JP5658539B2 - Water-containing particles, production method and use thereof - Google Patents

Description

  The present invention relates to water-containing particles, a production method thereof, and uses.

Thermally expandable microcapsules having a structure in which a thermoplastic resin is used as an outer shell and low-boiling hydrocarbons such as pentane and hexane are encapsulated as foaming agents have been known for a long time (see Patent Document 1). These thermally expandable microcapsules have high flammability due to the low-boiling hydrocarbons of the foaming agents, and need to be handled with care. Further, when the thermally expandable microcapsule expands, since low boiling point hydrocarbons may permeate the outer shell and leak out, there is a concern about air pollution.
Recently, a thermally expanded microsphere (see Patent Document 2) composed of a core portion made of an absorbent resin containing water as a foaming agent and a shell made of a thermoplastic resin has been developed. However, in this thermally expanded microsphere, since water easily permeates the thermoplastic resin, there is a problem that the encapsulated water is difficult to be retained and escapes before being heated and expanded.

US Pat. No. 3,615,972 JP 2009-67898 A

  An object of the present invention is to provide water-containing particles that have low flammability and can suppress the volatilization of water acting as a foaming agent even when stored for a long period of time, and can reduce the weight of the substrate, and a method for producing the same It is to be.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be achieved by forming a crosslinked layer containing a metal by surface-treating the surface of an absorbent resin containing water. The headline, the present invention has been reached.
That is, the water-containing particles according to the present invention are composed of a core part made of a water-absorbing resin containing water and a cross-linked layer containing a metal that covers the core part. This crosslinked layer is a layer derived from a water-soluble organic compound containing a metal.

It is preferable that the water-containing particles satisfy at least one of the following requirements (1) to (4).
(1) The metal belongs to Groups 3-14 of the periodic table.
(2) The core portion is made of a water-absorbing resin obtained by polymerizing a polymerizable component having a carboxyl group-containing monomer as an essential component, and the crosslinked layer contains the water-soluble organic compound containing the metal and the carboxyl group. It is a layer formed by the reaction of
(3) The weight ratio of the metal is 0.05 to 15% by weight with respect to the weight of the dry particles of the water-containing particles.
(4) The water content is 5 to 50% by weight of the whole particles.

The manufacturing method of the water inclusion particle | grains concerning this invention is a manufacturing method including the process B which surface-treats the raw material particle which consists of a water-absorbing resin containing water with the water-soluble organic compound containing a metal.
It is preferable that this method for producing water-containing particles satisfies at least one of the following requirements (A) to (E).

(A) The water-absorbing resin is a resin obtained by polymerizing a polymerizable component having a carboxyl group-containing monomer as an essential component.
(B) The metal belongs to Groups 3-14 of the periodic table.
(C) The water-soluble organic compound containing the metal is a compound having at least one bond represented by the following general formula (1) and / or a metal amino acid compound.
M-O-C (1)
(However, M is a metal atom belonging to groups 3 to 14 of the periodic table, carbon atom C is bonded to oxygen atom O, and other than oxygen atom O, only hydrogen atom and / or carbon atom are bonded.)
(D) The step B is performed in water.
(E) Prior to the step B, the step A for producing raw material particles is performed by polymerizing a polymerizable component essentially containing a carboxyl group-containing monomer.
The composition of the present invention is a composition comprising the water-containing particles and / or the water-containing particles obtained by the production method and a base material component.
The molded product of the present invention is a molded product obtained by molding the above composition.

The water-containing particles of the present invention have low flammability, and the volatilization of water acting as a foaming agent is suppressed even when stored for a long period of time, so that the weight of the substrate can be reduced.
The method for producing water-containing particles of the present invention can efficiently produce the water-containing particles.

Since the composition of the present invention contains the above-mentioned water-containing particles, the flammability is low, and the volatilization of water acting as a foaming agent is suppressed even when stored for a long period of time, thereby reducing the weight of the substrate. it can.
Since the molded product of the present invention is obtained by molding the above composition, it is highly safe and lightweight during production.

It is a schematic diagram showing an example of water inclusion particles. It is a graph which shows the relationship between the molding temperature and true specific gravity of the foam sheet of Examples 1-5 and Comparative Example 1. It is a graph which shows the relationship between the molding temperature and true specific gravity of the foam sheet of Example 3, Example 6, and Comparative Example 1.

[Method for producing water-containing particles]
The manufacturing method of the water inclusion particle | grains of this invention is a manufacturing method including the process B which surface-treats the raw material particle | grains which consist of a water-absorbing resin containing water with the water-soluble organic compound containing a metal. Hereinafter, for the sake of simplicity, “a water-soluble organic compound containing a metal” may be referred to as “a metal-containing water-soluble organic compound”.
Prior to Step B, the method for producing water-encapsulated particles of the present invention further comprises Step A for producing raw material particles by polymerizing a polymerizable component essentially comprising a carboxyl group-containing monomer. May be.

(Process A)
Step A is a step of producing raw material particles by polymerizing a polymerizable component.
The polymerizable component requires a carboxyl group-containing monomer. The carboxyl group-containing monomer is not particularly limited as long as it has one or more free carboxyl groups per molecule. For example, unsaturated monomers such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, cinnamic acid, etc. Monocarboxylic acid; unsaturated dicarboxylic acid such as maleic acid, itaconic acid, fumaric acid, citraconic acid, chloromaleic acid; anhydride of unsaturated dicarboxylic acid; monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, And unsaturated dicarboxylic acid monoesters such as monoethyl fumarate, monomethyl itaconate, monoethyl itaconate and monobutyl itaconate. These carboxyl group-containing monomers may be used alone or in combination of two or more. In the carboxyl group-containing monomer, some or all of the carboxyl groups may be neutralized during polymerization. Among the above carboxyl group-containing monomers, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and itaconic acid are preferred, acrylic acid and methacrylic acid are more preferred, and methacrylic acid is particularly preferred.

The weight ratio of the carboxyl group-containing monomer in the polymerizable component is preferably 10 from the viewpoint of sufficiently retaining water and suppressing volatilization and high reactivity with the metal-containing water-soluble organic compound used in Step B. % By weight or more, more preferably 30% by weight or more, further preferably 50% by weight or more, and particularly preferably 80% by weight or more. The upper limit of the weight ratio of the carboxyl group-containing monomer is 100% by weight. When the weight ratio of the carboxyl group-containing monomer is less than 10% by weight, sufficient retention of water and the effect of suppressing volatilization thereof may not be sufficiently obtained.
The polymerizable component may include a carboxyl group-containing monomer as an essential component, and one or more other monomer components may be used in combination. Other monomer components are not particularly limited. For example, nitrile monomers such as acrylonitrile, methacrylonitrile, and fumaronitrile; vinyl halide monomers such as vinyl chloride; halogenation such as vinylidene chloride Vinylidene monomers; vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl butyrate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc. (Meta) Acu Luric acid ester monomers; (meth) acrylamide monomers such as acrylamide, substituted acrylamide, methacrylamide, and substituted methacrylamide; maleimide monomers such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, α -Styrene monomers such as methyl styrene; Ethylene unsaturated mono-olefin monomers such as ethylene, propylene and isobutylene; Vinyl ether monomers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl methyl ketone Examples thereof include vinyl ketone monomers such as N-vinyl carbazole, N-vinyl monomers such as N-vinyl pyrrolidone, and vinyl naphthalene salts. In addition, (meth) acryl means acryl or methacryl.

