JPS624411B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermosetting resin and a polymerized foamed cured product having internal closed cells obtained from an inorganic colloid dispersed in acidic water, and a method for producing the same. An object of the present invention is to provide a cured polymer foam that is low cost, has excellent heat insulation properties, sound insulation properties, and moldability, and is lightweight and highly flame retardant, and a method for producing the same. Foamed urethane, foamed polystyrene, and the like are currently known as common heat insulating molding materials, but their use is limited because they are sensitive to heat and difficult to obtain flame resistance. Examples of materials made of flammable resins include halogenated plastics, plastics with large amounts of aluminum hydroxide or other hydrated metal oxides added, and halogenated waxes combined with antimony oxide or phosphorus compounds. However, none of these have sufficient flame retardant properties, and in addition, there is a high risk of generating large amounts of toxic gas and smoke when heated and burned.
Currently, it is difficult to use it for various purposes, and if it has high heat insulation and sound insulation properties, it will be heavy and disadvantageous in terms of cost and performance, and if it is lightweight and cheap, it will not be flame retardant. It is an inferior or far from ideal material. Therefore, the present inventors developed a foamed composite material or lining material that is inexpensive, lightweight, has excellent heat insulation and sound insulation properties, and is flame retardant regardless of the shape or method of use. As a result of various studies over many years, the present invention has been completed. In the present invention, an inorganic colloid dispersion stable in the pH range of 1 to 5 is added to a mixture containing a polymerizable unsaturated polyester resin and a metal carbonate that reacts with an acid to generate carbon dioxide gas, and the mixture is filtered. By curing at room temperature or by heating using an oxide catalyst or the like, a polymerized cured product having an internal closed cell structure is obtained. In addition, the cured product contains many types of anhydrous or hydrous metal oxides as fillers,
It is possible to include metal salts and glass fibers and other fibrous materials as reinforcing materials. This cured product can be used for casting materials, laminated materials, caulking materials, coating materials,
It can be used as a heat insulating material, etc., and the product after polymerization has many characteristics as a flame resistant material and a heat insulating material. The gist of the present invention is as follows. 1 Composition (1) is a mixture of a thermosetting unsaturated polyester resin or a thermosetting vinyl ester resin and a metal carbonate that generates carbon dioxide gas in an acidic aqueous solution, and contains aluminum, zirconium, Contains 1 to 50% by weight of colloidal particles of oxides or hydroxides such as silicon or titanium, and has a pH of at least 10% in the range of 1-5.
The composition (1 Composition (2) is a composition containing as an essential component a mixture of a metal carbonate contained in
Obtained by mixing 0.1 to 5 parts of composition (2) with 1 part of composition (1) and using a catalyst to cure the unsaturated polyester resin or vinyl ester resin contained in the components. Polymer foam cured product with closed cell structure inside. 2. The polymerized foam cured product according to claim 1, in which a metal salt that dissociates to make the aqueous solution acidic is used instead of the acid in composition (2). 3. The polymerized foam cured product contains one or more types of anhydrous or water-containing metal oxides, anhydrous or water-containing metal salts, metal hydroxides, etc. as fillers, as described in claim 1 or 2. Polymerized foam cured product. 4. The polymerized foam cured product according to any one of claims 1 to 3, wherein the polymerized foam cured product contains glass fiber or other fibrous reinforcing material. 5. When the two compositions are sprayed from separate sprays, the spray equipment is set so that the spray particles are sufficiently mixed with each other, or the two compositions are supplied separately before being sprayed from the spray nozzle. Using a spray device equipped with a mixing chamber for mixing the seed composition, the composition (1) whose essential components are a mixture of an unsaturated polyester resin or vinyl ester resin and a metal carbonate, and an inorganic colloid dispersion. 1. A method for producing a polymerized foam cured product, which comprises mixing a composition (2) containing as an essential component a mixture of 1 and an acid or a metal salt that becomes acidic when dissociated. The polymerized foam cured product of the present invention is a mixture of a composition (1) containing an unsaturated polyester resin or vinyl ester resin and a metal carbonate, and a composition (2) containing an inorganic colloid dispersion and an acid or metal salt. Manufactured by At that time, by simultaneously using various fillers, fibrous reinforcing materials, etc., a cured product with even better performance can be obtained. Note that the preferred weight ratio is in the following range. (The following are all parts by weight.) Composition (1) Unsaturated polyester resin or vinyl ester resin 10-90 parts Metal