JP2005120337A - Acid-curable phenolic resin foam and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acid-curable phenolic resin foam that is well cured even when using a neutralizer to control a drop in pH of the foam during manufacturing the phenolic resin foam, has superior resistance to water absorption, adhesion to a facing material and mechanical strength, and does not cause corrosion and discoloration in the facing material and a reinforcing member, and its manufacturing method. <P>SOLUTION: This manufacturing method of the acid-curable phenolic resin foam is characterized in that, when manufacturing the phenolic resin foam by formulating a foaming agent and an acid curing agent to a phenolic resin composition followed by foaming and curing it, pH change in the composition by adding the acid curing agent to the phenolic resin composition remains in a range of value equal to and lower than that represented by a formula: Y=0.0034X + 2.167. The acid curing agent is consumed with time by neutralization of the acid neutralizer and a filler resulting in pH change, so that, according the formula, a relationship between an elapsed time (X: 0≤X≤120 s) after addition of the acid curing agent to the phenolic resin composition which is adjusted at a fixed temperature and the pH value (Y) is measured at a fixed condition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention includes adding a foaming agent and an acidic curing agent to a phenolic resin composition, and foaming and curing the phenolic resin foam to produce a phenolic resin foam, and then adding the acidic curing agent to the phenolic resin composition. A method for producing an acid curable phenolic resin foam excellent in water absorption resistance, face material adhesion, mechanical strength, etc. and having no corrosion or discoloration of metals by adjusting the pH change of the composition to a specific range And its foam.

  Acidic curable phenolic resin foams are generally used in phenolic resins such as diluents, plasticizers, fillers, acid neutralizers, sulfates and other reaction modifiers, foam stabilizers, dispersants, thickeners, etc. It is produced by adding a foaming agent, an acidic curing agent, etc. to a phenolic resin composition obtained by adding a surfactant, a curing accelerator, a retarder, a colorant, a flame retardant, and the like, followed by foaming and heat curing. Phenolic resin foams are highly evaluated for their flame retardancy. Interior wall materials such as partition panels and clean room panels, outer wall materials such as metal siding, ceiling materials, roof base materials, underfloor insulation materials, roof insulation materials, and fire prevention It is widely used for building materials such as doors, storage tank plants such as methane, propane, and butane, cold storage and warming for tanks and pipes, and cold storage for freezers and refrigerators.

  However, when producing a phenolic resin foam, a large amount of an acidic curing agent is used to increase productivity. As a result, a lot of free acid remains in the phenolic resin foam after foaming and curing, the pH value of the foam is lowered to the acidic side, and the cell membrane forming the foam deteriorates over time. , Or promote destruction. As a result, the water absorption resistance and mechanical strength are lowered, and the metal surface of the face material and the resin coating film are corroded.

In order to solve these problems, a method of using a metal oxide such as zinc or aluminum or a metal powder as a corrosion inhibitor in a phenolic resin foam composition that requires a large amount of an acidic curing agent among formaldehyde resin compositions (Patent Documents 1 and 2), Group IIA carbonate (Patent Document 3) and a method using IA having a particle size of 10 to 500 μm and Group IIA carbonate (Patent Document 4), calcium carbonate, carbonate A method using a basic powder substance such as barium, calcium oxide or barium oxide, talc, mica, pearlite particles, shirasu balloon or the like (Patent Document 5) is disclosed.

  However, in the methods of Patent Documents 1 and 2, it is difficult to uniformly mix with the phenolic resin, causing precipitation, aggregation, etc., increasing the viscosity of the phenolic resin, or clogging the piping of the foam injection machine. Or drastically reduce productivity. Moreover, since it reacts with the acidic curing agent before the foaming step, the cells forming the foam become non-uniform, resulting in a decrease in water absorption resistance, brittleness, mechanical strength, and the like. Moreover, since it disperse | distributes without dissolving in a phenol-type resin, only the periphery of a neutralizing agent can be neutralized, Therefore It is difficult to fully neutralize the free acid which remains in a phenol-type resin foam. Therefore, only a phenolic resin foam that is insufficient to solve the corrosion resistance and has unstable quality can be obtained.

