JP3110235B2 - Foam curable phenolic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful for the production of a curable resin foam represented by a phenol foam, a phenol urethane foam and the like mainly used as a heat insulating material, a lightweight structural material, a soundproofing material and the like. The present invention relates to a foam-curable phenolic resin composition.

[0002]

2. Description of the Related Art Curable phenolic resin foams such as phenol foams and phenol urethane foams are prepared by adding an acidic curing agent and / or a polyisocyanate compound, a foaming agent and, if necessary, a foam to a liquid phenol resin. Agent,
It is manufactured by foam-curing a foam-curable phenolic resin composition constituted by adding a curing accelerator. However, in recent years, in the production of such foams, the use of specific fluorocarbon blowing agents, such as trichlorotrifluoroethane and trichloromonofluoromethane, which have been conventionally used, has been strictly regulated from the viewpoint of protecting the global environment. Is to be completely abolished.

[0003] Therefore, dichlorofluoromethane (HCFC-141) which replaces specific freon as a bubble forming source is used.
b), dichlorotrifluoroethane (HCFC-12
3), pentafluoropropane (HCFC-225c)
a, HCFC-225cb) and other alternative blowing agents, as well as conventionally known non-fluorocarbon blowing agents, for example, physical blowing agents such as methylene chloride, pentane, air, nitrogen, and carbon dioxide, and nitrogen generated by a chemical reaction. A review of chemical blowing agents using gaseous substances such as carbon dioxide has been conducted.

[0004]

However, the above-mentioned HCFC-141b, HCFC-123, and HCFC-
225ca, HCFC-225cb, foam obtained using a non-specific CFC blowing agent such as methylene chloride, pentane, carbon dioxide, etc., has a coarser and more non-uniform cell structure than a foam using a specific CFC, and therefore has a heat insulating performance. And a decrease in mechanical strength is inevitable. Further, when a non-CFC foaming agent is used, there is a problem that the density of the foam is larger than that of the specific CFC foam. Under such circumstances, it is still necessary to use a specific fluorocarbon in the production of foams, and the non-fluorocarbon production of foams has not yet been achieved.

Accordingly, an object of the present invention is to provide a cell structure formed by use of a non-specific CFC foaming agent, that is, by preventing the cells from becoming coarse and non-uniform, thereby providing a heat insulation performance comparable to that of the specific CFC foam. And mechanical strength,
Another object of the present invention is to provide a foam-curable phenolic resin-based composition that can generally make a foam non-fluorocarbon without increasing the density even when a non-fluorocarbon foaming agent is used.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, a foam-curable phenolic resin composition comprising a combination of a non-specific freon foaming agent and a specific silicon compound, The present inventors have found that it is possible to provide a foam having a cell structure and physical properties that are comparable to those of the specific CFC foam, and that it is possible to achieve a non-fluorocarbon foam, thereby completing the present invention.

That is, the present invention relates to (a) a liquid phenolic resin, (b) an acidic curing agent and / or a polyisocyanate compound, (c) a foaming agent and (d) the following general formulas (I) and / or (II) It is a foaming hardening type phenol resin type composition characterized by including the silicone compound represented by these.

[0008]

Embedded image

(In the formulas (I) and (II), R ^{1 to} R ¹² represent an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and n is 0 to 10.) .)

In the present invention, the liquid phenol resin used as the component (a) is a functional group such as a methylol group, a dimethylene ether group, or a phenolic hydroxyl group which causes a curing reaction in the presence of an acidic curing agent and / or a polyisocyanate compound. Is a resin solution containing a liquid resin or a solvent added as needed in the molecule.Examples of such a liquid phenol resin include, in addition to a general resol type phenol resin, a novolak type phenol resin Novolak resole phenolic resin with a methylol group added to it, ammonia resole phenolic resin,
Or a benzyl ether type phenol resin, or a reaction of these phenol resins with alkylene oxides such as ethylene oxide and propylene oxide, cyclic alkylene carbonates such as ethylene carbonate and propylene carbonate, epoxy compounds, melamine compounds, and guanamine compounds. Alternatively, a modified phenolic resin obtained by mixing may be mentioned, but it is a matter of course that the present invention is not limited thereto. Among them, resol type phenol resins, benzyl ether type phenol resins, and modified phenol resins thereof are preferable. These liquid phenol resins may be used alone or in combination of two or more. Further, a novolak type phenol resin can be used in combination as needed.

