JPH07118081A - Light weight formed body and production thereof - Google Patents

Abstract

PURPOSE:To improve strength while reducing a dimensional change by applying and/or impregnating a binder containing an aqueous type reactive org. substance on and/or in bubble-containing inorg. particles and allowing the binder to react and solidify so that an inorg. layer is incorporated. CONSTITUTION:Bubble-containing inorg. particles (A) having <=0.3g/cm<3> bulk density is obtained by selecting from among the artificial materials containing a vitreous material for such as a glass balloon or natural hollow particles. Then, a binder (B) consisting of an aqueous reactive org. substance is obtained by selecting from among the particles containing a compd. having a reactive functional group (F1) such as amino group and/or copolymer particles having the F1 and an aq. soln. of a compd. having a functional group (F2) such as methylol group and/or particles containing the compd. having the F2 and/or copolymer particles having the F2 and/or a mixed emulsion, etc., with a polyvalent metallic ion. Then, 2-30 pts.wt. B component is applied on 100 pts.wt. A component and subjected to a thermal.heat reaction under pressure to produce the objective light weight formed body.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded product obtained by combining inorganic foam-containing particles and a method for producing the molded product. More specifically, it is a molded product that is lightweight and has sufficient strength, such as boards used for construction, and that has little dimensional change with respect to changes in the humidity and / or temperature of the environment in which it is used, and a simple product thereof. And a safe manufacturing method.

[0002]

2. Description of the Related Art Porous pearlite, vermiculite, foamed shirasu, glass, alumina, fly ash, silica sand, shale, etc. obtained by heat-expanding inorganic foam-containing particles such as pearlite, obsidian, hirucite, and shirasu are used as raw materials. Molded bodies in which glass balloons, shirasu balloons, and the like, which are minute hollow bodies, are bonded with a binder have been conventionally produced.

For example, a method for producing a lightweight construction board by kneading cement and water into a mixture of foam-containing particles such as pearlite and shirasu balloon and inorganic fiber and molding the mixture by a method such as a papermaking method or a mold casting method (special JP-A-48-59114) or a method using a silicate such as water glass and an appropriate curing agent as a binder (JP-A-51-135924).
Issue).

Further, a method of using an organic resin alone as a binder (Japanese Patent Laid-Open No. 48-32127) or a method of using it together with an inorganic binder such as water glass and silica sol (Japanese Patent Laid-Open No. 1-290572). ) Has also been proposed.

Further, a method of foaming and curing using a urethane resin to consolidate the inorganic foam-containing particles (JP-A-61-2).
No. 01680 gazette) is also proposed, but each method has problems as described below, and can be manufactured by a simple and safe manufacturing method which is an object of the present invention, and a lightweight molded body with little dimensional change. Was insufficient to obtain.

[0006]

The method of using cement as a binder has a drawback that it takes a long time to set the cement used as a binder and the productivity is poor. There is also a method of using fast-setting cement, but both
Since it is dried after releasing from the mold, there is a problem that the dimensional accuracy of the molded product becomes low, and it is unsuitable when used as a highly accurate building member. Also, in order to obtain appropriate strength,
There is no choice but to increase the density of the molded body, and there is a limit to weight reduction.

When water glass is used as a binder, a large amount of salt remains in the molded product, so that when the molded product is left under high humidity for a long time, it tends to absorb moisture and its weight and size change greatly. There was a problem that

Resins that are commonly used in the method using an organic binder include, for example, non-aqueous curable resins such as epoxy resin and urethane resin, synthetic rubber diluted with an organic solvent, acrylic resin, and vinyl acetate. It is an aqueous dispersion of a thermoplastic resin such as an aqueous resin emulsion.

When such a non-aqueous resin or an organic solvent-diluted resin is used as a binder, it is necessary not only to use special equipment for mixing the inorganic foam-containing particles and the binder, but also to cope with troubles, Difficulties in simple cleaning and cleaning with water of mixing equipment and molding equipment.

In addition to the above-mentioned problems, in the method of foaming and hardening urethane resin to consolidate the inorganic particles, it is necessary to cut out a required shape from the urethane foam in order to obtain a molded body of a fixed size. However, it is an industrially unsuitable method.

Organic solvent-based resins and synthetic rubbers tend to have a high solvent concentration in the work environment, so special ventilation equipment and safety measures to reduce the concentration are required, and they do not remain in the molded product. It is necessary to take proper measures.

Further, in the case of a thermoplastic resin, the strength tends to be low in a situation where the environmental temperature in which the molded body is used is high,
Further, there is a problem that the size and shape are likely to change.

