JPH09328568A - Expandable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an expandable composition not causing an environmental pollution and having improved safety and dispersability by mixing an organic inorganic material with a specified azodicarboxylic acid diester. SOLUTION: This composition is obtained by mixing 100 pts.wt. organic material selected from among thermoplastic resins, thermosetting resins and ordinary-temperature-curing resins or inorganic material selected from among mixtures of calcium silicate, magnesium silicate, and aluminum silicate with an inorganic or organic binder, gypsum and cement with 0.2-15 pts.wt. azodicarboxylic acid diester represented by the formula: RCOOC-N=N-COOR (wherein R is a lower alkyl, phenyl or benzyl).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel foam composition such as a synthetic resin or an inorganic material. The present invention also provides
The present invention relates to a foam composition of an emulsion resin, a synthetic resin dissolved or dispersed in water and / or an organic solvent, or a water-soluble polymer substance, and a method for producing a foam therefrom.

[0002]

2. Description of the Related Art As a method for producing a foam made of a synthetic resin and an inorganic material, the following methods (1) to (6) are known. (1) Thermal decomposition type foaming agent which decomposes by heating to generate a large amount of gas, for example, inorganic compounds such as sodium bicarbonate and ammonium carbonate, azodicarbonamide, azobisisobutyronitrile, N, N'-di Nitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide,
p, p'-oxybis (benzenesulfonyl hydrazide)
Organic compound such as is mixed with synthetic resin or inorganic material,
A method in which a synthetic resin or an inorganic material is expanded by a gas generated from the foaming agent by heating the obtained mixture to a temperature above the decomposition temperature of the foaming agent to form a foam. (2) Impregnating or enclosing low-boiling point aliphatic hydrocarbons such as pentane, neopentane, hexane and butane in the synthetic resin after or after the production of the synthetic resin, and heating the synthetic resin at or above the softening temperature of the synthetic resin to reduce the temperature. A method of expanding a boiling compound to form a foam. (3) During molding of the synthetic resin, for example, during extrusion molding or injection molding, a low boiling point compound such as an aliphatic hydrocarbon, a chlorinated aliphatic hydrocarbon, or a fluorinated aliphatic hydrocarbon is press-fitted from the outside,
A method in which a low boiling point compound is expanded by heat during molding to form a foam. (4) A method for producing a foam by mixing a liquid synthetic resin or a rubber latex at a high speed while mixing a gas such as air and nitrogen gas, and heating or mixing a coagulant from the outside to solidify the foam. (5) A foam is produced by expanding a synthetic resin with a gas generated by the reaction, for example, carbon dioxide gas generated by a reaction between a polyol of a polyurethane resin and isocyanate, or hydrogen gas generated by an addition or condensation reaction of an organopolysiloxane. Method. (6) Powdered inorganic materials such as calcium silicate, aluminum silicate, gypsum, etc., and a mixture of water and an inorganic or organic binder with glass balloons, shirasu balloons, resin hollow beads, resin foam beads are dried or fired. To produce foam.

[0003]

However, the above methods (1) to (6) have various drawbacks and are not necessarily suitable as a method for producing a foam. That is, in the method (1), it is necessary to heat above the decomposition temperature of the foaming agent in order to generate the gas for obtaining the foam, and the viscosity of the synthetic resin that can expand due to this gas. In order to obtain the above, since the material is limited to the thermoplastic resin and there is a lot of dissipation in the inorganic material, in order to produce what can be said to be a foam, it is necessary to plan the timing of gas generation and solidification and the foam production itself. Will be difficult. (2)
In the above method, low boiling point compounds such as pentane, neopentane, hexane and butane are flammable, so there is a risk of fire and explosion, and it is necessary to soften the synthetic resin by heating in the foaming process. Yes, the synthetic resin material itself is limited to thermoplasticity. The method (3) has the problems of danger of fire and explosion, danger to human body, and environmental pollution represented by ozone depletion. (4)
The method requires a special device to uniformly mix air or other gas into the synthetic resin,
Expensive foam stabilizer to keep the generated bubbles in the resin,
For example, it is uneconomical because a large amount of silicone foam stabilizer must be added. Furthermore, it is difficult to produce low density foams. In the method (5), the synthetic resin that can be naturally foamed is limited to polyurethane resin and polysiloxane. In the method (6), expensive balloons or beads must be added in a large amount, which is uneconomical, and addition of a large amount thereof causes a problem that the strength of the foam itself is lowered.

Further, as a method for obtaining a foam such as an emulsion resin, a synthetic resin dissolved or dispersed in water and / or an organic solvent, and a water-soluble polymer substance, for example, the following (1) to
The method shown in (4) is known. (1) Thermal decomposition type foaming agent which decomposes by heating to generate a large amount of gas, for example, inorganic compounds such as sodium bicarbonate and ammonium carbonate, azodicarbonamide, azobisisobutyronitrile, N, N'-di Nitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide,
p, p'-oxybis (benzenesulfonyl hydrazide)
After mixing an organic compound such as with an emulsion resin or a resin composition dissolved in water or an organic solvent, coating the resulting mixture on a substrate such as paper, cloth, or inorganic board, applying it with a brush or a spray gun A method in which water and solvent are removed by heating with hot air or natural drying, and the foam is expanded by the gas generated from the foaming agent by heating above the decomposition temperature of these foaming agents to form a foam. (2) Emulsion resin, water, or organic solvent is used as a heat-expandable resin obtained by impregnating or containing a low boiling point aliphatic hydrocarbon such as pentane, neopentane, hexane or butane in a synthetic resin after or during the production of the synthetic resin. After mixing with the dissolved resin composition and coating or casting the resulting mixture on a substrate, the moisture and solvent are removed by heating with hot air or natural drying, and the heat-expandable resin is expanded by heating. How to make foam. (3) While stirring the emulsion resin or the resin composition dissolved in water or an organic solvent at a high speed, a gas such as air or nitrogen gas is mixed in, and the obtained mixture is coated or cast on a substrate, and then hot air, etc. A method in which water and solvent are removed by heating in air or natural drying to form a foam. (4) Heat-expandable resin, resin hollow beads, hollow glass beads, etc. that have been previously expanded by heat are mixed with a resin composition dissolved in an emulsion resin or water or an organic solvent, and the resulting mixture is used as a base material. A method for producing a foam by removing water and solvent by heating with air or natural drying after coating or casting.