In such a liquid phenol resin, the total amount of phenols and aldehydes is usually 0.8 to 4.0 mol, preferably 1 to 1.0 mol of phenols. After adjusting the concentration within a range of about 2.0 to 2.0 mol and reacting at a temperature of 50 ° C. to reflux in the presence of an acidic and / or basic reaction catalyst, a neutralization treatment is carried out in some cases, and then the pressure is reduced. It is manufactured by heating and concentrating to a predetermined characteristic value (for example, a viscosity at 25 ° C. of 300 to 200,000 cp) and cooling, and then adding various additives as necessary.

Examples of the phenols include phenol, cresol, xylenol, nonylphenol, para-tert-butylphenol, resorcinol, catechol, bisphenol A, bisphenol F, phenol, cresol, resorcinol, bisphenol A
And the like, but are not limited thereto. These phenols may be used alone or in combination of two or more. On the other hand, examples of aldehydes include formaldehyde such as formalin and paraformaldehyde, and formaldehyde synergistic substances such as glyoxal and furfural, but are not limited thereto. These aldehydes may be used alone or in combination of two or more. Examples of the reaction catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium phosphate, barium hydroxide, calcium hydroxide, magnesium oxide, ammonia, hexamethylenetetramine, and triethylamine. And basic catalysts such as triethanolamine, and acidic divalent metal salts such as lead naphthenate, zinc acetate, zinc borate and zinc chloride, and acidic catalysts such as oxalic acid, but of course are not limited thereto. Not something. These reaction catalysts may be used singly or in combination of two or more compounds of the same genus, or may be used in combination with separating an acidic catalyst and a basic catalyst like the novolak resole type phenol resin. .

In the present invention, the acidic curing agent or the polyisocyanate compound used as the component (b) has two isocyanate groups in the molecule which cause a curing reaction with the acidic compound having the function of accelerating the curing of the liquid phenol resin or the liquid phenol resin. Polyisocyanate compounds having the above, examples of such acidic curing agents include monocyclic aromatic compounds such as phenolsulfonic acid, benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, and ethylenesulfonic acid. Polycyclic aromatic sulfonic acids such as sulfonic acid, naphthalene sulfonic acid, naphthol sulfonic acid, anthracene sulfonic acid, anthranol sulfonic acid, alkylsulfonic acid such as methanesulfonic acid, sulfonated creosote oil, and monocyclic aromatic sulfonic acid; Holmualde Condensates of polycyclic aromatic sulfonic acids and / or condensates of sulfonated creosote oil and formaldehyde, sulfonated phenolic resins, sulfonated naphthalene resins, resin-based sulfonic acids such as acidic ion exchange resins, sulfuric acid, phosphoric acid And the like, but are not limited to these. On the other hand, examples of polyisocyanate compounds include aromatic polyisocyanates such as tolylene diisocyanate (TDI), crude TDI, xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate (crude MDI), and isophorone. Alicyclic polyisocyanates such as diisocyanates, aliphatic polyisocyanates such as hexamethylene diisocyanate, prepolymer-type modified products having isocyanate groups obtained by reacting polyisocyanates with polyols, or nurate-type modified products of polyisocyanates, etc. But of course is not limited to these.

The acidic curing agent and the polyisocyanate compound of the component (b) may be used alone or in combination. Of course, two or more compounds of the same genus may be used in combination. Also,
The amount of the component (b) varies depending on the curing mode and type and cannot be determined unconditionally, but is generally 2 to 6 in the case of an acidic curing agent per 100 parts by weight of the liquid phenol resin.
It is selected in the range of 0 parts by weight, and in the case of a polyisocyanate compound, in the range of 50 to 500 parts by weight.