The polymerizable component may contain a polymerizable monomer (crosslinking agent) having two or more polymerizable double bonds in addition to the carboxyl group-containing monomer and other monomer components described above. By polymerizing using a cross-linking agent, a three-dimensional network structure can be formed and sufficient retention of water can be enhanced.
Although it does not specifically limit as a crosslinking agent, For example, aromatic divinyl compounds, such as divinylbenzene; Allyl methacrylate, triacryl formal, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, PEG # 200 di (meth) acrylate, PEG # 600 di (meth) acrylate, trimethylolpropane trimethacrylate, pentaerythrul Examples include di (meth) acrylate compounds such as tall tri (meth) acrylate, dipentaerythritol hexaacrylate, and 2-butyl-2-ethyl-1,3-propanediol diacrylate. These crosslinking agents may be used alone or in combination of two or more.

The amount of the crosslinking agent is not particularly limited. However, if the weight ratio of the crosslinking agent is small, the crosslinking density of the water-absorbent resin is lowered, and the three-dimensional network formed by the crosslinking is increased. Will increase. However, from the viewpoint that the gel strength cannot be maintained if the weight ratio of the crosslinking agent is too small, the weight ratio of the crosslinking agent in the polymerizable component is preferably 0.01 to 5% by weight, more preferably 0.1%. ˜2% by weight, particularly preferably 0.2 to 1% by weight.
In step A, it is preferable to polymerize the polymerizable component in the presence of a polymerization initiator. Although there is no limitation in particular as a polymerization initiator, A peroxide, an azo compound, etc. can be mentioned.

Examples of the peroxide include diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-octyl peroxydicarbonate, and dibenzyl peroxydicarbonate. Peroxydicarbonates such as t-butyl peroxypivalate, t-hexyl peroxypivalate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-butylperoxy 3,5,5-trimethyl Examples thereof include peroxyesters such as hexanoate; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide.
Examples of the azo compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4- Dimethylvaleronitrile), 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), and the like. Among the polymerization initiators, peroxydicarbonate is preferable.

These polymerization initiators may be used alone or in combination of two or more. As the polymerization initiator, an oil-soluble polymerization initiator that is soluble in the polymerizable component is preferable.
Although there is no limitation in particular about the quantity of a polymerization initiator, it is preferable in it being 0.3-8 weight part with respect to 100 weight part of said polymeric components.

In step A, polymerization may be performed in the presence of a chain transfer agent or the like.
In step A, polymerization is usually performed in an aqueous dispersion medium. By dispersing a polymerizable component or the like in an aqueous dispersion medium, forming fine droplets containing the polymerizable component, and polymerizing the particles, it is possible to efficiently produce particulate raw material particles.

The aqueous dispersion medium is a medium mainly composed of water such as ion-exchanged water, and may further contain an alcohol such as methanol, ethanol or propanol, or a hydrophilic organic solvent such as acetone. The aqueous dispersion medium may further contain an electrolyte. Examples of the electrolyte include sodium chloride, magnesium chloride, calcium chloride, sodium sulfate, magnesium sulfate, ammonium sulfate, and sodium carbonate. These electrolytes may be used alone or in combination of two or more. Although there is no limitation in particular about content of an electrolyte, it is preferable to contain 0.1-50 weight part with respect to 100 weight part of aqueous dispersion media.
An aqueous dispersion medium is a water-soluble 1,1-substituted compound having a structure in which a hydrophilic functional group selected from a hydroxyl group, a carboxylic acid (salt) group, and a phosphonic acid (salt) group and a hetero atom are bonded to the same carbon atom , Potassium dichromate, alkali metal nitrite, metal (III) halide, boric acid, water-soluble ascorbic acids, water-soluble polyphenols, water-soluble vitamin Bs and water-soluble phosphonic acids (salts) It may contain at least one water-soluble compound. In addition, the water solubility in this invention means the state which melt | dissolves 1g or more per 100g of water.

The amount of the water-soluble compound contained in the aqueous dispersion medium is not particularly limited, but is preferably 0.0001 to 1.0 part by weight, more preferably 0.0003 to 100 parts by weight of the polymerizable component. 0.1 parts by weight, particularly preferably 0.001 to 0.05 parts by weight. If the amount of the water-soluble compound is too small, the polymerization inhibitory effect of the polymerizable component eluted in the aqueous dispersion medium may not be sufficiently obtained. On the other hand, when the amount of the water-soluble compound is too large, the polymerization rate may decrease, and the residual amount of the polymerizable component as a raw material may increase.
The aqueous dispersion medium may contain a dispersion stabilizer and a dispersion stabilization auxiliary agent in addition to the electrolyte and the water-soluble compound.

The dispersion stabilizer is not particularly limited, and examples thereof include tricalcium phosphate, magnesium pyrophosphate, calcium pyrophosphate obtained by a metathesis generation method, colloidal silica, alumina sol, and the like. These dispersion stabilizers may be used alone or in combination of two or more.
The blending amount of the dispersion stabilizer is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymerizable component.

The dispersion stabilizing aid is not particularly limited, and examples thereof include a polymer type dispersion stabilizing aid, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant. Mention may be made of activators. These dispersion stabilizing aids may be used alone or in combination of two or more.
The aqueous dispersion medium is prepared, for example, by blending water (ion-exchanged water) with a water-soluble compound and, if necessary, a dispersion stabilizer and / or a dispersion stabilizing aid. The pH of the aqueous dispersion medium at the time of polymerization is appropriately determined depending on the type of water-soluble compound, dispersion stabilizer, and dispersion stabilization aid.

In step A, polymerization may be performed in the presence of sodium hydroxide and zinc chloride.
In step A, the oily mixture is emulsified and dispersed in an aqueous dispersion medium so that spherical oil droplets having a predetermined particle diameter are prepared.

Examples of the method for emulsifying and dispersing the oily mixture include, for example, a method of stirring with a homomixer (for example, manufactured by Tokushu Kika Kogyo Co., Ltd.) and the like, and a static dispersion device such as a static mixer (for example, manufactured by Noritake Engineering Co., Ltd.). And general dispersion methods such as a method using a film, a membrane emulsification method, and an ultrasonic dispersion method.
Next, suspension polymerization is started by heating the dispersion in which the oily mixture is dispersed as spherical oil droplets in the aqueous dispersion medium.
During the polymerization reaction, it is preferable to stir the dispersion, and the stirring may be performed so gently as to prevent, for example, the floating of the monomer and the precipitation of the raw material particles after the polymerization.

  Although superposition | polymerization temperature is freely set by the kind of polymerization initiator, Preferably it is 30-100 degreeC, More preferably, it controls in the range of 40-90 degreeC. The time for maintaining the reaction temperature is preferably about 0.1 to 20 hours.

