JP3463923B2 - Method for producing cosmetic inorganic moldings - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a decorative inorganic molded article having good flame retardancy and flame resistance, which can be suitably used, for example, as an interior material for buildings and vehicles.

[0002]

2. Description of the Related Art A curable composition containing phosphoric acid and / or a phosphate and various metal compounds as an inorganic material usable as a building material, a fire-resistant / heat-resistant material, an electric insulating material, or the like, and An inorganic material obtained by curing a curable composition has been proposed. Also, various plate materials and molded products in which this inorganic material is reinforced with a reinforcing material have been proposed.

Among the above-mentioned inorganic materials, those used as interior materials for passenger cars such as railway cars and buses, and buildings such as office buildings and public facilities are the inorganic materials. It is desired that the surface of the product has a design property.

As a method for imparting a design property to the surface of an inorganic material, for example, Japanese Patent Publication No. 59-3958 and Japanese Patent Publication No. 60-228142 disclose phosphoric acid or a phosphate and various metal compounds. It is disclosed that, in the step of producing an inorganic material in which the curable composition and the fiber-based reinforcing material contained therein are composited, embossing is applied to impart an uneven pattern to the surface of the inorganic material.

In addition to the above methods, a method of adding a colorant such as a pigment to the curable composition, a method of coating the surface of the inorganic material with a paint, and a sheet-like decorative material for the inorganic material. There is known a method of joining the components with an adhesive.

Furthermore, as one of the methods for obtaining an inorganic material having good mechanical strength and appearance, Japanese Patent Laid-Open No. 31740/1992 has been proposed.
The following technique is disclosed in Japanese Patent Laid-Open No. That is, in the curable composition containing phosphoric acid and / or phosphate and various metal compounds, the pot life of the curable composition is suppressed by suppressing the reaction between phosphoric acid or phosphate and various metal compounds. To prevent the strength of the inorganic material from decreasing by improving the impregnability of the fibrous reinforcement by suppressing the gelation of the curable composition, and to prevent the occurrence of internal voids and surface layers. A curable composition for the purpose of improving the mechanical strength and appearance of the inorganic material by suppressing the occurrence of cracks, and also for improving the workability and moldability when obtaining the inorganic material. The addition of an organic liquid buffer to the product is disclosed in the same publication, and the publication discloses carboxylic acids, amines, urea and the like as the organic liquid buffer.

The inorganic material whose surface has been designed as described above is a fiber-reinforced resin (FRP) plate having a decorative material attached to its surface, which has been conventionally used as an interior material for passenger vehicles. In comparison, it has the advantage of excellent flame retardancy and flame resistance.

[0008]

However, in the method of imparting the design property to the inorganic material by embossing, adding a colorant or coating, the design property is not sufficient because it is limited to simple colors and patterns. However, there is a problem that the surface is inferior in smoothness and gloss.

On the other hand, according to the method of adhering the sheet-shaped decorative material, high designability can be imparted to the inorganic material, but this method has the following problems.

That is, when the inorganic material is exposed to a flame due to a fire or the like, since the resin-based adhesive which is an organic substance is used in the above method, it is burned to a portion other than the portion exposed to the flame. If the flame resistance of the base material is reduced, or if the shape of the inorganic material is relatively complicated and has curved parts and corners, it is difficult to bond the decorative material, or the inorganic material is used. Depending on the environment, the adhesive may deteriorate and the cosmetic material may peel off, and the problem that productivity will decrease due to one additional step of bonding the cosmetic material to the molded inorganic material Have.

The carboxylic acids and amines used as the organic liquid buffer in the technique disclosed in Japanese Patent Laid-Open No. 4-317403 are vaporized or decomposed by heating to complete the curing of the curable composition. I don't
Although it remains inside the hardened composition, that is, the inorganic material, when the carboxylic acid remains inside the inorganic material, there is a problem that the water resistance thereof becomes low. On the other hand, when amines remain inside the inorganic material, when the inorganic material is exposed to a high temperature of, for example, 400 ° C. or higher, carbonized amines remain inside the material, which is often the reason. Although not understood, since the strength of the inorganic material is remarkably reduced, there is a problem that the heat resistance that the inorganic material should have is impaired.

Further, in the curable composition disclosed in JP-A-4-317403, 0.25 to 1 mol of an organic liquid buffer is added to 1 mol of phosphoric acid. Converting the weight ratio of each type of organic liquid buffer agent corresponds to adding about 15 to 155 parts of the organic liquid buffer agent to 100 parts of phosphoric acid (concentration converted to 100%). When a relatively large amount of organic liquid buffer is used with respect to the acid, a large amount of organic matter remains in the obtained inorganic material, which causes a problem that the heat resistance of the inorganic material decreases. .

Furthermore, when urea is used as the organic liquid buffering agent in the above-mentioned quantitative ratio, when urea is decomposed to generate ammonia or ammonia when heated to cure the curable composition. Since the amount of carbon dioxide is large, there is a problem that voids are formed in the inorganic material, and the mechanical strength and the like of the obtained inorganic material becomes low.

Therefore, an object of the present invention is to produce a cosmetic inorganic molded article having high designability and mechanical strength, and excellent water resistance, heat resistance, flame retardancy and flame resistance with high productivity. To provide a method.

