JP3023502B2 - Manufacturing method of organic foam with epoxy resin skeleton - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention, the bone of an epoxy resin
And relates to a novel process for the preparation of organic foam to rank, more particularly, the organic foam to a 緻 dense epoxy resin as a skeleton with rigid having a flame retardant, by foaming and curing at room temperature under The present invention relates to a method for producing an organic foam having an obtainable epoxy resin as a skeleton .

[0002]

2. Description of the Related Art Conventionally, various resin foams have been used as heat insulating materials or lightweight members. Among them, polyurethane resin foams, phenol resin foams, and urea resin foams are widely used as thermosetting foams. However, in order to improve the heat resistance and mechanical properties of these resin foams, those obtained by adding a flame retardant to these resin foams are known.

[0003] In particular, phenolic resins are highly flame-retardant among thermosetting resins, and examples of phenolic resin foams obtained by adding an inorganic compound to them to improve mechanical properties, flame retardancy, and the like are given as examples. Many are known.

For example, Japanese Unexamined Patent Publication (Kokai) No. 61-176638 discloses that a resol type phenol resin having a methylol index of 0.7 or less, boric acid, aluminum hydroxide and / or magnesium hydroxide, an acidic curing agent and a foaming agent are mixed. A method for producing a quasi-incombustible organic foam material by foaming and curing this mixture has been disclosed, and a method for producing a phenol resin foam similar thereto has been disclosed in JP-A-61-268733.
JP-A-61-275335 and JP-A-62-89
It is also disclosed in JP-A-740.

Japanese Patent Application Laid-Open No. 63-137936 discloses that a high-concentration slurry containing a liquid acid-curable thermosetting resin, a liquid additive such as a foaming agent and a curing agent, and a liquid resin is used. There is disclosed a method for producing a foam in which a solid additive such as an inorganic powder is mixed and foam-cured.

[0006] Japanese Patent Application Laid-Open No. 2-182415 discloses that
Resol phenolic resin, surfactant, average particle size is 5
Disclosed is a non-combustible resin foamed building material containing aluminum hydroxide, a foaming agent, a curing agent, and the like containing at least a part of 0 μm or more.

Further, Japanese Patent Application Laid-Open No. 6-80814 discloses that
An acid-curable phenolic resin, by heating and foaming and curing a composition mixture containing aluminum hydroxide, a foam stabilizer, a foaming agent and a curing agent as essential components, whose pH has been previously adjusted to 6.5 to 7.4 with a weakly acidic substance. A method for producing a phenolic resin foam is disclosed.

On the other hand, epoxy resins which are excellent in adhesiveness to other materials, heat resistance, chemical resistance, dimensional stability and mechanical strength are also improved in mechanical properties and flame retardancy by adding inorganic compounds. Several examples of foams having an improved epoxy resin skeleton are known.

For example, JP-A-64-11138 discloses a method for producing a resin foam by mixing a synthetic resin such as an epoxy resin, a curing agent, and an inorganic oxide and / or an inorganic hydroxide. I have.

[0010] Also, JP-A-1-197553 discloses that
It is disclosed that an epoxy resin foam can be obtained at room temperature by using a composition comprising an epoxy resin, an amine-based curing agent, a curing accelerator, and an inorganic filler.

Japanese Patent Application Laid-Open No. 4-178440 discloses that
An epoxy resin composition for a flame-retardant lightweight composite material containing an epoxy resin, micro hollow spheres, a foaming agent, a flame retardant, a curing agent, and a curing accelerator is disclosed.

Further, JP-A-4-266940 discloses an epoxy resin composition for a composite material containing an epoxy resin, fine hollow spheres, a foaming agent, a flame retardant and an aromatic diamine.

As described above, various types of resin foams are widely used as heat insulating materials and lightweight members. Among them, building materials represented by heat insulating materials, core materials of sandwich panels and outer wall panels, etc. When it is used as, it is desired that the building material has flame retardancy and fire resistance. Therefore, various resin foams for these applications are preferably flame retardant or have fire resistance.

[0014]

However, although phenolic resin foams are flame-retardant, they have high friability,
Lack of adhesion to other materials such as steel plate and wood may cause a problem of peeling after construction.

The resol-type phenol resin uses an organic acid such as p-toluenesulfonic acid as a curing catalyst, but since the organic acid remains in the foam, it causes corrosion of the contacting metal and discoloration of the wood. And therefore,
As shown in the prior art (for example, see Japanese Patent Application Laid-Open No. 58-120644), the remaining organic acid is reacted with an epoxy resin and collected to modify the foam to remain. It is necessary to prevent the influence of the organic acid on other materials.

