JP2002348484A - Method for producing curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a curable resin composition obtained by combining a curable resin and an inorganic oxide, which can sufficiently exert characteristics of the inorganic oxide obtained by a hydrothermal synthesis and which can impart physical properties derived from an inorganic material which keeping workability of an organic material. SOLUTION: The method for producing the curable resin composition obtained by combining the curable resin and the inorganic oxide, which comprises a step of heating a mixture containing an organic compound forming a cured material of the curable resin, an inorganic compound forming the inorganic oxide, and water as essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a curable resin composition. More specifically, the present invention relates to a method for producing a curable resin composition in which a curable resin and an inorganic oxide are combined.

[0002]

2. Description of the Related Art Inorganic oxides are electrically,
Since it has various mechanical and chemical properties, for example, if useful properties can be imparted to an organic material, it can be used as an organic-inorganic composite material, such as electric / electronic parts, automobile parts, and building materials. It is expected to be used in various fields. Such inorganic oxides are required to be finely powdered, have high quality, and be well dispersible in organic substances in order to sufficiently exhibit their properties.

[0003] Among inorganic oxides, barium titanate [BaTiO ₃ ] obtained by hydrothermal synthesis has attracted attention for its synthesis method. As the hydrothermal synthesis method, for example, barium hydroxide and metatitanic acid [TiO
(OH) ₂ ] with a hydrous salt at 100 ° C. and at high pressure of 1 atm or more is known. BaTiO ₃ obtained by such hydrothermal synthesis has good crystallinity. Characteristic performance and high quality can be expected. In addition, the hydrothermal synthesis of titanium oxide (TiO ₂ ) has recently attracted attention. When titanium tetraalkoxide or titanium tetrachloride is subjected to hydrolysis or sol-gel reaction in the presence of water and then subjected to a heating reaction, it can be synthesized by controlling rutile-type and anatase-type crystal forms depending on the acidic and basic conditions. Has become known. The titanium oxide thus obtained has a photocatalytic effect, but because of its small particle size and large surface area, high performance can be expected when imparting antibacterial properties by irradiating ultraviolet rays such as fluorescent light sunlight. It is.

As a technique using such an inorganic oxide, Japanese Patent Application Laid-Open No. 2001-19798 discloses a pre-mixing step of attaching raw materials of an inorganic filler to each other.
There is disclosed a method for producing an inorganic-organic composite material in which a hydrothermal synthesis process for hydrothermal synthesis of an inorganic filler and a polymerization process for polymerization of a thermoplastic resin are simultaneously performed. In this manufacturing method,
An inorganic-organic composite material is manufactured using nylon 6 or the like as a thermoplastic resin.

[0005] However, such a production method is performed for the purpose of improving the mixing of the inorganic filler obtained by the hydrothermal synthesis method and the thermoplastic resin by the melt-kneading method using an extruder. There is room for studying not only the purpose but also a production method that can sufficiently exhibit the properties of the inorganic filler obtained by the hydrothermal synthesis method. That is, in such a production method, an inorganic-organic composite material having characteristics in which the inorganic filler is dispersed in the thermoplastic resin is obtained, but the performance of the inorganic filler obtained by the hydrothermal synthesis method in various fields is further improved. There is room for studying combinations of inorganic oxides and organic substances and methods for producing the same so that they can be demonstrated.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made of a curable resin and an inorganic oxide capable of sufficiently exhibiting the characteristics of an inorganic oxide obtained by hydrothermal synthesis. An object of the present invention is to provide a method for producing a curable resin composition in which an object is combined.

