JPWO2020080149A1 - Flame-retardant phenol resin composition and flame-retardant material obtained from it - Google Patents

Abstract

The problem in the case of blending ammonium polyphosphate, which can impart a high degree of flame retardancy, to a phenol resin composition containing a resole-type phenol resin as an essential component is solved, and it is stipulated by the Building Standards Law of Japan. Provided is a flame-retardant phenol resin composition capable of advantageously forming the flame-retardant material. In the phenol resin composition, at least ammonium polyphosphate having a surface coating layer is contained as a flame retardant together with the resol type phenol resin and the acid curing agent.

Description

The present invention relates to a flame-retardant phenol resin composition and a flame-retardant material obtained from the composition, and particularly advantageous is a flame-retardant material made of a cured phenol resin such as a flame-retardant phenol resin foam (phenol foam). It relates to a phenolic resin composition which can be formed in the above and a flame-retardant material obtained from such a phenolic resin composition.

Conventionally, a phenol resin material obtained by curing a phenol resin has been recognized by those skilled in the art as having a relatively high flame retardancy by itself, but as it is, construction, civil engineering, and electricity Difficulties stipulated by the Building Standards Law of Japan, which do not fully meet the safety standards required in the fields of products, electrical and electronic parts, automobile parts, etc., and are evaluated by a heat generation test using a cone calorimeter. A flame-retardant material having flame characteristics could not be given advantageously.

Therefore, in order to improve the flame retardant properties of such a phenol resin material, a predetermined flame retardant is blended with the phenol resin composition, and the curing thereof improves the flame retardancy of the target phenol resin material. It has been planned. For example, in Japanese Patent Application Laid-Open No. 2-49037, a phosphorus compound, a sulfur compound, or a boron compound is used as a flame retardant, and the flame retardant phenol foam is useful by blending them into a resin composition for producing a phenol foam. It has been clarified that it can be manufactured. Further, also in JP-A-2007-161810 and JP-A-2007-70511, aluminum hydroxide and magnesium hydroxide are used as inorganic fillers that are usually blended in a resin composition for producing a phenolic foam. Hydroxide of metal such as; Oxide of metal such as calcium oxide and aluminum oxide; Metal powder such as zinc powder; Phenol foam obtained by foaming by using carbonate of metal such as calcium carbonate and magnesium carbonate It has been clarified that the flame retardancy or fire resistance of the metal can be improved. Further, Japanese Patent Application Laid-Open No. 8-176334 reveals a resin composition in which ammonium polyphosphate is blended as a non-halogen flame retardant capable of imparting a high degree of flame retardancy to the resin.

By the way, a phenol composed of a cured product of a phenol resin such as phenol foam, which is obtained by using a resole-type phenol resin, which is one of the phenol resins, in combination with an acid curing agent, a foaming agent, etc., and foam-curing the resin. When a flame retardant composed of ammonium polyphosphate is used as proposed in JP-A-8-176334 above in order to impart a high degree of flame retardancy to the resin material, such polyphosphoric acid is used. It is difficult to effectively proceed with the curing reaction of the phenol resin composition containing ammonium, and therefore, there is a problem that the target phenol resin material (cured product) cannot be obtained. In particular, when heated at the characteristics required for flame-retardant materials specified by the Building Standards Law of Japan, that is, radiant heat intensity: 50 kW / m ² , the total calorific value for 5 minutes after the start of heating is 8.0 MJ. As the ^{blending amount of ammonium polyphosphate to the phenol resin composition is increased in order to obtain the property of / m 2} or less, the curing reaction of the phenol resin composition is less likely to proceed, and the desired phenol resin material such as phenol foam is used. It becomes impossible to obtain (cured product) at all.

According to the provisions of the Building Standards Law, the flame-retardant material satisfies the above-mentioned total calorific value and the maximum calorific value ^{does not continuously exceed 200 kW / m 2} for more than 10 seconds. It is said that there are no cracks or holes that penetrate to the back surface, which is harmful for flameproofing. It was not enough to respond.

Japanese Unexamined Patent Publication No. 2-49037 JP-A-2007-161810 Japanese Unexamined Patent Publication No. 2007-70511 Japanese Unexamined Patent Publication No. 8-1763343

Here, the present invention has been made against the background of the above-mentioned circumstances, and the problem to be solved thereof is that it is highly advanced with respect to a phenol resin composition containing a resole-type phenol resin as an essential component. A flame-retardant phenol resin that can solve the problem of blending ammonium polyphosphate, which can impart flame retardancy, and can advantageously form flame-retardant materials specified by the Building Standards Act of Japan. The purpose is to provide a composition, and to provide a flame-retardant material specified by the Building Standards Act by using such a flame-retardant phenol formaldehyde composition.

In order to solve such a problem, the present invention is characterized by containing at least an ammonium polyphosphate powder having a surface coating layer as a flame retardant together with a resole-type phenol resin and an acid curing agent. The gist of the composition is a flame-retardant phenolic resin composition.