The present invention has been made in view of the above-mentioned problems of the prior art, and can be manufactured by a simple method, and it can be manufactured with respect to changes in humidity and / or temperature of the environment in which it is used.
The purpose is to obtain a lightweight molded body with little dimensional change.

[0014]

[Means for Solving the Problems] As means for achieving the above object, a binder containing an aqueous reactive organic substance as an essential component is applied to inorganic foam-containing particles, and while or while being shaped. The present invention provides a lightweight molded product obtained by reacting the reactive organic substance.

That is, according to the present invention, firstly, a light weight having an inorganic layer obtained by coating and / or impregnating a binder containing an aqueous reactive organic substance on inorganic foam-containing particles and reacting and solidifying the reactive organic substance. Secondly, it is a molded body, and secondly the inorganic foam-containing particles are coated and / or impregnated with a binder containing a water-based reactive organic substance, filled in a mold, while applying a pressure necessary for the particles having the binder to come into contact with each other, Alternatively, the present invention relates to a method for producing a lightweight molded article, which comprises reacting a binder under a condition necessary for the binder to react after applying pressure.

The present invention will be described in more detail below.

The term "inorganic foam-containing particles" as used herein refers to particles composed of an inorganic material, which contain independent and / or continuous air bubbles, and the air bubbles may be completely included or a part thereof. It may be released to the outside. In the particles containing bubbles partially released to the outside, the binder is easily impregnated and held in the pores, and proper impregnation serves to reinforce the fragile portions of the particles. Desirably, hollow particles of artificial or natural material containing glass, in which air bubbles are completely included, are preferable because they are lightweight and have high strength.

As such inorganic foam-containing particles, pearlite, obsidian, hirucite, shirasu, etc., which are heated and foamed, are made of porous perlite or vermiculite, foamed shirasu, glass or alumina, fly ash, silica sand, shale, etc. Examples thereof include glass balloons and shirasu balloons, which are micro hollow bodies. Glass bubbles, shirasu balloons and the like are those in which air bubbles are completely included. In order to obtain a lightweight molded body, the bulk density of the inorganic foam-containing particles is
It is preferably 0.3 g / cm ³ or less.

The inorganic foam-containing particles may be surface-treated with a silane coupling agent or the like in order to improve the adhesiveness with the binder.

The aqueous reactive organic substance in the present invention is an aqueous solution of the reactive organic substance and / or a dispersion having water as a dispersion medium. A non-aqueous substance is not preferable because it causes handling problems such as the treatment of the solvent and the cleaning and cleaning of the apparatus as described above, and is restricted by the equipment used. Further, with a non-reactive substance, it is difficult to obtain sufficient strength, the dimensional change of the molded product becomes large due to changes in temperature and humidity, and there is a problem that the object of the present invention cannot be achieved. The use of organic organic substances is an essential requirement. The term "reactive organic substance" as used herein refers to a substance composed of one component or two or more components and capable of forming a polymer, a condensate, or a crosslinked product by reacting with heat or an appropriate curing agent.

The reactive organic substance is an inorganic foamed particle 100.
It is preferable to apply 2 to 30 parts by weight of the active ingredient to parts by weight. If the amount is less than 2% by weight, the strength of the resulting lightweight molded article becomes weak, and if it exceeds 30% by weight, the lightness is impaired. Further, in the case of imparting flame retardancy to the lightweight molded product, less than 10% by weight is desirable.

In carrying out the present invention, it is desirable that at least one component of the water-based reactive organic substance is an aqueous dispersion having a property of not dissolving in water. When it is composed of only water-soluble components, reactive organic substances easily move with the movement of water during the drying process, etc., causing unevenness in the content of the binder in the lightweight molded body, and contributing to the strength distribution. Could be. If at least one component of the water-based reactive organic substance is a water dispersion having a property of not dissolving in water, it is difficult to be entrained during the movement of water, and strength distribution is unlikely to occur. A water-soluble binder may be used if solidification of the binder occurs prior to the transfer of water, if the transfer of water is not rapid, or if some binder distribution is acceptable.

In carrying out the present invention, the binder may contain functional groups having reactivity with each other in the same phase, but in such a case, it is often the most suitable for binding the inorganic foam-containing particles. The reaction may proceed before the point of time, for example, during the polymerization or the storage, and is easily subject to so-called binder production / preparation and storage, and pot life restrictions.

Therefore, as a form of the binder for effectively carrying out the present invention, it is desirable that functional groups having reactivity are present in different phases. As such a form, a mixture of an aqueous dispersion of compound particles having a reactive functional group and an aqueous solution and / or an aqueous dispersion of a compound capable of reacting with the compound, or a mixture of different layers in the same particle may be used. An aqueous dispersion of particles having different functional groups capable of reacting can be exemplified, which is a desirable form from the viewpoint of long-term storage stability and suitability for pot life.

