KR20210075972A - Flame-retardant phenolic resin composition and flame-retardant material obtained therefrom - Google Patents

Abstract

To solve the problem in the case where ammonium polyphosphate capable of imparting high flame retardancy is blended with a phenol resin composition containing a resol type phenol resin as an essential component, a flame retardant material prescribed by the Japanese Building Standards Act is freed To provide a flame-retardant phenolic resin composition that can be formed to The phenol resin composition WHEREIN: The ammonium polyphosphate powder which has a surface coating layer was made to contain at least as a flame retardant together with a resol type phenol resin and an acid hardening|curing agent.

Description

Flame-retardant phenolic resin composition and flame-retardant material obtained therefrom

The present invention relates to a flame-retardant phenolic resin composition and a flame-retardant material obtained therefrom, in particular, a phenolic resin composition capable of advantageously forming a flame-retardant material comprising a cured phenolic resin, such as a flame-retardant phenolic resin foam (phenolic foam). And it relates to the flame-retardant material obtained from such a phenol resin composition.

Conventionally, a phenol resin material obtained by curing a phenol resin has been recognized by those skilled in the art as having relatively high flame retardancy per se, but as such, it is in the fields of architecture, civil engineering, electrical appliances, electrical and electronic parts, automobile parts, and the like. It does not sufficiently satisfy the safety standards required in the case, and it was not possible to advantageously impart a flame retardant material having a flame retardant property stipulated by the Japanese Building Standards Act, which is evaluated by an exothermic test by a cone calorimeter.

For this reason, in order to aim at the improvement of the flame-retardant characteristic of such a phenol resin material, a predetermined flame retardant is mix|blended with a phenol resin composition, and the improvement of the flame retardance of the target phenol resin material is aimed by the hardening. For example, in Japanese Patent Laid-Open No. 2-49037, a useful flame-retardant phenolic foam can be produced by using a phosphorus compound, a sulfur compound or a boron compound as a flame retardant and blending them into a resin composition for phenolic foam production. It turns out that there is In addition, in Japanese Patent Application Laid-Open No. 2007-161810 and Japanese Unexamined Patent Application Publication No. 2007-70511, etc., as an inorganic filler usually blended in the resin composition for phenol foam production, metal hydroxides such as aluminum hydroxide and magnesium hydroxide; oxides of metals such as calcium oxide and aluminum oxide; metal powder such as zinc powder; It has been found that the flame retardancy or fire resistance of a phenol foam obtained by foaming can be improved by using a carbonate of a metal such as calcium carbonate or magnesium carbonate. Moreover, in Unexamined-Japanese-Patent No. 8-176343, the resin composition formed by mix|blending ammonium polyphosphate as a non-halogen type flame retardant which can provide high flame retardance to resin is revealed.

By the way, with respect to a phenolic resin material composed of a cured product of a phenolic resin such as phenolic foam obtained by using a resol-type phenolic resin, which is one of the phenolic resins, and combining this with an acid curing agent or a foaming agent to foam and harden, a high degree of In order to impart flame retardancy, when a flame retardant composed of ammonium polyphosphate as proposed in Japanese Patent Application Laid-Open No. Hei 8-176343 is used, curing of the phenolic resin composition formed by blending such ammonium polyphosphate It was difficult to advance reaction effectively, and, therefore, there existed a problem that the target phenol resin material (hardened|cured material) became impossible to be obtained. In particular, the properties required for flame-retardant materials stipulated by the Japanese Building Standards Act, that is, radiant heat strength: when heated to 50 kW/m2, the total calorific value for 5 minutes after the start of heating is 8.0 MJ/m2 or less In order to obtain a property, As the compounding quantity of ammonium polyphosphate with respect to the phenol resin composition is increased, the hardening reaction of a phenol resin composition becomes difficult to advance, and it becomes impossible to obtain a phenol resin material (hardened|cured material) similar to the target phenol foam at all. will be.

In addition, according to the provisions of the Building Standards Act, the flame-retardant material satisfies the above total calorific value, and the maximum heat generation rate does not continuously exceed 200 kW/m for more than 10 seconds, and flame retardancy Although it is said that there are no cracks and holes penetrating to the rear surface that are harmful to the surface, conventional phenolic resin materials have not been able to sufficiently respond to such requests while ensuring useful properties as phenolic resins.

Japanese Laid-Open Patent Publication No. 2-49037 Japanese Laid-Open Patent Publication No. 2007-161810 Japanese Laid-Open Patent Publication No. 2007-70511 Japanese Patent Laid-Open No. 8-176343

Here, the present invention has been made on the background of the circumstances described above, and the problem to be solved is to provide a high degree of flame retardancy to a phenol resin composition containing a resol-type phenol resin as an essential component. It is to provide a flame retardant phenolic resin composition that can solve the problem in the case of blending ammonium polyphosphate that can be used, and can advantageously form a flame retardant material prescribed by the Japanese Building Standards Act, and such flame retardancy It is to provide the flame-retardant material prescribed|regulated by such a building standard law using a phenol resin composition.