[0015]

The first of the methods for producing a decorative inorganic molded article of the present invention made to solve the above-mentioned problems is characterized by including the following steps. (1) 100 parts by weight of acidic metal phosphate, its curing agent 80
To 200 parts by weight, 0.1 to 10 parts by weight of urea, and a step of obtaining a curable composition containing water, (2) 100 parts by weight of the curable composition (as solid content).
And a step of obtaining 5 to 100 parts by weight of an inorganic reinforcing material to obtain a molding material, (3) a step of molding the molding material into a desired shape to obtain a semi-cured material, and (4) thermosetting After the sheet-shaped decorative material containing a resin as a main component and the semi-cured material are laminated, the both are laminated and heated at a temperature of 120 ° C. or higher to complete the curing of the semi-cured material. A step of integrating the decorative material and the semi-cured material after curing.

Similarly, a second method for producing a decorative inorganic molded article of the present invention made to solve the above problems is characterized by including the following steps. (1) 100 parts by weight of acidic metal phosphate, its curing agent 80
To 200 parts by weight, 0.1 to 10 parts by weight of urea, and a step of obtaining a curable composition containing water, (2) 100 parts by weight of the curable composition (as solid content).
And a step of obtaining 5 to 100 parts by weight of an inorganic reinforcing material to obtain a molding material, (3) a sheet-shaped decorative material containing a thermosetting resin as a main component and the molding material are laminated, and then both Forming a desired shape in a laminated state to obtain a semi-cured material, and (4) heating the semi-cured material at a temperature of 120 ° C. or higher to complete the curing of the semi-cured material, and A step of integrating the decorative material and the semi-cured material after curing.

A preferred embodiment of the present invention further comprises the step of adjusting the water content of the molding material to 5 to 10% by weight before molding it into a desired shape.

Further, the thermosetting resin constituting the decorative material is preferably in a semi-cured state, and the decorative material preferably contains melamine resin as a main component.

Further, it is preferable that the inorganic reinforcing material is glass fiber or carbon fiber provided with a surface treatment agent containing an epoxy resin.

In the method for producing a cosmetic inorganic molding of the present invention,
According to the first, the curable composition and the inorganic reinforcing material are combined.
Semi-cured material obtained by molding the above molding material into a desired shape
Is laminated with a sheet-shaped decorative material containing thermosetting resin as the main component.
Curing of semi-cured material by heating in layers
And the semi-cured material after curing.
In addition, the decorative inorganic molded article of the present invention is integrated.
According to the second manufacturing method of, thermosetting resin as a main component
Sheet-shaped decorative material, curable composition and inorganic reinforcing material
After laminating a molding material that is a composite of
In this state, it is molded into the desired shape to obtain a semi-cured material.
Of the semi-cured material by heating the cured material
And the semi-curing after curing with the decorative material
Integrate with the material.

That is, according to the method for producing a decorative inorganic type molded article of the present invention, since the decorative material and the semi-cured material are integrated in the manufacturing step of the molded article, adhesion of the decorative material in a separate step, etc. Therefore, not only simple shapes such as flat plates but also cosmetic inorganic molded products with relatively complex shapes with curved parts and corners can be manufactured with high productivity. You can

Further, the semi-cured material and the decorative material can be joined and integrated without using an adhesive due to the excellent adhesiveness of the curable composition to the thermosetting resin constituting the decorative material. The joint strength is increased and the flame resistance is also improved, and peeling of the decorative material due to deterioration of the adhesive does not occur.

Further, by adding urea to the curable composition containing the acidic metal phosphate and the curing agent thereof, the reaction between the acidic metal phosphate and the curing agent is suppressed to increase the viscosity of the composition. Since the rise is suppressed and the inorganic reinforcing material, especially the inorganic fiber, can be easily and satisfactorily impregnated with the curable composition, the mechanical strength of the obtained molded product does not decrease.

Furthermore, since the reaction between the acid metal phosphate and its curing agent is suppressed by urea, even when the curable composition is heated and cured, the reaction does not occur between the surface portion and the inside of the composition. There is no big difference in the degree, and only the surface portion is not cured first. Therefore, since the water inside which is vaporized by heating is easily released to the outside, no cracks are generated during the curing of the composition and no voids are formed inside the obtained molded product.

Further, in the present invention, the sheet-shaped decorative material containing a thermosetting resin as a main component and the semi-cured material are laminated and heated at a temperature of 120 ° C. or higher to cure the semi-cured material. Since it is completed, the urea added to the curable composition decomposes into ammonia and carbon dioxide at this temperature and is released to the outside, and does not remain in the obtained molded product. Therefore, when carboxylic acids or amines are used as a component that suppresses the reaction of the composition, the component does not remain and adversely affect the molded article. In addition, the heat resistance and water resistance of the obtained molded article are improved by supplementing a part of the ammonia generated by the decomposition of urea with the primary metal phosphate.

Furthermore, in the present invention, since 0.1 to 10 parts by weight of urea is used with respect to 100 parts by weight of acidic metal phosphate, the amount ratio of urea is relatively small, and urea is heated when the semi-cured material is heated. Since the amount of ammonia and carbon dioxide generated by decomposing is small, voids cannot be formed in the obtained molded product,
There is no reduction in its strength.

In a preferred embodiment of the present invention, the water content of the molding material is adjusted to 5 before molding the molding material into a desired shape.
Since it further includes a step of adjusting the content to be 10 wt%, the handling property of the molding material becomes good, and the molded product does not expand due to the rapid vaporization of water in the subsequent steps.

