JPS6313449B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a polymerized foamed cured product having an internal cell structure obtained from a liquid unsaturated polyester resin or a liquid vinyl ester resin, and a method for producing the same. The polymerized foam cured product of the present invention has heat insulation properties, sound insulation properties,
Since it has excellent moldability, low density, and high strength, it is suitable for manufacturing various molded products such as furniture, conduits, boats, electrical parts, etc., and in particular, construction panels and molded construction panels. (Prior art) Many methods have been proposed for producing foamed cured products using liquid unsaturated polyester resins or liquid vinyl ester resins, but at present there is no industrialized method at all. . In other words, in order to obtain a good low-density foam molded product using a low-viscosity liquid unsaturated polyester resin or liquid vinyl ester resin with excellent workability, it is necessary to select an appropriate foaming method and to ensure a stable system for the generated gas. A thickening mechanism is essential for trapping hydrazine in the foam, and the foaming methods include thermal decomposition of carbonates and peroxides, neutralization reaction of acids and carbonates, and reaction of hydrazine and peroxides. etc. are used. (Tokuko Showa 58-29330,
In these known methods, in order to trap the generated gas in the system, a liquid unsaturated polyester resin or a liquid vinyl ester resin is increased by gelation. Although we use a method to match the timing of gas generation to the viscosity, gas generation and gelation time can be significantly affected by various conditions such as temperature, resin viscosity, type or amount of blowing agent, type or amount of catalyst, etc. Therefore, it is very difficult to stably obtain a uniform foam. (Objective of the Invention) The present invention improves the above-mentioned problems of the prior art, and stably provides a uniform foamed cured product based on a gas trapping mechanism that is completely different from the known method of polymerizing and gelling a resin. It is something to do. (Structure of the Invention) The present inventors have discovered that chlorinated rubber is a styrene monomer,
The present invention focused on the fact that it quickly dissolves in crosslinking monomers of unsaturated polyester or vinyl ester resins such as methyl methacrylate, and significantly increases its viscosity, and discovered that it is an excellent means for trapping generated gas. This is the completed version. In the present invention, a composition () having as essential components an aqueous solution of chlorinated rubber and an acid, a liquid unsaturated polyester resin or a liquid vinyl ester resin, and a metal carbonate or metal bicarbonate or a mixture thereof are essential. The foaming reaction caused by the aqueous acid solution and the carbonate or bicarbonate when the composition () as a component is mixed, and the rapid thickening caused by the contact and dissolution of the chlorinated rubber with the crosslinking monomers, Since the process proceeds simultaneously without being influenced by other conditions, a uniform foamed cured product can always be stably produced. In the present invention, when more rapid thickening is required, the method proposed by the present inventors in JP-A-58
It is very effective to use the acidic inorganic colloid aqueous dispersion described in No.-13639 in combination. The polymerized foamed cured product of the present invention is a composition () containing a chlorinated rubber and an aqueous solution of an inorganic or organic acid or an aqueous solution of a metal salt that dissociates to make the aqueous solution acidic;
It is produced by mixing a liquid unsaturated polyester resin or a liquid vinyl ester resin with a composition comprising a metal carbonate or metal bicarbonate or a mixture thereof. At that time, by simultaneously using various non-reactive inorganic or organic fillers, fibrous reinforcing agents, etc., a cured product with even better performance can be obtained. Note that the preferred weight ratio is in the following range. (All parts below are expressed in parts by weight.) Composition () Chlorinated rubber 2 to 20 parts Inorganic or organic acid or metal salts that dissociate to make the aqueous solution acidic 2 to 20 parts Water 1 to 30 parts PH in the range of 1 to 5 Stable acidic inorganic colloid aqueous dispersion 0-30 parts Polyhydric alcohol that is liquid at room temperature 0-20 parts Polymerization catalyst 0.5-6 parts Non-reactive inorganic filler powder 0-60 parts Non-reactive organic filler powder 0 ~20 parts Total 100 parts Composition () Liquid unsaturated polyester resin or liquid vinyl ester