And in the present invention, in order to solve the above problems, a flame retardant phenol resin composition comprising at least an ammonium polyphosphate powder having a surface coating layer as a flame retardant together with a resol-type phenol resin and an acid curing agent. , that is the gist of it.

Further, 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 poorly soluble thermosetting resin, and among them, as such a poorly soluble thermosetting resin, a melamine resin is preferable. will be hired

Moreover, according to another preferable aspect of the flame-retardant phenol resin composition which concerns on this invention, a flame retardant is contained in the ratio of 0.5-30 mass parts with respect to 100 mass parts of resol-type phenol resins.

Moreover, it is preferable that the said resol type phenol resin is adjusted so that it may have a viscosity of 2000 mPa*s or more at 25 degreeC.

In addition, according to another preferred aspect of the flame-retardant phenolic resin composition according to the present invention, a foaming agent is further contained, whereby a phenolic foam (phenolic resin foam) having special flame-retardant properties can be advantageously formed.

Further, as such a blowing agent, a halogenated alkene, or a chlorinated aliphatic hydrocarbon and/or an aliphatic hydrocarbon is preferably used, and among them, a mixture of isopentane and isopropyl chloride is advantageously used.

Further, in the present invention, a flame retardant material comprising a cured product obtained by curing the flame retardant phenol resin composition as described above is also a gist thereof, and further contains the above-described foaming agent. A flame-retardant material comprising a foam obtained by foaming and curing a flame-retardant phenol resin composition to be used is also a summary thereof.

In addition, in such a flame-retardant material, in general, the foam is, in accordance with the exothermic test method specified in ISO-5660, the radiant heat intensity: when heated to 50 kW/m 2 , the total calorific value for 5 minutes after the start of heating It has the characteristic of this 8.0 MJ/m<2> or less.

As described above, in the flame retardant phenol resin composition according to the present invention, as the flame retardant, not the ammonium polyphosphate itself, but the powder of ammonium polyphosphate on which the surface coating layer is formed is blended, so the resol-type phenol resin and the acid curing agent are used. The inhibitory action by ammonium polyphosphate on the curing reaction of the phenol resin composition comprising can be advantageously suppressed or prevented, thereby improving the flame retardancy of the target phenol resin material, which is a cured product of the phenol resin composition. can be effectively improved.

In particular, in the flame-retardant phenolic resin composition according to the present invention, a predetermined foaming agent is contained, and by foaming and curing, a phenolic foam excellent in flame-retardant properties can be advantageously formed, and therein, one of the major features of the present invention can be found

And, by using the flame-retardant phenolic resin composition according to the present invention, a flame-retardant phenolic resin material such as a flame-retardant phenolic foam can be easily and advantageously formed as a flame-retardant material prescribed by the Japanese Building Standards Act.

By the way, the resol-type phenolic resin used in the present invention as described above is in a liquid form, and advantageously contains aldehydes in a ratio of about 1.0 to 3.0 moles with respect to 1 mole of phenols, preferably Used in a ratio of about 1.5 to 2.5 moles, in the presence of an alkaline reaction catalyst, in the same manner as before, reacting at a temperature within the range of, for example, 50 ° C. to reflux temperature, followed by neutralization treatment; Next, dehydration and concentration are carried out under reduced pressure so that a predetermined characteristic value, for example, the viscosity at 25°C is 2000 mPa·s or more, and the moisture content is 3 to 20% by mass, preferably 5 to 18% by mass. After that, if necessary, a predetermined additive is added in the same manner as in the prior art, and it is manufactured.

Of course, in addition to the resol-type phenolic resin produced in this way, in the present invention, various known resol-type phenolic resins that can be cured with an acid curing agent can also be appropriately employed, and furthermore, modified with an appropriate modifying agent can be used. Even a resol type phenol resin can be used similarly.

Moreover, the liquid resol-type phenol resin obtained in this way is generally 2000 mPa*s or more at 25 degreeC, Preferably it is 2000-100000 mPa*s, More preferably, it is 3000-80000 mPa*s, and still more preferable. By having a viscosity of 4000 to 30000 mPa·s, the target preparation operation of the phenol resin composition, especially the dispersion and containing operation of the ammonium polyphosphate powder having a surface coating layer, can be realized more effectively, and further It becomes possible to increase the stability of a dispersed state advantageously, and thereby, the advantage of being able to aim at the further improvement of a flame retardance and thermal conductivity can be enjoyed. In addition, when the viscosity of such a resol-type phenolic resin is less than 2000 mPa·s, sedimentation of the ammonium polyphosphate powder having a surface coating layer becomes remarkable, localization thereof is caused, and non-uniformity in the phenolic resin material such as phenol foam to be formed is generated, sufficient flame retardancy and thermal conductivity are not obtained, and conversely, when the viscosity becomes too high, for example, exceeding 100000 mPa·s, it becomes difficult to obtain a phenolic resin material such as a phenolic foam. cause problems