(Process B)
Step B is a step of surface-treating the raw material particles with a metal-containing water-soluble organic compound. By the surface treatment, a crosslinked layer is formed of the metal-containing water-soluble organic compound on the surface of the raw material particles. Here, the term “crosslinking” means that the surface treatment forms a bond (so-called crosslink) so that the carboxyl group of the raw material particles and the metal of the metal-containing water-soluble organic compound are bridged.
The raw material particles used in Step B are made of a water-absorbing resin containing water. This water-absorbing resin is preferably a resin obtained by polymerizing a polymerizable component essentially containing a carboxyl group-containing monomer. In addition, about the polymerizable component which makes a carboxyl group-containing monomer essential, it is as having already demonstrated above. Some or all of the carboxyl groups of the raw material particles may be neutralized with an alkaline substance or the like.

The average particle diameter of the raw material particles is not particularly limited, but is preferably 1 to 100 μm, more preferably 2 to 80 μm, still more preferably 3 to 60 μm, and particularly preferably 5 to 50 μm. When the average particle diameter is more than 100 μm, the strength of a molded product obtained by molding a composition containing a base material and water-containing particles may be lowered. On the other hand, when the average particle size is less than 1 μm, the surface area of the water-containing particles obtained is increased, so that the long-term water retention may be reduced, and the composition containing the base material and the water-containing particles The dispersibility of water-containing particles in the product may be reduced.
As the raw material particles, those produced through the step A are preferable because the average particle diameter can be easily adjusted. However, the production method of the raw material particles is not limited to the above step A. In addition to the above step A, for example, known polymerization methods such as solution polymerization, emulsion polymerization, dispersion polymerization, and carboxyl group-containing It can also be obtained by a production method or the like in which a water-absorbent resin cross-linked product obtained by polymerizing a polymerizable component having an essential monomer is made into particles with an apparatus such as a jet mill.

The metal-containing water-soluble organic compound is a water-soluble organic compound containing at least one metal, and preferably dissolves 1 g or more per 100 g of water.
The metal contained in the metal-containing water-soluble organic compound is not particularly limited as long as it is a metal belonging to Groups 3 to 14 of the periodic table. For example, Group 3 metals such as scandium, ytterbium, and cerium; 4 such as titanium, zirconium, and hafnium Group metals: Group 5 metals such as vanadium, niobium and tantalum; Group 6 metals such as chromium, molybdenum and tungsten; Group 7 metals such as manganese and rhenium; Group 8 metals such as iron, ruthenium and osmium; Cobalt and rhodium Group 9 metals; Group 10 metals such as nickel and palladium; Group 11 metals such as copper, silver and gold; Group 12 metals such as zinc and cadmium; Group 13 metals such as aluminum and gallium; Group 14 metals such as tin and lead Etc. These metals may be used alone or in combination of two or more. The above metal classification is “Chemical and Education” published by the Chemical Society of Japan, Volume 54, No. 4 (2006), and the “Periodic Table of Elements (2005)” (2006 The Chemical Society of Japan atomic weight) Subcommittee).

Among these metals, metals belonging to Group 3-12 are preferable, transition metals (metals belonging to Group 3-11) are more preferable, and metals belonging to Group 4-5 are particularly preferable.
Examples of transition metals include scandium, ytterbium, cerium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, nickel, palladium, copper , Silver, gold and the like. Among them, transition metals belonging to 4 to 5 periods of the periodic table such as scandium, ytterbium, zirconium, titanium, vanadium, niobium, chromium, molybdenum, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, and silver are preferable. Titanium, zirconium, vanadium, and the like are more preferable because volatilization of water is sufficiently suppressed.

The valence number of the metal is not particularly limited, but is preferably 2 to 5 valence, more preferably 3 to 5 valence, and particularly preferably 4 to 5 valence in terms of high crosslinking efficiency per metal atom. . When the valence number is monovalent, the solvent resistance of the water-containing particles may be lowered. On the other hand, if it is 6 or more, the crosslinking efficiency may decrease, which is not preferable.
As a combination of metal species constituting the metal-containing water-soluble organic compound and its valence, zinc (II), cadmium (II), aluminum (III), vanadium (III), ytterbium are used from the viewpoint of improving heat resistance. (III), titanium (IV), zirconium (IV), lead (IV), cerium (IV), vanadium (V), niobium (V), tantalum (V) and the like are preferable.

The metal-containing water-soluble organic compound is preferably a compound having at least one bond represented by the following general formula (1) and / or a metal amino acid compound.
M-O-C (1)
(However, M is a metal atom belonging to groups 3 to 14 of the periodic table, carbon atom C is bonded to oxygen atom O, and other than oxygen atom O, only hydrogen atom and / or carbon atom are bonded.)
First, the compound having at least one bond represented by the general formula (1) will be described in detail.

-Compound having at least one bond represented by the general formula (1)-
The bond between the metal atom and the oxygen atom represented by the general formula (1) (the bond between MO) may be either an ionic bond or a covalent bond (including a coordination bond). preferable.
When the compound having at least one bond represented by the general formula (1) is a compound having a metal-alkoxide bond and / or a metal-aryloxide bond, a high inhibitory effect on water volatilization is imparted to the water-containing particles. can do. Hereinafter, for the sake of simplicity, “metal-alkoxide bond and / or metal-aryl oxide bond” will be referred to as “MO bond”, and “compound having metal-alkoxide bond and / or metal-aryl oxide bond” will be referred to as “ It may be described as “MO compound”.

The MO compound is a compound having at least one metal-alkoxide bond or metal-aryloxide bond. MO compounds include metal-O—C═O bond (metal-acylate bond), metal-OCON bond (metal-carbamate bond), metal = O bond (metal oxy bond), and the following general formula (2) (formula R ¹ and R ² are organic groups which may be the same or different from each other.) Further, it has a bond to a metal which is not an MO bond, such as a metal-acetylacetonate bond shown in the above. You may do it. M represents a metal.

As is apparent from the above, the MO bond and the metal-O—C═O bond (metal-acylate bond) are different concepts, and the metal-O—C═O bond (metal-acylate bond) has an MO. There is no binding.
The MO compound is classified into, for example, the following four compounds (1) to (4).

Compound (1):
Compound (1) is a metal alkoxide and a metal aryloxide, for example, a compound represented by the following chemical formula (A).
M (OR) _n (A)
(However, M represents a metal; n is a valence number of the metal M; R is a hydrocarbon group having 1 to 20 carbon atoms, and each n hydrocarbon group is the same or different. It may be linear, branched or cyclic.)

