JP2003286349A - Molded articles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide molded articles having properties suitable to use as an excellent fishing lure for fishing and fishery, which can solve problems of endocrine disrupters and dioxins and are mild to the environment with retention of the same softness, flexibility and moldability as a plastic worm made of a vinyl chloride resin. <P>SOLUTION: The molded articles comprise an acrylic acid polymer having a cross-linked structure. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a molded product.
More specifically, it relates to a molded article made of an acrylic acid polymer.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride plastic worms (soft lures) have been mainly used as a pseudo bait for fishing fish, etc. This plastic worm has excellent elasticity and binding property, good visibility for fish, and pseudo He had many achievements as bait. However, under such circumstances, many of these false baits are dumped in the natural world, such as falling off from the needle during use and being lost by being caught by rocks and trees in the water. As a result, the dumped dummy bait remains in its original form in the natural world, and fish and birds may be accidentally ingested and die. Once the plastic worm has been swallowed, its solvent (for example, plasticizer) is absorbed in the body, and it cannot be eaten because of its odor. In addition, when collected and incinerated, harmful substances such as dioxins may be generated, and in order to soften the plastic, it is necessary to add a phthalate ester which is a plasticizer, and there are problems such as environmental hormones.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above problems found in the prior art and has the same softness, suppleness and moldability as those of vinyl chloride plastic worms required for simulated baits. While solving the problems of environmental hormones and dioxins, we aim to develop environmentally friendly molded products.

[0004]

As a result of various studies, the present inventor has found that when an acrylic acid-based polymer having a crosslinked structure is used, a molded article having the property of being usable as a pseudo bait in which the above problems are improved. The inventors have found that the following can be obtained and completed the present invention. That is, the present invention is

(1) A molded article made of an acrylic acid-based polymer having a crosslinked structure, and (2) a molding as described in the above item (1), wherein the acrylic acid-based polymer having a crosslinked structure is polyacrylic acid or a metal salt thereof. Body, (3) the molded product according to the above item (1) or (2), in which the acrylic acid-based polymer having a crosslinked structure is water-insoluble, and (4) the crosslinked structure is formed by a crosslinking agent having an unsaturated bond. The molded product according to any one of the preceding items (1) to (3), (5) the molded product according to any one of the preceding items (1) to (4) which is a hydrous molded product, (6)
Water content is 50 to 90% by weight based on the total weight of the molded product.
(7) The molded article according to the above (5), wherein (7) an aqueous solution containing acrylic acid or a metal salt thereof and a cross-linking agent is placed in a molding die and then polymerized to obtain (1)
To (6), the content of acrylic acid or its metal salt in the aqueous solution (8) is 10 to 5
0% by weight of the molded article according to item (7) above, and (9) an article comprising the molded article according to any one of items (1) to (8) above.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The molded article of the present invention comprises an acrylic acid polymer having a crosslinked structure. Examples of the acrylic acid-based polymer having a crosslinked structure include a crosslinked product of polyacrylic acid or a metal salt thereof. Examples of the metal salt of polyacrylic acid include alkali metal salts of polyacrylic acid such as sodium polyacrylate or potassium polyacrylate, alkaline earth metal salts of polyacrylic acid such as magnesium polyacrylate or calcium polyacrylate, or polyacrylic acid. Examples thereof include aluminum acid salts, but sodium polyacrylate is preferable. A partially neutralized polyacrylic acid having a crosslinked structure is also a kind of the acrylic acid-based polymer having a crosslinked structure used in the present invention.

The acrylic acid-based polymer having a crosslinked structure used in the present invention may be either water-soluble or water-insoluble, but water-insoluble is preferable in view of morphological stability in water.

The molded product of the present invention is preferably a hydrous molded product, and more preferably a colored product, from the viewpoint of flexibility and elasticity. The water content of the hydrous shaped product of the present invention is preferably 50 to 90% by weight, more preferably 60 to 85% by weight, and particularly preferably 70 to 85% by weight. The hue of the colored body is not particularly limited, and examples thereof include hues of watermelon, black, brown, smoke, blue, red, white, pink, yellow, pumpkin and the like.

In order to produce a molded article of the present invention, for example, a water-containing molded article of an acrylic acid-based polymer having a crosslinked structure, for example, an aqueous solution of an acrylic acid-based water-soluble monomer can be put into a molding die and crosslinked. Polymerization may be carried out in a state (for example, static polymerization), and then the obtained polymer may be taken out from the mold. Alternatively, an aqueous solution of an acrylic acid-based water-soluble monomer may be polymerized in a crosslinkable state to obtain an agar-like hydropolymer, and then the obtained hydropolymer may be molded. It should be noted that, like the water-absorbent resin in the form of beads, those obtained by cross-linking polymerization without using a molding die such as emulsion polymerization are not included in the molded article of the present invention.

