JP2845641B2 - Method for producing phenolic resin foam and its application - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
Production method of phenolic resin foams and composite panels useful for applications such as insulation and heat insulating materials for refrigerators and refrigerators, sound and vibration proofing materials, structural panels, sword mountains, etc., and construction surfaces of buildings and other structures at construction sites Also, the present invention relates to a method for in-situ foaming of a phenolic resin foam for forming a phenolic resin foam layer in a space portion, and a method for producing a phenolic resin foam for Kenzan.

[0002]

2. Description of the Related Art Generally, a phenolic resin foam is obtained by adding a curing agent, a foaming agent, and, if necessary, a foam stabilizer to a liquid phenolic resin.
Various types of foaming such as continuous foaming, injection foaming, block foaming, or in-situ foaming (eg, spraying foaming, injection foaming, etc.) are performed on the reactive mixture obtained by mixing additives such as neutralizers and flame retardants. It is manufactured by foaming and curing according to the method. In the production of such a foam, a foaming agent and a curing agent are important components that determine the properties of the foam as well as the liquid phenol resin. Among them, a foaming agent, especially trichlorotrifluoroethane, which has been conventionally used, The use of certain CFC-based blowing agents, such as trichloromonofluoromethane, has been published since the hypothesis that they are chemical substances that destroy the stratospheric ozone layer and adversely affect the natural environment and the human body. Strictly regulated. Therefore, in the technical field, the development of specific CFC substitutes has been regarded as an important and urgent issue.In recent years, substitutes such as dichlorotrifluoroethane and dichlorofluoroethane, which have a smaller ozone depletion potential than conventional products, have been developed. At the same time, its practical application has been widely studied. On the other hand, from the viewpoint of non-fluorocarbon foam,
For example, a method of directly using a gas such as carbon dioxide, nitrogen, and air itself, or a method of using a chemical blowing agent having a function of indirectly generating carbon dioxide, nitrogen, and the like by a chemical reaction has been sought. However, the application of carbon dioxide is of particular interest.

[0003]

However, when carbon dioxide itself is directly used, it is extremely difficult to prepare a reactive mixture stably because carbon dioxide has a very low boiling point. Foams generally have strength problems due to the inclusion of voids. On the other hand, baking soda, which is known as a chemical blowing agent, generates carbon dioxide instantaneously when it comes into contact with an acidic curing agent, so that the foaming operation is extremely difficult and has the same problems as the use of carbon dioxide itself. Further, there is a problem that the organic ester curing system does not function as a foaming agent.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and uses a chemical blowing agent capable of chemically generating carbon dioxide even in an acid-curable system or an organic ester-curable system to reduce the use of non-fluorocarbons. A method for producing a phenolic resin foam that is easy to reduce the density and that does not involve the generation of voids, and a method for producing a composite panel and an on-site foaming construction method using the technology, and applying the technology It is an object of the present invention to provide a method for producing a phenolic resin foam for Kenzan.

[0005]

The present inventors have conducted intensive studies to achieve the above object, and as a result, a chemical foaming agent comprising a combination of hydrogen peroxide and an isocyanate compound has been found to be an acid-curable or organic compound. In any of the ester curing systems, carbon dioxide is generated at a rate very suitable for the foaming operation, so that foam production is easy and efficient, and the resulting foam is uniform without voids. I found something. Also, found to be able to very easily manufactured than 20 kg / m ³ production has been difficult, especially 17~18kg / m ³ less than the low density foam in the prior art, the present invention based on these findings It was completed.

That is, the present invention foams a reactive mixture comprising a liquid phenolic resin, a curing agent of one of an acidic curing agent and an organic ester, and a foaming agent comprising hydrogen peroxide and an isocyanate compound as essential components. A method for producing a phenolic resin foam characterized by being cured, a method for producing a composite panel to which the method is applied, a method for foaming in situ, a liquid phenolic resin, a foaming agent comprising hydrogen peroxide and an isocyanate compound, and acid curing. It is an object of the present invention to provide a method for producing a phenolic resin foam for Kenzan, which comprises foaming and curing a reactive mixture containing an agent, a foam stabilizer and a foam breaking agent as essential components.

