JP2002255622A - Method for manufacturing hardening composition of organic-inorganic complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for obtaining a phosphoric acid-based inorganic hardening composition which has excellent fluidity and water resistance and gives excellent strength to the hardened material and whose workability is excellent until the hardening work is completed. SOLUTION: This method for manufacturing a hardening composition of an organic-inorganic complex comprises a step to react a phosphoric acid aqueous solution containing 10-80 mass% P2 O5 and acid phosphates with at least one compound selected from alkaline metallic compounds of bivalent metal beforehand by the prescribed mass ratios and a step to add aluminum hydroxide of the prescribed mass ratio to the reaction product while heating at 70-100 deg.C in succession. The ratio of the total valence of the phosphoric acid ions to that of the metallic ions at each step is regulated to be in the prescribed range.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition suitably used for, for example, an adhesive, a coating agent, and a matrix of a fiber-reinforced molded product. By improving the fluidity of the composition as compared with the above, the handleability, workability during molding, moldability in various applications are improved, and the obtained cured product has excellent mechanical strength and excellent water resistance. The present invention relates to a method for producing an acid-based curable composition.

[0002]

2. Description of the Related Art Conventionally, a phosphoric acid-based curable composition has been widely used as a matrix of an adhesive, a binder, a coating agent, a molding material and the like. The phosphoric acid-based curable composition has advantages such as a high heat resistance, a short time to curing, and a high strength, as compared with a cement material, because it does not consist of a water curing reaction. Utilizing this property, various phosphoric acid-based curable compositions have been proposed.

For example, in Japanese Patent Publication No. 2-28547, 11 to 65 parts by weight of at least one metal oxide selected from the group consisting of Al ₂ O ₃ , MgO, CaO, ZnO, or a hydrate thereof is disclosed. A hard material, comprising about 80 to about 90 parts by weight of a phosphoric acid solution comprising about 5 to 75% by weight of phosphorus pentoxide in an equivalent amount based on the weight of the phosphoric acid solution, and about 100 parts by weight of calcium silicate; Water resistant phosphate ceramic materials have been proposed.

In Japanese Patent Application Laid-Open No. 9-241583,
An inorganic binder composition obtained by reacting phosphoric acid and a metal element compound in the presence of water to obtain a phosphate aqueous solution, and adjusting the water content of the phosphate aqueous solution, The composition of the binder composition is converted into P ₂ O ₅ + M _x O _y + H ₂ O, and P, M, and H ₂ O in the inorganic binder composition are converted.
When the ratio of the amount of H ₂ O is in the range of 2.8 to 3.6 equivalents and the amount of H ₂ O is in the range of 10 to 40 moles per mole of P ₂ O ₅ , Things have been suggested.

Further, Japanese Patent Application Laid-Open No. 5-282547 discloses that an inorganic fluid composition obtained by mixing an aqueous solution of aluminum phosphate with a metal compound and an inorganic filler as a thickening agent as a binder, a phenol resin, a silicone, A heat-resistant insulating material having improved mechanical strength and insulating properties has been proposed by mixing 2 to 15 parts by mass of a thermosetting resin such as a resin and a melamine resin, preferably with respect to 100 parts of aluminum phosphate. I have.

[0006]

However, in a curable composition comprising phosphoric acids such as an aqueous solution of phosphoric acid and an acidic metal phosphate and a metal compound such as a metal oxide and a metal hydroxide, the metal compound used Due to the fact that the curing reaction starts immediately after mixing,
Some of them require application of the above high temperature, and there is a problem that it is difficult to control a curing reaction as compared with an organic curable composition.

For example, Japanese Patent Publication No. 2-28 mentioned in the prior art
In the composition of No. 547, since the curing reaction starts immediately after mixing the phosphoric acid and the metal compound, the pot life of the curable composition is short, and the use as an adhesive, a coating agent, a binder or a molded article is limited. is there.

On the other hand, the composition disclosed in Japanese Patent Application Laid-Open No. 9-241583 has a long pot life and can be used as an adhesive, a coating agent, a binder or a molded product. In order to obtain a cured product having a high content and water resistance, a heating process of 1 to 2 hours is required under heating at 200 ° C. or higher, which has a problem that energy cost is high and productivity is poor. ing.

Further, since the curing reaction between phosphoric acid and metal oxide is a solid-liquid reaction, it takes place in the surface layer of the metal compound particles and hardly takes place inside the particles. Therefore, in order to react most of the hydroxyl groups of phosphoric acids in the curable composition without impairing the water resistance of the obtained cured product,
It is necessary to increase the equivalent ratio of the metal ions contained in the metal compound to the phosphate ions contained in the phosphates. However, in this case, there is a problem that the viscosity of the curable composition becomes high and the workability when used as an adhesive, a coating agent, a binder, or a molded product is impaired.

Further, as disclosed in Japanese Patent Application Laid-Open No. 5-182547, a thermosetting resin is conventionally blended with a curable composition comprising phosphoric acid and a metal compound. In this case, the inorganic skeleton and the resin component do not directly react with each other, and the inorganic skeleton and the organic polymer are simply mixed, so that the mechanical strength and the insulating properties can be improved. Above the temperature, there is a problem that the heat resistance is significantly reduced.

Accordingly, an object of the present invention is to provide a cured product having excellent mechanical strength, water resistance and heat resistance, low viscosity and fluidity, good workability until curing, and a long pot life. It is an object of the present invention to provide a method for producing a long curable organic-inorganic composite composition.