In the present invention, the foaming agent used as the component (c) has the function of forming air bubbles in the cured structure of the liquid phenolic resin or the liquid phenolic resin / polyisocyanate compound to provide heat insulation and lightness. Examples of such a blowing agent are preferably non-specific CFC blowing agents, for example, aliphatic hydrocarbons such as pentane and hexane known as physical blowing agents, and aliphatic hydrocarbons such as diethyl ether and diisopropyl ether. Ethers, H
CFC-141b, HCFC-123, HCFC-22
5ca, HCFC-225cb and other substitutes, halogenated hydrocarbons such as methylene chloride and propyl chloride, perfluorocarbons such as perfluorohexane and perfluoropentane, and chemicals that chemically generate nitrogen and carbon dioxide gas Foaming agents such as sodium bicarbonate, sodium carbonate, barium carbonate, calcium carbonate, hydrogen peroxide, water, paratoluenesulfonyl hydrazide, 4,4
-Oxybisbenzenesulfonyl hydrazide, azodicarbonamide, azobisisobutyronitrile, or a gas such as air, nitrogen, carbon dioxide, or butane, but is not limited thereto.

The foaming agents of component (c) may be used alone or in combination of two or more. The amount of the component (c) varies depending on the density and type of the foam and cannot be determined unconditionally, but is generally 0.5 to 50 per 100 parts by weight of the liquid phenol resin.
It is selected in the range of parts by weight.

In the present invention, the silicone compounds represented by the above general formulas (I) and (II) used as the component (d) (these are referred to as "specific silicon compounds") are used for the fine cells of the cells forming the cell structure. The silicone compound represented by the general formula (I), which functions very effectively for the formation and uniformization and the reduction of the density, and has such preferable properties, is a monoalkoxytrialkylsilane. The product name is SS201 manufactured and sold by Dow Corning Toray Silicone Co., Ltd.
0 (trimethylmethoxysilane). The silicone compound represented by the general formula (II) is a polyalkylpolysiloxane having a basic structural unit of n = 0 to 10, and is preferably a compound in which all of the alkyl groups are methyl groups. SH200 0.6cst (n = 0), SH200 manufactured and sold by Toray Dow Corning Silicone Co., Ltd.
1 cst (n = 1), SH200 1.5 cst (n = 2.
4), SH200 2cst (n = 3.4), SH200
3cst (n = 5.2), SH200 5cst (n =
8.2), but more preferably S
H200 0.6cst (n = 0)-SH200 2cst
(N = 3.4). The substituents R ^{1 to} R in the silicone compounds represented by the general formulas (I) and (II)
¹² is an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, and a propyl group (including a straight-chained one and a branched-chained one). May be.

The specific silicon compound as the component (d) may be used alone or in combination. Of course, two or more compounds of the same genus may be used in combination. The amount of the component (d) varies depending on the type, curing mode, physical properties of the foam, and the type of the foaming agent, and cannot be determined unconditionally, but is generally 0.1 to 100 parts by weight of the liquid phenol resin. 10 parts by weight,
Preferably, it is selected in the range of 0.5 to 5 parts by weight. Such a specific silicon compound has a particularly remarkable effect in combination with a foaming agent having high compatibility with the resin, for example, methylene chloride, chlorofluorocarbon, carbon dioxide, nitrogen gas and air (a chemical foaming agent or gas). Tends to occur. These may be used at the time of preparing the resin or after the preparation, at the time of preparing the foaming undiluted solution, or by adding and mixing with the foaming agent.

In the composition of the present invention, various additives, for example, a foam stabilizer, a urethanizing and / or nullating reaction accelerator, and other additives may be added, if necessary, in addition to the above essential components. it can. Examples of the foam stabilizer include polysiloxane / oxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, alkylphenol ethylene oxide adduct, tetraalkylammonium salt, and alkylphenol sulfonate. Further, as a reaction accelerator, for example, triethylenediamine, tetramethylhexamethylenediamine, phenylpropylpyridine, ethylmorpholine, dibutyltin dilaurate, dibutyltin diacetate, potassium octylate, lead naphthenate, zinc naphthenate, cobalt naphthenate, potassium acetate , Hexahydrotriazine and the like. Other additives include silane coupling agents represented by γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, etc., aluminum hydroxide, melamine, zinc borate, phosphorus-containing compounds, and Filling represented by flame retardants represented by halogen compounds, rock fibers, glass fibers, carbon fibers, phenol fibers, aramid fibers, shirasu balloons, porous aggregates
Reinforcing materials, as well as reactive diluents, plasticizers, colorants and the like can be used.