  In the methods of Patent Documents 3 and 4, a sufficient neutralization effect is obtained by the separation of carbonic acid as a gas. However, when the acidic curing agent and the carbonate are brought into contact with each other, the pH rises instantaneously and foaming occurs. It becomes abrupt and uniform density adjustment becomes difficult, and many voids are generated in the foam (foam), so the decrease in thermal conductivity and mechanical strength is extremely impractical.

  In order to solve these problems, a method of blending barium metaborate (Patent Document 5) has been proposed. However, this method makes the foam brittle and the water absorption resistance is deteriorated, or the explosion during combustion is large and the phenolic resin. There is a drawback that flame retardancy, which is the greatest advantage of the foam, is reduced.

  Also, using carbonate as the foaming agent, and changing the combined ratio of naphthalene sulfonic acid formalin condensate and aryl sulfonic acid as acidic curing agent to adjust and ease the foaming and curing rate by decomposition of carbonate (patent) Document 6) and a method of using formic acid, phosphoric acid and lactic acid in a mixed acid of naphthalene sulfonic acid formalin condensate and aryl sulfonic acid are disclosed (Patent Document 7), but the amount of acidic curing agent used is Since there are many, the cell which forms foam becomes weak, and mechanical strength and water absorption resistance fall. Further, in the case of phenolsulfonic acid which is usually used well, when it is mixed with a phenol resin, foaming occurs instantaneously and only an uncured foam with many voids can be obtained. This is also described in a comparative example of Patent Document 7.

If an acid neutralizer such as a metal oxide or metal powder with poor dispersibility is used in a phenolic resin, it may cause clogging of piping such as a foam injection machine, or work with poor mixing with an acidic curing agent or foaming agent. Sex is reduced. On the other hand, if an acidic curing agent is used in a large amount, the foam characteristics are reduced by the free acid. In addition, when carbonate is used as the acid neutralizer, problems such as deterioration of workability occur due to the rapid foaming rate associated with the decomposition of the carbonate due to contact with the acidic curing agent. Therefore, there has been a strong demand for the development of an acid curable phenolic resin foam excellent in corrosion resistance, water absorption resistance, mechanical strength, face material adhesion, and the like, without reducing workability and productivity.
Japanese Examined Patent Publication No. 4-11583 Japanese Examined Patent Publication No. 62-25689 JP 58-154734 A JP 59-152931 A JP 63-175042 A JP 7-173315 A JP-A-7-188446

  In view of the above-described problems in the production of an acid curable phenolic resin foam, the present invention uses a face plate, particularly a metal plate material such as iron, stainless steel, aluminum, and zinc on the surface, or uses the metal plate material as a reinforcing material. When the used phenolic resin foam is produced, even when an acid neutralizer is used to suppress foam pH reduction, the foam is sufficiently cured, resulting in corrosion resistance, water absorption resistance, and face material adhesion. It is an object of the present invention to provide an acidic curable phenolic resin foam excellent in properties, mechanical strength, etc., and free from corrosion and discoloration of face materials and reinforcing materials, and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have formulated a phenolic resin foam by mixing a foaming agent and an acidic curing agent with a phenolic resin composition, and then foaming and curing it. When carbonate is used as a neutralizer, by using sulfate as a carbonate decomposition inhibitor in the phenolic resin composition, rapid foaming associated with decomposition of carbonate even when an acidic curing agent is added, It is possible to suppress an increase in pH and limit the range of pH change of the composition obtained by adding an acidic curing agent to a phenolic resin composition, thereby impairing workability, productivity reduction and designability. The present invention was completed by finding that an acid-curable phenolic resin foam excellent in corrosion resistance, mechanical strength, water absorption resistance and the like can be produced.

