JP2003201165A - Fiber reinforced inorganic molding and production method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass fiber reinforced inorganic molding which has excel lent mechanical properties, heat resistance, and water resistance, and to provide a production method therefor. <P>SOLUTION: The fiber reinforced inorganic molding is obtained by reinforcing an inorganic matrix hardened by the reaction between the metal salt of phosphoric acid and a hardening agent with glass fiber. The glass fiber is treated with a sizing agent containing an epoxy resin, and an aminosilane compound expressed by the formula of RSiX<SB>3</SB>(R is an amino-containing organic functional group; and X is a halogen atom or an alkoxy group). The molding is produced by impregnating a mixture containing the metal salt of phosphoric acid and a hardening agent therefor into glass fiber treated with the sizing agent containing an epoxy resin and an aminosilane compound to produce a green sheet, and drying the green sheet so that the content of moisture therein is controlled to 5 to 15 wt.% to produce a prepreg, and next hardening the prepreg at 220 to 260°C. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced inorganic molded article suitably used as a building material, a structural material or member for industry, and a method for producing the same. More specifically, compared to conventional fiber-reinforced inorganic molded products, the handling, moldability and workability during molding are good, and further, mechanical strength, heat resistance,
And a fiber-reinforced inorganic molded article excellent in water resistance and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, cement plates, calcium silicate plates and the like have been widely used as structural materials and members for construction materials, industrial heat resistance and nonflammability. Among these, inorganic molded products obtained by reinforcing a phosphate-based inorganic material containing a phosphate and various metal compounds with an inorganic fiber such as glass fiber are proposed as a material having excellent mechanical strength and heat resistance. Has been used. As an example, Japanese Patent Laid-Open No. Sho 4
7-2424, JP-A-51-27272,
JP-A-55-51768, JP-A-59-3958
The gazette is mentioned.

The applicant of the present invention has also previously disclosed Japanese Patent Laid-Open No. 2000-863.
As No. 24, a fiber-reinforced inorganic molded article was proposed in which an inorganic matrix, which is one of the above-mentioned phosphate-based inorganic materials, is cured by a reaction with a curing agent and is reinforced with glass fibers. . That is, 100 parts by weight of the first metal phosphate (solid content) and 80 to 200 parts by weight of a curing agent are mixed to prepare an inorganic matrix raw material, and 100 parts by weight of this inorganic matrix raw material (solid content) is mixed with epoxy. Glass fiber 5-10 surface-treated with a sizing agent containing a resin
It is a fiber reinforced machine molded product by a method of containing 0 part by weight, molding it into a predetermined shape, and curing it under heating.

However, according to the findings of the present inventor, although these phosphate-based fiber-reinforced inorganic molded articles have high strength and excellent heat resistance, thermal shock resistance, and dimensional stability,
When immersed in water, the mechanical strength such as bending strength may decrease, or the acid content may elute, so the water resistance is not always sufficient and it can be used only in the parts that are not affected by moisture. Turned out to be.

The phosphate-based fiber-reinforced inorganic molded article is cured by a dehydration-condensation reaction between the metal phosphate and the curing agent through a heating process to form a crosslinked structure. However, in the conventional manufacturing, the curing process requires a relatively long time, and the manufacturing is not always efficient.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to the above-mentioned phosphate-based fiber-reinforced inorganic molded article, which is excellent in mechanical strength, heat resistance, thermal shock resistance and dimensional stability. It is possible to provide a phosphate-based fiber-reinforced inorganic molded article having characteristics and improved water resistance, shorten the curing process time in the production, and perform efficient production. It is an object of the present invention to provide a method for producing a phosphate-based fiber-reinforced inorganic molded article.

[0007]

In order to solve the above-mentioned problems, the present inventor has analyzed the phosphate-based fiber-reinforced inorganic molded article obtained in JP-A-2000-86324 and found that the conventional inorganic In some of the molded products, there is a part where the curing reaction between the metal phosphate and the curing agent is not completely completed, and when the resulting inorganic molded product comes into contact with moisture, the strength decreases. It was found that the acid content and the acid content were eluted.