Further, since the resole type phenol resin releases formaldehyde during the foaming and curing process, there is a case where there is a problem that the working environment is impaired by the odor.

On the other hand, foams having an epoxy resin skeleton utilizing the properties of the resin itself as described above are used as jointing agents, lightweight members for automobiles and the like, and building materials. Since resin foams used for building materials such as core materials of panels and outer wall panels are desired to be flame-retardant or have fire resistance, as shown in the prior art, foaming of epoxy resin skeletons is required. If a flame retardant or an inorganic filler is added to the body to increase the flame retardancy, it may be possible to provide a resin foam having no disadvantages of the phenol resin foam.

However, fiber reinforced plastics (F
Unlike the case where a flame retardant or inorganic filler is added to a molded article such as RP), in the case of a resin foam, a large amount is added, although it depends on the quality and particle size of the flame retardant or inorganic filler to be added. In such a case, the flowability of the resin during foaming is reduced and the moldability into a predetermined shape is deteriorated, or the size and distribution of bubbles after foaming become uneven and the mechanical strength of the foam is reduced. Or the thermal conductivity increases and the heat insulation decreases,
There was a problem that the amount of addition was restricted, resulting in insufficient flame retardancy.

Specifically, the amount of the flame retardant or the inorganic filler is generally in the range of 20 to 40 parts by weight with respect to 100 parts by weight of the epoxy resin, and the upper limit is about equal parts by weight with respect to the epoxy resin. As a result, there is a problem that the flame retardancy and the fire resistance become insufficient.

[0020] The present invention is to eliminate the drawbacks had prior art as described above, obtained by foaming and curing at room temperature under a foam 緻 dense epoxy resin skeleton in high rigidity having flame retardant The object of the present invention is to provide a method for producing an organic foam having an epoxy resin as a skeleton, which is capable of performing the following.

[0021]

Means for Solving the Problems To achieve the above object, the present invention employs a method for producing an organic foam having an epoxy resin as a skeleton, which comprises the following components A to D and E or E '. Is foamed and cured in the following quantitative ratio. A: Epoxy resin having two or more epoxy groups in a molecule: 100 parts by weight B: At least one flame retardant selected from metal hydroxides and metal oxide hydrates: 10 to 300 parts by weight C : Foaming agent: 1 to 50 parts by weight D: foam stabilizer: 0.01 to 10 parts by weight E: at least one phosphoric acid selected from phosphoric acid, polyphosphoric acid, and phenylphosphonic acid: the phosphorus An amount such that the ratio of the number of hydroxyl groups of the acids to the number of epoxy groups of the epoxy resin is 0.4 to 1.0, or E ': at least one phosphoric acid selected from phosphoric acid, polyphosphoric acid and phenylphosphonic acid And a mixture of at least one phosphoric acid compound selected from a phosphate having a hydroxyl group bonded to a phosphorus atom and a phosphoric acid ester. Phosphoric acid and phosphoric acid compound in the mixture Quantity ratio of the number of epoxy groups of the epoxy resin of the total number of hydroxyl groups is 0.4 to 1.0

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to specific examples.

The epoxy resin in the present invention is a compound having two or more epoxy groups in a molecule, and is a compound which can be cured by reacting with a curing agent for an epoxy resin. It is a compound also called a main agent or a polyepoxide.

As the epoxy resin, a compound having a glycidyl group as an epoxy group is preferred, and a glycidyl ether epoxy resin is particularly preferred, but is not limited thereto. For example, a cycloaliphatic epoxy resin, glycidyl ester Epoxy resin, heterocyclic aliphatic epoxy resin, etc. (These epoxy resins are oligomer-based
May be used), or
One of these epoxy resins may be selected, or two or more thereof may be used in combination.

The epoxy resin is preferably a liquid at ordinary temperature in view of the ease of mixing with a flame retardant and the fluidity during foaming. Examples of such an epoxy resin include bisphenol A diglycidyl. Glycidyl ether epoxy resins such as ether, bisphenol F diglycidyl ether, resorcin diglycidyl ether, phenol novolak polyglycidyl ether, cresol novolac polyglycidyl ether; glycidyl ester epoxy resins such as hexahydrophthalic acid glycidyl ester and dimer acid glycidyl ester Linear aliphatic epoxy resins and cycloaliphatic epoxy resins.

Examples of the flame retardant in the present invention include metal hydroxides such as aluminum hydroxide, calcium hydroxide, zirconium hydroxide, cerium hydroxide, and magnesium hydroxide, and calcium aluminate, montmorillonite, and Heidi. Light, hectorite, saponite,
Talc, pyrophyllite, vermiculite, mica, at least one selected from metal oxide hydrates including clay minerals such as dawsonite,
Among these, it is preferable to use aluminum hydroxide because of its large endothermic effect. Further, the flame retardant may be subjected to a surface treatment with stearic acid, a silane coupling agent or the like in order to improve the dispersibility in the epoxy resin.