resin 30-90 parts Metal carbonate or metal bicarbonate 5-50 parts Non-reactive inorganic filler powder 0-15 parts Reactive organic filler powder 0 to 15 parts Polymerization accelerator 0.01 to 5 parts Total 100 parts Next, each component of the present invention will be described in detail as follows. The chlorinated rubber contained in the composition () is a polymeric substance (generally refers to one with a chlorine content of 50% or more) obtained by highly chlorinating rubber, and is chemically extremely stable, inert, and acid-resistant. , non-toxic, flame retardant, and easily soluble in solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, esters, and ethers. The general formula is (C ₅ H ₇ Cl ₃ ) _x (C ₅ H ₆ Cl ₄ ) _y (C ₁₀ H ₁₁ Cl ₄ ) _z
(molecular weight 5000-100000). The solution viscosity, solubility, compatibility, chemical resistance, etc. of the chlorinated rubber in a solvent can be freely selected by adjusting the molecular weight of the chlorinated rubber. For example, Asahi Denka Kogyo Co., Ltd.'s CR-5, CR-10, CR-20, CR-40,
CR-90, CR-150, etc. are commercially available. The inorganic or organic acid contained in the composition () is one that reacts with the metal carbonate or metal bicarbonate contained in the composition () in the presence of water at a temperature of 0°C or higher and 95°C or lower. It refers to inorganic or organic acids that can generate carbon dioxide gas, and includes, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and boric acid, and organic acids such as sulfuric acid, citric acid, succinic acid, and maleic acid. . The metal salt contained in the composition () 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 can generate carbon dioxide gas by reacting with the metal carbonate or metal bicarbonate contained in (). Examples include anhydrous or hydrated materials such as sodium dihydrogen phosphate, sodium monohydrogen phosphate, potassium dihydrogen phosphate, aluminum chloride, aluminum sulfate, aluminum phosphate, and aluminum acetate. The acidic inorganic colloid aqueous dispersion that can be contained in the composition () contains 1 to 50% by weight of colloidal particles (particle size 2 to 150 mμ) of oxides or hydroxides of aluminum, zirconium, silicon, titanium, etc. It refers to an acidic aqueous dispersion that is stable within the pH range of 1 to 5. Generally, these colloidal aqueous dispersions use acids to stabilize the ions on the surface of each colloidal particle, and repulsion between the particles suppresses gelation and aggregation of the dispersion, but this stabilized charge balance is disrupted. When a factor (for example, PH change) occurs, bonding between particles immediately occurs, and the dispersion liquid becomes thick and gelled. When the composition () and the composition () are mixed, the acid in the composition () and the composition () are immediately mixed.
The metal carbonate or metal bicarbonate inside starts a reaction and generates carbon dioxide gas. (CO ₃ ) ^-- +2H ⁺ →CO ₂ ↑+H ₂ O As the reaction starts, the PH of the mixture shifts to the neutral side. As a result, the surface charge balance of the inorganic colloidal particles is disrupted, colloidal particles are bonded to each other, and the viscosity of the entire mixture increases rapidly. Examples of materials suitable for use in this case include aluminum oxide colloidal dispersions such as Alumina Sol #100 and #200 (Nissan Chemical Industries, Ltd.), Alumina Sol AS-1, AS-2, and AP (Catalysts Chemical Industry Co., Ltd.). etc,
As silicon oxide dispersions, Snowtex O, OL,
Examples include O-30 (Nissan Chemical Industry Co., Ltd.) and Cataloid SN (Catalyst Chemical Industry Co., Ltd.). Polyhydric alcohols that are liquid at room temperature that can be included in the composition () refer to glycols that are liquid at room temperature such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, hexylene glycol, etc. When mixing the product () and the composition (), it prevents separation of the two compositions and is very useful for smooth and stable thickening. Furthermore, after the mixture has been cured, it is also extremely effective in preventing the moisture remaining in the cured product from scattering over time. Composition () and non-reactive inorganic filler powder that can be included in composition () include many types of anhydrous or hydrated materials such as metal oxides, metal hydroxides, metal salts, or composites thereof. Minerals (e.g. kaolin, silica, talc, alumina,
Zircon, aluminum hydroxide, barium sulfate,
