JP3187479B2 - Deliquescent inorganic salt-containing complex - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel deliquescent inorganic salt containing
Related to complex . More specifically, the present invention relates to a deliquescent inorganic salt-containing composite having excellent moisture absorption properties and excellent workability and workability.

[0002]

BACKGROUND ART calcium chloride, deliquescent such as silica gel
Since inorganic salts have hygroscopicity, they are conventionally used as hygroscopic agents.
It is often used. Among them, calcium chloride is widely used because it is inexpensive and has a large hygroscopic capacity. However, calcium chloride is difficult to handle due to its granularity and liquefies due to moisture absorption, and thus has drawbacks such as spilling and soiling of others.

[0003] To overcome this drawback, calcium chloride
Mixed with water-soluble resin (Japanese Patent Publication No. 60-2853)
1 JP) and powdery water-absorbent resin was fixed on a fibrous substrate complex (are proposed KOKOKU 3-13359 JP) also may become slow rate of moisture absorption in the former case, the latter In such a case, there is a problem that the moisture absorbing ability is lacking.

[0004]

[0008] The present invention, I der intended to solve the above problems, a deliquescent inorganic salt, no dripping, moreover, excellent in moisture absorption characteristics, excellent form handling property Use
It is an object of the present invention to provide a deliquescent inorganic salt-containing composite which can be used.

[0005]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the deliquescent inorganic salt-containing resin produced under the limited conditions has been found to have a hygroscopic property. In terms of speed, moisture absorption, liquid dripping after moisture absorption, etc., it has much better properties than conventionally known combinations, and by including it in various base materials, it has excellent hygroscopic deliquescence. The present inventors have found that an inorganic salt-containing composite can be obtained, and have reached the present invention.

Namely, deliquescent inorganic salt-containing complexes according to the present invention, the water-soluble unsaturated monomer and component comprising a crosslinking agent obtained by polymerizing in the presence of a deliquescent inorganic salt, granular
Shape, flake, pearl, fiber and sheet
Deliquescent inorganic salt containing resin having a Re or shape, is a complex formed by incorporating in the substrate.

The deliquescent inorganic salt-containing resin according to the present invention is prepared by , for example, polymerizing a water-soluble unsaturated monomer in the presence of a crosslinking agent and a deliquescent inorganic salt by a known polymerization method such as heat, radiation and light. Can be manufactured.

[0008] Usable water-soluble unsaturated monomers include:
(Meth) acrylic acid, a monomer having a carboxyl group such as maleic anhydride; (meth) acrylic acid sodium salt,
Monomers having a carboxyl group in the form of salts such as potassium (meth) acrylate, ammonium (meth) acrylate and sodium maleate; vinyl sulfonic acid, styrene sulfonic acid, sulfopropyl (meth) acrylate, etc. Having a sulfonic acid group of: vinyl sulfonic acid sodium salt, vinyl sulfonic acid methylamine salt, (meth)
Monomers having a sulfonate such as sodium sulfopropyl acrylate; monomers having a hydroxyl group such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; ethylene glycol (meth) acrylate
Monomers having an ether group such as monomethyl ether, trioxyethylene glycol (meth) acrylate;
Monomers having an amino group such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; N, N'-dimethylacrylamide, (meth) acrylamide, N-vinylpyrrolidone, N-methylolation A monomer having an amide group such as acrylamide;
Monomers having a quaternary ammonium base, such as N ', N "-trimethyl-N- (meth) acryloyloxyethylammonium chloride, etc., and preferably (meth) acrylic acid, maleic anhydride, etc. A monomer having a carboxyl group; a monomer having a carboxyl group in the form of a salt such as sodium (meth) acrylate, potassium (meth) acrylate, ammonium (meth) acrylate, and sodium maleate; It is a monomer having an amide group such as N, N'-dimethylacrylamide, (meth) acrylamide, N-vinylpyrrolidone, N-methylolated acrylamide and the like.

Examples of the crosslinking agent include di- or tri- (meth) acrylates of polyols such as ethylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol and polyoxypropylene glycol. An unsaturated polyester obtained by reacting the polyols with an unsaturated acid such as maleic acid; N, N '
Bisacrylamides such as methylene-bisacrylamide; allyl compounds such as tetraallyloxyethane, triallylamine, and allylated cellulose; di- or tri- () obtained by reacting polyepoxide with (meth) acrylic acid; Examples thereof include (meth) acrylic acid esters, and in some cases, bifunctional compounds such as methylolated (meth) acrylamide, glyoxal, ethylene glycol, ethylene glycol diglycidyl ether, and hydroxylated compounds. Calcium and the like can also be used. Preferred is a crosslinking agent having at least two polymerizable double bonds copolymerizable with the water-soluble unsaturated monomer.