In the present invention, the flame retardant is used in the range of 10 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin. The moldability, flame retardancy, fire resistance and mechanical properties of the resulting foam are obtained. 30 from the viewpoint of balance of target strength
More preferably, it is used in the range of 250 parts by weight.

If the amount of the flame retardant is less than 10 parts by weight, the flame retardancy and fire resistance of the foam cannot be improved. Not only cannot the foam of a predetermined shape be obtained due to a decrease in the fluidity of the mixture at the time, but also the density of the foam increases, the weight increases, and the heat insulation performance decreases due to the destruction of the cells of the foam. It causes embrittlement.

Further, the flame retardant has an average particle diameter of 1 to 3.
The thickness is preferably 5 μm from the viewpoint of easy kneading to the resin and uniform dispersion in the foam.
More preferably, it is 100 μm.

If the average particle size of the above-mentioned flame retardant is less than 1 μm, the bulk may be increased and the handleability and the kneading to the resin may be poor. If the average particle size exceeds 300 μm, The bulk specific gravity increases, and depending on the specific gravity difference with the resin or the like, sedimentation is likely to occur, and it may be difficult to uniformly disperse the foam in the foam (the above-mentioned average particle diameter in the present invention refers to a sedimentation balance method). Alternatively, it means the value of D50 measured by dry sieve analysis (50% value of the cumulative distribution).

Examples of the foaming agent in the present invention include known ones such as halogenated hydrocarbons and hydrocarbons. Among them, halogenated hydrocarbons having a boiling point of 0 to 100 ° C. are preferable. In particular, halogenated hydrocarbons that are liquid at room temperature are preferred. These foaming agents can be used alone or as a mixture of two or more.

The halogenated hydrocarbons include, for example, chlorinated hydrocarbons such as methylene chloride and trichloroethylene; 2,2-dichloro-1,1,1-trifluoroethane (HCFC123), 1,1-dichloro -1-fluoroethane (HCFC141b), 1,1-dichloro-2,2,3,3,3-pentafluoropropane (HC
FC225ca), 1,3-dichloro-1,1,2,2
2,3-pentanefluoropropane (HCFC225c
b) chlorinated fluorinated hydrocarbons such as 1,1,1,2,2
3,3-hexafluoropropane (HFC236e
a) and fluorinated hydrocarbons such as 1,1,1,3,3-pentafluoropropane (HFC245fa).

In the present invention, the foaming agent is used in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin. If it exceeds, the number of open cells increases, the closed cell rate decreases, and the rigidity and heat insulation of the foam decrease.

Further, since the expansion ratio and density of the foam vary depending on the increase or decrease of the amount of the foaming agent used, the amount of the foaming agent is adjusted so that the foam density required according to the use of the foam is obtained. Adjustment is preferred.

Examples of the foam stabilizer in the present invention include known ones used for producing various resin foams such as polyurethane resin foam and phenol resin foam.

A surfactant is preferable as the foam stabilizer, and a nonionic surfactant is more preferable as the surfactant. These foam stabilizers may be used alone or in combination of two or more.

Examples of the nonionic surfactant which can be used as the above foam stabilizer include sorbitan esters such as sorbitan monostearate, sorbitan monooleate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan monooleate. Polyethylene glycol esters such as polyethylene glycol monostearate, polyethylene glycol monosoleate, polyethylene glycol distearate, and polyethylene glycol dioleate; polyoxyethylene alkyl ethers other than those described above; polyoxyethylene alkyl esters; polyoxyethylene Alkylphenyl ethers; polyoxyethylene alkylphenyl esters, dimethylpolysiloxane polyoxyalkylene copolymers, etc. It can gel.

In the present invention, the foam stabilizer is used in an amount of 0.01 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the epoxy resin. If the amount is less than 01 parts by weight, the effect of uniformizing the size and distribution of the bubbles after foaming is lacking. If the amount is more than 10 parts by weight, it acts as a plasticizer and lowers the rigidity of the foam.

The phosphoric acid in the present invention comprises at least one selected from phosphoric acid, polyphosphoric acid and phenylphosphonic acid, and this phosphoric acid reacts with the epoxy resin to form a skeleton of a resin foam. At the same time
It is also a component that imparts flame retardancy to the resin foam.

Among the above phosphoric acids, phosphoric acid is not particularly limited.
%, 85%, or 89%.

As for polyphosphoric acid, various grades are commercially available depending on the content of P ₂ O ₅ .
It can be used without particular limitation, and there is no limitation on phenylphosphonic acid.