Examples of the water-soluble acrylic acid-based monomer used for producing the molded article of the present invention include acrylic acid and / or its metal salt. Examples of the metal salt of acrylic acid include alkali metal acrylates such as sodium acrylate and potassium acrylate, alkaline earth metal acrylates such as magnesium acrylate and calcium acrylate, and aluminum acrylate. Acid alkali metal salts, especially sodium acrylate, are preferred. When a partially neutralized product of acrylic acid is used as the acrylic acid-based water-soluble monomer, a partially neutralized product of polyacrylic acid having a crosslinked structure is obtained. The partially neutralized product of acrylic acid can be obtained by adding an arbitrary amount of alkali to acrylic acid so as to have a desired pH. Examples of the alkali include sodium hydroxide and potassium hydroxide. In addition, acrylic acid, an alkali metal acrylate such as sodium acrylate or potassium acrylate, an alkaline earth metal acrylate such as magnesium acrylate or calcium acrylate, or a metal salt of acrylic acid such as aluminum acrylate may be used. In terms of the ratio, for example, the weight ratio of acrylic acid and acrylic acid metal salt is in the range of 7: 3 to 1:20, a partially neutralized product of acrylic acid can be obtained by mixing.

The content of the acrylic acid water-soluble monomer in the aqueous solution is preferably 10 to 50% by weight, more preferably 15 to 40% by weight, and most preferably 15 to 30% by weight. Particularly preferred.

Aqueous solution of acrylic acid water-soluble monomer,
A dye may be added. The addition of pigments gives a colored simulated bait. The dye is not particularly limited, but a water-soluble dye is preferable. For example, food blue No. 1, food red No. 102 or food yellow No. 4, etc. dyes, Kayacr
yl Yellow 3RL, Kayacryl Red
GRL or Kayacryl Blue GRL
Cation (basic) such as {trade name, manufactured by Nippon Kayaku Co., Ltd.}
Dyes or Kayacel Red CB Liquid,
Kayacel Blue CF Liquid, Kay
acel Yellow CG Liquid, Kaya
fect Red B Liquid or Kaya
basic dyes or direct dyes such as "Fact Red P Liquid" (trade name; manufactured by Nippon Kayaku Co., Ltd.). Two or more kinds of dyes may be mixed and used at an arbitrary ratio. The amount of the dye added is preferably 0.001 to 5.0%, and 0.01 to 2.0, based on the weight of the acrylic acid-based water-soluble monomer (converted to 100% by weight).
% Is more preferable.

When the molded product of the present invention is produced as a pseudo bait, a fish attractant may be added to the aqueous solution of the acrylic acid-based water-soluble monomer in order to increase fishing results. Examples of the fish attractant include amino acids containing essential amino acids such as valine, leucine, isoleucine, threonine, phenylalanine, tryptophan, lysine or methionine, fish oil or fish meal. Further, in an aqueous solution of an acrylic acid-based water-soluble monomer, within a range that does not impair the object of the present invention, depending on the purpose, fungicides, inorganic fillers, release agents, antistatic agents, ultraviolet absorbers,
Additives such as flame retardants, antioxidants, fluorescent dyes, aluminum reflectors, pigments, preservatives, peppermint, fragrances such as l-menthol, moisturizers, stimulants, disinfectants, etc. can be added. .

The mold used for producing the molded article of the present invention may be any mold suitable for the intended use and is not particularly limited. , Deep cups, straights, beaver tails, pin tails, claws, juz, goby, halves, curly tails or grabs are preferred in the form of what the fish prefers as bait. The mold is usually obtained by carving a resin into a desired shape according to the purpose. This resin may be, for example, a synthetic resin or a natural resin, but is preferably a synthetic resin such as an acrylic resin or an ABS (acrylonitrile, ternary copolymer of 1,4-butadiene and styrene) resin. . Further, a metal mold may be used, and any mold may be used as long as it does not inhibit polymerization. For example, a mold made of aluminum or an aluminum alloy may be used.

Polymerization of the acrylic acid-based water-soluble monomer is carried out in a state where it can be crosslinked. Specifically, the polymerization may be carried out under the condition that the acrylic acid water-soluble monomer self-crosslinks,
Further, although the crosslinking may be carried out by irradiation of radiation after the polymerization, it is preferable to carry out the polymerization in the presence of a crosslinking agent.
The polymerization is preferably static polymerization.