[0007]

Means for Solving the Problems The inventors of the present invention have studied various production methods for sufficiently exhibiting the characteristics of inorganic oxides, and found that the synthesized inorganic oxides are crystals. When the inorganic oxide is synthesized by a hydrothermal synthesis method in which synthesis is performed using hot water, the water used for synthesis promotes the equilibrium between different crystals, and It has the effect of growing, compared to normal manufacturing methods such as the solid phase method, because it can be synthesized under low temperature and mild conditions and the particle size is small, so that high crystallinity can be obtained, because water is used Paying attention to the fact that hydroxyl groups remain on the surface, and performing hydrothermal synthesis of inorganic oxide in the presence of an organic compound that forms a cured product of the curable resin, while maintaining processability as a curable resin Obtained by hydrothermal synthesis It is possible to impart physical properties derived from inorganic oxides, conceive that can be admirably solved the above problems, it is the present invention has been completed. In such a production method, it is considered that the hydroxyl group remaining on the surface of the inorganic oxide becomes compatible with the curable resin, and the curable resin and the inorganic oxide are complexed. In the curable resin composition thus obtained, the properties of the inorganic oxide are sufficiently exhibited in the curable resin by the complexation, and the function of the curable resin and the function of the inorganic oxide are In combination, characteristic performance and high quality are exhibited in various fields.

That is, the present invention relates to a method for producing a curable resin composition in which a curable resin and an inorganic oxide are combined, comprising an organic compound forming a cured product of the curable resin, and an inorganic oxide. This is a method for producing a curable resin composition, which comprises a step of heating a mixture essentially containing water and an inorganic compound forming water. Such a production method of the present invention is a method of reacting an inorganic compound without reacting a curable resin in a step of heating a mixture. It is considered that the inclusion of the curable resin stabilizes the generated inorganic oxide by interaction with the functional group of the curable resin. That is, it is a feature of the present invention that the curable resin does not react with the inorganic compound or the generated inorganic oxide in the step of heating the mixture. Hereinafter, the present invention will be described in detail.

[0009] The production method of the present invention is a method for producing a curable resin composition in which a curable resin and an inorganic oxide are combined. The curable resin means an organic compound forming a cured product, that is, an organic compound incorporated as a constituent element in the cured product. In the present invention, the organic compound constituting the curable resin may be an organic polymer compound, and its molecular weight is not particularly limited.
Moreover, it may be composed of one type or a combination of two or more types. Such a curable resin is constituted by part or all of the organic compound forming the cured product. That is, a part or all of the organic compound forming the cured product of the curable resin is an element constituting the curable resin composition produced by the present invention. When producing a curable resin composition by a part of the organic compound forming the cured product of the curable resin, the cured product is obtained from the curable resin composition obtained by adding the remainder of the organic compound forming the cured product of the curable resin. Although it will be formed, the curable resin composition in any of these states can be produced by the production method of the present invention.

Accordingly, as the curable resin constituting the curable resin composition produced by the present invention, for example, when the cured product is formed by an organic polymer compound and a crosslinking agent or a reactive diluent, Any of 1) an organic polymer compound, (2) a crosslinking agent or a reactive diluent, and (3) a mixture of an organic polymer compound and a crosslinking agent or a reactive diluent may be used. In the present invention, when forming a cured product as a solvent or the like, a compound that does not become a component of the cured product even when coexisting, that is, a compound that is removed before forming the cured product is not included in the curable resin. . In addition, the curable resin undergoes a chemical reaction to form a three-dimensional cured product, thereby forming a cured product. The curing in this case is distinguished from the formation of a chemical bond by hydrothermal synthesis described later. You.

As the organic compound that can constitute the above-mentioned curable resin, for example, two or more organic compounds having a reactive functional group can be used in combination. There is no particular limitation as long as it has reactivity. For example, the following (1) to (8)
And the like. In the present invention, in order to form a cured product, a polyfunctional compound having such a functional group, a compound modified with such a functional group, an oligomer, or a polymer can be used. It is preferable to use a polyfunctional compound which is a compound having a functional group so as to react as polyvalent so as to generate a structure. The combination of such functional groups is 2
It may be a combination of two functional groups, or a combination of three or more functional groups. However, in consideration of easy control of curability, the combination of two functional groups is required. Is preferred.