As the phosphoric acids, at least one of phosphoric acid, polyphosphoric acid and phenylphosphonic acid may be used, but two or more of them may be used. still,
Since phenylphosphonic acid among the above is a solid, it is preferable to use it in combination with phosphoric acid or polyphosphoric acid, which is a liquid, in order to easily flow during foaming and curing.

It is considered that the above-mentioned phosphoric acid reacts with the epoxy group of the epoxy resin and is taken into the molecular skeleton of the epoxy resin. Therefore, the phosphoric acid is obtained by controlling the amount of the phosphoric acid to an appropriate amount. Phosphoric acids can be prevented from remaining as free acids in the resulting foam. Therefore, by controlling in such a manner, even when the resin foam of the present invention is bonded to other materials such as metal and wood, for example, a neutralizing agent for preventing corrosion to metal and discoloration to wood is required. do not do

On the other hand, since phosphoric acid reacts rapidly with the epoxy group of the epoxy resin, as described later, both can react by simply mixing to form a foam. However, in some cases, the calorific value due to a rapid reaction with an epoxy group becomes too large, and foaming (vaporization) occurs at once depending on the type of a foaming agent, so that a dense foam may not be formed. In such a case, at least one type of phosphoric acid selected from a phosphate having a hydroxyl group bonded to a phosphorus atom and a phosphoric acid ester is used together with the phosphoric acid in order to control the reaction and suppress the heat generation. It is preferable to use a compound (hereinafter, sometimes simply referred to as a phosphoric acid compound) in combination.

In the present invention, by using the above phosphoric acid compound in combination, the reaction with the epoxy group is controlled to suppress the calorific value, and a good foam can be produced. Since it is also a component that imparts flame retardancy to the resin foam, even if it is used in a relatively large amount with respect to the phosphoric acids, there is little risk of lowering the flame retardancy of the obtained resin foam.

In the above phosphoric acid compound, at least one hydroxyl group bonded to a phosphorus atom is required to react with the epoxy group of the epoxy resin. At least one of them may be used, but two or more of them may be used.

Examples of the phosphate include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, and phosphoric acid phosphate. Examples thereof include calcium dihydrogen, calcium monohydrogen phosphate, aluminum dihydrogen phosphate, and dialuminum hydrogen phosphate. Examples of the phosphate include monomethyl phosphate, dimethyl phosphate, monoethyl phosphate, diethyl phosphate, propyl phosphate, isopropyl phosphate, and butyl phosphate.
, Lauryl phosphate, stearyl phosphate,
Examples thereof include 2-ethylhexyl phosphate and isodecyl phosphate.

In the present invention, the phosphoric acid is used in such an amount that the ratio of the number of hydroxyl groups of the phosphoric acid to the number of epoxy groups of the epoxy resin is 0.4 to 1.0. When the amount used is less than 0.4 in the above ratio, the heat of reaction generated by the reaction with the epoxy resin is small, the foaming (vaporization) of the foaming agent becomes insufficient, and the foam having a desired foaming ratio is obtained. Is difficult to obtain. When the amount of the phosphoric acid exceeds 1.0 in the above ratio, the phosphoric acid often becomes excessive, and the ratio of remaining as a free acid in the foam increases. In this case, The foamed state of the foam deteriorates, and when the foam comes into contact with metal or wood, the risk of corrosion or discoloration of the foam increases.

The amount of phosphoric acid used depends on the purpose of the foam,
It is preferable to adjust to a more appropriate amount depending on the production method and production conditions, etc., and from the workability during foaming, the uniformity of the mechanical strength and heat insulation of the foam, the above ratio is 0.4 to 0.8. It is more preferable to use an amount that results in

When the above phosphoric acid compound is used in combination,
The total amount of the phosphoric acid and the phosphoric acid compound is such that the ratio of the total number of hydroxyl groups of the phosphoric acid and the phosphoric acid compound to the number of epoxy groups of the epoxy resin is 0.4 to 1.0.

The amount of the phosphoric acid compound to be used with respect to the phosphoric acid can be selected in accordance with the use, production method, production conditions and the like of the foam in the same manner as described above. It can be adjusted appropriately so as to obtain the curing time.

Although not particularly limited, the ratio of phosphoric acid to the total of phosphoric acid and phosphoric acid compound is 40%.
If the amount of phosphoric acid is too small, the reactivity with the epoxy resin may be insufficient. When a solid phosphoric acid compound is used, it is preferable to use it in combination with a liquid phosphoric acid, polyphosphoric acid, or the like in order to easily flow during foaming and curing.