[0012]

Means for Solving the Problems To solve the above problems,
One of the methods for producing the organic-inorganic composite curable composition of the present invention
One is P_TwoO_FiveA phosphoric acid aqueous solution containing 10 to 80% by mass of
At least one selected from acidic organic phosphoric acid compounds
And a basic metal compound comprising a divalent metal,
Each of the phosphate ions and acidic organic phosphate compound
ON valence and metal ion of the basic metal compound
Of the total valence (A₁) Is 0.1 ≦ A₁A first step of mixing and reacting so that ≦ 0.6, and after the reaction,
Add aluminum hydroxide under heating at 70-100 ° C,
Of phosphate ion and acidic organic phosphate compound ion after addition
The ratio of the total valence to the total valence of the metal ion (A_Two) Is 0.7 ≦ A_TwoA second step of mixing and reacting so as to satisfy ≦ 1.2.
It is characterized by. (However, the ratio of total valences (A₁) And (A_Two)
Is A₁= (M₁× m₁+ M_Two× m_Two+ ...) / (P × 3 + N₁/ N₁
+ N_Two/ N_Two+…) A_Two= (M₀× m₀+ M₁× m₁+ M_Two× m_Two+ ...) / (P × 3
+ N₁/ N₁+ N_Two/ N_Two+ ...) where P is a phosphate ion contained in the aqueous phosphoric acid solution,
PO_Four ^3-Number of moles of N₁, N_Two, ... are acidic organic resources to be added
Weight of acid compound (g), n₁, N_Two, ... is the above N₁,
N_TwoHydroxyl equivalent of acidic organic phosphoric acid compound corresponding to, ...
(G / eq). Also M₀Is the added aluminum hydroxide
Number of metal ions contained in the metal, M₁, M_Two, ... is 2
Of the metal ion contained in the basic metal compound
Number, m ₀, M₁, M_Two, ... are the above metal ions
The valence of each corresponding metal ion is shown. )

According to the above-mentioned production method, a step of preliminarily reacting an aqueous phosphoric acid solution, at least one selected from acidic organic phosphoric acid compounds, and a basic metal compound comprising a divalent metal, It proceeds in two stages of a process of adding and reacting aluminum hydroxide under heating at 70 to 100 ° C.

Thus, in the first step, a linear metal phosphate is formed by the reaction between the phosphoric acid, the acidic organic phosphoric acid compound and the divalent basic metal compound. In addition, by the reaction between the acidic organic phosphoric acid compound and the divalent basic metal compound, an organic molecular chain having a high degree of freedom in molecular structure is introduced into the inorganic skeleton. Therefore, the resulting metal phosphate salt has a low viscosity even if the amount of water contained is small, and it is possible to obtain a curable composition having excellent handleability and molding fluidity without shortening the pot life. Become.

Further, by introducing an organic chain into the inorganic skeleton using an acidic organic phosphoric acid compound, inorganic brittleness is supplemented by the organic chain, and the resulting cured product has good mechanical strength and good water resistance. Further, compared to a system in which a thermosetting resin is simply mixed into a phosphoric acid-based curable composition, deterioration of heat resistance due to the use of an organic component can be reduced.

Further, by adding aluminum hydroxide in the second step, the reaction with phosphoric acids proceeds slowly,
It is possible to control the curing reaction and extend the pot life.

Further, by performing the above two-stage reaction at a specific quantitative ratio, it is possible to prevent a decrease in workability due to an increase in viscosity of the obtained curable composition, and it is excellent in mechanical strength, water resistance and heat resistance. A cured product can be obtained.

Further, another method for producing the organic-inorganic composite curable composition of the present invention is that at least one selected from an aqueous phosphoric acid solution containing 10 to 80% by mass of P ₂ O ₅ and an acidic organic phosphoric acid compound. One kind and a basic metal compound composed of a divalent metal, the total valence of phosphate ions and acidic organic phosphate compound ions contained therein, and the total valence of metal ions of the basic metal compound And a first step of mixing and reacting so that the ratio (A ₁ ) to the mixture becomes 0.1 ≦ A ₁ ≦ 0.3, and after the reaction, adding aluminum hydroxide under heating at 70 to 100 ° C. Aluminum hydroxide so that the ratio (A ₂ ) of the total valence of the phosphate ion and the acidic organic phosphate compound ion after addition to the total valence of the metal ion is 0.35 ≦ A ₂ ≦ 0.6. after mixing completely reacted and further wherein (a ₂₎ is 0.7 ≦ Characterized in that it consists of a second step of mixing and reacting aluminum hydroxide such that ₂ ≦ 1.2.

By dividing the mixing of the aluminum hydroxide in the second step into two as described above, the reaction rate of the obtained metal phosphate can be increased, and the cured product finally obtained can be obtained. Can be further improved in mechanical strength.

In the present invention, it is preferable that the acidic organic phosphoric acid compound is at least one selected from an esterified product of phosphoric acid and a polyhydric alcohol. Water resistance and heat resistance can be further improved.

Further, in the present invention, the basic metal compound comprising a divalent metal is at least one selected from metal oxides and metal hydroxides of magnesium, calcium, strontium, barium and zinc. Preferably, there is. Thereby, in the first step,
The reactivity with a phosphoric acid aqueous solution and an acidic organic phosphoric acid compound is further improved.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The curable composition of the present invention is obtained by reacting a phosphoric acid aqueous solution, an acidic organic phosphoric acid compound, and at least one selected from basic metal compounds composed of divalent metals in a specific quantitative ratio, Further, aluminum hydroxide is reacted in a specific ratio.