(1) a phenolic hydroxyl group or an amino group;
A combination of a double bond, a nitrile group, a mercapto group, a carboxyl group, and a hydroxyl group; (2) a combination of a halogen group such as a fluorine atom, a chlorine atom, and a bromine atom with a tertiary amine, a double bond, and a hydroxyl group; A) a combination of an amino group with a chlorosulfone group, an ester group, an isocyanate group, an epoxy group, a methylol group, a sulfonic acid group;
(4) Combination of isocyanate group with hydroxyl group, amino group, carboxyl group, mercapto group; (5) Combination of carboxyl group or acid anhydride group with epoxy group, hydroxyl group, isocyanate group; ) A combination of an aldehyde group with a double bond and a hydroxyl group; (7) a combination of an alcoholic hydroxyl group with a chlorosulfone group, a double bond and an epoxy group; and (8) an epoxy group with a chlorosulfone group and a mercapto group. , A double bond or an isocyanate group.

The preferred form of the curable resin is
An epoxy resin and / or a curing agent thereof may be used. The epoxy resin is not particularly limited, and may be any commonly used epoxy resin. Examples thereof include bisphenol A, bisphenol F, tetramethylbisphenol F, bisphenol S, and bisphenol K. Glycidylated compounds such as, biphenol, tetramethylbiphenol, hydroquinone, trimethylhydroquinone, di-tert-butylhydroquinone, resorcinol, methylresorcinol, catechol, methylcatechol, dihydroxynaphthalene, dihydroxydimethylnaphthalene; Condensates of phenols or naphtholes with aldehydes; Condensates of phenols or naphtholes with xylylene glycol; phenols or naphtholes with bismethoxymethyl Condensate with biphenyl; reaction product of phenols and dicyclopentadiene; Reaction products of Le acids - fluorene compound and phenol;
Glycidylated products of a reaction product of a terpene and a phenol are exemplified. These may be used alone or in combination of two or more. The method for producing these epoxy resins is not particularly limited, and the epoxy resin can be produced by a known method.

Examples of phenols used as a raw material for producing the epoxy resin include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, catechol, resorcinol. −
, Methylresorcinol, hydroquinone, phenylphenol, bisphenol A, bisphenol F, bisphenol S, biphenol, tetramethylbiphenol and the like. As naphtholes, for example,
Examples thereof include 1-naphthol, 2-naphthol, dihydroxynaphthalene, dihydroxydimethylnaphthalene, and trihydroxynaphthalene. Examples of the aldehydes include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, benzaldehyde, chlorbenzaldehyde, bromobenzaldehyde, and glyoxaza-
, Malonaldehyde, pimeraldehyde, sebacinaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like. These may be used alone or in combination of two or more.

The curing agent for the epoxy resin is not particularly limited as long as it can be generally used as a curing agent for an epoxy resin, and examples thereof include (1) amines and (2)
One or more of acid anhydrides, (3) polyhydric phenols, and (4) others can be used. In addition, what is called what is called a hardening accelerator is also contained in this. Among these, it is preferable to use the amines exemplified in (1).

(1) amines: diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine,
Aliphatic amines such as pentaethylenehexamine; aromatic amines such as diaminodiphenylmethane, diaminodiphenylsulfone, metaxylenediamine and metaphenylenediamine; benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1 Tertiary amines such as, 8-diazabicyclo (5,4,0) undecene-7,1,5-diazabicyclo (4,3,0) nonene-7 and salts thereof.

(2) Acid anhydrides: aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, Cyclic aliphatic acid anhydrides such as methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride;

(3) Polyphenols: Bisphenol A, Bisphenol F, Tetramethylbisphenol F, Bisphenol S, Bisphenol K, Biphenol
, Tetramethylbiphenol, hydroquinone, trimethylhydroquinone, di-t-butylhydroquinone,
Resorcinol, methyl resorcinol, catechol,
Novolaks of divalent phenols such as methyl catechol, dihydroxynaphthalene, dihydroxydimethylnaphthalene, phenol novolaks, cresol novolaks, and bisphenol A; trishydroxyoxyphenylmethanes; alkyl polyphenols Dicyclopentadiene polyphenols and the like;