In the present invention, the ratio of the number of hydroxyl groups in the phosphoric acid to the number of epoxy groups in the epoxy resin means a value obtained by dividing the number of hydroxyl groups in the phosphoric acid by the number of epoxy groups in the epoxy resin. The number of epoxy groups in the epoxy resin is the value obtained by dividing the amount of the epoxy resin used by the epoxy equivalent of the epoxy resin, and when two or more epoxy resins are used, the use of each epoxy resin It means the total value of the values obtained by dividing the amount by the epoxy equivalent of each epoxy resin, and the number of hydroxyl groups of the phosphoric acid is the value obtained by dividing the amount of the phosphoric acid used by the hydroxyl equivalent of the phosphoric acid. When two or more types of phosphoric acids are used, the total value of the values obtained by dividing the amount of each phosphoric acid used by the hydroxyl equivalent of each phosphoric acid is used, and the phosphoric acid and the phosphoric acid compound are used in combination. If it is also the same.

Here, the epoxy equivalent is a value obtained by dividing the average molecular weight of the epoxy resin by the number of epoxy groups per molecule, and the hydroxyl equivalent is the formula weight of the phosphoric acid or the phosphoric acid compound bonded to the phosphorus atom. This is a value obtained by dividing by the number of hydroxyl groups obtained.

In the method for producing an organic foam having an epoxy resin skeleton according to the present invention, in addition to the above-mentioned flame retardants, for the purpose of adjusting the fluidity at the time of foaming and curing, and economical effects, Fillers, pigments and the like may be used, and these can be mixed with an epoxy resin or the like according to a standard method.

Since a mixture containing an epoxy resin and phosphoric acid or the like usually reacts at room temperature, the method for producing an organic foam having an epoxy resin skeleton according to the present invention requires the epoxy resin and phosphoric acid or phosphoric acid and phosphoric acid. It is preferable that a mixture with an acid compound (hereinafter, may be simply referred to as phosphoric acid or the like) is mixed at room temperature to obtain a reactive mixture. Mixing of the resin with phosphoric acid or the like can be performed under heating.

The above-mentioned flame retardant, foaming agent and foam stabilizer can be mixed with them at the same time when they are mixed. However, at least one of the above two is preliminarily provided with a flame retardant, foaming agent or foam stabilizer. It is also possible to mix them, and if they are mixed in advance, they are mixed with a component containing an epoxy resin to prepare a premix from the ease of mixing, and the premix is mixed with a component containing phosphoric acids and the like. Preferably, it is a reactive mixture.

In particular, since the flame retardant is a powder, it is preferable to mix it with a component containing an epoxy resin in advance in order to improve the fluidity of the mixture during foaming and dispersion in the foam. These mixing can be performed using a kneader, a mixing roll, a Henschel mixer or the like.

A reactive mixture containing an epoxy resin, a flame retardant, a foaming agent, a foam stabilizer, phosphoric acid, and the like can start the reaction at room temperature, and the reaction progresses while generating heat, and the It is foamed by vaporization and reacts and hardens to form an organic foam having an epoxy resin as a skeleton.As a device for mixing such components and discharging and injecting the mixture, it is usually used for producing polyurethane resin foam and the like. It is preferred to use a mixing device called a multi-component mixer as used.

The epoxy resin obtained by the present invention
Examples of a method for molding an organic foam having a skeleton as a skeleton include a foaming method in which the raw material components are mixed and poured into a mold having a desired size and shape while foaming and curing, and the raw material is placed on a flat surface. A slab foaming method or the like can be employed in which the components are allowed to flow while being mixed, and before the mixture is cured, the surface of the mixture during foaming and curing is scraped to a predetermined thickness by a doctor blade or the like, and the mixture is cured.

The epoxy resin obtained according to the present invention
The organic foam as a skeleton may be used in the same manner as conventional resin foam applications. For example, the foam obtained by the slab foaming method is cut out into a desired shape by cutting out a foamed body, and it can be used for applications such as a plate-shaped heat insulating material used for a building such as a house such as a housing such as an underfloor heat insulating material. Also, it can be used for a heat insulating material by foaming between an inner wall and an outer wall of a building such as a refrigerated warehouse by an injection foaming method. It can also be used as a core material for doors and sandwich panels. Furthermore, a composite material such as synthetic wood can be obtained by impregnating a mixture of the above-mentioned raw materials with a reinforcing fiber such as a glass fiber and foaming and hardening the mixture.

[0062]

The mixture of the epoxy resin and phosphoric acid reacts rapidly at room temperature to generate heat. By utilizing the heat of reaction for vaporizing the foaming agent, the mixture of the epoxy resin and phosphoric acid can be used. Easily and quickly cures the mixture at room temperature without heating, with epoxy resin as the skeleton
An organic foam can be obtained.