As the cross-linking agent, any cross-linking agent can be used, but one having an unsaturated group such as a double bond is preferable, and one having a plurality of unsaturated groups is more preferable. A) di- or tri (meth) acrylic acid esters (acrylates) of polyols, (b) di- or tri (meth) maleic acid esters of polyols, (iii) di- or tri (meth) fumaric acid esters of polyols Compounds, (d) bisacrylamides, (e) di- or tri (meth) acrylic acid esters obtained by reacting (meth) acrylic acid with (meth) acrylic acid, (f) polyisocyanate and (meth) acrylic acid hydroxy ester Examples include di (meth) acrylic acid carbamyl esters and (to) polyvalent allyl compounds obtained by the reaction. It is.

(A) Di- or tri (meth) acrylic acid esters (acrylates) of polyols include
For example, ethylene glycol diacrylate, ethylene glycol tri (meth) acrylate, propylene glycol diacrylate, propylene glycol tri (meth) acrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate. (Meth) acrylate
Glycerin diacrylate, glycerin tri (meth) acrylate, polyethylene glycol diacrylate, polyethylene glycol tri (meth) acrylate
Polypropylene glycol diacrylate, polypropylene glycol tri (meth) acrylate, polyglycerin diacrylate, polyglycerine tri (meth)
Examples include acrylate.

Examples of the di- or tri (meth) maleic acid ester of (b) polyol include ethylene glycol dimaleic acid ester, ethylene glycol tri (meth) maleic acid ester, propylene glycol dimaleic acid ester, and propylene. Glycol tri (meth) maleic acid ester, trimethylolpropane dimaleic acid ester, trimethylolpropane tri (meth) maleic acid ester, glycerin dimaleic acid ester, glycerin tri (meth) maleic acid ester, polyethylene glycol Dimaleic acid esters, polyethylene glycol tri (meth) maleic acid esters, polyoxypropylene glycol dimaleic acid esters, polyoxypropylene glycol tri (meth) maleic acid Esters, polyglycerol di maleate esters, polyglycerol tri (meth) maleates and the like.

(C) Di- or tri (meth) fumaric acid esters of polyols include, for example, ethylene glycol difumaric acid esters, ethylene glycol tri (meth) fumaric acid esters, propylene glycol difumaric acid esters, propylene Glycol tri (meth) fumaric acid esters, trimethylolpropane difumaric acid esters, trimethylolpropane tri (meth) fumaric acid esters, glycerin difumaric acid esters, glycerin tri (meth) fumaric acid esters, polyethylene glycol Difumaric acid esters, polyethylene glycol tri (meth) fumaric acid esters, polyoxypropylene glycol difumaric acid esters, polyoxypropylene glycol tri (meth) fumar Esters, polyglycerol diphenyl Mar acid esters, polyglycerol tri (meth) fumaric acid esters and the like.

Examples of the (d) bisacrylamides include N, N-methylenebis (meth) acrylamide. In addition, in the di (meth) acrylic acid carbamyl esters obtained by reacting (f) polyisocyanate with (meth) acrylic acid hydroxyester, examples of the polyisocyanate include tolylene diisocyanate and hexamethylene diisocyanate. Alternatively, (to) polyvalent allyl compounds include, for example, allylated starch, allylated cellulose, diallyl phthalate, tetraallyloxyethane, pentaerythritol triallyl ether, trimethylolpropane triallyl ether, diethylene glycol diallyl ether or triallyl trimellitate. Tate etc. are mentioned.

The (average) molecular weight of these crosslinking agents is 20.
Those in the range of 0 to 2000 are preferable, and 200 to 800
The range of is more preferable. Further, in consideration of the flexibility of the simulated bait, water-soluble ones are preferable, and those having two unsaturated groups such as double bonds are more preferable, and di (meth) acrylic polyol such as polyethylene glycol diacrylate is preferable. Acid esters are more preferred.

The crosslinking agent is added to the aqueous solution of the acrylic acid-based water-soluble monomer. The amount added is, for example, considering the relationship between elongation and return when pulled (when the molded product of the present invention is used as a pseudo bait, shape, softness, suppleness, underwater posture, etc.), acrylic It is appropriately determined in relation to the weight of the acid water-soluble monomer. For example, addition of 0.01 to 5.0% is preferable with respect to the weight of the acrylic acid-based water-soluble monomer (converted to 100% weight), and 0.1 to 5.0% is preferable.
To 3.0% is more preferable, and 0.2 to 2.0 is more preferable.
% Is particularly preferable.