Further, in order to more reliably isolate the functional groups having reactivity with each other, an aqueous dispersion of particles in which a layer having no reactivity with the functional groups is provided on the outer periphery of the particles containing one kind of reactive functional group. Of a compound having a group having a group capable of reacting with the functional group and an aqueous dispersion and / or an aqueous dispersion of the compound, or by providing a core layer in the same particle with a layer containing a kind of reactive functional group There is a method of using an aqueous dispersion of particles in which a layer having no reactivity with the functional group is further provided, and a layer having a group reactive with the functional group is further provided as an outer layer, which is a more desirable method.

That is, the water-based reactive organic substance is a particle containing a compound having a reactive functional group (F1) and / or a copolymer particle having F1 and a compound having a functional group (F2) capable of reacting with F1. Of the aqueous solution and / or particles containing a compound having F2 and / or copolymer particles having F2 and / or a mixed emulsion with a polyvalent metal ion, or an aqueous reactive organic substance is present in the same particle. A form of an emulsion of multi-layered particles containing at least two layers of a copolymer layer having a reactive functional group (F3) and a copolymer layer having a functional group (F4) capable of reacting with F3, or an aqueous reaction Particles having a functional organic substance containing a compound having a reactive functional group F3 in the same particle, and an outer shell layer which does not react with F3,
In the form of a mixed emulsion with an aqueous solution of a compound having 4 and / or particles containing a compound having F4 and / or copolymer particles having F4, or the water-based reactive organic substance has F3 in the same particle. In a form such as an emulsion of multilayer constituent particles, which comprises at least two layers of a copolymer layer and a copolymer layer having F4, and has a copolymer layer which does not react with F3 and F4 between the two layers. is there.

When using a binder in which different functional groups are arranged in such different phases, it is essential that the two phases are uniformly mixed at the time of bonding the inorganic foam-containing particles, and heating, pressurization, This can be achieved by optimizing the volatilization of water. In the case of an aqueous dispersion in which different functional groups are introduced into different layers of the same particle, compared with a mixed dispersion in which different functional groups are introduced into different particles or when different functional groups are introduced into different phases, fluid mixing Is more likely to occur, a more homogeneous mixture is formed, and homogeneous binder performance is easily exhibited.

The water-based reactive organic material in the present invention is not particularly limited in terms of composition, but in order to obtain a molded product that is lightweight and has high strength and small dimensional change, a material containing a combination of the following functional groups is used. It is desirable to use.

As one of the combinations of F1 and F2 in the present invention, F1 is an amino group and / or an amide group and / or a methylol group and / or an N-methylolamide group and / or an N-alkoxymethylamide group and And / or a hydroxyl group, and F2 is a combination of a methylol group and / or an amino group and / or an amide group.

As a compound containing F2, a reaction product oligomer of an amino compound such as urea or melamine, which is a substance widely used in applications such as adhesives, and formaldehyde, or a reaction product of phenols and formaldehyde. Examples thereof include formaldehyde resins having an oligomer as a main component. These substances are reactive and can give a hardened and slightly brittle cured product by using an appropriate curing agent or by heating. It is a suitable material when high rigidity is required for a lightweight molded product. The same cured product can be obtained by using a resin which is made water-insoluble by increasing the degree of condensation of these resins and emulsified with water as a dispersion medium, or a resin powder which is a dispersion with water as a dispersion medium, and which can be used in the present invention. It is a thing.

When formaldehyde resins are used alone as a binder, unreacted formaldehyde may remain after curing, which is not suitable when the residual formaldehyde is an obstacle in the environment where the lightweight molded product is used. . Also, when a large amount of acids or alkalis is used in the production of resin, the acids, alkalis or generated salts remain in the lightweight molded product, and when the molded product is left under high humidity for a long time, moisture absorption Easy to change and weight and size change easily.

As a method for improving the brittleness of the cured product and eliminating the problems described above, it is desirable to use a copolymer emulsion having a functional group capable of reacting with the formaldehyde resin, mixed with the formaldehyde resin.

As the functional group (F1) capable of reacting with the formaldehyde resin of the present invention, an amino group, an amide group, N-
Methylolamide group, N-alkoxymethylamide group,
Hydroxyl groups are particularly preferred. The copolymer emulsion can be obtained by copolymerizing the monomers having both the functional group and the vinyl group with other vinyl monomers by a conventional method. The effect of mixed use is not only the effect of diluting the above-mentioned obstacles by the copolymer emulsion, but these functional groups have the effect of reacting with the terminal methylol group of formaldehyde resin and free formaldehyde to further reduce the residual amount of formaldehyde. Not only does it have the above property, but it also forms a cured product that reacts with the formaldehyde resin, and can exhibit the effect of improving brittleness.

