JP2010163502A - Expandable resol type phenolic resin moulding material and phenolic resin foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an expandable phenolic resin molding material which gives a phenolic resin foam having excellent strength and reduced shrinkage and a phenolic resin foam having the properties. <P>SOLUTION: In the expandable resol type phenolic resin molding material including a liquid resol type phenolic resin, a blowing agent, a foam stabilizer, and an acid curing agent, an ammonium compound is mixed as an additive. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a foamable resol-type phenol resin molding material and a phenol resin foam using the same. More specifically, the present invention relates to a foamable resol-type phenol resin molding material that provides a phenol resin foam having excellent strength and little shrinkage, and a phenol resin foam having the above-mentioned properties obtained by foaming and curing the same. is there.

  2. Description of the Related Art Conventionally, phenol resin foams are excellent in heat insulation, flame retardancy, fire resistance, and the like, and are therefore used as heat insulation materials in construction and other industrial fields.

  Phenolic resin foams are often used in various applications, but depending on the application, high mechanical properties, particularly those with low brittleness may be required. Conventionally, as a phenolic resin foam excellent in mechanical strength and brittleness, a resin material containing a liquid resol type phenolic resin, a foaming agent, a foam stabilizer and an acid curing agent and a molding material containing a nitrogen-containing crosslinked cyclic compound is used. It has been proposed (see Patent Document 1).

  As described above, the phenolic resin foam is very useful as a heat insulating material. However, since the curing of the resin proceeds by dehydration condensation in the production, the shrinkage occurs as the curing proceeds, and the space between the face material and the resin portion is increased. There has been a problem that defects such as peeling occur or the surface material is wavy and the surface is wavy.

  In addition, heat insulation performance increases in proportion to the thermal conductivity and thickness, so a thicker one is required, and lighter one is required from the viewpoint of workability, but this shrinkage increases as the thickness increases, Moreover, since there exists a tendency which becomes large as a density falls, the phenol resin foam of lower shrinkage was calculated | required.

  Under such circumstances, an object of the present invention is to provide a foamable phenol resin molding material that provides a phenol resin foam having excellent strength and low shrinkage, and a phenol resin foam having the above-described characteristics. Is.

  As a result of intensive studies to develop a foamable phenolic resin molding material having the above-mentioned properties, the present inventors have found that a foamable resol-type phenol containing a liquid resol-type phenolic resin, a foaming agent, a foam stabilizer, and an acid curing agent. In the resin molding material, it discovered that the objective could be achieved by mixing an ammonium compound as an additive in the same material, and came to complete this invention based on this knowledge.

That is, the present invention
(1) A foamable resole type characterized in that an ammonium compound is mixed as an additive in a foamable resole type phenolic resin molding material containing a liquid resol type phenolic resin, a foaming agent, a foam stabilizer and an acid curing agent. Phenolic resin molding materials,
(2) The foamable resol-type phenol resin molding material according to (1), wherein the ammonium compound is ammonium chloride,
(3) The foamable resol-type phenol resin molding material according to (1), wherein the ammonium compound is ammonium nitrate,
(4) The foamable resole type according to any one of (1) to (3) above, wherein 0.1 to 10 parts by weight of an ammonium compound is contained per 100 parts by weight of the liquid resol type phenol resin. Phenolic resin molding materials,
(5) The foamable resol-type phenol resin molding material according to any one of the above (1) to (4), further comprising a nitrogen-containing crosslinked cyclic compound,
(6) A phenol resin foam obtained by foam-curing the foamable resol-type phenol resin molding material according to any one of (1) to (5) above,
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, the foamable phenol resin molding material which gives the phenol resin foam excellent in an intensity | strength and few shrinkages, and the phenol resin foam which has the said characteristic can be obtained.

  First, the foamable resol type phenol resin molding material of the present invention will be described.

  The foamable resol-type phenol resin molding material of the present invention contains a liquid resol-type phenol resin, a foaming agent, a foam stabilizer, an acid curing agent, an ammonium compound, and optionally a plasticizer, an inorganic filler, and other additives. .

  The liquid resol-type phenol resin comprises phenols such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, and resorcin, and modified products thereof, and aldehydes such as formaldehyde, paraformaldehyde, furfural, and acetaldehyde. A phenol resin obtained by adding a catalytic amount of an alkali such as potassium hydroxide or calcium hydroxide and reacting the same is not limited thereto. The ratio of the phenols and aldehydes used is not particularly limited, but is usually about 1.0: 1.5 to 1.0: 3.0, preferably 1.0: 1.8 to 1.0 in molar ratio. : 2.5.

  Examples of the blowing agent include propane, butane, pentane, isopentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and other low-boiling hydrocarbons, ethers such as isopropyl ether, trichloromonofluoromethane, Those containing an organic non-reactive foaming agent such as halogenated hydrocarbons such as trichlorotrifluoroethane and isopropyl chloride, or a mixture of these compounds are used. Here, the non-reactive foaming agent refers to a substance that itself can volatilize under foaming conditions to foam a phenol resin.

