JPH07196838A - Expansion-curable phenolic resin composition - Google Patents

Abstract

PURPOSE:To provide an expansion-curable phenolic resin composition prevented from forming a product with such a cellular structure as the one formed when a nonspecified fluorocarbon blowing agent is used, that is, a cellular structure in which the cells are coarse and nonuniform, therefore having heat-insulation properties and mechanical properties at least equivalent to those of a foam produced by using a specified fluorocarbon and can give a foam not having an increased density even when produced by using a non-fluorocarbon blowing agent and generally having sufficiently practicable properties even when a fluorocarbon is not used as the blowing agent. CONSTITUTION:This composition comprises a liquid phenolic resin, an acidic curing agent and/or a polyisocyanate compound, a blowing agent, and silicone compounds represented by formulas I and/or II (wherein R<1> to R<12> which may be the same or different from each other, are each 1-3 Calkyl, and n is 0-10).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is useful for producing a curable resin foam represented by phenol foam, phenol urethane foam and the like, which are mainly used for heat insulating materials, lightweight structural materials, soundproofing materials and the like. It relates to a foam-curable phenol resin composition.

[0002]

2. Description of the Related Art A curable phenol resin foam represented by phenol foam, phenol urethane foam, etc. is a liquid phenol resin containing an acidic curing agent and / or a polyisocyanate compound, a foaming agent and, if necessary, a foam stabilizer. Agent,
It is produced by foam-curing a foam-curable phenol resin composition that is formed by adding a curing accelerator. However, in recent years, in the production of such foams, specific freon blowing agents such as trichlorotrifluoroethane and trichloromonofluoromethane that have been conventionally used are strictly regulated in their use from the viewpoint of global environmental protection, and in the near future. Is to be totally abolished.

Therefore, dichlorofluoromethane (HCFC-141) which replaces specific CFCs 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-CFC blowing agents, for example, physical blowing agents such as methylene chloride, pentane, air, nitrogen, carbon dioxide and nitrogen generated by chemical reaction. Chemical blowing agents that use gas such as carbon dioxide are being reviewed.

[0004]

However, the above-mentioned HCFC-141b, HCFC-123, HCFC-
225ca, HCFC-225cb, methylene chloride, pentane, carbon dioxide gas and other non-specific freon foaming agent, the foam structure is coarser than the foam using the specific freon, the non-uniform, the heat insulation performance. There is a problem that mechanical strength is unavoidable. Further, when a non-Freon foaming agent is used, there is a problem that the density of the foam is higher than that of the specific Freon foam. In addition, due to such circumstances, at the time of producing a foam, it is inevitable to use a specific chlorofluorocarbon together, and the non-fluorocarbon foam has not been achieved yet.

Therefore, an object of the present invention is to prevent the cell structure, ie, cell coarsening and non-uniformity, formed in the use of a non-specific CFC foaming agent, so that the insulation performance is comparable to that of the CFC foam. And has mechanical strength,
It is another object of the present invention to provide a foam-curable phenolic resin composition, which does not cause a rise in density even when a non-Freon foaming agent is used, and makes it possible to make the foam non-Freon.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a foam-curable phenol resin composition comprising a non-specific CFC blowing agent and a specific silicon compound in combination is The inventors have found that a foam having a cell structure and physical properties comparable to those of a specific freon foam can be provided, and that the foam can be made non-freon, and the present invention has been completed.

That is, the present invention comprises (a) a liquid phenol 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). A foam-curable phenol resin composition comprising a silicone compound represented by:

[0008]

[Chemical 2]