However, the above methods (1) to (4) have various drawbacks and are not always suitable as a method for producing a foam. That is, in the method (1), in order to obtain the foamed product, it is necessary to remove the water or the solvent and then heat it to a temperature higher than the temperature at which the foaming agent decomposes to generate a gas. Heating is required, and a large amount of heat energy is required to decompose the foaming agent, which is uneconomical. Also, large areas such as building paint,
Application to irregular shapes, such as molds, does not allow the necessary heating to decompose the blowing agent. Alternatively, it is difficult to obtain a foam due to uneven temperature distribution due to heating, or a non-uniform foam is obtained. Furthermore, in order to effectively capture the gas of the foaming agent in the resin composition and form a foam, it is necessary to plan the timing with a melt viscosity suitable for capturing the gas by melting the resin. There is a problem that limits oneself. In the method of (2), low boiling point compounds such as pentane, neopentane, hexane and butane are flammable, so that there is a risk of fire, explosion, etc., large area such as paints of buildings, amorphous materials, For example, when applied to a mold, there are problems that heating required for expanding the heat-expandable resin cannot be performed, or uniform heating cannot be performed and the foam becomes non-uniform. In the method of (3), in order to uniformly mix air, nitrogen gas or other gas into the resin composition, a special device is required, or in order to retain the generated bubbles in the resin composition. However, it is uneconomical because an expensive foam stabilizer such as a silicone foam stabilizer must be added in a large amount. Moreover, gas cannot be mixed into the high-viscosity resin composition. Further, in high pressure spray coating, there is a problem in that the generated bubbles themselves are collapsed and a foam is not formed. In the method of (4), it is uneconomical to add a large amount of expensive beads, and adding a large amount of these causes a decrease in the strength of the foam or a deterioration in the performance of the resin material. There's a problem.

An object of the present invention is to provide a foam composition capable of decomposing the foaming agent in a synthetic resin accompanied by a curing reaction in parallel with the curing reaction. Further, the object of the present invention is to add a decomposition accelerator to cause decomposition in a wide range of temperatures from near room temperature to the decomposition temperature of the foaming agent, and synthetic resin is not limited to thermoplasticity and foaming of inorganic material due to thermosetting property. It is to provide a foam composition that is even possible. Further, the object of the present invention is high safety to the human body, does not cause environmental pollution, and has excellent dispersibility in the foam composition because the foaming agent is liquid at room temperature, which enables the use of existing foaming equipment. To provide a foam composition. Further, an object of the present invention is to use a specific foaming agent in the foam composition so that the resin of the foam composition can be used as an emulsion resin and water and / or an organic solvent produced by an emulsion polymerization method or a solution polymerization method. It is another object of the present invention to provide a method for obtaining a foam by simultaneously dissolving and dispersing a synthetic resin and a water-soluble polymer substance and removing water or an organic solvent to decompose the resin.

[0007]

SUMMARY OF THE INVENTION The present invention provides organic or inorganic materials with the general formula ROOC-N = N-CO as a blowing agent.
The foam composition is characterized by containing an azodicarboxylic acid diester represented by OR (wherein R represents a lower alkyl group, a phenyl group or a benzyl group).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula, the lower alkyl group represented by R is, for example, a linear or branched chain having about 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl and tert-butyl. Alkyl groups are preferred. The azodicarboxylic acid diester of the present invention can be easily produced, for example, by reacting hydrazine hydrate with chlorocarbonic acid ester to produce a hydrazodicarboxylic acid ester, and oxidizing this with an oxidizing agent such as halogen. The present invention is a novel foam composition, which essentially contains an azodicarboxylic acid diester in a foaming agent,
It has succeeded in solving various problems recognized when a foam is produced by a known method. In particular, by allowing decomposition (foaming) from around room temperature, the target material can be wide range from thermoplastic resin, thermosetting resin and inorganic material.

The foam resin composition of the present invention is characterized in that the foaming agent is decomposed at the same time when water or an organic solvent is removed.
Furthermore, since foaming is possible at room temperature, that is, in a natural drying region, it is difficult to heat and dry and foam, for example, as a paint for a building such as a house, it can be foamed only by spraying or painting with a brush. The resulting foam is provided with improved heat insulation performance, improved design performance such as an uneven pattern, material saving and cushioning properties,
It is possible to obtain effects such as improved safety for people. Also,
It is used in a wide range of industries, such as a structure or a base material with a complicated shape, because it decomposes at room temperature, so a uniform foam can be obtained because the foaming performance does not change due to uneven heating during heating and drying. it can. Furthermore, the composition of the present invention has the advantages that it is highly safe for the human body and does not cause environmental pollution. The foam obtained according to the present invention has various functions such as heat insulating property, cushioning property, soundproofing property, sound insulating property, buoyancy property, cushioning property, etc. It can be preferably used in a wide range of industrial fields such as.