A polymerization initiator is usually used for the polymerization. The polymerization initiator is not particularly limited as long as it can generate radicals, and examples thereof include water-soluble polymerization initiators such as persulfates and azobis compounds. Examples of the persulfate include sodium persulfate, potassium persulfate, ammonium persulfate and the like. Examples of the azobis-based water-soluble polymerization initiator include 2,2′-azobis (2-methylpropionamidine) dihydrochloride and 2,2 ′.
-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis- [2-methyl-
N- (2-hydroxyethyl) -propionamide],
4,4'-azobis (4-cyanovaleric acid) or 2,2 '
-Azobis- (isobutyronitrile) and the like.

Among these polymerization initiators, from the viewpoint of preventing poor shape reproducibility of the molded product due to shrinkage of the polymer at the time of polymerization, reactivity, etc., initiation of water-soluble polymerization for generating gas such as azobis compound Agents are preferred. By using a water-soluble polymerization initiator that generates this gas, for example, nitrogen gas is generated at the time of polymerization to prevent shrinkage of the pseudo bait at the time of polymerizing the polymer into the mold to improve the shape reproducibility of the molded body, and The specific gravity can be adjusted by the amount of gas generated. Among the azobis-based water-soluble polymerization initiators, 2,2′-azobis (2-methylpropionamidine) dihydrochloride is preferable. The polymerization initiator is from 0.05 to 100% by weight of the acrylic acid-based water-soluble monomer (converted to 100% by weight).
It is used in an amount of 2.5%, preferably 0.05-1.5%. This polymerization initiator is added to an aqueous solution of acrylic acid-based water-soluble monomer.

In the polymerization, for example, a bisulfite such as sodium bisulfite or a polymerization accelerator such as L-ascorbic acid, and a chain transfer agent such as sodium hypophosphite as a polymerization degree regulator can be used. .

In addition, the usual mold is capped during the polymerization. Examples of the lid include glass, plastic, wood, and metal plates, and it is preferable to use glass. Alternatively, a pair of right and left molds having a monomer injection port may be formed, the molds may be superposed, and then an aqueous solution of the monomer may be injected through the monomer injection port, followed by polymerization. The polymerization temperature is not particularly limited as long as it is 0 ° C. or higher, but in order to complete the reaction in a short time, heating conditions, for example, about 40 to 70 ° C. are preferable. The polymerization time is usually about 1 to 30 hours. When the molded article of the present invention is manufactured as a pseudo bait, if the size of the pseudo bait is small, it is difficult to polymerize in the presence of air, and therefore, it is usually polymerized in nitrogen gas.

The molded product of the present invention obtained by the above method is
If necessary, it is surface-treated with metal ions. The time for surface treatment is usually 1 to 30 hours. By this process,
It is possible to control the elasticity and the disintegration rate and swelling rate when left in water. The metal ion used in the present invention is not limited as long as it does not show toxicity, but a metal ion that suppresses disintegration and swelling of the pseudo food in water is preferable, and examples thereof include polyvalent metal ions.

Examples of the polyvalent metal ion include alkaline earth metal ions such as magnesium ion, calcium ion, strontium ion or barium ion,
Examples thereof include transition metal ions such as manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion or tin ion, or aluminum ion.

The surface treatment is carried out by immersing the above-mentioned molded body in an aqueous solution containing metal ions. The aqueous solution containing metal ions is obtained by dissolving a water-soluble metal salt in water. The water-soluble metal salt is preferably a water-soluble polyvalent metal salt, for example, halogenated polyvalent metal salts such as magnesium chloride, calcium chloride, aluminum chloride, magnesium bromide, calcium bromide, aluminum bromide, magnesium sulfate, sulfuric acid. calcium,
Examples thereof include polyvalent metal sulfates such as aluminum sulfate, polyvalent metal nitrates such as magnesium nitrate, calcium nitrate and aluminum nitrate, and polyvalent metal carbonates such as magnesium carbonate, calcium carbonate and aluminum carbonate. These substances may be used alone or in combination.

The concentration of the metal ion in the aqueous solution is preferably 0.1 to 10.0%, more preferably 1.0 to 6.0% as the concentration of the water-soluble metal salt. The time for surface treatment varies depending on the molding die used, but when the molded product of the present invention is manufactured as a pseudo bait, for example, in the case of a straight system, it is preferably 3 to 7 hours. Further, in the case of a grab system, 10 to 25 hours are preferable. The disintegration rate and swelling rate can be controlled by the time of this surface treatment.