That is, in the present invention, a phenolic resin composition is blended with a foaming agent and an acidic curing agent, and foamed and cured to produce a phenolic resin foam. The pH value of the composition is the formula: Y = 0.0034X + 2.167 (Formula 1)
It is in the range below the value shown by this, It is the manufacturing method of the acidic curable phenolic resin foam characterized by the above-mentioned.
The above formula 1 is acidic to the phenolic resin composition in which the pH change caused by the consumption of the acidic curing agent over time due to the acid neutralizing agent, filler, etc. in the phenolic resin composition is adjusted to a constant temperature. The relationship between the elapsed time (X) (unit: second) after adding the curing agent and the pH value (Y) is measured under a certain condition.
Specifically, an acidic curing agent having an acid value of 200 to 300 mgKOH / g is added to a phenolic resin composition containing a phenolic resin, an acid neutralizer, a sulfate, a filler, and the like, and the composition is 20
After temperature adjustment to ° C., the pH change of the composition immediately after mixing and stirring at 4000 rpm for 15 seconds with a homodisper (trade name, mixer manufactured by Tokushu Kika Kogyo Co., Ltd.) was measured with a pH meter, and the elapsed time (X: Second, 0 ≦ X ≦ 120) and the pH value (Y).

The acidic curable phenolic resin foam of the present invention has a foam characteristic of a density of 10 to 500 kg / m ³ , a pH of 4 or more, and a water absorption of 1 to 15 g / 100 cm ² . It contains potassium element and / or sodium element.
In the method for producing an acid curable phenolic resin foam of the present invention, a phenolic resin composition is further mixed with sulfates such as potassium sulfate and sodium sulfate, and further metal powder as an acid neutralizer, aluminum compound, alkali metal or alkali. It is characterized by blending at least one member selected from the group consisting of carbonates, bicarbonates, oxides and hydroxides of earth metals.

Furthermore, in the method for producing an acidic curable phenolic resin foam of the present invention, a foaming agent and an acidic curing agent are added to the phenolic resin composition, the gelation time after mixing (Y ¹ ) and the amount of the curing agent (X ¹ ) Is in a range equal to or less than the value represented by the formula: Y ¹ = −X ¹ +16 (Formula 2).
Formula 2 shown here is a gelling time (Y ² minutes) and a curing agent amount (X ¹ weight based on 100 parts by weight of a solid content of a phenolic resin) measured under conditions of a liquid temperature of 20 ° C. and a drying temperature of 65 ° C. Part)).
In order for the relationship between the gelation time (Y ¹ ) and the amount of the curing agent (X ¹ ) to satisfy the above range, potassium sulfate and / or sodium sulfate and barium carbonate are added to the phenolic resin composition and mixed. It is preferable to use a method in which a foaming agent and an acidic curing agent are added and mixed after a lapse of more than a minute.

Further, in the method for producing an acid curable phenolic resin foam of the present invention, potassium sulfate and / or sodium sulfate and barium carbonate are added to and mixed with the phenolic resin composition, and after 10 minutes or more have passed, the foaming agent, After adding and mixing the acidic curing agent, the gelation time (Y ² ) and the amount of the curing agent (X ² ) are not more than the values represented by the formula: Y ² = −0.75X ² +14.5 (Formula 3) It is in the range.
Formula 3 shown here is the gelation time (Y ² min) and the amount of curing agent (Y ² minutes) measured under the same conditions as Formula 2.
X ² parts by weight).
In order for the relationship between the gelation time (Y ² ) and the amount of the curing agent (X ² ) to satisfy the above range, 1) potassium sulfate and / or sodium sulfate can be added as an aqueous solution or a hydrous alcohol solution, or 2) sulfuric acid. It is preferable to use a method of adding an aqueous solution of potassium and / or sodium sulfate or a hydrous alcohol solution and barium carbonate after mixing them in advance.
Furthermore, in the method for producing an acid curable phenolic resin foam of the present invention, it is particularly preferable that the cream time after adding and mixing the foaming agent and the acid curing agent to the phenol resin composition is 10 seconds or more. Here, cream time means that the foaming resin composition is mixed with the phenolic resin composition and all the components constituting the foamed body including the foaming agent and the acidic curing agent are prepared, and the foaming resin composition is foamed. Is the time to start.