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

The liquid phenol resin used as the component (a) in the present invention is a functional group such as a methylol group, a dimethylene ether group and a phenolic hydroxyl group which causes a curing reaction in the presence of an acidic curing agent and / or a polyisocyanate compound. A resin solution containing a liquid resin having in the molecule thereof or a solvent added as necessary, and examples of such a liquid phenol resin include general resol type phenol resin and novolac type phenol resin. Novolac / resole type phenolic resin with a methylol group added to ammonia, ammonia resol type phenolic resin,
Or benzyl ether type phenolic resin, or these phenolic resins are reacted with alkylene oxides such as ethylene oxide and propylene oxide, cyclic alkylene carbonates such as ethylene carbonate and propylene carbonate, epoxy compounds, melamine compounds, guanamine compounds, etc. Alternatively, a modified phenol resin obtained by mixing them may be mentioned, but the present invention is not limited to these. Of these, resol type phenolic resins, benzyl ether type phenolic resins and modified phenolic resins thereof are preferable. These liquid phenol resins may be used alone or in combination of two or more kinds. In addition, it is possible to use a novolac type phenol resin together if necessary.

In such a liquid phenol resin, phenols and aldehydes are usually added, and the total amount of aldehydes is usually 0.8 to 4.0 mols, preferably 1 mol, relative to 1.0 mol of phenols. It is adjusted within a range of about 0 to 2.0 mol, reacted at 50 ° C. to reflux temperature in the presence of an acidic and / or basic reaction catalyst, and then subjected to neutralization treatment in some cases, and then reduced pressure. It is manufactured by heating and condensing to a predetermined characteristic value (for example, 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-tertiarybutylphenol, resorcin, catechol, bisphenol A and bisphenol F, as well as phenol, cresol, resorcin and bisphenol A.
And the like, but are not limited to these. 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-like substances such as glyoxal and furfural, but are not limited to these. 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 hydrogen carbonate, sodium phosphate, barium hydroxide, calcium hydroxide, magnesium oxide, ammonia, hexamethylenetetramine, triethylamine. , Basic catalysts such as triethanolamine, acidic divalent metal salts such as lead naphthenate, zinc acetate, zinc borate, and zinc chloride; acidic catalysts such as oxalic acid; Not a thing. These reaction catalysts may use compounds of the same genus alone or in combination of two or more kinds, or may separate and use an acidic catalyst and a basic catalyst as in the above novolak-resole type phenol resin. .

The acidic curing agent or polyisocyanate compound used as the component (b) in the present invention has two isocyanate groups in the molecule which cause a curing reaction with the acidic compound or the liquid phenolic resin having the function of promoting the curing of the liquid phenolic resin. The polyisocyanate compound having the above, examples of such an acid curing agent include a monocyclic aromatic compound such as phenolsulfonic acid, benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, and ethylenesulfonic acid. Polycyclic aromatic sulfonic acid such as sulfonic acid, naphthalene sulfonic acid, naphthol sulfonic acid, anthracene sulfonic acid, anthranol sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, sulfonated creosote oil, monocyclic aromatic sulfonic acid Holmharde Condensation products, polycyclic aromatic sulfonic acids and / or condensation products of sulfonated creosote oil and formaldehyde, sulfonated phenol resins, sulfonated naphthalene resins, acidic ion exchange resins, and other resin-based sulfonic acids, sulfuric acid, phosphoric acid Examples of such inorganic acids include, but are not limited to, of course. On the other hand, examples of the polyisocyanate compound include aromatic diisocyanates such as tolylene diisocyanate (TDI), crude TDI, xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate (crude MDI), and isophorone. In addition to alicyclic polyisocyanates such as diisocyanates, aliphatic polyisocyanates such as hexamethylene diisocyanate, prepolymer-type modified products having isocyanate groups obtained by reacting polyisocyanates and polyols, or nurate-type modified products of polyisocyanates, etc. However, the present invention is not limited to these.

The acidic curing agent and the polyisocyanate compound as 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 blending 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 the polyisocyanate compound, in the range of 50 to 500 parts by weight.