The molded product of the present invention obtained by the above method can be used without being colored, but the surface thereof may be further colored. Examples of the dye used include the water-soluble dyes described above. The coloring on the surface is
The dye may be applied with a brush or a brush, or may be dipped in a dye solution. In the case of dipping, it can be performed simultaneously with the surface treatment with metal ions (for example, dipping in a metal ion aqueous solution containing a dye). It is also possible to use a pigment for coloring. Various pigments can be used as long as they do not adversely affect the molded product due to toxicity or the like. Coloring with a pigment is performed, for example, by applying the pigment to the molded body with a brush or a brush.

The pseudo bait using the molded article of the present invention is sea,
Any place where there is a fish such as a river, lake, pond or swamp can be used. Further, as target fish, fish eaters such as black bass, bull-gill, rainbow-trout, brown trout, catfish, sea bream, sea bass, scorpionfish, soybean, rockfish, eye shark, sea fish, flounder, maggot or dolphin. It can be used for all fish called-. The size of the simulated bait using the molded product of the present invention depends on the size of the target fish, but may be any size as long as it is possible in producing the simulated bait.

The article made of the molded article of the present invention includes, in addition to the above-mentioned pseudo bait, a cooling sheet, a moisturizing sheet (a cosmetic pack, etc.), a water expansion sealant (a waterproof packing of a seam of a pipe in water). Etc.), water retention agents for agricultural and horticultural use, sheets for raising rice seedlings, gelling agents for air fresheners, toys and the like.

When the molded product of the present invention is used as a cooling sheet, its size is preferably 3 to 5 cm in length, 5 to 15 cm in width, and about 2 to 5 mm in thickness, although it depends on the purpose of use. Further, when the molded body of the present invention is used as a cooling sheet, it is preferable that the water content is high in order to enhance the endothermic effect, but if the water content is too high, the strength of the sheet may be affected. Content is 70-95
%, Preferably 75-90%, more preferably 80-8
About 5% is preferable. In order to increase the water content to a desired value, the molded product has water absorbency, and therefore water may be added to and absorbed in the resulting molded product. Further, the cooling sheet using the molded body of the present invention is not particularly limited in the outer shape and can be appropriately selected and prepared depending on the application target, the sticking place, etc., but it is easy to handle, carry and store. From the viewpoint of, for example, a sheet shape is preferable. When a sheet-shaped object is intended, it is preferable to use a thin plate-shaped molding die (square, rectangle, etc.). In addition, select the type according to the application, animal,
It is also possible to create sheets of various shapes such as plants.

For the cooling sheet using the molded product of the present invention, the molded product of the present invention is taken out of the mold and used as it is, or a sheet-like moisture-permeable substrate (woven fabric, non-woven fabric) is placed in the mold. And film etc. in advance,
The molded product of the present invention may have a form in which it is laminated on a sheet-like moisture-permeable substrate, but in consideration of workability, cooling durability, stretchability, etc., the molded product is taken out of the mold and used as it is. Is preferred.

The above-mentioned cooling sheet comprises, for example, only the molded product of the present invention or the molded product and a moisture-permeable substrate, but from the viewpoints of handleability and hygiene, it is further peeled and removed at the time of use, if necessary. It is also possible to laminate a release film on the surface of the molded article of the present invention. Examples of such a release film include polyester, polypropylene, polyethylene,
Nylon, vinyl chloride, polyethylene terephthalate, etc. can be used.

[0037]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these.

Example 1 Two molds each made of ABS resin in the shape of a worm were carved into a grab, a deep cup, a straight, a beaver tail, a pin tail, a claw, a goby, a hook, and a curly tail.
To 100 g of 0% sodium acrylate aqueous solution, add 3 g of 0.3% edible red No. 102 aqueous solution, which is a red pigment,
Furthermore, a polymerization initiator V-50 {2 manufactured by Wako Pure Chemical Industries, Ltd.
2'-azobis (2-methylpropionamidine) dihydrochloride} 0.103 g and a crosslinking agent manufactured by Nippon Kayaku Co., Ltd.
KAYARAD PEG400DA {polyethylene glycol diacrylate: (average) molecular weight 522}
After adding 22 g and performing deaeration with nitrogen gas, it was injected. Cover the mold with a glass plate, and then at 60 ° C in a nitrogen atmosphere for 2
The polymerization reaction was carried out for 0 hours. After completion of the polymerization reaction, each cross-linked sodium polyacrylate hydrous molded product colored in red was taken out of the mold and immersed in a 5% magnesium chloride aqueous solution for 20 hours to obtain a simulated bait (cross-linked product) composed of the molded product of the present invention. Type worm made of sodium polyacrylate) was obtained.