In the present invention, the azodicarboxylic acid diester, which is a foaming agent, is compounded with a known synthetic resin such as polyethylene, polystyrene, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, Thermoplastic resins such as thermoplastic polyurethane, silicone resins, polyurethane, phenol resins, epoxy resins, unsaturated polyester resins, thermosetting and room temperature curable resins such as diallyl phthalate resins, inorganic materials such as calcium silicate, magnesium silicate, silicic acid Inorganic binder such as colloidal silica and silicone, or organic compound such as polyvinyl alcohol, carboxymethyl cellulose, methyl cellulose, polyvinyl acetate, acrylic resin, ethylene-vinyl acetate copolymer, polyurethane, etc. Mixture was Indah, and may include those containing gypsum or cement. In the present invention, in producing aerated concrete by foaming cement, except that the azodicarboxylic acid diester derivative of the present invention is used in place of the conventional foaming agent,
It can be carried out in the same manner as the conventional method. For example, cellular concrete can be produced by mixing a siliceous material and a calcareous material, adding water and an azodicarboxylic acid diester derivative to the mixture to prepare a slurry, and heating the slurry to foam and cure the slurry. Alternatively, aerated concrete may be produced by heating this slurry to foam and semi-cure it and then performing high-pressure and high-temperature steam curing using an autoclave or the like. Here, as the siliceous material, a known material containing silicon dioxide can be used, and examples thereof include silica stone. The siliceous material may include other inorganic materials such as alumina.
As the calcareous material, a known material containing lime can be used, and examples thereof include lime, quick lime and cement. Each of the siliceous material and the calcareous material may be used alone or in combination of two or more. Further, conventional additives such as gypsum can be added. In the present invention, in addition to the above, an emulsion resin produced by an emulsion polymerization method or a solution polymerization method as an organic material, a synthetic resin dissolved or dispersed in water and / or an organic solvent, or an aqueous solution of a water-soluble polymer substance, etc. Used.

Examples of the emulsion resin produced by the emulsion polymerization method or the solution polymerization method include vinyl acetate polymer emulsion, ethylene-vinyl acetate copolymer emulsion, vinyl acetate-versatate copolymer emulsion, vinyl acetate-acryl. Acid ester copolymer emulsion, ethylene-vinyl acetate-vinyl chloride copolymer emulsion, ethylene-vinyl acetate-acrylic acid ester copolymer emulsion, acrylic acid ester polymer emulsion, acrylic acid ester-styrene copolymer emulsion, chloride Vinyl polymer emulsion, urethane polymer emulsion, silicone polymer emulsion,
Examples thereof include epoxy polymer emulsions. The particle size is preferably in the range of 0.05 to 1.0 μm.

Examples of the synthetic resin which is dissolved or dispersed in water and / or an organic solvent include vinyl alcohol polymers, vinyl chloride polymers, vinyl chloride-acrylic acid ester copolymers, vinyl chloride-urethane copolymers, vinyl chloride- Acetic acid copolymer, vinyl acetate polymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid ester polymer, acrylic acid ester-styrene copolymer, styrene polymer, urethane polymer, styrene-butadiene copolymer, A chlorinated polypropylene etc. can be mentioned. As the water-soluble polymer substance, for example, sodium polyacrylate,
Examples include carboxymethyl cellulose and hydroxyethyl cellulose. These may be used alone or in combination of two or more. Of these resins, synthetic resins that are soluble in organic solvents are preferred.

The amount of the foaming agent azodicarboxylic acid ester used can be appropriately selected from a wide range depending on the intended composition material, the molding method, the density of the foam to be obtained, etc., but the gas generation amount is appropriate. The range in which the cells have an appropriate size is usually about 0.05 to 30% by weight, preferably about 0.1 to 25% by weight in the foam composition. If necessary, the composition of the present invention may contain a decomposition accelerator that lowers the decomposition temperature of the foaming agent azodicarboxylic acid ester. By adding a decomposition accelerator, the decomposition temperature of the foaming agent can be adjusted in a wide range from around room temperature to around the decomposition temperature of the foaming agent, and the thermosetting resin decomposes the foaming agent even at the curing reaction temperature. That is, foaming can be performed. Further, since it is possible to foam at around room temperature, it is difficult to produce a foam with a conventional thermal decomposition type foaming agent, and a room temperature curable resin or a foam of an inorganic material that is cured and dried near room temperature is also available. It can be easily manufactured.

Examples of the decomposition accelerator of the foaming agent used in the present invention include metal oxides such as zinc oxide, lead oxide and magnesium oxide, metal carbonates such as zinc carbonate and barium carbonate, zinc chloride and potassium chloride. Metal chlorides such as lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, barium stearate, zinc stearate, cadmium stearate, lead stearate, dibasic lead stearate,
Metal soaps such as calcium laurate, zinc laurate, zinc 2-ethylhexoate, and dibasic lead phthalate; inorganic salts such as tribasic lead sulfate, dibasic lead phosphite and basic lead sulfite; dibutyltin. Organotin compounds such as dilaurate and dibutyltin dimaleate, dibutyltin dilaurate series,
Composite stabilizers for PVC such as dibutyltin dimaleate type, calcium-zinc type, barium-zinc type, monohydric and polyhydric alcohols such as methanol, ethanol, propanol, ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, urea, Examples thereof include metal sulfonic acid compounds, metal sulfinic acid compounds, organic and inorganic acidic or alkaline substances, and the like.
Species or two or more can be used. This decomposition accelerator is a foaming agent azodicarboxylic acid ester type and usage amount, composition material type and other additive type and usage amount, molding method,
It may be appropriately selected and used according to foaming conditions and the like. Among these, zinc stearate, dibasic lead stearate,
Zinc 2-ethylhexoate, an organic tin compound, and a sulfonic acid compound can be preferably used, and the amount used is not particularly limited, the material to be foamed, the type of the foaming agent azodicarboxylic acid ester, the molding method, the foaming conditions and the acceleration of decomposition. It can be appropriately selected from a wide range depending on the type of the agent, etc.
The amount may be about 300 parts by weight, preferably about 2 to 250 parts by weight. In use, equipment which can be mixed in advance with the foam composition in the form of powder or liquid before the foaming operation, or equipment which can be mixed simultaneously with the foaming operation, for example, a mixing head capable of mixing two or more kinds of materials in a short time Can be mixed with a foaming machine having

In the foam composition of the present invention, other conventional foaming agents such as sodium bicarbonate, ammonium carbonate, azodicarbonamide, azobisisobutyro are used as long as the performance and effect of the foam are not impaired. Thermal decomposition type blowing agents such as nitrile, N, N'-dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, fluorinated aliphatic hydrocarbons,
One or more kinds of evaporative foaming agents such as carbon dioxide gas and nitrogen gas can be added. It can also be used in combination with a chemical reaction method, for example, a foaming method in which carbon dioxide gas is generated by a reaction between isocyanate and water.

