第二銅1質量部を水2質量部に溶解させて水溶液を得た。該水溶液3質量部をシリカゲル粉末3質量部に添加混合して粉末を得た。該粉末0.06gと水酸化マグネシウム粉末0.5gと無水塩化マグネシウム粉末10gとを混合し粉末状の乾燥剤組成物を得た。
恒温恒湿器内の温度および湿度を下記のとおりに変更した以外は比較例1にて行った銅板変色試験と同じ方法で試験を行った。結果を表6に示す。
(1)1時間かけて温度50℃、相対湿度90%に変更。
(2)温度50℃、相対湿度90%で11時間保持。
(3)1時間かけて温度20℃、相対湿度90%に変更。
(4)温度20℃、相対湿度90%で11時間保持。
なお、目視観察は3日、7日および14日経過時に行った。 Example 30
An aqueous solution was obtained by dissolving 1 part by mass of anhydrous cupric chloride in 2 parts by mass of water. 3 parts by mass of the aqueous solution was added to and mixed with 3 parts by mass of silica gel powder to obtain a powder. 0.06 g of the powder, 0.5 g of magnesium hydroxide powder and 10 g of anhydrous magnesium chloride powder were mixed to obtain a powdery desiccant composition.
The test was performed in the same manner as the copper plate discoloration test performed in Comparative Example 1 except that the temperature and humidity in the thermo-hygrostat were changed as follows. The results are shown in Table 6.
(1) Changed to 50 ° C and 90% relative humidity over 1 hour.
(2) Hold for 11 hours at a temperature of 50 ° C. and a relative humidity of 90%.
(3) Changed to 20 ° C and 90% relative humidity over 1 hour.
(4) Hold for 11 hours at a temperature of 20 ° C. and a relative humidity of 90%.
The visual observation was performed when 3 days, 7 days and 14 days had elapsed.
表6に示す組成となるように硫化水素吸収剤と塩基性物質の種類と量を変えた以外は実施例30と同じ方法で粉末状の乾燥剤組成物を得、実施例30と同じ方法で銅板変色試験を行った。結果を表6に示す。 Examples 31-32
A powdery desiccant composition was obtained in the same manner as in Example 30 except that the types and amounts of the hydrogen sulfide absorbent and the basic substance were changed so that the composition shown in Table 6 was obtained. A copper plate discoloration test was conducted. The results are shown in Table 6.
表6に示す組成になるように無水塩化マグネシウム粉末、硫化水素吸収剤、および塩基性物質を混合し粉末状の乾燥剤組成物を得、実施例30と同じ方法で銅板変色試験を行った。結果を表6に示す。 Examples 33-34
An anhydrous magnesium chloride powder, a hydrogen sulfide absorbent, and a basic substance were mixed so as to have the composition shown in Table 6 to obtain a powdery desiccant composition, and a copper plate discoloration test was performed in the same manner as in Example 30. The results are shown in Table 6.
無水塩化マグネシウム27gとカルボキシメチルセルロースナトリウム塩8gとを混合して粉末状の乾燥剤組成物を得た。
115mm×113mmの通気非透水性フィルム製の袋に、前記乾燥剤組成物を入れた。袋の口をヒートシールして乾燥剤を得た。該乾燥剤の重量を測定した。
340mm×270mm×高さ180mmで底板を有するプラスチック製の枠を用意した。前記枠内の底板に前記乾燥剤を設置した。厚さ0.9mmの濾紙製の箱(内寸345mm×275mm×高さ185mm)を前記枠に被せた。それを温度25℃、相対湿度90%の恒温恒湿器内に放置した。
放置開始から、24時間、48時間、120時間、および240時間経過時に、前記乾燥剤の重量を測定して、乾燥剤の重量当たり吸水量[g/g]を算出した。 Example 35
27 g of anhydrous magnesium chloride and 8 g of carboxymethylcellulose sodium salt were mixed to obtain a powdery desiccant composition.
The desiccant composition was put into a bag made of a breathable water-impermeable film of 115 mm × 113 mm. The bag mouth was heat sealed to obtain a desiccant. The weight of the desiccant was measured.
A plastic frame having a bottom plate of 340 mm × 270 mm × height 180 mm was prepared. The desiccant was placed on the bottom plate in the frame. A 0.9 mm thick filter paper box (inner dimensions: 345 mm × 275 mm × height 185 mm) was placed on the frame. It was left in a constant temperature and humidity chamber at a temperature of 25 ° C. and a relative humidity of 90%.