The phosphoric acid aqueous solution contains 10 to 80% by mass of P ₂ O _5.
It is preferable to use the one containing 40 to 60% by mass. Thereby, the fluidity when processing the curable composition as a paint, an adhesive, a binder, or a molding material is improved. As the phosphoric acid aqueous solution, 75% phosphoric acid (P
₂ O ₅ 54 wt% content), 89% phosphoric acid (P ₂ O ₅ 64 wt% content), polyphosphoric acid (P ₂ O ₅ 75.3 mass% content) and phosphorus pentoxide by diluting with water Can be obtained.

When the content of P ₂ O ₅ is less than 10% by mass, the amount of water contained in the curable composition obtained after the reaction with the metal compound composed of a divalent metal and aluminum hydroxide increases, The time required for the drying and curing steps is prolonged, which impairs productivity when used in the above-mentioned applications, and in addition, swelling and cracks are liable to occur in the product during the curing step, which is not preferable. If the content is more than 80% by mass, the reaction may proceed rapidly during the reaction with the metal compound, and a partially water-insoluble solid may be generated. Properties and physical properties of the cured product may be impaired, which is not preferred.

Further, in the present invention, in order to improve the fluidity of the curable composition, to improve the mechanical strength and water resistance of the cured product, and to improve the heat resistance, an acidic organic phosphoric acid compound is mixed. It is necessary to react. The acidic organic phosphoric acid compound is a phosphoric acid containing an organic group, a phosphorous acid, a hypophosphorous acid derivative, and is represented by P-OH so as to proceed with a metal compound to form an inorganic skeleton. It is not particularly limited as long as it has a functional group, and is an acidic condensed phosphoric acid ester, an esterified product of phosphoric acid and a polyhydric alcohol, or an acidic phosphoric acid ester represented by the following general formula (I); An acidic phosphite represented by (II), a phosphinic acid represented by the following general formula (III), a phosphonic acid represented by the following general formula (IV), or a phosphinic acid represented by the following general formula (V) And the like.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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The substituent R ₁ in the above general formulas (I) to (V) is
It is a linear or branched alkyl group or an alicyclic hydrocarbon group, and the substituent R ₂ is hydrogen or a linear or branched alkyl group or an alicyclic hydrocarbon group.

Examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-
Linear alkyl groups such as octyl, iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl, neo-
Examples include branched alkyl groups such as pentyl, iso-hexyl, methylhexyl, methylheptyl, dimethylhexyl, and 2-ethylhexyl. Examples of the alicyclic hydrocarbon include cyclopentyl, cyclohexyl, and cycloheptyl. Examples include alicyclic hydrocarbons, phenyl, benzyl, phenethyl, and aryl groups in which one or more hydrocarbons such as methyl, ethyl, propyl, and butyl are substituted.

As the acidic condensed phosphoric acid ester, various phosphoric acid ester oligomers obtained by dehydrating and condensing the above phosphoric acid ester can be used.

Among the acidic organic phosphoric acid compounds, the esterified product of the phosphoric acid and the polyhydric alcohol has the mechanical strength and water resistance of the cured product because an organic chain having a crosslinked structure is introduced inside the inorganic skeleton. It is most preferably employed because it is particularly excellent in heat resistance and heat resistance.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol and butylene glycol as dihydric alcohols, and diethylene glycol, triethylene glycol, tetraethylene glycol and the like as ethylene glycol oligomers. Examples of the trihydric alcohol include glycerin, trimethylolpropane, and triethanolamine, and examples of the tetrahydric alcohol include pentaerythritol, diglycerin, xylose, and sorbitan. Among the above-mentioned acidic phosphoric esters, it is preferable to use acidic phosphoric esters composed of dihydric alcohol from the viewpoint of fluidity of the curable composition. The use of an acidic phosphoric acid ester comprising an alcohol is preferably used from the viewpoint that the heat resistance of the cured product is less deteriorated.

The amount of the acidic organic phosphoric acid compound to be added to the phosphoric acid aqueous solution is not particularly limited, but preferably 1 to 150 parts by mass of the acidic organic phosphoric acid compound per 100 parts by mass of the solid content of the phosphoric acid aqueous solution. The addition amount is 1
If the amount is less than 10 parts by mass, the fluidity by adding the acidic organic phosphoric acid compound or the effect on the physical properties of the cured product is not sufficiently obtained, which is not preferable, and if it is more than 150 parts by mass, it is contained in the curable composition. It is not preferable because the organic matter increases and the cured product cannot have sufficient heat resistance.

Furthermore, when the esterified product of the above-mentioned phosphoric acid and polyhydric alcohol is used within the above range, the heat resistance is good even if the mixing amount is relatively large, so that the mechanical strength is improved. More preferably, the amount added to the aqueous phosphoric acid solution is 5 to 150 parts by mass. When an acidic organic phosphoric acid compound other than the esterified product of the phosphoric acid and the polyhydric alcohol is used, the amount of the cured product obtained is preferably 1 to the phosphoric acid aqueous solution from the viewpoint of mechanical strength and heat resistance. Most preferably, the amount is from 70 to 70 parts by mass.

Next, in the present invention, it is necessary to react the phosphoric acid aqueous solution and the acidic organic phosphoric acid compound with a basic metal compound comprising a divalent metal. As a result, an acidic metal phosphate is formed. However, since the metal contained in the metal compound is divalent, it is easy to form a linear acidic metal phosphate, and the acidic metal phosphates are easily formed. Less entanglement. For this reason, in combination with the property of viscosity reduction obtained by introducing the acidic organic phosphoric acid compound, even if the amount of water contained is small, the viscosity is suppressed to a low level, and the resulting curable composition is more The fluidity is further improved.