The foam-curable phenolic resin composition of the present invention (hereinafter referred to as "foaming stock solution") comprises a liquid phenolic resin,
A mixing method conventionally used in the art, for example, a mixing method of an acidic curing agent and / or a polyisocyanate compound, a foaming agent, a specific silicon compound, and a foam stabilizer, a reaction accelerator, and other additives added as needed, It can be manufactured by mixing uniformly with a stirring mixer, a high-pressure collision mixer, or a low-pressure collision mixer. Further, the foaming stock solution thus obtained is foamed and cured by a foaming method conventionally used in the art, for example, a continuous foaming method, an in-situ foaming method, an impregnating foaming method, or an injection foaming method, to form a phenol foam, phenol. It is shaped into a curable phenolic resin foam represented by a urethane foam, a phenol urethane foam having an isocyanurate structure, and the like.

More specifically, according to the continuous foaming method, an undiluted foaming liquid is discharged onto a face material or a model frame which is continuously conveyed by an endless conveyor device (with a built-in heating device) provided in two upper and lower stages. After being supplied from the nozzle, it is foamed and cured at normal temperature and / or under heating to obtain a foamed product. Here, when a release surface material such as Teflon or polyethylene is used, a single foam product can be obtained. In addition, when a flat surface material such as kraft paper, aluminum kraft paper, calcium silicate plate, perlite plate, rock wool plate, and wool cement plate is used, a laminated structure in which the surface material and the foam are integrated is used. A foam product can be obtained. Further, when a molded surface material obtained by embossing a surface of a thin metal plate or the like is used, a foamed product having a sandwich structure generally called metal siding can be obtained. According to the in-situ foaming method,
A foaming solution is sprayed onto a skeleton surface of a building requiring heat insulation by a spray gun, or is injected into a space of a building or a refrigerator or the like with a hose, and then foamed and hardened at room temperature to be foamed and hardened at room temperature. A heat insulating layer made of a foam can be formed in the space. In addition, a composite foam product is obtained by an impregnation foaming method in which glass foam or rock wool fiber is impregnated with a foaming solution and foamed and hardened, or an injection foaming method in which a foamed stock solution is injected and filled into a honeycomb structure and foamed and hardened. be able to.

As described above, a curable phenolic resin foam represented by a phenol foam, a phenol urethane foam, a phenol urethane foam having an isocyanurate structure, and the like obtained by using the foaming stock solution of the present invention is, for example, constructed Insulation and heat-insulating members such as goods, refrigerators, automobile ceiling panels, plants, pipes, etc., construction-related heat-insulating lightweight members such as ceiling materials, inner wall materials, outer wall materials, floor base materials, shutters, structural panels, soundproof walls, and equipment beds. It can be used for sound-proof and vibration-proofing members such as vibration-resistant floor base materials.

[0023]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

The physical properties and cell structure (cell diameter and cell homogeneity) of the obtained foam were measured or judged by the following test methods. (1) Density and compressive strength were measured according to JIS A 9514. (2) Thermal conductivity is measured by Kemtherm Q manufactured by Kyoto Electronics Industry Co., Ltd.
It measured by the hot-wire method using TM-D3 (trademark). (3) The cell diameter was measured using a microscope [V manufactured by Meishin Koki Co., Ltd.
MS-3000 (trademark)], and the homogeneity of the cell was visually determined. (4) Reactivity of the foaming stock solution (cream time / gel time = CT / GT) was measured in a 500 cc paper cup 25
It measured by the usual method using about 100 g of samples at ° C.

Reference Example 1 300 kg of phenol, 306 kg of 47% by weight formalin and 30 kg of a 20% by weight aqueous sodium hydroxide solution were charged into a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, and then stirred and mixed. 2 at 90 ° C
Allowed to react for hours. Thereafter, the mixture was cooled to 40 ° C., neutralized to pH 6.8 with phenolsulfonic acid, and further heated and concentrated under a vacuum of about 60 mmHg with stirring and mixing to obtain a liquid resol-type phenol resin. The obtained liquid resol type phenol resin had a viscosity of 8000 cp / 25 ° C. The viscosity is measured by a B-type viscometer.