According to one of the preferred embodiments of the flame-retardant phenol resin composition according to the present invention, the surface coating layer is formed of a sparingly soluble thermosetting resin, and among them, such sparingly soluble heat. As the curable resin, a melamine resin is preferably used.

Further, according to another one of the preferred embodiments of the flame-retardant phenol resin composition according to the present invention, the flame retardant is contained in a ratio of 0.5 to 30 parts by mass with respect to 100 parts by mass of the resole-type phenol resin. It is contained.

In addition, it is preferable that the resole-type phenol resin is adjusted to have a viscosity of 2000 mPa · s or more at 25 ° C.

Furthermore, according to another preferred mode of the flame-retardant phenolic resin composition according to the present invention, a foaming agent is further contained, whereby a phenol foam (phenol resin) having exceptional flame-retardant properties is contained. Phenol formaldehyde) can be formed advantageously.

As such a foaming agent, a halogenated alkane or a chlorinated aliphatic hydrocarbon and / or an aliphatic hydrocarbon is preferably used, and among them, a mixture of isopentane and isopropyl chloride is preferably used. Will be done.

The gist of the present invention is also a flame-retardant material characterized by being composed of a cured product obtained by curing the flame-retardant phenol resin composition as described above. Furthermore, a flame-retardant material characterized by being composed of a foam obtained by foaming and curing a flame-retardant phenol resin composition containing a foaming agent as described above is also a gist thereof.

Further, in such a flame-retardant material, in general, when the foam is ^{heated at a radiant heat intensity of 50 kW / m 2} in accordance with the heat generation test method specified in ISO-5660, 5 after the start of heating. It has the characteristic that the total calorific value per minute is 8.0 MJ / m ^{2 or less.}

As described above, in the flame-retardant phenol resin composition according to the present invention, the flame-retardant agent is not ammonium polyphosphate itself but a powder of ammonium polyphosphate having a surface coating layer formed therein. Therefore, the inhibitory effect of ammonium polyphosphate on the curing reaction of the phenol resin composition containing the resol type phenol resin and the acid curing agent can be advantageously suppressed or prevented, and thus the phenol resin composition. It has become possible to effectively improve the flame retardancy of the target phenol resin material, which is composed of the cured product of.

In particular, in the flame-retardant phenol resin composition according to the present invention, a phenol foam having excellent flame-retardant properties can be advantageously formed by containing a predetermined foaming agent and foaming and curing the composition. Therefore, one of the major features of the present invention can be found there.

Then, by using the flame-retardant phenol resin composition according to the present invention, a flame-retardant phenol resin material such as flame-retardant phenol foam can be easily used as a flame-retardant material specified by the Building Standards Act of Japan. Moreover, it can be formed advantageously.

By the way, the resol-type phenol resin used in the present invention as described above exhibits a liquid form, and is advantageous in that aldehydes are added to 1 mol of phenols in an amount of 1.0 to 3. It is used at a ratio of about 0 mol, preferably about 1.5 to 2.5 mol, and they are used in the presence of an alkaline reaction catalyst in the same manner as before, for example, within the range of 50 ° C. to reflux temperature. After the reaction at the above temperature, neutralization treatment is carried out, and then under reduced pressure, the viscosity at a predetermined characteristic value, for example, 25 ° C. is 2000 mPa · s or more, and the water content is 3 to 20% by mass. It is produced by dehydration and concentration so as to preferably be 5 to 18% by mass, and then, if necessary, adding a predetermined additive in the same manner as in the conventional case.

Of course, in addition to the resol-type phenol resin produced in this manner, in the present invention, various known resol-type phenol resins that can be cured by an acid curing agent can be appropriately adopted, and further. A resol type phenol resin modified with an appropriate modifier can be used in the same manner.

The liquid resol-type phenol resin thus obtained is generally 2000 mPa · s or more, preferably 2000 to 100,000 mPa · s, more preferably 3000 to 80,000 mPa · s, still more preferably 4000 to 30000 mPa at 25 ° C. -By having the viscosity of s, the preparation work of the target phenol resin composition, in particular, the dispersion and inclusion operation of the ammonium polyphosphate powder having the surface coating layer can be realized more effectively, and further. The stability of the dispersed state can be advantageously enhanced, and thus the advantage of further improving the flame retardancy and the thermal conductivity can be enjoyed. When the viscosity of the resol-type phenol resin is less than 2000 mPa · s, the precipitation of the ammonium polyphosphate powder having the surface coating layer becomes remarkable, and its localization is induced, and the phenol resin such as phenol foam formed is formed. If the material becomes uneven and sufficient flame retardancy and thermal conductivity cannot be obtained, and conversely, the viscosity becomes too high and exceeds, for example, 100,000 mPa · s, the target phenol foam or the like can be used. It causes problems such as difficulty in obtaining a phenol resin material.