The basic metal compound comprising a divalent metal used in the present invention includes magnesium, calcium,
Metal oxides, metal hydroxides and metal carbonates of strontium, barium and zinc can be mentioned, and these can be used alone or in combination. Among them, it is preferable to use a metal oxide or a metal hydroxide from the viewpoint of reactivity, and it is more preferable to use zinc oxide, magnesium oxide, calcium hydroxide, and barium hydroxide.

In the present invention, the amount of the metal compound used is determined by the ratio (A ₁₎ of the total valence of phosphate ions and acidic organic phosphate compound ions to the total valence of metal ions of the basic metal compound. ) Are mixed and reacted so that 0.1 ≦ A ₁ ≦ 0.6, and more preferably 0.25 ≦ A ₁ ≦ 0.5. Here, A ₁ is the ratio of the total valence of the basic metal compound to the total valence of the phosphate ion and the acidic organic phosphate compound ion, and is defined below. A ₁ = (M ₁ × m ₁ + M ₂ × m ₂ + M ₃ × m ₃ ...) / (P × 3 +
_{N 1 / n 1 + N 2} / n 2 + ...) ( where, phosphate PO P is contained in the aqueous phosphoric acid
₄ ³ moles, N _1, N _2, ... are the weight of the acidic organic phosphoric acid compound to be added to _{(g), n 1, n} 2, ... is the N _1, N _2,
The hydroxyl equivalent (g / g) of the acidic organic phosphoric acid compound corresponding to ...
eq), M ₁ , M ₂ ,... represent the number of moles of metal ions contained in the divalent basic metal compound, and m ₁ , m ₂ ,.
Represents the valence of each metal ion corresponding to the above metal ion. )

When the total valence ratio (A ₁ ) is less than 0.1, a linear metal phosphate formed by reaction of phosphoric acid and acidic organic phosphoric acid with a divalent metal ion is used. The content ratio of the salt decreases, the component which reacts with aluminum hydroxide mixed later increases, and the curable composition obtained has an increased viscosity and lacks fluidity. Furthermore, the ratio of the hydroxyl groups of phosphoric acid remaining in the cured product obtained by curing the curable composition may increase, and the water resistance may be impaired. On the other hand, when the ratio (A ₁ ) of the total valences exceeds 0.6, a water-insoluble solid is generated depending on the type of the metal compound used, and the curable composition becomes non-uniform.
In some cases, the physical properties of the cured product may be reduced.

The basic metal compound comprising a divalent metal is
It has a high reactivity with phosphoric acid, and starts mixing and generates heat only by mixing and stirring in phosphoric acid. Therefore,
When synthesizing this reactant, it is necessary to add the metal compound little by little so that the reactant does not generate excessive heat and the water contained in the phosphoric acid aqueous solution does not bump. Further, it is necessary to sufficiently stir the reaction solution to suppress the reaction with phosphoric acid only on the surface of the particles of the metal compound as much as possible. By sufficiently stirring and reacting, the metal compound is dissolved in the phosphoric acid aqueous solution.

In the present invention, following the above steps, aluminum hydroxide is mixed and reacted at a specific ratio under heating at 70 to 100 ° C. The aluminum hydroxide used in the present invention is used for slowing the reaction with phosphoric acids and acidic organic phosphoric acid compounds, and for controlling the curing reaction rate of the resulting curable composition and extending the pot life. Things. In addition, the addition of aluminum hydroxide makes it possible to improve the heat resistance of the final cured product.

In the present invention, it is important to mix aluminum hydroxide with the aqueous solution of an acidic metal phosphate under heating at 70 to 100 ° C., and more preferably at 85 to 98 ° C. This makes it possible to suppress the evaporation of water, suppress the curing reaction, improve the miscibility between aluminum hydroxide and the metal acid phosphate, and uniformly disperse the aluminum hydroxide. Heating temperature is 1
If the temperature is higher than 00 ° C., it is not preferable because water evaporates and the curing reaction is accelerated. If the temperature is lower than 70 ° C., the reaction between the aluminum hydroxide and the acidic metal phosphate becomes insufficient, and the physical properties of the obtained cured product Will be reduced. The stirring after the addition of aluminum hydroxide is performed at 70 to 100 ° C.
It is more preferable to stir and mix under heating for 1 to 6 hours. The aluminum hydroxide to be used is not particularly limited in quality such as particle size, but it is preferable to use one having an average particle size of 10 μm or less.

The amount of aluminum hydroxide used in the present invention
Means that phosphate ions and acid
Total valence of the organic organophosphate ion and the total
Valence ratio (A_Two) Is 0.7 ≦ A_TwoIt is characterized by mixing and reacting so as to satisfy the range of ≦ 1.2.
But 0.8 ≦ A_TwoIt is more preferred that ≦ 1.1. Where A_TwoIs phosphate ion
To the total valency of cations and acidic organophosphate ions
It is the ratio of the total valencies of metal ions and is defined below. A_Two= (M₀× m₀+ M₁× m₁+ M_Two× m_Two+ M_Three× m_Three…) /
(P × 3 + N₁/ N₁+ N_Two/ N_Two+ ...) (where P is a phosphate ion (P
O_Four ^3-) Moles, N₁, N_Two, ... are acidic organic resources to be added
Weight of acid compound (g), n₁, N_Two, ... is the above N₁,
N_TwoHydroxyl equivalent of acidic organic phosphoric acid compound corresponding to, ...
(G / eq). Also M₀Is the added aluminum hydroxide
The number of moles of metal ions contained in₁, M _Two, ...
Of the metal ion contained in the divalent basic metal compound
Represents the number of moles, m₀, M₁, M_Two, ... are the above metal ions
The valence of each corresponding metal ion is shown. )

