JPH04364908A - Manufacture of phenol resin foamable body and its application - Google Patents

Abstract

PURPOSE:To use no foaming agent falling under the restriction of use of chlorofluorocarbon and realize no generation of chlorofluorocarbon, and also particularly provide a method of manufacturing a low density phenol resin foamable body ad also a method of manufacturing a composite panel to which the first manufacturing method is applied and the foaming-in-place application method. CONSTITUTION:To provide a method of manufacturing a phenol resin foamable body prepared by foaming and curing a reactive mixture of a foaming agent composed of liquid phenol resin, hydrogen peroxide and an isocyanate compound and a curing agent of either of an oxidized curing agent or an organic ester group and also the manufacturing method of a composite panel in which the first manufacturing method is applied, and also a foaming-in-place application method and a manufacturing method of a phenol resin foamable body for KENZAN, (frog in flower arrangement).

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention mainly relates to construction materials,
Methods for manufacturing phenolic resin foams and composite panels useful for uses such as refrigerator-freezers and heat insulation materials for plants, soundproofing and vibration-proofing materials, structural panels, and tsurugisan, and construction surfaces of structures of buildings, etc. at construction sites. The present invention also relates to an on-site foaming method for a phenolic resin foam, which forms a phenolic resin foam layer in a space, and a method for producing a phenolic resin foam for a tsurugisan.

0002

[Prior Art] Generally, phenolic resin foam is made by adding a curing agent, a foaming agent, and, if necessary, a foam stabilizer to a liquid phenolic resin.
Various foaming methods such as continuous foaming method, injection foaming method, block foaming method, or on-site foaming construction method (e.g., spray foaming method, injection foaming method, etc.) are carried out using reactive mixtures made by mixing additives such as neutralizing agents and flame retardants. It is manufactured by foaming and curing using a method. In the production of such foams, blowing agents and curing agents, like liquid phenolic resins, are important components that affect the properties of the foam. Since the hypothesis was announced that specific fluorocarbon foaming agents such as trichloromonofluoromethane are chemical substances that destroy the stratospheric ozone layer and have a negative impact on the natural environment and the human body, their use has been discouraged from the perspective of protecting the global environment. It is strictly regulated. Therefore, the development of substitutes for specific CFCs has been positioned as an important and urgent issue in this technical field, but in recent years, substitutes such as dichlorotrifluoroethane and dichlorofluoroethane, which have a lower ozone depletion coefficient than conventional products, have been developed. At the same time, its practical application is being widely studied. On the other hand, from the viewpoint of CFC-free foams, there are two methods, for example, which directly use gases such as carbon dioxide, nitrogen, and air, or indirectly by chemical reactions.
Methods of using chemical blowing agents capable of generating nitrogen and other gases are being explored, but the application of carbon dioxide is of particular interest.

0003

[Problems to be Solved by the Invention] However, when carbon dioxide itself is used directly, it is extremely difficult to stably prepare a reactive mixture because carbon dioxide has a very low boiling point, and it is difficult to obtain a reactive mixture. Foams generally have strength problems because they contain voids. On the other hand, baking soda, which is known as a chemical blowing agent, instantaneously generates carbon dioxide when it comes into contact with an acidic curing agent, making foaming operations extremely difficult and having the same problems as using carbon dioxide itself. Furthermore, organic ester curing systems have a problem in that they do not function as blowing agents.

The present invention has been made in view of the problems of the prior art, and uses a chemical blowing agent that can chemically generate carbon dioxide even in acid curing systems or organic ester curing systems. A method for manufacturing a phenolic resin foam that is easy to reduce density and does not cause voids, as well as a method for manufacturing composite panels using the technology, a method for on-site foaming construction, and an application of the technology. The purpose of the present invention is to provide a method for producing a phenolic resin foam for kenzan.

