JP2002179805A - O/w type aqueous thermosetting resin dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an O/W type aqueous thermosetting resin dispersion comprising an aqueous dispersion in which resin particles are homogeneously dispersed by mixing and dispersing a radical polymerization type thermosetting resin with water. SOLUTION: This O/W type aqueous thermosetting resin dispersion is obtained by mixing a radically polymerizable thermosetting resin with water in (90:10)-(60:40) weight ratio in a liquid state and homogeneously dispersing the resin particles in the water phase. The aqueous dispersion of this invention is stable, thixotropic and excellent in workability, capable of being cured at room temperatures or by heating like conventional polymerization type thermosetting resins. The obtained cured product is a porous body having continuous micro pores by mutual binding of the fine particles and capable of being applied to various applications by treating to add high performance such as a precision filter, an absorber adsorber, a carrier and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous O / W type thermosetting resin dispersion obtained by mixing a liquid radical polymerization type thermosetting resin with water and dispersing resin particles in an aqueous phase. The aqueous O / W type thermosetting resin dispersion of the present invention can be easily cured at room temperature or under heating by adding a curing agent and, if necessary, an accelerator, and is a porous material having fine continuous air holes. A cured product can be obtained. The porous cured product can be used for various purposes after being subjected to high-performance treatment, for example, as a microfiltration material, an absorption / adsorption material, and as a carrier.

[0002]

2. Description of the Related Art Conventionally, an aqueous dispersion obtained by mixing and dispersing a radical polymerization type thermosetting resin such as an unsaturated polyester resin or an epoxy acrylate resin with water is one in which water droplets are dispersed in a resin, that is, W / O-type emulsion-type thermosetting resin aqueous dispersions are known and commercially available. This conventional thermosetting resin aqueous dispersion is used as one of the methods for making the resin flame-retardant by adding moisture to the resin, and means for suppressing the curing shrinkage of the unsaturated polyester resin or epoxy acrylate resin. Has been used as.

[0003] On the other hand, for example, an aqueous dispersion obtained by mixing and dispersing a radical polymerization type thermosetting resin such as an unsaturated polyester resin with water and dispersing resin particles in an aqueous phase, ie, O / O
W-type emulsion type thermosetting resin aqueous dispersion is
Recognition that a cured product having mechanical strength sufficient for practical use is not obtained due to poor bonding between resin particles, so far, a radical polymerization type thermosetting resin and water in which water is mixed and dispersed have been used.
Almost no studies have been made on the / W type aqueous dispersion.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a method of mixing a radical polymerization type thermosetting resin and water, which has hardly been studied, from the recognition that a cured product that can withstand practical use has not been obtained. It is an object of the present invention to provide a stable O / W type thermosetting resin aqueous dispersion comprising an aqueous dispersion in which resin particles are uniformly dispersed in a dispersed aqueous phase.

The present inventor has conducted various studies on radically polymerizable thermosetting resins, such as unsaturated polyester resins, epoxy acrylate resins, and urethane acrylate resins. A radical polymerization type thermosetting resin and water are mixed and dispersed to find an O / W-type aqueous dispersion in which resin particles are uniformly dispersed in an aqueous phase. The aqueous dispersion is stable, has thixotropic properties, and has improved workability. As well as being excellent, the aqueous dispersion can be cured at room temperature or heat cured similarly to the conventional radical polymerization type thermosetting resin, and the resulting cured product has fine continuous air holes that can withstand practical use. Was found.

[0006]

That is, (1) The present invention relates to a method of mixing a liquid radical polymerization type thermosetting resin and water in a weight ratio of 90:10 to 60:40 and mixing the resin in an aqueous phase. The present invention relates to an aqueous O / W type thermosetting resin dispersion in which particles are uniformly dispersed.

(2) The liquid radical polymerization type thermosetting resin is selected from a liquid unsaturated polyester resin, a liquid epoxy (meth) acrylate resin, a liquid urethane (meth) acrylate resin, and a liquid (meth) acrylic resin. The present invention relates to the O / W type thermosetting resin aqueous dispersion according to (1), which is at least one kind.

(3) The present invention also relates to the above-mentioned (1) or (2), wherein the liquid radical polymerization type thermosetting resin is a liquid radical polymerization type thermosetting resin containing a curing agent. The present invention relates to an aqueous dispersion of a W-type thermosetting resin.