Conventionally, the curing reaction between the metal phosphate and the curing agent is carried out under the temperature condition of 120 to 200 ° C.
In order to sufficiently complete the curing reaction, it is considered that the temperature of the curing reaction should be higher and the curing reaction should be performed for a long time. However, the curing reaction exceeds 200 ° C, 220 to 2
When it is carried out at 60 ° C., the curing reaction itself can be completed efficiently in a short time, but on the other hand, the severe temperature conditions and the acidic components contained therein cause deterioration of the glass fiber as the reinforcing fiber. As a result, it was found that the excellent mechanical strength, heat resistance, and thermal shock resistance originally possessed by the fiber-reinforced inorganic molded product were impaired.

The present inventor can solve the above-mentioned problem of glass fiber deterioration by using glass fibers treated with a specific sizing agent adapted to the curing reaction between the metal phosphate and the curing agent. Found. By using the glass fiber treated with a specific sizing agent, the glass fiber does not deteriorate even under the severe curing reaction conditions of the above-mentioned high temperature and acidic atmosphere. This is because the above-mentioned specific sizing agent forms a film on the surface of glass fiber, and the formed film has its film thickness increased and its strength further increased due to the high temperature in the curing reaction. It is considered that the fibers are sufficiently protected and the deterioration of the glass fibers due to high temperature and acid content is suppressed.

Thus, the present invention is a fiber-reinforced inorganic molded article in which an inorganic matrix, which is cured by reacting a metal phosphate with a curing agent, is reinforced with glass fibers, the glass fibers being an epoxy resin, A fiber reinforced, which is a glass fiber treated with a sizing agent containing an aminosilane compound represented by RSiX ₃ (R is an amino-containing organic functional group, and X is a halogen atom or an alkoxy group). It is an inorganic molded product.

The present invention also provides a mixture containing a metal phosphate and a curing agent thereof, an epoxy resin, and a compound of formula RSiX.
₃ (R and X are as defined above) are impregnated with a glass fiber treated with a sizing agent containing an aminosilane compound represented by the above formula to prepare a pre-molding material. moisture content by drying such that 5 to 15 wt% to prepare a prepreg, then the prepreg 220-260
It is a method for producing a fiber-reinforced inorganic molded article, which is characterized by curing at ° C.

The present invention is also a glass fiber for reinforcing a fiber-reinforced inorganic molded product epoxy resin comprising an inorganic matrix which is hardened by reacting a metal phosphate with a curing agent. ₃ (R is an amino-containing organic functional group, and X is a halogen atom or an alkoxy group), and a glass fiber characterized by being treated with a sizing agent containing the aminosilane compound. Hereinafter, the present invention will be described in more detail.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the fiber-reinforced inorganic molded article of the present invention, an inorganic matrix obtained by curing a metal phosphate with a curing agent is reinforced with glass fibers. Examples of the metal salt of phosphoric acid include a metal salt of a first phosphoric acid, a metal salt of a second phosphoric acid, and a metal salt of a third phosphoric acid, and among them, the metal salt of a first phosphoric acid has good reactivity with a curing agent. Therefore, it is preferable.

As the metal of the metal salt of phosphoric acid, aluminum, magnesium, zinc, calcium, sodium and the like are preferable, and aluminum is particularly preferable because it improves the mechanical strength of the molded product. Preferred specific examples of the metal phosphate include aluminum monophosphate, which is highly soluble in water,
A phase change occurs by heating at around 0 ° C., and an inorganic molded article having high water resistance is obtained. Aluminum monophosphate is commercially available not only in the form of an aqueous solution but also in solid form, and it is easy to control the water content of the green sheet before curing as described later.

The above-mentioned metal phosphate used in the present invention is preferably used in the form of an aqueous solution of 40 to 90% by weight. Above all, the fluidity during molding and the inorganic matrix after curing become dense. From this viewpoint, it is preferably used in the form of an aqueous solution of 50 to 70% by weight.

As the curing agent for the metal phosphate, it is preferable to use at least one selected from the group consisting of metal hydroxides, basic metal oxides and complex oxides containing basic metal oxides. As the metal hydroxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide and the like are preferable. As the basic metal oxide, aluminum oxide, magnesium oxide, zinc oxide, calcium oxide and the like are preferable. Further, as a complex oxide containing a basic metal oxide, calcium silicate, wollastonite (wollastonite), calcium aluminate (alumina cement), kaolinite, cordierite (2MgO · 2Al ₂ O ₃
5SiO ₂ ), magnesite, talc, etc. are preferred.

The metal phosphate curing agent can be used alone or in combination of two or more. Of these, calcium silicate, wollastonite, aluminum hydroxide, or aluminum oxide is preferably used because it reacts with the metal phosphate to form a strong bond.