The foaming agent used as the component (c) in the present invention plays a role of forming bubbles in the cured structure of the liquid phenol resin or the liquid phenol resin / polyisocyanate compound to impart heat insulation and light weight. However, as an example of such a foaming agent, preferably a non-specific freon foaming agent, for example, pentane known as a physical foaming agent, an aliphatic hydrocarbon such as hexane, an aliphatic hydrocarbon such as diethyl ether, diisopropyl ether, etc. Ethers, H
CFC-141b, HCFC-123, HCFC-22
5ca, alternative CFCs such as HCFC-225cb, halogenated hydrocarbons such as methylene chloride and propyl chloride, perfluorocarbons such as perfluorohexane and perfluoropentane, as well as chemicals that chemically generate nitrogen and carbon dioxide gas. Effervescent agents such as sodium hydrogen carbonate, sodium carbonate, barium carbonate, calcium carbonate, hydrogen peroxide, water, paratoluenesulfonyl hydrazide, 4,4
Examples thereof include, but are not limited to, oxybisbenzenesulfonyl hydrazide, azodicarbonamide, azobisisobutyronitrile, and gas forms such as air, nitrogen, carbon dioxide, butane, and the like.

The foaming agent as the component (c) may be used alone or in combination of two or more kinds. The blending amount of the component (c) varies depending on the density and type of the foamed product 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 within 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 fine cells of cells forming a cell structure. The silicone compound represented by the general formula (I), which functions extremely effectively for homogenization and homogenization and reduction in density, and has such preferable properties is a monoalkoxytrialkylsilane, The product name SS201 manufactured and sold by Toray Dow Corning Silicone Co., Ltd.
0 (trimethylmethoxysilane) can be exemplified. Further, the silicone compound represented by the general formula (II) is a polyalkylpolysiloxane having a basic structural unit of n = 0 to 10 and, preferably, the alkyl groups are all methyl groups. SH200 0.6cst (n = 0), SH200 manufactured and sold by Toray Dow Corning Silicone Co., Ltd.
1cst (n = 1), SH200 1.5cst (n = 2.
4), SH200 2cst (n = 3.4), SH200
3cst (n = 5.2), SH200 5cst (n =
8.2) can be exemplified, but more preferably S
H200 0.6cst (n = 0) to SH200 2cst
(N = 3.4). The substituents R ^{1 to} R in the silicone compound represented by the general formulas (I) and (II) are
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 chain group and a branched chain group), which may be the same or different. 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. Further, the amount of the component (d) blended 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 it is generally 0.1 to 100 parts by weight of the liquid phenol resin. 10 parts by weight,
It is preferably 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 a large compatibility with the resin, such as methylene chloride, alternative CFCs, carbon dioxide gas, nitrogen gas and air (chemical foaming agent or gas body). Tends to occur. Further, these may be used at the time of preparing the resin or after the preparation, at the time of preparing the foaming stock solution, or by adding and mixing with the foaming agent.

In addition to the above-mentioned essential components, various additives such as a foam stabilizer, a urethanization and / or nurate-forming reaction accelerator and other additives may be added to the composition of the present invention as required. 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. Examples of the reaction accelerator include 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 typified by γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, aluminum hydroxide, melamine, zinc borate, phosphorus-containing compounds, and the like. Flame retardant typified by halogen compounds, rock fiber, glass fiber, carbon fiber, phenolic fiber, aramid fiber, shirasu balloon, and filled aggregate typified by porous aggregate.
Reinforcing agents as well as reactive diluents, plasticizers, colorants and the like can be used.

The foam-curable phenol resin composition of the present invention (hereinafter referred to as the foaming stock solution) is a liquid phenol resin,
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 which are optionally added are mixed by a conventional mixing method, for example, high speed. It can be manufactured by uniformly mixing with a stirring mixer, a high-pressure collision mixer, and a low-pressure collision mixer. Furthermore, the foaming undiluted 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 impregnation foaming method, or an injection foaming method to obtain a phenol foam or a phenol foam. It is shaped into a curable phenol resin-based foam represented by a urethane foam and a phenol urethane foam having an isocyanurate structure.