Example 2 Two types of molds were carved into a glove, a deep cup, a straight, a beaver tail, a pin tail, a claw, a goby, a hook and a curly tail in the shape of a worm on ABS resin, respectively.
To 100 g of 0% sodium acrylate aqueous solution, 3 g of 0.3% food blue No. 1 aqueous solution, which is a blue pigment, was added, and further polymerization initiator V-50 {2,2 'manufactured by Wako Pure Chemical Industries, Ltd.
-Azobis (2-methylpropionamidine) dihydrochloride} 0.103 g and a cross-linking agent K manufactured by Nippon Kayaku Co., Ltd.
AYARAD PEG400DA {polyethylene glycol diacrylate: (average) molecular weight 522} 0.2
2 g was added, degassed with nitrogen gas, and then injected.
After the mold was covered with a glass plate, a polymerization reaction was carried out at 60 ° C. for 20 hours in a nitrogen atmosphere. After the completion of the polymerization reaction, each blue-colored water-containing molded product of cross-linked sodium polyacrylate was taken out of the mold and immersed in a 5% magnesium chloride aqueous solution for 20 hours to obtain a simulated bait (cross-linked product) of the molded product of the present invention. Type worm made of sodium polyacrylate) was obtained.

Example 3 Grab, deep cup, straight, beaver tail, pin tail, acrylic resin in the form of a worm, respectively.
For the mold carved on the claw, goby, hook, curly tail,
To 100 g of 20% sodium acrylate aqueous solution, 3 g of 0.3% edible yellow No. 4 aqueous solution, which is a yellow pigment, was added, and further polymerization initiator V-50 {2 manufactured by Wako Pure Chemical Industries, Ltd.
2'-azobis (2-methylpropionamidine) dihydrochloride} 0.103 g and a crosslinking agent manufactured by Nippon Kayaku Co., Ltd.
KAYARAD PEG400DA {polyethylene glycol diacrylate: (average) molecular weight 522}
After adding 22 g and performing deaeration with nitrogen gas, it was injected. Cover the mold with a glass plate, and then at 60 ° C in a nitrogen atmosphere for 2
The polymerization reaction was carried out for 0 hours. After the completion of the polymerization reaction, each yellow-colored crosslinked sodium polyacrylate hydrous molded product was taken out of the mold and immersed in a 5% magnesium chloride aqueous solution for 20 hours to obtain a simulated bait (crosslinked product) of the molded product of the present invention. Type worm made of sodium polyacrylate) was obtained.

Example 4 Acrylic resin in the shape of a worm grab, deep cup, straight, beaver tail, pin tail,
For the mold carved on the claw, goby, hook, curly tail,
To 100 g of a 20% aqueous sodium acrylate solution, 3 g of 0.3% food blue No. 1 aqueous solution which is a blue dye and 4.5 g of 0.3% food yellow No. 4 aqueous solution which is a yellow dye are added,
Furthermore, a polymerization initiator V-50 {2 manufactured by Wako Pure Chemical Industries, Ltd.
2'-azobis (2-methylpropionamidine) dihydrochloride} 0.103 g and a crosslinking agent manufactured by Nippon Kayaku Co., Ltd.
KAYARAD PEG400DA {polyethylene glycol diacrylate: (average) molecular weight 522}
After adding 22 g and performing deaeration with nitrogen gas, it was injected. Cover the mold with a glass plate, and then at 60 ° C in a nitrogen atmosphere for 2
The polymerization reaction was carried out for 0 hours. After the completion of the polymerization reaction, each of the crosslinked sodium polyacrylate hydrous molded products colored in green was taken out of the mold and immersed in a 5% magnesium chloride aqueous solution for 20 hours to obtain a simulated bait (crosslinked product) of the molded product of the present invention. Type worm made of sodium polyacrylate) was obtained.

Example 5 Grab, deep cup, straight, beaver tail, pin tail, acrylic resin in the form of worm, respectively.
For the mold carved on the claw, goby, hook, curly tail,
Basic dye 0.5% Kayacryl manufactured by Nippon Kayaku Co., Ltd. in 100 g of 20% sodium acrylate aqueous solution.
2.03 g of a yellow 3RL aqueous solution was added, and a polymerization initiator V-50 {2,2 ′ manufactured by Wako Pure Chemical Industries, Ltd. was further added.
-Azobis (2-methylpropionamidine) dihydrochloride} 0.103 g and a cross-linking agent K manufactured by Nippon Kayaku Co., Ltd.
AYARAD PEG400DA {polyethylene glycol diacrylate: (average) molecular weight 522} 0.2
2 g was added, degassed with nitrogen gas, and then injected.
After the mold was covered with a glass plate, a polymerization reaction was carried out at 60 ° C. for 20 hours in a nitrogen atmosphere. The polymerization proceeded well. After the completion of the polymerization reaction, each crosslinked sodium polyacrylate hydrous molded article colored in yellow was taken out from the molding die, and 5
% Magnesium chloride aqueous solution for 20 hours to obtain a simulated bait (a worm made of crosslinked sodium polyacrylate) composed of the molded product of the present invention.