(4) The present invention also relates to the above (1) or (2), wherein the liquid radical polymerization type thermosetting resin is a liquid radical polymerization type thermosetting resin containing a curing agent and an accelerator. O / W type thermosetting resin aqueous dispersion.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous O / W thermosetting resin dispersion of the present invention is obtained by mixing a liquid radical polymerization type thermosetting resin and water by physical means, and forming resin particles in an aqueous phase. This is an O / W type (oil-in-water type) aqueous dispersion which is uniformly dispersed. The O / W-type aqueous thermosetting resin dispersion of the present invention (hereinafter sometimes simply referred to as “O / W-type aqueous dispersion”) is generally used for a conventional liquid radical polymerization type thermosetting resin. A cured product can be easily obtained by adding a curing agent and, if necessary, an accelerator and curing at room temperature or under heating.

The O / W type thermosetting resin aqueous dispersion of the present invention is an aqueous dispersion in which fine resin particles are uniformly dispersed in an aqueous phase in a state of being covered with water. Sea Minister)
And an O / W type aqueous dispersion in which the resin particles are in a discontinuous phase (so-called island phase). Therefore, the O / W-type thermosetting resin aqueous dispersion of the present invention has a molding processing step, since volatilization of a polymerizable monomer having an ethylenically unsaturated double bond such as styrene is suppressed. Further, the odor of styrene is remarkably reduced in the curing process, the working environment for molding can be improved, and this is also excellent in terms of environmental hygiene. In addition, because it is an aqueous dispersion in which resin particles are dispersed in water, it is possible to wash with water without the need for an organic solvent as in the past, thereby improving the working environment and reducing molding costs. It also has advantages.

The liquid radical polymerization type thermosetting resin in the present invention is a liquid unsaturated polyester resin, a liquid epoxy (meth) acrylate resin, a liquid urethane (meth) acrylate resin or a liquid (meth) acrylic resin (so-called acrylic syrup). Is used.

The liquid unsaturated polyester resin in the present invention comprises a polyhydric alcohol containing a glycol as a main component, an α, β-unsaturated dibasic acid and / or an anhydride thereof, and if necessary, a saturated dibasic acid. And / or a liquid resin in which an unsaturated polyester obtained by polycondensation with an anhydride thereof is dissolved in a polymerizable monomer having an ethylenically unsaturated double bond such as styrene.

The above glycols include, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, Examples thereof include pentaerythritol derivatives such as pentaerythritol dialiether, allyl glycidyl ether, hydrogenated bisphenol A, bisphenol A, bisphenol A derivatives, and the like. These can be used alone or in combination of two or more.

The α, β-unsaturated dibasic acid and / or anhydride thereof include, for example, maleic acid or anhydride thereof, fumaric acid, itaconic acid or anhydride thereof, and the like. These can be used alone or in combination of two or more.

Examples of the saturated dibasic acid and / or its anhydride include, for example, phthalic anhydride, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, adipic acid, sebacin Acid, tetrabromophthalic anhydride, heptonic acid, hexahydrophthalic anhydride, 1,3
-Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like. These can be used alone or in combination of two or more.

Examples of the polymerizable monomer having an ethylenically unsaturated double bond include vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, vinyl acetate, methyl methacrylate and ethyl methacrylate, and diallyl. Allyl monomers such as phthalate, diallyl isophthalate, triallyl isocyanurate, diallyl tetrabromophthalate, phenoxyethyl acrylate,
Examples thereof include 1,6-hexanediol acrylate, trimethylolpropane triacrylate, and 2-hydroxyethyl acrylate. These can be used alone or in combination of two or more. Of these, vinyl monomers such as styrene and vinyltoluene are generally used.

Commercially available liquid unsaturated polyester resins can also be used. Commercially available liquid unsaturated polyester resins are, for example, trade names “FG-104” and “GC-560” manufactured by Dainippon Ink and Chemicals, “CR211” and “RG2” manufactured by Mitsui Chemicals, Inc.
2 ", Nippon Shokubai Co., Ltd. product name" N-300 ",
“G-226”, trade name “226” manufactured by Showa Kogyo Co., Ltd.
0N "," RI-201 ", trade names" 5250 "and" 8408 "manufactured by Takeda Pharmaceutical Co., Ltd., trade names" Yupika 6510 "and" 5602 "manufactured by Nippon Yupika Co., Ltd., manufactured by Hitachi Chemical Co., Ltd. Product name "2305", "262
0 "and the like.