In addition, as phenols used as one raw material of the resol-type phenol resin used in the present invention, phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, m-xylenol, bisphenol F, bisphenol A etc. are mentioned, Moreover, as aldehydes used in combination with these phenols, which are other raw materials, formaldehyde, paraformaldehyde, trioxane, polyoxymethylene, glyoxal, etc. are mentioned. . Moreover, potassium hydroxide, sodium hydroxide, barium hydroxide, calcium hydroxide, potassium carbonate, ammonia etc. are mentioned as a reaction catalyst. Of course, all of these phenols, aldehydes and reaction catalysts are by no means limited to the above examples, and various known ones may be appropriately used, and they may be used either alone or in combination of two or more. there will be

And, in the present invention, in the case of producing phenolic foam as a flame retardant phenolic resin material, various known foaming agents are used as the foaming agent together with the resol-type phenolic resin as described above, especially in the present invention. In this case, chlorinated aliphatic hydrocarbons and/or aliphatic hydrocarbons and halogenated alkenes, which have a low global warming coefficient, are advantageously used, and phenol resin foams such as phenol foam are formed.

Among them, as for the chlorinated aliphatic hydrocarbon as the blowing agent, generally, a chlorinated product of a linear or branched aliphatic hydrocarbon having about 2 to 5 carbon atoms is preferably used, and the number of bonds of the chlorine atom is generally , about 1 to 4 pieces. Specific examples of the chlorinated aliphatic hydrocarbon include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Although these may be used individually by 1 type, or may combine 2 or more types, among them, chloropropanes, such as a propyl chloride and isopropyl chloride, are preferable, and especially isopropyl chloride comes to be used preferably.

In addition, as the aliphatic hydrocarbon as the blowing agent, a conventionally known hydrocarbon-based blowing agent having about 3 to 7 carbon atoms can be appropriately selected and used, and specifically, propane, butane, pentane, isopentane, hexane, isohexane, Neohexane, heptane, isoheptane, cyclopentane, etc. are mentioned, Among them, it will be used 1 type or in combination of 2 or more type.

Further, in the present invention, a mixed foaming agent obtained by combining the above chlorinated aliphatic hydrocarbon and an aliphatic hydrocarbon is preferably used, and the mixing ratio thereof is, in mass ratio, aliphatic hydrocarbon: chlorinated aliphatic hydrocarbon = 25: 75 to 5: 95. Within the scope, it is advantageously employed. In addition, 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 more advantageously achieved.

Further, in the present invention, as the foaming agent, halogenated alkene is also advantageously used, thereby contributing to further improvement of the properties of the resulting phenolic foam, in particular, flame retardancy and heat insulation properties. Halogenated alkenes having such properties include those referred to as halogenated olefins and halogenated hydroolefins, and are unsaturated hydrocarbon derivatives having about 2 to 6 carbon atoms, which are generally made by bonding and containing chlorine or fluorine as halogens, For example, tetrafluoropropene, fluorochloropropene, tri, which is obtained by substituting and containing halogen such as fluorine or chlorine in propene, butene, pentene and hexene having 3 to 6 fluorine substituents and fluoromonochloropropene, pentafluoropropene, fluorochlorobutene, and hexafluorobutene, and mixtures of two or more thereof.

Specifically, as a hydrofluoroolefin (HFO) which is one of such halogenated alkene (halogenated olefin), for example, pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO1225ye) Proprofen, 1,3,3,3-tetrafluoropropene (HFO1234ze), 2,3,3,3-tetrafluoropropene (HFO1234yf), 1,2,3,3-tetrafluoropropene Tetrafluoropropene such as phen (HFO1234ye), trifluoropropene such as 3,3,3-trifluoropropene (HFO1243zf), tetrafluorobutene isomer (HFO1354), pentafluorobutene isomer ( HFO1345), hexafluorobutene isomers (HFO1336) such as 1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz), heptafluorobutene isomers (HFO1327), heptafluoro and lopentene isomers (HFO1447), octafluoropentene isomers (HFO1438), and nonafluoropentene isomers (HFO1429). In addition, as the hydrochlorofluoroolefin (HCFO), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene ( HCFO-1233xf), dichloro trifluoropropene (HCFO1223), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 1-chloro-1,3,3-trifluoroprop phen (HCFO-1233zb), 2-chloro-1,3,3-trifluoropropene (HCFO-1233xe), 2-chloro-2,2,3-trifluoropropene (HCFO-1233 xc), 3-chloro-1,2,3-trifluoropropene (HCFO-1233ye), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc), and the like.

In addition, each foaming agent as mentioned above is 1-30 mass parts generally with respect to 100 mass parts of resol-type phenol resins in the total amount, Preferably it will be used in the ratio of 5-25 mass parts.