[0007] The liquid phenolic resin used in the present invention comprises a crosslinkable functional group (a methylol group and / or a dimethylene ether group) which causes a curing reaction in the presence of any one of an acidic curing agent and an organic ester. ) In the molecule or a resin solution dissolved in an appropriate solvent as required. Specific examples thereof include a resol phenol resin and a benzylic ether phenol resin. A novolak resol type phenol resin in which a methylol group is added to the resin is exemplified. One of these liquid phenol resins may be used, or two or more of them may be used in combination. In addition, as a liquid phenol resin when an organic ester is used as a curing agent, from the viewpoint of curing speed, for example, a large amount of an inorganic alkali such as potassium hydroxide, sodium hydroxide, or lithium hydroxide is used during or after the production of the resin. Alkaline liquid phenolic resin obtained by the above is usually preferably used.

[0008] Such a liquid phenol resin is usually
Phenols and aldehydes are used, for example, in a ratio of 0.8 to 4.0 moles of aldehydes to 1 mole of phenols,
After performing an addition condensation reaction at 50 ° C. to reflux temperature in the presence of a reaction catalyst (in some cases, performing a neutralization treatment), it is desirably further dehydrated and concentrated to a predetermined characteristic value (for example, a viscosity at 25 ° C. of 5%). After adjusting to 2,000 poise), it is manufactured by adding additives such as a foam stabilizer and a cup linking agent as needed. Examples of the phenols include phenol, cresol, xylenol, resorcin, catechol, pyrogallol, bisphenol A, bisphenol F, and purified residues of phenols. As aldehydes,
For example, there are formaldehyde, paraformaldehyde, glyoxal, furfural and the like. As the reaction catalyst, for example, potassium hydroxide, sodium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, magnesium oxide, sodium phosphate, potassium carbonate, ammonia, zinc acetate, lead acetate, zinc borate, zinc chloride , Lead naphthenate and oxalic acid.

The acidic curing agent or the organic ester used in the present invention functions as a curing agent for accelerating the curing reaction of the liquid phenolic resin. acid,
Monocyclic aromatic sulfonic acid such as xylene sulfonic acid, benzene sulfonic acid, phenol sulfonic acid and styrene sulfonic acid, or resin sulfonic acid such as sulfonated phenol resin and sulfonated polystyrene resin, or naphthalene sulfonic acid and methyl naphthalene sulfonic acid , Naphthalene sulfonic acids such as ethyl naphthalene sulfonic acid, butyl naphthalene sulfonic acid, isopropyl naphthalene sulfonic acid, dibutyl naphthalene sulfonic acid, naphthol sulfonic acids such as naphthol sulfonic acid, anthracene sulfonic acids such as anthracene sulfonic acid, and anthranol sulfone Polycyclic aromatic sulfonic acid such as anthranol sulfonic acid such as acid, sulfonated creosote oil, polycyclic aromatic sulfonic acid and / or sulfonated creosote oil and formaldehyde Condensate or phosphoric acid, and inorganic acids such as sulfuric acid. On the other hand, as organic esters,
For example, methyl formate, ethyl formate, propyl formate, methyl acetate, dimethyl oxalate, ethylene glycol monoacetate, triethylene glycol diacetate, diacetin, aliphatic esters such as triacetin, β-propiolactone, γ-butyrolactone, δ -Valerolactone, oxyacid cyclic esters such as ε-caprolactone,
Dioxolone-2 (commonly known as ethylene carbonate), 4
-Methyldioxolone (commonly referred to as propylene carbonate), 4-ethyldioxolone, 4-butyldioxolone, 4,4'-dimethyldioxolone, 4,5-dimethyldioxolone, 4-pentyldioxo And cyclic carbonates such as lon. The acidic curing agent and the organic esters are not limited to those exemplified above, and each of them can be used alone or in combination of two or more. The amounts of these are not particularly limited, but are 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 for utilizing carbon dioxide generated by the reaction between hydrogen peroxide and an isocyanate compound to form bubbles in a foam. The amount used is not specifically limited because it is a required amount mainly considering the density and economics of the desired foam, but is generally 0.005 gram equivalent or more per 100 parts by weight of liquid phenol resin, preferably It is chosen in the range of 0.01 to 2.0 gram equivalents. On the other hand, the use ratio of the isocyanate compound to the hydrogen peroxide is determined by the isocyanate group (NCO) of the isocyanate compound.
Ratio) to hydrogen peroxide (NCO group / hydrogen peroxide)
Is usually 0.1 or more, preferably 0.2 to 10, more preferably
It is selected in the range of 0.2 to 1.0. The amount of hydrogen peroxide used
If it is less than 0.005 gram equivalent and the equivalent ratio of NCO group / hydrogen peroxide is less than 0.1, the amount of carbon dioxide generated is small and not practical.

