JP2979229B2 - Polymerizable composition, method for producing the same, and cured product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]

INDUSTRIAL APPLICABILITY The present invention is useful for a wide variety of molded articles or structural substrates, and has excellent moldability, and when cured, a polymerizable composition having high impact strength and a desired elastic modulus, a method for producing the same, and a method for producing the same. The present invention relates to a cured product, and further relates to a dental and / or medical cured product, an adhesive composition, and a coating composition using the polymerizable composition.

[Prior art]

In European Patent No. 14,515 or JP-A-55-149,302, an uncrosslinked polymer, a radical polymerizable monomer, a crosslinked polymer expanded by the radical polymerizable monomer by Roemer and Tateosian et al. And a dental composition comprising a cross-linking agent. A molded article having an interpenetrating polymer network structure is obtained by molding the polymerizable composition comprising the four components and then curing the composition by heating or irradiation with electromagnetic waves. It is known to be obtained. However, in the polymerizable compositions, there are many glass transition points as crosslinked polymer particles, and only those that are in a powder state at room temperature can be used. The disadvantage is that low particles are difficult to use. For this reason, the range of physical properties at the time of preparing the molded product is limited, and the application range is narrow. Further, when particles having a high glass transition point are used, there is a problem that a long time is required for swelling with the polymerizable monomer. According to Hourston et al., Journal of Applied Polymer Science, 29
Vol. 2959-2980 (1984), Vol. 34, 1955-1962 (1986), and Vol. 33, pp. 215-225 (1987) disclose formulations of latex interpenetrating polymer network structures. ing. Specifically, the crosslinked polymer particles obtained by emulsion polymerization are impregnated with monofunctional and polyfunctional vinyl polymerizable monomers in the latex, and then polymerized again to form an interpenetrating polymer network inside the latex particles. However, it has been proposed that the particles are separated from the latex, dried, and pressed under heating. In each of the above two techniques, a polymerizable composition or a molded article is obtained by using crosslinked polymer particles obtained in the form of a dry powder. However, also in the above method, a separation operation of the particles is required, and it is difficult to use particles having a low glass transition point. In addition, latex particles produced by emulsion polymerization,
It is necessary to impregnate the polymerizable monomers in an aqueous state, and it is difficult to uniformly absorb the monomers in the particles. Therefore, in the polymer particles obtained by this method, shells formed by polymerizing the second-stage monomer layer with the first-stage particles as nuclei are formed only of core-shell structure type particles that cover the first-stage particles. In fact, the molded article obtained from the particles cannot actually have a uniform interpenetrating polymer network structure. Conventionally, when dentures are used, the gap between the palatal mucosa and the denture base tends to widen with the lapse of time of use, which causes problems such as a decrease in the feeling of use of the denture base and damage to the palate mucous membrane due to the denture base. Therefore, paste-like fillers, which are generally denture fixatives, are commercially available and used. However, the use of these paste-like fillers has disadvantages such as the need for training until uniform filling can be achieved, the necessity of cleaning every day for new replacement, and the need to apply again. is there. Further, in recent years, metal or ceramic artificial joints have been used. For example, slippage between joints is poor, or a hard part hits at the time of bending, so that discomfort is caused. There are drawbacks.

[Problems to be solved by the invention]

An object of the present invention is useful for a wide variety of molded articles or structural base materials, and does not impair the advantages of the interpenetrating polymer network structure, and can freely change the flow characteristics of the system according to the purpose. An object of the present invention is to provide a polymerizable composition having excellent workability and moldability, and having high impact strength and a desired elastic modulus when cured, a method for producing the same, and a cured product thereof. Another object of the present invention is to provide a dental and / or medical cured product, an adhesive composition and a coating composition having the advantages of the polymerizable composition.

[Means for Solving the Problems]

 According to the present invention, (a) a monofunctional reactive compound and / or
Is a solution containing 20 to 99% by weight of a polyfunctional reactive compound,
(B) the average particle size of the glass transition temperature of 80 ° C. or less is 0.
01-1000 μm crosslinked polymer fine particles 1-80% by weight
The relationship between the component (a) and the component (b)
Thus, the equilibrium swelling degree (S¹) Is 2
Polymerization characterized by satisfying the condition of being in the range of ~ 100
A composition is provided.(In equation (1), ρp¹Is the dryness of (b) the crosslinked polymer fine particles.
Indicates the density in the dry state, ηs¹Is the (a) monofunctional
Solution comprising reactive compound and / or polyfunctional reactive compound
And (b) the viscosity of the dispersion of the crosslinked polymer fine particles.
Then ηo¹Represents the (a) monofunctional reactive compound and / or
Shows the viscosity of the solution consisting of the functional reactive compound alone, m¹Is
(A) Monofunctional reactive compound and / or polyfunctional reactive compound
A solution comprising a compound; and (b) the crosslinked polymer fine particles.
Dispersion of 1cm^ThreeSolid content of the (b) crosslinked polymer fine particles in the above
Indicates weight. Also, according to the present invention, (a) a monofunctional reactive compound and
2 or 80% by weight of a solution comprising a polyfunctional reactive compound
And (b) an average particle diameter having a glass transition temperature of 80 ° C. or less.
Is 1 to 80% by weight of the crosslinked polymer fine particles having a particle size of 0.01 to 1000 μm.
(C) reacting with the component (a) to form a three-dimensional network
Polyfunctional reactive oligomer solution forming eye structure 10-80 layers
% And the relationship between the component (a) and the component (b)
In the equation, the equilibrium swelling degree (S¹)of
Satisfies the condition that the value is in the range of 2 to 100, and the
In the relationship between the component (b) and the component (c),
Equilibrium swelling degree (S) expressed by (2)^Two) Is in the range of 1 to 10
A polymerizable composition characterized by satisfying the following conditions is provided.
Provided.(In equation (2), ρp¹Is the dryness of (b) the crosslinked polymer fine particles.
Indicates the density in the dry state, ηs^TwoIs the above-mentioned (b) crosslinked polymer
Fine particles and the (c) polyfunctional reactive oligomer solution
Of the dispersion of ηo^TwoIs the above-mentioned (c) polyfunctional reactivity
Indicates the viscosity of the oligomer solution alone, m^TwoIs the above-mentioned (b) crosslinking
Polymer fine particles and the polyfunctional reactive oligomer solution (c)
Dispersion with liquid 1cm^ThreeOf the crosslinked polymer fine particles (b)
Indicates the form weight. Further, according to the present invention, the polymerizable composition may be used in an amount of from 20 to 160.
Characterized by being cured in the temperature range of ℃
A cured body is provided. Furthermore, according to the present invention, the polymerizable composition is
It is characterized by being cured by irradiation with rugi rays
A cured body is provided. According to the present invention, the polymerizable composition is cured
Provided a medical and dental hardened body characterized in that:
You. Further according to the present invention, the polymerizable composition is an essential component
Is provided. Furthermore, according to the present invention, the polymerizable composition is an essential component.
A coating composition comprising as an ingredient is provided. According to the present invention, in the method for producing a polymerizable composition,
(A) mixing in the step (C) (a) monofunctional reactivity
With a solution consisting of a compound and / or a polyfunctional reactive compound
In relation, the equilibrium swelling degree represented by the above formula (1)
(S¹) Satisfies the range of 2 to 100 and the glass transition temperature
Is 80 ° C. or less, and the average particle diameter is 0.01 to 1000 μm.
Polymer prepared by emulsion polymerization or suspension polymerization
Organic solvent and water-soluble in aqueous dispersion containing fine particles (b)
The crosslinked polymer fine particles (b) are dissolved in an organic solvent by adding a neutral salt.
After the transfer to the drug phase, the organic solvent phase and aqueous solution phase are separated into two layers.
(B) an organic solvent phase containing the crosslinked polymer fine particles (b).
, Add an aqueous solution containing water-soluble salts, stir,
The aqueous phase is removed after the two layers are separated into an organic phase and the organic phase.
The residual moisture in the phase is dehydrated and contains the crosslinked polymer fine particles (b).
And (C) the crosslinked polymer fine particles obtained in the step (B).
In the organic phase containing (b), (a) a monofunctional reactive compound and
And / or mixing components including solutions comprising polyfunctional reactive compounds
After mixing, component (a) 20-99% by weight, component (b) component 1-80
% By weight of the composition.
A manufacturing method is provided. Further according to the present invention, the method for producing the polymerizable composition
(A) mixing in the step (C) (a) monofunctional reactivity
With a solution consisting of a compound and / or a polyfunctional reactive compound
In relation, the equilibrium swelling degree represented by the above formula (1)
(S¹) Satisfies the range of 2 to 100 and the glass transition temperature
Is 80 ° C. or less, and the average particle diameter is 0.01 to 1000 μm.
Polymer prepared by emulsion polymerization or suspension polymerization
Organic solvent and water-soluble in aqueous dispersion containing fine particles (b)
The crosslinked polymer fine particles (b) are dissolved in an organic solvent by adding a neutral salt.
After the transfer to the drug phase, the organic solvent phase and aqueous solution phase are separated into two layers.
(B) an organic solvent phase containing the crosslinked polymer fine particles (b).
, Add an aqueous solution containing water-soluble salts, stir,
The aqueous phase is removed after the two layers are separated into an organic phase and the organic phase.
The residual moisture in the phase is dehydrated and contains the crosslinked polymer fine particles (b).
And (C) the crosslinked polymer fine particles obtained in the step (B).
In the organic phase containing (b), (a) a monofunctional reactive compound and
And / or a solution comprising a polyfunctional reactive compound;
Reacts with the component (a) to form a three-dimensional network structure;
In relation to the component (b), it is represented by the above formula (2).
Equilibrium swelling (S^Two) Is in the range of 1 to 10
The components containing the multifunctional reactive oligomer solution
After that, 2 to 80% by weight of the component (a) and 1 to 80% by weight of the component (b)
%, Component (c) 10 to 80% by weight.