In addition, the blowing agent preferably used in the present invention is characterized in that it contains the above-mentioned chlorinated aliphatic hydrocarbons and/or aliphatic hydrocarbons, or halogenated alkene, as long as it does not adversely affect the object of the present invention. For example, fluorinated hydrocarbons such as 1,1,1,3,3-pentafluorobutane (alternative Freon), chlorinated hydrocarbons such as trichloromonofluoromethane and trichlorotrifluoroethane, water, iso It is also possible to contain an ether compound such as propyl ether, a gas such as nitrogen, argon and carbon dioxide gas, air, and the like in an appropriate proportion.

The acid curing agent used in the present invention is a component (curing catalyst) for accelerating the curing reaction of the resol-type phenol resin as described above, and a conventionally known acid curing agent is appropriately selected and used. And as such an acid hardening|curing agent, For example, Aromatic sulfonic acids, such as benzenesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, toluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid; aliphatic sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid; Inorganic acids, such as sulfuric acid, phosphoric acid, polyphosphoric acid, and hydroboric acid, etc. are mentioned, These may be used independently and even if 2 or more types are used in combination, there is no problem. In addition, among these exemplary acid curing agents, aromatic sulfonic acids such as phenolsulfonic acid, toluenesulfonic acid, and naphthalenesulfonic acid can achieve an appropriate curing rate in the production of phenolic foam. Since the balance of foaming becomes further more favorable, and by this, a preferable foaming structure is implement|achieved, it comes to be used especially preferably. Especially, in this invention, the combined use of para-toluenesulfonic acid and xylenesulfonic acid is recommended. As their usage ratio, it is preferable that the usage-amount of para-toluenesulfonic acid is larger than the usage-amount of xylenesulfonic acid on a mass basis. Specifically, in a mass ratio, para-toluenesulfonic acid:xylenesulfonic acid is 51:49-95: Within the range of 5, it is advantageously employed.

In addition, the usage-amount of such an acid hardening agent is set suitably according to the type, temperature conditions at the time of mixing with the said resol-type phenol resin, etc., but in this invention, 100 mass parts of resol-type phenol resins , generally 1 to 50 parts by mass, preferably 5 to 30 parts by mass, particularly preferably 7 to 25 parts by mass. When the amount used is less than 1 part by mass, the progress of curing is slow, and conversely, when it exceeds 50 parts by mass, the curing rate becomes excessively high, which causes a problem in that it is difficult to advantageously obtain the target phenolic foam.

And, according to the present invention, the phenol resin composition constituted by containing the resol-type phenol resin and the acid curing agent as described above contains at least an ammonium polyphosphate powder having a surface coating layer as a flame retardant, whereby the polyphosphoric acid Compared to the case of using ammonium as it is, the curing reaction of the phenol resin composition can proceed effectively, thereby exhibiting useful properties in compressive strength and initial thermal conductivity, etc. along with excellent flame retardant properties. Curing of phenol resins such as phenol foam The product can be obtained advantageously.

In addition, the ammonium polyphosphate powder having a surface coating layer used therein is one in which particles of ammonium polyphosphate are coated or microencapsulated with a thermosetting resin, or the surface of the ammonium polyphosphate particles is coated with a melamine monomer or other nitrogen-containing organic compound. The thing which coat|covered, the thing which gave surfactant or silicone treatment, etc. are mentioned, Usually, it selects suitably from a commercial item, and is used. For example, Exolit AP462 available from Clariant Chemicals Co., Ltd., FR CROS486, FR CROS487, Terage C30, Terage C60, Terage C70, Terage C80, etc. available from CBC Corporation. And it is preferable that the surface coating layer in such an ammonium polyphosphate powder is sparingly soluble, ie, poorly soluble in water, with respect to the phenol resin composition used as a liquid, and especially, as such a sparingly soluble thermosetting resin, phenol Resin, a melamine resin, etc. are used, Especially, a melamine resin will be used preferably. Moreover, even if it is a soluble thermosetting resin, by advancing the hardening reaction of the surface coating layer formed by it, and setting it as a poorly soluble surface coating layer, it will be used advantageously. And, by having a surface coating layer made of such a poorly soluble thermosetting resin, a cured product such as a phenol foam having excellent properties such as compressive strength and initial thermal conductivity can be advantageously obtained.

Moreover, as the usage-amount of the ammonium polyphosphate powder which has such a surface coating layer, with respect to 100 mass parts of resol-type phenol resins, generally 0.5-30 mass parts, Preferably it is 1-25 mass parts, More preferably, 2 - In the range of 20 mass parts, it will determine suitably. When the amount of the ammonium polyphosphate powder having such a surface coating layer is too small, it is difficult to sufficiently exhibit the effect of imparting flame retardancy to the phenol resin material composed of a cured product such as phenol foam, and the addition amount is too large. In addition to making it difficult to avoid the inhibitory action on the curing reaction of the phenolic resin composition, it increases the viscosity of the composition to which it is added, causing problems such as poor stirring, and the compressive strength of the phenolic resin material It causes problems such as deterioration of properties such as thermal conductivity.