The deliquescent inorganic salt refers to an inorganic salt in which the saturated aqueous solution has a water vapor pressure lower than the atmospheric water vapor partial pressure,
Specific examples include chlorides such as calcium, magnesium, lithium, zinc, aluminum and tin, and halides such as bromide and iodide. Among them, magnesium chloride and calcium chloride in terms of moisture absorption ability
At least one selected from the above can be suitably used.

The composition of the water-soluble unsaturated monomer, the cross-linking agent and the deliquescent inorganic salt is not particularly limited, but from the viewpoint of moisture absorption properties, the water-soluble unsaturated monomer, the cross-linking agent and the deliquescent inorganic salt are used. The weight ratio of the crosslinking agent is 0.0001 to 10, and the deliquescent inorganic salt is 10 to 1000 with respect to 100 of the water-soluble unsaturated monomer.
Is preferable.

As the polymerization solvent, for example , water, methano-
, Ethanol, acetone, DMF and mixtures thereof can be used, preferably water.

When water is used as the polymerization solvent, for example, if necessary, a drying step or a pulverizing step may be used for the present invention .
Deliquescent inorganic salt-containing resin. A deliquescent inorganic salt-containing resin can be obtained without a pulverization or drying step. Further, it is also possible to adjust the particle size to a desired particle size by performing classification as needed. No particular limitation on the shape of the deliquescent inorganic salt containing resin, particulate, frame - click shaped, Pa - Le, fibrous, sheet - DOO shape or the like may be in any form.

The deliquescent inorganic salt-containing resin obtained by the polymerization is contained in various base materials by a method such as spraying or mixing to form the deliquescent inorganic salt-containing composite of the present invention. As the base material, natural fibers such as pulp, rayon and cotton; synthetic fibers such as polyolefin and polyester; webs, nonwoven fabrics, woven fabrics and papers formed from natural fibers and synthetic fibers, and the like; rubber sponges and urethane foam -Porous substrates such as sponge-like substrates such as rubber and thermoplastic resin sheets, gypsum, sawdust, sand,
Various things such as soil can be used. Preferably deliquescent inorganic salt
As a product that can maximize the moisture absorption capacity of the contained resin,
A sheet-like porous fibrous base material can be used.
Since it is easy to handle and store by being formed into a sheet shape, it can be widely used. Deliquescence of cases present invention in one stage performs the polymerization in the presence of a fibrous substrate
It is also possible to obtain a complex containing an inorganic salt . The deliquescent inorganic salt-containing composite of the present invention can also be used in a moisture-permeable bag or box.

Further, a deodorant; an antiseptic / antifungal agent; a fragrance; a coloring agent and the like may be added to the deliquescent inorganic salt-containing composite of the present invention.

The present inventionDeliquescent inorganic salt-containing complexIs excellent
Liquefaction after moisture absorption
It can be used for various purposes because there is no need to worry about it. For example,
B) In a room, closet, getter box, shoes, rocker, etc.
Dehumidifying material. B) In a closed container, dislike moisture absorption such as glue and rice crackers
Drying material for products put in and sold. C) Condensation prevention materials.
D) Packaging materials for devices that do not like rusting. E) Humidity control materials. Effective for etc.
Can be used for Further according to the inventionDeliquescent inorganic salt-containing complex
Loses initial moisture absorption ability by drying after moisture absorption
It also has the feature that it can be used repeatedly without any.

[0017]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
Parts and percentages in the examples and comparative examples are by weight.

[0018] (Reference Example 1) 3 360 parts of 7% sodium acrylate aqueous solution, 34 parts of acrylic acid, methylenebisacrylamide 0.03 parts 3
450 parts of a 7% magnesium chloride aqueous solution was charged into an openable and closable container, and the liquid temperature was adjusted to 35 ° C. under a nitrogen atmosphere.
30 parts of a 3% ammonium persulfate aqueous solution and 0.3% l
-25 parts of an aqueous solution of ascorbic acid were added to initiate the polymerization. After aging at 80 ° C. for 1 hour, the gel polymer was taken out and dried in a hot air drier at 150 ° C.
The resin was pulverized to a particle size of about 50 mesh to obtain a deliquescent inorganic salt-containing resin (1).