The weight of the desiccant was measured at the elapse of 24 hours, 48 hours, 120 hours, and 240 hours from the start of standing, and the water absorption [g / g] per weight of the desiccant was calculated.
A:固体または硬いゲル
B:一部が軟らかいゲル
C:全体が軟らかいゲル状
D:一部が液状化
E:全体が液状化 After 24 hours, 48 hours, 120 hours, and 240 hours from the start of standing, the state of the desiccant was observed and evaluated according to the following indicators.
A: Solid or hard gel B: Partially soft gel C: Entirely soft gel D: Partially liquefied E: Entirely liquefied
A:液漏れなし
B:シール部にて微少量の液漏れ
C:フィルム面にて微小量の液漏れ
D:フィルム面にて完全な液漏れ
これらの結果を表7に示す。 Furthermore, when 240 hours elapsed from the start of standing, the state of liquid leakage from the desiccant was evaluated using the following indicators.
A: No liquid leakage B: Small amount of liquid leakage at the seal portion C: Small amount of liquid leakage at the film surface D: Complete liquid leakage at the film surface These results are shown in Table 7.
表7および8に示す組成に変えた以外は実施例35と同じ方法で乾燥剤組成物を得、該組成物の評価試験を行った。結果を表7および8に示す。 Examples 36 to 46 and Comparative Examples 7 to 13
A desiccant composition was obtained in the same manner as in Example 35 except that the compositions shown in Tables 7 and 8 were changed, and the composition was evaluated. The results are shown in Tables 7 and 8.
実施例1で使用したものと同じ無水塩化マグネシウム粉末2gを秤量ビンに入れた。比較例1で使用したものと同じ無水塩化カルシウム顆粒を粉砕してなる粉末2gを秤量ビンに入れた。これらを、温湿度計が設置されたプラスチック容器内に設置した。所定相対湿度に調節可能な濃度の硫酸水溶液100gを入れたガラス製広口容器を前記プラスチック容器内に設置した。プラスチック容器全体をガスバリア性樹脂フィルムの袋の中に入れ、袋口をヒートシールした。これを25℃の恒温器内で1週間放置した。その後、秤量ビンを取り出して重量を測定した。温度25℃で且つ相対湿度8%、12%、22%、27%または50%における質量当たりの吸水量、モル当たりの吸水量、および塩化カルシウムの吸水量に対する塩化マグネシウムの吸水量の比を算出した。結果を表9に示す。 [Relationship between humidity and hygroscopicity]
2 g of the same anhydrous magnesium chloride powder as used in Example 1 was placed in a weighing bottle. 2 g of powder obtained by pulverizing the same anhydrous calcium chloride granules as used in Comparative Example 1 was placed in a weighing bottle. These were installed in a plastic container in which a temperature and humidity meter was installed. A glass wide-mouth container containing 100 g of an aqueous sulfuric acid solution having a concentration adjustable to a predetermined relative humidity was placed in the plastic container. The entire plastic container was placed in a gas barrier resin film bag, and the bag mouth was heat sealed. This was left in a 25 ° C. incubator for 1 week. Thereafter, the weighing bottle was taken out and the weight was measured. Calculate water absorption per mass, water absorption per mole, and ratio of water absorption of magnesium chloride to water absorption of calcium chloride at a temperature of 25 ° C. and a relative humidity of 8%, 12%, 22%, 27% or 50%. did. The results are shown in Table 9.
塩化カルシウムを含有する乾燥剤が使用される機械部品の錆防止のためには相対湿度を50~60%以下に保つ必要があるが、この湿度領域の吸湿能力は無水塩化カルシウムと無水塩化マグネシウムで大きな相違はない。しかしながら、わずかの湿気でも錆が発生する精密機械や電子部品ではより低湿度に保つことが要求されている。密封空間内に無水塩化マグネシウムを含有する乾燥剤を同封することにより長期間低湿度に保つ梱包包装が可能になり、極度に湿気を嫌う精密機械や電子部品の保管、輸送に有効である。
密封空間の形成には樹脂製のフィルムで密封包装する、樹脂製や金属製の密封コンテナに収納する等各種公知の方法が使用可能である。 As shown in Table 9, anhydrous magnesium chloride has more water absorption per weight or water absorption per mole than anhydrous calcium chloride, and is excellent in moisture absorption capacity in a low humidity environment.