In compound (1), M (metal) and n (valence number) are as described above.
R may be aliphatic or aromatic, and may be saturated or unsaturated. R may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, allyl, n-decyl, tridecyl, stearyl. Group, an aliphatic hydrocarbon group such as a cyclopentyl group; an aromatic hydrocarbon group such as a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

Examples of the compound (1) include zinc (II) alkoxides such as diethoxyzinc and diisopropoxyzinc; cadmium (II) alkoxides such as cadmium dimethoxide and cadmium diethoxide; aluminum triisopropoxide and aluminum triethoxide Aluminum (III) alkoxides such as vanadium triethoxide, vanadium triisopropoxide, etc .; ytterbium triethoxide, ytterbium triisopropoxide, etc. ytterbium (III) alkoxide; tetramethoxy titanium, tetraethoxy Titanium, tetraisopropoxy titanium, tetra normal propoxy titanium, tetra normal butoxide titanium, tetrakis (2-ethylhexyloxy) titanium, teto Titanium (IV) alkoxide such as phenoxytitanium; zirconium such as tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, tetranormalpropoxyzirconium, tetranormalbutoxyzirconium, tetrakis (2-ethylhexyloxy) zirconium, tetraphenolatozirconium ( IV) Alkoxy; lead (IV) alkoxides such as tetranormal propoxy lead and tetranormal butoxy lead; tetramethoxycerium, tetraethoxycerium, tetraisopropoxycerium, tetranormalpropoxycerium, tetranormalbutoxycerium, tetrakis (2-ethylhexyloxy) ) Cerium (IV) alkoxides such as cerium and tetraphenolate cerium; Niobium (V) alkoxides such as bium pentamethoxide, niobium pentaethoxide, niobium pentaboxide; trimethoxyoxyvanadium, triethoxyoxyvanadium, tri (n-propoxy) oxyvanadium, isopropoxyoxyvanadium, tri (n- Butoxydo) alkoxyoxyvanadium (V) such as oxyvanadium, isobutoxyoxyvanadium; and other metal alkoxides of metals such as tantalum, manganese, cobalt, copper, gallium, and tin.
Among the examples of the metal-containing water-soluble organic compounds described above and below, those having “ ^* ” at the end of the compound name are preferable because of high water solubility.

Compound (2):
The compound (2) is an oligomer or polymer of the compound (1) and is generally obtained by condensing the compound (1). Compound (2) is, for example, a compound represented by the following chemical formula (B). The chemical formula (B) shows a partially hydrolyzed structure.
RO [-M (OR) ₂ O-] _x-1 R (B)
(However, M and R are the same as chemical formula (A); x is an integer of 2 or more.)

The molecular weight of the compound (2) is not particularly limited, but the number average molecular weight is preferably 200 to 5000, particularly preferably 300 to 3000. If the number average molecular weight is less than 200, the crosslinking efficiency may be low. On the other hand, if the number average molecular weight exceeds 5000, it may be difficult to control the degree of crosslinking.
Examples of the compound (2) include titanium alkoxy polymers and titanium alkoxy dimers that satisfy x = 2 to 15 in the chemical formula (B).

Specific examples of the compound (2) include, for example, titanium methoxy polymers such as hexamethyl dititanate and octamethyl trititanate; titanium ethoxy polymers such as hexaethyl dititanate and octaethyl trititanate; hexaisopropyl dititanate and octaisopropyl tritate. Titanium propoxy polymer such as titanate, hexanormal propyl dititanate, octa normal propyl trititanate, etc .; Titanium butoxy polymer such as hexabutyl dititanate, octabutyl trititanate, etc .; Titanium phenoxy polymer such as hexaphenyl dititanate, octaphenyl trititanate; hydroxy titanium stearate (formula: _i-C 3 _{H 7} O _{[Ti (OH) (OCOC 17 H} 35) O ] _{n -i-C} 3 _{H 7)} or the like Al of Kishichitan - acylate polymer; titanium methoxy dimer, titanium ethoxy dimer, titanium butoxy dimer, titanium phenoxy dimer, and titanium alkoxy dimer.

Compound (3):
Compound (3) is a metal chelate compound having an MO bond. In the compound (3), a ligand compound having at least one MO bond and having at least one electron donating group selected from a hydroxyl group, a keto group, a carboxyl group and an amino group is coordinated to M Metal chelate compound. The ligand compound may have at least one electron donating group, but preferably has 2 to 4 electron donating groups. Compound (3) may have a plurality of MO bonds, M, and a ligand compound.
The ligand compound is not particularly limited, and examples thereof include alkanolamines, carboxylic acids, hydroxycarboxylic acids (salts), β-diketones, β-ketoesters, diols and amino acids.

Examples of alkanolamines include ethanolamine, diethanolamine, and triethanolamine.
Examples of carboxylic acids include acetic acid and the like.

Examples of the β-ketoester include ethyl acetoacetate and the like.
Examples of diols include ethylene glycol, diethylene glycol, 3-methyl-1,3-butanediol, triethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, and 1,5-pentanediol. Hexylene glycol, octylene glycol and the like.

Examples of the compound (3) in which the ligand compound is an alkanolamine include, for example, titanium tetrakis (diethanolaminate) ^* , isopropoxytitanium tris (diethanolamate) ^* , diisopropoxytitanium bis (diethanolaminate) ^* , triisopropoxy titanium mono (diethanol aminate) ^*, dibutoxy titanium bis (diethanol aminate) ^*, titanium tetrakis (triethanolaminato) ^*, dimethoxy titanium (triethanolaminate) ^*, diethoxy titanium (triethanolaminate) ^*, isopropoxy titanium tris (triethanolaminate) ^*, diisopropoxy titanium bis (triethanolaminate) ^*, triisopropoxy titanium mono (triethanolaminato Sulfonate) ^*, di -n- butoxy titanium (triethanolaminate) ^* such alkanolamine - alkoxy titanium chelate compound ^*; zirconium tetrakis (diethanol aminate) ^*, isopropoxycarbonyl zirconium tris (diethanol aminate) ^*, diisopropoxy zirconium Bis (diethanolaminate) ^* , triisopropoxyzirconium mono (diethanolamate) ^* , dibutoxyzirconium bis (diethanolamate) ^* , zirconium tetrakis (triethanolaminate) ^* , dimethoxyzirconium bis (triethanolamate) ^* , di Ethoxyzirconium bis (triethanolaminate) ^* , isopropoxyzirconium tris (triethanolaminate) ^*, Diisopropoxy zirconium bis (triethanolaminate) ^*, triisopropoxy zirconium mono (triethanolaminate) ^*, di -n- butoxy zirconium bis (triethanolaminate) ^* such alkanolamine - alkoxy zirconium chelate Compound ^* ; cerium tetrakis (diethanolamate) ^* , isopropoxycerium tris (diethanolamate) ^* , diisopropoxycerium bis (diethanolamate) ^* , triisopropoxycerium mono (diethanolamate) ^* , dibutoxycerium bis (diethanolamate) ) ^*, cerium tetrakis ^{(triethanolaminato) *,} dimethoxy cerium ^{(triethanolaminate) *,} Jietokishise Umubisu (triethanolaminate) ^*, isopropoxycarbonyl cerium tris (triethanolaminate) ^*, diisopropoxy cerium (triethanolaminate) ^*, triisopropoxy cerium mono (triethanolaminate) ^*, di -n - butoxy cerium (triethanolaminate) ^* such alkanolamine - alkoxy cerium chelate compound ^*, lead tetrakis (diethanol aminate) ^*, isopropoxy lead tris (diethanol aminate) ^*, diisopropoxy lead bis (diethanol aminate) ^* , triisopropoxy lead mono (diethanol aminate) ^*, dibutoxy lead bis (diethanol aminate) ^*, lead tetrakis (triethanolaminato) ^*, dimethoxy lead bis (G Aminate) ^*, diethoxy lead bis (triethanolaminate) ^*, isopropoxy lead tris (triethanolaminate) ^*, diisopropoxy lead bis (triethanolaminate) ^*, triisopropoxy lead mono (triethanolamine Aminato) ^* , di-n-butoxy lead bis (triethanolaminate) ^{* and the} like alkanolamine-alkoxy lead chelate compounds ^{* and the} like.