  In addition to the blowing agent, a gas such as nitrogen gas, oxygen gas, argon gas, carbon dioxide gas, or a mixed gas thereof may be used.

  In the foamable phenol resin molding material of the present invention, the amount of the foaming agent used is usually 1 to 20 parts by weight, preferably 5 to 10 parts by weight, with respect to 100 parts by weight of the liquid resol type phenol resin.

  As the foam stabilizer, one containing castor oil ethylene oxide (hereinafter, ethylene oxide is abbreviated as “EO”) adduct is preferably used.

  Castor oil is a non-drying oil obtained by pressing from seeds such as castor sesame, and mainly contains unsaturated acids such as ricinoleic acid, oleic acid and linoleic acid, and small amounts of saturated acids such as stearic acid and dioxystearic acid. Is included.

  In the said foam stabilizer, what added EO more than 20 mol and less than 50 mol with respect to 1 mol of said castor oil is suitable.

  The reason why the added mole number of EO is more than 20 moles and less than 50 moles is that when the added mole number of EO is more than 20 moles and less than 50 moles, a hydrophobic group mainly composed of a long-chain hydrocarbon group of castor oil The hydrophilic groups mainly composed of polyoxyethylene groups formed by EO of more than 20 mol and less than 50 mol are arranged in a balanced manner in the molecule, and a good surface activity can be obtained. By using a castor oil EO adduct having surface activity, the bubble diameter of the phenol resin foam is kept small, the flexibility is given to the bubble wall, and cracking of the bubble wall is prevented. This is because an effect can be obtained. The added mole number of EO is more preferably 25 to 45 moles.

  In the present invention, the castor oil EO adduct is used as a suitable component as the foam stabilizer, but in addition to this, a dimethylpolysiloxane-polyoxyalkylene copolymer, a dimethylpolysiloxane-polyoxyethylene-polyoxypropylene copolymer. Polymers, castor oil propylene oxide adducts, and the like can also be used.

  In the foamable phenol resin molding material of the present invention, the content of the castor oil EO adduct is preferably 1 to 5 parts by weight and more preferably 2 to 4 parts by weight per 100 parts by weight of the phenol resin. . When the content of the castor oil EO adduct is less than 1 part by weight, the bubbles are difficult to be uniformly reduced. On the other hand, when the content exceeds 5 parts by weight, the water absorption of the produced phenolic resin foam is increased and the production cost is increased. Becomes higher.

  Examples of the acid curing agent include inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphtholsulfonic acid, and phenolsulfonic acid. These acid curing agents may be used alone or in combination of two or more.

  Examples of the ammonium compound include ammonium salts such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium carbonate, ammonium oxalate, and organic ammonium compounds such as alkyl quaternary ammonium salts. These ammonium compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the foamable phenol resin molding material of the present invention, the addition amount of the ammonium compound is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the liquid resol type phenol resin. 5 parts by weight.

  As the method for adding the ammonium compound, it can be used by dissolving it in water or another solvent or in a solid state. When the compound is used as a solid, it may take time to dissolve in the liquid resol type phenol resin.

  In the foamable phenolic resin molding material of the present invention, it is preferable to add a nitrogen-containing crosslinked cyclic compound. Examples of the nitrogen-containing bridged cyclic compound include quinuclidine, pyridine, hexamethylenetetramine (hexamine) and the like. These may be used alone or in combination of two or more. Of these, hexamethylenetetramine is preferred from the standpoints of effects and availability. The nitrogen-containing bridged cyclic compound is preferably used in the form of a furfuryl alcohol solution or the like.

  The amount of the nitrogen-containing crosslinked cyclic compound added is preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the liquid resol type phenolic resin, from the viewpoint of balance between effect and economy. Is 0.3 to 7 parts by weight.

  Polyester polyol, polyethylene glycol, etc., which are reaction products of phthalic acid and diethylene glycol, are used as plasticizers that are optional additives, and inorganic fillers that are also optional additives include calcium carbonate, magnesium carbonate, calcium sulfate, sulfuric acid Barium, calcium silicate, magnesium hydroxide, aluminum hydroxide, mica, talc, bentonite, zeolite, silica gel, aluminum oxide, titanium oxide, antimony oxide, and the like are used. Urea may be used as a formaldehyde catcher agent.

  The foamable resol-type phenol resin molding material of the present invention includes, for example, additives such as the above-mentioned liquid resol-type phenol resin, a foam stabilizer, an ammonium compound, and, if necessary, an inorganic filler, a plasticizer, and a formaldehyde catcher agent. And the whole is mixed, and after adding a foaming agent and an acid curing agent to the mixture, the composition is supplied to a mixer and stirred.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. Further, some comparative examples not belonging to the present invention are listed.

  In addition, the physical property of the phenol resin foam obtained in each example was measured according to the method shown below.

(1) Density The density was measured according to JIS A 9511.

(2) Compressive strength Compressive strength was measured according to JIS A 9511.