Example 6 Grab, deep cup, straight, beaver tail, pin tail, acrylic resin in the shape of a worm, respectively.
For the mold carved on the claw, goby, hook, curly tail,
Basic dye Kayacel Red CB manufactured by Nippon Kayaku Co., Ltd. in 100 g of 20% sodium acrylate aqueous solution.
Liquid stock solution (0.10 g) was added, and a polymerization initiator V-50 {2,2′-azobis (2-methylpropionamidine) dihydrochloride} manufactured by Wako Pure Chemical Industries, Ltd. was further added.
103 g and cross-linking agent KAYARA manufactured by Nippon Kayaku Co., Ltd.
0.22 g of D PEG400DA {polyethylene glycol diacrylate: (average) molecular weight 522} was added, degassed with nitrogen gas, and then injected. After the mold was covered with a glass plate, a polymerization reaction was carried out at 60 ° C. for 20 hours in a nitrogen atmosphere. After the completion of the polymerization reaction, each cross-linked sodium polyacrylate hydrous molded product colored in red was taken out from the mold and treated with a 5% magnesium chloride aqueous solution for 20 minutes.
Immersion for a period of time gave a simulated bait (a worm made of crosslinked sodium polyacrylate) composed of the molded product of the present invention.

Example 7 Grab, deep cup, straight, beaver tail, pin tail, acrylic resin in the shape of a worm, respectively.
For the mold carved on the claw, goby, hook, curly tail,
Basic dye Kayacel Blue C manufactured by Nippon Kayaku Co., Ltd. in 100 g of 20% sodium acrylate aqueous solution.
0.10 g of F Liquid stock solution was added, and 0.103 g of a polymerization initiator V-50 {2,2′-azobis (2-methylpropionamidine) dihydrochloride} manufactured by Wako Pure Chemical Industries, Ltd. was added to Japan. Crosslinking agent KAYA manufactured by Kayaku Co., Ltd.
0.22 g of RAD PEG400DA {polyethylene glycol diacrylate: (average) molecular weight 522} was added, degassed with nitrogen gas, and then injected. After the mold was covered with a glass plate, a polymerization reaction was carried out at 60 ° C. for 20 hours in a nitrogen atmosphere. After the completion of the polymerization reaction, each crosslinked type sodium polyacrylate hydrous molded product colored in blue was taken out of the mold and treated with a 5% magnesium chloride aqueous solution.
Immersion was carried out for 0 hours to obtain a simulated bait (a worm made of crosslinked sodium polyacrylate) composed of the molded product of the present invention.

Example 8 Grab, deep cup, straight, beaver tail, pin tail, acrylic resin in the form of a worm, respectively.
For the mold carved on the claw, goby, hook, curly tail,
100 g of a 20% sodium acrylate aqueous solution was added to Nippon Kayaku Co., Ltd. basic dye Kayacel Yellow.
CG Liquid stock solution 0.09 g was added, and a polymerization initiator V-50 {2,2'- manufactured by Wako Pure Chemical Industries, Ltd. was further added.
Azobis (2-methylpropionamidine) dihydrochloride}
0.103 g and a cross-linking agent KAY manufactured by Nippon Kayaku Co., Ltd.
0.22 g of ARAD PEG400DA {polyethylene glycol diacrylate: (average) molecular weight 522}
After adding and degassing with nitrogen gas, it was injected. After the mold was covered with a glass plate, a polymerization reaction was carried out at 60 ° C. for 20 hours in a nitrogen atmosphere. After the completion of the polymerization reaction, each cross-linked sodium polyacrylate hydrous molded product colored in yellow was taken out of the mold and immersed in a 5% magnesium chloride aqueous solution for 20 hours to form a pseudo bait (cross-linked mold) of the molded product of the present invention. A worm made of sodium polyacrylate) was obtained.

In the same manner as in Examples 1 to 8 above, the following Table 1
As described above, a pseudo bait comprising the molded product of the present invention was produced.