Moreover, as an average particle diameter of the ammonium polyphosphate powder which has such a surface coating layer, it is generally about 1-100 micrometers, Preferably it is about 5-50 micrometers. When the particle diameter of the ammonium polyphosphate powder having the surface coating layer is too small, problems such as handling and uniform dispersion in the phenol resin composition become difficult, and even if the particle diameter becomes too large, in the phenol resin composition It is difficult to obtain a uniform dispersion effect, thereby causing a problem that the object of the present invention cannot be sufficiently achieved.

As described above, in the present invention, as the flame retardant, an ammonium polyphosphate powder having a surface coating layer is used, but if necessary, it is also possible to use other known flame retardants that do not impair the object of the present invention in combination. In addition, such other known flame retardants include, for example, phenylphosphonic acid, guanidine phosphate derivatives, phosphate carbamate derivatives, red phosphorus, phosphorus-based flame retardants such as ammonium phosphate, sulfamic acid-based flame retardants, boric 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, together with the resol-type phenol resin or acid curing agent as described above, as a flame retardant, ammonium polyphosphate powder having a surface coating layer is added as an essential component. In the case of production of phenolic foam, a predetermined foaming agent, in particular, a chlorinated aliphatic hydrocarbon and/or an aliphatic hydrocarbon, or a halogenated alkene is blended, and in addition, if necessary, a conventionally known foam stabilizer, inorganic filler , it is also possible to contain a plasticizer, urea, and the like.

Here, among the additives added and contained according to such necessity, the foam stabilizer is blended in order to aid in mixing and emulsification of the mixed components in the phenol resin composition, dispersion of the generated gas, stabilization of the foam cell membrane, and the like. In addition, as such a foaming agent, it is not specifically limited, Although all of the various foaming agents conventionally used in this technical field are all selectively used, Among them, polysiloxane-type compound, polyoxyethylene sorbitan fatty acid ester, alkylphenol Nonionic surfactants, such as an ethylene oxide adduct and the ethylene oxide adduct of castor oil, are used especially preferably. In addition, these foam stabilizers can also be used in combination of 2 or more types other than being used independently. Moreover, there is no restriction|limiting in particular also about the usage-amount, Generally, it will be used within the range of 0.5-10 mass parts with respect to 100 mass parts of resol-type phenol resins.

Other examples of the inorganic filler include hydroxides of metals such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide, oxides of metals such as magnesium oxide, aluminum oxide, and zinc oxide, metal powders such as zinc, calcium carbonate, carbonate and carbonates of metals such as magnesium, barium carbonate and zinc carbonate. In addition, these inorganic fillers can also be used in combination of 2 or more types other than being used independently. Of course, by use of such an inorganic filler, the improvement of flame retardancy and fire resistance can be achieved, but it goes without saying that the amount of the use is appropriately determined within the range of the amount of use that does not impair the purpose of the present invention. there is no

In addition, the plasticizer is a cured phenolic resin material, which can be advantageously used in the case of manufacturing a phenolic foam. By its use, the plasticizer imparts flexibility to the cell wall of the phenolic foam, and the thermal insulation performance is improved over time. It is to exhibit characteristics, such as suppressing deterioration. There is no restriction|limiting in particular as this plasticizer, Well-known plasticizer conventionally used for manufacture of phenolic foam, for example, triphenyl phosphate, dimethyl terephthalate, dimethyl isophthalate, etc. can be used, In addition, the use of polyester polyol is also valid In particular, since the polyester polyol has a structure including an ester bond and a hydroxyl group, which is hydrophilic and has excellent surface activity, compatibility with the hydrophilic phenol resin solution is good, and it can be uniformly mixed with the phenol resin. have. In addition, by using this polyester polyol, it is easy to produce a phenol resin foam (phenol foam) that is homogeneous in quality by avoiding the uneven distribution of the cells, uniformly distributing the cells throughout the foam, and is said to be a preferable plasticizer. can Moreover, such a plasticizer is 0.1-20 mass parts normally with respect to 100 mass parts of resol-type phenol resin, Preferably it is 0.5-15 mass parts, More preferably, it is used in the range of 1-12 mass parts, Thereby, the effect of imparting flexibility to the cell wall is well exhibited without impairing the other performance of the obtained phenolic foam, and the object of the present invention can be achieved even more favorably.

In addition, in the flame retardant phenolic resin composition constituted according to the present invention, urea can be preferably added and contained. By containing such urea, the initial thermal conductivity of the obtained phenolic resin material such as phenolic foam can be effectively reduced, and furthermore, a phenolic resin material such as a phenolic foam having low strength and particularly low brittleness can be obtained, among them. It also contributes advantageously to keeping the thermal conductivity low over a long period, and thereby, it becomes easy to obtain a phenolic resin material, such as a phenolic foam, which has the outstanding heat insulation performance stably for a long time.