The mixing ratio of the copolymer emulsion and the formaldehyde resin and the functional group introduction ratio in the copolymer emulsion are not particularly limited as long as the mixing ratio and the functional group introduction ratio can solve the above problems. good.

As another combination of F1 and F2 in the present invention, it can be recommended that F1 is an isocyanate group and F2 is an active hydrogen group. Examples of the dispersion-state isocyanate compound having water as a dispersion medium include those obtained by emulsifying an isocyanate compound having two or more isocyanate groups in the same molecule and capable of being emulsified and dispersed in water.

An isocyanate compound having two or more isocyanate groups in the same molecule and capable of being emulsified and dispersed in water is
For example, tolylene diisocyanate (TDI), 4-
4'-diphenylmethane diisocyanate (MDI),
Hexamethylene diisocyanate (HMDI), xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), polymethylene polyphenyl polyisocyanate (polymeric MDI) and the like, a mixture of an isocyanate compound and an emulsifier, and the above-mentioned isocyanate compound and monofunctional alcohol with alkylene oxide. Illustrative are isocyanate compounds which are made easily emulsifiable by the action of added compounds. Since an isocyanate compound that easily volatilizes easily contaminates the work environment, a compound having a low vapor pressure such as polymeric MDI is desirable.

These isocyanate compounds may be used alone as a binder, but an aqueous solution of a compound having an active hydrogen group which reacts with an isocyanate group is used in order to improve the adhesiveness to the inorganic foam-containing particles and the brittleness of the lightweight molded product. And / or it is desirable to use it as a mixture with an aqueous emulsion. The compound having an active hydrogen group is, for example, a hydroxyl group,
Examples thereof include an amino group, an amide group and a carboxyl group. It can be used in the form of a polyvinyl alcohol aqueous solution, the above-mentioned formaldehyde resin, polyols, or a copolymer emulsion having a functional group described later.

Further, as another combination, a combination with a polyvalent metal ion in which F1 is a carboxyl group can be mentioned. As a method of introducing a carboxyl group into the reactive organic substance dispersed particles, acrylic acid, methacrylic acid,
One or more monomers of vinyl monomers containing carboxyl groups such as ethylenically unsaturated carboxylic acids such as crotonic acid, maleic acid or its monoalkyl ester, itaconic acid or its monoalkyl ester, and functional groups thereof There is a method of copolymerizing with a vinyl monomer having no functional group that reacts with. The polyvalent metal ion may be provided in the form of an aqueous solution or a salt aqueous dispersion. The polyvalent metal may be any one capable of forming a divalent or higher valent ion and forming a salt with a carboxyl group,
Examples thereof include zinc and calcium.

Further, as a preferable combination of the functional group F3 and the functional group F4, the reactivity and the strength of the obtained molded body,
From the viewpoint of physical properties such as dimensional stability, F3 is a glycidyl group, and the functional group F4 is a carboxyl group and / or an amino group and / or an amide group and / or an N-methylolamide group and / or an N-alkoxymethylamide group. Is desirable.

The molar ratio of F4 to F3 is preferably 0.5 to 1.5 in order to obtain a strong reaction product.

When F3 is a glycidyl group, as a method of introducing the glycidyl group into the reactive organic substance dispersed particles, a method of dispersing or compatibilizing an epoxy resin in a vinyl polymer emulsion, glycidyl acrylate, glycidyl methacrylate or allyl is used. There is a method of copolymerizing one or more kinds of monomers such as glycidyl ether and vinyl monomers having no functional group which reacts with a glycidyl group.

As the compound having F4, for example, an aqueous solution or emulsion of amines may be directly used, or a copolymer emulsion containing such a functional group may be used.

As a method of introducing such a functional group into the copolymer emulsion, acrylic acid, methacrylic acid, crotonic acid, maleic acid or a monoalkyl ester thereof,
Of vinyl monomers containing amide groups such as ethylenically unsaturated carboxylic acids such as itaconic acid or its monoalkyl ester, acrylamide, methacrylamide, N-methylolacrylamide, N-alkoxymethylacrylamide, N-methylaminoethyl acrylate. There is a method of copolymerizing one or more monomers and a vinyl monomer having no functional group that reacts with these functional groups.

A vinyl polymer emulsion having a reactive functional group, an emulsion of an isocyanate compound, a formaldehyde resin, and the like are mixed with an emulsion having a functional group that reacts with the functional group and a water-soluble substance, and heated as necessary. The reaction can be carried out. Further, the copolymer emulsion having functional groups that react with each other in different layers within the same particle can be reacted by fluidly mixing the respective phases by heating.