As the hydrogen peroxide, an aqueous hydrogen peroxide solution (commercially available) having a concentration of 35 to 60% by weight, which is easily available, 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,
Xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate,
Polymethylene polyphenyl polyisocyanate (commonly known as
Examples thereof include aromatic polyisocyanates such as crude MDI), alicyclic polyisocyanates such as isophorone diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, and prepolymer or nurate modified products thereof.

Examples of the foam stabilizer optionally used in the present invention include siloxane / oxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, alkylphenol ethylene oxide adduct, tetraalkyl Examples thereof include ammonium salts and alkylphenol sulfonates. One of these foam stabilizers may be used, or two or more thereof may be used in combination. The amount of the foam stabilizer is selected within the range of 0.3 to 10 parts by weight per 100 parts by weight of the liquid phenol resin. Examples of the foam breaking agent include sodium dodecylsulfonate, sodium dibutylnaphthalenesulfonate, and sodium hexylbenzenesulfonate. One of these foam breakers may be used, or two or more thereof may be used in combination.
It is selected in the range of 0.3 to 10 parts by weight per 100 parts by weight. Other optional additives include silane-based, titanate-based, aluminum-based coupling agents, resorcinol, curing accelerators such as alkylresorcin, urea, formaldehyde scavengers such as melamine, zinc powder, and alumina. Neutralizing agents, borate / phosphoric acid / halogen compounds, flame retardants such as melamine, aluminum hydroxide, talc, glass fibers, shirasu balloons, reinforcing / filling materials such as porous aggregates,
Other examples include a plasticizer and a coloring agent.

Next, a typical embodiment of the method of the present invention using the above-described components will be described. First,
The first method is the application of a continuous foaming method. Specifically, a liquid phenol resin, a peroxide, and the like are placed on a surface material that is continuously conveyed by an endless conveyor (with a built-in heating device) provided in upper and lower two stages. Hydrogen water, any one of an isocyanate compound and an acidic curing agent or an organic ester, a curing agent,
If necessary, a reactive mixture prepared by uniformly mixing a foam stabilizer and other additives with a high-speed stirring mixer is supplied from a supply nozzle, and then heated to complete foaming and curing, and have a predetermined thickness. To a foam, and then cut it to a predetermined size with a suitable cutting device to form a single foam,
Formed steel sheets such as kraft paper, aluminum kraft paper, plywood, calcium silicate board, rock wool board, gypsum board, wood wool cement board, etc. A phenolic resin foam product such as metal siding integrated with the face material can be obtained.

The second method is the application of an in-situ foaming method. Specifically, a reactive mixture prepared by uniform mixing by a high-pressure collision mixing method in place of the high-speed stirring and mixing method is used to form a building such as a building. After spraying onto the work surface with a spray gun or press-fitting into the space of the body with a hose, foaming and curing are performed at room temperature to form a phenol resin foam on the work surface or in the space.

The third method is to apply a block foaming method. Specifically, a reactive mixture prepared by uniform mixing by a high-speed stirring and mixing method is supplied to a box, and then foamed and cured at room temperature or under heating. To form a block-shaped foam, and then cut into a predetermined size to produce a phenolic resin foam for a sword. In addition, the reactive mixture prepared by uniform mixing by the high-pressure collision mixing method is press-filled into the heat-insulated space of refrigerators and refrigerators and the space of the model for manufacturing partition panels for clean rooms, and is injected and foamed by foaming and hardening at room temperature or by heating. The phenolic resin foam of the present invention can be produced by a foaming operation such as a method of impregnating glass fibers or the like and foaming.