Further, in the foam composition of the present invention, various compounding agents conventionally added to foam compositions, such as plasticizers, stabilizers, crosslinking agents, antioxidants, ultraviolet absorbers, colorants, A flame retardant, a reinforcing material, a curing agent, an adhesive, an optical brightening agent and the like can be added. Further, in the foam composition of the present invention, as an example of a preferred embodiment when a thermosetting resin is used as a synthetic resin, 100 parts by weight of a liquid epoxy resin, 15 to 130 parts by weight of a room temperature curing type curing agent, and a phenol resin 0 An epoxy resin-based foam composition containing 0.1 to 60 parts by weight and 0.2 to 15 parts by weight of an azodicarboxylic acid diester which is a foaming agent of the present invention can be mentioned. In the above composition, the liquid epoxy resin is not particularly limited, and known ones can be used, for example, bisphenol A.
Type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, etc. Can be mentioned. The liquid epoxy resin may be used alone or in combination of two or more.

The room temperature curing type curing agent is not particularly limited, and known ones can be used. Examples thereof include polymercaptan type, aliphatic amine type, aromatic amine type, modified amine type, polyamide type, ketimine type and the like. A quick-hardening material can be preferably used. The curing agents may be used alone or in combination of two or more. The room temperature curable curing agent is usually mixed in an amount of about 15 to 130 parts by weight, preferably about 25 to 65 parts by weight, based on 100 parts by weight of the liquid epoxy resin. 1
If it is much less than 5 parts by weight, curing may be insufficient, or desired foam strength and expansion ratio may not be obtained. On the other hand, if it exceeds 130 parts by weight, the calorific value is increased to cause resin burning, or the balance between curing and foaming is lost, resulting in deterioration of moldability of the resulting foamed resin, which is economically disadvantageous. Is. Incidentally, a curing accelerator may be used together with the curing agent. The curing accelerator is not particularly limited and one or more known ones can be used, and among them, for example, tertiary amines, imidazole derivatives, dialkylureas such as dimethylurea and the like are preferable.

The phenol resin is effective in increasing the foaming ratio of the foam composition of the present invention, and improving the stability of cells and the denseness. The phenol resin also has an effect as a foaming agent for the epoxy resin. The phenol resin is not particularly limited and known ones can be used, but among them, the water-soluble resol type phenol resin is preferable. The water-soluble resol-type phenol resin can be produced, for example, by reacting a phenol compound and an aldehyde compound in the presence of an alkali catalyst. Here, as the phenol compound, known compounds can be used, for example, phenol,
Cresol, xylenol, p-alkylphenol,
Examples thereof include p-phenylphenol, resorcin, homologs thereof, and a mixture of two or more of these. Known aldehyde compounds can be used, and examples thereof include formaldehyde, p-formaldehyde, acetaldehyde, furfural, hexamethylenetetramine, and a mixture of two or more of these. Phenolic resin is epoxy resin 1
The amount is 0.1 to 60 parts by weight, preferably 5 to 40 parts by weight, based on 00 parts by weight. When the amount is less than 0.1 part by weight, the expansion ratio does not sufficiently increase and it becomes difficult to obtain the denseness of the foamed cells, which may result in non-uniformity. 6
Even if it is compounded in an amount of more than 0 parts by weight, there is little improvement in the expansion ratio relative to the compounding amount, it is economically disadvantageous, and there is a fear that it causes a decrease in the strength of the resulting foam.

The azodicarboxylic acid diester, which is a foaming agent, is usually 0.2 to 100 parts by weight of the epoxy resin.
The amount is about 15 parts by weight, preferably about 0.5 to 10 parts by weight. If the amount is less than 0.2 parts by weight, the expansion ratio may be insufficient. On the other hand, if the amount is more than 15 parts by weight, the expansion ratio is not improved relative to the compounding amount, which is economically disadvantageous. Is. Further, the amount of decomposed gas increases, the bubbles become coarse, and there is a fear that outgassing may occur or the moldability may deteriorate. Known additives can be added to the epoxy foam composition, if necessary. Examples of the additive include a decomposition accelerator, a foam stabilizer, a nucleating agent, and a reactive diluent for epoxy resin.
Species or two or more can be used. Examples of the decomposition accelerator include those exemplified above. The foam stabilizer is blended for the purpose of obtaining a foam having a more dense and uniform cell structure. As a specific example, for example, a product name:
L-501, L-520, L-530, L-540, L
-5320, L-5420 (manufactured by Nippon Unicar Co., Ltd.),
F-114, F-121, F-138, F-244, F
Silicone-based surfactants such as -305, F-317, F-345 (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like can be mentioned, and one or more of these can be used. The compounding amount of the foam stabilizer is not particularly limited and can be appropriately selected from a wide range, but in consideration of the foam stabilizing effect, usually the epoxy resin 10 is used.
The amount may be about 0.05 to 5 parts by weight, preferably about 0.1 to 2 parts by weight, relative to 0 parts by weight.

The nucleating agent is blended for the purpose of improving the uniformity and denseness of cells and suppressing the shrinkage of the foam. Specific examples thereof include inorganic fine powders of calcium carbonate, talc, clay, mica, silica and the like. Further, the metal soaps such as magnesium stearate, aluminum stearate, calcium stearate, barium stearate, zinc stearate, cadmium stearate, and lead stearate which have already been exemplified as the decomposition accelerator also have a function as a nucleating agent. ing. Nucleating agent is 1
The species can be used alone or in combination of two or more. The blending amount of the nucleating agent is not particularly limited and can be appropriately selected from a wide range, but considering that the effect is satisfactorily exhibited or the viscosity of the foam is prevented from increasing due to the addition, the epoxy resin is added to 100 parts by weight. On the other hand, it is usually about 0.1 to 50 parts by weight, preferably about 0.5 to 30 parts by weight. The reactive diluent for epoxy resin is added for the purpose of facilitating the mixing of the components or increasing the amount of the nucleating agent. Specific examples of the diluent include butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether and the like, and one or more of them are used. it can.