The binder is reacted and solidified by the method described below, but the binder after the reaction has a softening temperature of 6
It is preferably 0 ° C or higher. When the temperature is 60 ° C. or lower, the strength is likely to be lowered under normal temperature, or deformation at high temperature may be caused.

In the binder, in addition to the above-mentioned water-based reactive organic substance, starch and other water-soluble polymers for improving coating properties and moldability, curing catalysts, flame retardants, antifungal agents, preservatives. Etc. may be included.

In the present invention, the method of coating or impregnating the inorganic foam-containing particles with the binder is not particularly limited. In order to obtain a strongly adhered molded product, the inorganic foam-containing particles coated and / or impregnated with the binder should have the temperature and time necessary for the binder to react while applying the pressure necessary for the particles to come into contact with each other. It is necessary to react the binder under the conditions of. However, in the case where the particles can be kept in contact with each other during the reaction, the binder may be reacted in a state where pressure is not applied and pressure is applied after the particles are pressure-molded.

Further, for the purpose of improving the strength of the molded product of the present invention, and improving the appearance of the outer surface and the processability, the inorganic foamed particles are made of glass fiber, rock wool, carbon fiber,
Mixing fibers such as aramid fibers, arranging fibers with or without a binder applied to the surface, plate-like objects such as metal plates and fiber plates, cloth-like objects such as glass cloth, films, etc. It can be molded. Also,
After molding, the plate-shaped material, the cloth-shaped material, or the plate-shaped material may be bonded to the molded body.

The inorganic foam-containing particles keep the molded body lightweight,
Since the reactive organic substance is solidified by reaction and the particles are adhered to each other, it is possible to suppress a dimensional change of the molded body due to a change in temperature and humidity. Further, by using the water-based binder, a molded product can be obtained with simple equipment, the molding operation can be performed safely, and problems such as environmental pollution are less likely to occur.

[0050]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Also,
Parts are parts by weight unless otherwise specified.

Reference Example 1 A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 370 parts of pure water and 1 part of sodium dodecylbenzenesulfonate (hereinafter abbreviated as DBS),
2.3 parts of potassium persulfate were added at a temperature of 70 ° C. under stirring in a nitrogen atmosphere. In advance, an emulsified monomer obtained by emulsifying 180 parts of pure water, 380 parts of methyl methacrylate, 20 parts of butyl acrylate, 50 parts of glycidyl methacrylate, 0.5 part of t-dodecyl mercaptan, 1.0 part of DBS was dropped into a reactor, Aged for 7 hours, then cooled,
Adjust the pH to 7.4 with aqueous ammonia and emulsion 1
(Hereinafter abbreviated as AE1) was obtained. The nonvolatile content was 44.7%. The non-volatile content here is regarded as an active ingredient. The same applies to the nonvolatile components of Reference Examples 2 to 13 below.

Reference Example 2 As emulsifying monomer, pure water 180 parts, methyl methacrylate 400 parts, butyl acrylate 20 parts, methacrylic acid 30 parts, t-dodecyl mercaptan 0.5 part, D
Other than using the emulsified monomer obtained by emulsifying 1.0 part of BS,
Perform the same operation as in Reference Example 1 to prepare emulsion 2 (hereinafter referred to as A
(Abbreviated as E2) was obtained. The nonvolatile content was 44.8%.

Reference Example 3 As an emulsifying monomer, pure water 180 parts, methyl methacrylate 395 parts, butyl acrylate 20 parts, methacrylic amide 30 parts, t-dodecyl mercaptan 0.5.
Part, and the same procedure as in Reference Example 1 was used except that an emulsifying monomer obtained by emulsifying 1.0 part of DBS was used.
(Hereinafter abbreviated as AE3) was obtained. The nonvolatile content was 44.3%. Reference Example 4 As an emulsifying monomer, an emulsifying monomer obtained by emulsifying 180 parts of pure water, 390 parts of methyl methacrylate, 20 parts of butyl acrylate, 35 parts of N-methylol acrylate, 0.5 part of t-dodecyl mercaptan and 1.0 part of DBS is used. The same operation as in Reference Example 1 was carried out except that it was obtained to obtain an emulsion 4 (hereinafter abbreviated as AE4). The nonvolatile content is 44.
It was 6%.

Reference Example 5 As an emulsifying monomer, 180 parts of pure water, 390 parts of methyl methacrylate, 20 parts of butyl acrylate, 40 parts of N-methoxymethylmethacrylic amide, 0.5 part of t-dodecyl mercaptan and 1.0 part of DBS were emulsified. The same operation as in Reference Example 1 was performed except that the emulsified monomer was used.
Emulsion 5 (hereinafter abbreviated as AE5) was obtained. The nonvolatile content was 44.8%.