Further, examples of the phenols used as a raw material for the resol-type phenol resin used in the present invention include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, m-xylenol, and bisphenol F. Bisphenol A and the like can be mentioned, and as the other raw material aldehydes used in combination with the phenols, formaldehyde, paraformaldehyde, trioxane, polyoxymethylene, glioxal and the like can be mentioned. Further, examples of the reaction catalyst include potassium hydroxide, sodium hydroxide, barium hydroxide, calcium hydroxide, potassium carbonate, ammonia and the like. Of course, these phenols, aldehydes and reaction catalysts are not limited to those of the above examples, and various known ones can be appropriately used, and each of them can be used as appropriate. It can be used alone or in combination of two or more.

In the present invention, when producing phenol foam as a flame-retardant phenol resin material, various known foaming agents are used as the foaming agent together with the above-mentioned resole-type phenol resin. However, particularly in the present invention, chlorinated aliphatic hydrocarbons and / or aliphatic hydrocarbons having a low global warming coefficient and alken halides are advantageously used, and phenol resins such as phenol foams are used advantageously. Phenol formaldehyde will be formed.

In this case, as the chlorinated aliphatic hydrocarbon as a foaming agent, a chlorinated linear or branched aliphatic hydrocarbon having about 2 to 5 carbon atoms is generally preferably used, and the chlorine thereof is used. The number of bonds of atoms is generally about 1 to 4. Specific examples of such chlorinated aliphatic hydrocarbons include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. These may be used alone or in combination of two or more, but among them, chloropropanes such as propyl chloride and isopropyl chloride are preferable, and isopropyl chloride is particularly preferably used. ..

Further, as the aliphatic hydrocarbon as the foaming agent, a conventionally known hydrocarbon-based foaming agent having about 3 to 7 carbon atoms can be appropriately selected and used. Specifically, Examples thereof include propane, butane, pentane, isopentane, hexane, isohexane, neohexane, heptane, isoheptan, cyclopentane, and the like, and one or a combination of two or more of them will be used.

Further, in the present invention, a mixed foaming agent obtained by combining the above-mentioned chlorinated aliphatic hydrocarbon and the aliphatic hydrocarbon is also preferably used, and the mixing ratio is the aliphatic hydrocarbon in terms of mass ratio. : Chlorinated aliphatic hydrocarbons will be advantageously adopted in the range of 25:75 to 5:95. As a combination of such two types of foaming agents, a combination of isopentane and isopropyl chloride is recommended, whereby the object of the present invention can be achieved even more advantageously.

In addition, in the present invention, an alkene halide is also advantageously used as a foaming agent, thereby contributing to further improvement of the properties of the obtained phenol foam, particularly flame retardancy and heat insulating properties. You can. Halogenated alkene having such characteristics also includes those called halogenated olefins and halogenated hydroolefins, and generally contains chlorine and fluorine as halogens and has 2 to 2 carbon atoms. Tetrafluoro, which is an unsaturated hydrocarbon derivative having about 6 pieces, for example, propene, butene, penten and hexene having 3 to 6 fluorine substituents, substituted with halogen, for example, fluorine or chlorine. Examples thereof include propene, fluorochloropropene, trifluoromonochloropropene, pentafluoropropene, fluorochlorobutene, hexafluorobutene, and mixtures of two or more of these.

Specifically, examples of the hydrofluoroolefin (HFO), which is one of such halogenated alkene (halogenated olefin), are pentafluoro such as 1,2,3,3,3-pentafluoropropene (HFO1225ye). Tetrafluoro such as propene, 1,3,3,3-tetrafluoropropene (HFO1234ze), 2,3,3,3-tetrafluoropropene (HFO1234yf), 1,2,3,3-tetrafluoropropene (HFO1234ye) Propen, trifluoropropene such as 3,3,3-trifluoropropene (HFO1243zf), tetrafluorobutene isomers (HFO1354), pentafluorobutene isomers (HFO1345), 1,1,1,4,4 Hexafluorobutene isomers (HFO1336) such as 4-hexafluoro-2-butene (HFO1336mzz), heptafluorobutene isomers (HFO1327), heptafluoropentene isomers (HFO1447), octafluoropentene isomers (HFO1438). ), Nonafluoropentene isomer (HFO1429) and the like. Examples of the hydrochlorofluoroolefin (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). Dichlorotrifluoropropene (HCFO1223), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb), 2-chloro- 1,3,3-trifluoropropene (HCFO-1233xe), 2-chloro-2,2,3-trifluoropropene (HCFO-1233xc), 3-chloro-1,2,3-trifluoropropene (HCFO-) 1233ye), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc) and the like can be mentioned.

Then, each foaming agent as described above is generally used in a ratio of 1 to 30 parts by mass, preferably 5 to 25 parts by mass with respect to 100 parts by mass of the resol type phenol resin in the total amount.

The foaming agent preferably used in the present invention is characterized by containing a chlorinated aliphatic hydrocarbon and / or an aliphatic hydrocarbon or a halogenated alkene as described above. As long as it does not cause adverse effects, for example, fluorinated hydrocarbons such as 1,1,1,3,3-pentafluorobutane (alternative frones), salt fluorinated hydrocarbons such as trichloromonofluoromethane and trichlorotrifluoroethane, It is also possible to contain water, an ether compound such as isopropyl ether, a gas such as nitrogen, argon or carbon dioxide, air or the like in an appropriate ratio.