(4) Others: 2-methylimidazole,
2-ethyl-4-methyl-imidazo - methylphenol, 2-phenyl-imidazo - like Le imidazo - Le compounds and their salts; BF ₃ complex compound of an amine, aliphatic sulfonium salts, Bronsted acids such as aromatic sulfonium salts salts;
Dicyandiamides; organic acid hydrazides such as adipic dihydrazide and phthalic dihydrazide;
Polycarboxylic acids such as adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxyl group-containing polyester; organic phosphine compounds such as triphenylphosphine; trimethylolpropane trithioglycolate and pentaerythritol pentathioglycolate. And polyhydric mercaptan compounds such as esters of polyhydric alcohols and thioglycolic acid.

Examples of the organic compound that can constitute the curable resin include resins other than epoxy resins, such as phenol resins, amino resins such as melamine resins and urea resins, phenoxy resins, epoxy-modified polyimide resins, Resins such as unsaturated polyester resin, polyimide resin, urethane resin, and diallyl phthalate resin are exemplified. In addition, as a radical curable resin, a photosensitive resin composed of a compound having a (meth) acryloyl group such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, or a monomer. Resins; radical curable monomer mixtures, etc. can also be used.

The inorganic oxide in the present invention preferably contains at least one element selected from the group consisting of group IVa, group Va, group IIb and group III in the periodic table. Thus, various properties can be imparted to the inorganic oxide, and the inorganic oxide can be easily prepared and obtained industrially. Among these, barium titanate and titanium oxide are preferred. In addition, the inorganic oxide in this invention may be comprised by 1 type and may be comprised combining 2 or more types.

The production method of the present invention includes a step of heating a mixture which essentially comprises an organic compound forming the cured product of the curable resin, an inorganic compound forming the inorganic oxide, and water. . Through such a process, an inorganic oxide that is hydrothermally synthesized from the inorganic compound is generated in the curable resin. At this time, it is preferable that the curable resin is not reacted, but the inorganic compound is reacted, and the produced inorganic oxide is stabilized by the interaction with the functional group of the curable resin. It is preferable to adjust the reaction conditions and the like. Thereby, the properties of the inorganic oxide are sufficiently exhibited in the cured product formed from the curable resin composition. The hydrothermal synthesis method is a method of synthesizing a compound by the action of hot water, and in the present invention, an inorganic oxide is formed by including the above steps.
In addition, in the present invention, it is essential to include the above steps, but other steps may or may not be included.

In the above process, for example, when barium titanate [BaTiO ₃ ] is synthesized as an inorganic oxide,
A method using a titanium alkoxide as a source of titanium atoms and a method using titanium oxide are preferable.
Further, as a supply source of barium atoms, barium compounds such as barium hydroxide, barium chloride, and barium acetate can be used. That is, as the inorganic compound forming the inorganic oxide, such a compound can be used.

In the above-mentioned step, the method using titanium alkoxide is preferably a method of hydrothermal reaction using titanium alkoxide and barium hydroxide as an inorganic compound forming an inorganic oxide, for example, titanium tetrabutoxide [ Ti (OC ₄ H ₉ )] and ethanol, and barium hydroxide octahydrate [Ba (OH) _2.
An aqueous solution of 8H ₂ O] was prepared, how mixed with these organic compounds to form a cured product of the curable resin to hydrothermal reaction. In the method using titanium oxide, a method of performing a hydrothermal reaction using titanium oxide and barium hydroxide is preferable. For example, titanium dioxide [Ti
O _2] The organic compound to form a cured product of the particles and a curable resin is dispersed in water was heated to 100 ° C., was added barium hydroxide octahydrate _{[Ba (OH) 2 · 8H 2} O ] And a hydrothermal reaction. In the above step, the reaction is preferably performed under alkaline conditions, for example,
By adding an aqueous solution of potassium hydroxide, alkaline conditions can be achieved. In the method using titanium alkoxide, a hydrothermal reaction can be performed after an aqueous potassium hydroxide solution is added. Further, in the method using the titanium oxide, barium hydroxide octahydrate after addition of aqueous potassium hydroxide _{[Ba (OH) 2 · 8H 2} O ]
Can be added to cause a hydrothermal reaction.