By the way, the flame-retardant phenolic resin composition according to the present invention containing the above-described compounding components is, for example, the above-described resol-type phenolic resin, and as a flame retardant, ammonium polyphosphate powder having the above-mentioned surface coating layer is added. to the mixture, further, if necessary, adding and mixing the other flame retardants, inorganic fillers, foam stabilizers, plasticizers, urea, etc., and to the obtained mixture, if necessary, a predetermined foaming agent, in particular, the above It is possible to prepare by adding a chlorinated aliphatic hydrocarbon and/or an aliphatic hydrocarbon, or a halogenated alkene, and then supplying this together with an acid curing agent to a mixer and stirring.

In addition, when the phenol resin composition prepared in this way is used and cured to form a target phenol resin material such as a solid material or a foam, various conventionally known methods can be employed, For example, as a method for producing a phenol foam, (1) a molding method in which a phenol resin composition is poured on an endless conveyor belt to foam and harden, (2) a method for partially foaming and curing by spot filling , (3) a method of filling in a mold and foaming and curing under pressure, (4) a method of forming a foam block by filling in a predetermined large space, foaming and curing, (5) press-fitting into a cavity The method of filling and foaming is mentioned.

And among these phenol foam molding methods, according to the molding method of (1) above, the phenol resin composition as described above is discharged on a continuously moving carrier, and the discharged product is foamed via a heating zone and Methods are employed that are molded together to produce the desired phenolic foam. Specifically, after discharging the phenolic resin composition 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 and moved to the curing furnace, and in the curing furnace, from above to another conveyor belt Press to adjust this resin material to a predetermined thickness, foam and harden it under conditions of about 60 to 100 ° C. for 2 to 15 minutes, and then cut the foam taken out of the curing furnace to a predetermined length. A phenolic foam of the shape is to be manufactured.

In addition, the face material used here is not particularly limited, and in general, natural fibers, synthetic fibers such as polyester fibers and polyethylene fibers, nonwoven fabrics such as inorganic fibers such as glass fibers, papers, aluminum foil coated nonwoven fabrics, metal plates, Although metal foil and the like are used, in general, glass fiber nonwoven fabric, spunbond nonwoven fabric, aluminum foil coated nonwoven fabric, metal plate, metal foil, plywood, structural panel, particle board, hard board, wood-based cement plate, flexible plate, pearlite plate, silicic acid Calcium board, magnesium carbonate board, pulp cement board, seizing board, medium density fiber board, gypsum board, lath sheet, volcanic vitreous composite board, natural stone, brick, tile, glass molded body, lightweight foam concrete molded body, cement mortar molded body, A molded article containing, as a binder component, a water-setting cement hydrate, such as a glass fiber reinforced cement molded article, is preferably used. In addition, this face material may be formed on one side of a phenolic foam, and even if it forms on both surfaces, there is no trouble at all. Moreover, when it forms on both surfaces WHEREIN: The same thing may be sufficient as a face material, and a different thing may be sufficient as it. Moreover, even if it forms by bonding face materials together later using an adhesive agent, there is no trouble.

Therefore, since a predetermined ammonium polyphosphate powder is dispersed and contained in a phenolic resin material (cured product) such as phenolic foam obtained in this way, the flame retardancy as a whole material can be effectively increased, and exothermicity due to the cone calorimeter The test WHEREIN: It is supposed to be equipped with the characteristic as a flame retardant material prescribed|regulated by the Japanese Building Standards law advantageously. Specifically, based on the exothermic test method specified in ISO-5660, when heated to radiant heat intensity: 50 kW/m2, the total calorific value from the start of heating until 5 minutes has elapsed is 8.0 MJ/m2 or less. It becomes a material to be advantageously provided, and thereby, as a flame retardant material, can be advantageously used in various applications.

Also, such a phenolic resin material such as phenolic foam is advantageously generally 0.0230 W/m·K (20° C.) or less, preferably 0.0200 W/m·K (20° C.) or less, more preferably has an initial thermal conductivity of 0.0195 W/m·K (20° C.) or less, and can be easily manufactured, and in the case of a phenol foam, the closed cell ratio is generally 80% or more, preferably is constituted so as to be 85% or more, more preferably 90% or more, whereby it is produced as one that advantageously exhibits excellent low thermal conductivity properties along with excellent flame retardancy.

Further, in the phenolic resin material such as phenolic foam obtained according to the present invention, the density is generally 10 to 150 kg/m 3 , preferably 15 to 100 kg/m 3 , more preferably 15 to 70 kg /m 3 , more preferably 20 to 50 kg/m 3 , and most preferably 20 to 40 kg/m 3 . In addition, in the phenolic foam having a density lower than 10 kg/m 3 , the strength is low, and there is a fear that the foam (foam) may be damaged during transportation or construction. Moreover, when a density is low, there exists a tendency for a bubble film to become thin. And when the cell membrane is thin, the foaming agent in the foam (foam) is easily replaced with air, and the cell membrane is easily torn during foaming, so it is difficult to obtain a high closed cell structure, and the long-term thermal insulation performance is lowered. tends to be On the other hand, when the density exceeds 150 kg/m 3 , heat conduction of the solid derived from the solid component including the phenol resin increases, so that the thermal insulation performance of the phenol foam tends to decrease.