[0005]

[Means for Solving the Problems] As a result of intensive research to achieve the above object, the present inventors have found that a chemical blowing agent consisting of a combination of hydrogen peroxide and an isocyanate compound is an acid curing type or an organic blowing agent. All ester curing systems generate carbon dioxide at a rate that is extremely suitable for foaming operations, making foam production easy and efficient, and the resulting foams are void-free and uniform. I discovered something. In addition, the weight is less than 20 kg/m3, especially 17 to 18 kg/m3, which is difficult to manufacture with conventional technology.
It was discovered that a foam with a low density of less than

That is, the present invention involves foaming a reactive mixture containing as essential components a liquid phenolic resin, a curing agent of either an acidic curing agent or an organic ester, and a blowing agent consisting of hydrogen peroxide and an isocyanate compound. A method for producing a phenolic resin foam characterized by curing, a method for producing a composite panel applying the method, and an on-site foaming construction method, a blowing agent comprising a liquid phenol resin, hydrogen peroxide and an isocyanate compound, and acid curing. agent,
It is an object of the present invention to provide a method for producing a phenolic resin foam for kenzan, which is characterized by foaming and curing a reactive mixture containing a foam stabilizer and a foam breaker as essential components.

The liquid phenolic resin used in the present invention has a crosslinkable functional group (methylol group and/or dimethylene ether group) that causes a curing reaction in the presence of an acidic curing agent or an organic ester curing agent. ) in the molecule, or a resin solution dissolved in an appropriate solvent as necessary. Specifically, it is represented by resol type phenol resin or benzylic ether type phenol resin, but also novolak type phenol resin. Examples include novolac resol type phenolic resins, which are resins with methylol groups added thereto. One type of these liquid phenol resins may be used, or two or more types may be used in combination. In addition, when using organic esters as a hardening agent, from the viewpoint of curing speed, a large amount of inorganic alkali such as potassium hydroxide, sodium hydroxide, lithium hydroxide, etc. is added during or after the resin production. Usually, an alkaline liquid phenol resin obtained from the above method is preferably used.

[0008] Such liquid phenolic resin is usually
Phenols and aldehydes are subjected to addition condensation reaction at a ratio of 0.8 to 4.0 mol of aldehyde per 1 mol of phenol in the presence of a reaction catalyst at 50°C to reflux temperature (in some cases). Depending on the case, neutralization treatment may be performed), and desirably, further dehydration and concentration may be performed to achieve a predetermined characteristic value (e.g. 25°C).
After adjusting the viscosity to 5 to 2000 poise, additives such as a foam stabilizer and a cup linking agent are added as necessary. Examples of the above phenols include phenol, cresol, xylenol, resorcinol, catechol, pyrogallol, bisphenol A, and bisphenol F.
, phenol purification residues, etc. Examples of aldehydes include formaldehyde, paraformaldehyde, glyoxal, and furfural. Examples of reaction catalysts include potassium hydroxide, sodium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, magnesium oxide, sodium phosphate, potassium carbonate, ammonia, zinc acetate, lead acetate, zinc borate, and zinc chloride. , lead naphthenate, and oxalic acid.

[0009] The acidic curing agent or organic ester used in the present invention functions as a curing agent that promotes the curing reaction of liquid phenolic resin. acid,
Monocyclic aromatic sulfonic acids such as xylene sulfonic acid, benzenesulfonic acid, phenolsulfonic acid, and styrene sulfonic acid, or resin-based sulfonic acids such as sulfonated phenol resin and sulfonated polystyrene resin, or naphthalene sulfonic acid and methylnaphthalene sulfonic acid. , naphthalene sulfonic acids such as ethylnaphthalene sulfonic acid, butylnaphthalene sulfonic acid, isopropylnaphthalene sulfonic acid, dibutylnaphthalene sulfonic acid, naphthol sulfonic acids such as naphthol sulfonic acid, anthracene sulfonic acids such as anthracene sulfonic acid, anthranol sulfone Polycyclic aromatic sulfonic acids such as anthranol sulfonic acids, sulfonated creosote oil, condensates of polycyclic aromatic sulfonic acids and/or sulfonated creosote oil with formaldehyde, phosphoric acid, sulfuric acid, etc. Examples include inorganic acids. On the other hand, as organic esters,
For example, aliphatic esters such as methyl formate, ethyl formate, propyl formate, methyl acetate, dimethyl oxalate, ethylene glycol monoacetate, triethylene glycol diacetate, diacetin, triacetin, β-propiolactone, γ-butyrolactone, δ - Oxyacid cyclic esters such as valerolactone and ε-caprolactone,
Dioxolone-2 (commonly known as ethylene carbonate), 4
-Methyldioxolone (commonly known as propylene carbonate), 4-ethyldioxolone, 4-butyldioxolone, 4,4'-dimethyldioxolone, 4,5-dimethyldioxolone, 4-pentyldioxolone Examples include cyclic carbonate esters such as Ron. Note that the acidic curing agent or the organic ester is not limited to those exemplified, and each can be used alone or in combination of two or more types. There is no particular restriction on the amount of these used, but it is generally selected in the range of 3 to 60 parts by weight per 100 parts by weight of the liquid phenol resin.