Examples of the compound (3) in which the ligand compound is a hydroxycarboxylic acid (salt) include, for example, titanium lactate ^* , dihydroxytitanium bis (lactate) ^* , dihydroxytitanium bis (lactate) monoammonium salt ^* , dihydroxytitanium bis (lactate) di ammonium salts ^*, dihydroxy titanium bis (glycolate) ^*, hydroxycarboxylic acids, such as titanium lactate ammonium salt (salt) - alkoxy titanium chelate compound ^*; zirconium lactate ^*, monohydroxy zirconium tris (lactate) ^*, dihydroxy zirconium bis (lactate) ^*, dihydroxy zirconium bis (lactate) monoammonium salt ^*, dihydroxy zirconium bis (lactate) diammonium salt ^*, dihydroxy Jill Niumubisu (glycolate) ^*, zirconium lactate ammonium salt hydroxycarboxylic acids such as (salt) - alkoxy zirconium chelate compound ^*; cerium lactate ^*, monohydroxy cerium tris (lactate) ^*, dihydroxy cerium bis (lactate) ^*, dihydroxy cerium bis (Lactate) monoammonium salt ^* , dihydroxycerium bis (lactate) diammonium salt ^* , dihydroxycerium bis (glycolate) ^* , hydroxycarboxylic acid (salt) -alkoxycerium chelate compound ^* such as cerium lactate ammonium salt, lead lactate ^* , monohydroxy lead tris ^{(lactate) *,} dihydroxy lead bis ^{(lactate) *,} dihydroxy lead bis (lactate) monoammonium salt Dihydroxy lead bis (lactate) diammonium salt ^*, dihydroxy lead bis (glycolate) ^*, hydroxycarboxylic acids (salts) such as lead lactate ammonium salt - alkoxy cerium chelate compound ^*, and the like.

Examples of the compound (3) in which the ligand compound is a β-diketone include alkoxy zinc-β-diketone chelate compounds such as zinc acetylacetonate; β-diketone-alkoxyaluminum chelate compounds such as aluminum acetylacetonate; vanadium Β-diketone-alkoxyvanadium chelate compounds such as acetylacetonate; titanium tetrakis (acetylacetonate), dimethoxytitanium bis (acetylacetonate), diethoxytitanium bis (acetylacetonate), diisopropoxytitanium bis (acetylacetate), dinormal Propoxytitanium bis (acetylacetonate), dibutoxytitanium bis (acetylacetonate), titanium tetrakis (2,4-hexanedionate), titanium tetrakis (3,5-he Β-diketone chelate-alkoxytitanium compounds such as Tandionato; dihydroxyzirconium bis (acetylacetonate), zirconium tetrakis (acetylacetonate), tributoxyzirconium mono (acetylacetonate), dibutoxyzirconium bis (acetylacetonate), Β-diketone-alkoxyzirconium chelate compounds such as monobutoxyzirconium tris (acetylacetonate); dihydroxycerium bis (acetylacetonate), cerium tetrakis (acetylacetonate), tributoxycerium mono (acetylacetonate), dibutoxycerium Β-diketone-alkoxycerium chelates such as bis (acetylacetonate) and monobutoxycerium tris (acetylacetonate) Compounds and the like.
Examples of the compound (3) in which the ligand compound is a β-ketoester include β-ketoester-alkoxytitanium chelate compounds such as diisopropoxytitanium bis (ethylacetoacetate); dibutoxyzirconium bis (ethylacetoacetate) and the like Examples include β-ketoester-alkoxyzirconium chelate compounds.

Examples of the compound (3) in which the ligand compound is a β-diketone and β-ketoester include alkoxytitanium-β-diketone and β-ketoester such as monobutoxytitanium mono (acetylacetonate) bis (ethylacetoacetate) Chelate compounds; β-diketones such as monobutoxyzirconium mono (acetylacetonate) bis (ethylacetoacetate) and β-ketoester-alkoxyzirconium chelate compounds; monobutoxycerium mono (acetylacetonate) bis (ethylacetoacetate) Examples include β-diketone and β-ketoester-alkoxycerium chelate compound.
Examples of the compound (3) in which the ligand compound is a diol include alkoxy titanium-diol chelate compounds such as dioctyloxy titanium bis (octylene glycolate).
The compound (3) may be a metal chelate compound in which the ligand compound is coordinated to a metal atom such as tantalum, manganese, cobalt, copper, or the like, or a derivative thereof.

Compound (4):
The compound (4) is a compound having at least one MO bond and metal-acylate bond.
Compound (4) is, for example, a compound represented by the following chemical formula (C).
M (OCOR ¹ ) _nm (OR) _m (C)
(However, M, n, and R are the same as chemical formula (A); R ¹ may be the same as or different from R; m is a positive that satisfies 1 ≦ m ≦ (n−1). (It is an integer.)

The compound (4) may be obtained by condensing the compound represented by the chemical formula (C).
Examples of the compound (4) include alkoxytitanium-acylate compounds such as tributoxyzirconium monostearate; alkoxyzirconium-acylate compounds such as tributoxyzirconium monostearate; alkoxycerium-acylate compounds such as tributoxycerium monostearate Etc.

-Metal amino acid compounds-
The metal-containing water-soluble organic compound may be a metal amino acid compound. The metal amino acid compound is an amino acid chelate metal compound obtained by a reaction between a metal salt belonging to Groups 3 to 14 of the periodic table and amino acids shown below.
Amino acids include not only amino acids having an amino group (—NH ₂ ) and a carboxyl group (—COOH) in the same molecule, but also iminos such as proline and hydroxyproline having an imino group (—NH) instead of an amino group. Also includes acids. The amino acid is usually an α-amino acid, but may be a β, γ, δ or ω-amino acid.

Amino acids include amino acid derivatives such as those in which one or two hydrogen atoms of the amino group of the amino acid are substituted, and complexes chelated with nitrogen of the amino acid amino group and oxygen of the carboxyl group.
The pKa of amino acids is preferably 1-7.

Examples of amino acids include dihydroxymethyl glycine, dihydroxyethyl glycine, dihydroxypropyl glycine, dihydroxybutyl glycine, glycine, alanine, valine, leucine, isoleucine, serine, histidine, threonine, glycylglycine, 1-aminocyclopropane carboxylic acid 1-aminocyclohexanecarboxylic acid, 2-aminocyclohexanehydrocarboxylic acid, and the like. Among these, dihydroxyethyl glycine, glycine, serine, threonine, and glycylglycine are preferable from the viewpoint of crosslinking efficiency.
As a metal salt belonging to Groups 3 to 14 of the periodic table that reacts with the amino acids, basic zirconyl chloride is preferable. As a commercial item of a metal amino acid compound, for example, ORGATICS ZB-126 ^* (manufactured by Matsumoto Pharmaceutical Co., Ltd.) and the like can be mentioned.