A method for producing a polymerizable composition is provided. Hereinafter, the present invention will be described in more detail. The polymerizable composition of the present invention comprises a monofunctional reactive compound and / or
Or a solution comprising a polyfunctional reactive compound [component (a)]
And specific crosslinked polymer fine particles [component (b)],
Further, if necessary, a specific polyfunctional reactive oligomer solution
It is characterized by containing [(c) component]. In the present invention, the monofunctional reactivity as the component (a) is used.
As the compound and / or polyfunctional reactive compound, for example,
Radical polymerizable resins such as (meth) acrylates
Tylene unsaturated monomers, ionic polymerizable unsaturated monomers,
Addition of oxy group-containing compounds, isocyanate compounds, etc.
Polymerizable compound, alkoxymethylated melamine resin, etc.
Polycondensation compound and addition polymerizable by reacting partner
Hydroxyl-containing compounds and amino-containing compounds
Preferred compounds, carboxylic anhydrides, etc.
And the equilibrium swelling degree (S¹) Is between 2 and 100
It is desirable that the compound has a relatively small molecular weight.
New Specifically, for example, a radical polymerizable unsaturated monomer
As styrene, α-methylstyrene, p-vinyl
Ruene, (meth) acrylonitrile, methyl (meth) a
Acrylate, ethyl (meth) acrylate, n-propyl
(Meth) acrylate, iso-propyl (meth) acryl
Relate, n-butyl (meth) acrylate, iso-butyl
Chill (meth) acrylate, sec-butyl (meth) acryl
, Cyclohexyl (meth) acrylate, benzi
(Meth) acrylate, 2-ethylhexyl (meth)
Acrylate, stearyl (meth) acrylate, (meth
T) fucric acid, 2-hydroxyethyl (meth) acryl
Rate, 2-hydroxypropyl (meth) acrylate
G, methyl-2-cyanoacrylate, ethyl-2-cy
Anoacrylate, n-propyl-2 cyanoacrylate
G, iso-propyl-2-cyanoacrylate, n-butyl
Tyl-2-cyanoacrylate, iso-butyl-2-si
Anoacrylate, divinylbenzene, ethylene glyco
Rudi (meth) acrylate, diethylin glycol di
(Meth) acrylate, triethylene glycol di
TA) acrylate, 1,3-butylene (meth) acryle
1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate, neo
Pentyl glycol di (meth) acrylate, diallyl
Phthalate, allyl (meth) acrylate, 2-hydro
Xy-1,3-di (meth) acryloxypropane, 2,2-bi
[4-((meth) acryloxyethoxy] phenyl]
Propane, trimethylolpropane tri (meth) acryl
Rate, tetramethylolmethane (meth) aclay
Pentaerythritol tri (meth) acrylate,
Dipentaerythritol tri (meth) acrylate,
Nantaerythritol penta (meth) acrylate, dipe
Nantaerythritol hexa (meth) acrylate, tet
Ramethylol methanetetra (meth) arylate, etc.
Can be As the ionic polymerizable unsaturated monomer, radical polymerization
In compatible unsaturated monomers, vinyl groups have large electron-withdrawing properties.
Anionic polymerizable unsaturated monomer to which a suitable substituent is bonded,
Cationic polymerizability with electron-donating functional group bonded to vinyl group
Unsaturated monomer, and methyl vinyl ketone other than the above,
Diethyl nitroethylene methylene malonate, cyanide
Nilidene, isobutyl vinyl ether, N-vinyl carb
Bazol, vinyltrimethylsilyl ether, β-pine
Vinyl group-containing monomers such as
Tons, aldehydes, cycloalkanes, cyclic ethers
And the like. As the epoxy group-containing compound, diglycidyl ether
-Tel, commercial product "ADEKARESIN ED" (trade name, Asahi Denka
Co., Ltd.), "Epototo PG-202", "Epototo PG-207",
"PP-101", "Neo Tote E" (trade name, Toto Kasei
Co., Ltd.), "Epicoat DX-500" (trade name, Yuka Shi
(Product name), "Kajura E-10" (trade name,
Le Chemical Co., Ltd.), “Blemmer DGT” (trade name, Japan
Oil & Fat Co., Ltd.), "PES-10" (trade name, Fuso Chemical Co., Ltd.)
And the like). As the isocyanate compound, p-phenylene
Diisocyanate, biphenyl diisocyanate, tol
Endiisocyanate, 3,3'-dimethyl-4,4'-biph
Phenylene diisocyanate, 1,4-tetramethylenediyl
Socyanate, hexamethylene diisocyanate, 2,2,
4-trimethylhexane-1,6-diisocyanate, methyl
Lenbis (phenyl isocyanate), lysine methyl e
Stels, diisocyanates, bis (isocyanate
F) fumarate, isophorone diisocyanate, methyl
And cyclohexyl diisocyanate.
You. As the alkoxymethylated melanin resin,
Samethoxymethylmelamine, hexa-n-butoxymethi
Lumelamine, hexa-iso-butoxymethylmelamine,
Methoxy-n-butoxy mixed melamine and the like may be mentioned.
it can. Examples of the hydroxyl group-containing compound include 1,4-butanediol.
, 1,3-butylene glycol, ethylene glycol,
Diethylene glycol, triethylene glycol, 1,6
-Hexanediol, decanediol, glycerin,
Chlorohexanedimethanol, trimethylolethane, etc.
Can be mentioned. Examples of the amino group-containing compound include ethylene diamine.
, Hexamethylenediamine, diethylenetriamine,
Triethylenetetramine, 3-diethylaminopropyl
Amine, dibutylaminopropylamine, tetramethyl
Ethylenediamine, 4,9-dioxadodecane-1,12-di
Amine, 4,7,10-trioxatridecane-1,13-diamid
, Commercially available "bis (3-aminopropyl) polytetra
Hydrofuran-750 ”,“ 1100 ”,“ 2100 ”(commercial
(Product name, manufactured by BASF). As the carboxylic anhydride, phthalic anhydride, anhydride
Tetrahydrophthalic acid, hexahydrophthalic anhydride, none
Water methyl nadic acid, dodecenyl succinic anhydride,
Lorendecic acid, trimellitic anhydride, pyromellitic anhydride
Tonic acid and the like, polyamide resin, polysulfur
Fid resin or the like can also be used. In the present invention, in the composition of the component (a),
The content ratio is in the range of 2 to 99% by weight, preferably 5% by weight.
To 90% by weight, more preferably 8 to 80% by weight.
Are combined. (A) When the content of the component is less than 2% by weight
In the polymerizable composition of the present invention, uniform interpenetration
The formation of a polymer network structure becomes impossible, and the desired physical properties
Is not obtained and exceeds 99% by weight, the composition of the present invention
Adjust the physical properties of the cured product obtained from the product to the desired range.
It becomes difficult. In the present invention, in the polymerizable composition component,
Equilibrium swelling (S¹) Satisfy the condition that the value is in the range of 2 to 100.
Need to be When the value of the equilibrium swelling degree is less than 2,
Does not provide a uniform swelling state and
Can not be used because the viscosity of the final composition is too high
No. Where the equilibrium swelling degree (S¹) Is represented by the above formula (1).
And the equilibrium swelling degree (S^Two)
The relationship is expressed by the above equation (2).
Le of Coating Technology (J.Coating.Te
ch.) From page 33 onwards, Volume 52, Issue 669, October (1980)
Can be measured based on the method of measuring the viscosity of
You. Glass transition of crosslinked polymer fine particles as component (b)
The temperature is not higher than 80 ° C, more preferably not higher than 60 ° C.
You. When the glass transition temperature exceeds 80 ° C, the polymerizability of the present invention
Swelled in a mixture of components (a) and (c) of the composition
Because the particles themselves are hard, the viscosity of the composition increases,
Problems with the workability at the time of
I can't do that. Average particle size of the crosslinked polymer fine particles as the component (b)
Is in the range of 0.01 to 1000 μm, more preferably 0.1.
The range is from 04 to 500 μm. Average particle size less than 0.01μm
In this case, use a large amount of emulsifier when synthesizing component (b).
Must be used, and its removal becomes very difficult.
Finally, the emulsifier is mixed into the polymerizable composition of the present invention,
Performance of cured product obtained by curing, such as water resistance and chemical resistance
And causes the component (b) to be significantly reduced.
When converting from an aqueous system to an organic solvent system,
The viscosity of the solvent system increases, which hinders operation. Mean
When the particle size exceeds 1000 μm, the polymerizable composition of the present invention
Interpenetrating polymer networks formed during curing of objects
Is lost, and the desired physical properties cannot be obtained.
There is no problem that a cured product with a smooth appearance cannot be obtained.
You. In the present invention, the specific glass transition temperature and the average grain size
Component (b) having a diameter is at least one or more monofunctional
Radical polymerizable unsaturated monomer, polyfunctional radical polymerizable
Organic peroxides with unsaturated monomer and / or hydrogen abstraction ability
The emulsion polymerization method, soap-free emulsion polymerization method, suspension
It can be obtained by polymerizing by turbid polymerization method
In addition, one or more monofunctional radical polymerizable in advance
Emulsion polymerization, soap-free emulsion polymerization of unsaturated monomers
Polymerized by the suspension and polymerization methods to combine the non-crosslinked polymer particles.
After that, use energy rays such as gamma rays or electron beams.
It can also be obtained by radiation crosslinking.
Wear. Monofunctional radical polymerizable unsaturated compound forming component (b)
As the sum monomer, for example, methyl (meth) acrylate
, Ethyl (meth) acrylate, n-propyl (meth
TA) Acrylate, isopropyl (meth) acrylate
, N-butyl (meth) acrylate, isobutyl (meth)
T) acrylate, t-butyl (meth) acrylate,
n-hexyl (meth) acrylate, cyclohexyl
(Meth) acrylate, 2-ethylhexyl (meth) a
Acrylate, lauryl (meth) acrylate, 2-hydride
Roxyethyl (meth) acrylate, 2-hydroxyp
Ropyl (meth) acrylate, 3-hydroxypropyl
(Meth) acrylate, glycerin (meth) acrylate
G, acetoacetoxyethyl (meth) acrylate, 3
-(Meth) acryloyloxypropylene carbonate,
(Meth) acrylic acid, (meth) acrylamide,
T) Acrylonitrile, vinyl acetate, vinyl propionate
, Vinyl butyrate, vinyl caproate, 2-ethylhexa
Vinyl phosphate, vinyl laurate, vinyl stearate,
Styrene, α-methylstyrene, p-vinyltoluene,
Vinyl chloride, vinylidene chloride, dibutyl fumarate, etc.