[0016]

In the method of the present invention, a water-containing reactive mixture comprising a liquid phenolic resin, hydrogen peroxide, an isocyanate compound, a curing agent, and, if necessary, a foam stabilizer and a foam breaking agent is generally used instead of a physical foaming agent. Easy and effective production of low-density, void-free foams that exhibit favorable foaming behavior (cream time / gel time) despite the use of chemical foaming agents that are difficult to control foaming The reason why the reaction can be carried out is not clear, but it is inferred as follows from the results of the reactivity comparison experiment between the hydrogen peroxide solution and the isocyanate compound or the water and the isocyanate compound in the presence or absence of the curing agent.

That is, in a system containing no hydrogen peroxide, the generation of carbon dioxide is extremely slow irrespective of the presence or absence of a curing agent, whereas when hydrogen peroxide is present, the reaction induction period is short and extremely rapid. Since carbon dioxide is generated, it is considered that hydrogen peroxide promotes the generation of carbon dioxide. However, when an acidic curing agent further coexists, the reaction induction period is prolonged, and thereafter rapid generation of carbon dioxide is observed. From this fact, a low-density, void-free foam can be obtained even with an acid-curing system that cures slowly.

On the other hand, in the organic ester curing system, since the curing speed of the resin is much higher than that of the acid curing system, a more rapid generation of carbon dioxide is required. However, since the generation of carbon dioxide in the presence of an alkaline substance is extremely promoted, a large amount of carbon dioxide can be contained in the system before the resin is cured. Therefore, it is presumed that a foam having a low density and no voids can be obtained even with an organic ester curing system that cures quickly.

【Example】

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The properties of the foam were measured by the following test methods.

1. The density and compressive strength were measured according to JIS A-9514.

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

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

Example 1 (1) Production of Resol Type Liquid Phenol Resin A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 10 kg of phenol, 10.2 kg of 47% formalin and 1 kg of a 20% aqueous potassium hydroxide solution. It took about 1 hour to warm up to a temperature of about 90 ° C. while stirring and charging, and further reacted at the same temperature for 2 hours to obtain a reaction product. Next, the obtained reaction product was
After cooling to ℃, the mixture was neutralized and adjusted to pH 7.0 with phenolsulfonic acid, and further dehydrated and concentrated while keeping the inside of the reaction vessel at a vacuum of about 60 mmHg to obtain a resole type liquid phenol resin. The obtained resole type liquid phenol resin has a viscosity of 3,0
00 cp / 25 ° C. This is designated as resin A.

(2) Production of a phenolic resin foam 100 g of the resin A was used as a foam stabilizer as a polysiloxane.
2 g of an oxyalkylene copolymer (trade name: SH-193, manufactured by Toray Silicone Co., Ltd.) and 6 g of 35% hydrogen peroxide solution (produced by Mitsubishi Gas Chemical Co., Ltd.) were mixed and adjusted to 20 ° C. . Crude MDI whose NCO% adjusted to 20 ° C is 31% (trade name: MDICR-200, Mitsui Toatsu Chemicals, Inc.)
Xylene sulfonic acid [trade name: Teica Tox 100, Teica Corporation] in 16 g and 200 g of water as an acidic curing agent
80% xylene sulfonic acid aqueous solution in which 800 g was dissolved 18
g, and add 15 g with a homogenizer (about 5,000 rpm).
The mixture was mixed for 2 seconds to prepare a uniform reactive mixture (hereinafter referred to as “foaming stock solution”). Next, the obtained foaming stock solution was laid on kraft paper, quickly injected into a mold (280 × 280 × 40 mm) having two directions free preheated to 60 ° C., and foamed and cured to produce a phenolic resin foam. . The cream time of the foaming stock solution was 32 seconds, and the gel time was 65 seconds. Various properties of the obtained phenolic resin foam were measured by the above-mentioned test methods. 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 no aqueous hydrogen peroxide was used. In addition, the cream time of the foaming stock solution was 25 seconds, and the gel time was 35 seconds. Various properties of the obtained phenolic resin foam were measured by the above-mentioned test methods. The results are shown in the table.