Among the above-mentioned metal-containing water-soluble organic compounds, when diisopropoxy titanium bis (triethanolaminate) ^* , titanium lactate ^* , titanium lactate ammonium salt ^* , basic zirconyl chloride ^*, etc., water volatilization is sufficiently suppressed, It is preferable because it is easy to handle.
In step B, the molar ratio of the metal-containing water-soluble organic compound (number of moles of metal-containing water-soluble organic compound / number of moles of carboxyl groups (including carboxylate groups) contained in the raw material particles) is not particularly limited. , Preferably 0.001 to 0.5, more preferably 0.002 to 0.4, still more preferably 0.003 to 0.3, particularly preferably 0.004 to 0.2, most preferably 0.005. ~ 0.1. If the molar ratio of the metal-containing water-soluble organic compound is less than 0.001, volatilization of water may not be sufficiently suppressed, and it may be difficult to reduce the weight of the substrate. On the other hand, when the molar ratio of the metal-containing water-soluble organic compound is more than 0.5, the cross-linked layer may be formed unevenly or aggregates may be formed by the surface treatment, resulting in poor dispersibility in the substrate. It may be difficult to reduce the weight.
The step B is not particularly limited as long as it is a step of bringing the raw material particles and the metal-containing water-soluble organic compound into contact with each other and performing a surface treatment to form a crosslinked layer on the surface thereof. In particular, it is preferable to prepare a dispersion mixture containing raw material particles, a metal-containing water-soluble organic compound and the above-mentioned aqueous dispersion medium, and perform surface treatment. This dispersion mixture is preferably prepared, for example, by mixing a metal-containing water-soluble organic compound with a polymerization dispersion obtained after the polymerization in Step A, in which raw material particles are dispersed in an aqueous dispersion medium.

When Step B is performed in an aqueous dispersion medium, the weight ratio of the raw material particles to the dispersion mixture containing the raw material particles, the metal-containing water-soluble organic compound and the aqueous dispersion medium is not particularly limited, but preferably 0.5 to 50 weights. %, More preferably 3 to 40% by weight, still more preferably 5 to 35% by weight. On the other hand, when the weight ratio of the raw material particles is less than 0.5% by weight, the efficiency with which the crosslinked layer is formed by the surface treatment may be lowered. On the other hand, if the raw material particle ratio exceeds 50% by weight, the crosslinked layer may be formed unevenly.
The weight ratio of the metal-containing water-soluble organic compound in the dispersion mixture is not particularly limited, but is preferably 0.05 to 20% by weight, more preferably 0 in order to form a crosslinked layer uniformly by the surface treatment. 0.5 to 15% by weight. When the weight ratio of the metal-containing water-soluble organic compound is less than 0.05% by weight, the formation efficiency of the crosslinked layer by the surface treatment may be lowered. On the other hand, when the weight ratio of the metal-containing water-soluble organic compound exceeds 20% by weight, the crosslinked layer is formed unevenly or aggregates are formed.

Step B is preferably performed subsequent to Step A, that is, the metal-containing water-soluble organic compound is added to the polymerization solution obtained in Step A to form a dispersion mixture, and Step B is performed to produce water-containing particles. In addition, since Step B is performed in an aqueous dispersion medium, the metal-containing water-soluble organic compound is preferably highly water-soluble in order to increase the efficiency of forming a crosslinked layer on the surface of the raw material particles.
Step B may be performed by a method other than that described above. For example, a method of forming a crosslinked layer on the surface of wetted raw material particles (wet cake-like raw material particles) can be exemplified. This method includes, for example, raw material particles, a metal-containing water-soluble organic compound and an aqueous dispersion medium (uniformly), and the weight ratio of the raw material particles is preferably 50% by weight or more, more preferably 60% by weight or more. Particularly preferred is a method in which a mixture of 70% by weight or more is prepared and water-containing particles are obtained by removing the aqueous dispersion medium by performing operations such as air drying and drying under reduced pressure.

Although there is no limitation in particular about the processing temperature in the process B, Preferably it is 30-180 degreeC, More preferably, it is 40-150 degreeC, Most preferably, it is the range of 50-120 degreeC. The time for maintaining this treatment temperature is preferably about 0.1 to 20 hours.
Although there is no limitation in particular about the pressure in process B, it is 0-5.0 Mpa by gauge pressure from a viewpoint of suppressing evaporation of water, More preferably, it is 0.1-3.0 Mpa, Most preferably, it is 0.2-2. The range is 0 MPa.
In step B, usually, after the operations such as suction filtration, centrifugal separation, and centrifugal filtration, the water-containing particles having a crosslinked layer formed on the surface thereof are separated from the aqueous dispersion medium to obtain water-containing particles.

[Water-containing particles and their use]
Hereinafter, the water-containing particles and their uses will be described in detail.
For example, as shown in FIG. 1, the water-containing particles of the present invention include a core portion 1 and a crosslinked layer 2 that covers the core portion 1 and contains a metal. The metal is usually contained in a state where an ionic bond or a covalent bond (including a coordination bond) is formed. Further, the metal is preferably contained in the crosslinked layer 2 in the state of 2 to 5 valent metal ions and not in the 0 valence simple substance state. The core part 1 is composed of a water-absorbing resin containing water, and is preferably obtained by polymerizing a polymerizable component essentially containing a carboxyl group-containing monomer. The crosslinked layer 2 is preferably a layer formed by a reaction between a metal-containing water-soluble organic compound and the carboxyl group.

The structure of the water-encapsulated particles of the present invention is not much different in appearance, except for the crosslinked layer 2, as compared with the structure of the raw material particles described above. However, the physical properties may vary greatly.
The water-containing particles of the present invention can be produced by, for example, a production method including the step B described above (preferably a production method including the step A and the step B), but is not limited to these production methods. Matters that have already been described in the above production method and that also relate to the description of the water-containing particles and the application may not be specifically described below in order to avoid redundancy. In that case, the description of the manufacturing method is incorporated as it is.

The weight ratio of the metal to the weight of the dry particles of the water-containing particles is preferably 0.05 to 15% by weight, more preferably 0.5 to 14% by weight, and still more preferably 1.5 to 10% by weight. If the weight ratio of the metal is less than 0.05% by weight, suppression of water volatilization may be insufficient. On the other hand, if the weight ratio of the metal exceeds 15% by weight, the water content of the water-containing particles may be lowered. Here, the dry particles are particles obtained by drying the water-containing particles at an environmental temperature of 80 ° C. for 48 hours.
The detailed description of the metal contained in the water-containing particles is the same as the description of the metal constituting the metal-containing water-soluble organic compound. Among metals belonging to Groups 3-14 of the periodic table, metals belonging to Groups 3-12 are preferred, transition metals (metals belonging to Groups 3-11) are more preferred, and metals belonging to Groups 4-5 are particularly preferred.