When forming the inorganic matrix in the present invention, a metal metaphosphate can be used as a part of the metal phosphate. It is preferable to use 2 to 40% by weight of the metal phosphate as the metal phosphate metal. The metal metaphosphate imparts excellent plasticizing property during molding and accelerates the curing reaction, so that the curing temperature can be kept relatively low. As a result, in the present invention, the mechanical strength of the molded product can be improved in combination with the use of the glass fiber treated with the specific sizing agent. As the metal salt of metaphosphate, sodium metaphosphate, potassium metaphosphate, magnesium metaphosphate, aluminum metaphosphate, ammonium metaphosphate and the like are preferable,
Among them, sodium metaphosphate is preferable.

The metal phosphate curing agent is preferably used in an amount of 80 to 300 parts by weight per 100 parts by weight of the metal phosphate (as a solid content). If the amount of the curing agent used is less than 80 parts by weight based on 100 parts by weight of the metal phosphate, the metal phosphate remains in the final product after heat curing, and sufficient mechanical strength cannot be obtained. , The water resistance may be impaired. On the other hand, when the amount of the curing agent exceeds 300 parts by weight, the amount of metal phosphate is less than that of the curing agent, the structure of the final product becomes rough, and sufficient mechanical strength cannot be obtained. More preferably, the curing agent is used in an amount of 100 to 180 parts by weight based on 100 parts by weight of the metal phosphate.

Further, the metal phosphate curing agent used in the present invention has a particle size of 5 to less than 30 μm.
It is preferably contained in a weight percentage. If the particle diameter of the particles is 5 μm or less and is less than 30% by weight, the adhesive force between the obtained inorganic matrices is insufficient, and it becomes difficult to obtain sufficient mechanical strength. On the other hand, if it exceeds 90% by weight, the inorganic matrix may expand or crack during heat curing.

Further, of the above-mentioned curing agent having a particle size of 5 μm or less, it is more preferable that 5 to 20% by weight of a particle size of 1 μm or less is contained. Further, there is no particular limitation on the particle size of the above-mentioned curing agent other than those having a particle size of 5 μm or less. However, when many particles with a considerably large particle size, for example 50 μm or more, are included, the particle size is 5 μm.
It is necessary to use m or less in many cases, but it is appropriately optimized depending on the particle size of the entire curing agent used.

As the glass fiber in the present invention, general glass fiber can be widely used. Above all, it is preferable to use glass fibers having an E glass composition which is low in cost and widely used. The diameter of the monofilament constituting the glass fiber is preferably 8 to 15 μm,
It is more preferably 13 μm. When the diameter of the monofilament is less than 8 μm, the monofilament is apt to be deteriorated by an acid content or heat, and the surface area of the glass fiber is increased, so that it is necessary to increase the amount of the sizing agent, which is uneconomical. If the diameter of the monofilament exceeds 15 μm, the rate of decrease in mechanical strength of the inorganic molded product due to acid content or heat decreases, but the glass fiber becomes hard and moldability and surface property deteriorate, which is not preferable.

As the form of the glass fiber used, short fibers such as chopped strands, continuous fibers such as roving, or processed into mat, cloth, non-woven fabric, etc. may be used alone or in combination of two or more. be able to. Above all, it is preferable to use chopped strands obtained by cutting the roving into 10 to 60 mm because an excellent reinforcing effect can be obtained. A roving is a bundle in which a predetermined number of monofilaments are bundled and aligned in a predetermined number, and the roving is cut into chopped strands. The number of bundled filaments is preferably 30 to 300. When it is less than 30, the strands dispersed in the inorganic matrix do not exhibit a sufficient reinforcing effect, which is not preferable. On the contrary, when the number is 300 or more, the strand becomes hard and the shapeability at the time of molding is deteriorated, which is not preferable.

In the present invention, it is important to treat the glass fiber with a specific sizing agent. The sizing agent here needs to contain an epoxy resin and an aminosilane compound represented by the formula RSiX ₃ (R is an amino-containing organic functional group, and X is a halogen atom or an alkoxy group). X in the aminosilane compound forms a silanol group by a hydrolysis reaction and forms a covalent bond by dehydration condensation with the silanol group on the glass surface of the glass fiber, and thus plays a role of enhancing the adhesiveness between the aminosilane compound and the glass fiber. To do. On the other hand, it is considered that the amino group of the aminosilane compound reacts with the glycidyl group of the epoxy resin to enhance the adhesiveness with the epoxy resin, and as a result, a stronger coating film is formed on the glass fiber. This prevents heat deterioration of the glass fiber,
Moreover, it seems that the wettability or adhesiveness between the inorganic matrix and the glass fiber can be improved.