More specifically, according to the continuous foaming method, the undiluted foaming solution is discharged onto a face material or a model frame which is continuously conveyed by endless conveyor devices (with built-in heating devices) provided in upper and lower two stages. After supplying from a nozzle, it can be foam-cured at room temperature and / or under heating to obtain a foam product. Here, when a release surface material such as Teflon or polyethylene is used, a single foam product can be obtained. When a flat plate face material such as kraft paper, aluminum kraft paper, calcium silicate board, pearlite board, rock wool board, and wood wool cement board is used, it has a laminated structure in which the face material and the foam are integrated. A foam product can be obtained. When a molding surface material obtained by subjecting a thin metal plate to surface design processing such as embossing or shaping is used, a foam product having a sandwich structure generally called metal siding can be obtained. According to the in-situ foaming method,
After spraying the foaming undiluted solution onto the body surface of the building requiring heat insulation with a spray gun, or by injecting and filling with a hose into the space of the building or the refrigerator / freezer, foam-curing at room temperature to cure the body surface or A heat insulating layer made of foam can be formed in the space. In addition, a composite foam product is obtained by applying an impregnation foaming method in which glass fiber or rockwool fiber is impregnated with a foaming raw material solution to foam and harden it, or an injection foaming method in which the foaming raw material liquid is injected and filled into a honeycomb structure to foam and cure. be able to.

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

[0023]

EXAMPLES Next, the present invention will be specifically described by way of 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) The thermal conductivity is Kemtherm Q manufactured by Kyoto Electronics Manufacturing Co., Ltd.
It was measured by the hot wire method using TM-D3 (trademark). (3) The cell diameter is a microscope [V manufactured by Meisho Machine Co., Ltd.
MS-3000 (trademark)], and the homogeneity of the cell was visually determined. (4) The reactivity (cream time / gel time = CT / GT) of the foaming stock solution was measured in a 500 cc paper cup.
The measurement was carried out by a conventional method using about 100 g of a sample at ℃.

(Reference Example 1) 300 kg of phenol, 306 kg of 47% by weight formalin and 30 kg of 20% by weight sodium hydroxide aqueous solution were charged into a reaction kettle equipped with a thermometer, a stirrer and a reflux condenser, and then mixed with stirring. 2 at 90 ° C
Reacted for hours. Then, 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 while 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 with a B-type viscometer.

(Reference Example 2) 300 kg of phenol and 92% by weight of paraformaldehyde 1 were added to the reaction vessel used in Reference Example 1.
After charging 50 kg and 4 kg of lead naphthenate, the mixture was reacted at reflux temperature for 2.5 hours while mixing with stirring. Then, 40 kg of trischloroethyl phosphate and 180 kg of water were added to prepare a mixture. Then, the mixture was applied to a long tubular concentrator with a jacket (length / inner diameter = 1000, steam pressure in the jacket: 3 kg / c).
m ² ) is continuously supplied to the concentrator at a flow rate of 60 kg / Hr and is connected to the concentrator (internal temperature: about 120).
Water and unreacted monomers were separated and removed at ℃ and vacuum degree: about 100 mmHg) to obtain a liquid benzyl ether type phenol resin. The obtained liquid benzyl ether type phenol resin has a viscosity of 15000 cp / 25 ° C and a hydroxyl value of 500 mg.
It was KOH / g.

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

(Examples 2 to 5) Phenol foaming was carried out in the same manner as in Example 1 except that the foaming stock solution was prepared by changing the kind and amount of the specific silicon compound as shown in Table 1. Created the body. Further, the obtained foam was examined for physical properties and cell structure (cell diameter and cell homogeneity) in the same manner as in Example 1. The results are shown in Table 1.

Example 6 To 100 kg of the liquid resol-type phenol resin prepared in Example 1, 1 kg of the SS2010 as a specific silicon compound and 2 kg of Pionine D-225 as a foam stabilizer were added and stirred, and then foamed. 15 kg of R-141b [trade name: alternative CFC manufactured by Asahi Glass Co., Ltd.] as an agent was additionally mixed to adjust the temperature to 20 ° C., and the resin / foaming agent mixed solution (liquid I) was adjusted to 20 ° C. as an acid curing agent.
Example 1 except that a 3 wt% phenolsulfonic acid (II) solution was prepared and these were mixed by the foaming machine at a solution I: solution II = 100: 19 (weight ratio) to prepare a foaming stock solution.
A phenol foam was prepared in the same manner as in. Further, the obtained foam was examined for physical properties and cell structure (cell diameter and cell homogeneity) in the same manner as in Example 1. The result is first
Shown in the table.