Although there is no limitation in particular about the water content of the water inclusion particle | grains, Preferably it is 5 to 50 weight% of the whole particle | grain, More preferably, it is 10 to 30 weight%, Especially preferably, it is 20 to 30 weight%. If the water content of the water-containing particles is less than 5% by weight, the substrate may not be sufficiently lightened. On the other hand, when the water content of the water-containing particles exceeds 50% by weight, the dispersibility in the base material can be reduced and the base material can be reduced in weight, but the strength may be reduced.
The average particle size of the water-containing particles is not particularly limited, but is preferably 1 to 100 μm, more preferably 2 to 80 μm, still more preferably 3 to 60 μm, and particularly preferably 5 to 50 μm. When the average particle diameter is more than 100 μm, the strength of a molded product obtained by molding a composition containing a base material and water-containing particles may be lowered. On the other hand, when the average particle size is less than 1 μm, the surface area of the water-containing particles obtained is increased, so that the long-term water retention may be reduced, and the composition containing the base material and the water-containing particles The dispersibility of water-containing particles in the product may be reduced.

The composition of this invention contains the water inclusion particle | grains obtained by the water inclusion particle | grains of this invention and / or the manufacturing method of the water inclusion particle | grains of this invention, and a base material component.
The base material component is not particularly limited. For example, rubbers such as natural rubber, butyl rubber, silicon rubber, ethylene-propylene-diene rubber (EPDM); thermosetting resins such as epoxy resin and phenol resin; polyethylene wax, paraffin Waxes such as wax; ethylene-vinyl acetate copolymer (EVA), polyethylene, polypropylene, polyvinyl chloride (PVC), acrylic resin, thermoplastic polyurethane, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene- Styrene copolymer (ABS resin), polystyrene (PS), polyamide resin (nylon 6, nylon 66, etc.), polycarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacetal (POM) Thermoplastic resins such as polyphenylene sulfide (PPS); ionomer resins; thermoplastic elastomers such as olefin elastomers and styrene elastomers; bioplastics such as polylactic acid (PLA), cellulose acetate, PBS, PHA, starch resins; modified silicon -Based, urethane-based, polysulfide-based, acrylic-based, silicon-based, polyisobutylene-based, butyl rubber-based sealing materials; urethane-based, ethylene-vinyl acetate copolymer-based, vinyl chloride-based, acrylic-based coating components; cement and mortar And inorganic materials such as cordierite.
The composition of the present invention can be prepared by mixing these base component and water-containing particles.

Examples of the use of the composition of the present invention include a molding composition, a coating composition, a clay composition, a fiber composition, an adhesive composition, and a powder composition.
In particular, the composition of the present invention contains a compound having a relatively low melting point and a thermoplastic resin (for example, waxes such as polyethylene wax and paraffin wax, ethylene-vinyl acetate co-polymer) as a base component together with water-containing particles. Polymer (EVA), polyethylene, polypropylene, polyvinyl chloride (PVC), acrylic resin, thermoplastic polyurethane, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polystyrene ( PS), polycarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and other thermoplastic resins; ionomer resins; olefin elastomers, styrene elastomers and other thermoplastic elastomers) It can be used as a masterbatch form. In this case, this resin molding masterbatch composition is used for injection molding, extrusion molding, press molding, and the like, and is suitably used for introducing bubbles during resin molding. The resin used at the time of resin molding is not particularly limited as long as it is selected from the above base material components. For example, ethylene-vinyl acetate copolymer (EVA), ionomer resin, polyethylene, polypropylene, polyvinyl chloride (PVC) , Acrylic resin, thermoplastic polyurethane, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polystyrene (PS), polyamide resin (nylon 6, nylon 66, etc.), polycarbonate, Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacetal (POM), polyphenylene sulfide (PPS), olefin elastomer, styrene elastomer, polylactic acid (PLA), cellulose acetate, P S, PHA, starch resins, natural rubber, butyl rubber, silicone rubber, ethylene - propylene - diene rubber (EPDM) or the like, and mixtures thereof and the like. Moreover, you may contain reinforcing fibers, such as glass fiber and carbon fiber.

The molded product of the present invention is obtained by molding this composition. Examples of the molded article of the present invention include molded articles such as molded articles and coating films. In the molded product of the present invention, various physical properties such as lightness, porosity, sound absorption, heat insulation, low thermal conductivity, low dielectric constant, design, impact absorption, and strength are improved.
A ceramic filter or the like can be obtained by further firing a molded product containing an inorganic substance as a base component.

  The molded product of the present invention is reduced in weight as compared with a molded product composed of only the same base material component. This weight reduction is because water in the core of the water-containing particles contained in the composition of the present invention is vaporized during molding and leaks to the outside of the water-containing particles. As a result, the water-containing particles in the base component Since a space is formed around the substrate and the volume is increased, and at the same time, the weight of the water-containing particles is reduced, the molded product is reduced in weight.

  Below, the Example of the water inclusion particle | grains of this invention is described concretely. The present invention is not limited to these examples. In the following Examples and Comparative Examples, “%” means “% by weight” unless otherwise specified.

(Measurement of average particle size)
As a measuring apparatus, a Nikkiso Co., Ltd. microtrack particle size distribution meter (model 9320-HRA) was used, and the D50 value was defined as the average particle diameter of the particles.

[Measurement of water content of water-containing particles]
Using a Karl Fischer moisture meter (MKA-510N type, manufactured by Kyoto Denshi Kogyo Co., Ltd.), the water content of the water-containing particles is adjusted to about 60%, and then left to dry at an environmental temperature of 40 ° C. for 24 hours. The water content of the particles was measured. After the moisture content was measured, the moisture content after one month after the water-containing particles were further left at ambient temperature of 25 ° C. for one month was also measured.

[Measurement of true specific gravity]
The true specific gravity of the sample was measured by the following measurement method using an immersion method (Archimedes method) using distilled water in an atmosphere having an environmental temperature of 25 ° C. and a relative humidity of 50%.
Specifically, the volumetric flask with a capacity of 100 ml was emptied and dried, and the weight of the volumetric flask (WB ₁ ) was weighed. After the weighed volumetric flask was accurately filled with distilled water up to the meniscus, the weight (WB ₂ ) of the volumetric flask filled with 100 ml of distilled water was weighed.
Further, the volumetric flask with a capacity of 100 ml was emptied and dried, and the weight of the volumetric flask (WS ₁ ) was weighed. The weighed volumetric flask was filled with about 50 ml of vinyl chloride resin, and the weight (WS ₂ ) of the volumetric flask filled with the vinyl chloride resin was weighed. Then, the weight (WS ₃ ) after accurately filling the meniscus with distilled water so that bubbles do not enter into the volumetric flask filled with the vinyl chloride resin was weighed. Then, the obtained WB ₁ , WB ₂ , WS ₁ , WS ₂ and WS ₃ were introduced into the following formula, and the true specific gravity (d) of the vinyl chloride resin was calculated.
d = {(WS ₂ −WS ₁ ) × (WB ₂ −WB ₁ ) / 100} / {(WB ₂ −WB ₁ ) − (WS ₃ −WS ₂ )}

Example 1
[Process A]
Dissolve 205 g of sodium chloride in 680 g of ion-exchanged water, then add 4.1 g of polyvinylpyrrolidone, 30 g of colloidal silica which is 20% by weight of silica active ingredient, and 0.5 g of carboxymethylated polyethyleneimine, and use sulfuric acid to adjust the pH to 2. An aqueous dispersion medium was prepared by adjusting to 8 to 3.2.
An oily mixture was prepared by mixing 200 g of methacrylic acid, 2 g of 1,9-nonanediol diacrylate and 14 g of a di-sec-butyl peroxydicarbonate-containing liquid containing 50% of the active ingredient.
The aqueous dispersion medium and the oily mixture were mixed, and the resulting mixture was dispersed by Kleamix (M Technique Co., Ltd.) to prepare a suspension. The suspension was transferred to a 1.5 liter pressurized reactor and purged with nitrogen, then the initial reaction pressure was set to 0.3 MPa, and polymerization was performed at a polymerization temperature of 60 ° C. for 15 hours while stirring at 80 rpm. A polymerization solution containing was obtained.