It refers to powders of calcium sulfate, etc.), and is appropriately selected depending on the viscosity and specific gravity of the composition, the cost of the final product, the required performance, etc. Composition () and non-reactive organic filler powder that can be included in composition () refer to powders of vinyl chloride resin, polyethylene, polypropylene, tetrafluoroethylene, etc. Effective for reducing and adjusting composition viscosity. The polymerization catalyst contained in the composition () refers to an organic peroxide catalyst used for curing general unsaturated polyester resins and vinyl ester resins. For example, it refers to benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, etc., and is selected from them depending on the purpose. As the liquid unsaturated polyester resin contained in the composition (), commonly used unsaturated polyester resins can be used. Unsaturated polyester resins include saturated polycarboxylic acids (e.g. phthalic anhydride, isophthalic acid, terephthalic acid, hettic acid, sebacic acid, etc.), unsaturated polycarboxylic acids (e.g. maleic anhydride, fumaric acid, citraconic acid, etc.) ) and glycols (e.g., ethyl glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl glycol, etc.) and polymerizable monomers (e.g., styrene, vinyl toluene, acrylic acid, etc.). esters, methacrylic esters, vinyl acetate, allyl esters, etc.), or those dissolved in liquid polymerizable prepolymers. In the present invention, in addition to these unsaturated polyester resins, a resin produced by a reaction between an epoxy resin and an unsaturated monobasic acid such as acrylic acid or methacrylic acid may be used as a polymerizable monomer or a polymerizable monomer thereof in the same manner as the unsaturated polyester. So-called vinyl ester resins dissolved in liquid polymerizable prepolymers can also be used. The metal carbonate or metal bicarbonate contained in the composition () has a temperature of 0°C to 95°C and a pH of 1 to 95°C.
Refers to metal carbonates or metal bicarbonates that, when added to an acidic aqueous solution in the range of 5, react with the acid contained in the aqueous solution and generate carbon dioxide gas. In general, calcium carbonate, sodium bicarbonate, etc., which are inexpensive and easily available, are used, but carbonates of other alkali metals and alkaline earth metals can also be used. The polymerization accelerator contained in the composition () refers to an agent that functions to promote the generation of polymerization radicals of an organic peroxide catalyst used for curing general unsaturated polyester resins and vinyl ester resins, such as , N-N dimethylaniline, N-N diethylaniline, tertiary amines such as diethanolamine, and metal soaps such as cobalt naphthenate and cobalt octenoate. Next, the numerical values limited in the claims will be explained as follows. (b) If the mixing ratio of composition () to composition () is too small, the strength of the cured product will be significantly reduced, and workability will be poor; if it is too large, , the thickening effect is significantly reduced and the internal cell structure becomes incomplete. The preferred range is based on 1 part of the composition (),
The composition () is 0.5 to 5.0 parts. (b) Content of colloid particles in the acidic inorganic colloid aqueous dispersion. When the content of colloid particles in the acidic inorganic colloid aqueous dispersion used for the main body is less than 1%, almost no thickening effect is observed due to the bonding of colloid particles that occurs when mixing composition () and composition (). I can't. Further, if the content of colloidal particles is 50% or more, the acidic inorganic colloid aqueous dispersion itself is insufficiently stable and cannot be used. (Function) In the present invention, since the composition contains water, the temperature at which the composition is placed throughout the work should be in the range from 0°C or higher, which is the freezing point of water, to 95°C or lower, where evaporation becomes active. It is. In the present invention, each of the composition () and the composition () is
They are thoroughly stirred and mixed in advance in separate containers, and used in a ratio of 0.5 to 5 parts of composition () to 1 part of composition (2). When composition () and composition () are mixed,
Immediately, the metal carbonate or metal bicarbonate in the composition () starts to react with the acid in the composition (), generating carbon dioxide gas. (CO ₃ ) ^-- +2H ⁺ →CO ₂ ↑+H ₂ O At the same time as this reaction, the chlorinated rubber contained in the composition () is mixed with the liquid unsaturated polyester resin or liquid vinyl ester contained in the composition (). It comes into contact with resin and quickly dissolves in crosslinking monomers. As a result, the viscosity of the entire mixing system increases significantly, and the generated carbon dioxide gas is reliably and stably captured within the mixture. In addition, when an acidic inorganic colloid aqueous dispersion is used as a thickening agent,