When a thermosetting resin in a semi-cured state is used, even if the shape of the semi-cured material is relatively complicated with curved portions and corners, the makeup is applied to the shape. The material is easy to fit in, the adhesive strength between the decorative material and the semi-cured material after curing can be further increased, and there is a process different from the manufacturing process of the molded product, which is only for heat-curing the thermosetting resin. Not only does productivity become high because it is unnecessary, but it is not necessary to heat the decorative material, which has been cured of the thermosetting resin in a separate process, again in the manufacturing process of the molded product. The appearance does not deteriorate due to heat deterioration.

Further, when a decorative material using a melamine resin as a thermosetting resin is used, a molded article having excellent surface smoothness, glossiness and weather resistance can be obtained.

Furthermore, when glass fiber or carbon fiber provided with a surface treatment agent containing an epoxy resin is used as the inorganic reinforcing material, it is formed by reaction curing of acidic metal phosphate and its curing agent. The wettability or adhesiveness between the matrix and the glass fiber or carbon fiber is improved, and the mechanical strength and the like of the obtained molded product are improved.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

The curable composition in the method for producing a cosmetic inorganic molded article of the present invention contains an acidic metal phosphate, its curing agent and urea in a specific amount ratio.

The acidic metal phosphate used in the present invention is a metal phosphate having at least one hydroxyl group bonded to a phosphorus atom, and is a primary metal phosphate (metal dihydrogen phosphate). ) And secondary metal phosphates (hydrogen metal phosphates).

As the primary metal phosphate, aluminum monophosphate, magnesium monophosphate, zinc monophosphate and the like are preferably used. Among them, the solubility in water is good and the economical efficiency is also high. From the viewpoint of goodness, it is preferable to use aluminum monophosphate. Incidentally, since the monoaluminum phosphate is not only an aqueous solution but also a solid one is commercially available, by combining the aqueous solution and the solid material,
It becomes easy to adjust the water content before curing the curable composition.

Further, as the dibasic metal salt, aluminum diphosphate, ferric phosphate or the like can be used. Since the second metal phosphate has a poor solubility in water unlike the first metal phosphate, it is preferably used as a dispersion in which the second metal phosphate is dispersed in water.

Further, from the viewpoint that the fluidity at the time of molding processing described later becomes good and the structure of the obtained molded product can be made dense, the acidic metal phosphate has a solid content of 40 to 90. It is preferably used in an aqueous solution or dispersion of 50% by weight, and more preferably in an aqueous solution or dispersion of 50 to 70% by weight.

The acidic metal phosphate and its curing agent react and harden by mixing and heating to form a matrix of the resulting cosmetic inorganic molded article. As the agent, a metal hydroxide, a basic metal oxide, a complex oxide containing a basic metal oxide as a component, or a metal compound such as a hydrated metal chloride can be used. From these, one kind can be used alone, or two or more kinds can be used in combination.

Aluminum hydroxide, calcium hydroxide, magnesium hydroxide and the like are used as metal hydroxides, and aluminum oxide, magnesium oxide, zinc oxide, calcium oxide and the like are used as basic metal oxides, and basic metal oxides are used. As complex oxides contained as components, calcium silicate (wollastonite), calcium aluminate (alumina cement), kaolinite, cordierite (2MgO.2Al ₂ O ₃ .5SiO ₂ ), magnesite, talc, etc., Examples of hydrated metal chlorides include hydrated aluminum chloride, polyaluminum chloride, magnesium chloride hexahydrate and the like.

The above-mentioned curing agent is an acid metal phosphate 100
80 to 200 parts by weight are used relative to parts by weight (as solids). When the amount of the curing agent used is less than 80 parts by weight, the acidic metal phosphate is left in the cosmetic inorganic molded product obtained by molding, heating and curing the curable composition, resulting in sufficient mechanical strength. Not only can it not be obtained, but the water resistance of the molded product may be impaired. On the other hand, when the amount of the curing agent used exceeds 200 parts by weight, the amount of the acidic metal phosphate is reduced with respect to the curing agent, and the matrix of the molded product becomes rough, so that sufficient mechanical strength cannot be obtained. In addition, acidic metal phosphate 100
It is more preferable to use 100 to 180 parts by weight of the above curing agent with respect to parts by weight.

Among the above curing agents, metal hydroxides,
When a basic metal oxide or a composite oxide containing a basic metal oxide as a component is used, it is preferable that 30% by weight or more of the whole curing agent is contained in one having an average particle diameter of 5 μm or less. If the curing agent having an average particle diameter of 5 μm or less is contained in an amount of 30% by weight or more, the matrix of the obtained molded article becomes dense and the adhesion between the inorganic reinforcing material and the matrix becomes good, so that the mechanical strength of the molded article is improved. Good strength. However, if the amount of the curing agent having an average particle diameter of 5 μm or less is less than 30% by weight, the resulting molded article may lack the denseness of the matrix.