Reference Example 6 As an emulsifying monomer, 180 parts of pure water, 385 parts of methyl methacrylate, 20 parts of butyl acrylate, 45 parts of hydroxyethyl methacrylate, 0.5 part of t-dodecyl mercaptan and 1.0 part of DBS were emulsified. Emulsion 6 (hereinafter abbreviated as AE6) was obtained by performing the same operation as in Reference Example 1 except that the emulsifying monomer was used. Nonvolatile content is 4
It was 4.8%.

Reference Example 7 As an emulsifying monomer, pure water 180 parts, methyl methacrylate 150 parts, butyl acrylate 300 parts, t-dodecyl mercaptan 0.5 part, and DBS 1.0 part were used, except that the emulsifying monomer was used. The same operation as in Reference Example 1 was performed to obtain Emulsion 7 (hereinafter abbreviated as AE7).
The nonvolatile content was 44.7%.

Reference Example 8 A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 370 parts of pure water and 1 part of DBS.
2.3 parts of potassium persulfate were added at a temperature of 70 ° C. under stirring in a nitrogen atmosphere. Preliminarily, 90 parts of pure water, 190 parts of methyl methacrylate, 10 parts of butyl acrylate, 25 parts of glycidyl methacrylate, 0.25 part of t-dodecyl mercaptan, and an emulsified monomer obtained by emulsifying DBS of 0.5 part were dropped into a reactor, Pure water 90 after aging for 3 hours
Parts, 200 parts of methyl methacrylate, 10 parts of butyl acrylate, 15 parts of methacrylic acid, 0.25 parts of t-dodecyl mercaptan, 0.5 parts of DBS, an emulsified monomer is added dropwise to the reactor and aged for 4 hours and cooled. Then, adjust the pH to 7.4 with aqueous ammonia and emulsion 8
(Hereinafter abbreviated as AE8) was obtained. The nonvolatile content was 44.9%.

Reference Example 9 A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 370 parts of pure water and 1 part of DBS.
2.3 parts of potassium persulfate were added at a temperature of 70 ° C. under stirring in a nitrogen atmosphere. In advance, 70 parts of pure water, 147 parts of methyl methacrylate, 8 parts of butyl acrylate, 25 parts of glycidyl methacrylate, 0.25 part of t-dodecyl mercaptan, and an emulsified monomer obtained by emulsifying 0.4 part of DBS were dropped into a reactor, Pure water 40 after aging for 3 hours
Parts, 88 parts of methyl methacrylate, 2 parts of butyl acrylate, and 0.2 parts of DBS emulsified monomer were added dropwise to the reactor and aged for 3 hours.
Parts, 155 parts of methyl methacrylate, 10 parts of butyl acrylate, 15 parts of methacrylic acid, 0.2 parts of t-dodecyl mercaptan, 0.4 parts of DBS, an emulsified monomer is added dropwise to the reactor and aged for 4 hours and cooled. Then, the pH was adjusted to 7.4 with aqueous ammonia to obtain emulsion 9 (hereinafter abbreviated as AE9). The nonvolatile content was 44.5%.

Reference Example 10 In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, 370 parts of pure water and 1 part of sodium dodecylbenzene sulfonate (hereinafter abbreviated as DBS) were put,
2.3 parts of potassium persulfate were added at a temperature of 70 ° C. under stirring in a nitrogen atmosphere. In advance, an emulsion obtained by mixing 180 parts of pure water, 380 parts of methyl methacrylate, 20 parts of butyl acrylate, 50 parts of bisphenol type epoxy resin, 0.5 part of t-dodecyl mercaptan, and 1.0 part of DBS and emulsifying the mixture into a reactor. After dropping, aging for 7 hours and cooling, the pH was adjusted to 7.4 with aqueous ammonia to obtain emulsion 10 (hereinafter abbreviated as AE10). Nonvolatile content is 4
It was 4.9%.

Reference Example 11 370 parts of pure water and 1 part of DBS were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer.
2.3 parts of potassium persulfate were added at a temperature of 70 ° C. under stirring in a nitrogen atmosphere. 90 parts of pure water, 190 parts of methyl methacrylate, 30 parts of styrene, 20 parts of butyl acrylate, 30 parts of bisphenol type epoxy resin, t
An emulsion obtained by mixing 0.3 parts of dodecyl mercaptan and 0.6 part of DBS and emulsifying the mixture was dropped into a reactor and aged for 3 hours, and then 90 parts of pure water and 160 parts of methyl methacrylate.
Parts, butyl acrylate 20 parts, t-dodecyl mercaptan 0.2 parts, DBS 0.4 part emulsified monomer was added dropwise to the reactor, aged for 4 hours and cooled, and the pH was adjusted to 7.4 with aqueous ammonia. The emulsion was adjusted to obtain Emulsion 11 (hereinafter abbreviated as AE11). The nonvolatile content was 44.8%.