As the reaction between the acid and the metal carbonate or metal bicarbonate progresses, the pH of the mixture shifts to the neutral side, causing the charge balance on the surface of the inorganic colloid particles to collapse, causing aggregation and bonding of the colloid particles, which leads to damage to the entire system. Contributes to rapid thickening. Due to this high viscosity, carbon dioxide gas bubbles generated inside the mixture are retained inside 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, gelation and curing of the unsaturated polyester resin occur, and after curing, the molding is completed. The apparent form of the mixture hardly changes from the completion of thickening and foaming to the completion of curing. This cured product becomes a low-density, high-strength foam cured product with a specific gravity of 0.1 to 1.2 that has a cell structure inside, and is extremely effective for reinforcing materials for low-rigidity materials, lightweight structural materials, heat insulators, lining materials, etc. be. In addition, by using fibrous reinforcing materials such as glass fiber, glass cloth, asbestos, metal fiber, and synthetic fiber,
It becomes stronger. Next, specific means for molding the polymerized foam cured product of the present invention will be explained. Composition () Composition () must be sufficiently stirred and mixed in separate containers. For stirring, a dissolver type stirrer commonly used for mixing liquids is sufficient. Since the composition (I) 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. During molding, to mix the composition () and the composition (), each composition is sprayed from a separate sprayer, so that the spray patterns can be overlapped so that the spray particles are sufficiently mixed. Spraying, casting, etc. using a set external mixing type spray device or a feed mixing and dispensing device with a chamber or mixer for mixing the respective separately supplied compositions immediately before dispensing. A polymerized foamed cured product is molded by the method. When composition () and composition () are mixed, a reaction occurs immediately and a significant increase in viscosity occurs immediately. Therefore, if each component is properly mixed, it can be used not only on a horizontal surface but also on a vertical surface. , it will not flow down. The viscosity after mixing composition () and composition () is determined by the viscosity of the liquid unsaturated polyester resin, the type and amount of chlorinated rubber, the amount of acidic inorganic colloid aqueous dispersion, and the type and addition of non-reactive filler. You can adjust the amount, etc. Further, the viscosity of each of the compositions (I) and (I) is adjusted to 100 to 5000 CP, preferably 800 to 2500 CP, which is suitable for molding operations. The present invention will be explained in more detail with reference to Examples below. (Example) Example 1 (1) Preparation of unsaturated polyester resin Unsaturated polyester resin 63 with an acid value of about 20 obtained by esterification of 5 mol of isophthalic acid, 5 mol of maleic anhydride, and 10.5 mol of propylene glycol. 1 part was dissolved in 37 parts of styrene monomer along with an appropriate amount of polymerization inhibitor to determine the viscosity,
Approximately 300CP liquid unsaturated polyester resin UPE
-1 was obtained. (2) Preparation of composition Composition ()-1 Chlorinated rubber CR-10 (Asahi Denka Kogyo Co., Ltd.) 10 parts phosphoric acid 5 parts ethylene glycol 10 parts water 25 parts aluminum hydroxide (325 mesh) 48 parts benzoyl par Oxide 2 parts Total 100 parts Composition ()-1 UPE-1 60 parts Calcium carbonate (325 mesh) 39.7 parts N-N dimethylaniline 0.3 parts Total 100 parts (3) Molding Composition ()-1, Composition Composition ()-1 is sufficiently stirred and mixed in separate containers, and then the composition () -1 and composition ()
-1 at a mixing ratio of 1:1.5, the mixture was sprayed to a thickness of about 10 mm on a 50 cm square glass plate that had been coated with a release agent in advance. The mixture immediately started to react and expand, and the expansion stopped in about 1 minute after the spraying was completed. After about 10 minutes, the resin generated heat, and curing was completed after about 30 minutes. The room temperature at this time was 25°C. The cured product was demolded from the glass plate to obtain a plate-shaped polymerized cured product -(). This plate-shaped cured product had a skin layer on the surface, was pale yellowish white, and had a specific gravity of about 0.60. When the cross section was cut near the center and viewed with the naked eye, numerous foam structures were observed inside. Example 2 Composition ()-2 Chlorinated rubber CR-5 (Asahi Denka Kogyo Co., Ltd.) 8 parts Alumina sol #100 (Al ₂ O ₃ 10% Nissan Chemical Industries, Ltd.)