Further, the acid curing agent used in the present invention is a component (curing catalyst) for accelerating the curing reaction of the resole-type phenol resin as described above, and a conventionally known acid curing agent is appropriately selected. , Will be used. As such an acid curing agent, for example, aromatic sulfonic acids such as benzene sulfonic acid, phenol sulfonic acid, cresol sulfonic acid, toluene sulfonic acid, xylene sulfonic acid and naphthalene sulfonic acid; methane sulfonic acid and trifluoromethane sulfonic acid. Etc., such as aliphatic sulfonic acids; inorganic acids such as sulfuric acid, phosphoric acid, polyphosphoric acid, and hydrofluoric acid, etc., which may be used alone or in combination of two or more. However, there is no problem. Among these exemplified acid curing agents, aromatic sulfonic acids such as phenol sulfonic acid, toluene sulfonic acid, and naphthalene sulfonic acid can realize an appropriate curing rate in the production of phenol foam. In addition, the balance between the curing of the resol type phenol resin and the foaming by the foaming agent is further improved, and thus a desirable foaming structure is realized, so that the resin type phenol resin is particularly preferably used. Above all, in the present invention, the combined use of paratoluenesulfonic acid and xylenesulfonic acid is recommended. As for their usage ratio, it is desirable that the amount of paratoluenesulfonic acid used is larger than the amount of xylenesulfonic acid used on a mass basis. Specifically, in terms of mass ratio, paratoluenesulfonic acid: xylenesulfonic acid is used. It will be advantageously adopted in the range of 51:49 to 95: 5.

Further, the amount of such an acid curing agent used is appropriately set according to the type thereof, the temperature condition at the time of mixing with the resol type phenol resin, and the like, but in the present invention, the resol type phenol is used. It is generally desirable to use 1 to 50 parts by mass, preferably 5 to 30 parts by mass, and particularly preferably 7 to 25 parts by mass with respect to 100 parts by mass of the resin. If the amount used is less than 1 part by mass, the progress of curing is slow, and conversely, if it exceeds 50 parts by mass, the curing rate becomes too fast and it becomes difficult to obtain the desired phenol foam advantageously. To provoke.

Then, according to the present invention, at least ammonium polyphosphate powder having a surface coating layer is contained as a flame retardant in the phenol resin composition composed of the above-mentioned resol type phenol resin and acid curing agent. However, as a result, the curing reaction of the phenol resin composition can be effectively promoted as compared with the case where ammonium polyphosphate is used as it is, and thus, together with excellent flame retardant properties, It has become possible to advantageously obtain a phenol resin cured product such as phenol foam, which exhibits useful properties in terms of compressive strength and initial thermal conductivity.

The ammonium polyphosphate powder having a surface coating layer used therein is obtained by coating or microencapsulating ammonium polyphosphate particles with a thermosetting resin, or using a melamine monomer or other nitrogen-containing organic compound for polyphosphoric acid. Examples thereof include those coated on the surface of ammonium particles, those subjected to a surfactant or silicon treatment, and the like, and usually, they are appropriately selected from commercially available products and used. For example, Exolit AP462 available from Clariant Chemicals, Inc., FR CROS486, FR CROS487, Terrage C30, Terrage C60, Terrage C70, Terrage C80, etc. available from CBC Co., Ltd. can be mentioned. The surface coating layer in such ammonium polyphosphate powder is preferably sparingly soluble in the liquid phenolic resin composition, that is, sparingly soluble in water, and in particular, such poorly soluble heat. As the curable resin, a phenol resin, a melamine resin, or the like is used, and among them, the melamine resin is preferably used. Further, even an easily soluble thermosetting resin can be advantageously used by advancing the curing reaction of the surface coating layer formed therein to form a poorly soluble surface coating layer. By having a surface coating layer made of such a sparingly soluble thermosetting resin, a cured product such as phenol foam having excellent compressive strength and initial thermal conductivity can be advantageously obtained. You can do it.

The amount of ammonium polyphosphate powder having such a surface coating layer used is generally 0.5 to 30 parts by mass, preferably 1 to 25 parts by mass, based on 100 parts by mass of the resole-type phenol resin. It is preferably determined appropriately within the range of 2 to 20 parts by mass. This is because if the amount of ammonium polyphosphate powder having such a surface coating layer added is too small, it becomes difficult to sufficiently exert the flame-retardant effect on the phenol resin material made of a cured product such as phenol foam. Further, if the amount added is too large, it becomes difficult to avoid an inhibitory effect on the curing reaction of the phenol resin composition, and the viscosity of the composition to which the phenol resin composition is added is increased, causing problems such as poor stirring. In addition to causing problems such as deterioration of properties such as compressive strength and thermal conductivity of the phenolic resin material.