The blowing agent used in the present invention is a chemical blowing agent that utilizes carbon dioxide generated by the reaction between hydrogen peroxide and an isocyanate compound to form bubbles in the foam. The amount used is not strictly limited as it is determined mainly based on the density and economical efficiency of the desired foam, but generally it is 0.005 gram equivalent or more per 100 parts by weight of the liquid phenolic resin. It is preferably selected within the range of 0.01 to 2.0 gram equivalent. On the other hand, the ratio of the isocyanate compound to hydrogen peroxide is the equivalent ratio of the isocyanate group (NCO group) of the isocyanate compound to hydrogen peroxide (NCO
group/hydrogen peroxide) is usually 0.1 or more, preferably 0.2
-10, more preferably 0.2-1.0. If the amount of hydrogen peroxide used is less than 0.005 gram equivalent and the NCO group/hydrogen peroxide equivalent ratio is less than 0.1, the amount of carbon dioxide generated is so small that it is not practical.

[0011] As the hydrogen peroxide, an easily available aqueous hydrogen peroxide solution (commercially available) having a concentration of 35 to 60% by weight is usually used. On the other hand, as the isocyanate compound, any compound having an NCO group can be used without limitation, but typical examples include tolylene diisocyanate (commonly known as TDI), crude TDI, etc.
, aromatic polyisocyanates such as xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl polyisocyanate (commonly known as crude MDI), alicyclic polyisocyanates such as isophorone diisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate. Examples include polyisocyanates, prepolymer type or nurate type modified products thereof, and the like.

[0012] Foam stabilizers used as necessary in the present invention include, for example, siloxane/oxyalkylene copolymers, polyoxyethylene sorbitan fatty acid esters, castor oil ethylene oxide adducts, alkylphenol ethylene oxide adducts, and tetraalkyl phenol ethylene oxide adducts. Examples include ammonium salts and alkylphenol sulfonates. These foam stabilizers may be used alone or in combination of two or more, and the amount used is selected within the range of 0.3 to 10 parts by weight per 100 parts by weight of the liquid phenolic resin. Examples of the foam-breaking agent include sodium dodecylsulfonate, sodium dibutylnaphthalenesulfonate, and sodium hexylbenzenesulfonate. These foam-breaking agents may be used alone or in combination of two or more, and the amount used is selected within the range of 0.3 to 10 parts by weight per 100 parts by weight of the liquid phenolic resin. In addition, other optional additives include coupling agents such as silane-based, titanate-based, and aluminum-based, curing accelerators such as resorcinol and alkylresorcinol,
Formaldehyde scavengers such as urea and melamine, neutralizing agents such as zinc powder and alumina, boric acid, phosphoric acid and halogen compounds, flame retardants such as melamine, aluminum hydroxide, talc, glass fiber, shirasu balloons, porous materials Examples include reinforcing/filling materials such as aggregates, plasticizers, coloring agents, etc.