As a method for producing a foam from the foam composition of the present invention, known methods can be widely adopted. Specifically, for example, a method of foam-molding by mixing and molding the foam composition of the present invention with an extruder or roll, and then heating it to the decomposition temperature of the foaming agent in a mold under normal pressure or press pressure, A slab method that is a method of manufacturing a urethane resin foam, a continuous laminating method, a molding method, a coating method, a casting method, a spraying method, a method of mixing water and a binder with an inorganic material, and then casting and drying can be adopted, These are appropriately selected depending on the nature and shape of the composition material, for example, solid at room temperature, liquid or viscous liquid, and the shape or intended use of the desired foam. When an emulsion resin produced by an emulsion polymerization method or a solution polymerization method, a synthetic resin dissolved in water or an organic solvent, or an aqueous solution of a water-soluble polymer substance is used as the resin, the obtained foam composition is After spraying onto the substrate by spraying, the foaming is performed while removing water or organic solvent by natural drying. After coating the substrate by the coating method, water or organic solvent is removed by natural drying or heat drying. However, a method of foaming, a method of foaming while removing water or an organic solvent by natural drying or heat drying after pouring into a mold by a casting method, and the like can be adopted. The foam may be appropriately selected and used according to the shape of the foam, the purpose of use, and the like. Foams can be produced from the foam composition of the present invention by methods other than these, and the present invention is not limited by the above methods.

[0022]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples and Examples. Reference Example 1 To a mixed solution of 12.5 g of 80% hydrazine hydrate and 200 g of water, 37.8 g of methyl chlorocarbonate and 21.2 g of sodium carbonate were added, and after reacting at 25 ° C. for 2 hours, 200 ml of methylene chloride was added, 14.2 g of chlorine were introduced below 10 ° C. Next, the methylene chloride layer was separated, dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 26.3 g (yield 90%) of oily dimethyl azodicarboxylate.
It has a purity of 97% or more and can be used as it is as the blowing agent of the present invention.

Reference Example 2 In place of the methyl chlorocarbonate of Reference Example 1, 43.4 g of ethyl chlorocarbonate was used, the reaction and post-treatment were carried out in the same manner as in Reference Example 1, and 32.0 g of oily diethyl azodicarboxylate (yield: Rate 92%) was obtained. This can also be used as it is as the blowing agent of the present invention.

Reference Example 3 Instead of the methyl chlorocarbonate of Reference Example 1, 49.0 g of isopropyl chlorocarbonate was used, and the reaction and post-treatment were carried out in the same manner as in Reference Example 1 to obtain oily diisopropyl azodicarboxylate 3
7.6 g (yield 93%) was obtained. This can also be used as it is as the blowing agent of the present invention.

Example 1 Material Mixing (parts by weight) Component A Component B Component C Component Resol type phenol resin (Note 1) 100 Silicone foam stabilizer (Note 2) 2 Acid neutralizer (Note 3) 2 Curing agent (Note 4) 10 Dimethyl azodicarboxylate 15 Note 1: Nonvolatile content 80%, viscosity 3500 cps (25 ° C) Note 2: L-5420 manufactured by Nippon Unicar Co., Ltd. Note 3: Dioctyl phthalate mixed paste of zinc powder 50% Note 4: The material was fed into the phenol foaming machine having resininol PS-65 mixing head manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. in the composition shown above, and a mixture of the same material was discharged from the head portion into a polypropylene container to obtain a foaming agent. After decomposition and curing reaction of phenol, the mixture was left to stand until it reached room temperature. After cooling, the foam taken out from the polypropylene container was a phenol resin foam having an apparent density of 0.039 g / cc and having uniform fine cells.

Example 2 Foaming was performed in the same manner as in Example 1 except that dibenzyl azodicarboxylate was used instead of dimethyl azodicarboxylate. The foam taken out from the polypropylene container after cooling was a phenol resin foam having an apparent density of 0.056 g / cc and having fine bubbles.

Example 3 Material Compounding (parts by weight) A component B component C component Branched polyether polyol (Note 5) 100 Silicone foam stabilizer 1.5 Catalyst (tetramethylene hexadiamine) 0.5 Decomposition accelerator (olein Acid potassium) 2 Decomposition accelerator (ethylene glycol) 10 Polymeric methylene diisocyanate (Note 6) 123 Diethyl azodicarboxylate 20 Note 5: OHV450 Note 6: Isocyanate index 105 In a urethane foaming machine having a mixing head of three-component system, the above With the composition shown in (3), the three-component materials were fed, a mixture of the same materials was discharged from the head into a wooden container, the foaming agent was decomposed and the polyol and isocyanate were reacted, and the mixture was left to stand until it reached room temperature. The foam taken out from the wooden container after cooling was a hard urethane resin foam having an apparent density of 0.047 g / cc and having uniform fine cells.

Example 4 * 7: manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 815 * 8: Phenol / formaldehyde modified polyamine * 9: Resol-type phenol resin Propeller high-speed stirrer was used to mix the above-mentioned materials in a polypropylene container 30 After stirring and mixing for 2 seconds, the mixture was allowed to stand for 10 minutes to decompose and cure the foaming agent and allowed to stand at room temperature. The foam taken out from the polypropylene container after cooling was an epoxy resin foam having an apparent density of 0.12 g / cc.