As the liquid epoxy (meth) acrylate resin in the present invention, the epoxy resin having two or more glycidyl ether groups in one molecule is reacted with acrylic acid or methacrylic acid to obtain an epoxy group at the molecular terminal. Epoxy (meth) acrylate resin having
A liquid resin dissolved in a polymerizable monomer having an ethylenic α, β-unsaturated double bond. Examples of the epoxy resin having two or more glycidyl ether groups in one molecule include bisphenol A, bisphenol F, bisphenol S and the like, or bisphenol type epoxy resins derived from these derivatives, bixylenol and bixylenol derived therefrom. Epoxy resins, biphenol-type epoxy resins from biphenol and its derivatives, or naphthalene-type epoxy resins from naphthalene and its derivatives, and epoxy resins such as novolak-type epoxy resins. These may be used alone or in combination of two or more. Can be used in combination. Ethylenic α,
As the polymerizable monomer having a β-unsaturated double bond, the same polymerizable monomer as used in the above-described unsaturated polyester resin can be used. The liquid epoxy acrylate or epoxy methacrylate resin is a liquid resin obtained by dissolving the above epoxy acrylate or epoxy methacrylate in a liquid polymerizable monomer such as styrene or diethylene glycol dimethacrylate.

As the above liquid epoxy (meth) acrylate resin, a commercially available liquid epoxy (meth) acrylate resin can be used. Examples of the commercially available liquid epoxy (meth) acrylate resin include "UE3505" manufactured by Dainippon Ink and Chemicals, Inc. ,
“UE5210”, trade name of Mitsui Chemicals, Inc. “H67
00, H8100, trade names "RF1001" and "RF1051" manufactured by Nippon Shokubai Co., Ltd., trade names "R-800" and "H-600" manufactured by Showa Polymer Co., Ltd., manufactured by Takeda Pharmaceutical Co., Ltd. Product names "P350", "P31
0 ", a product name of Neopol 82
50 "," 8411 "and trade names" 6120 "and" 6200 "manufactured by Hitachi Chemical Co., Ltd.

The liquid urethane (meth) acrylate resin of the present invention is reacted with a polyalcohol and / or a polyester polyol and / or a polyether polyol with a diisocyanate to react the molecular end with an isocyanate to form an isocyanate.
This is reacted with an acrylate or methacrylate having an alcoholic hydroxyl group, or the acrylate or methacrylate having an alcoholic hydroxyl group is first reacted with an isocyanate while leaving an isocyanate group in a polyalcohol and / or polyester polyol and / or
Or a liquid obtained by dissolving urethane acrylate having a double bond of acrylate or methacrylate at the molecular terminal obtained by reacting with polyether polyol, or urethane methacrylate in a liquid polymerizable monomer such as styrene or diethylene glycol dimethacrylate. Resin. These can be used alone or in a mixture of two or more.

This liquid urethane (meth) acrylate resin is commercially available, for example, trade names "Yupika 8921" and "Yupika 8" manufactured by Nippon Yupika Co., Ltd.
940 "," Yupika 8932 ", and the brand name" 8200 "manufactured by Dainippon Ink and Chemicals, Inc.

The liquid acrylic resin or methacrylic resin used in the present invention may be a methyl methacrylate copolymer containing methyl methacrylate as a main component and partially copolymerizing another polymerizable monomer, or A liquid resin obtained by dissolving this copolymer in methyl methacrylate, which is usually called an acrylic syrup.For example, commercially available from Mitsubishi Rayon Co., Ltd., Nippon Yushi Co., Ltd., Nippon Shokubai Co., Ltd., Kuraray Co., Ltd., etc. Are included. In order to make these liquid resins thermosetting, for example, polyfunctional methacrylates such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate or acrylate monomers are used in combination.

The aqueous O / W thermosetting resin dispersion of the present invention is obtained by mixing a liquid radically polymerizable thermosetting resin (sometimes simply referred to as “liquid resin”) and water by a physical mixing means. Thus, it can be easily manufactured. Specifically, a predetermined amount of water is added to a liquid radically polymerizable thermosetting resin to which a curing agent and, if necessary, an accelerating agent are added, and a physical solution such as a dissolver (high-speed rotation mixer) or a homomixer is added. A stable aqueous dispersion can be obtained by mixing using a mixing means or ultrasonic irradiation. The water used may be any of ion-exchanged water, distilled water and tap water.

In the present invention, the mixing ratio of the liquid radically polymerizable thermosetting resin to water is 90:10 to 6 by weight.
0:40, preferably 85: 15-7.
0:30. If the mixing ratio of water is higher than the above range, the bonding between the resin particles of the cured product becomes weak, and the strength of the cured product is reduced, which is not preferable. On the other hand, when the mixing ratio of water is less than the above range, the form of the aqueous dispersion becomes W / O type, and the stable O /
A W-type aqueous dispersion cannot be obtained.