Next, a typical embodiment of the method of the present invention using each of the constituent components detailed above will be explained. First of all,
The first method is to apply a continuous foaming method. Specifically, liquid phenolic resin, peroxide Supply a reactive mixture prepared by uniformly mixing hydrogen water, an isocyanate compound, an acidic curing agent or an organic ester curing agent, a foam stabilizer and other additives as necessary using a high-speed stirring mixer. After being supplied from a nozzle, it is heated to complete foaming and curing, and adjusted to a predetermined thickness to form a foam, which is then cut to a predetermined size with an appropriate cutting device to produce a single foam or kraft paper. , composite foam integrated with flat plate facing materials such as aluminum kraft paper, plywood, calcium silicate board, rock wool board, gypsum board, wood wool cement board, etc., formed steel sheet facing materials such as embossed steel sheets, shaped steel sheets, etc. It is possible to obtain phenolic resin foam products such as metal siding integrated with.

[0014] The second method is the application of the in-situ foaming construction method, and specifically, the reactive mixture prepared by homogeneously mixing the high-pressure impingement mixing method instead of the high-speed stirring mixing method described above is applied to the framework of buildings, etc. After spraying onto the work surface with a spray gun or press-fitting into the space of the structure with a hose, it can be foamed and cured at room temperature to form a phenol resin foam on the work surface or inside the space.

The third method is the application of a block foaming method, specifically, a reactive mixture prepared by uniformly mixing using a high-speed stirring mixing method is supplied to a box, and then foamed and hardened at room temperature or under heating. A phenolic resin foam for a sword mountain can be manufactured by forming a block-shaped foam and then cutting this into a predetermined size. In addition, injection foaming is performed by press-filling a reactive mixture prepared by uniformly mixing it using a high-pressure impingement mixing method into the insulation-required space of a refrigerator-freezer or the space of a model for manufacturing partition panels for clean rooms, and then foaming and hardening by heating at room temperature or heating. The phenolic resin foam of the present invention can be produced by a foaming operation such as a foaming method or a method of impregnating glass fiber or the like and foaming it.

[0016]

[Operation] In the method of the present invention, a hydrous reactive mixture consisting of a liquid phenolic resin, hydrogen peroxide, an isocyanate compound, a curing agent, and optionally a foam stabilizer and a foam-breaking agent is generally used as a foaming agent rather than a physical blowing agent. To easily and effectively produce a low-density, void-free foam that exhibits favorable foaming behavior (cream time/gel time) despite using a chemical foaming agent that is difficult to control foaming. Although it is not clear why this is possible, it is inferred as follows from the results of experiments comparing the reactivity of ■ hydrogen peroxide and isocyanate compounds in the presence or absence of a curing agent, or ■ water and isocyanate compounds. .

That is, in a system that does not contain hydrogen peroxide, the generation of carbon dioxide is extremely slow regardless of the presence or absence of a curing agent, whereas when hydrogen peroxide is present, the reaction induction period is short and the generation is extremely rapid. Since carbon dioxide is generated, hydrogen peroxide seems to promote the generation of carbon dioxide. However, when an acidic curing agent is further present, the reaction induction period becomes longer and thereafter rapid generation of carbon dioxide is observed. From this, even with an acid curing system that cures slowly, a foam with low density and no voids can be obtained.

On the other hand, in organic ester curing systems, the curing speed of the resin is much faster than in acid curing systems, and therefore more rapid carbon dioxide generation is required. However, since the generation of carbon dioxide in the presence of an alkaline substance is extremely accelerated, it becomes possible to incorporate a large amount of carbon dioxide into the system before curing the resin. Therefore, it is presumed that even with a fast-curing organic ester curing system, a low-density, void-free foam can be obtained.

【Example】

[0019] The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples. Note that various properties of the foam were measured by the following test methods.

1. Density and compressive strength are JIS・A-9
It was measured according to 514.

2. Thermal conductivity was measured using a thermal conductivity meter, TC-32 (hot wire method) manufactured by Kyoto Electronics Industry.