[0019] (Reference Example 2) 2 - acryloyl ethanesulfonic acid aqueous solution of sodium 1
30 parts, 280 parts of a 37% aqueous lithium chloride solution and 0.2 parts of methylenebisacrylamide were charged into a polymerization vessel, and the liquid temperature was adjusted to 25 ° C. under a nitrogen atmosphere. 10 parts of 1-ascorbic acid aqueous solution and 10 parts of 3% 2,2′-azobis (2-amidinopropane) dihydrochloride aqueous solution were added to initiate polymerization. After aging at 90 ° C. for 2 hours, the gel polymer was taken out and dried in a hot air drier at 120 ° C.
It was pulverized to a particle size of 100 mesh to obtain a deliquescent inorganic salt-containing resin (2).

[0020] (Example 1) 1 00 parts of deliquescent inorganic salt containing resin (1), after 100 parts of crushed pulp, and 20 parts of synthetic pulp were dry mixed, aspirated laminated, heat treatment at 0.99 ° C. Deliquescence of the present invention
The composite (1) containing a conductive inorganic salt was obtained. Compound containing deliquescent inorganic salt
Put 1.0 g of coalescing (1) in a 500 ml glass container,
Increase weight by leaving it in a thermo-hygrostat at 25 ° C and 90% relative humidity
The amount of addition was measured over time to determine the amount of moisture absorption. This result and
Table 1 shows the surface state after 10 hours. As a blank
Table 1 also shows the results when only magnesium chloride was used.
The sample after moisture absorption is dried again, and the above operation is repeated.
The back moisture absorption effect was compared . Table 2 shows the results of the fourth repetition.
Showed fruit.

[0021] (Example 2) 1 After 00 parts of deliquescent inorganic salt-containing resin (2) and 100 parts of crushed pulp were dry mixed, the present invention is aspirated laminated
A deliquescent inorganic salt-containing composite (2) was obtained. Including deliquescent inorganic salts
The complex (2) was evaluated in the same manner as in Example 1.
Was. The results are shown in Tables 1 and 2.

[0022] (Comparative Example 1) 1 Magnesium chloride 00 parts, 100 parts of crushed pulp,
And 20 parts of the synthetic pulp were dry-mixed, laminated by suction, and heat-treated at 150 ° C. to obtain Comparative Composite (1).
The comparative complex (1) was evaluated in the same manner as in Example 1.
did. The results are shown in Tables 1 and 2.

[0023]

[Table 1]

[0024]

[Table 2]

In Table 1, all the samples used were previously sufficiently dried. As is clear from Table 1, the deliquescence of the present invention
The complex containing an inorganic salt is excellent in the rate of moisture absorption and the amount of moisture absorption, and there is no liquid dripping after moisture absorption, so that surface condensation does not occur.

From Table 2, it can be seen that the deliquescent inorganic salt-containing composite of the present invention is used.
It can be seen that the coalescence can be used repeatedly and the effect at that time does not decrease.

[0027]

Industrial Applicability The deliquescent inorganic salt-containing complex of the present invention is
Dissolves inorganic salts without dripping and has excellent moisture absorption properties
It is a composite with excellent handleability.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tadao Shimomura 5-8 Nishiburi-cho, Suita-shi, Osaka Inside of Nippon Shokubai Central Research Laboratory Co., Ltd. (56) References JP-A-63-31522 (JP, A) ( 58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 2/44

Claims (7)

(57) [Claims] A powder obtained by polymerizing a component comprising a water-soluble unsaturated monomer and a crosslinking agent in the presence of a deliquescent inorganic salt.
Granular, flake, pearl, fibrous and sheet
Deliquescent inorganic salt containing resin having any shape, formed by incorporating in the substrate deliquescent inorganic salt-containing complex. 2. The deliquescent inorganic salt-containing composite according to claim 1, wherein the deliquescent inorganic salt-containing composite is a sheet. 3. The deliquescent inorganic salt-containing composite according to claim 1, wherein the substrate is a porous fibrous substrate. 4. The deliquescent inorganic salt is 10 to 1000 parts by weight based on 100 parts by weight of the water-soluble unsaturated monomer.
4. The complex comprising a deliquescent inorganic salt according to any one of items 1 to 3. 5. The deliquescent inorganic salt-containing composite according to claim 1, wherein the crosslinking agent is 0.0001 to 10 parts by weight based on 100 parts by weight of the water-soluble unsaturated monomer. . 6. The deliquescent inorganic salt-containing composite according to claim 1, wherein the deliquescent inorganic salt is at least one selected from magnesium chloride and calcium chloride. 7. A deliquescent inorganic according to any one of claims 1 to 6.
Hygroscopic material using a salt-containing composite.