Comparative Example 2 Water 3.
A phenolic resin foam was prepared in the same manner as in Example 1 except that 9 g was used. The foaming stock solution had a cream time of 42 seconds and a gel time of 60 seconds. or,
Various properties of the obtained phenolic resin foam were measured by the above-mentioned test methods. The results are shown in the table.

Examples 2 to 6 A phenol resin foam was prepared in the same manner as in Example 1 except that the mixing ratio of the hydrogen peroxide solution and the isocyanate compound to the resin A was changed. 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 methods. The results are shown in the table.

[Examples 7 and 8] A phenol resin foam was prepared in the same manner as in Example 1 except that the type of the isocyanate compound and the mixing ratio of the isocyanate compound to the resin A were changed. 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 methods. The results are shown in the table.

Example 9 (1) Production of benzylic ether type liquid phenol resin 100 kg of phenol, 102 kg of 47% formalin and 1 kg of lead acetate were charged into a reactor equipped with a thermometer, a stirrer and a reflux condenser, and stirred. The temperature was raised to a temperature of 100 ° C. in about 1 hour while the reaction was continued for 5 hours at the same temperature to obtain a hydrous initial condensate. Next, the above-mentioned solution was fed from the undiluted solution supply port of a long tubular outer jacketed reaction device (length L = 23 m, inner diameter D = 23 mm, L / D = 1,000), which was heated by applying a steam pressure of 3.0 kg / cm ^{2 to} the outer jacket. The initial condensate was continuously injected at a flow rate of 50 kg / Hr, and led to an evaporator with a jacket provided at the rear of the apparatus (inside temperature: about 120 ° C., degree of vacuum: about 100 mmHg), and was flushed.
While removing water and unreacted monomers from the system, the mixture was continuously dehydrated and concentrated to obtain a benzylic liquid phenol resin. The obtained benzylic ether type liquid phenol resin had a viscosity of 6,000 cp / 25 ° C. This is called resin B.

(2) Production of phenolic resin foam 2 g of SH-193 as a foam stabilizer was added to 100 g of the resin B.
3 g of 35% hydrogen peroxide solution was blended, mixed and adjusted to 20 ° C. Subsequently, 8 g of CR-200 adjusted to 20 ° C. and 16 g of an 80% aqueous xylene sulfonic acid solution as an acidic curing agent were added, and mixed with a homogenizer for 15 seconds to prepare a uniform foaming stock solution. Next, the same operation as in Example 1 was performed to prepare a phenol resin foam. The cream time of the foaming stock solution was 32 seconds, and the gel time was 42 seconds. Various properties of the obtained phenolic resin foam were measured by the above-mentioned measuring methods. The results are shown in the table.

Examples 10 to 11 A phenolic resin foam was prepared in the same manner as in Example 9 except that the mixing ratio of the aqueous hydrogen peroxide and the isocyanate compound to the resin B was changed. 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 methods. The results are shown in the table.

Example 12 (1) Production of Alkaline Resol Type Liquid Phenolic Resin A reactor equipped with a thermometer, stirrer, reflux condenser and dropping funnel was charged with 10 kg of phenol and 13.6 kg of 47% formalin, and then stirred. 50% aqueous solution of potassium hydroxide while mixing 7.
It takes about 1.5 hours while dropping 2 kg from the separatory funnel
The temperature was raised to 75 ° C., and the reaction was carried out at the same temperature for 8 hours 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 is called resin C.

(2) Production of Phenolic Resin Foam To 100 g of the resin C, 2 g of SH-193 and 6 g of 35% hydrogen peroxide were blended and mixed as a foam stabilizer and adjusted to 20 ° C. Subsequently, 16 g of CR-200 and 15 g of γ-butyrolactone adjusted to 20 ° C. were added and mixed with a homogenizer for 15 seconds to prepare a uniform foaming stock solution. Next, the same operation as in Example 1 was performed to prepare a phenol resin foam. The cream time of the foaming stock solution was 12 seconds, and the gel time was 27 seconds. Various properties of the obtained phenolic resin foam were measured by the above-mentioned measuring methods. The results are shown in the table.

Examples 13 and 14 A phenol resin foam was prepared in the same manner as in Example 12, except that the mixing ratio of the aqueous hydrogen peroxide and the isocyanate compound to the resin C was changed. 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 methods. The results are shown in the table.