The reaction conditions in the above steps are not particularly limited. For example, the reaction temperature may be appropriately set depending on the inorganic oxide to be prepared, and the reaction pressure may be normal pressure or may be increased. However, in the present invention, the synthesis is performed under milder conditions than the normal hydrothermal reaction conditions. For example, the reaction temperature is 100 ° C. or lower, preferably 50 to 100 ° C., and more preferably 70 to 10 ° C.
The temperature can be 0 ° C., the reaction pressure can be normal pressure, and the reaction time can be 4 to 10 hours.

In the above step, the inorganic oxide has a surface hydroxyl group mole number of 2.0 × 10 ^{−3 to} 3.0 × 10 ⁻² mol / g.
It is preferable to set reaction conditions and the like such that When the number of moles of hydroxyl groups on the surface of the inorganic oxide is within the above range, the function and effect of the present invention will be exhibited more reliably. Preferably, 3.0 × 10 ^{−3 to} 1.5 × 10 ^−2.
mol / g, and more preferably 3.5 × 10 ⁻³ or more.
1.0 × 10 ⁻² mol / g, more preferably,
It is 4.0 × 10 ^{−3 to} 8.0 × 10 ⁻³ mol / g.

The number of moles of hydroxyl groups on the surface can be measured by the following ignition loss method. In general, as the metal oxide is heated, so-called adsorbed water on the surface is desorbed at around 100 to 150 ° C.
By 000 ° C., surface hydroxyl groups are condensed and released as water (H ₂ O). The number of moles of hydroxyl groups on the surface does not include adsorbed water.

[0028]Ignition loss method  The sample used for measurement is dried under vacuum at 150 ° C for 2 hours in advance.
And remove the surface adsorbed water. Sample Wg (usually 1
２2 g) in a crucible having a constant weight in advance.
After heating and gradually raising the temperature, ignite at 1000 ° C for 2 hours
I do. Then, after radiating heat in the desiccator,
Weight of sample after: W_Two) To determine the ignition loss. This
From these measured values, calculate the amount of hydroxyl groups on the surface by the following formula
I do. Surface hydroxyl group content (mol / oxide 1 g) = 2 × (W−
W_Two) / W / 18 W: Dry sample (g) W_Two: Sample after ignition (g)

The curable resin composition produced according to the present invention is a composition in which a curable resin and an inorganic oxide are combined. As a form of such a curable resin composition,
There is no particular limitation as long as these essential components are present in the composition and the functions of each component can be exhibited. A preferable embodiment is, for example, a composition in which a curable resin and an inorganic oxide are in a composite state.

In the production method of the present invention, one or more auxiliary materials, additives, solvents, etc., which are usually added to the resin, may be added, if necessary, as long as the functions and effects of the present invention are exhibited. May be. In this case, it is preferable to add after the above step, but it may be added during the above step or may be added before the above step. The solvent and the like are not particularly limited, but it is preferable that the liquid phase be uniform. For example, when an epoxy resin is used as the curable resin in the above process, it is also possible to cause a reaction using a water-soluble solvent in combination. Further, the total weight of the curable resin and the inorganic oxide is preferably, for example, 50% by weight or more based on 100% by weight of the curable resin composition. More preferably, it is 70% by weight or more, and still more preferably 90% by weight or more. The weight ratio between the curable resin and the inorganic oxide may be appropriately set depending on the use of the curable resin composition, desired physical properties, and the like, and is not particularly limited. For example, 99.9 / 0.1 It is preferably from 10 to 90. More preferably, 99/1 to 20/8
0, more preferably 98/2 to 25/75.