REFERENCE EXAMPLE 2 300 kg of phenol, 92% by weight of paraformaldehyde 1 were added to the reactor used in Reference Example 1.
After charging 50 kg and 4 kg of lead naphthenate, the mixture was reacted at a reflux temperature for 2.5 hours while stirring and mixing. Thereafter, 40 kg of trischloroethyl phosphate and 180 kg of water were added to prepare a mixture. Then, the mixture was applied to a tubular concentrator with a jacket (length / inner diameter = 1000, jacket vapor pressure: 3 kg / c).
m ² ) continuously at a flow rate of 60 kg / Hr and connected to the concentrator.
Water and unreacted monomers were separated and removed at a temperature of about 100 ° C and a degree of vacuum of about 100 mmHg to obtain a liquid benzyl ether type phenol resin. The obtained liquid benzyl ether type phenol resin has a viscosity of 15,000 cp / 25 ° C. and a hydroxyl value of 500 mg.
KOH / g.

(Example 1) First, SS2010 (trade name, trimethylmethoxysilane manufactured by Dow Corning Toray Silicone Co., Ltd.) as a specific silicon compound was added to 100 kg of the liquid resol type phenol resin prepared in Reference Example 1.
kg and castor oil ethylene oxide adduct as foam stabilizer [trade name: Pionin D-225, manufactured by Takemoto Yushi Co., Ltd.]
After adding 2 kg and stirring and mixing, 10 kg of methylene chloride was additionally mixed as a foaming agent, and a resin / foaming agent mixture (solution I) adjusted to 20 ° C. and an acidic curing agent were adjusted to 20 ° C. 6
3% by weight phenolsulfonic acid (solution II) was prepared. Next, these were mixed by a foaming machine (trade name: PA-210, manufactured by Toho Kikai Co., Ltd.) at a weight ratio of I liquid: II liquid = 100: 18 to prepare a foaming stock solution, which was then preliminarily crafted. The phenol foam (900mm × 900mm ×
25 mm). The cream time of the foaming stock solution is 2
1 second and the gel time was 70 seconds. After leaving the obtained foam at 20 ° C. for 7 days, physical properties such as density, compressive strength, thermal conductivity and the cell structure (cell diameter and cell uniformity) were examined by the above-mentioned test methods. The result is
It is shown in the table.

Examples 2-5 Phenol foaming was carried out in the same manner as in Example 1 except that the type and amount of the specific silicon compound were changed as shown in Table 1 to prepare a foaming stock solution. Created body. The physical properties and cell structure (cell diameter and cell homogeneity) of the obtained foam were examined in the same manner as in Example 1. Table 1 shows the results.

Example 6 1 kg of SS2010 as a specific silicon compound and 2 kg of Pionin D-225 as a foam stabilizer were added to 100 kg of the liquid resole phenolic resin prepared in Example 1, and the mixture was stirred and mixed. 15 kg of R-141b (trade name: Asahi Glass Co., Ltd. alternative Freon) was added as an agent, and a resin / foaming agent mixture (solution I) adjusted to 20 ° C. and an acidic curing agent adjusted to 20 ° C. 6
Example 1 except that a 3% by weight phenolsulfonic acid (II) solution was prepared and mixed with the foaming machine at a ratio of I solution: II solution = 100: 19 (weight ratio) to prepare a foaming stock solution.
A phenol foam was prepared in the same manner as described above. The physical properties and cell structure (cell diameter and cell homogeneity) of the obtained foam were examined in the same manner as in Example 1. The result is
It is shown in the table.

(Comparative Example 1) Example 1 was repeated except that the specific silicon compound was omitted to prepare a foaming stock solution.
A phenol foam was prepared in the same manner as described above. The physical properties and cell structure (cell diameter and cell uniformity) of the obtained foam were examined in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 2) In Example 2, the specific silicon compound SH200 was replaced by 0.6 cst (n = 0)
A phenol foam was prepared in the same manner as in Example 1, except that a foaming stock solution was prepared using H200 50cst (n = 50). In addition, about the obtained foam, Example 1
Physical properties and cell structure (cell diameter and cell homogeneity)
Was examined. Table 1 shows the results.