Further, the average particle size of the ammonium polyphosphate powder having such a surface coating layer is generally about 1 to 100 μm, preferably about 5 to 50 μm. If the particle size of the ammonium polyphosphate powder having the surface coating layer becomes too small, problems such as difficulty in handling the powder and uniform dispersion in the phenol resin composition occur, and the particle size becomes large. If it is too much, it is difficult to obtain a uniform dispersion effect in the phenol resin composition, which causes a problem that the object of the present invention cannot be sufficiently achieved.

As described above, in the present invention, ammonium polyphosphate powder having a surface coating layer is used as the flame retardant, but if necessary, other known substances that do not impair the object of the present invention. It is also possible to use the flame retardant of. Examples of such other known flame retardants include phosphorus-based flame retardants such as phenylphosphonic acid, guanidine phosphate derivative, phosphoric acid carbamate derivative, red phosphorus and ammonium phosphate, sulfamic acid-based flame retardants, and hoe. Examples thereof include acid-based flame retardants, halogen-based flame retardants, and inorganic flame retardants such as metal hydroxides, metal oxides, and graphite.

By the way, in the flame-retardant phenol resin composition according to the present invention, ammonium polyphosphate powder having a surface coating layer as a flame retardant is added and blended as an essential component together with the above-mentioned resole-type phenol resin and acid curing agent. In addition to being urged, in the case of the production of phenol foams, certain foaming agents, in particular chlorinated aliphatic hydrocarbons and / or aliphatic hydrocarbons, or halogenated alkene, are added, and more. If necessary, it is also possible to contain a conventionally known foam stabilizer, inorganic filler, plasticizer, urea and the like.

Here, among the additives added and contained as necessary, the defoaming agent can be used for mixing mixed components in the phenol resin composition, assisting emulsification, dispersing generated gas, stabilizing the foam cell membrane, and the like. It is compounded for the purpose of planning. The defoaming agent is not particularly limited, and various defoaming agents conventionally used in the technical field are selectively used. Among them, poly Nonionic surfactants such as siloxane compounds, polyoxyethylene sorbitan fatty acid esters, alkylphenol ethylene oxide adducts, and ethylene oxide adducts of castor oil are particularly preferably used. In addition, these defoaming agents can be used alone or in combination of two or more of them. The amount used is also not particularly limited, but is generally used within the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the resol type phenol resin.

Other examples of the inorganic filler include metal hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, metal oxides such as magnesium oxide, aluminum oxide and zinc oxide, and metal powders such as zinc. Examples include metal carbonates such as calcium carbonate, magnesium carbonate, barium carbonate, and zinc carbonate. In addition, these inorganic fillers can be used alone or in combination of two or more of them. Of course, the use of such an inorganic filler can improve flame retardancy and fire resistance, but the amount used is appropriately determined within the range of the amount used that does not impair the object of the present invention. It goes without saying that it is something that is done.

Further, the plasticizer can be advantageously used as a cured phenol resin material in the case of producing phenol foam, and by its use, flexibility is imparted to the bubble wall of the phenol foam, and the heat insulating performance is improved. It exhibits features such as suppressing deterioration over time. The plasticizer is not particularly limited, and known plasticizers conventionally used for producing phenol foam, for example, triphenyl phosphate, dimethyl terephthalate, dimethyl isophthalate and the like can be used, and polyester. The use of polyols is also effective. In particular, since the polyester polyol has a structure containing an ester bond and a hydroxyl group, which is hydrophilic and has excellent surface activity, it has good compatibility with a hydrophilic phenol resin solution and is uniformly mixed with the phenol resin. Can be done. Further, by using this polyester polyol, uneven distribution of bubbles is avoided, bubbles are uniformly distributed throughout the foam, and a phenol resin foam (phenol foam) having a uniform quality can be easily produced, which is preferable plasticization. It can be called an agent. Such a plasticizer is usually 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, and more preferably 1 to 12 parts by mass with respect to 100 parts by mass of the resole-type phenol resin. Used in the range, thereby satisfactorily exerting the effect of imparting flexibility to the cell wall without compromising the other performance of the resulting phenolic foam, and the object of the present invention can be achieved even better. It becomes.

Further, urea is suitably added and contained in the flame-retardant phenol resin composition constructed according to the present invention. By containing such urea, the initial thermal conductivity of the obtained phenol resin material such as phenol foam can be effectively lowered, and further, a phenol resin material having strength, particularly low brittleness, can be obtained. It also contributes to maintaining a low thermal conductivity over the medium to long term, and thus it is easy to obtain a phenol resin material such as phenol foam having excellent heat insulating performance for a long period of time. It becomes.

By the way, in the flame-retardant phenol resin composition according to the present invention containing the above-mentioned compounding components, for example, ammonium polyphosphate powder having the above-mentioned surface coating layer is added as a flame retardant to the above-mentioned resole-type phenol resin. Then, if necessary, the other flame retardants, inorganic fillers, foam stabilizers, plasticizers, ureas, etc. described above are added and mixed, and the resulting mixture is added as required. After adding a predetermined foaming agent, particularly the above-mentioned chlorinated aliphatic hydrocarbon and / or aliphatic hydrocarbon, or halogenated alkene, this is supplied to the mixer together with the acid curing agent and stirred. This makes it possible to prepare.