carbonate 5-80 parts Inorganic filler 0-80 parts Polymerization catalyst 0-5 parts Polymerization accelerator 0 ~5 parts Total: 100 parts Composition (2) Inorganic colloid dispersion stable in the pH range of 1 to 5 10 to 95 parts Inorganic or organic acid or metal salt that dissociates to make the aqueous solution acidic 0.5 to 30 parts Inorganic filler 0 to 80 parts Polymerization catalyst 0 to 5 parts Polymerization accelerator 0 to 5 parts Total 100 parts Next, each component of the present invention will be described in detail below. The unsaturated polyester resin contained in composition (1) refers to saturated carboxylic acids (e.g., phthalic anhydride, isophthalic acid, terephthalic acid, hettic acid, sebacic acid, etc.), unsaturated carboxylic acids (e.g., maleic anhydride, fumaric acid, citraconic acid, etc.) and glycols (e.g., ethylene glycol, propylene glycol, butanediol,
An unsaturated polyester resin esterified with neopentyl glycol, hydrogenated bisphenol A, etc.) is combined with polymerizable monomers (e.g., styrene, vinyltoluene, acrylic ester, methacrylic ester, vinyl acetate, allyl ester, etc.) , or those dissolved in liquid polymerizable prepolymers. The vinyl ester resin contained in composition (1) is
Refers to an epoxy polyacrylate having an acrylic or methacrylic group at the end of a bisphenol A skeleton dissolved in a polymerizable monomer or liquid polymerizable prepolymer. The metal carbonate contained in composition (1) is defined as
Refers to metal carbonates that, when added to an acidic aqueous solution in the PH range of 1-5 at a temperature below 95°C, react with the acid contained in the aqueous solution and generate carbon dioxide gas. In general, cheap and stable calcium carbonate is used, but anhydrous and hydrated carbonates of other alkaline earth metals and alkali metals can also be used. The inorganic fillers contained in compositions (1) and (2) include anhydrous or hydrated metal oxides, anhydrous or hydrated metal salts,
Metal hydroxides or their composite minerals (e.g., clay, kaolin, silica, talc, alumina, zircon, aluminum hydroxide,
Powders of hydrated borax, barium sulfate, calcium sulfate, etc.) can be used, and are appropriately selected depending on the viscosity and specific gravity of the composition (1), the cost of the final product, the required performance, etc. The most suitable materials are aluminum hydroxide and hydrated borax, which are useful for improving the fire resistance, strength, hardness, and abrasion resistance of molded products. The inorganic colloidal dispersion stable in the pH range of 1 to 5 contained in composition (2) refers to colloidal particles (particle size 2 to 150 mμ) of oxides or hydroxides of aluminum, zirconium, silicon, titanium, etc. ~50
An acidic aqueous dispersion with a pH range of 1 to 5 containing a weight percent of acidic water maintains a liquid state with a viscosity of 5000 centipoise or less for a period of at least 10 minutes. Generally, these colloidal dispersions are made by stabilizing the ions on the surface of each colloidal particle with acid or alkali, and suppressing gelation and aggregation of the dispersion by repulsion between the particles, but this stabilized charge As soon as a factor that disrupts the balance occurs, particles bond together, causing thickening, gelation, aggregation, etc. of the dispersion. Suitable for this use, for example, as a colloidal dispersion of aluminum oxide,
Alumina sol #100, #200 (Nissan Chemical Industries, Ltd.),
Alumina sol AS-1, AS-2, AS-3, AP
(Catalyst Chemical Industry Co., Ltd.), etc., as a silicon oxide dispersion,
Snorchicks O, OL, O-30 (Nissan Chemical Industries)
Co., Ltd.), Cataloid SN (Catalyst Chemical Industry Co., Ltd.), etc. The inorganic or organic acid contained in composition (2) is
The composition (1) in the presence of water at a temperature of not less than 95°C.
An inorganic or organic acid that reacts with the metal carbonate contained therein to generate carbon dioxide gas, such as hydrochloric acid,
These include inorganic acids such as sulfuric acid, phosphoric acid, and boric acid, and organic acids such as oxalic acid, citric acid, succinic acid, and maleic acid. The metal salt contained in the composition (2) that dissociates and makes the aqueous solution acidic is a metal salt that is partially or completely dissolved in water at a temperature of 0°C or higher and 95°C or lower, and the aqueous solution has a pH of 1 to 5.
Refers to a salt that reacts with the metal carbonate contained in the composition (1) to generate carbon dioxide gas. for example,
Sodium dihydrogen phosphate, sodium monohydrogen phosphate, potassium dihydrogen phosphate, aluminum chloride,
Anhydrous or hydrated materials such as aluminum sulfate and aluminum phosphate are included. The polymerization catalyst contained in compositions (1) and (2) refers to an organic peroxide catalyst used for curing unsaturated polyester resins and vinyl ester resins. For example, methyl ethyl ketone peroxide (content 20-60
%), benzoyl peroxide (content 25-100
%), cumene hydroperoxide (content 40-100
%) etc. depending on the purpose. Composition
When added to (1) or (2), it is generally added to the composition (2) side that does not contain unsaturated polyester resin, but when molded products are cured by heating at 40°C or higher, it may be added alone. However, composition (1) is limited to high-temperature catalysts because it does not generate polymerization radicals at working temperatures (5 to 35°C).