Comparative Example 3 The procedure of Example 6 was repeated except that the specific silicon compound was omitted to prepare a foaming stock solution.
A phenol foam was prepared in the same manner as described above. The physical properties and cell structure (cell diameter and cell uniformity) of the obtained foam were examined in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 4 In Example 1, a resin mixture (solution I) was adjusted to 20 ° C. by omitting the specific silicon compound and methylene chloride, and adjusted to 20 ° C. as an acidic curing agent.
3% by weight phenolsulfonic acid (II) solution and R-113 as a foaming agent (trade name: Specified Freon manufactured by Asahi Glass Co., Ltd.) (II
I) Prepare liquids and mix them with the above foaming machine.
Liquid: III solution = 102: 22: 15 (weight ratio), except that a foaming stock solution was prepared to prepare a phenol foam in the same manner as in Example 1. The physical properties and cell structure (cell diameter and cell uniformity) of the obtained foam were examined in the same manner as in Example 1. Table 1 shows the results.

Example 7 1 kg of the above-mentioned SS2010 as a specific silicon compound was added to 100 kg of the liquid benzyl ether type phenol resin prepared in Reference Example 2 and 2 parts of a foam stabilizer.
kg of SH193 (trade name, polysiloxane / oxyalkylene copolymer manufactured by Toray Silicone Co., Ltd.), 0.5 g of dibutyltin dilaurate as a curing accelerator, and stirring and mixing, and then 40 kg of the R-141b as a foaming agent.
And a CR / 200 mixed with a resin / foaming agent mixture (liquid I) adjusted to 20 ° C. and a polyisocyanate compound adjusted to 20 ° C. (trade name: Crude MDI manufactured by Mitsui Toatsu Chemicals, Inc., NCO content 31) % By weight] (Liquid II), and these were prepared by the above-mentioned foaming machine.
A phenolurethane foam was prepared in the same manner as in Example 1 except that the mixture was mixed at 00 (weight ratio) to prepare a foaming stock solution. The physical properties and cell structure (cell diameter and cell homogeneity) of the obtained foam were examined in the same manner as in Example 1. Table 1 shows the results.

[0035]

[Table 1]

[0036]

[Table 2]

As is clear from Table 1, the composition of the present invention using the specified silicon compound can provide an alternative CFC or non-CFC foam having physical properties and cell structure comparable to those of the specified CFC foam. Moreover, it was confirmed that the density of the alternative CFC foam can be reduced. Further, as shown in Comparative Example 2, it was confirmed that among the specific silicon compounds, those having a high degree of condensation could not achieve the object of the present invention.

[0038]

According to the foam-curable phenolic resin composition of the present invention, by using a non-specific freon foaming agent and a specific silicon compound together, a uniform and fine cell structure comparable to the specific freon foam can be obtained. Foam using non-fluorocarbon alternative or non-fluorocarbon alternative which can avoid deterioration of the natural environment due to destruction of the ozone layer without lowering of heat insulation performance and mechanical strength unlike the conventional composition because foam having the same can be produced. Foamed article can be provided. Also,
Since the specific silicon compound used in the present invention has a function of surprisingly reducing the density of the foam, it has a density comparable to that of the specific fluorocarbon foam even when a non-fluorocarbon foaming agent is used. The use of a foaming agent makes it possible to produce a foam having a lower density, which is extremely useful economically.

────────────────────────────────────────────────── ─── Continuing on the front page (51) Int.Cl. ⁷ Identification code FI C08L 75/04 C08L 75/04 (72) Inventor Shuji Okumura 26, Niitsu, Niizumi, Oyama, Fuso-cho, Niwa-gun, Aichi Pref. (72) Inventor: Shigeki Inatomi, 26, Niitsu, Niizumi, Fuso-cho, Niwa-gun, Niwa-gun, Aichi Prefecture Asahi Organic Materials Industry Co., Ltd. Aichi Factory (56) References JP-A-59-6230 (JP, A) JP-A-61-120837 (JP, A) JP-A-59-152931 (JP, A) JP-A-61-268331 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C08J 9/00-9/42 C08G 18/54 C08K 5/5419 C08L 61/04-61/16 C08L 75/04-75/16 CA (STN)

Claims (1)

(57) [Claims] 1. A liquid phenolic resin, (b) an acidic curing agent and / or a polyisocyanate compound, (c) a foaming agent and (d) represented by the following general formulas (I) and / or (II) A foam-curable phenolic resin composition comprising a silicone compound. Embedded image (In the formulas (I) and (II), R ^{1 to} R ¹² represent an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and n is 0 to 10.)