Further, since phosphoric acids and the like react and are taken into the epoxy resin skeleton constituting the organic foam, the phosphoric acids and the like function in the same manner as the reactive flame retardant, and the epoxy resin having a high flame retardancy is used. A skeletal foam can be obtained.

Further, since a part of the flame retardant reacts with phosphoric acid or the like and is incorporated into the epoxy resin skeleton constituting the organic foam, the flame retardant and the flame retardant remaining without being incorporated are not included. The wettability of the resin foam is good, and a large amount of the flame retardant can be uniformly dispersed in the foam without destroying the cells as compared with the conventional resin foam. The obtained epoxy resin skeleton
The organic foam with using a core material such as a sandwich panel, if the sandwich panel is exposed to e.g. flames, the temperature of the foam reached 200 to 500 ° C., by releasing the dehydrated or crystalline water Since heat is absorbed, it is possible to suppress the temperature rise of the panel and the heat transfer to the opposite surface.

Further, phosphoric acids and the like incorporated into the epoxy resin skeleton constituting the organic foam act as a dehydration and carbonization accelerator when exposed to the above high temperature, Since the release of water from the resin skeleton is promoted to form a heat insulating layer of carbonized cells, the shape and heat insulating properties of the foam are maintained even after exposure to high temperatures.

[0066]

The present invention will be described in more detail with reference to the following examples.

Example 1 100 parts by weight of a bisphenol A diglycidyl ether epoxy resin having an epoxy equivalent of 180 g / eq
1 part by weight of a dimethylpolysiloxane polyoxyalkylene copolymer as a foam stabilizer and 100 parts by weight of aluminum hydroxide having an average particle diameter of 30 μm as a flame retardant are kneaded using a three-roll kneader, and further a foaming agent. 1, as
What added 10 parts by weight of 1-dichloro-1-fluoroethane was designated as X component, and the mixture was placed in a raw material tank of a multi-component mixed foaming machine. Next, 85% phosphoric acid for industrial use was used as the Y component and placed in another raw material tank. X: Y = 10
0: 8.1 discharge weight ratio, a total of 3
The mixture was fed at a flow rate of Kg / min to discharge the mixture. still,
This corresponds to a ratio of the number of hydroxyl groups of phosphoric acid to the number of epoxy groups of the epoxy resin of 0.8. When 3750 g of this mixture was immediately placed in a 500 × 500 × 100 mm room-temperature metal frame, foaming started 20 seconds after injection, and foam hardening was completed 2 minutes later.

Example 2 Based on 100 parts by weight of a bisphenol A diglycidyl ether epoxy resin having an epoxy equivalent of 180 g / eq.
1 part by weight of a dimethylpolysiloxane polyoxyalkylene copolymer as a foam stabilizer, and 100 parts by weight of bentonite having an average particle diameter of 150 μm as a flame retardant are kneaded using a three-roll kneader, and further kneaded as a foaming agent. 1,1-
The X-component obtained by adding 10 parts by weight of dichloro-1-fluoroethane was placed in a raw material tank of a multi-component mixed foaming machine. Next, 85% phosphoric acid for industrial use was used as the Y component and placed in another raw material tank. X: Y = 100:
With a discharge weight ratio of 8.1, a total of 3 kg for the mixing head
/ Min, and the mixture was discharged. This corresponds to 0.8 in the ratio of the number of hydroxyl groups of phosphoric acid to the number of epoxy groups of the epoxy resin. This mixture 37
When 50 g was immediately placed in a 500 × 500 × 100 mm room temperature metal frame, foaming started 40 seconds after injection,
After 3 minutes the foam hardening was complete.

Example 3 100 parts by weight of a phenol novolak polyglycidyl ether-based epoxy resin having an epoxy equivalent of 175 g / eq and a molecular weight of about 600, 2 parts by weight of a polyoxyethylene sorbitan monostearate as a foam stabilizer, and a flame retardant 250 parts by weight of magnesium hydroxide having an average particle diameter of 30 μm were kneaded using a three-roll kneader, and further 15 parts by weight of 1,1-dichloro-2,2,3,3,3-pentafluoropropane as a foaming agent The resulting mixture was used as an X component and placed in a raw material tank of a multi-component mixed foaming machine. Next, 85% phosphoric acid for industrial use was put into another raw material tank as a Y component. The components X and Y were fed into the mixing head at a discharge weight ratio of X: Y = 100: 6.0 at a total flow rate of 3 kg / min to discharge the mixture. This corresponds to a ratio of the number of hydroxyl groups of phosphoric acid to the number of epoxy groups of the epoxy resin of 1.0. When 3750 g of this mixture was immediately placed in a 500 × 500 × 100 mm room temperature metal frame, foaming started 1 minute after injection, and foam hardening was completed 5 minutes later.