As described above, the O / W aqueous dispersion of the present invention can be easily obtained by mixing a liquid radically polymerizable thermosetting resin and water by physical mixing means. In preparing the O / W type aqueous dispersion, it is necessary to sufficiently mix the liquid resin and water. For example, when mixing with a dissolver (high-speed rotation mixer), a homomixer, or the like, the liquid resin and water are mixed. Is stirred and mixed at a rotation speed of 2000 to 8000 rpm for 1 to 20 minutes. By mixing under such conditions, fine resin particles are uniformly dispersed in the aqueous phase in a state of being covered with water, and an aqueous dispersion having stable and good viscosity and showing thixotropic properties is obtained. The end of the stirring and mixing can be easily determined by visual observation of the viscosity and thixotropic state of the dispersion while stirring and mixing under the above conditions. If the mixing is insufficient, the resulting aqueous dispersion has a low viscosity and has poor stability and separates in a short time,
A good aqueous dispersion cannot be obtained.

The O / W type thermosetting resin aqueous dispersion of the present invention has a particle diameter of 1 in a state where fine resin particles are coated with water.
O / W type aqueous dispersion uniformly dispersed in the aqueous phase as spherical fine particles of 0 μm or less, having good viscosity,
No. at room temperature (25 ° C.) When using 4 rotors, 1 to 20 poise at 60 rotations, 10 to 1 at 6 rotations
It is a stable aqueous dispersion having a viscosity of 00 poise, thixotropic property, and a thixotropic degree (value of 6 rotations / value of 60 rotations) of 3 to 10.

The O / W type thermosetting resin aqueous dispersion of the present invention is a stable dispersion in a form in which fine resin particles are uniformly dispersed in an aqueous phase in a state of being coated with water as described above. However, in the process of curing such an aqueous dispersion,
The stable dispersion state of the resin particles breaks due to the heat generated by the curing reaction, the polarity change, and the slight pressure from the outside in the gel-like stage, and the gel-like fine particles come into contact with each other and a chemical reaction occurs between the fine particles at the contact surface. It is presumed that the cured product having the strength enough to withstand practical use is obtained by bonding of the components to each other and bonding of the whole system. Such a cured product is a cured product having a continuous aqueous phase, forming a particle aggregate in which spherical fine resin particles of an aqueous dispersion are combined in a particulate form, and removing water from the cured product. By drying, a porous cured product in which air gaps between fine particles form continuous pores can be obtained. The cured product obtained from the O / W type aqueous dispersion of the present invention comprising such fine particles has fine continuous pores having a controlled effective pore diameter of 0.1 to 1.0 μm. Porosity is 10 to 40% by volume
Is obtained.

The O / W type aqueous dispersion of the present invention is used by adding a curing agent and, if necessary, an accelerator. The accelerator to be added if necessary is added to the liquid thermosetting resin in advance. To prepare an O / W type aqueous dispersion. The curing agent is usually added at the time of use. If the curing agent takes a long time to dissolve uniformly in the resin in the form of powder or paste, it is desirable to add the curing agent to the liquid thermosetting resin in advance to prepare an O / W type aqueous dispersion. In that case, the accelerator added as needed is added at the time of use.

As the curing agent used in the present invention, an organic peroxide is usually used. Representative examples of such a curing agent include ketone peroxides represented by methyl ethyl ketone peroxide and 1,1-bis (t-
(Hexylperoxy) peroxyketals represented by 3,3,5-trimethylcyclohexane, hydroperoxides represented by cumene hydroperoxide, dialkyl peroxides represented by dicumyl peroxide, benzoyl peroxide And peroxydicarbonates represented by bis (4-t-butylcyclohexyl) peroxydicarbonate, peroxybenzoates represented by t-butylperoxybenzoate, and the like. . Such a curing agent is usually used in an amount of 0.5 to 100 parts by weight of the liquid radical polymerization type thermosetting resin.
It is used in a range of 3.0 parts by weight, preferably 0.5 to
2.0 parts by weight are used.

The above accelerators include metal salts (metal soaps) of organic acids represented by cobalt naphthenate, tertiary amines such as N, N-dimethylaniline and N, N-dimethylparatoluidine, ferrocene and the like. An accelerator usually used for curing an unsaturated polyester resin at room temperature is used. These accelerators are preferably used in combination with a metal soap such as cobalt naphthenate when ketone peroxide or hydroperoxide is used as a curing agent, or 3 when the curing agent is diacyl peroxide.
A combination with a secondary amine is preferred, and when the curing agent is peroxycarbonate, a combination with ferrocene is preferred. As such an accelerator, the metal soap has a metal content of 6 parts by weight based on 100 parts by weight of the liquid radical polymerization type thermosetting resin.
%, And used in the range of 0.02 to 2.0 parts by weight, preferably 0.2 to 1.0 part by weight. Tertiary amines are liquid radical polymerization type thermosetting resins 1
It is used in the range of 0.05 to 1.0 part by weight, preferably 0.1 to 0.5 part by weight, per 100 parts by weight.