3. Adhesion and the presence or absence of voids were determined visually.

[Example 1] (1) Production of resol type liquid phenol resin Phenol 10 was added to a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser.
10.2 kg of 47% formalin, and 1 kg of 20% potassium hydroxide aqueous solution were heated to a temperature of about 90°C over about 1 hour while stirring, and the reaction was further carried out at the same temperature for 2 hours. The product was obtained. Next, the obtained reaction product was cooled to 40°C, and then neutralized to pH 7.0 with phenolsulfonic acid, and the inside of the reaction vessel was adjusted to about 60 mmH.
Dehydration and concentration were carried out while maintaining a vacuum of 1.5 g to obtain a resol type liquid phenol resin. The obtained resol type liquid phenol resin had a viscosity of 3,000 cp/25°C. This is called resin A.

(2) Production of phenolic resin foam 2 g of polysiloxane/oxyalkylene copolymer [trade name: SH-193, manufactured by Toray Silicone Co., Ltd.] and 35% filtration were added as a foam stabilizer to 100 g of the resin A. Hydrogen oxide water [
Made by Mitsubishi Gas Chemical Co., Ltd.] 6g, mixed and heated at 20°C.
Adjusted to. Continuing to adjust to 20℃, NCO% is 31
% Crude MDI [Product name: MDICR-200
, manufactured by Mitsui Toatsu Chemical Co., Ltd.] and 200 g of water as an acidic curing agent, 18 g of an 80% xylene sulfonic acid aqueous solution in which 800 g of xylene sulfonic acid [trade name: Teikatox 100, manufactured by Teika Co., Ltd.] was dissolved was added. ,
Mix with a homogenizer (rotation speed of about 5,000 rpm) for 15 seconds to obtain a homogeneous reactive mixture (hereinafter referred to as foaming stock solution).
adjusted. Next, the obtained foaming stock solution was placed in a mold (2 directions free), which was preheated to 60°C and covered with kraft paper.
280 x 280 x 40 mm) and was foamed and cured to produce a phenolic resin foam. The cream time of the foaming stock solution is 32 seconds, and the gel time is 6 seconds.
It was 5 seconds. Further, various properties of the obtained phenolic resin foam were measured by the above test method. The results are shown in the table.

[Comparative Example 1] A phenol resin foam was prepared in the same manner as in Example 1 except that hydrogen peroxide solution was not used. In addition, the cream time of the foaming stock solution is 25
The gel time was 35 seconds. Further, various properties of the obtained phenolic resin foam were measured by the above test method. The results are shown in the table.

[Comparative Example 2] Water 3 instead of hydrogen peroxide solution
．． A phenolic resin foam was produced in the same manner as in Example 1 except that 9 g was used. The cream time of the foaming stock solution was 42 seconds, and the gel time was 60 seconds. Further, various properties of the obtained phenolic resin foam were measured by the above test method. The results are shown in the table.

[Examples 2 to 6] Phenol resin foams were prepared in the same manner as in Example 1, except that the blending ratio of hydrogen peroxide solution and isocyanate compound to resin A was changed. In addition, the cream time and gel time of the foaming stock solution and various properties of the obtained phenolic resin foam were measured by the above-mentioned measuring method. The results are shown in the table.

[Examples 7 to 8] Phenol resin foams were prepared in the same manner as in Example 1, except that the type of isocyanate compound and the blending ratio of the isocyanate compound to resin A were changed. In addition, the cream time and gel time of the foaming stock solution and various properties of the obtained phenolic resin foam were measured by the above-mentioned measuring method. The results are shown in the table.

[Example 9] (1) Production of benzylic ether type liquid phenol resin A reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser was charged with 100 kg of phenol, 102 kg of 47% formalin, and 1 kg of lead acetate and stirred. It took about 1 hour while
The temperature was raised to 00°C, and the reaction was further carried out at the same temperature for 5 hours to obtain a water-containing initial condensate. Next, 3.0 kg in the mantle.
/cm2 of steam pressure and heating with a long tubular jacket (length L = 23 m, inner diameter D = 23 mm, L/cm2).
5 of the initial condensate from the stock solution supply port of D=1,000).
Moisture and unreacted monomers are removed by continuously injecting at a flow rate of 0 kg/Hr and leading to a jacketed evaporator installed at the rear of the device (temperature inside the can: approx. 120°C, degree of vacuum: approx. 100 mmHg) for flushing. A benzylic liquid phenol resin was obtained by continuously dehydrating and concentrating the resin while removing other substances from the system. The obtained benzylic ether type liquid phenol resin had a viscosity of 6,000 cp/25°C. This will be referred to as resin B.