Example 4 100 parts by weight of a phenol novolak polyglycidyl ether-based epoxy resin having an epoxy equivalent of 175 g / eq and a molecular weight of about 600, 2 parts by weight of a polyoxyethylene sorbitan monostearate as a foam stabilizer, and a flame retardant 250 parts by weight of magnesium hydroxide having an average particle diameter of 30 μm were kneaded using a three-roll kneader, and further 15 parts by weight of 1,1-dichloro-2,2,3,3,3-pentafluoropropane as a foaming agent The resulting mixture was used as an X component and placed in a raw material tank of a multi-component mixed foaming machine. Next, a mixture of industrial 89% phosphoric acid and monoethyl phosphate at a molar ratio of 1: 1 and a weight ratio of 0.7: 1 was placed in another raw material tank as a Y component. X and Y are represented by X:
At a discharge weight ratio of Y = 100: 7.4, the mixture was fed into the mixing head at a total flow rate of 3 kg / min to discharge the mixture. This corresponds to a ratio of the number of hydroxyl groups of phosphoric acid and monoethyl phosphate to the number of epoxy groups of the epoxy resin of 1.0. When 3750 g of this mixture was immediately placed in a 500 × 500 × 100 mm room-temperature metal frame, foaming started 1 minute after injection, and foam hardening was completed 5 minutes 30 seconds later.

Comparative Example 1 100 parts by weight of a bisphenol A diglycidyl ether epoxy resin having an epoxy equivalent of 180 g / eq
1 part by weight of a dimethylpolysiloxane polyoxyalkylene copolymer as a foam stabilizer and 100 parts by weight of aluminum hydroxide having an average particle diameter of 30 μm as a flame retardant are kneaded using a three-roll kneader, and further a foaming agent. 1, as
What added 10 parts by weight of 1-dichloro-1-fluoroethane was designated as X component, and the mixture was placed in a raw material tank of a multi-component mixed foaming machine. Next, 85% phosphoric acid for industrial use was used as the Y component and placed in another raw material tank. X: Y = 10
0: 3.5 discharge weight ratio, a total of 3
The mixture was fed at a flow rate of Kg / min to discharge the mixture. still,
This corresponds to a ratio of 0.3 of the number of hydroxyl groups of the phosphoric acid to the number of epoxy groups of the epoxy resin. When 3750 g of this mixture was immediately placed in a 500 × 500 × 100 mm room temperature metal frame, foaming started 3 minutes after injection, and foaming was completed 7 minutes later, but curing was insufficient,
No foam of the desired dimensions was obtained.

Comparative Example 2 100 parts by weight of a bisphenol A diglycidyl ether epoxy resin having an epoxy equivalent of 180 g / eq was
1 part by weight of a dimethylpolysiloxane polyoxyalkylene copolymer as a foam stabilizer, and 350 parts by weight of bentonite having an average particle diameter of 150 μm as a flame retardant were kneaded using a three-roll kneader, and further kneaded as a foaming agent. 1,1-
The X-component obtained by adding 10 parts by weight of dichloro-1-fluoroethane was placed in a raw material tank of a multi-component mixed foaming machine. Next, 85% phosphoric acid for industrial use was used as the Y component and placed in another raw material tank. X: Y = 100:
With a discharge weight ratio of 3.7, a total of 3 kg is added to the mixing head.
/ Min, and the mixture was discharged. This corresponds to 0.8 in the ratio of the number of hydroxyl groups of phosphoric acid to the number of epoxy groups of the epoxy resin. This mixture 37
When 50 g was immediately placed in a 500 × 500 × 100 mm room temperature metal frame, foaming started 40 seconds after injection,
The foaming was completed after 3 minutes, but immediately after that, shrinkage began,
Eventually a partially foamed mass was obtained.

Comparative Example 3 100 parts by weight of a phenol novolak polyglycidyl ether-based epoxy resin having an epoxy equivalent of 175 g / eq and a molecular weight of about 600, 2 parts by weight of a polyoxyethylene sorbitan monostearate as a foam stabilizer, and a flame retardant 250 parts by weight of magnesium hydroxide having an average particle diameter of 30 μm were kneaded using a three-roll kneader, and further 15 parts by weight of 1,1-dichloro-2,2,3,3,3-pentafluoropropane as a foaming agent The resulting mixture was used as an X component and placed in a raw material tank of a multi-component mixed foaming machine. Next, 85% phosphoric acid for industrial use was placed in another raw material tank as a Y component. The X and Y components were fed into the mixing head at a discharge weight ratio of X: Y = 100: 9.0 at a total flow rate of 3 kg / min to discharge the mixture. This corresponds to 1.5 in the ratio of the number of hydroxyl groups of phosphoric acid to the number of epoxy groups of the epoxy resin. When 3750 g of this mixture was immediately placed in a 500 × 500 × 100 mm room temperature metal frame, foaming started 1 minute after injection, and foam hardening was completed 5 minutes later. However, the obtained foam had a large cavity therein and was easily buckled.