When used, one or a mixture of two or more
Can be used as Crosslinking as component (b)
As a method for imparting a crosslinked structure to polymer fine particles,
Radical polymerizable unsaturated monomer is converted to the polyfunctional radical polymer.
There is a method for radical copolymerization with a compatible unsaturated monomer.
You. Examples of the polyfunctional radically polymerizable unsaturated monomer include:
For example, divinylbenzene, diallyl phthalate, diallyl
Terephthalate, ethylin glycol di (meth) acryl
Rate, diethylene glycol di (meth) aclay
G, trimethylene glycol di (meth) acrylate,
Polyethylene di (meth) acrylate, 1,4-butanedi
Alldi (meth) acrylate, 1,3-butylene clicquot
L- (meth) acrylate, 1,6-hexanediol
Di (meth) acrylate, neopentyl alcohol di
(Meth) afrylate, 2-hydroxy-1,3-di (me
) Acryloxypropane, 2,2-bis [4-((me
TA) acryloxyethoxy) phenyl] propane, tri
Methylolpropane tri (meth) acrylate, tetra
Methylol methane tri (meth) acrylate, pentae
Litol tri (meth) dipentaerythritol tri (meth)
Acrylate, pentaerythritol tetra (meth)
Acrylate), dipentaerythritol penta (meth)
Acrylate), dipentaerythritol hexa (meth)
Acrylate), tetramethylolmethanetetra
Ta) acrylate and the like.
It can be used as a species or a mixture of two or more species. Highly produced by the emulsion polymerization or suspension polymerization,
Has the hydrogen abstraction ability for crosslinking molecular microparticles
Organic peroxides include diacyl peroxides,
-Oxyesters, dialkyl peroxides,
-Oxyketals and the like.
Is acetylperoxide as diacyl peroxides
Oxide, isobutyryl peroxide, octanoyl
Peroxide, decanoyl peroxide, lauroy
Luper oxide, 3,5,5-trimethylhexanoylpa
-Oxide, succinic peroxide, benzoylpa
-Oxide, 2,4-dichlorobenzoyl peroxide
And m-toluoyl peroxide.
Wear. As the peroxyesters, t-butyl par
Oxyacetate, t-butyl peroxyisobutyrate
T, t-butyl peroxypivalate, t-butyl per
Oxylodecanoate, cumyl peroxy neodecano
Ethate, t-butylperoxy, 2-ethylhexanoe
Tert-butylperoxy-3,5,5-trimethylhexyl
Sanoate, t-butyl peroxylaurate, t-butyl
Tilperoxybenzoate, di-t-butyl peroxy
Thiophthalate, 2,5-dimethyl-2,5-di (benzoy
Luperoxy) hexane, t-butyl peroxymale
Acid, t-butyl peroxyisopropyl carbonate
G, cumyl peroxy octoate, t-hexyl par
Oxyneodecanoate, t-hexylperoxypivale
, T-butyl peroxyneohexanoate, t-
Hexyl peroxy neohexanoate, cumyl pero
Xineohexanoate and the like can be mentioned. As the dialkyl peroxides, di-t-
Butyl peroxide, t-butylcumyl peroxide
, Dicumyl peroxide, α, α'-bis (t-butyl
Tylperoxy-m-isopropyl) benzene, 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexa
, 2,5-dimethyl-2,5-di (t-butylperoxy)
Hexane-3 and the like can be mentioned. The peroxyketals include 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexyl
Sun, 1,1-bis (t-butylperoxy) cyclohex
Sun, 2,2-bis (t-butylperoxy) octane,
n-butyl-4,4-bis (t-butylperoxy) vale
Rate, 2,2-bis (t-butylperoxy) butane, etc.
Can be mentioned. In the present invention, a monofunctional radically polymerizable unsaturated monomer
To obtain crosslinked polymer fine particles as the component (b).
The polyfunctional radically polymerizable unsaturated monomer and / or
Or, the amount of the organic peroxide or the energy ray is
Moisture (S¹) And the glass transition temperature of the crosslinked polymer particles
It should be determined in consideration of the degree of
After curing the conductive composition, the effect of the interpenetrating polymer network
The amount is sufficient to give the crosslink density sufficient for
It is also necessary to To satisfy these conditions
Is relative to the monofunctional radically polymerizable unsaturated monomer,
0.02 to 10% by weight of a polyfunctional radically polymerizable unsaturated monomer, preferably
More preferably, in the range of 0.05 to 8% by weight,
In the range of 0.5 to 15% by weight, preferably 1 to 10% by weight
And about 0.5 to 10 Mrad for energy rays,
Preferably, all components forming component (b) are in the range of 1 to 7 Mard.
It is preferred to irradiate the polymerizable monomer. these
When the crosslinking means is below the lower limit of the above range, the present invention
Interpenetrating polymer networks when curing polymerizable compositions
Impact strength and elasticity expected from molded products
Physical or physicochemical properties such as coefficients cannot be obtained.
Not good. If the upper limit is exceeded, uniform mutual immersion
No permeable polymer network structure is formed or the equilibrium swelling
Time to reach is very long, workability decreases, etc.
It is not preferable because it causes trouble. In the polymerizable composition of the present invention, the emulsion polymerization method
Water obtained by turbid polymerization or soap-free emulsion polymerization
-Based crosslinked polymer microparticles are prepared according to the method for producing the polymerizable composition described below.
By making it non-aqueous by the method shown in the law,
(B) It can be a component. Polymerizability of the component (b)
The content ratio in the composition is 1 to 80% by weight, preferably
Ranges from 5 to 60% by weight. Content of the component (b)
If the amount is less than 1% by weight,
The effect of the child network structure cannot be obtained, and exceeds 80% by weight.
In some cases, the viscosity of the final composition will be too high to be practical
Therefore, it is necessary to set the above range. In the polymerizable composition of the present invention, (a)
In addition to the component (b), a polyfunctional reactive resin
Add sesame. Component (c), a polyfunctional reactive orifice
Gomer undergoes a polymerization reaction with component (a) to form a three-dimensional network structure.
Component, that is, the polymerizable composition of the present invention and a molded body
Is a component that gives the interpenetrating polymer network structure
And the degree of equilibrium swelling in relation to the component (b)
(S^Two) Is adjusted to an appropriate range, and the polymerizable composition has an appropriate viscosity.
Curing obtained by imparting degree and flow characteristics and effecting polymerization
It is a component that plays a role in adjusting the physical properties of an object. The equilibrium swelling degree (S^Two) Value is in the range of 1 to 10
Needs to be satisfied. At this time, the equilibrium swelling degree (S^Two) Value is 10
If the condition exceeds, the viscosity of the final composition will increase.
Can not be used because it is too much. Examples of the polyfunctional reactive oligomer include epo
Xyprepolymer poly (meth) acrylate, urethane
Poly (meth) acrylate, polyester poly (meth)
Acrylate, commercially available “Aloni” manufactured by Toa Gosei Chemical Co., Ltd.
X (trade name), Showa High Polymer Co., Ltd. "RIPOXY"
(Trade name), Kyoeisha Yushi Co., Ltd. “Light Axle Relay”
To (product name), "Neomer" manufactured by Sanyo Chemical Industries, Ltd.
(Trade name), "KAYARAD" (trade name) manufactured by Nippon Kayaku Co., Ltd.
And other polyfunctional radical polymerizable oligomers;
KAREJIN EP-4100, EP-4000, EPU-
6, "ED-501", "Epiclon 840", "85"
0 "," 830 "," N-660 "," 705 "(product name,
Asahi Denka Co., Ltd.), "Epicoat 801", "Dome 802",
"834-X-90", "RXY-400", "DX-255"
(Trade name, manufactured by Yuka Shell Co., Ltd.), "Epotote YD-11
5, YD-001, YD-8124, YDM-12
0 ”,“ San Thoth ST-1000 ”,“ ST-100 ”,“ Epo
Tote YD-171 ”and“ Tou YU-100 ”(trade name, Toto Kasei
Epoxy-containing compounds such as those manufactured by K.K.
Rex 188-50 "," Flexoritz UD-320 "(product
Name, King Industry Co., Ltd.)
DM-55, Acryloid B-48N, John Krill
−500 ”(trade name, Rohm and Haas Japan
"Super Veccosol EL-8011", "The same EL"
-8001 "," Barnock D-220 "," D-161 "(Product
Name, manufactured by Dainippon Ink and Chemicals, Inc.)
Range 5774 ”,“ 5780 ”(trade name, Cargill
Co., Ltd.), "NIAX Caprolactone Polyol PC
P-0300 ”and“ PCP-0301 ”(brand name, Union Car
Hydroxyl-containing compounds such as Bidet Co .;
IP, isocyanate type, block isocyanate
And Coronate EH,
HL ”,“ DC-2717 ”(trade name, Nippon Polyurethane)
"Sumijur N", "HT", "Desmodi"
N-3390 ”,“ BL-3175 ”(brand name, Sumitomo Buyer
Elurethane Co., Ltd.), "Takenate D-110N",
"D-165N" and "D-170N" (trade name, Takeda Pharmaceutical Co., Ltd.)
Co., Ltd.), "Duranate TPA-100" (trade name, Asahi
Polyvalent isocyanate compounds such as those manufactured by Kasei Kogyo
Preferably, when used, it may be used alone or
Or as a mixture. In the present invention, in the polymerizable composition of the component (c),
The content ratio is in the range of 0 to 80% by weight, and the polymerizable composition
10-80% by weight, preferably 10-60% by weight
Range. (C) When the component exceeds 80% by weight
Provides the viscosity and flow characteristics required for molding the polymerizable composition.