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

Example 15 A mixture of 2 kg of SH-193 and 6 kg of 35% hydrogen peroxide solution (liquid I), MDICR-200 (liquid II), and an acidic hardener as a foam stabilizer in 100 kg of resin A 80% xylene sulfonic acid aqueous solution (solution III)
It adjusted to ° C and was 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 form a foaming stock solution. Was adjusted. After supplying the foaming undiluted solution onto a lower surface material (glass fiber mixed calcium carbonate paper) continuously conveyed by endless conveyors provided in two upper and lower stages, and after stacking glass fiber mixed calcium carbonate paper as an upper surface material, Subsequently, the mixture was introduced into the endless conveyor maintained at 80 ° C., foamed and cured, and further cut to a predetermined size by a cutting device, thereby producing a phenolic resin foam panel of 1800 × 920 × 25 mm. The cream time and the gel time of the foaming stock solution were 25 seconds and 46 seconds, respectively. Various properties of the obtained phenolic resin foam panel were measured by the above-mentioned measuring methods. The results are shown in the table.

Example 16 Castor oil and ethylene oxide adduct as a foam stabilizer for 100 kg of resin A [CX]
-100: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] A mixture of 3 kg and 3 kg of 35% hydrogen peroxide solution (Solution I), MDICR-200 (Solution II), and an 80% xylene sulfonic acid aqueous solution as an acidic curing agent ( III
Solution) was prepared by adjusting the temperature to 20 ° C. Next, these were mixed using a foaming material PA-210 for phenol foam at a weight ratio of liquid I / liquid II / liquid III = 106/8/12 to prepare a raw foaming liquid. Next, the foaming stock solution was injected using a flexible hose into a mold formed by combining a molded steel sheet and a polyester frame material preheated to 60 ° C. by a hot press, foamed and cured, and a phenol resin foam metal of 2700 × 920 × 40 mm was formed. A sandwich panel was created. The foaming stock solution had a cream time of 50 seconds and a gel time of 90 seconds. Various properties of the obtained phenolic resin foam metal sandwich panel were measured by the above-mentioned measuring methods. The results are shown in the table.

Example 17 100 kg of resin A mixed with 2 kg of SH-193 and 3 kg of 35% hydrogen peroxide solution as a foam stabilizer (Solution I) and Crude MD having an NCO% of 31%
I [trade name: MDICR-100, manufactured by Mitsui Toatsu Chemicals, Inc.] (II
Liquid) and an 80% aqueous solution of xylene sulfonic acid (Liquid III) as an acidic curing agent were each adjusted to 25 ° C. and prepared. Next, these were mixed using a foaming material for phenol foam PA-210 at a weight ratio of I solution / II solution / III solution = 105/8/18 to prepare a foaming stock solution. The foaming stock solution is also supplied onto a lower surface material (formed steel plate) preheated to 70 ° C., which is continuously conveyed by endless conveyors provided in upper and lower stages, and after laminating aluminum-deposited calcium carbonate paper as an upper surface material Subsequently, the mixture was introduced into the endless conveyor maintained at 80 ° C., foamed and cured, and further cut into a predetermined length with a guillotine cutter to prepare a phenolic resin foam metal siding of 3600 × 350 × 25 mm. The foaming stock solution had a cream time of 10 seconds and a gel time of 30 seconds. Further, various properties of the obtained phenolic resin foam metal siding were measured by the above-mentioned test methods. The results are shown in the table.

Example 18 A mixture of 2 kg of SH-193 and 6 kg of 35% hydrogen peroxide solution as a foam stabilizer (100 kg of resin A) (solution I), CR-100 (solution II) and an acid hardener As
A 63% aqueous solution of phenolsulfonic acid [trade name: PS-63, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] (III solution) was prepared by adjusting the temperature to 30 ° C. Next, each discharge temperature was further adjusted so as to be 38 ° C., and mixed using a three-liquid mixing type in-situ sprayed foam at a weight ratio of I liquid / II liquid / III liquid = 108/16/30. A phenol resin foam having a thickness of 25 mm was prepared by spraying the mixture on a plywood and foaming and curing at room temperature. The cream time was 5 seconds and the gel time was 10 seconds. Various properties of the obtained phenolic resin foam were measured by the above-mentioned measuring methods. The results are shown in the table.