Example 5 Note 10: Polylight F, manufactured by Dainippon Ink and Chemicals, Inc.
H-123S * 11: Benzoyl peroxide * 12: Dainippon Ink and Chemicals, Inc., RA Small size dual-arm kneader was used to prepare the above-described composition, and the composition was separated on a 1 mm thick stainless steel plate. A molded 15 mm thick crate was placed and the mixture was cast to half the crate at 7.5 mm. Then, a 1 mm-thick stainless plate was placed on top and heated in a hot air oven at 120 ° C. for 1 hour to decompose the foaming agent and carry out a curing reaction. The foam taken out from the wooden frame after cooling was a polyester resin foam which expanded to a thickness of 15 mm and had uniform fine cells.

Example 6 Material Mixing (parts by weight) Emulsion paint (Note 13) 100 Silicone foam stabilizer 0.2 Decomposition accelerator (Dioctyltin mercapto) 0.2 Diisopropyl azodicarboxylate 1 Note 13: Acrylic / styrene Polymerized resin type, manufactured by Suzuka Fine Co., Ltd., rubber coat jumbo high-gloss propeller-type stirrer was used to mix and prepare the above-described composition, and the mixture was prepared on a polyester film having a thickness of 0.12 mm of 0.5.
After coating to a thickness of mm, the foaming agent was decomposed and dried by leaving it at room temperature for 24 hours. The sheet peeled from the polyester film was an acrylic resin foam sheet which expanded to a thickness of 1.1 mm and had fine bubbles.

Example 7 Note 14: A composition having the above composition was prepared using a Movinyl 8020 propeller stirrer manufactured by Hoechst Synthetic Co., Ltd., and a 15 mm thick wooden frame was placed on a 1 mm thick stainless steel plate. It was poured to a position of 7.5 mm, which is half of the wooden frame, and a 1 mm-thick stainless plate was placed thereon, and left at room temperature for 40 minutes to decompose and condense the foaming agent. Then, the stainless plate and the wooden frame were removed, and the mixture was allowed to stand at room temperature for 7 days for coagulation and drying. The obtained foam expanded to a thickness of 15 mm and was a gypsum foam board having uniform fine cells.

Example 8 Material Blend (parts by weight) Room temperature curing silicone rubber (Note 15) 100 Curing agent (Note 16) 20 Curing accelerator / decomposition accelerator (Note 17) 2.5 Decomposition accelerator (dibasic Lead stearate) 2.5 Diethyl azodicarboxylate 4 Note 15: Shin-Etsu Chemical Co., Ltd., KE1404 Note 16: Shin-Etsu Chemical Co., Ltd., CAT-1404 Note 17: Asahi Denka Co., Ltd., TN -12 A small twin-arm kneader was used to prepare a composition having the above composition, which was poured into a 500 cc polypropylene container and left at room temperature for 2 hours to decompose and cure the foaming agent. The foam taken out from the container after standing for 2 hours was a silicone resin foam having an apparent density of 0.42 g / cc and having fine cells and excellent in impact resilience.

Example 9 Material Blend (parts by weight) Polyvinyl chloride (Note 18) 80 Polyvinyl chloride (Note 19) 20 Plasticizer (Note 20) 110 Heat stabilizer and decomposition accelerator (Note 21) 1.5 Filler (calcium carbonate) 200 Diluent (Note 22) 10 Diisopropyl azodicarboxylate 3 Note 18: Vinyl acetate 5% copolymer Note 19: Homopolymer Note 20: Diisonolyl phthalate Note 21: Dibutyltin laurate Note 22 : Mineral terpene A homogenizer was used to prepare a composition having the above composition, which was coated on an iron plate having a thickness of 0.5 mm to a thickness of 0.5 mm. Then, it was heated in a hot air oven at 150 ° C. for 15 minutes to decompose the foaming agent and gel the polyvinyl chloride. The foam separated from the iron plate after cooling was a foam of polyvinyl chloride that foamed to a thickness of 1.3 mm and had fine cells.

Example 10 * 23: Sumitomo Chemical Co., Ltd., Sumikasen G-201 * 24: Talc powder A composition was prepared by the Shinagawa mixer with the above-mentioned composition,
Using a 25 mm single screw extruder equipped with a die having a nozzle diameter of 7 mm, extrusion molding was performed under the following conditions. Extrusion molding conditions: temperature; cylinder 1 (130 ° C), cylinder 2 (14
5 ℃), Cylinder 3 (155 ℃), Head (140
), Die (135 ° C.) screw rotation speed; 50 rpm screen; 60 mesh wire netting, 80 mesh wire netting 1 piece The obtained molded body has an outer diameter of 11 mm and an apparent density of 0.1.
It was a 51 g / cc polyethylene resin foam.

Comparative Example 1 Material Blending (parts by weight) Component A Component B Component C Component Resol type phenolic resin (Note 25) 100 Silicone foam stabilizer (Note 26) 2 Acid neutralizer (Note 27) 2 Curing agent (Note 28) 10 Azodicarbonamide (Note 29) 15 Dispersant (Note 30) 20 Note 25: Nonvolatile content 80%, viscosity 3500 cps (25 ° C) Note 26: Nippon Unicar Co., Ltd., L-5420 Note 27: Zinc powder 50% dioctyl phthalate mixed paste Note 28: Dai-ichi Kogyo Seiyaku Co., Ltd., Resinol PS-65 Note 29: Otsuka Chemical Co., Ltd., Uniform AZ H Note 30: Polyethylene glycol Disperse powdery azodicarbonamide in advance. A liquid C component was prepared by dispersing it in the agent, and foaming was performed in the same manner as in Example 1. The mixture taken out from the polypropylene container after cooling was a phenol resin solid and did not become a foam.

Comparative Example 2 Curing and foaming were performed in the same manner as in Example 8 except that azobisisobutyronitrile was used instead of diethyl azodicarboxylate. The mixture taken out of the container was a solid substance excellent in impact resilience, which is a characteristic of silicone, but did not become a foam.

Comparative Example 3 Foaming was performed in the same manner as in Example 5 except that azodicarbonamide was used instead of diisopropyl azodicarboxylate. The mixture taken out from the wooden frame after cooling expanded to a thickness of 8 mm, but contained only coarse cells, and a sufficiently satisfactory foam was not obtained.