Not adjusted, and when cured, adjust physical properties to desired range
It becomes difficult. The polymerizable composition of the present invention has a fluidity of the system depending on the purpose.
It can be changed freely and has excellent workability
Therefore, in order to change the flow characteristics, the above two or three components are appropriately used.
The ratio can be changed by changing the ratio of
Component (b), which is a crosslinked polymer fine particle in the polymerizable composition,
Reduce the proportion or increase the proportion of component (c)
You can do it. To suppress flowability and improve moldability
Should be increased by increasing the viscosity and thixotropic properties of the system.
Increase the proportion of component (b) or the proportion of component (a)
Can be adjusted by reducing. In the present invention, to produce the polymerizable composition,
First, as the step (A), the emulsion polymerization or the suspension polymerization is carried out.
Water containing crosslinked polymer microparticles as component (b)
To the system dispersion, an organic solvent and water-soluble salts were added,
After transferring the crosslinked polymer fine particles to the organic solvent phase,
The aqueous phase is removed by separating the medium phase and the aqueous phase into two layers.
I do. That is, it contains crosslinked polymer fine particles as the component (b).
Aqueous dispersion does not cause particle agglomeration and water separation
An organic solvent which does not form is added. With such organic solvents
Has an amphipathic property with the hydrated phase on the surface of the crosslinked polymer fine particles.
Of the organic solvent to be contained is preferably 20 to 100% by weight. This
Organic solvents having amphiphilic properties such as
, Ketones, and ethers are suitable.
Particles formed by hydrogen bonding with water of hydration on the surface of fine particles
Aggregation between each other can be prevented. Where amphiphilic
If the organic solvent is less than 20% by weight, the aggregation of particles and
It is not preferable because water separation occurs. Examples of such amphiphilic organic solvents include, for example, 2-
Ethyl-1-butyl alcohol, 3-heptyl alcohol
, N-butyl alcohol, n-pentyl alcohol,
sec-butyl alcohol, isobutyl alcohol, 2-
Pentyl alcohol, 3-pentyl alcohol, 2-meth
Alcohols such as tyl-1-butyl alcohol; methyl
n-propyl ketone, methyl isopropyl ketone, die
Tyl ketone, methyl n-butyl ketone, methyl isobutyl
Ketones such as ketones and di-n-propyl ketones;
Diether, di-n-propyl ether, diisopropyl
Ether, di-n-butyl ether and the like are preferred.
Can be used alone or as a mixture
Can be used. In addition, organic solvents other than those described above, that is, having no amphiphilic property
The organic solvent performs a residual water removal step after the non-aqueous conversion of the particles.
Preferably used in the range of 0 to 80% by weight for the purpose of simplification.
Water solubility at 20 ° C.
Until the solvent is less than 15% by weight
It is desirable to mix. With the organic solvent having no amphipathic property
For example, n-pentane, n-hexane, n-heptane
Tan, cyclohexane, methylcyclohexane, ethyl
Aliphatic solvents such as cyclohexane; benzene, toluene
Aromatic solvents such as ethyl acetate and xylene; ethyl acetate, n-acetic acid
Propyl, isopropyl acetate, n-butyl acetate, isoacetate
Ester solvents such as butyl and sec-butyl acetate are preferred.
When used, they may be used alone or mixed.
It can be used as a product. Further, an organic solvent to be added to the aqueous dispersion containing the component (b)
The amount of the solvent is 40 to 95 of the total weight of the aqueous dispersion and the organic solvent.
% By weight, preferably in the range of 60 to 90% by weight.
You. If the amount of organic solvent is less than 40% by weight,
The particles coagulate, increasing the viscosity of the system and increasing the stirring efficiency and water
It is not preferable because the separation efficiency is lowered. 95% by weight
If it exceeds, polymerizable monomer in the next solvent removal step
It is not preferable because the loss of the ink becomes large. On the other hand, water added to the aqueous dispersion together with the organic solvent
Soluble salts can be used to form crosslinked polymer particles
With the goal of completely transferring to the phase without agglomeration
Add. At this time, the water-soluble salts are mixed with the aqueous dispersion.
The temperature to be added to the mixed solution is preferably 95 ° C. or less, particularly
Preferably at a temperature of 30 to 80 ° C, acidic, basic or
Can be added in any neutral state. Here,
If the temperature of the mixture exceeds 95 ° C, foaming of the
Therefore, it is not preferable. If the temperature is lower than 30 ° C, the viscosity of the organic phase
And the efficiency of the two-phase separation between the organic phase and the aqueous solution phase is poor.
This is not preferred because In addition, the amount of the water-soluble salts used is the water in the mixed solution.
Preferably in the range from 0.5 to 20% by weight, especially preferred
Or 1 to 10% by weight. At this time, water-soluble salt
Less than 0.5% by weight, salting out effect is fully exhibited
Not more than 20% by weight, salt tends to remain in the organic phase
This is not preferred because As the water-soluble salts,
Organic or inorganic medieval, acidic or basic water-soluble
Can be used, specifically, for example, formic acid,
Carboxyls such as acetic acid, propionic acid, oxalic acid and malonic acid
Acids, methanesulfonic acid, ethanesulfonic acid, paratoluene
Sulfonic acids such as enesulfonic acid, monomethyl phosphoric acid,
Monoethyl phosphate, dimethyl phosphate, diethyl phosphate, etc.
Organic acids such as organic phosphoric acids and monoethylamine,
Pyramine, isopropylamine, n-butylamine,
Isobutylamine, sec-butylamine, t-butylamido
Primary amines such as dimethylamine, diethylamine
, Dipropylamine, diisopropylamine, diiso
Secondary amines such as butylamine and dipentylamine;
Limethylamine, triethylamine, tripropylami
Tertiary amines such as butane, tributylamine and pyridine
Organic water-soluble salts containing amine; sodium hydroxide
, Potassium hydroxide, sodium carbonate, sodium sulfate
Inorganic water such as sodium chloride, sodium chloride and ammonium chloride
And soluble salts. In the step (A), the water-soluble salts are added and then stirred.
Stop stirring and allow to stand.
And water-soluble salts and emulsifiers or dispersion stabilizers, etc.
To separate the aqueous phase from the aqueous phase.
Can be. Next, in the step (B), the crosslinked polymer fine particles are dispersed.
Aqueous solution containing water-soluble salts was added to the organic solvent phase
After stirring, separate the two layers and remove the aqueous phase containing the emulsifier
And dehydrating residual water in the organic phase to form crosslinked polymer fine particles.
Get a child. That is, the organic solvent phase separated in the step (A)
Preferably 100 to 100 parts by weight of the organic solvent phase.
Parts, particularly preferably 20 to 50 parts by weight of water-soluble salts.
When the mixed solution is uniformly dispersed,
Stop stirring and let the organic phase and the aqueous phase separate into two layers.
The emulsifier, dispersant, etc. remaining in the organic phase are washed with water. this
At this time, the water-soluble salts are favorable to the deionized water used.
Preferably, it is added in the range of 1 to 5% by weight to promote two-layer separation.
It is also possible. When washing with water
Are separated and removed when basic water-soluble salts are used.
Water-soluble salts so that the pH of the aqueous phase becomes 5 to 8
It is preferable to wash with water while changing the acid-basicity of the compound. The pH
Is less than 5 or more than 8, the crosslinkable polymer fine
Hydrolysis of the esters used as particles or solvent
It is not preferable because it progresses. To remove residual moisture in the organic phase separated into two layers
Is, for example, water distillation under reduced pressure, specifically an azeotrope with water
760mmHg at 50-100 ℃ with water only
Distillation under reduced pressure of less than;
Solution removal, specifically methyl orthoformate, orthoformate
Ortho, such as chill, methyl orthoacetate and ethyl orthoacetate
Carboxylic esters, diketene, formamide or
Add dicyclohexylcarbodiimide, etc.
Decompose residual moisture by reacting at 30-90 ° C
If the decomposition temperature is below 30 ° C,
It takes a long time to solve the solution.
Water droplets adhere to the gaps during installation, thus resulting in insufficient water removal
Is not preferred. In the above water removal method,
When using orthocarboxylic esters, decomposition products
As methyl alcohol, ethyl alcohol, methyl formate
, Ethyl formate, methyl acetate, ethyl acetate, etc.
When ketene is used, low-boiling solvents such as acetone are by-produced.
But these are completely removed by solvent removal
There is no problem because it can be used, but when using formamide,
Ammonium formate, but also dicyclohexylcarbodii
When using amide, dicyclohexylurea is by-produced.
Therefore, after each water decomposition reaction, it is necessary to filter the decomposition products.
It is necessary; removal by water absorption treatment with a water absorbing agent, concrete
Specifically, a polymer water-absorbing material, for example, "Sumikagel S-50",
"SP-520", "N-100", "NP-1020", "
F-03 ”,“ F-51 ”,“ F-75 ”(all products
Name, manufactured by Sumitomo Chemical Co., Ltd.), "Aqua Keep 4S",
"10SH" (both trade names, manufactured by Iron and Steel Chemical Industry Co., Ltd.)
Alternatively, if the column is packed with molecular sieves
Pass through the phase or the polymer water absorbing material, molecular sieve
Probe, sodium sulfate, calcium chloride, calcium oxide
Selected from the group consisting of inorganic salts such as
The dehydrating agent is mixed with the organic phase, stirred, and filtered.
Method; water removal by azeotropic distillation, specifically, for example, UK
Water is removed after emulsion polymerization, cited in Patent No. 967051
Method commonly used to remove water and organic solvents
Azeotropic distillation, preferably removing water at 50-100 ° C
Methods and the like can be preferably mentioned. (B) In the process
Is an organic material containing crosslinked polymer fine particles by the dehydration treatment.
Phase can be obtained. Next, the crosslinked polymer fine particles obtained in the step (B)
In step (C), the organic phase containing
Monofunctional reactive compound and / or polyfunctional reactive compound
Of the present invention by mixing components including
And a polyfunctional component (c).