Example

In the following, some examples of the present invention are shown and compared with comparative examples to clarify the characteristics of the present invention more specifically, but the present invention is not subject to any restrictions by the description of such examples. things needless to say. Further, in addition to the following examples, in addition to the specific techniques described above, various changes, corrections, improvements, etc. can be added to the present invention based on the knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that In addition, the percentage (%) and a part shown below are all shown on a mass basis, unless there is particular notice.

-Example 1-

In a three-necked reaction flask equipped with a reflux device, a thermometer, and a stirrer, 1600 parts of phenol, 2282 parts of 47% formalin, and 41.6 parts of a 50% aqueous sodium hydroxide solution were charged, and the reaction was performed at a temperature of 80°C for 70 minutes. Then, after cooling to 40 degreeC, it neutralized with 50% para-toluenesulfonic acid aqueous solution, and then dehydrated and concentrated under reduced pressure and heating to 10% of moisture content: a liquid resol type phenol resin was obtained. This obtained phenol resin had the characteristic of viscosity: 10000 mPa*s/25 degreeC, number average molecular weight: 380, and free phenol content: 4.0%.

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

Next, with respect to 108 parts of the phenol resin mixture thus obtained, 10 parts of ammonium polyphosphate powder having a surface coating layer made of a melamine resin as a flame retardant (Tage C80 sold by CBC Co., Ltd., average particle diameter: 19 µm) and iso as a foaming agent 9.0 parts of a mixture consisting of a mass ratio of propyl chloride: isopentane = 85: 15, and 16 parts of a mixture of para-toluenesulfonic acid: xylenesulfonic acid = 2:1 (mass ratio) as a curing agent, stirred and mixed, resin for phenol foam production A foamable phenol resin molding material as a composition was prepared.

Thereafter, using the foamable phenolic resin molding material prepared in this way, it is heated to 70 to 75°C in advance, and is poured into a mold having a length: 300 mm, a width: 300 mm, and a thickness: 50 mm. The mold was accommodated in a drying machine at 70 to 75°C, foam cured for 10 minutes, and then post-cured by heating in a heating furnace at a temperature of 70°C for 12 hours to prepare a phenolic foam (phenolic resin foam).

-Example 2-

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

-Example 3-

In Example 1, the blowing agent was changed to hydrofluoroolefin (1,1,1,4,4,4-hexafluoro-2-butene: HFO-1336mzz, manufactured by Chemours), and the amount added was 17.5 Except having set it as part, it carried out similarly to Example 1, and manufactured the phenol foam.

-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 was not added as a flame retardant.

-Comparative Example 2-

In Example 1, the same procedure as in Example 1 was followed except that ammonium polyphosphate powder having no surface coating layer (FR CROS484 sold by CBC Co., Ltd., average particle diameter: 18 µm) was used as the flame retardant. was attempted, but the curing reaction of the phenol resin composition did not proceed sufficiently, and thus a foam capable of measuring physical properties could not be obtained.

Then, using the various phenolic foams (phenolic resin foams) obtained in this way, a combustion test for evaluation of the density, initial thermal conductivity, closed cell rate, compressive strength, and flame retardancy (total calorific value, maximum exothermic rate, situation after the test) , respectively, were measured or evaluated according to the following method, and the results obtained are shown in Table 1 below.

(1) Determination of density

According to the description of "5.6 density" in JIS-A-9511 (2003), the density of each foam was measured.

(2) Measurement of initial thermal conductivity

Using a phenolic resin foam sample having a width of 300 mm, cut it to a length of 200 mm (thickness is 50 mm), and set the low-temperature plate: 10°C and the high-temperature plate: 30°C, JIS-A-1412- 2 (1999), it is measured using a thermal conductivity measuring device: HC-074 304 (manufactured by Eiko Seiki Co., Ltd.) in accordance with the "Heat Flow Meter Method" specified in (1999). In addition, here, the thermal conductivity after leaving the phenol resin foam sample to stand in 70 degreeC atmosphere for 4 days was measured as initial stage thermal conductivity.

(3) Measurement of closed cell ratio

In accordance with the provisions of ASTM-D2856, the closed cell ratio of the phenolic resin foam sample was measured.

(4) Measurement of compressive strength

According to the description of "5.9 compressive strength" in JIS-A-9511 (2003), the compressive strength of the phenol resin foam sample was measured.