The above-mentioned epoxy resin contained in the sizing agent is preferably contained in an amount of 50 to 97% by mass in the total amount of the solid content (solid content adhering to the glass fiber) in the sizing agent, particularly 7
It is more preferable that the content is 0 to 85% by mass. If the content is less than 50% by mass, another sizing agent component for forming a coating film is required, and the reaction with the aminosilane compound cannot be expected, so that the heat resistance of the glass fiber is deteriorated. On the other hand, if the above content exceeds 97% by mass, the amount of the aminosilane compound added is reduced, and the heat resistance of the glass fiber is poor, which is not preferable. Further, the aminosilane compound contained in the sizing agent is preferably contained in an amount of 3 to 25% by mass, particularly 5 to 25% by mass in the total amount of the solid content (solid content adhering to the glass fiber) in the sizing agent. Is more preferable. When the content is less than 3% by mass,
The heat resistance of the glass fiber is inferior, which is not preferable, and when it exceeds 25% by mass, the heat resistance effect of the glass fiber cannot be expected to be higher and the cost is not preferable.

Preferred examples of the epoxy resin include bisphenol A diglycidyl ether and bisphenol F.
Aromatic polyglycidyl ethers such as diglycidyl ether, phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, neopentyl glycol diglycidyl ether, aliphatic polyglycidyl ethers such as trimethylolpropane triglycidyl ether, hexahydrophthalic acid diglycidyl anhydride Examples thereof include esters, poly (meth) acrylic acid glycidyl esters, and aliphatic polyglycidyl esters such as copolymers of (meth) acrylic acid glycidyl esters with other acrylic acid monomers and methacrylic acid monomers.

As the epoxy resin, it is preferable to use an aromatic polyglycidyl ether-based epoxy resin from the viewpoint of heat resistance, since heating is required to cure the inorganic matrix, and in particular, a phenol novolac polyglycidyl ether-based epoxy resin is used. It is preferable to use a resin, a cresol novolac polyglycidyl ether-based epoxy resin, or a bisphenol A diglycidyl ether-based epoxy resin.

The aminosilane compound represented by the formula RSiX ₃ (R is an amino-containing organic functional group, and X is a halogen atom or an alkoxy group) is
R is preferably an organic functional group having an amino group having 1 to 12 carbon atoms, and X is preferably a halogen atom or an alkoxy group having 1 to 3 carbon atoms. Also,
It is preferable that a plurality of amino groups contained in the organic functional group are contained. Examples of these aminosilane compounds include monoaminosilane, diaminosilane, triaminosilane and the like, but preferred examples are γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxy. Silane, N-β
-(Aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl ) -N'-β '-(aminoethyl) -γ-aminopropyltriethoxysilane and N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane.

Among them, γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane are preferably used because of their high reactivity with epoxy resin and their low cost. Particularly, it is preferable to use diaminosilane such as N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane from the viewpoint of improving the mechanical strength of the molded product.

The sizing agent used in the present invention includes, in addition to the epoxy resin and the aminosilane compound, a urethane resin, a vinyl acetate resin, an epoxy cross-linked polyvinyl acetate, and a urethane for the purpose of improving the sizing property of the glass fiber. Cross-linked polyvinyl acetate and the like can be added. Further, for the purpose of suppressing the generation of static electricity, an antistatic agent such as ammonium chloride or a quaternary ammonium salt, and various additives usually used depending on the purpose can be contained.

The above sizing agent is preferably 0.5 to 3.0% by weight, and particularly 0.7, based on the glass fiber to be treated.
It is preferable to make it adhere to about 2.0% by weight. When the amount of the sizing agent is less than 0.5% by weight, the thickness of adhesion to the surface of the glass fiber is small, the effect of protecting the glass fiber is not sufficiently obtained, and the mechanical strength of the final product is brought about. Further, since a sufficient filament focusing force cannot be obtained, the strands dispersed in the inorganic matrix are opened, and the reinforcing effect of the glass fiber is reduced, which is not preferable. On the other hand, when the amount of the sizing agent exceeds 3.0% by weight, the glass fiber is sufficiently protected, but the glass fiber becomes hard and the shapeability during molding is deteriorated.