Comparative Example 4 A sheet was prepared in the same manner as in Example 6 except that p-toluenesulfonyl hydrazide was used instead of diisopropyl azodicarboxylate. The obtained acrylic resin sheet had a thickness of 0.43 mm, which was thinner than the thickness at the time of coating and did not become a foam.

Example 11 Materials other than the foaming agent (diethyl azodicarboxylate) shown in Table 1 below were mixed with a sand mill and a propeller-type high-speed stirrer, then the foaming agent was added and further mixed with a propeller-type high-speed stirrer. The foamable resin composition of the present invention was produced. The resulting foamable resin composition was applied to a polyester film having a thickness of 0.12 mm by using a knife coater, and the temperature was adjusted to room temperature (20
(° C) for 15 minutes to complete foaming and remove part of water. Further, it was left at room temperature (20 ° C.) for 24 hours to completely remove water and dried. At this time, the coating amount of the foam composition was the same as above except that the foaming agent was not added to the composition, and the water content was completely removed at room temperature (20 ° C.). The amount is about 0.15 mm. Table 2 shows the film thickness of the obtained dry film.

[0040]

[Table 1]

The polymer emulsions used in each example are as follows. Example 11: Vinyl acetate polymer emulsion (trade name:
Movinyl 303, Hoechst Synthetic Co., Ltd. Example 12: Ethylene-vinyl acetate copolymer emulsion (trade name: Sumikaflex S-510, Sumitomo Chemical Co., Ltd.) Example 13: Acrylic ester polymer emulsion (Brand name: Boncoat 3981, manufactured by Dainippon Ink and Chemicals, Inc.) Example 14: Ethylene-vinyl acetate-vinyl chloride copolymer emulsion (Brand name: Movinyl 123E, manufactured by Hoechst Synthesis Co., Ltd.) Example 15: Styrene-acrylic acid ester copolymer emulsion (trade name: Movinyl 937, manufactured by Hoechst Synthesis Co., Ltd.) Example 11 except that a foaming agent was not added as a blank.
A resin composition was produced, applied to a polyester film and dried in the same manner as in Nos. 15 to 15, respectively. Table 2 shows the film thickness of the obtained dry film.

[0042]

[Table 2]

Examples are the dry film thickness after foaming and drying of the foam resin composition. The blank is the dry film thickness of the resin composition containing no foaming agent after drying. The expansion ratio was calculated according to the following formula. Expansion ratio = dry film thickness of example / dry film thickness of blank From Table 2, it can be seen that the foam resin composition of the present invention has an expansion ratio of about 2 to 3 times and can perform effective foaming even at room temperature. it is obvious.

Examples 16 to 20 The foam resin composition of the present invention was produced in the same manner as in Example 11 except that the materials shown in Tables 3 to 4 below were used, and the composition was further foamed and dried. Then, the film thickness of the obtained dried film was measured. Table 5 shows the results.

[0045]

[Table 3]

[0046]

[Table 4]

The polymer emulsion used in each example is as follows. Examples 16 and 19: Ethylene-vinyl acetate copolymer emulsion (trade name: Sumikaflex S-510, manufactured by Sumitomo Chemical Co., Ltd.) Example 17: Acrylic ester polymer emulsion (trade name: Boncoat 3981, large) Nippon Ink Chemical Industry Co., Ltd. Examples 18 and 20: Styrene-acrylic acid ester copolymer emulsion (trade name: Movinyl 933H, Hoechst Synthetic Co., Ltd.) Except that no foaming agent was added as a blank. 16
A resin composition was produced, applied to a polyester film and dried in the same manner as in Examples 1 to 20. Table 5 shows the film thickness of the obtained dried film.

[0048]

[Table 5]

The examples are the dry film thickness after foaming and drying of the foam resin composition. The blank is the dry film thickness of the resin composition containing no foaming agent after drying. From Table 5, the foam resin composition of the present invention reaches a foaming ratio of about 2-3 times,
It is clear that effective foaming can be performed even at room temperature.

Examples 21 to 22 Foam resin compositions of the present invention were produced in the same manner as in Example 11 except that the materials shown in Table 6 below were used. This composition was sprayed on a gypsum board with a high pressure spray gun to form a coating film having an uneven pattern, and allowed to stand outdoors at a temperature of 25 ° C. for 24 hours for foaming and drying. The resulting dry coating is
The concave portions are 1.5 times larger than the thickness direction, and the convex portions are 2.4 times larger than that in the thickness direction.
The foam was highly elastic and flexible.

[0051]

[Table 6]

The polymer emulsions used in each example are as follows. Example 21: Styrene-acrylic acid ester copolymer emulsion (trade name: Movinyl 937, manufactured by Hoechst Synthesis Co., Ltd.) Example 22: Vinyl acetate-vinyl versatate copolymer emulsion (trade name: Movinyl DM21, Hoechst synthesis) (Made by)

Examples 23 to 25 After mixing materials other than the foaming agent shown in Table 7 below with a propeller type high speed agitator and a paint mill, the foaming agent was added and further mixed with a propeller type high speed agitator to obtain the present invention. Was produced. The foamable resin composition thus obtained was applied onto an aluminum plate having a thickness of 0.8 mm by using a knife coater, and left in a hot air circulation dryer at 50 ° C. for 4 hours for drying and foaming. Then 2 in the room (20 ℃)
It was left to cool for a period of time. The coating amount of the foam resin composition was based on the solid content of the composition, and was such that the film thickness of the dry film was about 0.1 mm. Table 8 shows the film thickness of the obtained dried film.

[0054]

[Table 7]

The polymer emulsions used in each example are as follows. Examples 23 and 24: Ethylene-vinyl acetate copolymer emulsion (trade name: Esdyne # 6051, manufactured by Sekisui Chemical Co., Ltd.) Example 25: Vinyl acetate-vinyl versatate copolymer emulsion (trade name: Movinyl DM21, Hoechst Synthetic Co., Ltd. Example 23 except that a foaming agent was not added as a blank.
A resin composition was produced, applied to a polyester film and dried in the same manner as in Examples 1 to 25. Table 8 shows the film thickness of the obtained dried film.