(2) Production of phenolic resin foam SH-193 2 was added as a foam stabilizer to 100 g of the resin B.
Blend and mix 3g of 35% hydrogen peroxide solution and heat at 20°C.
Adjusted to. CR-200 subsequently adjusted to 20℃
8 g and 16 g of an 80% xylene sulfonic acid aqueous solution as an acidic curing agent were added and mixed for 15 seconds using a homogenizer to prepare a uniform foaming stock solution. Next, the same procedure as in Example 1 was carried out to prepare a phenolic resin foam. The foaming stock solution had a cream time of 32 seconds and a gel time of 42 seconds. Further, various properties of the obtained phenolic resin foam were measured by the above-mentioned measuring method. The results are shown in the table.

[Examples 10 to 11] Phenol resin foams were prepared in the same manner as in Example 9, except that the blending ratio of hydrogen peroxide solution and isocyanate compound to resin B was changed. In addition, the cream time and gel time of the foaming stock solution and various properties of the obtained phenolic resin foam were measured by the above-mentioned measuring method. The results are shown in the table.

[Example 12] (1) Production of alkaline resol type liquid phenolic resin 10 kg of phenol and 47% formalin were placed in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a dropping funnel.
After charging 6 kg, 7.2 kg of a 50% potassium hydroxide aqueous solution was added dropwise from the separating funnel while stirring and mixing, and the temperature was raised to 75°C over about 1.5 hours, and then the temperature was raised to 75°C at the same temperature. The reaction was carried out for a period of time to obtain a reaction product. Subsequently, the obtained reaction product was dehydrated and concentrated under a vacuum of about 60 mmHg to obtain an alkaline resol type liquid phenol resin. The obtained alkaline resol type liquid phenol resin had a viscosity of 5,000 cp/25°C. This will be referred to as resin C.

(2) Production of phenolic resin foam SH-193 was added as a foam stabilizer to 100 g of the resin C.
2g and 6g of 35% hydrogen peroxide solution and mix.
The temperature was adjusted to 0°C. CR-20 subsequently adjusted to 20℃
0 and 15 g of γ-butyrolactone were added and mixed for 15 seconds using a homogenizer to prepare a uniform foaming stock solution. Next, the same procedure as in Example 1 was carried out to prepare a phenolic resin foam. The cream time of the foaming stock solution is 12
The gel time was 27 seconds. Further, various properties of the obtained phenolic resin foam were measured by the above-mentioned measuring method. The results are shown in the table.

[Examples 13 to 14] Phenol resin foams were prepared in the same manner as in Example 12, except that the blending ratio of hydrogen peroxide solution and isocyanate compound to resin C was changed. In addition, the cream time and gel time of the foaming stock solution and various properties of the obtained phenolic resin foam were measured by the above-mentioned measuring method. The results are shown in the table.

[Comparative Example 3] 2 g of SH-193 as a foam stabilizer and trichlorotrifluoroethane as a blowing agent for 100 g of resin A [Product name: Asahi Flon 113]
, manufactured by Asahi Glass Co., Ltd.] were blended and mixed, and the temperature was adjusted to 20°C. Subsequently, 18 g of an 80% xylene sulfonic acid aqueous solution as an acidic curing agent adjusted to 20° C. was added and mixed for 15 seconds with a homogenizer to prepare a uniform foaming stock solution. Next, a phenol resin foam was produced in the same manner as in Example 1. Note that the cream time was 31 seconds and the gel time was 62 seconds. Further, various properties of the obtained phenolic resin foam were measured by the above-mentioned measuring method. The results are shown in the table.