As a means for treating the glass fiber with a sizing agent, preferably, a liquid containing the sizing agent dissolved or dispersed in an appropriate solvent is sprayed or applied on the surface of the glass fiber, or a liquid containing the above sizing agent. It is carried out by immersing glass fiber in. As a result, a film of the sizing agent is formed on the surface of the glass fiber. Water or the like is preferably used as the solvent of the liquid containing the sizing agent, and it is more preferable to prepare a solution or dispersion liquid of 2 to 20% by weight.

In the inorganic molded article of the present invention, the glass fiber is preferably used in an amount of 5 to 100 parts by weight with respect to 100 parts by weight of the inorganic matrix (as a solid content).
More preferably, it is 15 to 80 parts by weight. When the amount of the glass fiber used is less than 5 parts by weight based on 100 parts by weight of the inorganic matrix, sufficient strength as an inorganic molded product cannot be obtained, and when it exceeds 100 parts by weight, the inorganic matrix is sufficiently contained against the glass fiber. If the amount is not sufficient, the structure of the inorganic molded article becomes rough and sufficient mechanical strength cannot be obtained.

Further, in the present invention, the weight of the inorganic molded article is reduced,
It is also possible to contain various fillers for the purpose of cost reduction or imparting design characteristics. Examples of such fillers include, for example, shirasu balloon, glass balloon, lightweight aggregate such as perlite, silica sand containing acidic oxide as a main component, glass powder, clay filler, titanium oxide, zinc oxide, phthalocyanine, Examples include pigments such as Benji and Mabiko. These materials can be used in an appropriate amount according to the respective uses of the inorganic molded article.

In the method for producing an inorganic molded article of the present invention, a glass fiber treated with a sizing agent containing an epoxy resin and an aminosilane compound is impregnated with a mixture containing a metal phosphate and a curing agent thereof before molding. A material is prepared and dried so that the water content of the material before molding is 5 to 15% by weight to prepare a prepreg, and then the prepreg is heated at 220 to 260 ° C.
It consists of curing with. A preferred specific embodiment of the production method of the present invention will be described below.

First step: An aqueous solution of a metal phosphate that constitutes an inorganic matrix, a curing agent, and various fillers such as a metal phosphate, which is optionally used, are mixed and stirred to prepare a slurry mixture. To do.

Second step: Glass fibers are impregnated with the slurry-like mixture obtained above to form a composite of the two. As a method of impregnation, when the glass fiber is in a mat shape, a method of soaking the glass fiber mat in a slurry-like mixture and pulling it out, or making the slurry mixture in a highly viscous state and applying it to a carrier material such as a film Then, a uniform length of chopped strands is evenly sprinkled on it, and impregnated to create a pre-molding material such as a green sheet (hereinafter,
This method is referred to as the first impregnation method) or the glass fiber reinforced plastic manufacturing method (hereinafter, this method is referred to as the second impregnation method), as is generally done by a hand layup method or a spray up method. There is a method of making the material, and it can be selected depending on the molding method of the inorganic molded product and the application.

Third step: For the purpose of improving the handleability up to the subsequent molding step and adjusting the water vaporization at the time of molding before molding, the water content of the material before molding such as a green sheet is adjusted to 5 relative to the material before molding. A prepreg is prepared by adjusting the content to be about 15% by weight. However, depending on the slurry-like mixture used in the first step, when the pre-molding material already obtained has a water content in the above range, it is not necessary to adjust the water content at this stage, and thus this step is not necessary.

Further, in the second step, when the inorganic matrix and the glass fiber are combined / shaped by the second impregnation method such as the hand layup method or the spray up method, the hardness is such that demolding is possible. Fully dry and demold. This drying is performed at a relatively low temperature of 55 to 110 ° C. for 2 hours.
It is preferably carried out for about 17 hours. This is because the surface layer of the inorganic matrix is first cured to prevent expansion of the molded product caused by the evaporation of water remaining inside the molded product afterwards.

Fourth step: When the obtained prepreg is heated, curing is started. Therefore, before the curing is sufficiently performed,
It is preferable to shape. As shaping, a prepreg with adjusted water content is formed into a desired shape such as a plate shape, a corrugated shape, or an uneven shape. Examples of the molding method include a method of pressing with a flat plate press, a belt press, a roll press, or the like, or a device capable of heating at the same time as pressing.
The heating temperature at this time is preferably 170 to 250 ° C. and about 2 minutes to 1 hour. The second impregnation method described above can be molded without the fourth step.