The components containing the reactive oligomer solution should be in a specific ratio
To form a polymerizable composition. As needed
The solvent can be removed in the same manner. In the step (C), essential components of the present invention
In addition to the component (a) and the component (b), the component (c)
Group consisting of catalysts, polymerization catalysts, additives and mixtures thereof.
Alternatively, selected components can be mixed. The polymerization touch
The medium is added particularly when the polymerizable composition of the present invention is used as a cured product.
Specifically, for example, organic peroxide polymerization
Examples include an initiator or a photochemical polymer. As the organic peroxide polymerization initiators, ketone par
Oxides, peroxyketals, hydroperiods
Oxides, dialkyl peroxides, diacylpa
-Oxides, peroxydicarbonates, peroxide
Xyesters can be used, and specifically,
The ketone peroxides include methyl ethyl keto
Peroxide, cyclohexanone peroxide,
Methyl acetoacetate peroxide, cetyl aceto
Peroxide and the like. The peroxyketals include 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexyl
Sun, 1,1-bis (t-butylperoxy) cyclohex
Sun, 2,2-bis (t-butylperoxy) octane,
Use 2,2-bis (t-butylperoxy) butane or the like
be able to. As the hydroperoxides, t-butyl
Hydroperoxide, cumene hydroperoxide
, Diisopropylbenzene hydroperoxide,
p-menthane hydroperoxide, 2,5-dimethyl
Hexane-2,5-dihydroperoxide, 1,1,3,3-
Examples include tetramethylbutyl hydroperoxide and the like.
be able to. As the dialkyl peroxides, di-t-
Butyl peroxide, t-butylcumyl peroxide
And dicumyl peroxide. As the diacyl peroxides, acetyl
-Oxide, isobutyryl peroxide, octano
Il peroxide, decanoyl peroxide, lau
Loyl peroxide, 3,5,5-trimethylhexanoy
Luper oxide, succinic peroxide, benzoy
Luper oxide, 2,4-dichlorobenzoyl peroxy
Side, m-toluyl peroxide, etc.
it can. Examples of the peroxydicarbonates include di-isocarbonate.
Propyl peroxydicarbonate, di-2-ethyl
Xyl peroxydicarbonate, di-n-propylpa
-Oxydicarbonate, di-myristyl peroxydi
Carbonate, di-2-ethoxyethyl peroxydica
Bonate, di-methoxyisopropyl peroxydica
Carbonate, diallyl peroxydicarbonate and the like
Can be As the peroxyesters, t-butyl par
Oxyacetate, t-butyl peroxyisobutyrate
T, t-butyl peroxypivalate, t-butyl per
Oxyneodecanoate, Cumyl peroxyneodecae
3,3 ', 4,4'-tetra (t-butylperoxyca
Rubonyl) benzophenone, t-butylperoxy-2
-Ethylhexanoate, t-butylperoxylaure
Tert-butyl peroxybenzoate, di-t-butyl
Tilperoxyisophthalate, t-butylperoxy
Maleic acid, t-butyl peroxyisopropylcarbo
Nate, cumyl peroxy octoate, t-hexyl
Peroxy neodecanoate and the like can be mentioned. These organic peroxide polymerization initiators are polymerized according to the present invention.
To the total weight of component (a) and component (c) in the hydrophilic composition
On the other hand, it can be used in a range of 0.02% by weight to 10% by weight,
For curing, heat is preferably applied in a temperature range of 20 to 160 ° C.
It is preferable to cause the polymerization and curing reaction by heat. On this occasion
If less than 0.02% by weight, sufficient amount of radicals to cure
However, it is not preferable because the curing reaction becomes insufficient.
If the content exceeds 10% by weight, the polymerization reaction proceeds rapidly.
This makes it difficult to control the reaction and causes bubbles in the molded product.
This is not preferable because troubles such as occurrence of trouble occur. Further, as the photopolymerization initiator, benzoin, benzoin
Inmethyl ether, benzoin propyl ether,
Benzoin butyl ether, benzophenone, 3,3 ', 4,
4'-tetra- (t-butylperoxycarbonyl)
Nzophenone, diacetyl, benzyl, dibutyldisul
And dibenzyl disulfide can be used.
You. These photopolymerization initiators in the polymerizable composition of the present invention
0.5 to 1 based on the total weight of the components (a) and (c)
It can be used in the range of 0% by weight.
Energy rays such as visible light, ultraviolet rays, γ-rays,
It can be polymerized and cured by irradiation. The photopolymerization
If the content of the initiator is less than 0.5% by weight, the polymerization reaction will be insufficient.
Minutes, the desired physical properties could not be obtained and exceeded 10% by weight.
In such cases, it is difficult to control the polymerization reaction.
It is not preferable because problems such as coloring by the initiator occur.
No. To cure the cured product using photopolymerization reaction,
Pressure mercury lamp, metal halide lamp, mercury short arc
Lamps, ultra-high pressure mercury lamps or electrodeless lamps
Can be used. In addition, radicals may be used as the components (a) and (c).
When a polymerizable unsaturated monomer is used, electron beams, γ-rays, etc.
Radiation curing by irradiation of any high energy beam
It is possible to use a photopolymerization initiator in this case.
The composition is similar to that of the photocurable polymerizable monomer mixture except for
It is a thing. In the polymerizable composition of the present invention, the component (a)
When an ionic polymerizable compound is used as the component (c)
Is an alkali metal or alkali metal complex as a polymerization catalyst
(Na-naphthalene, K-benzophenone ketyl, etc.),
Organometallic compounds (metal alkyls, metal alkoxides,
Linear anion polymerization catalyst); protonic acid
(Phosphoric acid, trichloroacetic acid, p-toluenesulfonic acid
Etc.), metal halides (boron trifluoride,
Metal, titanium tetrachloride, etc.)
Acid oxides (chromium oxide, acid, etc.)
Molybdenum fluoride), stable cations, ((C_TwoH_Five)_ThreeO⁺BF_Three
^-, (C_TwoH_Five)_ThreeO⁺SbF₆ ^-And other cationic polymerization catalysts
Can be used. Curing the polymerizable composition of the present invention by ionic polymerization
In such a case, it is preferably 0.0001 to 1 based on the polymerizable composition.
% By weight of the polymer selected by the ionic polymerizable compound.
Medium can be added and cured at a temperature range of -40 ° C to 30 ° C.
it can. When the amount of the polymerization catalyst is less than 0.0001% by weight
Causes problems such as delayed curing and poor curing.
Absent. When used in excess of 1% by weight,
Control becomes extremely difficult, which is not preferable. In the polymerizable composition of the present invention, the component (a)
Use of a mixture of addition polymerizable compounds as (c)
In this case, the combination of the addition polymerizable compound includes: (1) a hydroxyl group-containing compound and a polyvalent isocyanate compound (2) an epoxy group-containing compound epoxy group-containing compound and amino group-containing compound epoxy group-containing compound and polycarboxylic acid epoxy group-containing Compounds and polyamides Epoxy group-containing compounds and polysulfide resins can be used. As a polymerization catalyst in the case of the combination of the above (1)
Are amine compounds, metal salts or organometallic compounds.
Which can be used. As amine compounds, triethyl
Luamine, N-methylmorpholine, tetramethyl-1,3
-Butanediamine, triethylenediamine, 1,4-dia
The-2,2,2-bicyclooctane, N, N'-dimethylpipera
Gins and the like, metal salts such as manganese, lead,
G, zinc, copper, iron, cadmium, vanadium, tin, d
Naphthenate or octylate such as
Metal compounds such as tin (II) octoate and jib
Cyltin dilaurate, iron (III) chloride and copper (II) ace
Tilacetonate and the like can be mentioned. These polymerization catalysts
From the addition-polymerizable polyol-polyisocyanate
The polymerizable composition of the present invention in the case of mixing the
Can be cured under heat or heat
You. The range of use of the polymerization catalyst is in the range of a hydroxyl-containing compound.
Depends on the combination of trivalent isocyanate,
Is a polyol and polyisomers in the polymerizable composition of the present invention.
0.001 to 5% by weight based on the total weight of cyanate
% Range. If it is less than 0.001% by weight, poor curing will result.
If it exceeds 5% by weight, it is difficult to control the curing reaction.
Troubles such as inability to set time
Not preferred. In the case of the combination of the above (2), the polymerizable group of the present invention
As catalysts for the product, tertiary amine compounds, boron trifluoride
Complex, carboxylic anhydride, dicyandiamide, imi
Dazole or the like can be used, and preferably, a polymerizable composition
0.02 to 5 times the weight of the epoxy group-containing compound in the product
It can be used in the range of the amount%. 0.02 weight of polymerization catalyst
%, Poor curing results in unsatisfactory physical properties.
If not more than 5% by weight, the curing reaction is difficult
Is not preferred. The epoxy group-containing compound
Mix as component (a) and, if necessary, component (c)
In some cases, the polymerizable composition of the present invention is molded or applied.
After that, it is possible to cure at room temperature or under heating.
It can be selected according to the application. Component (a) in the polymerizable composition of the present invention and if necessary
When a polycondensable monomer is used as the component (c),
The following combinations are possible. (3) Hydroxyl-containing compound, methamine resin, urea resin,
Combination with amino resin such as nzogranamine resin. When composing the polymerizable composition with these combinations
Is used as a curing catalyst, for example, organic sulfonic acid or organic sulfur.
Amine-blocked sulfonic acids can be used. Organic sul
P-Toluenesulfonic acid, dodecylbenzene
Benzenesulfonic acid, nonylnaphthalenesulfonic acid, dino
Nilnaphthalenesulfonic acid, nonylnaphthalenedisulfonic acid
Acid, dinonylnaphthalenedisulfonic acid, etc.