[Example 15] 100 kg of resin A was mixed with 2 kg of SH-193 as a foam stabilizer and 6 kg of 35% hydrogen peroxide (liquid I) and MDICR-
200 (Liquid II) and an 80% xylene sulfonic acid aqueous solution (Liquid III) as an acidic curing agent were each adjusted to 20° C. and prepared. Next, these were mixed using a foaming material for phenol foam [trade name: PA-210, manufactured by Toho Kikai Co., Ltd.] at a weight ratio of liquid I/liquid II/liquid III = 108/16/16 to obtain a foaming stock solution. adjusted. The foaming stock solution is supplied onto the bottom material (glass fiber-containing calcium carbonate paper) which is continuously conveyed by an endless conveyor provided in two upper and lower stages, and the glass fiber-mixed calcium carbonate paper as the top material is overlaid. Subsequently, the foam was introduced into the endless conveyor kept at 80°C, where it was foamed and cured, and then cut into predetermined dimensions using a cutting device, measuring 1800 x 920 x 25 mm.
phenolic resin foam panels were created. The cream time and gel time of the foaming stock solution are each 2
They were 5 seconds and 46 seconds. Further, various properties of the obtained phenolic resin foam panel were measured by the above-mentioned measuring method. The results are shown in the table.

[Example 16] For 100 kg of resin A, 3 kg of castor oil and ethylene oxide adduct [trade name: CX-100: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] as foam stabilizers and 3 kg of 35% hydrogen peroxide solution (Liquid I)
and MDICR-200 (liquid II) and an 80% xylene sulfonic acid aqueous solution (liquid III) as an acidic curing agent were prepared by adjusting the temperature to 20°C. Next, using foaming material PA-210 for phenolic foam, liquid I/liquid II/liquid
Liquid III = mixed at a weight ratio of 106/8/12,
A foaming stock solution was prepared. Next, the foaming stock solution was injected into a mold made by combining a molded steel plate preheated to 60°C with a heat press and a polyester frame material using a flexible hose, and foamed and hardened to form a mold of 2700 x 920 x 40 mm.
A phenolic resin foam metal sandwich panel was created. The cream time of the foaming stock solution was 50 seconds, and the gel time was 90 seconds. Further, various properties of the obtained phenolic resin foam metal sandwich panel were measured by the above-mentioned measuring method. The results are shown in the table.

[Example 17] 100 kg of resin A was mixed with 2 kg of SH-193 as a foam stabilizer and 3 kg of 35% hydrogen peroxide (liquid I), and crude MDI with an NCO% of 31%. Product name: MDICR-1
00, manufactured by Mitsui Toatsu Chemical Co., Ltd.] (Liquid II) and an 80% xylene sulfonic acid aqueous solution as an acidic curing agent (Liquid III) were adjusted to 25° C. and prepared. Next, these were mixed in a weight ratio of liquid I/liquid II/liquid III = 105/8/18 using foaming material PA-210 for phenol foam to prepare a foaming stock solution. The foaming stock solution was also supplied onto the bottom material (formed steel plate) preheated to 70°C, which was continuously conveyed by an endless conveyor installed in two stages, upper and lower, and after overlapping aluminum vapor-deposited calcium carbonate paper as the top material. Subsequently, the product was introduced into the endless conveyor kept at 80° C., allowed to foam and harden, and further cut into a predetermined length using a guillotine cutter to create a phenolic resin foam metal siding measuring 3600 x 350 x 25 mm. The cream time of the foaming stock solution was 10 seconds, and the gel time was 30 seconds. Further, various properties of the obtained phenolic resin foam metal siding were measured by the above test method. The results are shown in the table.

[Example 18] 100 kg of resin A was mixed with 2 kg of SH-193 as a foam stabilizer and 6 kg of 35% hydrogen peroxide (liquid I) and CR-100.
(Liquid II) and a 63% aqueous phenol sulfonic acid solution as an acidic curing agent [Product name: PS-63, Daiichi Kogyo Seiyaku Co., Ltd.
Co., Ltd. (Liquid III) was adjusted to 30°C and prepared. Next, the discharge temperature of each was further adjusted to 38℃, and a three-component mixed type sprayed foam material was used for liquid I/liquid II/liquid
Liquid III = mixed in a weight ratio of 108/16/30, sprayed on a plywood board at 20°C, foamed and hardened at room temperature,
A phenolic resin foam with a thickness of 25 mm was created. Note that the cream time was 5 seconds and the gel time was 10 seconds. Further, various properties of the obtained phenolic resin foam were measured by the above-mentioned measuring method. The results are shown in the table.