10 parts Hydrated aluminum chloride (AlcO ₃ 6H ₂ O) 10 parts Propylene glycol 7 parts Water 15 parts Aluminum hydroxide (325 mesh) 48 parts Benzoyl peroxide 2 parts Total 100 parts Composition ()-2 UPF-1 65 parts Calcium carbonate (325 mesh) 27.7 parts Sodium bicarbonate (325 mesh) 7 parts N-N dimethylaniline 0.3 parts Total 100 parts Example with a mixing ratio of composition ()-2 and composition ()-2 at 1:1.5 Molded using the same method as 1,
A plate-shaped cured product (2) having a skin layer on the surface and having a pale yellowish white color and a specific gravity of about 0.35 was obtained. When the material was cut and the interior was visually observed, a very uniform foam structure was observed. Example 3 Composition ()-3 Chlorinated rubber CR-5 (Asahi Denka Kogyo Co., Ltd.) 10 parts Snowtex 0-40 (SiO ₂ 40% Nissan Chemical Industries, Ltd.)
Co., Ltd.) 20 parts hydrated aluminum chloride (Alcl ₃ , 6H ₂ O) 5 parts maleic anhydride 5 parts ethylene glycol 7 parts water 10 parts kaolin (325 mesh) 41 parts lauroyl peroxide 2 parts Total 100 parts Composition ( )-3 and the composition ()-1 used in Example 1 were molded at a mixing ratio of 1:2 using the same method as in Example 1 to form a pale yellowish white product with a skin layer on the surface and a specific gravity of approximately 0.40. A plate-shaped cured product (3) was obtained. The internal foam structure was somewhat non-uniform. Example 4 Composition ()-3 UPE-1 55 parts Styrene monomer 10 parts Powdered polyvinyl chloride resin (Nissan Chemical Industries, Ltd.) 15 parts Sodium bicarbonate (325 mesh) 10 parts Aluminum hydroxide 9.6 parts N-N - Diethylaniline 0.4 parts Total 100 parts Composition ()-2 and Composition ()-3 used in Example 2 were molded using the same method as Example 1 at a mixing ratio of 1:1.5, and the surface A plate-shaped cured product (4) having a skin layer and having a pale yellowish white color and a specific gravity of about 0.25 was obtained. The internal foam structure was very uniform, but the size of the bubbles was slightly larger than that of the others. The strength of the foamed cured products obtained in Examples 1 to 4 was measured and was as follows.

[Table] (Effects of the invention) As is clear from the examples, according to the present invention,
It is possible to produce a foamed cured product with extremely low density and high strength.

Claims (1)

[Scope of Claims] 1. A composition () containing as essential components chlorinated rubber and an aqueous solution of an inorganic or organic acid, or an aqueous solution of a metal salt that becomes acidic when dissociated,
A composition () is a composition containing as essential components a liquid unsaturated polyester resin or a liquid vinyl ester resin and one or more metal carbonates and metal bicarbonates that generate carbon dioxide gas in an acidic aqueous solution, A material having an internal cell structure obtained by mixing 0.5 to 5 parts of the composition () with 1 part of the composition () and curing the liquid unsaturated polyester resin or liquid vinyl ester resin with a polymerization catalyst. Polymerized foam cured product. 2 The composition () contains silicon, as a thickening adjuvant,
The polymerized foam cured product according to claim 1, which contains an acidic inorganic colloid aqueous dispersion containing 1 to 50% by weight of one or more colloidal particles of oxides or hydroxides such as aluminum, zirconium, titanium, etc. . 3. The polymerized and foamed cured product according to claim 1 or 2, wherein the composition () contains one or more polyhydric alcohols that are liquid at room temperature. 4 Inorganic compound powder or organic polymer such as anhydrous or water-containing metal oxide, metal hydroxide, metal salt, etc., as a non-reactive filler in either or both of the composition () or the composition (). Claims 1 to 3 containing one or more compound powders
The polymerized foam cured product according to any one of the above. 5. An external mixing type spray device set so that the spray particles are sufficiently mixed with each other when two types of compositions are sprayed from separate sprayers, or
An aqueous solution of chlorinated rubber and an inorganic or organic acid, or an aqueous solution after dissociation, is prepared using a spray device equipped with a chamber that mixes the two separately supplied compositions before spraying them from a spray nozzle. A composition containing an aqueous solution of a metal salt that becomes acidic as an essential component, a liquid unsaturated polyester resin or a liquid vinyl ester resin, and a metal carbonate or metal bicarbonate that generates carbon dioxide gas in an acidic aqueous solution. Composition containing a species or two or more species as an essential component ()
, for 1 part of composition ()
A method for producing a polymerized foam cured product, which comprises mixing 0.5 to 5 parts.