In preparing the O / W type aqueous dispersion of the present invention, a surfactant can be used if necessary.
Since the use of a surfactant can enhance the stability of the O / W aqueous dispersion of the present invention, the aqueous dispersion of the present invention is not used immediately after preparation, but is left as it is after being left for several days to obtain a cured product. In such a case, it is desirable to add a surfactant.

The surfactant used in the present invention includes:
Nonionic surfactants are desirable. Nonionic surfactants include (1) ester type, (2) ether type,
Any of (3) alkylphenol type, (4) sorbitan ester type, (5) polyoxyethylene sorbitan ester type, and (6) special nonionic type can be used. The addition amount of such a surfactant is used in the range of 0.1 to 10 parts by weight, preferably 0.5 to 2.0 parts by weight, based on 100 parts by weight of the liquid radical polymerization type thermosetting resin. Is done. When the amount of the surfactant is less than 0.1 part by weight, the effect of the addition is not exhibited, and when the amount exceeds 10 parts by weight, the water resistance may decrease, which is not preferable.

In order to impart strength, durability and the like to a cured product obtained from the O / W type thermosetting resin aqueous dispersion of the present invention, a reinforcing material is used as required. As such a reinforcing material, for example, glass cloth, carbon cloth, glass chop strand mat, aramid fiber, polyester fiber, acrylic fiber, synthetic fiber cloth such as polypropylene fiber, or synthetic fiber nonwoven fabric, rayon nonwoven fabric, etc. No.

[0035]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

(Preparation of O / W Type Thermosetting Resin Aqueous Dispersion) Example 1 In a metal container having an inner diameter of 10 cm and a height of 20 cm, a liquid epoxy acrylate resin (trade name "Neopol 8250H" manufactured by Nippon Yupika Co., Ltd.) was used. (Specific gravity 1.06)) 3000 g was weighed, and 60 g of commercially available benzoyl peroxide having a concentration of 50% by weight (pure content:
g) As a surfactant, 30 g of polyoxyethylene sorbitan monolaurate was added, and the mixture was mixed well with slow mixing. Then, 1000 g of tap water (2 g for 75 g of resin) was added.
5 g) and stirred at a high speed of 2,000 rpm for 15 minutes using a dissolver having an outer diameter of the blade of 8 cm.
A W-type aqueous dispersion was obtained. The resulting aqueous dispersion averages about 4
μm fine resin particles are uniformly dispersed in the aqueous phase, When a 4-rotor was used, the viscosity at 60 rotations was 9 poise, the viscosity at 6 rotations was 40 poise, and it was a thixotropic stable O / W type aqueous dispersion. The O / W type aqueous dispersion of the present invention was allowed to stand at room temperature for 30 days, but no separation was observed.

Example 2 In a metal container having an inner diameter of 20 cm and a height of 30 cm, 3000 g of a liquid unsaturated polyester resin (trade name "Yupika 6510" (specific gravity: 1.10), manufactured by Nippon Yupika Co., Ltd.) was measured. 60 g of a commercially available 50% by weight benzoyl peroxide as a curing agent (1 g of pure content per 100 g of resin),
"Pluronic L-61" (polyoxyethylene propylene ether type, manufactured by Asahi Denka Kogyo KK) as a surfactant
After adding 30 g and mixing well while mixing slowly, 1615 g of tap water (35 g for 65 g of resin) was added, and the mixture was stirred at a high speed of 3000 rpm for 8 minutes using a dissolver having an outer diameter of the blade of 8 cm. A W-type aqueous dispersion was obtained. In the obtained aqueous dispersion, fine resin particles having an average of about 3 μm were uniformly dispersed in the aqueous phase.
When a 4-rotor was used, the viscosity at 60 rotations was 11 poise, and the viscosity at 6 rotations was 70 poise, and was a stable O / W type aqueous dispersion having thixotropic properties. The O / W type aqueous dispersion of the present invention was allowed to stand at room temperature for 30 days, but no separation was observed.

Example 3 In a metal container having an inner diameter of 15 cm and a height of 20 cm, 1000 g of a liquid urethane acrylate resin (trade name "Yupika 8921" (specific gravity: 1.08), manufactured by Nippon Yupika Co., Ltd.) was weighed. 20 g of benzoyl peroxide having a concentration of 50% by weight commercially available as a curing agent (1 g of pure content per 100 g of resin)
Then, 333 g of distilled water (25 g with respect to 75 g of resin) is added thereto, and the number of revolutions is 5000 r using a dissolver having an outer diameter of the blade of 4 cm.
The mixture was stirred at a high speed at pm for 5 minutes to obtain an O / W type aqueous dispersion.
In the obtained aqueous dispersion, fine resin particles having an average of about 3 μm were uniformly dispersed in the aqueous phase. When a 4-rotor was used, the viscosity at 60 rotations was 8 poise, and the viscosity at 6 rotations was 65 poise, and was a stable O / W aqueous dispersion having thixotropic properties. The O / W type aqueous dispersion was allowed to stand at room temperature for 30 days, but no separation was observed.