(5) Combustion test (flammability evaluation)

From each phenol foam, a test body was cut out so that a length x width might become 99 ± 1 mm, and each test body was prepared. In addition, the thickness of this test body 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 provisions of ISO-5660, compiled by the Japan Construction Testing Laboratory, "fireproofing performance test and evaluation work method 4.12. 1 Exothermicity test and evaluation method", the total calorific value and the maximum exothermic rate at heating time: 5 minutes were measured, respectively. As a measurement result, it measured about 3 test bodies cut out from each foam, and employ|adopted the average value of the obtained measured value. Moreover, it observed about the test body after an evaluation test, and the presence or absence of the crack or hole penetrating to the back surface was investigated.

As is evident from the results of Table 1, all of the phenolic foams formed in Examples 1 to 3 had a total calorific value of 8 MJ/m 2 or less, and a maximum exothermic rate of not more than a specified value in the combustion test, It was confirmed that it was useful as a flame retardant material prescribed by the Japanese Building Standards Act. Among them, all of the phenolic foams obtained in Examples 1 and 3 had an initial thermal conductivity of 0.0193 W/m·K or less, a closed cell ratio of 91% or more, and a compressive strength of about 16 N/cm 2 or more. It became this, and it confirmed that it was excellent also in mechanical properties with heat insulating property.

On the other hand, since the phenolic foam obtained in Comparative Example 1 does not contain any flame retardants, effective flame retardancy cannot be imparted, it is easily combusted, and the powder of ammonium polyphosphate that does not have a surface coating layer as it is. In the used comparative example 2, the hardening reaction of a phenol resin composition did not advance smoothly, Therefore, the foam in which a physical-property measurement was possible was not obtained.

-Flame retardant dispersion stability test-

Using the resol-type phenol resin obtained in the same manner as in Example 1, water was appropriately added thereto, and various resol-type phenol resins having viscosities shown in Table 2 below were prepared. Here, the viscosity of each resol type phenol resin was measured at test temperature: 25 degreeC using a Brookfield type rotational viscometer according to JIS-K-7117-1. Next, 100 parts of each of these resol-type phenolic resins and 10 parts of Terageu C80 powder, which is a flame retardant used in Example 1, were mixed, then placed in a glass screw tube bottle having a capacity of 110 ml and a body diameter of 40 mm, and allowed to stand at room temperature for 1 week. (靜置) was carried out, and the presence or absence of deposits generated in these screw tube bottles and the height of the sedimentation layer were evaluated. In the evaluation, the case in which no sediment can be observed is denoted as ○, the case where the height of the sedimentation layer is 5 mm or less is denoted by , and the case where the height of the sedimentation layer exceeds 5 mm is denoted by ×, and the results are shown in the table below. 2 is shown.

As shown in Table 2, when the viscosity of the resol-type phenolic resin is 1000 mPa·s (25° C.), mixing with the Terageu C80 powder causes significant precipitation, resulting in the formation of a high precipitation layer. occurrence was confirmed. On the other hand, in the resol-type phenolic resin having a viscosity of 3000 mPa·s (25° C.) or higher, even when the Teragee C80 powder was mixed, the formation of the precipitate was not confirmed, and therefore the presence of the precipitate layer was not confirmed. In addition, when the viscosity of the resol-type phenol resin was 2000 mPa·s (25°C), the presence of a certain amount of precipitate was confirmed by mixing the Terageu C80 powder, but it is a problem in practical use. was judged to be non-existent.

Claims (11)

A flame-retardant phenol resin composition comprising at least an ammonium polyphosphate powder having a surface coating layer as a flame retardant together with a resol-type phenol resin and an acid curing agent. The method of claim 1,
The flame-retardant phenolic resin composition in which the said surface coating layer is formed with a sparingly soluble thermosetting resin. 3. The method of claim 2,
The flame-retardant phenol resin composition in which the said sparingly soluble thermosetting resin is a melamine resin. 4. The method according to any one of claims 1 to 3,
The flame-retardant phenol resin composition in which the said flame retardant is contained in the ratio of 0.5-30 mass parts with respect to 100 mass parts of the said resol-type phenol resin. 5. The method according to any one of claims 1 to 4,
The flame-retardant phenolic resin composition, characterized in that the resol-type phenolic resin is adjusted to have a viscosity of 2000 mPa·s or more at 25°C. 6. The method according to any one of claims 1 to 5,
A flame retardant phenolic resin composition further containing a blowing agent. 7. The method of claim 6,
A flame-retardant phenolic resin composition comprising, as the blowing agent, a halogenated alkene, or a chlorinated aliphatic hydrocarbon and/or an aliphatic hydrocarbon. 7. The method of claim 6,
The flame-retardant phenol resin composition, wherein the blowing 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. 11. The method of claim 10,
In accordance with the exothermic test method specified in ISO-5660, when the foam is heated to a radiant heat intensity of 50 kW/m2, the total calorific value for 5 minutes after the start of heating is 8.0 MJ/m2 or less. Flame-retardant material .