Reference Example 12 As an emulsifying monomer, 180 parts of pure water, 260 parts of methyl methacrylate, 40 parts of styrene, 110 parts of butyl acrylate, 40 parts of N-methoxymethylmethacrylate amide 40.
Part, methacrylic acid 10 parts, t-dodecyl mercaptan 0.5 part, except that the emulsified monomer emulsifying DBS 1.0 part was used, the same operation as in Reference Example 1 was carried out to prepare an emulsion 12 (hereinafter abbreviated as AE12). Got Nonvolatile content is 4
It was 5.2%.

Reference Example 13 As an emulsifying monomer, pure water 180 parts, methyl methacrylate 245 parts, styrene 100 parts, butyl acrylate 110 parts, t-dodecyl mercaptan 0.5 part, DB
The same operation as in Reference Example 1 was carried out except that an emulsifying monomer obtained by emulsifying S1.0 part was used, and emulsion 13 (hereinafter referred to as A
(Abbreviated as E13) was obtained. The nonvolatile content was 44.6%.

Example 1 100 parts by weight of Shirasu balloon (bulk density: 0.2 g / cm ³ ) was added to the copolymer emulsion (AE) obtained in Reference Example 4.
4) 11 parts by weight and melamine formaldehyde resin (Euroid 811, manufactured by Mitsui Toatsu Chemicals, Inc., nonvolatile content 65%)
A mixture prepared by previously mixing 5 parts by weight and 9 parts by weight of water was used as a binder and uniformly sprayed and mixed. 260 g of the mixture was evenly dispersed in a 25 cm square frame and pressed to obtain a premat. Heat to 170 ° C, sandwich the premat in a hot press equipped with a 9 mm spacer, and gradually apply pressure to 2.4.
The molded plate was obtained by heating and pressing at a pressure of 5 MPa for 30 minutes.
The molded product under these conditions was homogeneous and the adhesion between the particles was good. A test body was cut out from the obtained molded body, left for 1 week in an atmosphere having a temperature of 20 ° C. and a relative humidity of 60%, and then the density and bending strength were measured. The bending strength was measured at an ambient temperature of 20 ° C. and 40 ° C. Further, the test body was left for 1 week in an atmosphere having a temperature of 50 ° C. and a relative humidity of 90%, and the hygroscopic coefficient and the hygroscopic coefficient of linear expansion were measured from changes in weight and length before and after standing.

The washability of the coating apparatus was also evaluated. The softening temperature of the product obtained by drying and solidifying the mixed binder at 105 ° C. for 3 hours was 105 ° C. or higher. The respective results are shown in Table 1.

Examples 2 to 25 Molded articles were produced in the same manner as in Example 1 except that the raw materials shown in Tables 1 to 4 were used. The results are shown in Tables 1-5. In all cases, the water-washability of the binder is good, there is no hindrance in handling, and it can be easily molded, and the molded products obtained show low density and sufficient strength compared to the comparative examples, and dimensional change. The rate was also low. The isocyanate-based compound that can be emulsified and dispersed in water used in the examples is Euroid UR-4000 (active ingredient 99 manufactured by Mitsui Toatsu Chemicals, Inc.).
%), The phenol resin emulsion is Euroid EP-7501 (active ingredient 49%) manufactured by Mitsui Toatsu Chemicals, Inc. Further, as a compound having a water-soluble active hydrogen group, polyol MN-300 manufactured by Mitsui Toatsu Chemicals Inc. (active ingredient 99.
9%), H-600 (active ingredient 40%) manufactured by Mitsui Toatsu Chemicals, Inc. as an emulsion of aromatic amines, H-700 (active ingredient 30) manufactured by Mitsui Toatsu Chemicals, as an aqueous solution of a water-soluble amine. %), And a zinc ammonium carbonate aqueous solution (zinc content 6%) was used as the polyvalent metal ion.