Fifth step: In this step, the metal phosphate obtained by the fourth step is completely reacted with the curing agent and cured. The heating temperature at this time is higher than 200 ° C., and it is preferable to perform heat treatment in a heating device at 220 to 260 ° C. for about 1 to 5 hours until the curing is completed. In addition, the fourth step and the fifth step can be carried out without distinction between the steps, by heating while shaping and further by heating the heating to complete the reaction.

The fiber-reinforced inorganic molded product of the present invention thus obtained has a strong crystal structure, and the glass fiber does not deteriorate even during the curing process at high temperature, and the inorganic molded product obtained has excellent mechanical strength. It has water resistance, heat resistance, thermal shock resistance and dimensional stability. Hereinafter, examples of the present invention will be shown together with comparative examples, but it is needless to say that the present invention should not be construed as being limited to the examples.

[0043]

Example: 100 parts by weight of monobasic aluminum phosphate (50% by weight aluminum biphosphate aqueous solution, manufactured by Nippon Kagaku Kogyo Co., Ltd.) in terms of solid content was added to aluminum oxide (“A-4
3-M ", Showa Denko KK, average particle size: 1.8 μm,)
150 parts by weight, 5 parts by weight Wollastonite (“# 400”, manufactured by Kinsei Matex Co., average particle size 4 μm,) and sodium hexametaphosphate (15 parts by weight manufactured by Yoneyama Chemical Co., Ltd.) were stirred and mixed with a homodisper to form a slurry. A mixture was obtained.

As the glass fiber, roving of E glass fiber surface-treated with a sizing agent (8 kinds) having the composition shown in Table 1 was used. Roving has 250 bundles
Use four strands of a book,
The chopped strands cut into mm and the above slurry-like mixture were compounded in the formulations shown in Table 2 as described below to prepare inorganic molded articles of Examples 1 to 8 and Comparative Examples 1 and 2. did.

In order to produce an inorganic molded article, a predetermined amount of the slurry mixture is applied on a polypropylene film, the chopped strands are sprinkled evenly on the polypropylene film, and a composite is formed into a sheet by a mesh belt press. I got a green sheet. This green sheet was dried in a hot air drier at 80 ° C. so that the amount of water was 10% by weight with respect to the weight of the sheet, and the flat sheet was pressed at 200 ° C., 20 kg / cm ² , Heat-press molding was carried out under the condition of 10 minutes to obtain a plate-shaped molded product. These molded products were heated in a heating device under the heating conditions shown in Table 2 and then naturally cooled to obtain respective inorganic molded products.

The bulk specific gravity and thickness of the inorganic molded articles of Examples 1 to 8 and Comparative Examples 1 and 2 were measured by the method of JIS A5430, and the bending strength was measured by the method of JIS A1408. Further, the bending strength after being immersed in water at 20 ° C. for 24 hours was measured. The results of these evaluations are shown in Table 2.

As shown in Table 2, in Examples 1 to 4, 6 and 7 which were cured at a high heating temperature, the water resistance was improved as compared with Examples 5 and 8 at a low heating temperature, and the normal state was obtained. The decrease in bending strength after immersion in water was less than that in bending strength. Further, Examples 1 to 8 using glass fibers treated with a sizing agent containing an epoxy resin and an aminosilane compound.
Shows that deterioration of the glass fiber is suppressed and exhibits excellent bending strength as compared with Comparative Examples 1 and 2.

Further, as compared with Example 1 in which monoaminosilane was used as the aminosilane compound, Example 2 in which diaminosilane was used exhibited a higher glass fiber protecting effect and exhibited higher bending strength. In addition, Example 1 and Example 2
In addition, in Example 4, the monofilament diameter of the glass fiber is larger than that in Example 3, and Examples 1 to 3 are Example 4
Since glass fibers having a larger amount of the sizing agent attached thereto are used, the glass fibers are less likely to be deteriorated by heat or acidic components in Examples 1 and 2, and the mechanical strength has a high value.