When a metal hydroxide, a basic metal oxide, or a complex oxide containing a basic metal oxide as a component is used as the curing agent, the average particle diameter is 20 μm.
It is preferable that m or more is contained in an amount of 0.1 to 10% by weight based on the whole curing agent. When the curing agent having an average particle size of 20 μm or more is contained in an amount of 0.1 to 10% by weight, the water contained in the curable composition is easily released to the outside when vaporized, and the vaporized water is It is possible to suppress the expansion of the matrix or the generation of voids that are caused by the difficulty in being released, so that the mechanical strength of the obtained cosmetic inorganic type molded article is improved. A curing agent having an average particle diameter of 20 μm or more can obtain its effect if it is contained in a small amount, but if it is contained in an amount of more than 10% by weight with respect to the entire curing agent, a molding obtained can be obtained. The product matrix may not be dense.

In the present invention, urea is used in order to suppress the high reactivity between the acidic metal phosphate contained in the curable composition and its curing agent. That is, to the acidic metal phosphate before mixing with the curing agent, or to the mixture immediately after mixing the acidic metal salt and the curing agent, by adding urea, two amino groups of urea and The hydroxyl group of the acidic metal phosphate salt interacts with each other, the reaction between the acidic metal phosphate salt and the curing agent thereof is suppressed, and the increase in viscosity of the curable composition is suppressed. As a result, since the fluidity of the curable composition is not impaired, it becomes easy to impregnate a fibrous reinforcing material described later and to mold it into a desired shape.

Further, urea does not decompose up to a temperature of about 120 ° C., and starts to decompose when heated to a temperature higher than 120 ° C. Therefore, it is necessary to heat the curable composition to complete the curing. Also, since the urea suppresses the reaction between the acidic metal phosphate and its curing agent until most of the water contained in the curable composition is vaporized and released to the outside, the surface of the curable composition is Only the part does not harden, expansion and cracking due to vaporization of water inside are suppressed, and the mechanical strength, appearance, etc. of the resulting cosmetic inorganic molded article are not impaired.

Further, in the present invention, a semi-cured material obtained by molding a molding material, which is a composite of a curable composition and an inorganic reinforcing material, into a desired shape is used as a sheet containing a thermosetting resin as a main component. In the state where it is laminated with the decorative material, the heating of the semi-cured material is completed by heating it at a temperature of 120 ° C. or higher, and at this temperature, urea is decomposed into ammonia and carbon dioxide by heat and released to the outside. Therefore, it does not remain in the cosmetic inorganic molded product. Therefore, unlike the case where amines and the like are added to the curable composition, the organic matter does not remain in the inorganic molded article and the performance thereof is not adversely affected.

Furthermore, a part of the ammonia generated by the thermal decomposition of urea is obtained because it is supplemented by the acidic metal phosphate contained in the curable composition to accelerate the curing of the curable composition. The heat resistance and water resistance of the decorative inorganic molded article are improved.

In the present invention, acidic metal phosphate 10
0.1 to 10 parts by weight of urea are used for 0 parts by weight (as solid content). When the amount of urea used is less than 0.1 part by weight, the reaction suppressing effect of urea is insufficient, while when the amount of urea used exceeds 10 parts by weight, heating for curing the curable composition occurs. At that time, the amount of ammonia and carbon dioxide generated by the decomposition of urea increases, so that voids are formed in the decorative inorganic molded product, and its mechanical strength and the like decrease. The amount of urea used is 1 acidic metal phosphate.
It is more preferably 0.5 to 8 parts by weight with respect to 00 parts by weight.

The molding material in the method for producing a decorative inorganic molded article of the present invention is a composite of the above curable composition and inorganic reinforcing material in a specific amount ratio.

As the inorganic reinforcing material used in the present invention, those similar to the reinforcing materials used in conventional inorganic materials can be used, and among them, it is preferable to use inorganic fibers or whiskers. It is preferable to use the inorganic fiber because of its versatility.

Glass fibers, ceramic fibers, carbon fibers and the like can be used as the inorganic fibers, and aluminum borate whiskers and the like can be used as the whiskers.

The glass composition of the above glass fiber is A
Examples thereof include glass, E glass, ECR glass, S glass, and AR glass, and examples of the ceramic fiber include alumina fiber, silicon-alumina fiber, and silicon nitride fiber.

The above-mentioned inorganic fibers can be used in any form of short fibers and long fibers, including inorganic fibers processed into the form of mat, woven fabric, non-woven fabric, paper, etc.
Inorganic fibers of various forms can be appropriately selected and used according to the processing method of the curable composition, the use of the molded product, and the like. As the inorganic fiber, it is particularly preferable to use the glass fiber having the E glass composition because the cost is low and it is widely used. Glass fiber of E glass composition is short fiber such as milled fiber or chopped strand,
Continuous fibers such as yarns and rovings, mats, woven fabrics,
It is possible to use a processed non-woven fabric or the like. Incidentally, the inorganic reinforcing material is selected appropriately in quality and form,
One kind may be used alone, or two or more kinds may be used in combination.

The above-mentioned inorganic reinforcing material is a curable composition 100.
5 to 100 parts by weight are used, based on parts by weight (as solids). If the amount of the inorganic reinforcing material used is less than 5 parts by weight, the mechanical strength of the decorative inorganic molded article becomes insufficient,
On the other hand, when the amount of the inorganic reinforcing material used exceeds 100 parts by weight, the composition becomes insufficient with respect to the reinforcing material, so that the matrix becomes rough, and the mechanical strength of the decorative inorganic molded article is also insufficient. The amount of the inorganic reinforcing material used is more preferably 15 to 80 parts by weight with respect to 100 parts by weight of the curable composition.