Relative humidity must be kept at 50-60% or less to prevent rust of machine parts that use desiccant containing calcium chloride. The moisture absorption capacity in this humidity range is anhydrous calcium chloride and anhydrous magnesium chloride. There is no big difference. However, it is required to maintain a lower humidity in precision machines and electronic parts that generate rust even with a slight humidity. By enclosing a desiccant containing anhydrous magnesium chloride in the sealed space, it becomes possible to package and keep it at low humidity for a long time, and it is effective for storage and transportation of precision machines and electronic parts that are extremely sensitive to moisture.
Various known methods can be used for forming the sealed space, such as sealing and packaging with a resin film, and storing in a sealed container made of resin or metal.
保管方法(比較例A)
115mm×113mmの通気非透水性フィルム製の袋(包装材)に、塩化カルシウム系乾燥剤(無水塩化カルシウム、水溶性ポリマー(カルボキシメチルセルロースナトリウム塩)、および無機吸水剤(セピオライト)の混合物 30g)を充填し、袋の口をヒートシールして乾燥剤を得た。乾燥剤12個を横230mm×縦550mm×厚さ0.08mmのポリエチレンフィルム製の保管用袋の中に縦に積み上げて収納した。保管用袋の口をひねり絞って折り畳みゴムバンドで閉じ、温度25℃、相対湿度90%の恒温恒湿器内に17週間放置した。ゴムバンドを外し保管用袋から乾燥剤を取り出し、その重量を測定して、収納位置〔段数〕別の吸湿率を算出した。乾燥剤の収納位置と吸湿率との関係を表10に示す。 [Test on storage method of desiccant]
Storage method (Comparative Example A)
In a bag (packaging material) made of a breathable water-impermeable film of 115 mm × 113 mm, a calcium chloride-based desiccant (a mixture of anhydrous calcium chloride, a water-soluble polymer (carboxymethylcellulose sodium salt), and an inorganic water-absorbing agent (sepiolite) 30 g) After filling, the mouth of the bag was heat sealed to obtain a desiccant. Twelve desiccants were vertically stacked and stored in a polyethylene film storage bag having a width of 230 mm, a length of 550 mm, and a thickness of 0.08 mm. The mouth of the storage bag was twisted and closed with a folded rubber band, and left in a constant temperature and humidity chamber at a temperature of 25 ° C. and a relative humidity of 90% for 17 weeks. The rubber band was removed, the desiccant was taken out from the storage bag, and the weight was measured. Table 10 shows the relationship between the storage position of the desiccant and the moisture absorption rate.
115mm×113mmの通気非透水性フィルム製の袋(包装材)に、塩化マグネシウム系乾燥剤(無水塩化マグネシウム、カルボキシメチルセルロースナトリウム塩、および無機吸水剤(セピオライト)の混合物 24g)を充填し、袋の口をヒートシールして乾燥剤を得た。乾燥剤12個を横230mm×縦550mm×厚さ0.08mmのポリエチレンフィルム製の保管用袋の中に縦に積み上げて収納した。保管用袋の口をひねり絞って折り畳みゴムバンドで閉じ、温度25℃、相対湿度90%の恒温恒湿器内に17週間放置した。ゴムバンドを外し保管用袋から乾燥剤を取り出し、その重量を測定して、収納位置〔段数〕別の吸湿率を算出した。乾燥剤の収納位置と吸湿率との関係を表10に示す。 Storage method (Comparative Example B)
Fill a bag (packaging material) made of a breathable and water-impermeable film of 115 mm × 113 mm with a magnesium chloride-based desiccant (24 g of a mixture of anhydrous magnesium chloride, sodium carboxymethylcellulose, and an inorganic water-absorbing agent (sepiolite)). The mouth was heat sealed to obtain a desiccant. Twelve desiccants were vertically stacked and stored in a polyethylene film storage bag having a width of 230 mm, a length of 550 mm, and a thickness of 0.08 mm. The mouth of the storage bag was twisted and closed with a folded rubber band, and left in a constant temperature and humidity chamber at a temperature of 25 ° C. and a relative humidity of 90% for 17 weeks. The rubber band was removed, the desiccant was taken out from the storage bag, the weight was measured, and the moisture absorption rate for each storage position [number of steps] was calculated. Table 10 shows the relationship between the storage position of the desiccant and the moisture absorption rate.