Example 19 A resol type liquid phenol resin containing a foam stabilizer [trade name: PF-0165L, manufactured by Asahi Organic Materials Industry Co., Ltd.] 10 kg, 35 kg hydrogen peroxide water 0.6 kg and pigment 0 .2
kg, premixed, and subsequently added 0.25 kg of a foam breaker (trade name: SA-9, manufactured by Asahi Organic Materials Co., Ltd.), 1.6 kg of CR-100, and 0.8 kg of acid hardener PS-63. And with a large homogenizer
By mixing for 120 seconds, a uniform foaming stock solution was prepared. Then
The obtained foaming stock solution was laid on kraft paper and preheated to 50 ° C.
It was quickly poured into a 1200 × 700 × 500 mm mold and foam-hardened to produce a phenolic resin foam for Kenzan.
The obtained phenolic resin foam was cut into a size of 230 × 110 × 80 mm and various properties were measured. The density was 0.0228 g / cm.
³ , compressive strength 0.5 kg / cm ² , water absorption time 90 seconds, water absorption 1800
g was very excellent as a material for sword mountain. still,
The water absorption time and the water absorption were measured by floating the block having the above dimensions in a 20-liter bucket filled with water, measuring the time required for the block to completely sink and the weight of the block taken out of the water after the water absorption time was measured.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

[Table 4]

[0045]

[Table 5]

[0046]

As described in detail above, in the present invention, since a chemical blowing agent comprising hydrogen peroxide generating carbon dioxide and an isocyanate compound is used, it is a non-fluorocarbon type free from ozone layer destruction and a void. The present invention can provide a phenolic resin foam free from harmful effects, thereby contributing to the prevention of adverse effects on the natural environment and the human body due to ozone layer destruction.
In addition, since carbon dioxide is generated in accordance with the curing speed of the curing system, a low-density phenol resin foam which has been conventionally difficult can be easily and effectively produced, and the economic unit can be reduced. . Further, since the technology suppresses the generation of voids, the technology has an extremely high industrial value, such as an advantage that it can be applied particularly to in-situ foaming construction.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/20 C08K 3/20 5/16 5/16 E04B 1/76 E04B 1 / 76F // B29K 61:04 105: 04 B29L 31:10 C08L 61:06 (56) References JP-A-2-26713 (JP, A) JP-A-2-67337 (JP, A) JP-B-45-15874 (JP, B1) (58) Survey ⁶ (Int.Cl. ⁶ , DB name) B29C 39/00-39/44 A47G 7/02-7/03 B32B 5/18 B32B 15/08 C08J 9/00-9/08 C08K 3/20 C08K 5 / 16 E04B 1/76

Claims (6)

(57) [Claims] 1. A process for producing a phenolic resin foam, comprising foaming and curing a reactive mixture comprising a liquid phenolic resin, an acidic curing agent, and a chemical foaming agent comprising hydrogen peroxide and an isocyanate compound as essential components. . 2. Production of a phenolic resin foam comprising foaming and curing an alkaline liquid phenolic resin, an organic ester, and a reactive mixture containing a chemical foaming agent comprising hydrogen peroxide and an isocyanate compound as essential components. Method. 3. A method for producing a composite panel, wherein a face material is integrally fixed to at least one surface of a phenolic resin foam obtained from the reactive mixture according to claim 1. 4. The method for manufacturing a composite panel according to claim 3, wherein the face material is a formed face material obtained by embossing or shaping a metal plate. 5. The reactive mixture according to claim 1 or 2, which is sprayed onto a building-construction surface of a building or the like or injected into a space portion of the framework and foam-hardened to form the reactive mixture on the construction surface or inside the space portion. An in-situ foaming method for a phenolic resin foam, which comprises forming a phenolic resin foam layer. 6. A reactive mixture containing a liquid phenolic resin, an acidic curing agent, a foam stabilizer and a foam breaking agent, and a chemical foaming agent comprising hydrogen peroxide and an isocyanate compound as essential components. A method for producing a phenolic resin foam for Kenzan.