Further, when the phenol resin composition thus prepared is used and cured to form a desired phenol resin material such as a solid material or a foam, various conventionally known materials are used. (1) A molding method in which the phenol resin composition is allowed to flow out onto an endless conveyor belt to be foamed and cured, and (2) spot filling. Partially foaming and curing, (3) Filling in a mold and foaming and curing under pressure, (4) Foaming by filling in a predetermined large space and foaming and curing Examples thereof include a method of forming a body block and (5) a method of filling and foaming while press-fitting into a cavity.

Then, among the molding methods of these phenol foams, according to the molding method of (1) above, the phenol resin composition as described above is discharged onto a continuously moving carrier, and the discharged product passes through a heating zone. A method is adopted in which the phenol foam is foamed and molded to produce the desired phenolic foam. Specifically, after the phenol resin composition is discharged onto the face material on the conveyor belt, the face material is placed on the upper surface of the resin material on the conveyor belt, moved to the curing furnace, and then the curing furnace. Inside, the resin material is pressed from above with another conveyor belt to adjust the resin material to a predetermined thickness, and foam-cured under the conditions of about 60 to 100 ° C. for about 2 to 15 minutes, and then a curing furnace. By cutting the foam taken out from the above into a predetermined length, a phenol foam having a desired shape is produced.

The face material used here is not particularly limited, and generally, natural fibers, synthetic fibers such as polyester fibers and polyethylene fibers, non-woven fabrics such as inorganic fibers such as glass fibers, papers, and aluminum. Foil-covered non-woven fabrics, metal plates, metal foils, etc. are used, but usually glass fiber non-woven fabrics, spunbond non-woven fabrics, aluminum foil-clad non-woven fabrics, metal plates, metal foils, plywood, structural panels, particle boards, hard boards, etc. , Wood-based cement board, flexible board, pearlite board, calcium silicate board, magnesium carbonate board, pulp cement board, sheathing board, medium density fiber board, gypsum board, lath sheet, volcanic vitreous composite board, natural stone, brick, tile , A molded body containing a water-curable cement hydrate as a binder component, such as a glass molded body, a lightweight bubble concrete molded body, a cement mortar molded body, and a glass fiber reinforced cement molded body, is preferably used. The face material may be provided on one side of the phenol foam, or may be provided on both sides. Further, when provided on both sides, the face materials may be the same or different. Further, even if it is formed by laminating face materials later using an adhesive, there is no problem.

Thus, since a predetermined ammonium polyphosphate powder is dispersed and contained in the phenol resin material (cured product) such as the phenol foam thus obtained, the material as a whole is flame-retardant. The properties can be effectively enhanced, and in the heat generation test using a cone calorimeter, the properties as a flame-retardant material specified by the Building Standards Law of Japan are advantageously provided. Specifically, in accordance with the exothermic test method specified in ISO-5660, ^{when heated at a radiant heat intensity of 50 kW / m 2} , the total calorific value from the start of heating to the elapse of 5 minutes is calculated. The material advantageously has the property of 8.0 MJ / m ² or less, and thus can be advantageously used as a flame-retardant material in various applications.

Further, a phenol resin material such as a phenol foam is advantageous in general, generally 0.0230 W / m · K (20 ° C.) or less, preferably 0.0200 W / m · K (20 ° C.) or less, more preferably 0.0200 W / m · K (20 ° C.) or less. It can be easily produced as having an initial thermal conductivity of 0.0195 W / m · K (20 ° C.) or less, and in the case of phenol foam, its closed cell ratio is Generally, it is configured to be 80% or more, preferably 85% or more, more preferably 90% or more, whereby it is produced as having excellent flame retardancy and excellent low thermal conductivity characteristics. It will be.

Further, in the phenol resin material such as phenol foam obtained according to the present invention, the density thereof is generally 10 to 150 kg / m ³ , preferably 15 to 100 kg / m ³ , and more preferably 15 to 70 kg / m ³ . It is more preferably 20 to 50 kg / m ³ , and most preferably 20 to 40 kg / m ³ . In addition, in the case of ^{phenol foam having a density lower than 10 kg / m 3} , the strength is low and the foam (foam) may be damaged during transportation or construction. Further, when the density is low, the bubble film tends to be thin. If the bubble film is thin, the foaming agent in the foam (foam) is likely to be replaced with air, and the bubble film is easily torn during foaming, which makes it difficult to obtain a high closed cell structure. Long-term insulation performance tends to deteriorate. On the other hand, when the density ^{exceeds 150 kg / m 3} , the heat conduction of solids derived from solid components such as phenol resin increases, so that the heat insulating performance of phenol foam tends to deteriorate.

Hereinafter, the features of the present invention will be clarified more concretely by showing some examples of the present invention and comparing them with the comparative examples. Needless to say, it is not subject to any restrictions. Further, in addition to the following examples, various modifications and modifications to the present invention are made based on the knowledge of those skilled in the art, as long as the gist of the present invention is not deviated from the specific description described above. It should be understood that improvements can be made. Unless otherwise specified, the percentages (%) and parts shown below are all indicated on a mass basis.