The curable resin composition produced according to the present invention is a material in which a curable resin and an inorganic oxide are combined and the properties of the inorganic oxide can be sufficiently exhibited.
A cured product will be formed. Such a curable resin composition, while maintaining the processability of an organic substance, can impart physical properties derived from an inorganic substance to the cured substance, so that the cured substance of the curable resin has improved mechanical strength, Heat resistance, water resistance, flame retardancy, gas barrier properties, etc. can be imparted. In addition, when the inorganic oxide contains titanium dioxide [TiO ₂ ], it is possible to impart anti-sono properties. Becomes The curable resin composition imparted with such properties is a material suitable as a molding material, a paint, an adhesive, or the like, as an electric / electronic part, an automobile part, a building material, or the like.

[0032]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Preparation of Powder Samples in Examples and Comparative Examples
Method, method for analyzing the crystallinity of inorganic oxide crystals, and inorganic acid
The method for measuring the amount of hydroxyl groups on the surface of the halide crystal is shown below.Powder sample preparation method  The obtained reaction product is centrifuged (5,000 to 10,000).
separation and washing (water, methanol, etc.)
After returning to the slurry state, a trace amount of methanol remains.
The sample was vacuum dried at 70 ° C to completely remove volatile components.
Thus, a powder of fine particles was obtained, and this was used as a sample.

[0034]Analysis method of crystallinity  X-ray diffractometer (Rigaku Corporation, product name "Wide-angle goniometer"
RINT2400 ”) using a powder sample preparation method
The crystallinity of the prepared sample was measured. Sample is aluminum
The cells were filled and mounted. (Measurement conditions) X-ray: Cu-Kα1 (40 kV, 50 mA) Divergence slit: 1/2 ° Scattering slit: 1/2 ° Light receiving slit: 0.3 mm Scanning speed: 7.000 ° / min Scanning axis: 2θ / θ

[0035]The amount of hydroxyl groups on the surface of the inorganic oxide crystal (ignition loss
Method)  The sample used for measurement is dried under vacuum at 150 ° C for 2 hours in advance.
Then, the one from which surface adsorbed water was removed was used. Dry sample 1
~ 2g (Wg) in a constant weight crucible
After heating weakly and gradually increasing the temperature, 2 hours at 1000 ° C
Heated for a while. Then, after radiating heat in the desiccator,
(W_Two) Was measured to determine the ignition loss. These measurements
The amount of surface hydroxyl groups was calculated using the following equation. Surface hydroxyl group content (mol / oxide 1 g) = 2 × (WW
_Two) / W / 18 W: Dry sample (g) W_Two: Sample after ignition (g)

Example 1 1 dm equipped with a stirrer, dropping funnel, thermometer and reflux condenser
^In the glass reactor ( ³ ), tetraethylenepentamine 20
0 g, was weighed deionized water 100 g, TiO ₂ P25
10 g of titanium dioxide (trade name, manufactured by Aerosil Co., Ltd., average particle diameter: 20 nm) was added thereto with stirring, and 1 g was added under a nitrogen stream.
The temperature was raised to 00 ° C. After holding for 10 minutes, barium hydroxide 8
Add 40 g of hydrate, and stir at 100 ° C.
By holding for a time, a white dispersion was obtained. The obtained dispersion was treated according to a powder sample preparation method, and the obtained sample was analyzed by an X-ray diffractometer. As a result, the dispersed fine particles were crystallographically barium titanate crystals, and the crystallite size according to the Wilson method was 25 nm. The amount of surface hydroxyl groups was 7.0 × 10 ⁻³ mol / g.

The above dispersion was heated to 120 ° C. while stirring, and the pressure was reduced. 120 g of water was removed to obtain a white uniform inorganic oxide and amine. 100 g of YDF-170 (trade name, manufactured by Toto Kasei Co., bis-F epoxy resin, epoxy equivalent: 169) was added to 20 g of the above composition, mixed well, and then made of silicone rubber on a glass plate subjected to release treatment. A frame was formed, poured into a thickness of 3 mm, and heated in an oven at 60 ° C. for 4 hours and at 100 ° C. for 4 hours to obtain a white uniform cured product. The physical properties of the cured product were measured by the following methods. Table 1 shows the results.