You can also pre-add it to the side. The accelerator contained in compositions (1) and (2) refers to a substance that functions to promote the generation of polymerization radicals of an organic peroxide catalyst used for curing unsaturated polyester resins and vinyl ester resins. . For example, metal soaps such as cobalt naphthenate and cobalt octenoate, amines such as Nn-dimethylaniline, Nn-diethylaniline, diethanolamine, etc. are generally used. During curing, a catalyst,
If it is desired to use both promoters, the catalyst should be placed in either composition (1) or (2), and the promoter should always be added to the other side. If a catalyst and a promoter are added to one side at the same time, rapid decomposition of the catalyst will occur immediately, which is extremely dangerous. Next, the numerical values limited in the claims are explained below. (1) Content of colloidal particles in colloidal dispersion If the content of colloidal particles in the colloidal dispersion used in this case is less than 1%, it may be caused by mixing composition (1) and composition (2). The viscosity of the entire system due to the joining of colloidal particles is insufficient, and the ability to retain the carbon dioxide gas generated inside is insufficient, making it impossible to obtain a good closed cell structure. In some cases, it becomes easy to flow down. When the colloidal particle content is greater than 50%, it is difficult to obtain an acidic dispersion that is stable and has a suitable viscosity for the present use. (2) PH of colloidal dispersions and mixtures of colloidal dispersions and acids or salts If the pH is below 1, they are unsuitable for use in terms of corrosivity and safety. If the number is 5 or more, carbon dioxide gas is not sufficiently generated by the reaction with the carbonate, and a good foaming phenomenon does not occur, making it impossible to obtain an excellent closed cell structure. (3) Viscosity of colloidal dispersion In order to obtain a composition viscosity suitable for spray work, it is necessary to maintain the viscosity below 5000 centipoise for at least 10 minutes. (4) Temperature range The temperature at which the composition can be kept throughout the work is:
Since the composition contains a large amount of water, the temperature should range from 0°C, which is the freezing point of water, to 95°C, where evaporation is active. (5) Mixing ratio of composition (1) and composition (2) If the mixing ratio of composition (2) to composition (1) is too small, one of the most important characteristics of the cured product The flame retardancy, which is the main characteristic of oxidation, is significantly reduced, and the closed cell structure is not perfected. If the amount is too high, the strength will decrease and workability will be poor. Therefore, it is preferable to use it in a range of 0.1 to 5 parts. In the present invention, when mixing composition (1) and composition (2), compositions (1) and (2) are sufficiently stirred in separate containers, and 1 part of composition (1) is mixed with 1 part of composition (1). Against the composition (2)
They are mixed and used in a ratio of 0.1 to 5 parts. Composition (1) and
As soon as (2) is mixed, the metal carbonate in composition (1) and the acid in composition (2) begin to react, generating carbon dioxide gas. (CO ₃ ) ^-- +2H ⁺ →CO ₂ ↑+H ₂ O With the start of the reaction, the PH of the mixture rapidly shifts to the neutral side. As a result, the charge balance on the surface of the inorganic colloid particles contained in composition (2) is disrupted,
Coalescence of colloidal particles occurs, and the viscosity of the entire mixture increases rapidly, becoming almost fluid and reaching gelation. Due to this high viscosity, carbon dioxide gas bubbles generated inside the mixture are retained within the mixture, causing expansion of the entire mixture. In appropriately selected systems, this series of reactions is completed within minutes, even at room temperature. Thereafter, curing of the unsaturated polyester occurs, and after curing, the molding is completed. The apparent form of the mixture hardly changes during the period from completion of thickening and foaming to completion of curing. This cured product is a substance with a specific gravity of 0.5 to 1.8 that has many closed cells inside and has excellent fire resistance and heat insulation properties. It is extremely effective for fireproof coatings, etc. In addition, glass fiber materials such as glass roving, glass fiber mat, glass cloth, and milled fiber used in the production of general glass fiber reinforced plastics, asbestos,
A laminated material with excellent strength can also be obtained by combined use of fibrous reinforcing materials such as metal fibers and various synthetic fibers. The fibrous reinforcement is
It is used in an amount of about 2 to 50% by weight. Further, to explain the specific molding means for producing the polymerized foam cured product of the present invention, it is necessary to thoroughly mix the compositions (1) and (2) in separate containers before starting molding. For stirring, a high speed dissolver type stirrer commonly used for mixing liquids is sufficient. Since the composition (2) is an acidic liquid, the parts of the container and the stirrer that come into contact with the liquid are preferably made of stainless steel.