(3) Dimensions The dimensions were measured according to JIS A 9511.

  Liquid resol type phenolic resin (product number: PF-339 manufactured by Asahi Organic Materials Co., Ltd.) 3 parts by weight of polyester polyol obtained by reacting phthalic acid and diethylene glycol as a plasticizer in a molar ratio of 1: 2 and foam stabilizer 3 parts by weight of castor oil EO adduct (added mole number 30), 1 part by weight of ammonium chloride, 4 parts by weight of urea as a formaldehyde catcher agent, 0.4 parts by weight of hexamethylenetetramine as a nitrogen-containing crosslinked cyclic compound, The whole was mixed and left at 20 ° C. for 8 hours.

  With respect to 111.4 parts by weight of this phenol resin mixture, 3 parts by weight of calcium carbonate as an inorganic filler, 5.5 parts by weight of isopropyl chloride and 1 part by weight of isopentane as a foaming agent, and paratoluenesulfonic acid: xylenesulfonic acid mass as an acid curing agent 12 parts by weight of a mixture having a ratio = 2: 1 was supplied to a stirrer, and the whole was stirred and mixed to prepare a foamable phenol resin molding material.

  Subsequently, this molding material is discharged into a mold (W300 × D300 × H95 mm) that has been adjusted to 75 ° C., put in a dryer at 75 ° C., cured until the resin temperature starts to drop, and molded. Was taken out of the mold and placed in a dryer at 85 ° C. and cured for 9.5 hours to prepare a phenolic resin foam. The physical properties and molding time of this foam are shown in Table 1.

  A phenol resin foam was produced in the same manner as in Example 1 except that ammonium chloride was changed to 1 part by weight of ammonium nitrate in Example 1.

  In Example 1, a phenol resin foam was produced in the same manner as in Example 1 except that ammonium chloride was changed to 2 parts by weight of a 25% aqueous ammonium chloride solution and the amount of the curing agent was changed to 14 parts by weight.

  100 parts by weight of a liquid resol type phenolic resin (product number: PF-339 manufactured by Asahi Organic Materials Co., Ltd.), 2.2 parts by weight of a polyester polyol obtained by reacting phthalic acid and diethylene glycol as a plasticizer in a molar ratio of 1: 2, 3 parts by weight of castor oil EO adduct (added mole number 30) as a foaming agent, 1.5 parts by weight of ammonium chloride, and 4 parts by weight of urea as a formaldehyde catcher agent were added, and the whole was mixed and allowed to stand at 20 ° C. for 8 hours.

  To 110.7 parts by weight of this phenol resin mixture, 4 parts by weight of a furfuryl alcohol solution of 20% hexamethylenetetramine as a nitrogen-containing crosslinked cyclic compound, 2.2 parts by weight of calcium carbonate as an inorganic filler, and isopropyl chloride as a blowing agent 7.6 parts by weight, 1.4 parts by weight of isopentane, and 12.5 parts by weight of a mixture of paratoluenesulfonic acid: xylenesulfonic acid mass ratio = 2: 1 as an acid curing agent were supplied to a stirrer, and the whole was stirred and mixed. Thus, a foamable phenol resin molding material was prepared.

  Subsequently, the molding material is discharged into a mold (W300 × D300 × H50 mm) that has been adjusted to 75 ° C. in advance, placed in a dryer at 75 ° C., cured until the resin temperature begins to drop, and molded. After taking out from the mold, it was put into a dryer at 85 ° C. and cured for 5 hours to prepare a phenol resin foam. The physical properties and molding time of this foam are shown in Table 1.

Comparative Example 1

  In Example 1, a phenol resin foam was produced in the same manner as in Example 1 except that ammonium chloride was not used.

Comparative Example 2

In Example 4, a phenol resin foam was produced in the same manner as in Example 4 except that ammonium chloride was not used.

  ADVANTAGE OF THE INVENTION According to this invention, the foamable phenol resin molding material which gives the phenol resin foam excellent in intensity | strength and with few shrinkages, and the phenol resin foam which has the said characteristic can be provided.

JP 2006-335868 A

Claims (6)

Foamable resole-type phenol resin molding characterized in that an ammonium compound is mixed as an additive in a foamable resole-type phenol resin molding material containing a liquid resol-type phenol resin, a foaming agent, a foam stabilizer, and an acid curing agent material. 2. The foamable resol-type phenol resin molding material according to claim 1, wherein the ammonium compound is ammonium chloride. The foamable resol-type phenol resin molding material according to claim 1, wherein the ammonium compound is ammonium nitrate. The foamable resol-type phenol resin molding material according to any one of claims 1 to 3, wherein the ammonium compound is contained in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the liquid resol-type phenol resin. . The foamable resol type phenolic resin molding material according to any one of claims 1 to 4, further comprising a nitrogen-containing crosslinked cyclic compound. A phenolic resin foam obtained by foaming and curing the foamable resol-type phenolic resin molding material according to any one of claims 1 to 5.