− Example 1-
In a three-necked reaction flask equipped with a refluxer, a thermometer and a stirrer, 1600 parts of phenol, 2482 parts of 47% formalin and 41.6 parts of a 50% sodium hydroxide aqueous solution were charged and charged at a temperature of 80 ° C. for 70 minutes. It was reacted. Then, after cooling to 40 ° C., the mixture was neutralized with a 50% aqueous solution of paratoluenesulfonic acid, and then dehydrated and concentrated to a moisture content of 10% under reduced pressure and heating to obtain a liquid resol type phenol resin. .. The obtained phenol resin had the characteristics of viscosity: 10000 mPa · s / 25 ° C., number average molecular weight: 380, and free phenol content: 4.0%.

Then, to 100 parts of the obtained liquid resol-type phenol resin, 3 parts of castor oil ethylene oxide adduct (additional number of moles 22) as a foam stabilizer and 5 parts of urea as an additive were added. Mixing gave 108 parts of a uniform phenolic resin mixture.

Next, with respect to 108 parts of the obtained phenol resin mixture, 10 of ammonium polyphosphate powder (Terage C80 sold by CBC Co., Ltd., average particle size: 19 μm) having a surface coating layer made of melamine resin as a flame retardant. 9.0 parts of a mixture consisting of parts and a mass ratio of isopropyl chloride: isopentan = 85: 15 as a foaming agent, and a mixture of paratoluene sulfonic acid: xylene sulfonic acid = 2: 1 (mass ratio) as a curing agent. A foamable phenol resin molding material, which is a resin composition for producing phenol foam, was prepared by stirring and mixing 16 parts of the above.

Then, using the foamable phenol resin molding material prepared in this manner, it is injected into a mold having a length of 300 mm, a width of 300 mm, and a thickness of 50 mm, which is preheated to 70 to 75 ° C. After that, the mold was housed in a dryer at 70 to 75 ° C., foam-cured for 10 minutes, and then post-cured by heating at a temperature of 70 ° C. for 12 hours in a heating furnace. Phenol foam (phenol resin foam) was prepared.

− Example 2-
In Example 1, FR CROS486 (sold by CBC Co., Ltd .; polyphosphorus having an average particle size of 18 μm) is an ammonium polyphosphate powder in which a silane coating layer is formed as a surface coating layer instead of the tellage C80 used as a flame retardant. A phenol foam was prepared in the same manner as in Example 1 except that ammonium acid powder (surface-treated with silane) was used.

− Example 3-
In Example 1, the foaming agent was changed to a hydrofluoroolefin (1,1,1,4,4,4-hexafluoro-2-butene: HFO-1336 mzz, a product of The Chemours Company), and the amount of the foaming agent added was 17. Phenol foam was prepared in the same manner as in Example 1 except that 5 parts were used.

-Comparative example 1-
In Example 1, a phenol foam was prepared in the same manner as in Example 1 except that ammonium polyphosphate powder having a surface coating layer as a flame retardant was not added.

-Comparative example 2-
In Example 1, as the flame retardant, ammonium polyphosphate powder having no surface coating layer (FR CROS484 sold by CBC Co., Ltd., average particle size: 18 μm) was used as the flame retardant. Similarly, an attempt was made to prepare a phenol foam, but the curing reaction of the phenol resin composition did not proceed sufficiently, and a foam whose physical properties could be measured could not be obtained.

Then, using the various phenol foams (phenol resin foams) thus obtained, a combustion test (total heat generation) for evaluation of its density, initial thermal conductivity, closed cell ratio, compressive strength, and flame retardancy. The amount, maximum heat generation rate, and the situation after the test) were measured or evaluated according to the following methods, and the results obtained are shown in Table 1 below.

(1) Measurement of Density The density of each foam was measured according to the description of "5.6 Density" in JIS-A-9511 (2003).

(2) Measurement of initial thermal conductivity Using a 300 mm square phenol resin foam sample, cut it into 200 mm square (thickness is 50 mm), and then set the low temperature plate: 10 ° C and the high temperature plate: 30 ° C. Measurement is performed using a thermal conductivity measuring device: HC-074 304 (manufactured by Eiko Seiki Co., Ltd.) in accordance with the "heat flow metering method" specified in JIS-A-1412-2 (1999). Here, the thermal conductivity of the phenol resin foam sample after being left in an atmosphere of 70 ° C. for 4 days was measured as the initial thermal conductivity.

(3) Measurement of closed cell ratio The closed cell ratio of the phenol resin foam sample was measured according to the regulations of ASTM-D2856.

(4) Measurement of Compressive Strength The compressive strength of the phenol resin foam sample was measured according to the description of "5.9 Compressive strength" in JIS-A-9511 (2003).