Among the above-mentioned inorganic reinforcing materials, alumina fibers, silicon-alumina fibers, whiskers and the like can react with the acidic metal phosphate contained in the curable composition, and have wettability or adhesiveness with the matrix. The surface treatment is not necessarily required because of the relatively high value, but it is preferable that the reinforcing material excluding these, particularly glass fiber and carbon fiber, is provided with a surface treatment agent containing an epoxy resin. Epoxy resin has good compatibility with phosphoric acid compounds,
Further, since it easily reacts with a phosphoric acid compound, by adding a surface treatment agent containing an epoxy resin to the glass fiber and the carbon fiber, the wettability or adhesiveness between the matrix and the glass fiber or the carbon fiber is improved. The mechanical strength and the like of the obtained molded product are improved.

As the epoxy resin used for the surface treatment agent, an aromatic polyglycidyl ether type epoxy resin, an aliphatic polyglycidyl ether type epoxy resin, an aliphatic polyglycidyl ester type epoxy resin or the like can be used. Although not particularly limited, since it is heated to cure the curable composition, it is preferable to use an aromatic polyglycidyl ether-based epoxy resin from the viewpoint of the heat resistance of the surface treatment agent. Among them, phenol novolac polyglycidyl is preferred. Ether-based epoxy resin, cresol novolac polyglycidyl ether-based epoxy resin,
It is particularly preferable to use a bisphenol A diglycidyl ether-based epoxy resin.

There are no particular restrictions on the components other than the epoxy resin contained in the surface treatment agent, but since the components are heated to cure the curable composition, the components other than the epoxy resin are not thermoplastic. Is preferred. This is because when a thermoplastic component is used, the surface treatment agent applied to the inorganic reinforcing material at the time of heating and curing may flow, which may impair the adhesion at the interface between the curable composition and the inorganic reinforcing material. is there. In addition, as a component other than the epoxy resin of the surface treatment agent, epoxy-crosslinked polyvinyl acetate or urethane-crosslinked polyvinyl acetate is exemplified.

The surface treatment agent has a solid content of 0.1% based on the weight of the inorganic reinforcing material provided with the surface treatment agent.
It is preferable to add an amount of 5 to 1.5% by weight.
If the amount of the surface treatment agent applied is less than 0.5% by weight, the effect of improving the wettability or adhesiveness between the curable composition and the inorganic reinforcing material is insufficient, while the amount of the surface treatment agent applied is insufficient. Even if it exceeds 1.5% by weight, the effect of improving the adhesiveness at the interface is not observed for the applied amount, which is uneconomical.

The sheet-shaped decorative material containing a thermosetting resin as a main component used in the present invention is a thermosetting resin formed into a sheet according to a conventional method.

As the thermosetting resin for obtaining the above-mentioned decorative material, melamine resin, phenol resin, epoxy resin and the like can be used, and among them, the versatility as a decorative material is high and the cosmetic material is excellent. It is preferable to use a melamine resin because it can impart weather resistance, smoothness and gloss. Incidentally, for the above thermosetting resin,
If necessary, a colorant such as a pigment, an additive such as a filler, a lubricant, and a leveling agent may be mixed and used as a resin composition.

The thermosetting resin constituting the decorative material may be in a completely cured state or in a semi-cured state that can be handled as a sheet. In this case, even if the shape of the semi-cured material on which the decorative material is laminated is relatively complicated with curved portions and corners, it is easy to adapt to the shape, and You can increase the adhesive strength,
Further, it is preferable in that the step for only heating and hardening the thermosetting resin can be omitted.

Further, the above-mentioned decorative material may be a thermosetting resin or a resin composition containing an additive added thereto and formed into a sheet by itself, but the decorative material has high strength and is easy to handle. From the viewpoint of goodness, it is preferable to use a decorative material prepared by impregnating a paper or nonwoven fabric made of organic fibers or inorganic fibers with a thermosetting resin or a resin composition containing an additive added thereto.

The above-mentioned decorative material is obtained by imparting a design property to a thermosetting resin molded into a sheet according to a conventional method, but this method is not particularly limited, and for example, a thermosetting resin may be used. A method of adding a colorant to a curable resin, a method of imparting a color or a pattern to a thermosetting resin formed into a sheet by printing, a thermosetting resin or a paper or a non-woven fabric to which a color or a pattern is imparted by printing or the like. Examples thereof include a method of impregnating a resin composition containing an additive.

Further, the thickness of the above-mentioned decorative material is not particularly limited, but for example, one having a thickness of 0.1 to 2 mm can be used. Further, two or more kinds of decorative materials having different thermosetting resins may be laminated and used.

In the present invention, various additives may be added to the curable composition for the purpose of reducing the weight and cost of the cosmetic inorganic molding. As such an additive, a lightweight aggregate, a filler or the like can be used.

Shirasu balloon, glass balloon, pearlite, etc. are used as the above-mentioned lightweight aggregate, and silica sand, silica fume, glass powder containing an acidic oxide as a main component is used as a filler.
Clay or the like can be exemplified, and these materials may be appropriately selected and used in appropriate amounts according to their respective purposes.

The method for producing a cosmetic inorganic molded article of the present invention comprises the following steps (1) to (4) using the composition, material and cosmetic material as described above, and the mode of each step Is not particularly limited, but specific examples can be shown as follows.