Example 4 A metal container having an inner diameter of 10 cm and a height of 15 cm was weighed with 200 g of a liquid unsaturated polyester resin (trade name "Yupika 6510" (specific gravity: 1.10), manufactured by Nippon Yupika Co., Ltd.).
As a curing agent, commercially available "Parcadox 16" (trade name) (manufactured by Nippon Kayaku Co., Ltd., compound name: bis (4-t-
Butylcyclohexyl) peroxydicarbonate))
2 g (1 g of pure content per 100 g of resin) and "Nonion HS-206" (polyoxyethylene octylphenol ether type, Nippon Oil & Fat Co., Ltd.) as a surfactant
And then mixed thoroughly while slowly mixing, and then adding 110 g of distilled water (35 g to 65 g of resin) and using a dissolver having an outer diameter of the blade of 4 cm to rotate at 500 rpm.
The mixture was rapidly stirred at 0 rpm for 5 minutes to obtain an O / W type aqueous dispersion. In the obtained aqueous dispersion, fine resin particles having an average of about 3 μm were uniformly dispersed in the aqueous phase. When 4 rotors are used, the viscosity at 60 rotations is 12 poises, the viscosity at 6 rotations is 77 poises, and a stable O / W having thixotropic properties.
It was a type aqueous dispersion. The O / W type aqueous dispersion was allowed to stand at room temperature for 30 days, but no separation was observed.

Example 5 In a metal container having an inner diameter of 35 cm and a height of 40 cm, 10 kg of a liquid unsaturated polyester resin (trade name “Yupika 6510” (specific gravity: 1.10), manufactured by Nippon Yupika Co., Ltd.) was weighed. Commercially available "Permec N" as a curing agent (trade name)
100 g of methyl ethyl ketone peroxide having a concentration of 55% by weight (manufactured by Nippon Oil & Fats Co., Ltd.) (1 g of pure content per 100 g of resin), "Pluronic L-61" as surfactant
(Trade name) (trade name) (polyoxyethylene polyoxypropylene ether type, manufactured by Asahi Denka Kogyo Co., Ltd.) 100 g
And then mix well with slow mixing, then add 4.3 kg of tap water (30 g for 70 g of resin) and use a dissolver with an outer diameter of the blade of 12 cm to rotate at 200 rpm.
The mixture was rapidly stirred at 0 rpm for 10 minutes to obtain an O / W type aqueous dispersion. In the obtained aqueous dispersion, fine resin particles having an average of about 4 μm were uniformly dispersed in the aqueous phase, and were measured using a B-type viscometer, When using 4 rotors, the viscosity at 60 rotations is 10 poise,
The viscosity at the rotation is 58 poise and stable O /
It was a W-type aqueous dispersion. The O / W type aqueous dispersion was allowed to stand at room temperature for 30 days, but no separation was observed.

Example 6 In a metal container having an inner diameter of 10 cm and a height of 15 cm, 1000 g of a liquid unsaturated polyester resin (trade name "Yupika 6510" (specific gravity: 1.10), manufactured by Nippon Yupika Co., Ltd.) was weighed.
As a curing agent, 20 g of a commercially available 50% by weight benzoyl peroxide (1 g of a pure content with respect to 100 g of resin) as a curing agent, and “Pluronic L-61” (trade name) (polyoxyethylene polyoxypropylene ether type, Add 10 g of Asahi Denka Kogyo Co., Ltd.), mix well while mixing slowly, and then add 190 g of tap water (1 to 85 g of resin).
5 g) and stirred at a high speed of 4000 rpm for 4 minutes using a dissolver having an outer diameter of the blade of 4 cm, and O / W
A type aqueous dispersion was obtained. The resulting aqueous dispersion has an average of about 3μ.
m resin particles are uniformly dispersed in the aqueous phase, When using 4 rotors, the viscosity at 60 rotations is 10
This was a stable O / W type aqueous dispersion having a viscosity of 62 poise and thixotropic properties at 6 rotations. This O / W
The aqueous dispersion was left at room temperature for 30 days, but no separation was observed.