Comparative Example 4 100 parts by weight of a resole type phenol resin, 2 parts by weight of a dimethylpolysiloxane polyoxyalkylene copolymer as a foam stabilizer, and an average particle diameter of 30 μm as a flame retardant
m of aluminum hydroxide was kneaded using a three-roll kneader, and 20 parts by weight of 1,1-dichloro-1-fluoroethane as a foaming agent was added to X.
The components were placed in a raw material tank of a multi-component mixed foaming machine. Next, a 60% aqueous solution of phenylphosphonic acid was used as the Y component and placed in another raw material tank. X: Y = 10
0K: 15 discharge weight ratio, total 3K for mixing head
The mixture was fed at a flow rate of g / min to discharge the mixture. 3750 g of this mixture was immediately poured into a 500 × 500 × 100 mm room-temperature metal frame and heated to 60 ° C., and foaming started 3 minutes and 30 seconds after heating, and foam hardening was completed 10 minutes later.

Table 1 below shows the physical properties of the foams obtained by the above Examples and Comparative Examples.

[0076]

[Table 1]

[0077]

According to the method for producing an organic foam having an epoxy resin skeleton of the present invention, as shown in the above Examples,
It is possible to obtain an organic foam having a heat-insulating property, a high rigidity, and a dense flame-retardant epoxy resin as a skeleton, which easily foams and hardens quickly and easily at normal temperature.

In the organic foam obtained by the present invention, phosphoric acid and the like are incorporated in the epoxy resin skeleton constituting the foam, and the use of phosphoric acid and the like makes it possible to compare with the prior art. Therefore, a larger amount of the flame retardant can be uniformly dispersed in the foam, so that the flame retardancy and the fire resistance are excellent.

Continuation of the front page (56) References JP 9-324064 (JP, A) JP 10-87869 (JP, A) JP 10-53664 (JP, A) JP 9-227709 (JP) JP-A-9-235404 (JP, A) JP-A-1-197553 (JP, A) JP-A-4-178440 (JP, A) JP-A-4-266940 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08J 9/00-9/42

Claims (4)

(57) [Claims] 1. A method for producing an organic foam having an epoxy resin skeleton , comprising foaming and curing a mixture containing the following components A to E at the following quantitative ratios. A: Epoxy resin having two or more epoxy groups in a molecule: 100 parts by weight B: At least one flame retardant selected from metal hydroxides and metal oxide hydrates: 10 to 300 parts by weight C : Foaming agent: 1 to 50 parts by weight D: foam stabilizer: 0.01 to 10 parts by weight E: at least one phosphoric acid selected from phosphoric acid, polyphosphoric acid, and phenylphosphonic acid: the phosphorus An amount such that the ratio of the number of hydroxyl groups of acids to the number of epoxy groups of the epoxy resin is 0.4 to 1.0. 2. A process for producing an organic foam having an epoxy resin skeleton , comprising foaming and curing a mixture containing the following components A to E ′ in the following quantitative ratios. A: Epoxy resin having two or more epoxy groups in a molecule: 100 parts by weight B: At least one flame retardant selected from metal hydroxides and metal oxide hydrates: 10 to 300 parts by weight C : Foaming agent: 1 to 50 parts by weight D: foam stabilizer: 0.01 to 10 parts by weight E ′: at least one phosphoric acid selected from phosphoric acid, polyphosphoric acid and phenylphosphonic acid, and phosphorus A mixture comprising at least one phosphoric acid compound selected from a phosphate salt and a phosphoric acid ester having a hydroxyl group bonded to an atom: the total number of the phosphoric acids and the hydroxyl groups of the phosphoric acid compound in the mixture, and the epoxy groups of the epoxy resin The ratio of which is 0.4 to 1.0 with respect to the number of 3. The epoxy resin according to claim 1, wherein the epoxy resin is at least one selected from a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a linear aliphatic epoxy resin and a cycloaliphatic epoxy resin.
4. A method for producing an organic foam having an epoxy resin as a skeleton according to 1). 4. The epoxy resin according to claim 1, wherein the flame retardant has an average particle size of 1 to 300 μm.
A method for producing an organic foam as a skeleton .