(1) In this first step, a curable composition is obtained by mixing the acidic metal phosphate aqueous solution, its curing agent and urea in a predetermined ratio. The mixing method at this time is not particularly limited, and various additives can be added as necessary.

(2) In the second step, the curable composition obtained in the first step and the inorganic reinforcing material are compounded in a predetermined ratio and used for molding in the next step into a desired shape. Get the material. In addition, as a method of compounding the curable composition and the inorganic reinforcing material, among the methods exemplified in [1] to [4] below, the molding method adopted in the next step or the obtained cosmetic inorganic molded article is obtained. The method can be appropriately selected depending on the purpose of use, etc., but is not limited to these methods.

[1] Using a matt inorganic reinforcing material,
A method of impregnating and adhering the composition to the mat-like reinforcing material while immersing the mat-like reinforcing material in the bath of the curable composition while pulling it out. [2] The curable composition is preliminarily made to have a high viscosity to some extent, and the composition is applied to the surface of a carrier material such as a resin film,
While the roving is cut into a predetermined length on the applied composition, or the chopped strands that have been cut in advance are sprinkled, and the composition is reinforced by compressing it with a compression device through the carrier material. A method of impregnating cut rovings or chopped strands with a composition. [3] A method of using a curable composition instead of plastic (resin) by a hand lay-up method or a spray-up method, which is adopted when manufacturing a glass fiber reinforced plastic. [4] Whiskers or short fiber inorganic fibers such as milled fibers and chopped strands are used as the inorganic reinforcing material, and the curable composition and the inorganic reinforcing material are kneaded using a dispersion mixer such as a kneader. How to make. In the above method [3], the curable composition and the inorganic fiber as the inorganic reinforcing material may be composited on a mold having a desired shape, and the molding material may be molded together. preferable.

Although not essential, it is possible to improve the handling property of the molding material up to the next step, suppress the amount of water vaporized when the molding and curing are completed, and perform the rapid vaporization of the internal water. For the purpose of preventing the product from expanding, the amount of water contained in the molding material may be adjusted to be 5 to 10% by weight with respect to the molding material. However, when it is possible to reduce the amount of water when the curable composition is obtained in the first step, this step is not required, and the curable composition is obtained by the method of [3] in the second step. When the compound and the inorganic fiber are compounded and molded, it is preferable that the curable composition be dried until most of the water in the curable composition is vaporized and then demolded. In order to adjust the water content of the molding material within the above range, 80 to 1
It is preferable to heat and dry at a temperature of 10 ° C. for 2 to 8 hours.

(3) In the third step, the molding material obtained in the previous step is molded into a desired shape such as a plate shape, a corrugated plate shape, or an uneven shape, which is appropriately set according to the intended use of the molded product. To obtain a semi-cured material. The molding material can be molded by a device such as a mold pressing device, a flat plate pressing device, a belt pressing device, a roll pressing device, or the like that can apply only pressure or can simultaneously apply pressure and heat. Further, the molding material obtained by the method [4] of the second step can be molded by a transfer molding method such as that employed when manufacturing glass fiber reinforced plastic.

(4) In this fourth step, after the semi-cured material obtained in the previous step and the decorative material are laminated, they are heated in a laminated state to form the acidic metal phosphate contained in the semi-cured material. And the curing agent thereof are completely reacted to complete the curing of the semi-cured material, and the cured semi-cured material and the cosmetic material are integrally bonded by the adhesive force of the curable composition contained in the semi-cured material. To obtain a cosmetic inorganic molded product.

In the fourth step, it is necessary to heat the semi-cured material to a temperature of 120 ° C. or higher so that urea is decomposed and released to the outside. When the semi-cured material and the decorative material are heated in a laminated state, they may be in a non-pressurized state or a pressurized state, but the bonding state of the two and the resulting inorganic inorganic molded product 5 to improve the surface condition of
It is preferable to heat while applying a pressure of about 50 kg / cm ² .

The conditions for heating the semi-cured material are as follows:
It is preferable to heat in a heater at 120 to 200 ° C. for about 1 to 8 hours. When the semi-cured material is heated at a temperature lower than 120 ° C., urea remains inside the semi-cured material and inhibits the reaction, so that the curing is incomplete and the resulting molded article has water resistance and mechanical properties. The strength is insufficient.

Furthermore, when a primary metal phosphate is used as the acidic metal phosphate to be added to the curable composition, the primary metal phosphate and its curing agent are sufficiently reacted to give It is preferable to heat the semi-cured material at a temperature of 150 ° C. or higher in order to prevent deterioration of physical properties such as water resistance of the resulting cosmetic inorganic molded article, and specifically, 150 to 2
It is preferable to heat in a heater at 00 ° C. for about 1 to 8 hours.

Each step of the method for producing a cosmetic inorganic molded article described above is an example showing the first aspect of the production method of the present invention, and the second step of the production method of the present invention is the same as that in the fourth step. Instead of laminating the semi-cured material and the decorative material on the above, after laminating the molding material and the decorative material obtained in the above second step, both are laminated in the same manner as in the above third step. A semi-cured material is formed into a desired shape, and the semi-cured material is heated in the same manner as in the fourth step,
The semi-cured material is completely cured, and the semi-cured material and the decorative material are joined and integrated to obtain a decorative inorganic molded article.