Examples of sulfonic acid blocking agents include cyclohexane
Xylamine, benzylamine, morpholine, N-methyl
Rumorpholine, N, N-diethylaniline, pyridine,
Niline, n-butylamine, diethanolamine, tri
Amine compounds such as ethanolamine and epoxy compounds
And the like. Organic as a catalyst when using the polycondensable monomer
Sulfonic acid is used for condensation polymerization in the polymerizable composition of the present invention.
Preferably 0.05 to 5% by weight based on the total weight of the
It can be used in a range, and as the curing means, heat curing
Is used. When using a blocking agent together,
Equimolar to the organic sulfonic acid added to the polymerizable composition
From 3 to 3 moles of the blocking agent.
Is desirable. The amount of the organic sulfonic acid used is 0.05% by weight.
% Or less causes poor curing and exceeds 5% by weight
Not only makes it difficult to control the curing reaction, but also
Is preferable because it causes distortion of water and deterioration of water resistance, chemical resistance, etc.
I don't. In addition, a blocking agent is used for an organic sulfonic acid or the like.
When mixed in less than a mole, the effect of blocking occurs.
When mixing more than 3 times the mole,
It inhibits the catalytic action of sulfonic acid, causing poor curing or hardening.
Is not preferable because it causes problems such as marked coloring of the compound.
I don't. The polymerizable composition of the present invention comprises a crosslinking agent contained in the composition.
The three-dimensional network structure of the polymer fine particles, the component (a)
And, if necessary, component (c) reacts to produce three-dimensional
The polymer network penetrates each other to form entanglement
Forming a cured product having an interpenetrating polymer network structure
Can be applied to various fields. By curing the polymerizable composition of the present invention, medical and / or
When used for dental hardened materials, for example, palate
A flexible layer with an interpenetrating polymer network structure at the part in contact with the membrane
It can be formed and used as a mucosal protective layer. The polymerizable composition of the present invention is cured and formed on a denture base.
Protective layer with flexible and flexible interpenetrating polymer network
To prevent damage to the mucous membrane,
Eliminates the difference in shape between the lids and improves usability
You. In addition, because it has an interpenetrating polymer network structure,
It has excellent durability such as resistance and abrasion resistance.
It has advantages such as necessity. Other medical and / or dental cured products include
Base material. From the polymerizable composition of the present invention.
The obtained cataplasm base material can freely adjust the degree of expansion and contraction.
And excellent toughness.
Suitable for use in areas where movement is performed. Also artificial
It can also be applied as a joint surface protection material in joints. In applying the polymerizable composition of the present invention to artificial joints
Coats one of the joint surfaces as a thin film
Or by coating and curing both
Thus, a flexible bonding layer can be formed. Also mutual
Abrasion resistance, water resistance, chemical resistance due to penetrating polymer network structure
Advantages such as long-term use
There is. Further, a coating composition is prepared by using the polymerizable composition of the present invention.
If necessary, use a room temperature curing type, baking drying type,
It can be used as a photocurable coating. How to apply
Methods include air spray, roll coater, brush coating
Can be used in the same manner as conventional paints.
You. The coating film obtained by curing the coating composition of the present invention
Compared to conventional coatings to form a penetrating polymer network
Weather, stain, water, abrasion, and chemical resistance.
It has excellent characteristics. Applying the polymerizable composition of the present invention as an adhesive composition
In case, instant adhesive, cold setting adhesive, heat setting type
It can be used as an adhesive,
Process into thixotropic paste due to the presence of particles
It is easy to do. By applying to instant adhesive,
Various adherends made of porous materials such as wood, paper and leather
The set time is short and the workability is excellent in bonding
Can improve impact resistance, heat resistance and water resistance
You.

【The invention's effect】

INDUSTRIAL APPLICABILITY The polymerizable composition of the present invention is useful for a wide variety of molded articles or structural bases, and can freely change the flow characteristics of the system according to the purpose, and is excellent in workability. By curing, a molded article having an interpenetrating polymer network structure can be obtained. The molded body has a uniform internal structure,
It has features that can provide a very wide range of physical properties. That is, according to the polymerizable composition, the method for producing the same, and the cured product according to the present invention, it is possible to use crosslinked polymer fine particles having a low glass transition point, which were conventionally unusable due to the problem of fusion and adhesion. Therefore, when forming a molded product, a product having a very low glass transition point can be produced. Therefore, the polymerizable composition of the present invention is extremely useful for medical and / or dental cured products, adhesive compositions, coating compositions, and the like.

【Example】

Hereinafter, the present invention will be described in detail with reference to Examples, but these Examples do not limit the scope of the present invention.
In the examples, “parts” and “%” are based on weight. Production Example 1 Production of aqueous dispersion containing crosslinked polymer fine particles (I) Stirrer, nitrogen inlet tube, temperature controller, condenser,
850 deionized water was added to two reaction vessels equipped with dropping funnels.
Parts, sodium dioctylsulfosuccinate (trade name "Lapisol B-9" manufactured by NOF Corporation) 10 parts, Rongalit 0.75 part, tetrasodium ethylenediaminetetraacetate 0.35
And 4 parts of trisodium phosphate dodecahydrate, and heated to 50 ° C. under a nitrogen stream. Next, 50 parts of an aqueous solution obtained by dissolving 0.25 part of ferrous sulfate heptahydrate in deionized water and 0.625 part of t-butyl hydroperoxide (trade name “Perbutyl-H” manufactured by NOF CORPORATION) were added to deionized water. After adding 50 parts of the dissolved aqueous solution, a monomer mixture of 490 parts of methyl acrylate and 10 parts of 1,6-hexanediol dimethacrylate was added dropwise over 5 hours while maintaining the temperature of the content at 50 ° C. Next, every hour after the start of the dropping of the monomer mixture,
Ten parts of an aqueous solution of 0.125 part of t-butyl hydroperoxide dissolved in deionized water were added in five portions. After the completion of the dropping of the monomer mixture, the temperature was maintained at 50 ° C. for 2 hours, and then the temperature was raised to 80 ° C., and stirring was continued for 2 hours to complete the reaction. The resulting aqueous dispersion containing the crosslinked polymer fine particles had a solid content of 32.8% and an average particle size of 86 nm. Each measurement shown in Table 1 was performed. The results and formulations are shown in Table 1. Further, the methods for measuring the solid content and the average particle size, and the methods for measuring the glass transition temperature and the equilibrium swelling degree are described below. Measurement of fixed amount (residue after heating) Approximately 1 g of a sample is precisely weighed in a tin plate and placed in a hot air circulation oven.
After drying at 0 ° C. for 30 minutes, the ratio of hot air residue was determined. Measurement of average particle size Measurement value by "NICOMP370" (trade name, Pacific Scientific) Measurement of glass transition temperature Each emulsion was dried at 80 ° C. in a glass petri dish, and the obtained film was subjected to ATM measurement. Measurement of Equilibrium Swelling Equilibrium swelling (S ¹ ) or (S ² ) is known
J.Coating Tec
h.) It can be measured by the method described in page 52 and thereafter, Vol. 52, No. 669, October (1980). That is, the concentration of the crosslinked polymer fine particles in the polymerizable monomer dispersion was dispersed in a predetermined polymerizable monomer so as to be 4 g /, the viscosity of the dispersion was measured, and determined by substituting into the following equation. . ρp ¹ : density of the crosslinked polymer fine particles in a dry state ηs ¹ : viscosity of the polymerizable monomer dispersion ((a) a solution comprising a monofunctional reactive compound and / or a polyfunctional reactive compound; and (b) a crosslinked polymer Viscosity of dispersion with fine particles) ηo ¹ : Viscosity of polymerizable monomer solution alone ((a) Viscosity of solution containing monofunctional reactive compound and / or polyfunctional reactive compound alone) m ¹ : Polymerizable monomer dispersion A solution ((a) a solution comprising a monofunctional reactive compound and / or a polyfunctional reactive compound;
(B) Dispersion with crosslinked polymer fine particles) Solid content weight of crosslinked polymer fine particles in 1 cm ³ ρp ¹ : density of crosslinked polymer fine particles in a dry state ηs ² : viscosity of polymerizable monomer (oligomer) dispersion (viscosity of dispersion of (b) crosslinked polymer fine particles and (c) polyfunctional reactive oligomer solution) Ηo ² : viscosity of polymerizable monomer (oligomer) solution alone ((c) viscosity of polyfunctional reactive oligomer solution alone m ² : polymerizable monomer (oligomer) dispersion ((b) crosslinked polymer fine particles, (c) ) Dispersion with polyfunctional reactive oligomer solution) Solid content weight of crosslinked polymer fine particles in 1 cm ³ Production Example 2 Production of aqueous dispersion containing crosslinked polymer fine particles (II) Stirrer, cooler, temperature controller Then, 1200 parts of deionized water was charged into two reactors equipped with a nitrogen inlet tube and a dropping funnel, and the temperature was raised under a nitrogen stream. When the temperature was suitable at 40 ° C., 120 parts of a 10% aqueous solution of sodium lauryl sulfate was added. When temperature reaches 50 ° C, potassium persulfate After adding 18 parts of a 5% aqueous solution of
Maintained at 60 ° C. Next, 179.3 parts of ethyl acrylate and 1,6
-A monomer mixture of 0.72 parts of hexanediol dimethacrylate was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was kept at 60 ° C for 30 minutes, then heated to 90 ° C and continuously stirred for 1 hour to complete the reaction. The resulting aqueous dispersion containing the crosslinked polymer fine particles had a solid content of 12.3% and an average particle size of 20 nm. The results and formulations are shown in Table 1. Production Examples 3, 4, 5 Production of Aqueous Dispersion Containing Crosslinked Polymer Fine Particles (III), (IV) and (V) Aqueous Dispersion (III) Containing Crosslinked Polymer Fine Particles Instead of Methyl Acrylate in Production Example 1 In the same manner as in Production Example 1 except that ethyl acrylate is used for the production of (IV), n-butyl acrylate is used for the production of (IV), and n-butyl methacrylate is used for the production of (V), the crosslinked polymer fine particles are contained. Aqueous dispersions (III), (IV) and (V) were obtained.