(Comparative Example 1) Example 1 was repeated except that the foaming stock solution was prepared by omitting the specific silicon compound.
A phenol foam was prepared in the same manner as in. Further, the obtained foam was examined for physical properties and cell structure (cell diameter and cell homogeneity) in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2) In Example 2, S200 was used instead of the specific silicon compound SH200 0.6cst (n = 0).
A phenol foam was prepared in the same manner as in Example 1 except that the foaming stock solution was prepared using H200 50cst (n = 50). In addition, regarding the obtained foam,
Similar to the physical properties and bubble structure (cell diameter and cell homogeneity)
I checked. The results are shown in Table 1.

(Comparative Example 3) Example 6 was repeated except that the foaming stock solution was prepared by omitting the specific silicon compound.
A phenol foam was prepared in the same manner as in. Further, the obtained foam was examined for physical properties and cell structure (cell diameter and cell homogeneity) in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 4) In Example 1, the specific silicon compound and methylene chloride were omitted, and the resin mixture (solution I) adjusted to 20 ° C. and the acid curing agent adjusted to 20 ° C. 6
3 wt% phenolsulfonic acid (II) liquid and R-113 as a foaming agent [trade name: Asahi Glass Co., Ltd. specific CFC] (II
I) Liquids are prepared, and these are treated by the foaming machine as I liquid: II.
Liquid: III liquid = A phenolic foam was prepared in the same manner as in Example 1 except that a foaming stock solution was prepared by mixing at a ratio of 102: 22: 15 (weight ratio). Further, the obtained foam was examined for physical properties and cell structure (cell diameter and cell homogeneity) in the same manner as in Example 1. The results are shown in Table 1.

(Example 7) 100 kg of the liquid benzyl ether type phenol resin prepared in Reference Example 2 was added with 1 kg of SS2010 as the specific silicon compound and 2 as the foam stabilizer.
SH193 [trade name, polysiloxane / oxyalkylene copolymer manufactured by Toray Silicone Co., Ltd.] and 0.5 g of dibutyltin dilaurate as a curing accelerator were added and mixed with stirring, and then 40 kg of the R-141b as a foaming agent.
Was added and mixed to adjust the temperature to 20 ° C. of the resin / foaming agent mixture (liquid I), and the polyisocyanate compound was adjusted to 20 ° C. CR200 [trade name, manufactured by Mitsui Toatsu Kagaku Co., Ltd. Crude MDI, NCO content 31 % By weight] (solution II) and prepared by the foaming machine using solution I: solution II = 100: 1.
A phenol urethane foam was prepared in the same manner as in Example 1 except that the undiluted foaming solution was prepared by mixing the mixture at a weight ratio of 00 (weight ratio). Further, the obtained foam was examined for physical properties and cell structure (cell diameter and cell homogeneity) in the same manner as in Example 1. The results are shown in Table 1.

[0035]

[Table 1]

[0036]

[Table 2]

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

[0038]

EFFECT OF THE INVENTION According to the foam-curable phenol resin composition of the present invention, by using a non-specific CFC foaming agent and a specific silicon compound in combination, a uniform and fine cell structure comparable to that of the CFC foam can be obtained. Since it is possible to produce a foam having the above-mentioned composition, a foam or a non-Freon using a CFC alternative that does not cause deterioration in heat insulation performance and mechanical strength as in the conventional composition and can avoid deterioration of the natural environment due to destruction of the ozone layer. A foamed product can be provided. Also,
Since the specific silicon compound used in the present invention surprisingly has a function of lowering the density of the foam, it has a density comparable to the specific CFC foam even when a non-CFC foaming agent is used, and an alternative CFC substitute. The foaming agent is capable of producing a foam having a lower density and is extremely useful economically.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeki Inatomi 4 of 26 Niitsu, Minamiyama, Fuso-cho, Niwa-gun, Aichi 4 Asahi Organic Materials Co., Ltd. Aichi factory

Claims (1)

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