When the ratio (A ₂ ) of the total valence is less than 0.7, a large amount of hydroxyl groups of phosphoric acids remains in the cured product, impairing the water resistance of the cured product, and causing the cured product to come into contact with water. Then, when it is used as an adhesive or a binder, for example, it may cause deterioration of a metal used as a base material or a ceramic material, which is not preferable, and the ratio (A ₂ ) of the total valence is 1 If it exceeds 0.2, aluminum hydroxide is likely to be present in a lump, aluminum hydroxide is not sufficiently dispersed, and the pot life of the curable composition is shortened. Is unfavorable because it reduces the workability when used as an adhesive, a binder or a molding material.

Further, in the present invention, a phosphoric acid aqueous solution containing 10 to 80% by mass of P ₂ O ₅ , at least one selected from acidic organic phosphoric acid compounds, and a basic metal compound comprising a divalent metal are used. The ratio (A ₁ ) of the total valence of the phosphate ion and the acidic organic phosphate compound ion contained therein to the total valence of the metal ion of the basic metal compound is 0.1 ≦ A ₁ A first step of mixing and reacting so as to satisfy ≦ 0.3, and after the reaction, aluminum hydroxide is added under heating at 70 to 100 ° C., and the total of the phosphate ion and the acidic organic phosphate compound ion after the addition is added. and valence, after the total valence of the ratio of the metal ion (a ₂₎ is obtained by 0.35 ≦ a ₂ ≦ 0.6 and mixed completely reacted aluminum hydroxide so, further wherein (a ₂ ) Is 0.7 ≦ A ₂ ≦ 1.2. And a second step of mixing and reacting. The total valence ratios A ₁ and A ₂ are defined below as above. A ₁ = (M ₁ × m ₁ + M ₂ × m ₂ + ...) / (P × 3 + N ₁ / n ₁
+ N ₂ / n ₂ +...) A ₂ = (M ₀ × m ₀ + M ₁ × m ₁ + M ₂ × m ₂ + ...) / (P × 3
+ N ₁ / n ₁ + N ₂ / n ₂ +...) Where P is a phosphate ion (P
O ₄ ^3-) the number of moles of, N _1, N _2, ... are the weight of the acidic organic phosphoric acid compound to be added to _{(g), n 1, n} 2, ... it is the N _1, N _2, corresponding to ... Represents the hydroxyl equivalent (g / eq) of the acidic organic phosphoric acid compound. M ₀ is the number of moles of metal ions contained in the added aluminum hydroxide, M ₁ , M ₂ ,.
Represents the number of moles of the metal ion contained in the divalent basic metal compound, and m ₀ , m ₁ , m ₂ ,... Represent the valence of each metal ion corresponding to the metal ion.

According to the above embodiment, by setting the ratio A ₁ of the total valences to 0.1 or more, the linear carboxylic acid obtained by the reaction of the phosphoric acid or acidic organic phosphoric acid compound with the divalent metal compound can be used. The content ratio of the metal phosphate increases, the viscosity of the curable composition decreases, and the fluidity becomes good. On the other hand, by setting the total valence ratio A ₁ to 0.3 or less, the amount of aluminum hydroxide that can be added in the second step can be increased, and the mechanical strength of the finally obtained cured product is reduced. It is possible to further improve.

Further, in the second step after the reaction of A ₁ to 0.1 ≦ A ₁ ≦ 0.3, aluminum hydroxide
After the aluminum hydroxide to be mixed in advance is completely reacted, aluminum hydroxide is further added.
Thereby, since the previously added aluminum hydroxide can be completely reacted, it becomes possible to improve the reactivity of the aluminum hydroxide added later, and as a result, the cured product finally obtained Can be improved in mechanical strength.

The amount of aluminum hydroxide to be mixed first is
By setting the ratio A ₂ of the total valency 0.35 above, by phosphoric acid metal salt was completely reacted is formed, it is possible to further improve the mechanical strength of the cured product. On the other hand, by setting A ₂ to 0.6 or less, it is possible to suppress the formation of water-insoluble solids and obtain a completely reacted and dissolved metal phosphate.

Further, the curable composition of the present invention can contain various additives in terms of suppressing the reaction and reducing the cost. Urea is an example of a reaction inhibitor that suppresses the curing reaction of the curable composition and prolongs the pot life, and urea is 0.1 with respect to 100 parts by mass of the curable composition.
It is preferred to use from 10 to 10 parts by weight.

Other additives include lightweight aggregates, fillers,
Pigments and the like can be used. As a lightweight aggregate, shirasu balloon, glass balloon, pearlite, etc., as a filler, alumina, silica sand, silica fume, glass powder, clay, etc. containing an acid oxide as a main component, as a pigment, titanium oxide, Examples include phthalocyanine, red petals, ultramarine blue, and the like. These materials can be appropriately selected and used in an appropriate amount according to each purpose, and are not particularly limited.

The curable inorganic composition thus obtained is
A cured product is obtained by heating and can be used for various applications. The heating conditions vary depending on the application, but, for example, after evaporating water in advance by preheating or the like to prepare a semi-cured product, and heating the semi-cured product at a temperature of 120 ° C. or more, a desired cured product is obtained. Obtainable.