[0056]

[Table 8]

The examples are dry film thicknesses after foaming and drying of the foam resin composition. The blank is the dry film thickness of the resin composition containing no foaming agent after drying. From Table 8, it is clear that the foam resin composition of the present invention reaches a foaming ratio of about 2 times and can perform effective foaming even at room temperature.

Examples 26 to 27 Materials other than the foaming agent shown in Table 9 below were mixed with a Shinagawa stirrer, and then the foaming agent was added and further stirred and mixed to produce the foamable resin composition of the present invention. . The polyvinyl alcohol used in Example 26 was N type, the degree of polymerization was 1100, and the degree of saponification was 9
It is 9 mol% polyvinyl alcohol. The foamable resin composition thus obtained was poured into a wooden frame having a depth of 4 mm so as to have a thickness of 0.2 mm, and allowed to stand in a hot air circulation dryer at 40 ° C. for 20 minutes for drying and foaming. Further, it was left to stand in a dryer at 60 ° C. for 5 hours to dry, and then cooled to room temperature. The cured product taken out from the wooden frame after cooling was 4 mm thick,
It was a foam containing air bubbles inside.

[0059]

[Table 9]

Examples 28 to 30 100 g of epoxy resin and each component at the compounding ratio (parts by weight) shown in Table 10 were placed in a polypropylene container of 1 liter, and mixed by stirring with a propeller high speed stirrer for 1 minute. After allowing the foaming agent to decompose and cure for 5 minutes, it was allowed to stand until it reached room temperature. Table 10 shows the evaluation results of the appearance, cells and expansion ratio of the foam excluding the skin layer, which was taken out from the polypropylene container. From Table 10,
It is clear that the foam of the present invention has uniform and fine foam cells at high magnification.

Comparative Examples 5 to 7 Foams were produced in the same manner as in Examples 28 to 30 except that the phenol resin was not blended and each component was used in the blending ratio (parts by weight) shown in Tables 10 to 11. As shown in Tables 10-11,
These foams had a low expansion ratio, the foam cells were coarse and non-uniform, many large cavities were observed, and the discoloration due to burning of the resin was large.

[0062]

[Table 10]

[0063]

[Table 11]

Examples 31 to 32 Materials having the composition (parts by weight) shown in Table 12 below, excluding the foaming agent, were uniformly mixed with an omni mixer (manufactured by Chiyoda Giken Kogyo Co., Ltd.), and the foaming agent was added to the mixture to give a further 40 parts. Mixing for 2 seconds to prepare a foamable inorganic slurry. Then, inside dimension 300 × 3
After pouring the slurry of the foamable inorganic material up to a height of 35 mm in an iron box-shaped mold of 00 mm and a height of 75 mm and vibrating the box-shaped mold from the outside to make it a uniform height, in a dryer at 60 ° C. Foamed and semi-cured. Then, the semi-cured product was taken out from the iron box mold and autoclaved (12 atm, 1
It was cured at 90 ° C for 6 hours. The cured product after cooling was a lightweight cellular concrete having uniform and fine cells with a bulk specific gravity shown in Table 12 after drying.

[0065]

[Table 12]

[0066]

INDUSTRIAL APPLICABILITY In the foam composition of the present invention, it is possible to decompose the foaming agent in a synthetic resin accompanied by a curing reaction in parallel with the curing reaction. Further, in the foam composition of the present invention, by adding a decomposition accelerator, it can be decomposed in a wide range of temperatures from around room temperature to the decomposition temperature of the foaming agent, and the synthetic resin is not limited to thermoplasticity, but thermosetting property. It is possible to even foam an inorganic material. Furthermore, the foam composition of the present invention is highly safe to the human body, does not cause environmental pollution, and has excellent dispersibility in the foam composition because the foaming agent is a liquid at room temperature, and existing foaming equipment is used. Can be used. Further, the foam composition of the present invention is capable of decomposing the foaming agent simultaneously with the removal of water or an organic solvent, and further foaming at room temperature, that is, in a natural drying region. Therefore, as a paint for a building such as a house, a foam can be obtained only by spraying with a spray or painting with a brush or the like. Further, even for a structure and a base material having a complicated shape, since it is decomposed at room temperature, a homogeneous foam can be obtained. Furthermore, since the epoxy resin foam composition containing the epoxy resin, the curing agent and the phenol resin together with the azodicarboxylic acid diester which is the foaming agent of the present invention has the characteristics as described above, for example, a mixing head is used. On-site construction can be performed using the continuous injection foaming machine.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location // C08L 101: 00 (72) Inventor Masato Kanagawa 463 Kagasuno, Kawauchi-cho, Tokushima-shi, Tokushima Otsuka Chemical Tokushima Factory Co., Ltd.

Claims (6)

[Claims] 1. An azodicarboxylic acid diester represented by the general formula ROOC-N = N-COOR (wherein R represents a lower alkyl group, a phenyl group or a benzyl group) as a foaming agent in an organic or inorganic material. A foam composition comprising: 2. The foam composition according to claim 1, which contains a decomposition accelerator together with the foaming agent azodicarboxylic acid diester. 3. The foam composition according to claim 1, wherein the organic material is a thermoplastic resin, a thermosetting resin, or a room temperature curable resin. 4. The foam composition according to claim 1, wherein the inorganic material is calcium silicate, magnesium silicate, aluminum silicate mixed with an inorganic binder or an organic binder, gypsum or cement. 5. The organic material is an emulsion resin produced by an emulsion polymerization method or a solution polymerization method, a synthetic resin dissolved or dispersed in water and / or an organic solvent, or an aqueous solution of a water-soluble polymer substance. The foam composition according to. 6. A method for producing a foam by producing a foam from the foam composition according to claim 5, wherein the foaming agent is decomposed simultaneously with the removal of water or an organic solvent.