When mixing compositions (1) and (2) during molding, each composition is sprayed from a separate sprayer, and the spray patterns are overlapped so that each other's spray particles are sufficiently mixed. Most suitable is the use of a spray device or a spray device equipped with a mixing chamber in which the two compositions coming from different routes can be mixed with each other just before being sprayed from the spray nozzle. If you want a laminated product that requires strength, you can easily manufacture it by linking the rolling cut type glass fiber continuous supply device attached to the spray up device used for general glass fiber reinforced plastic manufacturing with the spray equipment. I can do it. The amount of glass fiber mixed is about 2 to 50 percent by weight based on the entire mixture. The spray-mixed mixture immediately starts to react and the inorganic colloid particles rapidly increase the viscosity significantly, so that it does not flow down not only on horizontal surfaces but also on vertical surfaces and overhanging surfaces. The viscosity of compositions (1) and (2) and the viscosity of compositions (1) and (2) after mixing are determined by the viscosity of the unsaturated polyester resin, the monomer content, the amount of inorganic colloid added, and the type of filler. It is adjusted by the amount added, etc. The viscosity of compositions (1) and (2) is adjusted to about 40 to 4000 centipoise, which is suitable for spraying. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 (1) Preparation of unsaturated polyester 65 parts of unsaturated polyester with an acid value of about 20 obtained by esterification of 5 moles of isophthalic acid, 5 moles of maleic anhydride, and 10.5 moles of propylene glycol was dissolved in 35 parts of styrene monomer. Unsaturated polyester resin with a viscosity of approximately 1000 centipoise
UPE-1 was obtained. (2) Preparation of composition

[Table] (3) Molding Composition (1)-1 and Composition (2)-1 were thoroughly stirred and mixed in separate containers, and then sprayed from separate sprays to form Composition (1)-1 and Composition ( 2) Set the sprayer so that the spray particles are sufficiently mixed with each other at a mixing ratio of 2:1, and place one side on which the release agent has been applied in advance.
A 50 cm square glass plate was sprayed with the mixture approximately 10 mm thick. The mixture applied onto the glass plate immediately started to react and expand, and the expansion stopped approximately 2 minutes after the spraying was completed. glass plate
Transfer it to a drying oven at 50℃ and let it harden for about 60 minutes, then take it out and remove it from the glass plate to form a plate-shaped cured product.
I got (1). (4) Test This plate-shaped cured product was milky white and had a specific gravity of about 0.75. When the cross section was cut near the center and viewed with the naked eye, numerous independent cavities were found inside. This board was exposed to flame from a Bunsen burner from approximately 50 mm below. A small amount of smoke was detected for about the first two minutes, but no smoke was observed after that. Further terms
Even after heating for 10 minutes, the board perfectly retained its original shape. Example 2

[Table] 〓
100 copies
N〓n〓dimethylaniline 1 part

Claims (1)

[Scope of Claims] 1. A composition (1) containing as essential components a mixture of a thermosetting unsaturated polyester resin or a thermosetting vinyl ester resin and a metal carbonate that generates carbon dioxide gas in an acidic aqueous solution. Contains 1 to 50 percent by weight of colloidal particles of oxides or hydroxides such as aluminum, zirconium, silicon, titanium, etc., and maintains a liquid state with a viscosity of 5000 centipoise or less for at least 10 minutes in the pH range of 1-5. An acidic colloid aqueous dispersion having a pH of 1 to 5 reacts with the metal carbonate contained in the composition (1) in the presence of water at a temperature of 0°C to 95°C to generate carbon dioxide gas. Composition (2) is a composition containing a mixture of acid and acid as an essential component.
A polymeric foam cured product having an internal closed cell structure obtained by mixing 0.1 to 5 parts of (2) and curing the unsaturated polyester resin or vinyl ester resin contained in the components using a catalyst. 2. The polymerized foam cured product according to claim 1, in which a metal salt that dissociates to make the aqueous solution acidic is used instead of the acid in composition (2). 3. The polymerized foam cured product contains one or more types of anhydrous or water-containing metal oxides, anhydrous or water-containing metal salts, metal hydroxides, etc. as fillers, as described in claim 1 or 2. Polymerized foam cured product. 4 Claims 1 to 3 in which the polymerized foam cured product contains glass fiber or other fibrous reinforcing material
The polymerized foamed cured product according to any one of the above items. 5. When the two types of compositions are sprayed from separate sprays, the spray equipment is set so that the spray particles are sufficiently mixed with each other, or the two compositions are supplied separately before being sprayed from the spray nozzle. Using a spray device equipped with a mixing chamber for mixing the seed composition, the composition (1) whose essential components are a mixture of an unsaturated polyester resin or vinyl ester resin and a metal carbonate, and an inorganic colloid dispersion. 1. A method for producing a polymerized foam cured product, which comprises mixing a composition (2) containing as an essential component a mixture of 1 and an acid or a metal salt that becomes acidic when dissociated.