[0054]

The present invention will be described in more detail with reference to the following examples. Example 1 900 g of 89% phosphoric acid aqueous solution (containing 64% by mass of P ₂ O ₅ )
And phosphoric acid ethylene glycol ester (hydroxyl equivalent 80
g / eq) of 100 g and 455 g of ion-exchanged water are charged into a 4 L reaction vessel, and while stirring with a disper, zinc oxide 4 g is added.
20 g were added slowly. At this time, the temperature of the reaction solution was 95 ° C.
Up. Ratio of total valences after addition of zinc oxide (A
₁ ) was 0.4. While maintaining the reaction kettle at 95 ° C. with a mantle heater, 335 g of aluminum hydroxide was added and stirred for 2 hours, and 10 g of urea was further added.
The mixture was stirred until dissolved to obtain a curable composition. The ratio (A ₂ ) of the total valences in this curable composition was 0.9.

Example 2 500 g of an 89% phosphoric acid aqueous solution (containing 64% by mass of P ₂ O ₅ )
And propylene glycol phosphate (hydroxyl equivalent 7
(0 g / eq) and 500 g of ion-exchanged water were charged into a 4 L reaction vessel, and 170 g of zinc oxide was gradually added while stirring with a disper. At this time, the temperature of the reaction solution was 95
° C. The ratio of the total valences (A ₁ ) after the addition of zinc oxide was 0.2. While maintaining the reaction kettle at 95 ° C. with a mantle heater, aluminum hydroxide 380
g was added and the mixture was stirred for 2 hours. Further, 30 g of urea was added and the mixture was stirred until dissolved to obtain a curable composition. The ratio (A ₂ ) of the total valences in this curable composition was 0.9.

Example 3 800 g of 89% phosphoric acid aqueous solution (containing 64% by mass of P ₂ O ₅ )
And acidic phosphoric acid ethyl ester (hydroxyl equivalent 110g / e
q) 200 g and 415 g of ion-exchanged water were put into a 4 L reaction vessel, and 385 g of zinc oxide was added while stirring with a disper.
Was slowly added. At this time, the temperature of the reaction solution rose to 95 ° C. The ratio (A ₁ ) of the total valences after the addition of zinc oxide was 0.4. The reactor is heated by a mantle heater to 95
While maintaining the temperature at ° C, 210 g of aluminum hydroxide was added, and the mixture was stirred for 2 hours to obtain a curable composition. The ratio (A ₂ ) of the total valences in this curable composition was 0.8.

Example 4 950 g of 89% phosphoric acid (containing 64% by mass of P ₂ O ₅ ) and ethyl acid phosphate (hydroxyl equivalent 110 g / eq) 5
0 g and 435 g of ion-exchanged water are charged into a 4 L reaction vessel,
While stirring with a disper, 155 magnesium hydroxide
g was added slowly. At this time, the temperature of the reaction solution rose to 95 ° C. The ratio (A ₁ ) of the total valences after the addition of magnesium hydroxide was 0.2. While maintaining the reactor at 95 ° C. with a mantle heater, aluminum hydroxide 13
When 5 g was added and the mixture was stirred for 2 hours, a translucent metal phosphate aqueous solution which was completely reacted was obtained. At this time, the ratio (A ₂ ) of the total valences was 0.4. Next, the mantle heater was removed from the reactor, 400 g of aluminum hydroxide was added, and the mixture was stirred for 1 hour.
g was added and stirred until dissolved to obtain a curable composition. The ratio (A ₂ ) of the total valences in this curable composition is 1.0
Met.

Comparative Example 1 89% phosphoric acid aqueous solution (containing 64% by mass of P ₂ O ₅ ) 1000
g and 455 g of ion-exchanged water were charged into a 4 L reaction vessel, and 445 g of zinc oxide was gradually added while stirring with a disper. At this time, the temperature of the reaction solution rose to 95 ° C. The ratio (A ₁ ) of the total valences after the addition of zinc oxide was 0.4. While the reactor was maintained at 95 ° C. with a mantle heater, 355 g of aluminum hydroxide was added and the mixture was stirred for 2 hours, 15 g of urea was further added, and the mixture was stirred until dissolved to obtain a curable composition. The ratio (A ₂ ) of the total valences in this curable composition was 0.9.

Comparative Example 2 900 g of 89% phosphoric acid aqueous solution (containing 64% by mass of P ₂ O ₅ )
And phosphoric acid ethylene glycol ester (hydroxyl equivalent 80
g / eq) 100 g and ion-exchanged water 585 g are charged into a 4 L reaction vessel, and zinc oxide 4
20 g were added slowly. At this time, the temperature of the reaction solution was 95 ° C.
Up. Ratio of total valences after addition of zinc oxide (A
₁ ) was 0.4. While the reactor was maintained at 95 ° C. with a mantle heater, 735 g of aluminum hydroxide was added, and the mixture was stirred for 2 hours to obtain a curable composition. The ratio (A ₂ ) of the total valences in this curable composition was 1.5.

Comparative Example 3 800 g of 89% phosphoric acid aqueous solution (containing 64% by mass of P ₂ O ₅ )
And propylene glycol phosphate (hydroxyl equivalent 7
(0 g / eq) 200 g and ion-exchanged water 360 g were charged into a 4 L reactor, and 300 g of zinc oxide was gradually added while stirring with a disper. At this time, the temperature of the reaction solution was 95
° C. The ratio of the total valences (A ₁ ) after the addition of zinc oxide was 0.3. While maintaining the reaction kettle at 95 ° C. with a mantle heater, aluminum hydroxide 130
g was added and stirred for 2 hours to obtain a curable composition. The ratio (A ₂ ) of the total valences in this curable composition was 0.5.