Comparative Examples 1 to 10 Molded bodies were molded in the same manner as in Example 1 except that the raw materials shown in Tables 6 to 7 were used. The results are shown in Tables 6 to 7, and unlike the examples, a lightweight and high-strength molded body could not be easily obtained. That is, an inorganic binder has poor moldability, and sufficient strength cannot be obtained at low density. In the case of a non-reactive water-based organic binder, the strength of the molded body is low and the dimensional change is large. With the non-aqueous organic binder, not only was the washability of the binder extremely poor and washing was not possible, but also the strength of the molded body was insufficient. The vinyl acetate resin emulsion used in the comparative example is
Bond CH18 (nonvolatile content 41%) manufactured by Konishi Co., Ltd., and the epoxy resin is Cemedine 15 manufactured by Cemedine Co., Ltd.
It is 10.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

[0070]

[Table 4]

[0071]

[Table 5]

[0072]

[Table 6]

[0073]

[Table 7]

[0074]

INDUSTRIAL APPLICABILITY According to the present invention, a molded article such as lightweight boards used for construction, which has not been achieved by the prior art, has a sufficient strength with a small dimensional change with respect to changes in environmental temperature and humidity. It has become possible to obtain a lightweight molded product having

Further, as shown in the examples, by carrying out the present invention, it was possible to avoid the poor handling and productivity of the binder, which had been a problem in the prior art, and to realize a sufficient practical use that could not be obtained by the prior art. It is now possible to obtain a lightweight foam having strength and small dimensional change.

Claims (16)

[Claims] 1. A lightweight molded article having an inorganic layer obtained by coating and / or impregnating inorganic foam-containing particles with a binder containing a water-based reactive organic substance and solidifying the reactive organic substance. 2. The lightweight molded product according to claim 1, wherein the inorganic foam-containing particles are hollow particles of artificial or natural substances containing glass. 3. The reactive organic substance is applied in an amount of 2 to 30 parts by weight to 100 parts by weight of the inorganic foam-containing particles.
Alternatively, the lightweight molded article according to item 2. 4. At least one of water-based reactive organic substances
The component has a property of being insoluble in water, and is used as an aqueous dispersion.
Alternatively, the lightweight molded article according to item 3. 5. A compound in which the water-based reactive organic substance contains particles containing a compound having a reactive functional group (F1) and / or copolymer particles having F1 and a functional group (F2) capable of reacting with F1. 5. The lightweight molded article according to claim 1, which is a mixed emulsion with the aqueous solution of the above and / or particles containing a compound having F2 and / or copolymer particles having F2 and / or polyvalent metal ions. . 6. A two-layer structure comprising an aqueous reactive organic substance, a copolymer layer having a reactive functional group (F3) in the same particle, and a copolymer layer having a functional group (F4) capable of reacting with F3. The lightweight molded product according to claim 1, which is an emulsion of multi-layered particles containing at least. 7. A layer in which an aqueous reactive organic substance contains a compound having a reactive functional group F3 in the same particle, and F
3. A mixed emulsion of multilayer particles comprising an outer shell layer that does not react with 3, and an aqueous solution of a compound having F4 and / or particles containing a compound having F4 and / or copolymer particles having F4. 2, 3 or 4
The lightweight molded article according to the item. 8. The aqueous reactive organic substance comprises at least two layers, a copolymer layer having F3 and a copolymer layer having F4 in the same particle, and a copolymer layer which does not react with F3 and F4 between the two layers. The lightweight molded product according to claim 6, which is an emulsion of multi-layered particles having a polymerized layer. 9. F1 is an amino group and / or an amide group and / or a methylol group and / or an N-methylolamide group and / or an N-alkoxymethylamide group and / or a hydroxyl group, and F2 is a methylol group and / or The lightweight molded product according to claim 5, which is an amino group and / or an amide group. 10. The lightweight molded article according to claim 5 or 9, wherein the compound containing F2 is a condensate of phenol and / or amino compound and formaldehyde. 11. F1 is an isocyanate group,
The lightweight molded product according to claim 5, wherein F2 is an active hydrogen group. 12. F1 is a glycidyl group, and F2
Is a caboxyl group and / or an amino group and / or an amide group and / or an N-methylolamide group and / or an N-alkoxymethylamide group.
The lightweight molded article according to the item. 13. The lightweight molded product according to claim 5, wherein F1 is a carboxyl group and always contains a polyvalent metal ion. 14. F4 is a glycidyl group, and F4
9. The lightweight molded product according to claim 6, wherein the is a caboxyl group and / or an amino group and / or an amide group and / or an N-methylolamide group and / or an N-alkoxymethylamide group. 15. The lightweight molded product according to claim 1, wherein the softening temperature of the binder after the reaction solidification is 60 ° C. or higher. 16. Inorganic foam-containing particles are coated and / or impregnated with a binder containing a water-based reactive organic substance, sprayed or filled in a mold, and while applying a pressure necessary for contact of the particles having the binder, or A method for producing a lightweight molded article, which comprises reacting a binder under a condition necessary for the binder to react after applying a pressure.