[0047] Table 1                    Simulated bait obtained in Examples 9 to 15                                Dye polymerization initiator metal ion Example 9 A 1.5% aqueous solution of ammonium persulfate Magnesium ion Example 10 B C magnesium ion Example 11 AC calcium ion Example 12 B C calcium ion Example 13 A 1.5% ammonium persulfate aqueous solution calcium ion Example 14 DC magnesium ion Example 15 D 1.5% Ammonium Persulfate Aqueous Solution Calcium Ion

In Table 1, A is Kayacel Red
CB Liquid, B is Kayacel Blue
CF Liquid, Kayacel Yellow
CG Liquid and Kayacel Red C
B Liquid, C is 2,2′-azobis (2-methylpropionamidine) dihydrochloride, and D is Kayac.
ryl Yellow 3RL is shown respectively. In addition, in Examples 14 and 15, coloring of the pseudo bait is performed after the surface treatment with metal ions, not during polymerization.

Example 16 To 200 g of a 20% sodium acrylate aqueous solution, 0.103 g of a polymerization initiator V-50 and KAYRAD PEG4 were added.
0.320 g of 00DA was added, and the obtained mixed solution was poured into a thin plate of 4.5 mm × 200 mm × 200 mm with a glass plate, and a polymerization reaction was carried out at 70 ° C. for 5 hours to obtain the molded product of the present invention. (Water content 80%) was obtained.

Example 17 To 300 g of a 20% sodium acrylate aqueous solution, 0.1545 g of a polymerization initiator V50 and KAYRAD PEG4 were added.
00DA (0.660 g) was added, and the obtained mixed solution was poured into a mold made into a thin plate of 3.0 mm × 200 mm × 200 mm with a glass plate, and a polymerization reaction was carried out at 60 ° C. for 10 hours. After the completion of the polymerization reaction, the water-containing molded product of crosslinked sodium polyacrylate was taken out from the mold and treated with a 5% magnesium chloride aqueous solution for 20 hours to obtain the molded product of the present invention (water content 80%).
Got

Example 18 Polymerization initiator V-500.103 g and KAYRAD PEG 40 were added to 200 g of 15% sodium acrylate aqueous solution.
0.690 g of 0DA was added, and the obtained mixed solution was poured into a mold made of a glass plate into a thin plate shape of 4.5 mm × 200 mm × 200 mm, and a polymerization reaction was carried out at 70 ° C. for 5 hours to obtain the molded product of the present invention. (Water content 85%) was obtained.

[0052]

The molded product of the present invention can control the swelling speed and the disintegrating speed arbitrarily, has the same softness and flexibility as a vinyl chloride plastic worm, and has no taste.
It is odorless, can be colored arbitrarily, and has little color loss. Moreover, since it is produced by polymerizing an acrylic acid-based water-soluble monomer, it does not require a large-scale device and has good moldability. Furthermore, the main materials of the molded product of the present invention are a non-toxic acrylic acid polymer and water, and since it does not contain the solvent used in conventional plastic worms, it is used as a pseudo-bait and fish and birds are used. Even if the food is mistakenly eaten, the risk of death is expected to be greatly reduced, and there is no problem of solvent odor. Further, since the molded product of the present invention does not contain a plasticizer such as phthalic acid esters and chlorine-based organic compounds used in conventional plastic worms, there is no problem of environmental hormones, and further harmful substances such as dioxins during incineration. Does not occur. Further, the molded article of the present invention has high adhesiveness, elasticity, flexibility, and stretchability,
The flexibility when the joint is bent (the degree of elongation when applied to the same part) is good, and the water content is high, so
A cooling sheet using this is not only applied to the forehead when heat is generated, but also cools the hot flashes of the eyes, jaws, legs, feet, etc., an emergency coolant for bruising and spraining, and analgesia for muscle aches. -It is useful as a sedative adjunct and for cooling down muscles after sports. It is also useful in that it can be used immediately without any hassle and can be used in a disposable manner.

Claims (9)

[Claims] 1. A molded article made of an acrylic acid-based polymer having a crosslinked structure. 2. The molded article according to claim 1, wherein the acrylic acid-based polymer having a crosslinked structure is polyacrylic acid or a metal salt thereof. 3. The molded product according to claim 1, wherein the acrylic acid-based polymer having a crosslinked structure is water-insoluble. 4. The molded product according to claim 1, wherein the crosslinked structure is formed by a crosslinking agent having an unsaturated bond. 5. The molded product according to claim 1, which is a hydrous molded product. 6. The moisture content is 50 relative to the weight of the entire molded body.
The molded product according to claim 5, which is about 90% by weight. 7. The molded article according to claim 1, which is obtained by placing an aqueous solution containing acrylic acid or a metal salt thereof and a cross-linking agent in a molding die, and then polymerizing the solution. 8. The molded product according to claim 7, wherein the content of acrylic acid or its metal salt in the aqueous solution is 10 to 50% by weight. 9. An article comprising the molded article according to any one of claims 1 to 8.