[Example 19] Resol type liquid phenol resin containing a foam stabilizer [Product name: PF-0165L, manufactured by Asahi Yokuzai Kogyo Co., Ltd.] 35% hydrogen peroxide solution 0 to 10 kg
．． 6 kg and 0.2 kg of pigment were premixed, and then
Foam-breaking agent [Product name: SA-9, manufactured by Asahi Yokuzai Kogyo Co., Ltd.] 0
．． 25 kg of CR-100, 1.6 kg of CR-100, and 0.8 kg of acidic curing agent PS-63 were added and mixed for 120 seconds using a large homogenizer to prepare a uniform foaming stock solution. Next, the obtained foaming stock solution was laid down on kraft paper.
The mixture was quickly injected into a 1200 x 700 x 500 mm mold preheated to 0°C, and foamed and cured to create a phenol resin foam for tsurugisan. The obtained phenolic resin foam was 230× 110×
When cut out to a size of 80 mm and measured its various properties, the density was 0.0228 g/cm3, and the compressive strength was 0.5 kg/cm.
2. It was an excellent material for a sword mountain with a water absorption time of 90 seconds and a water absorption amount of 1800 g. In addition, water absorption time and water absorption amount are determined by floating a block of the above dimensions in a 20L bucket filled with water, measuring the time until the block completely sinks, and measuring the water absorption time, then measuring the weight of the block taken out from the water. did.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

[Table 4]

[0045]

[Table 5]

[0046]

Effects of the Invention As explained in detail above, the present invention uses a chemical blowing agent consisting of hydrogen peroxide and isocyanate compounds that generate carbon dioxide, so it is a CFC-free type that does not deplete the ozone layer and has no voids. Therefore, it is possible to provide a phenolic resin foam that is free from ozone layer depletion, thereby contributing to the prevention of adverse effects on the natural environment and the human body due to ozone layer depletion. In addition, since carbon dioxide is generated in accordance with the curing speed of the curing system, it is possible to easily and effectively produce low-density phenolic resin foam, which has been considered difficult in the past, and it is possible to reduce the economic unit. . Furthermore, since the generation of voids is suppressed, this technique has the advantage of being particularly applicable to on-site foaming construction, and has extremely high industrial value.

Claims (6)

[Claims] [Claim 1] A method for producing a phenolic resin foam, which comprises foaming and curing a reactive mixture whose essential components are a liquid phenolic resin, an acidic curing agent, and a chemical blowing agent consisting of hydrogen peroxide and an isocyanate compound. . 2. Production of a phenolic resin foam, characterized by foaming and curing a reactive mixture containing an alkaline liquid phenol resin, an organic ester, and a chemical blowing agent consisting of hydrogen peroxide and an isocyanate compound as essential components. Method. 3. A method for producing a composite panel, comprising integrally fixing a facing material to at least one side of a phenolic resin foam obtained from the reactive mixture according to claim 1 or 2. 4. The method for manufacturing a composite panel according to claim 3, wherein the facing material is a molded facing material obtained by embossing or shaping a metal plate. 5. The reactive mixture according to claim 1 or 2 is sprayed onto the construction surface of a building frame or the like or injected into the space of the framework and foamed and hardened to form the reactive mixture on the construction surface or inside the space. A method for on-site foaming construction of phenolic resin foam, characterized by forming a phenolic resin foam layer. 6. A reactive mixture comprising as essential components a liquid phenolic resin, an acidic curing agent, a foam stabilizer and a foam-breaking agent, and a chemical blowing agent consisting of hydrogen peroxide and an isocyanate compound is foam-cured. A method for producing phenolic resin foam for tsurugisan.