Further, in Example 8, since the glass fiber using the sizing agent composed of the epoxy resin and the aminosilane compound is used, excellent mechanical strength can be obtained even when heated at a relatively low heating temperature for a long time. A molded product having was obtained. On the other hand, in Example 1 in which the same glass fiber as in Example 8 was used, the heating temperature was raised, and thus a molded product excellent in mechanical strength was obtained in a short time.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

According to the present invention, it has excellent mechanical strength, heat resistance, thermal shock resistance, and dimensional stability, and is suitable as a construction material or a structural material or member for industry, and is water resistant. A phosphate-based fiber-reinforced inorganic molded article having improved properties is also provided. Further, there is provided a method for producing a phosphate-based fiber-reinforced inorganic molded article that can shorten the curing process time and perform efficient production.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D06M 15/55 D06M 15/55 // C04B 111: 20 C04B 111: 20 111: 27 111: 27 111: 28 111: 28 (72) Inventor, Seitaro Onoe, 3-6 Kanda, Kajimachi, Chiyoda-ku, Tokyo 3 Asahi Fiber Glass Co., Ltd. (72) Hideki Endo, 3-6, Kanda, Blacksmith, Chiyoda-ku, Tokyo 3 Asahi Fiber Glass Co., Ltd. (72) Inventor Koichi Sugino 3-6-3 Kanda Kajimachi, Chiyoda-ku, Tokyo Asahi Fiber Glass Co., Ltd. (72) Inventor Naoaki Fujita 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Asahi Glass Co., Ltd. (72) Inventor, Masaki Tsujino, Asahi Glass Co., Ltd., 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture (72) Inventor, Naoyuki Tsuda, Kanagawa Kanagawa-ku, Yokohama-shi Hazawa-cho, 1150 address by Asahi Glass Co., Ltd. in the F-term (reference) 4G012 MA00 MA01 PA17 PB03 PC04 PC06 PC11 PC12 PC15 4L033 AA09 AB09 AC11 BA39 BA47 BA97 CA49

Claims (10)

[Claims] 1. A fiber-reinforced inorganic molded article in which an inorganic matrix, which is cured by reacting a metal phosphate with a curing agent, is reinforced with glass fibers, wherein the glass fibers are an epoxy resin and a compound of formula RSiX ₃ (R Is an amino-containing organic functional group,
X is a halogen atom or an alkoxy group. ) A fiber-reinforced inorganic molded article, which is a glass fiber treated with a sizing agent containing an aminosilane compound represented by the formula (1). 2. The fiber-reinforced inorganic molded article according to claim 1, wherein the metal phosphate is a primary metal phosphate and the aminosilane compound has a plurality of amino groups. 3. The method according to claim 1, wherein the curing agent is at least one selected from the group consisting of metal hydroxides, basic metal oxides and complex oxides containing basic metal oxides. The fiber-reinforced inorganic molded article described. 4. The fiber-reinforced inorganic molded article according to claim 1, 2 or 3, wherein the glass fiber monofilament has a diameter of 8 to 15 μm. 5. The sizing agent comprises 50 to 50% of the total solid content.
The fiber-reinforced inorganic molded article according to any one of claims 1 to 4, comprising 97% by mass of an epoxy resin and 3 to 25% by mass of an aminosilane compound. 6. The sizing agent is added to a glass fiber in the range of 0.
The fiber-reinforced inorganic molded product according to any one of claims 1 to 5, wherein the fiber-reinforced inorganic molded product adheres to 5 to 3.0% by weight. 7. The fiber-reinforced inorganic molded article according to claim 1, wherein the inorganic matrix contains a metal salt of metaphosphoric acid. 8. A mixture containing a metal phosphate and a curing agent therefor is represented by an epoxy resin and a formula RSiX ₃ (R is an amino-containing organic functional group, and X is a halogen atom or an alkoxy group). A glass fiber treated with a sizing agent containing an aminosilane compound is impregnated to prepare a pre-molding material, which is then dried so that the pre-molding material has a water content of 5 to 15% by weight to prepare a prepreg. And then curing the prepreg at 220 to 260 ° C., a method for producing a fiber-reinforced inorganic molded article. 9. Before curing the prepreg, 170-
The method for producing a fiber-reinforced inorganic molded article according to claim 7, wherein shaping is performed at 250 ° C. 10. A glass fiber for reinforcing a fiber-reinforced inorganic molded article comprising an inorganic matrix which is cured by reacting a metal phosphate with a curing agent, the glass fiber comprising an epoxy resin and a compound of formula RSiX ₃ (where R is an amino-containing compound). An organic functional group, wherein X is a halogen atom or an alkoxy group.), And a glass fiber treated with a sizing agent containing the aminosilane compound.