The method for measuring the physical properties of the cured product is described below.Flame retardance  Test piece cut to 20 mm x 20 mm (thickness 3 mm)
Was contacted with a 4 cm high flame of a Bunsen burner for 2 seconds.
The state of combustion of the test piece was observed. In addition, until fire extinguishing
The time was measured.

[0039]Mechanical strength  A test piece prepared by cutting a cured product was subjected to JIS K-71.
According to No. 13, a tensile test and a bending test were performed.

Example 2 15 g of TiO ₂ P25 and 60 g of barium hydroxide octahydrate were heated and reacted in the same manner as in Example 1 to obtain a white dispersion. When this white dispersion was analyzed by processing, it was crystallographically a barium titanate crystal, and the crystallite size according to the Wilson method was 30 nm. The amount of surface hydroxyl groups was 7.0 × 10 ⁻³ mol / g. Further, similarly, 130 g of water was removed by heating and reduced pressure to obtain a composition composed of a white inorganic oxide and an amine. 21 g of the above composition
And YDF-170 was added thereto and cured in the same manner to obtain a white uniform cured product. The physical properties of this cured product were measured in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 200 g of tetraethylenepentamine and 15 g of titanium tetrabutoxide were weighed into the same glass reactor as in Example 1, and 100 g of ion-exchanged water was added from a dropping funnel with vigorous stirring. The mixture was heated to 100 ° C. while stirring the mixture under a nitrogen stream. Thereafter, the same operation as in Example 1 was performed. The generated fine particles were crystallographically barium titanate crystals, and the crystallite size according to the Wilson method was 30 nm. The amount of surface hydroxyl groups is 6.5 ×
It was 10 ⁻³ mol / g. The cured product was similarly white and uniform.

Example 4 Example 3 except that barium hydroxide octahydrate was not added.
The same operation as described above was performed. The generated fine particles were crystallographically rutile-type titanium oxide, and had a crystallite size of 30 nm according to the Wilson method. The amount of surface hydroxyl groups is 6.
It was 0 × 10 ⁻³ mol / g. The cured product was similarly white and uniform.

Comparative Example 1 A cured product was obtained in the same manner as in Example 1 except that no inorganic substance was added. Physical properties of the cured product were measured in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 3.2 g of barium titanate (manufactured by Kyoritsu Materials Co., Ltd.) was added to 16 g of tetraethylenepentamine and thoroughly stirred and mixed, and then 100 g of YDF-170 was added and cured in the same manner as in Example 1. However, the cured product was white and uniform.

[0045]

[Table 1]

Table 1 is described below. The inorganic crystal content (wt%) in the cured product is the weight ratio (wt%) of the inorganic crystal contained in the produced cured product to 100% by weight of the cured product. For flame retardancy, the value is
It is time to extinguish the fire.

[0047]

The method for producing the curable resin composition of the present invention has the above-described structure, and therefore, the curable resin having the physical properties derived from the inorganic substance is imparted while maintaining the processability of the organic substance. A composition can be manufactured. That is, in the cured product of the curable resin, mechanical strength can be improved, heat resistance, water resistance, flame retardancy, gas barrier properties, antibacterial properties, etc. can be imparted, and molding materials, paints, adhesives, etc. As a result, it is possible to produce a curable resin composition which is a suitable material for electric / electronic parts, automobile parts, building materials and the like.

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Claims (4)

[Claims] 1. A method for producing a curable resin composition in which a curable resin and an inorganic oxide are combined, wherein an organic compound forming a cured product of the curable resin and the inorganic oxide are formed. A method for producing a curable resin composition, comprising a step of heating a mixture containing an inorganic compound and water as essential components. 2. The inorganic oxide is selected from Group IVa and V of the periodic table.
The curable resin composition according to claim 1, wherein at least one element selected from the group consisting of group a, group IIb, and group III elements is essential. 3. The curable resin composition according to claim 2, wherein the inorganic oxide is barium titanate. 4. The curable resin is an epoxy resin and / or
4. The curable resin composition according to claim 1, which is a curing agent thereof.