Comparative Example 4 900 g of 89% phosphoric acid (containing 64% by mass of P ₂ O ₅ ) and ethylene glycol phosphate (having a hydroxyl equivalent of 80 g / e)
q) 100 g and 435 g of ion-exchanged water were charged into a 4 L reaction vessel, and while mixing with a disper, the reaction vessel was maintained at 95 ° C. with a mantle heater, and 155 g of magnesium hydroxide and 537 g of aluminum hydroxide were mixed in advance. Was added slowly and stirred for 2 hours to obtain a curable composition. The ratio (A ₁ ) of the total valences of this curable composition was 1.0.

Comparative Example 5 A curable composition was prepared by mixing 100 parts by mass of alumina, 10 parts by mass of magnesium silicate, and 11.5 parts by mass of a thermosetting novolak phenol resin with 100 parts by mass of powdered aluminum biphosphate. I got something. The organic content of this composition was 5.5%, which was equal to the organic content of the curable composition of Example 1. Test Example 1 The curable compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were kept at 25 ° C. in a constant temperature bath, and the viscosities 48 hours after blending were measured with a B-type viscometer. Table 1 shows the results.

Test Example 2 The curable compositions of Examples 1 to 4 and Comparative Examples 1 to 5
0.1 g / c on the surface of a 0 × 100 mm calcium silicate plate
The workability at the time of application at a rate of m ² was evaluated as ○ for a curable composition obtained by a conventional formulation containing no acidic phosphates, and ◎ for workability even better than that. The evaluation was evaluated as x when the evaluation was inferior. Table 1 shows the results.

Test Example 3 The curable compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were
It was applied at a rate of 0.1 g / cm ^{2 on} the surface of a 00 mm × 100 mm × 10 mm calcium silicate plate, and water in the curable composition was removed at 80 ° C. × 4 hours. Then, a calcium silicate plate of the same size is superimposed, a pressure of 5 kg / cm ² is applied so as to adhere, and the plate is placed in an atmosphere of 140 ° C. for 1 kg.
The curable composition was left to stand for a time to cure.

The obtained test piece was heated at room temperature (25 ° C.), under heating (80 ° C.), 300 ° C. × 24 hours, and then heated at 25 ° C. ×
After immersion in ion-exchanged water for 24 hours, the tensile strength in the peeling direction was measured for the samples in the four test sections. Table 1 shows the results.

[0066]

[Table 1]

From the evaluation results of Test Example 1 and Test Example 2 in Table 1, in Examples 1 to 4, the addition of the acidic organic phosphoric acid compound did not cause the viscosity to be too high, and the curing was excellent in workability. It can be seen that the hydrophilic composition can be obtained. Here, comparing Example 1 and Comparative Example 1, both A ₁ and A ₂
Are equal to 0.4 and 0.9 respectively, and the solid content is 7
Example 1 in which the acidic organic phosphoric acid compound was added had a lower viscosity, although the same was at 5%, and the addition of the acidic organic phosphoric acid compound improved the flowability and improved the workability. It can be seen that the hydrophilic composition can be obtained.

On the other hand, in Comparative Example 2 in which A ₂ is 1.5, which is larger than the range specified in the present invention, since the amount of aluminum hydroxide added is too large, a water-insoluble solid is formed.
This resulted in a large increase in viscosity and a decrease in workability.

Next, according to the results of Test Example 3, in Examples 1 to 4 in which A ₁ and A ₂ are within the specified ranges in the step of obtaining the curable composition, Comparative Example 2 in which A ₁ and A ₂ are out of the specified ranges. Further, it is understood that the cured product is superior in tensile strength, water resistance and heat resistance as compared with Comparative Example 3.

On the other hand, in Comparative Example 2 in which A ₂ is 1.5, which is larger than the specified range, the viscosity is greatly increased, the workability is reduced, and a water-insoluble solid is formed, and the curability is lowered. composition becomes non-uniform, will be the mechanical strength of the cured product is impaired, in Comparative example 3 a ₂ is less than the specified range of 0.5, curing is insufficient, the degree of moisture absorption It can be seen that sufficient mechanical strength cannot be obtained because of the increase.

Also, in Comparative Example 4 in which the divalent metal compound and aluminum hydroxide were reacted without dividing the steps, the viscosity was greatly increased, the workability was reduced, and a water-insoluble solid was formed. And the curable composition becomes non-uniform,
The mechanical strength of the obtained cured product was poor.

Further, Examples 1 to 4 in which an acidic organic phosphoric acid compound was added to the curable composition and Comparative Example 1 in which no acidic organic phosphoric acid compound was added.
The tensile strength is 4 kgf / cm ² or more, which is sufficient, but the mechanical strength is further improved by adding an acidic organic phosphoric acid compound and reinforcing the inorganic skeleton with organic chains. It can be seen that a cured product can be obtained.

Further, when comparing Examples 1 to 4 with Comparative Example 5, in Comparative Example 5, after the heat test at 300 ° C. for 24 hours, the organic portion was carbonized and the adhesive strength was greatly reduced. It can be seen that the curable composition according to the present invention has a small rate of decrease in strength and is excellent in heat resistance due to the introduction of organic chains inside the inorganic skeleton.

Further, in Example 4, it can be seen that the mechanical strength is particularly excellent by adding aluminum hydroxide in two parts in the second step.