Comparative Example 1 (Preparation of Aqueous Thermosetting Resin Dispersion) In a metal container having an inner diameter of 10 cm and a height of 15 cm, a liquid unsaturated polyester resin (trade name "Yupika 6510" manufactured by Nippon Yupika Co., Ltd. (specific gravity 1) .10)) 500 g was weighed, and 10 g of a commercially available 50% by weight benzoyl peroxide (resin 10) was used as a curing agent.
(Puronic L-61) (trade name) (polyoxyethylene polyoxypropylene ether type, manufactured by Asahi Denka Kogyo KK) 10 as a surfactant
g of water, and 500 g of tap water (50 g of water with respect to 50 g of resin) is added. The number of revolutions is 400 using a dissolver having an outer diameter of the blade of 4 cm.
The mixture was rapidly stirred at 0 rpm for 4 minutes to obtain an aqueous dispersion. The obtained aqueous dispersion was an O / W type aqueous dispersion in which fine resin particles having an average of about 3 μm were uniformly dispersed in an aqueous phase.
Type viscometer, No. When a 4-rotor was used, the viscosity at 60 rotations was 30 centipoise, and the viscosity at 6 rotations was 32 centipoise, and was an aqueous dispersion with poor thixotropic properties. When this aqueous dispersion was allowed to stand at room temperature, it was separated in 10 minutes and was completely lacking in stability.

Comparative Example 2 (Preparation of Aqueous Thermosetting Resin Dispersion) In a metal container having an inner diameter of 20 cm and a height of 30 cm, a liquid unsaturated polyester resin (trade name "Yupika 6510" (product of Nippon Yupika Co., Ltd.) (specific gravity 1) .10)) 4000 g was weighed, and 80 g of a commercially available 50% by weight benzoyl peroxide (resin 1) was used as a curing agent.
(Puronic L-61) (trade name) (polyoxyethylene polyoxypropylene ether type, manufactured by Asahi Denka Kogyo KK) 4 as a surfactant
After adding 0 g and mixing gently while mixing well, 350 g of tap water (8 g of water with respect to 92 g of resin) is added, and the number of revolutions is 300 using a dissolver having an outer diameter of the blade of 8 cm.
The mixture was rapidly stirred at 0 rpm for 8 minutes to obtain an aqueous dispersion. The obtained aqueous dispersion was an aqueous dispersion in which fine resin particles were uniformly dispersed, but the obtained aqueous dispersion was of a W / O type.

(Preparation of Cured Product) Example 7 Example 1 After 6 g of N, N-dimethylaniline was added to the obtained O / W aqueous dispersion and sufficiently dissolved, the aqueous dispersion was 50 mm wide. The mixture was poured into a container having a length of 200 mm and a depth of 100 mm, and the liquid surface was covered with cellophane paper and a polyester film. After curing, the cellophane paper and the polyester film were removed, water was removed, and the mixture was allowed to stand at room temperature for 24 hours and dried to obtain a block-shaped porous cured product. The porosity of the obtained cured product was about 27% by volume, and the effective pore size was 0.5 μm.

Example 8 Example 2 6 g of N, N-dimethylaniline was added to the obtained O / W aqueous dispersion and dissolved sufficiently, and then the mixture was coated with a hydrophilic soap as a mold release agent. 450 g of the aqueous dispersion
After impregnating 3 plies of the glass chopped strand mat of g / m ^2, the glass mat impregnated with the aqueous dispersion was covered with cellophane paper and polyester film, and allowed to cure at room temperature for 24 hours. After curing, the cellophane paper and polyester film were removed, and the mixture was allowed to stand at room temperature for 24 hours and dried to obtain a glass fiber reinforced porous cured product having a thickness of 3 mm. The porosity of the obtained cured product was about 30% by volume, and the effective pore size was 0.5 μm.

Example 9 To the O / W type aqueous dispersion obtained in Example 5 was added 50 g of 6% cobalt naphthenate (content of metal cobalt: 6% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) and sufficiently dissolved. After that, the aqueous dispersion was made 100 mm wide, 500 mm long and 300 m deep.
m, and the liquid surface was covered with cellophane paper and a polyester film, and allowed to cure at room temperature for 24 hours. After curing, the cellophane paper and the polyester film were removed, and the mixture was allowed to stand at room temperature for 24 hours and dried to obtain a block-shaped cured product. The porosity of the cured product was about 31% by volume, and the effective pore diameter was 0.45 μm.