Next, each measurement shown in Table 1 was performed. The results and formulations are shown in Table 1. Production Example 6 Production of Aqueous Dispersion Containing Crosslinked Polymer Fine Particles (VI) 850 parts of deionized water, dioctyl sulfosuccinic acid in two reaction vessels equipped with a stirrer, a cooler, a temperature controller, a nitrogen inlet tube, and a dropping funnel. 10 parts sodium, Rongalit 0.
75 parts, 0.35 parts of tetrasodium ethylenediaminetetraacetate and 4 parts of trisodium phosphate dodecahydrate are charged, and are heated at 30 ° C. under a nitrogen stream.
Kept. Next, 0.25 part of ferrous sulfate heptahydrate is deionized water
After adding an aqueous solution dissolved in 50 parts and an aqueous solution dissolving 0.625 parts of t-butyl hydroperoxide in 50 parts of deionized water, benzoyl peroxide was added to 475 parts of methyl acrylate while maintaining the temperature of the contents at 30 ° C. A monomer mixture in which 25 parts of an oxide (trade name "Niper B" manufactured by NOF Corporation) was dissolved was added dropwise over 3 hours. Next, every 30 minutes after the start of the dropping of the monomer mixture, a solution of 0.125 part of t-butyl hydroperoxide dissolved in 10 parts of deionized water was added five times. Then, after the dropping of the monomer mixture is completed, 1
The resulting emulsion of the aqueous dispersion (VI) containing the crosslinked polymer fine particles after the completion of the reaction was maintained at 30 ° C. for 30 hours, and then heated to the reflux temperature and stirred for 2 hours.
1.5% and an average particle size of 92 nm. Next, each measurement shown in Table 1 was performed. The results and formulations are shown in Table 1. Production Example 7 Production of Aqueous Dispersion (VII) Containing Crosslinked Polymer Fine Particles 1080 parts of deionized water were charged into two reaction vessels equipped with a stirrer, a cooler, a temperature controller, a nitrogen inlet tube, and a dropping funnel. The temperature was raised under a gas stream and kept at 80 ° C. Next, an aqueous solution in which 3.0 parts of potassium persulfate was dissolved in 57 parts of deionized water was charged, and then 300 parts of ethyl acrylate was added dropwise over 3 hours. After the start of dropping, every 30 minutes, potassium persulfate
An aqueous solution in which 0.3 part was dissolved in 29.7 parts of deionized water was added five times. After completion of the dropping of ethyl acrylate, 80 ° C
For 2 hours to complete the reaction. Next, after cooling to room temperature, the obtained aqueous dispersion of non-crosslinked ethyl acrylate fine particles was placed in a glass test tube with a screw pig having an inner diameter of 30 mm and a length of 200 mm, degassed with argon gas, and then sealed, 2.2 Mrad To obtain an aqueous dispersion of crosslinked polyethyl acrylate fine particles (VII). This aqueous dispersion had a solid content of 20.8% and an average particle size of 354 nm. Next, each measurement shown in Table 1 was performed. The results and formulations are shown in Table 1. Example 1 Production of Polymerizable Composition (K) 500 parts of an aqueous dispersion liquid containing crosslinked polymer fine particles (I) in two containers equipped with a stirrer, a temperature controller, a Dean-Stark trap and a cooling pipe, and methyl 600 parts of isobutyl ketone were charged, the temperature was raised to 60 ° C., and while stirring vigorously, 40 parts of an aqueous solution of sodium chloride at 20 ° C. was added to stop stirring. By allowing to stand, a methyl isobutyl ketone phase containing the crosslinked polymer fine particles (I) was formed in the upper layer, and an aqueous solution layer was formed in the lower layer. Thus, 365 parts of the lower aqueous solution phase was removed. Then add 200 parts of deionized water while maintaining at 60 ° C,
The temperature was raised to 60 ° C. with vigorous stirring, and 10 parts of a 20% aqueous sodium chloride solution was added to stop stirring, and the mixture was allowed to stand. After the two layers were separated again, 203 parts of the lower aqueous phase was removed, and azeotropic distillation was performed under reduced pressure to remove 16 parts of water. The resulting methyl isobutyl ketone dispersion containing the crosslinked polymer fine particles (I) was transferred into a planetary mixer, and 164 parts of diethylene glycol dimethacrylate and diacrylate of polyester diol (trade name “KAYARAD HX-220” manufactured by Nippon Kagaku Co., Ltd. ), 164 parts, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (trade name "BTTB")
After adding 4.9 parts of Nippon Oil & Fats Co., Ltd., methyl isobutyl ketone was distilled off under reduced pressure at room temperature to mix. Next, 593 parts of methyl isobutyl ketone were recovered to obtain 503 parts of a polymerizable composition (K). Table 2 shows the mixing composition, mixing conditions, and the water content (wt%) of the obtained polymerizable composition. The water content was measured by a Karl Fischer moisture meter. Examples 2 to 7 Production of polymerizable compositions (L) to (Q) Polymerizable compositions (L) to (Q) were produced in the same manner as in Example 1 under the compositions and conditions shown in Table 1. Table 2 shows the mixed composition, mixing conditions, and the water content and weight of the obtained polymerizable composition. Examples 8 to 14 Preparation of Film Having Interpenetrating Polymer Network Structure Using the polymerizable composition obtained in Examples 1 to 7, a film having an interpenetrating polymer network structure was produced by the following operation. . Each polymerizable composition was spread between high-quality glass plates with a thickness of 3 mm using a Teflon sheet with a thickness of 0.20 mm as a spacer, and fixed with clips. Then, at room temperature, a light irradiation device (trade name “Asphalite” Morita (Manufactured by Tokyo Seisakusho) (at a distance of 5 cm, light energy of about 60 mW / min.cm ² )
After curing by photopolymerization curing reaction for about 1 minute, colorless and transparent films K 'to Q' having a thickness of about 0.2 mm were obtained. The resulting films of K 'to Q' were observed with an optical microscope at a magnification of 1000, but none of them could observe a non-uniform structure such as a particle structure or an aggregate. Table 3 shows the results of the property tests of the films shown in Table 3. The methods of the tensile test and the water absorption test are shown below. Tensile test Measured at a temperature of 20 ° C. and a tensile speed of 4 mm / min using a product name “Tensilon UTN-III-200” (manufactured by Orientec Co., Ltd.). Water Absorption Test The obtained film of 40 × 75 × 0.2 mm was immersed in water at 20 ° C. and allowed to stand for 7 days to measure a weight increase rate. Comparative Example 1 10 parts of diethylene glycol dimethacrylate, 10 parts of trade name "KAYARAD HX-220" (manufactured by Nippon Kayaku Co., Ltd.), and 0.30 parts of trade name "BTTB" (manufactured by NOF Corporation) were uniformly mixed. A polymerizable composition containing no crosslinked polymer fine particles at all was obtained. Using the obtained polymerizable composition, films were prepared in the same manner as in Examples 8 to 14, and each test was performed. Table 3 shows the results. Comparative Example 2 A stirrer, a cooler, a temperature controller, and a nitrogen inlet tube were provided.
A 500 ml reactor was charged with 300 parts of an aqueous emulsion of crosslinked polymer fine particles (II), 35.56 parts of t-butyl acrylate, and 0.14 parts of diethylene glycol dimethacrylate, and stirred at 30 ° C. for 90 hours in a nitrogen atmosphere. After that, the temperature was raised, and when the temperature reached 40 ° C, a 5% aqueous solution of potassium persulfate was used.
3.4 parts were added, the temperature was raised to 60 ° C., and the reaction was carried out at 60 ° C. for 2 hours. Then, the temperature was raised to 90 ° C., and stirring was continued for 1 hour to complete the reaction. Then, after cooling to room temperature, 100 parts of methanol was added to coagulate and sediment the particles, and the solid was separated by suction filtration. The obtained white solid was thoroughly loosened in a 500 ml conical beaker, 140 parts of deionized water was added, and the mixture was stirred for 1 hour, filtered and washed four times, and then at 40 ° C. under reduced pressure for 80 hours. Drying gave 33 parts of a white granular solid. Next, 80 parts of methyl isobutyl ketone was added to 20 parts of the obtained white granular solid, and the mixture was stirred for 5 hours. The resulting solution was filtered with Kiriyama Filter Paper No. 5A (Kiriyama Seisakusho) (retained particles of 7 μm).
m), and 21.2 parts of the obtained filtrate were collected, poured into a Petri dish tin thin having an inner diameter of 15.0 cm, and the solvent was air-dried, and then dried at 80 ° C. under reduced pressure for 8 hours. Medicine 0.2mm
Was produced. The obtained film was peeled from the tin thin, and a tensile test was performed. The film was translucent, slightly turbid in appearance, and was found to have a heterogeneous structure when examined by optical microscopy. Table 3 shows the results. Comparative Example 3 Emulsion of crosslinked polymer fine particles in exactly the same manner as in Production Example 1 except that methyl methacrylate was used instead of methyl acrylate and ethylene glycol dimethacrylate was used instead of 1,6-hexanediol dimethacrylate in Production Example 1. I got The solid content of the obtained emulsion was 32.0%, and the average particle size was 75 nm. Dilute hydrochloric acid and methanol were added to this emulsion to coagulate and settle the particles, and separated by suction filtration. An operation of adding 400 parts of water to 100 parts of the obtained solid, stirring vigorously for 1 hour, and separating the solid by suction filtration was repeated four times. The obtained solid was dried under reduced pressure at 60 ° C. for 8 hours, crushed in a mortar,
The mixture was passed through a mesh sieve to obtain 62 parts of a white powder. This powder 50
Parts by weight of diethylene glycol dimethacrylate 50
Department, product name "KAYARAD HX-220" (manufactured by Nippon Kayaku Co., Ltd.)