(5) Combustion test (flame retardancy evaluation)
Specimens were cut out from each phenol foam so that the vertical × horizontal size was 99 ± 1 mm, and each test specimen was prepared. The thickness of the test piece was 50 mm. Next, for these test specimens, using a cone calorimeter (CONE III manufactured by Toyo Seiki Seisakusho Co., Ltd.), in accordance with the regulations of ISO-5660, "Fireproof performance test / evaluation work" edited by Japan Building Research Institute. The total calorific value and the maximum calorific value at a heating time of 5 minutes were measured according to the method manual 4.12.1 Heat generation test / evaluation method. As the measurement result, the measurement was performed on three test pieces cut out from each foam, and the average value of the obtained measured values was adopted. In addition, the test piece after the evaluation test was observed to check for cracks and holes penetrating to the back surface.

As is clear from the results in Table 1, all of the phenol foams formed in Examples 1 to 3 have a total calorific value of 8 MJ / m ² or less and a specified maximum calorific value in the combustion test. From the following points, it was confirmed that it is useful as a flame-retardant material specified by the Building Standards Law of Japan. Among them, the phenol foams obtained in Examples 1 and 3 both have an initial thermal conductivity of 0.0193 W / m · K or less, a closed cell ratio of 91% or more, and a compressive strength. It was about 16 N / cm ² or more, and it was confirmed that it was excellent not only in heat insulation but also in mechanical properties.

On the other hand, the phenol foam obtained in Comparative Example 1 cannot impart effective flame retardancy and is easily burned because no flame retardant is added and contained. Further, in Comparative Example 2 using the powder of ammonium polyphosphate as it is which does not have a surface coating layer, the curing reaction of the phenol resin composition does not proceed smoothly, and therefore, a foam whose physical properties can be measured is obtained. I couldn't get it.

-Flame retardant dispersion stability test-
Using the resol-type phenol resin obtained in the same manner as in Example 1, water was appropriately added to the resol-type phenol resin to prepare various resol-type phenol resins having the viscosities shown in Table 2 below. Here, the viscosity of each resol type phenol resin was measured at a test temperature of 25 ° C. using a Brookfield type rotational viscometer according to JIS-K-7117-1. Next, 100 parts of each of the resole-type phenolic resins and 10 parts of the Terrage C80 powder, which is the flame retardant used in Example 1, were mixed, and then placed in a glass screw tube bottle having a capacity of 110 ml and a body diameter of 40 mm. It was housed and allowed to stand at room temperature for 1 week, and the presence or absence of precipitates and the height of the precipitate layer were evaluated in the screw tube bottle. In the evaluation, the case where the precipitate cannot be observed is marked with ◯, the case where the height of the settling layer is 5 mm or less is marked with Δ, and the case where the height of the settling layer exceeds 5 mm is marked with ×, and the results are shown in the table below. Shown in 2.

As shown in Table 2, when the viscosity of the resole-type phenol resin is 1000 mPa · s (25 ° C.), mixing with the Terrage C80 powder causes a remarkable precipitation, and a high precipitation layer. Was observed. On the other hand, in the resol type phenol resin having a viscosity of 3000 mPa · s (25 ° C.) or more, no precipitation was observed even when the Terrage C80 powder was mixed, and therefore the presence of a precipitate layer was observed. Was not confirmed. Further, when the viscosity of the resole-type phenol resin was 2000 mPa · s (25 ° C.), the presence of a certain amount of precipitate could be confirmed by mixing the Terrage C80 powder. It was judged that there was no problem in practical use.

Claims (11)

A flame-retardant phenol resin composition comprising at least ammonium polyphosphate having a surface coating layer as a flame retardant together with a resole-type phenol resin and an acid curing agent. The flame-retardant phenol resin composition according to claim 1, wherein the surface coating layer is formed of a sparingly soluble thermosetting resin. The flame-retardant phenol resin composition according to claim 2, wherein the sparingly soluble thermosetting resin is a melamine resin. The flame retardant according to any one of claims 1 to 3, wherein the flame retardant is contained in a proportion of 0.5 to 30 parts by mass with respect to 100 parts by mass of the resol type phenol resin. Sexual phenol resin composition. The flame-retardant phenol resin according to any one of claims 1 to 4, wherein the resol-type phenol resin is adjusted to have a viscosity of 2000 mPa · s or more at 25 ° C. Composition. The flame-retardant phenol resin composition according to any one of claims 1 to 5, further comprising a foaming agent. The flame-retardant phenol resin composition according to claim 6, wherein a halogenated alkene or a chlorinated aliphatic hydrocarbon and / or an aliphatic hydrocarbon is contained as the foaming agent. The flame-retardant phenol resin composition according to claim 6, wherein the foaming agent is a mixture of isopentane and isopropyl chloride. A flame-retardant material comprising a cured product obtained by curing the flame-retardant phenol resin composition according to any one of claims 1 to 5. A flame-retardant material comprising a foam obtained by foaming and curing the flame-retardant phenol resin composition according to any one of claims 6 to 8. ^{When the foam is heated at a radiant heat intensity of 50 kW / m 2} in accordance with the exothermic test method specified in ISO-5660, the total calorific value for 5 minutes after the start of heating is 8.0 MJ / m. The flame-retardant material according to claim 10, wherein the amount is ^{2 or less.}