In the present invention, the resin particle size of the O / W type thermosetting resin aqueous dispersion was measured by observing with an electron microscope photograph. The porosity and pore diameter of the cured product were measured as follows. (1) Porosity The weight of the cured product before and after drying was measured, and the difference in the value {(weight before drying) − (weight after drying)} was defined as the volume (a) of the pore portion, with the specific gravity of water being 1.0. I do. Further, the weight (b) of the cured product after drying and the value of the reinforcing material content in the cured product (combustible material weight (c) and combustion residue weight (d) by the combustion method) were determined, and the porosity (X) was obtained from the following equation. I asked. [When the reinforcing material is glassy] X (%) = a / ｛(c /
Cured product true specific gravity + d / glass true specific gravity) x 100 [When the reinforcing material is organic (an approximate value is used assuming that the organic true specific gravity is the same as that of the cured resin)] X (%) = a / (b / curing) Material specific gravity + a) x 100 (2) Pore diameter Shimadzu porosity meter "Autopore III942"
Using “0”, the effective pore diameter was determined from the pressure and the amount of the injected mercury.

[0048]

(1) The O / W type thermosetting resin aqueous dispersion of the present invention is an aqueous dispersion in which fine resin particles are uniformly dispersed in a state of being covered with water. So-called sea minister)
And the resin particles are in a discontinuous phase (so-called island phase), have good viscosity, and have thixotropic stable O / W
It is a type aqueous dispersion. (2) The O / W type thermosetting resin aqueous dispersion of the present invention is an aqueous dispersion in which fine resin particles are uniformly dispersed in an aqueous phase in a state of being covered with water. Since the volatilization of the monomer is suppressed, the odor of styrene is remarkably reduced in the molding and curing steps, and the molding working environment can be improved.
In addition, since it is an aqueous dispersion in which resin particles are dispersed in water, it can be washed with water without the need for an organic solvent as in the related art, thereby improving the working environment and reducing molding work costs. It also has the advantage of: (3) By adding a curing agent and / or an accelerator to the aqueous O / W thermosetting resin dispersion of the present invention and curing at room temperature or under heating, a cured product that can withstand ordinary practical use is obtained. The obtained cured product is a porous cured product having fine continuous air holes, and this porous cured product is subjected to various functionalizing treatments, for example, as a microfiltration material, an absorbing / adsorbing material, and as a carrier. Can be used for applications.

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[Procedure amendment]

[Submission date] December 11, 2001 (2001.12.
11)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

[0019] liquid epoxy (meth) acrylate resin in the present invention, the molecular ends are obtained found by addition reaction of acrylic acid or methacrylic acid to an epoxy resin having two or more glycidyl ether groups in one molecule
It is a liquid resin obtained by dissolving an epoxy (meth) acrylate resin having a (meth) acryloyl group in a polymerizable monomer having an ethylenic α, β-unsaturated double bond. 1 above
Epoxy resins having two or more glycidyl ether groups in the molecule include, for example, bisphenol A, bisphenol F, bisphenol S, and the like, or bisphenol type epoxy resins derived from these derivatives, and bixylenol type epoxy resins derived from bixylenol and derivatives thereof. resin,
Biphenol-type epoxy resins from biphenol and its derivatives, or naphthalene-type epoxy resins from naphthalene and its derivatives, and further epoxy resins such as novolak-type epoxy resins, these may be used alone or in combination of two or more. Can be used. As the polymerizable monomer having an ethylenic α, β-unsaturated double bond, the same polymerizable monomer as used in the above-described unsaturated polyester resin can be used. The liquid epoxy acrylate or epoxy methacrylate resin is a liquid resin obtained by dissolving the above epoxy acrylate or epoxy methacrylate in a liquid polymerizable monomer such as styrene or diethylene glycol dimethacrylate.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F070 AA32 AA46 AA49 AA53 AC19 AC24 AE08 CA03 CB03 CB12 FA02 4J002 BG031 BG071 CD191 CF211 CK021 EG016 EK026 EK046 EK066 EK076 EN016 EN066 FD146 HA07

Claims (4)

[Claims] An O / W type heat in which a liquid radical polymerization type thermosetting resin and water are mixed at a weight ratio of 90:10 to 60:40 and resin particles are uniformly dispersed in an aqueous phase. Curable resin aqueous dispersion. 2. The liquid radical polymerization type thermosetting resin is at least one selected from a liquid unsaturated polyester resin, a liquid epoxy (meth) acrylate resin, a liquid urethane (meth) acrylate resin, and a liquid (meth) acryl resin. The O / W type thermosetting resin aqueous dispersion according to claim 1, which is a seed. 3. The O / W type thermosetting resin aqueous dispersion according to claim 1, wherein the liquid radical polymerization type thermosetting resin is a liquid radical polymerization type thermosetting resin containing a curing agent. body. 4. The O / W type thermosetting resin according to claim 1, wherein the liquid type radical polymerization type thermosetting resin is a liquid type radical polymerization type thermosetting resin containing a curing agent and an accelerator. Aqueous resin dispersion.