[Process B]
2 g of titanium lactate having an active ingredient content of 44%, which is a metal-containing water-soluble organic compound, is added to 160 g of the resulting polymer solution, and the mixture is heated at 70 ° C. for 3 hours while stirring at 80 rpm, and the raw material particles are made of metal-containing water-soluble organic compound Was subjected to a surface treatment to form a crosslinked layer on the surface of the raw material particles.
The obtained polymerization solution was suction filtered to remove the water content to about 60% to obtain water-containing particles. Thereafter, the particles were dried at an environmental temperature of 40 ° C. for 24 hours in order to remove moisture on the particle surface, and the water content of the water-containing particles was measured. After the moisture content was measured, the moisture content was also measured after one month after being further left for one month at an environmental temperature of 25 ° C.
The water-containing particles after the water content measurement were dried at an environmental temperature of 80 ° C. for 48 hours to obtain dry particles. The dry particles were subjected to ICP mass spectrometry, and the weight ratio of the metal contained in the dry particles was calculated. These results are shown in Table 1.

[Evaluation of water-containing particles]
A PVC paste made of 900 g of vinyl chloride resin (Bestlit, E-701), 850 g of calcium carbonate (Bikita Flour Chemicals, BF-200), and 1500 g of diisononyl phthalate was prepared. Next, 10 g of water-containing particles were added to 90 g of PVC paste. K was dispersed with homodisper type 2.5 (Primics) at a stirring speed of 700 rpm for 10 minutes, and then applied at a thickness of 0.3 mm to prepare a green sheet. The obtained green sheets were heated for 20 minutes in ovens set to molding temperatures of 110 ° C., 120 ° C. and 130 ° C., respectively, to obtain three foamed sheets, and the true specific gravity of each was measured. Table 1 shows the true specific gravity of the foamed sheet obtained by heating at a molding temperature of 110 ° C., 120 ° C. and 130 ° C. for 20 minutes.
Further, the true specific gravity of the three foam sheets obtained by changing the molding temperature in Example 1 and the molding temperature thereof are plotted, and a graph showing the relationship between the molding temperature and the true specific gravity of the foam sheet is shown in FIG. Shown in In the blank of FIG. 2 and FIG. 3, it measured about the green sheet obtained only from the said PVC paste.

(Examples 2 to 5)
In Example 1, except that the amount of the metal-containing water-soluble organic compound was changed, water-containing particles were obtained in the same manner, the physical properties were evaluated, and the results are shown in Table 1.
Subsequently, each foam sheet was obtained in the same manner as in Example 1, and the true specific gravity was measured. The results are shown in Table 1, FIG. 2 and FIG. 3 as in Example 1.

(Example 6)
In Example 3, except that the type of the metal-containing water-soluble organic compound was changed, water-encapsulated particles were obtained in the same manner, the physical properties were evaluated, and the results are shown in Table 1.
Subsequently, each foam sheet was obtained in the same manner as in Example 1, and the true specific gravity was measured. The results are shown in Table 1 and FIG.

(Comparative Example 1)
Except for not performing Step B, water-containing particles were obtained by the same production method as in Example 1, the physical properties were evaluated, and the results are shown in Table 1.
Subsequently, each foam sheet was obtained in the same manner as in Example 1, and the true specific gravity was measured. The results are shown in Table 1, FIG. 2 and FIG. 3 as in Example 1.

実施例１〜６では、得られる水内包粒子の含水率と１ヶ月後含水率とを比較しても、ほとんど変化しないのに対して、比較例１では１ヶ月後に約３％も低下している。以上から、本発明の水内包粒子では、長期間保管においても発泡剤として作用する水の揮散が抑制されていることが分かる。

In Examples 1 to 6, the water content of the water-containing particles obtained and the water content after one month were almost unchanged, whereas in Comparative Example 1, the water content decreased by about 3% after one month. Yes. From the above, it can be seen that in the water-containing particles of the present invention, volatilization of water acting as a foaming agent is suppressed even during long-term storage.

1 Core part 2 Cross-linked layer

Claims (11)

A water-soluble organic compound comprising a core part made of a water-absorbing resin containing water and a crosslinked layer covering the core part and containing a metal, wherein the crosslinked layer contains a metal belonging to Group 3-14 of the periodic table Water-containing particles that are derived layers. The core part is made of a water-absorbing resin obtained by polymerizing a polymerizable component having a carboxyl group-containing monomer as an essential component, and the cross-linked layer is formed by a reaction between the water-soluble organic compound containing the metal and the carboxyl group. The water-containing particles according to claim 1, which is a layer to be formed. The water-containing particles according to claim 1 or 2 , wherein a weight ratio of the metal is 0.05 to 15% by weight with respect to a weight of the dry particles of the water-containing particles. The water-containing particles according to any one of claims 1 to 3 , wherein the water content is 5 to 50% by weight of the whole particles. The manufacturing method of the water inclusion particle | grains including the process B which surface-treats the raw material particle | grains which consist of the water absorbing resin containing water with the water-soluble organic compound containing the metal which belongs to the periodic table 3-14 group . The method for producing water-encapsulated particles according to claim 5 , wherein the water-absorbent resin is a resin obtained by polymerizing a polymerizable component having a carboxyl group-containing monomer as an essential component. The water-containing organic compound according to claim 5 or 6, wherein the water-soluble organic compound containing a metal is a compound having at least one bond represented by the following general formula (1) and / or a metal amino acid compound. .
M-O-C (1)
(However, M is a metal atom belonging to groups 3 to 14 of the periodic table, carbon atom C is bonded to oxygen atom O, and other than oxygen atom O, only hydrogen atom and / or carbon atom are bonded.) Performing the step B in water, method of producing a water-containing particles according to any one of claims 5-7. Prior to the step B, the water-containing particles according to any one of claims 5 to 8 , wherein the step A of producing the raw material particles is performed by polymerizing a polymerizable component essentially containing a carboxyl group-containing monomer. Production method. It comprises water containing particles obtained in claims 1 to water containing particles according to any one of the 4 and / or method of producing a water-containing particles according to any one of claims 5-9, and a base component, composition object. By molding the composition of claim 1 0, moldings.

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