[0076]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example 1 First, 100 parts by weight of aluminum monophosphate as an acidic metal phosphate, 3 parts by weight of wollastonite (average particle diameter: 10 μm) as a curing agent thereof, aluminum hydroxide (average particles) Diameter: 50 μm) 2 parts by weight, aluminum hydroxide (average particle size: 10 μm) 15 parts by weight, aluminum oxide (average particle size: 60 μm) 10 parts by weight, aluminum oxide (average particle size: 15 μm) 20 parts by weight, and Aluminum oxide (average particle diameter: 3.7 μm) 70
By weight, 2 parts by weight of urea as a reaction inhibitor was mixed by a dissolver to obtain a curable composition. In addition, all the above-mentioned amount ratios show the amount as a solid content.

Further, a surface treatment agent obtained by mixing 5% by weight of an epoxy resin having an epoxy equivalent of 450 g / eq, 5% by weight of epoxy cross-linked polyvinyl acetate, and 90% by weight of ion-exchanged water was used as an E glass composition. After being applied to continuous glass fiber and dried by heating, it was cut into a length of 50 mm to obtain a glass chopped strand used as an inorganic reinforcing material. still,
Surface treatment was performed so that 1% by weight of solid content was adhered based on the weight of the continuous glass fiber provided with the surface treatment agent.

Furthermore, a sheet-shaped decorative material having a thickness of 0.5 mm and a density of 1.2 g / cm ³ is obtained by impregnating a melamine resin into a cellulose fiber type paper having a pattern based on white by printing. Obtained. The melamine resin in the decorative material was semi-cured.

Next, the above-mentioned curable composition is applied to the surface of a PET (polyethylene terephthalate) resin film which is a carrier material, and the glass chopped strands are sprinkled thereon to form a layer of a reinforcing material. To a PET resin film whose surface is coated with the above curable composition,
After placing so that the surface coated with the composition is in contact with the layer of the reinforcing material, it is sandwiched by a mesh belt press and compressed, and the layer of the reinforcing material made of glass chopped strands is impregnated with the curable composition Was compounded to obtain a sheet-shaped molding material. This molding material was heated and dried in a dryer at a temperature of 80 ° C., and the amount of water contained in the molding material was adjusted to about 5% by weight based on the molding material. still,
In the production of the above molding material, the amount ratio as a solid content was adjusted so that the glass chopped strand was 40 parts by weight with respect to 100 parts by weight of the curable composition.

Subsequently, the above molding material was pressure-molded using a flat plate press under the conditions of a temperature of 120 ° C., a pressure of 35 kg / cm ² , and a pressing time of 5 minutes to obtain a flat semi-cured material. . One piece of each of the above-mentioned decorative material and one obtained by peeling the carrier material on both sides from this semi-cured material is laminated, and the temperature is 200 ° C., the pressure is 30 kg / cm ² , and the pressing time is 70 minutes by using a flat plate press. Heat and pressure are applied under the conditions to complete the curing of the semi-cured material, and after the cosmetic material and the semi-cured material are joined and integrated, the pressure is released and the product is naturally cooled, and the flat inorganic makeup product Got The total thickness of this decorative inorganic molded product was 2.5 mm, and the density of the inorganic part was 1.
It was 8 g / cm ³ .

Example 2 First, 100 parts by weight of dibasic aluminum phosphate as an acidic metal phosphate, 3 parts by weight of wollastonite (average particle diameter: 10 μm) as a curing agent thereof, aluminum hydroxide (average particles) Diameter: 50 μm) 2 parts by weight, aluminum hydroxide (average particle size: 10 μm) 5 parts by weight, aluminum oxide (average particle size: 60 μm) 5 parts by weight, aluminum oxide (average particle size: 15 μm) 30 parts by weight, and Dissolver of 70 parts by weight of aluminum oxide (average particle diameter: 3.7 μm) and 2 parts by weight of urea as a reaction inhibitor
To obtain a curable composition. In addition, all the above-mentioned amount ratios show the amount as a solid content. Next, Example 1
Using the same glass chopped strands and decorative material as described above, a flat plate-shaped decorative inorganic molded article was obtained by the same method and conditions as in Example 1 except that the temperature at which the semi-cured material was heated and pressed was 140 ° C. . The total thickness of this inorganic molded product is 2.5 mm, and the density of the inorganic part is 1.8 g.
/ Cm ³ .

Example 3 A flat plate pressing apparatus was prepared by laminating a molding material obtained in the same manner as in Example 1 with the carrier films on both sides peeled off and a decorative material similar to that in Example 1, respectively. Was subjected to pressure molding in a state in which both were laminated under the conditions of a temperature of 120 ° C., a pressure of 35 kg / cm ² , and a pressure time of 5 minutes to obtain a flat semi-cured material on which a decorative material was laminated. This semi-cured material was heated at a temperature of 200 ° C. and a pressure of 30 kg / c using a flat plate press.
m ^{2 at} a pressing time of 70 minutes to heat and pressurize to complete the curing of the semi-cured material, join and integrate the decorative material and the semi-cured material, and then release the pressure and naturally cool. ,
A flat inorganic molded article was obtained. The total thickness of the inorganic molded product was 2.5 mm, and the density of the inorganic part was 1.8 g / cm ³ .