比較例Bと同一組成、同一方法で塩化マグネシウム系乾燥剤を得た。
乾燥剤12個を横230mm×縦550mm×厚さ0.08mmのポリエチレンフィルム製の保管用袋の中に縦に積み上げて収納した。180mm×180mm×厚さ0.08mmのポリエチレンフィルムを積み上げた乾燥剤の上に被せ、ポリエチレンフィルムの端を袋と乾燥剤との間に挟み込んだ。ポリエチレンフィルムの端は、積み上げた乾燥剤の5段目あたりに達した。保管用袋の口をひねり絞って折り畳みゴムバンドで閉じ、温度25℃、相対湿度90%の恒温恒湿器内に17週間放置した。ゴムバンドを外し保管用袋から乾燥剤を取り出し、その重量を測定して、収納位置〔段数〕別の吸湿率を算出した。乾燥剤の収納位置と吸湿率との関係を表10に示す。 Storage method (Example C)
A magnesium chloride desiccant was obtained by the same composition and method as Comparative Example B.
Twelve desiccants were vertically stacked and stored in a polyethylene film storage bag having a width of 230 mm, a length of 550 mm, and a thickness of 0.08 mm. The polyethylene film of 180 mm × 180 mm × thickness 0.08 mm was placed on the stacked desiccant, and the end of the polyethylene film was sandwiched between the bag and the desiccant. The edge of the polyethylene film reached around the 5th stage of the accumulated desiccant. The mouth of the storage bag was twisted and closed with a folded rubber band, and left in a constant temperature and humidity chamber at a temperature of 25 ° C. and a relative humidity of 90% for 17 weeks. The rubber band was removed, the desiccant was taken out from the storage bag, the weight was measured, and the moisture absorption rate for each storage position [number of steps] was calculated. Table 10 shows the relationship between the storage position of the desiccant and the moisture absorption rate.
Claims (10)
- 無水塩化マグネシウムと硫化水素吸収剤とを含有する乾燥剤組成物。 A desiccant composition containing anhydrous magnesium chloride and a hydrogen sulfide absorbent.
- 硫化水素吸収剤が、重金属含有化合物、金属単体、アルカリ金属水酸化物、酸化剤、および活性炭からなる群より選ばれる少なくとも一つである、請求項1に記載の乾燥剤組成物。 The desiccant composition according to claim 1, wherein the hydrogen sulfide absorbent is at least one selected from the group consisting of a heavy metal-containing compound, a simple metal, an alkali metal hydroxide, an oxidizing agent, and activated carbon.
- 硫化水素吸収剤が、銅化合物、銀化合物、および亜鉛化合物からなる群より選ばれる少なくとも一つである請求項1に記載の乾燥剤組成物。 The desiccant composition according to claim 1, wherein the hydrogen sulfide absorbent is at least one selected from the group consisting of a copper compound, a silver compound, and a zinc compound.
- 塩化マグネシウムとカルボキシメチルセルロースナトリウム塩および/またはポリアクリルアミドとを含有する乾燥剤組成物。 A desiccant composition containing magnesium chloride and carboxymethylcellulose sodium salt and / or polyacrylamide.
- 無機吸水剤または3価の金属塩をさらに含有する請求項4に記載の乾燥剤組成物。 The desiccant composition according to claim 4, further comprising an inorganic water-absorbing agent or a trivalent metal salt.
- セピオライトまたはアパタルジャイトをさらに含有する請求項4に記載の乾燥剤組成物。 The desiccant composition according to claim 4, further comprising sepiolite or apatal gite.
- 水溶性アルミニウム塩および/または水溶性鉄(III)塩をさらに含有する請求項4に記載の乾燥剤組成物。 The desiccant composition according to claim 4, further comprising a water-soluble aluminum salt and / or a water-soluble iron (III) salt.
- 少なくとも1面が通気非透水性フィルムからなる包装材で請求項1~7のいずれかひとつに記載の乾燥剤組成物を包装してなる乾燥剤。 A desiccant obtained by packaging the desiccant composition according to any one of claims 1 to 7 with a packaging material comprising at least one surface made of a breathable water-impermeable film.
- 密閉空間内に無水塩化マグネシウムを含有する乾燥剤を同封することを特徴とする低湿度梱包包装方法。 A low-humidity packaging method characterized by enclosing a desiccant containing anhydrous magnesium chloride in a sealed space.
- 塩化マグネシウムを含有する乾燥剤組成物を包装してなる乾燥剤を非透湿性樹脂製保管用袋の中に積み重ねて収納し、 収納された乾燥剤の上に蓋い用樹脂フィルムを被せ、 次いで前記保管用袋の口を閉じることを含む乾燥剤の保管方法。 A desiccant obtained by packaging a desiccant composition containing magnesium chloride is stacked and stored in a non-breathable resin storage bag, and a lidding resin film is placed on the stored desiccant, A method for storing a desiccant comprising closing a mouth of the storage bag.
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