[0075]

As described above, in the present invention, first, an aqueous phosphoric acid solution, an acidic organic phosphoric acid compound,
After preliminarily reacting with a basic metal compound (at least one selected from the group consisting of divalent metals), and further reacting with aluminum hydroxide, the curable composition has sufficient fluidity. It has good workability up to curing, and is excellent in handling because it can be cured at a low temperature. Also, by introducing an organic chain inside the inorganic skeleton,
It is possible to obtain a curable composition having excellent mechanical strength, water resistance and heat resistance. Furthermore, since the quantitative ratio of each reaction is defined in a specific range, the obtained cured product has excellent strength, heat resistance, and water resistance are not reduced. The obtained curable composition can be suitably used as an adhesive, a binder, a coating agent, or a matrix material of a fiber-reinforced molded article.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Koichi Shigeno 3-6-3 Kanda Kaji-cho, Chiyoda-ku, Tokyo Asahi Fiberglass Corporation F-term (reference) 4G012 MA00 MA02 PB03 PC01 PC12 PC13 PD01 PE01

Claims (4)

[Claims] 1. An aqueous phosphoric acid solution containing 10 to 80% by mass of P ₂ O ₅ , at least one selected from acidic organic phosphoric acid compounds, and a basic metal compound composed of a divalent metal, respectively. The ratio (A ₁ ) of the total valence of the contained phosphate ion and acidic organic phosphate compound ion to the total valence of the metal ion of the basic metal compound is 0.1 ≦ A ₁ ≦ 0.6. A first step of mixing and reacting such that, after the reaction, aluminum hydroxide is added under heating at 70 to 100 ° C., and the total valency of the phosphate ion and the acidic organic phosphate compound ion after the addition, A second step of mixing and reacting so that the ratio (A ₂ ) of the total valences of the metal ions is 0.7 ≦ A ₂ ≦ 1.2. Manufacturing method.
(However, the ratios (A ₁ ) and (A ₂ ) of the total valences are A ₁ = (M ₁ × m ₁ + M ₂ × m ₂ + ...) / (P × 3 + N ₁ / n ₁₎
+ N ₂ / n ₂ +...) A ₂ = (M ₀ × m ₀ + M ₁ × m ₁ + M ₂ × m ₂ + ...) / (P × 3
+ N ₁ / n ₁ + N ₂ / n ₂ +...), Where P is the number of moles of phosphate ions (PO ₄ ³⁻ ) contained in the aqueous phosphoric acid solution, and N ₁ , N ₂ ,. weight of the organic phosphate compound _{(g), n 1, n} 2, ... represents a hydroxyl group equivalent of the n _1, n _2, acidic organic phosphoric acid compounds corresponding to ... (g / eq). M ₀ is the number of moles of metal ions contained in the added aluminum hydroxide, M ₁ , M ₂ ,.
Represents the number of moles of the metal ion contained in the divalent basic metal compound, and m ₀ , m ₁ , m ₂ ,... Represent the valence of each metal ion corresponding to the metal ion. ) _2. A phosphoric acid aqueous solution containing 10 to 80% by mass of P ₂ O ₅ , at least one selected from acidic organic phosphoric acid compounds, and a basic metal compound composed of a divalent metal, respectively. The ratio (A ₁ ) of the total valence of the contained phosphate ion and acidic organic phosphate compound ion to the total valence of the metal ion of the basic metal compound is 0.1 ≦ A ₁ ≦ 0.3. A first step of mixing and reacting such that, after the reaction, aluminum hydroxide is added under heating at 70 to 100 ° C., and the total valency of the phosphate ion and the acidic organic phosphate compound ion after the addition; after the total valence of the ratio of the metal ion (a ₂₎ is reacted 0.35 ≦ a ₂ ≦ 0.6 as aluminum hydroxide were mixed completely becomes, further the (a ₂₎ is 0. 7 mixture was reacted aluminum hydroxide such that ≦ a ₂ ≦ 1.2 Method for producing an organic-inorganic hybrid curable composition characterized by comprising a two steps. (However, the ratios (A ₁ ) and (A ₂ ) of the total valences are A ₁ = (M ₁ × m ₁ + M ₂ × m ₂ + ...) / (P × 3 + N ₁ / n ₁₎
+ N ₂ / n ₂ +...) A ₂ = (M ₀ × m ₀ + M ₁ × m ₁ + M ₂ × m ₂ + ...) / (P × 3
+ N ₁ / n ₁ + N ₂ / n ₂ +...), Where P is the number of moles of phosphate ions (PO ₄ ³⁻ ) contained in the aqueous phosphoric acid solution, and N ₁ , N ₂ ,. weight of the organic phosphate compound _{(g), n 1, n} 2, ... represents a hydroxyl group equivalent of the n _1, n _2, acidic organic phosphoric acid compounds corresponding to ... (g / eq). M ₀ is the number of moles of metal ions contained in the added aluminum hydroxide, M ₁ , M ₂ ,.
Represents the number of moles of the metal ion contained in the divalent basic metal compound, and m ₀ , m ₁ , m ₂ ,... Represent the valence of each metal ion corresponding to the metal ion. ) 3. The method for producing an organic-inorganic composite curable composition according to claim 1, wherein the acidic organic phosphoric acid compound is at least one selected from an esterified product of phosphoric acid and a polyhydric alcohol. 4. The basic metal compound comprising a divalent metal contained in the curable composition is at least selected from a metal oxide and a metal hydroxide of magnesium, calcium, strontium, barium and zinc. The method for producing an organic-inorganic composite curable composition according to claim 1, which is a kind.