Comparative Example A semi-cured material similar to that in the example was heated and pressed using a flat plate press at a temperature of 200 ° C., a pressure of 30 kg / cm ² , and a pressing time of 70 minutes to complete the curing of the semi-cured material. After that, the pressure was released, and the plate was naturally cooled to obtain a flat inorganic molded article. In addition, the same decorative material as in the example was applied at a temperature of 120.
The melamine resin was cured by heating at 60 ° C. for 60 minutes and cooled to room temperature. Using the epoxy resin adhesive, the above-mentioned inorganic molded product and the above-mentioned resin-cured decorative material were bonded and integrated to obtain a flat-plate-shaped decorative inorganic molded product.
The total thickness of this decorative inorganic molding is 2.5 m.
m, and the density of the inorganic portion was 1.8 g / cm ³ .

Test Examples For each of the cosmetic inorganic molded articles of Examples 1 to 3 and Comparative Example, a Bunsen burner using propane gas as a fuel was used, and the cosmetic inorganic molded article was placed 20 cm away from the tip of the burner. 30 on the surface of the decorative material side of the flame
The flame resistance was evaluated by a method of exposing for 2 seconds and then observing the state of the surface.

Results In the cosmetic inorganic moldings of Examples 1, 2 and 3, the decorative material of the burner exposed to the flame was carbonized, but it was not burned to the non-flamed area. Moreover, the decorative material did not peel off from the inorganic part including the part exposed to the flame. On the other hand, in the inorganic molded article of the comparative example, the decorative material peels off from the inorganic portion in the portion exposed to the flame of the burner, and the thickness of the organic portion including the adhesive layer increases, resulting in a flame. A flame was emitted to the part not exposed to the fire. Moreover, the peeling of the decorative material spread to the part not exposed to the flame.

From the above results, the cosmetic inorganic moldings of Examples 1, 2 and 3 obtained by the production method of the present invention have good flame resistance, while the adhesives are used to prepare the cosmetic materials. It can be seen that the decorative inorganic molded article of the comparative example which is pasted is inferior in flame resistance.

[0088]

As described above, according to the present invention,
A semi-cured material obtained by molding a molding material that is a composite of a curable composition and an inorganic reinforcing material into a desired shape is heated in a state of being laminated with a sheet-shaped decorative material containing a thermosetting resin as a main component. By completing the curing of the semi-cured material, the semi-cured material and the cosmetic material can be used without using an adhesive by utilizing the excellent adhesiveness of the curable composition to the thermosetting resin constituting the cosmetic material. Since it is joined and integrated, it does not burn even when exposed to a flame, so it has excellent flame resistance,
Moreover, not only is the shape like a flat plate simple, but even if the shape is relatively complicated with curved parts and corners, the bonding strength between the two is high and there is the problem of peeling of the cosmetic material. It is possible to obtain a cosmetic inorganic molded article that does not occur and has excellent designability.

Further, since urea is added to the curable composition in a relatively small specific amount, the composition expands during heat curing, voids are formed in the obtained molded product, and the water resistance of the molded product is increased. There is no decrease in sex.

In addition, the inorganic type molded product obtained by the manufacturing method of the present invention has excellent designability as compared with the conventional one.
Since it has mechanical strength, water resistance, heat resistance, flame resistance, and flame resistance, it can be used as an interior material for passenger vehicles or buildings.

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Claims (6)

(57) [Claims] 1. A method for producing a decorative inorganic molded article, which comprises the following steps. (1) 100 parts by weight of acidic metal phosphate, its curing agent 80
To 200 parts by weight, 0.1 to 10 parts by weight of urea, and a step of obtaining a curable composition containing water, (2) 100 parts by weight of the curable composition (as solid content).
And a step of obtaining 5 to 100 parts by weight of an inorganic reinforcing material to obtain a molding material, (3) a step of molding the molding material into a desired shape to obtain a semi-cured material, and (4) thermosetting After the sheet-shaped decorative material containing a resin as a main component and the semi-cured material are laminated, the both are laminated and heated at a temperature of 120 ° C. or higher to complete the curing of the semi-cured material. A step of integrating the decorative material and the semi-cured material after curing. 2. A method for producing a decorative inorganic molded article, which comprises the following steps. (1) 100 parts by weight of acidic metal phosphate, its curing agent 80
To 200 parts by weight, 0.1 to 10 parts by weight of urea, and a step of obtaining a curable composition containing water, (2) 100 parts by weight of the curable composition (as solid content).
And a step of obtaining 5 to 100 parts by weight of an inorganic reinforcing material to obtain a molding material, (3) a sheet-shaped decorative material containing a thermosetting resin as a main component and the molding material are laminated, and then both Forming a desired shape in a laminated state to obtain a semi-cured material, and (4) heating the semi-cured material at a temperature of 120 ° C. or higher to complete the curing of the semi-cured material, and A step of integrating the decorative material and the semi-cured material after curing. 3. The cosmetic inorganic system according to claim 1, further comprising a step of adjusting the water content of the molding material to 5 to 10% by weight before molding the molding material into a desired shape. Molded article manufacturing method. 4. The thermosetting resin constituting the decorative material,
The method for producing a decorative inorganic molded article according to claim 1, which is in a semi-cured state. 5. The thermosetting resin constituting the decorative material,
The method for producing a decorative inorganic molded article according to claim 1, which comprises a melamine resin as a main component. 6. The method for producing a decorative inorganic molded article according to claim 1, wherein the inorganic reinforcing material is a glass fiber or a carbon fiber provided with a surface treatment agent containing an epoxy resin.