50 parts and 0.5 parts of benzoyl peroxide were mixed at room temperature, loaded into a planetary mixer, mixed until visually homogeneous, and aged at room temperature for 2 weeks. Then, a 0.2 mm thick Teflon sheet was used as a spacer to spread between high-quality glass plates and fixed with clips. Then, the mixture was cured by heating in a hot air circulating oven at 60 ° C. for 4 hours, at 80 ° C. for 4 hours, and further at 110 ° C. for 4 hours to obtain a colorless and translucent film having a thickness of about 0.2 mm. Observation of the obtained film with an optical microscope revealed that the obtained film had an uneven structure with a size of several μm to several hundred μm.
Table 3 shows the results. As shown in Table 3, the film having an interpenetrating polymer network structure obtained by the polymerizable composition of the present invention has a uniform interior, excellent transparency, a wide range of initial Young's modulus and tensile strength, and Show very high growth rates,
Further, it was found that the water absorption was small. In contrast,
In Comparative Example 1 containing no crosslinked polymer fine particles at all, it was found that although the initial Young's modulus and the tensile strength were large, there were problems such as a very small elongation, a brittle property, and a high water absorption. The film of Comparative Example 2 produced according to the Herston et al., "Journal of Applied Polymer Science", Vol. 29, pp. 2969-2980, is more transparent than the film of Example 9 in terms of transparency, elongation, water absorption and the like. It turned out to be inferior. Further, the film of Comparative Example 3 manufactured based on European Patent No. 14515 of Romer and Tateosian et al. And Japanese Patent Application Laid-Open No. 55-149,302 has higher transparency and elongation ratio than the films of Examples 8 to 14. Was inferior in physical performance, and it was also found that aging of the polymerizable composition required much time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 133/06 C09J 133/06

Claims (10)

(57) [Claims] (1) 20 to 99% by weight of a solution comprising a monofunctional reactive compound and / or a polyfunctional reactive compound; and (b) an average particle diameter of 0.01 to 1000 having a glass transition temperature of 80 ° C. or lower.
1 to 80% by weight of crosslinked polymer fine particles having a particle diameter of 1 μm, and the value of the equilibrium swelling degree (S ¹ ) represented by the following formula (1) is 2 A polymerizable composition, which satisfies a condition that satisfies a range of 100 to 100. (In the formula (1), .rho.p ¹ represents the density in the dry state of the (b) crosslinked polymer microparticles, and the solution .eta.s ¹ is composed of the (a) monofunctional reactive compound and / or a polyfunctional reactive compound And (b) the viscosity of the dispersion with the crosslinked polymer fine particles, ηo ¹ represents the viscosity of the solution alone comprising the (a) monofunctional reactive compound and / or polyfunctional reactive compound, and m ¹ Solid weight of the (b) crosslinked polymer fine particles in 1 cm ³ of a dispersion of the (a) monofunctional reactive compound and / or the polyfunctional reactive compound and the (b) crosslinked polymer fine particles Is shown.) 2. An aqueous solution of (a) a monofunctional reactive compound and / or a polyfunctional reactive compound in an amount of from 2 to 80% by weight, and (b) an average particle diameter having a glass transition temperature of 80 ° C. or less of from 0.01 to 1000%.
1 to 80% by weight of crosslinked polymer fine particles of
(C) 10 to 80% by weight of a polyfunctional reactive oligomer solution which reacts with the component (a) to form a three-dimensional network structure,
In the relationship between the component (a) and the component (b), the value of the equilibrium swelling degree (S ¹ ) represented by the following formula (1) is 2 to 100.
And the value of the equilibrium swelling degree (S ² ) represented by the following formula (2) is in the range of 1 to 10 in the relationship between the component (b) and the component (c). A polymerizable composition satisfying the conditions. (In the formula (1), .rho.p ¹ represents the density in the dry state of the (b) crosslinked polymer microparticles, and the solution .eta.s ¹ is composed of the (a) monofunctional reactive compound and / or a polyfunctional reactive compound And (b) the viscosity of the dispersion with the crosslinked polymer fine particles, ηo ¹ represents the viscosity of the solution alone comprising the (a) monofunctional reactive compound and / or polyfunctional reactive compound, and m ¹ Solid weight of the (b) crosslinked polymer fine particles in 1 cm ³ of a dispersion of the (a) monofunctional reactive compound and / or the polyfunctional reactive compound and the (b) crosslinked polymer fine particles Is shown.) (In the formula (2), .rho.p ¹ represents the density in the dry state of the (b) crosslinked polymer microparticles, and .eta.s ² is the (b) crosslinked polymer microparticles, said (c) multifunctional reactive oligomer solution Ηo ² indicates the viscosity of the (c) multifunctional reactive oligomer solution alone, and m ² indicates the (b) crosslinked polymer fine particles and the (c) polyfunctional reactive oligomer solution. The solid content weight of the crosslinked polymer fine particles (b) in 1 cm ³ of the dispersion is shown below.) 3. The polymerizable composition according to claim 2, wherein
A cured product obtained by curing in a temperature range of 0 ° C. 4. A cured product obtained by curing the polymerizable composition according to claim 2 by irradiation with energy rays. 5. A cured medical product obtained by curing the polymerizable composition according to claim 2. 6. A cured dental product obtained by curing the polymerizable composition according to claim 2. 7. An adhesive composition comprising the polymerizable composition according to claim 2 as an essential component. 8. A coating composition comprising the polymerizable composition according to claim 2 as an essential component. 9. The method for producing a polymerizable composition according to claim 1, comprising (A) a monofunctional reactive compound and / or a polyfunctional reactive compound mixed in the steps (A) and (C). In relation to the solution, the value of the equilibrium swelling degree (S ¹ ) represented by the following formula (1) satisfies the range of 2 to 100, the glass transition temperature is 80 ° C. or less, and the average particle diameter is 0.01 to 1000 μm. An organic solvent and water-soluble salts are added to an aqueous dispersion containing crosslinked polymer fine particles (b) prepared by emulsion polymerization or suspension polymerization so that the crosslinked polymer fine particles (b) are converted to an organic solvent phase. After the transfer, a step of separating the organic solvent phase and the aqueous solution phase into two layers and removing the aqueous solution phase, (In the formula (1), .rho.p ¹ represents the density in the dry state of the (b) crosslinked polymer microparticles, and the solution .eta.s ¹ is composed of the (a) monofunctional reactive compound and / or a polyfunctional reactive compound And (b) the viscosity of the dispersion with the crosslinked polymer fine particles, ηo ¹ represents the viscosity of the solution alone comprising the (a) monofunctional reactive compound and / or polyfunctional reactive compound, and m ¹ Solid weight of the (b) crosslinked polymer fine particles in 1 cm ³ of a dispersion of the (a) monofunctional reactive compound and / or the polyfunctional reactive compound and the (b) crosslinked polymer fine particles (B) An aqueous solution containing water-soluble salts is added to the organic solvent phase containing the crosslinked polymer fine particles (b), and the mixture is stirred to separate the aqueous phase and the organic phase into two layers. The organic phase containing the crosslinked polymer fine particles (b) is removed, and the residual moisture in the organic phase is dehydrated. And (C) adding a solution comprising (a) a monofunctional reactive compound and / or a polyfunctional reactive compound to the organic phase containing the crosslinked polymer fine particles (b) obtained in the step (B). After mixing the components, the component (a) is 20 to 99% by weight, and the component (b) is 1 to 80% by weight.
A method for producing a composition by weight. 10. The method for producing a polymerizable composition according to claim 2, comprising: (A) a monofunctional reactive compound and / or a polyfunctional reactive compound mixed in the steps (A) and (C). In relation to the solution, the value of the equilibrium swelling degree (S ¹ ) represented by the following formula (1) satisfies the range of 2 to 100, the glass transition temperature is 80 ° C. or less, and the average particle diameter is 0.01 to 1000 μm. An organic solvent and water-soluble salts are added to an aqueous dispersion containing crosslinked polymer fine particles (b) prepared by emulsion polymerization or suspension polymerization so that the crosslinked polymer fine particles (b) are converted to an organic solvent phase. After the transfer, a step of separating the organic solvent phase and the aqueous solution phase into two layers and removing the aqueous solution phase, (In the formula (1), .rho.p ¹ represents the density in the dry state of the (b) crosslinked polymer microparticles, and the solution .eta.s ¹ is composed of the (a) monofunctional reactive compound and / or a polyfunctional reactive compound And (b) the viscosity of the dispersion with the crosslinked polymer fine particles, ηo ¹ represents the viscosity of the solution alone comprising the (a) monofunctional reactive compound and / or polyfunctional reactive compound, and m ¹ Solid weight of the (b) crosslinked polymer fine particles in 1 cm ³ of a dispersion of the (a) monofunctional reactive compound and / or the polyfunctional reactive compound and the (b) crosslinked polymer fine particles (B) An aqueous solution containing water-soluble salts is added to the organic solvent phase containing the crosslinked polymer fine particles (b), and the mixture is stirred to separate the aqueous phase and the organic phase into two layers. The organic phase containing the crosslinked polymer fine particles (b) is removed, and the residual moisture in the organic phase is dehydrated. And (C) adding a solution comprising (a) a monofunctional reactive compound and / or a polyfunctional reactive compound to the organic phase containing the crosslinked polymer fine particles (b) obtained in the step (B). (C) reacting with the component (a) to form a three-dimensional network structure, and in relation to the component (b), the value of the equilibrium swelling degree (S ² ) represented by the following formula (2): And a polyfunctional reactive oligomer solution that satisfies the condition that is in the range of 1 to 10, (a) 2 to 80% by weight of component, (b) 1 to 80% by weight of component, and (c) component. A method for producing a polymerizable composition, comprising: a step of adding 10 to 80% by weight. (In the formula (2), .rho.p ¹ represents the density in the dry state of the (b) crosslinked polymer microparticles, and .eta.s ² is the (b) crosslinked polymer microparticles, said (c) multifunctional reactive oligomer solution Ηo ² indicates the viscosity of the (c) multifunctional reactive oligomer solution alone, and m ² indicates the (b) crosslinked polymer fine particles and the (c) polyfunctional reactive oligomer solution. The solid content weight of the crosslinked polymer fine particles (b) in 1 cm ³ of the dispersion is shown below.)