The phenolic resin used in the present invention is an acidic curing agent described below and / or obtained by reacting phenols and aldehydes in the presence of a reaction catalyst and / or a primary amine as necessary. A phenolic resin having a curable functional group that promotes a curing reaction by heating, such as a methylol group, a dimethylene ether group, and a benzoxazine ring in the molecule, and a modified resin thereof. Specifically, for example, a resol type phenolic resin obtained by reacting in the presence of a basic catalyst, or a novolak resol type phenolic resin obtained by reacting in an acidic catalyst and then reacting in a basic catalyst. Or obtained by reacting a benzyl ether type phenolic resin obtained by reacting under weak acidity or a combination of basic and acidic catalysts, or phenols, aldehydes and primary amines. Benzoxazine type phenolic resin, or any compound after the production of these resins, or after the production thereof, such as xylene resin, urea resin, melamine resin, epoxy resin, superabsorbent resin, urea compound, melamine compound, epoxy compound , Furfurals, resorcin, alkylresorcin, tannin and other compounds And the like are modified resin obtained by response. Among these, a resol type phenol resin is preferable from the viewpoint of foam curability. These may be used alone and / or in combination of two or more.

  The resol type phenolic resin used in the present invention has a molar ratio (formaldehyde / phenols) of 0.50 to 3.00, preferably 1.00 to 2.00, and a molar ratio of alkali catalyst to phenols (phenols). / Alkali catalyst) is 0.01 or more, the number average molecular weight is 190 to 370, the water content is 2 to 40% by weight, the non-volatile content is 50 to 96% by weight, and the viscosity is 800 to 300,000 mPa · s / 23 ° C. Is preferably included.

  Examples of the phenolic acid-cured phenolic resin used in the present invention include phenol, cresol, ethylphenol, xylenol, bisphenol A, bisphenol F, paratertiary butylphenol, resorcin, catechol and the like, and modified products thereof. Examples of aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane, furfural, acetaldehyde, and glyoxal. Examples of primary amines include methylamine, cyclohexylamine, and aniline. Examples of the reaction catalyst include basic catalysts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonia, triethylamine, Acidic catalysts such as hydrochloric acid, sulfuric acid, phosphoric acid, zinc acetate, boric acid, succinic acid, formic acid, lactic acid, paratoluenesulfonic acid, methanesulfonic acid and the like can be mentioned. These reactants and reaction catalysts may be used alone and / or in combination of two or more.

The other raw material aldehydes used in combination with the phenols are not particularly limited, and can be appropriately selected from those conventionally used in the production of phenolic resins. These aldehydes may be used alone and / or in combination of two or more.
The use ratio of the phenols and aldehydes is exactly the same as in the case of conventional phenol resins, and the aldehydes are usually 0.5 to 3.0 moles, preferably 1.0 to 1 mole per mole of phenols. It is used in the range of 2.0 mol, and is produced by neutralizing and concentrating as necessary after reaction for 0.5 to 24 hours at a temperature of 10 ° C. to reflux temperature depending on the resin type. Reaction catalyst (no addition, batch addition or split addition), use of aldehydes (lump, split), reaction atmosphere (air, nitrogen, normal pressure, reduced pressure, pressurization), reaction method (dropping, one stage, two stages) The reaction procedure such as) is appropriately selected according to the purpose.

Examples of the sulfate in the present invention include potassium sulfate, potassium hydrogen sulfate, sodium sulfate, sodium hydrogen sulfate, barium sulfate, calcium sulfate, ammonium sulfate, and aluminum sulfate. These may be used alone or in combination of two or more. May be. Of these, potassium sulfate and / or sodium sulfate is preferred. The addition amount of these sulfates is 0.01-10.0 weight part with respect to 100 weight part of acidic curable phenolic resin, Preferably it is 0.1-7.0 weight part. Furthermore, in the case of potassium sulfate and / or sodium sulfate, 2.0 parts by weight or less is particularly preferable.
The addition of the sulfate to the phenolic resin composition includes the addition of those that form a sulfate in the composition, such as the addition of sodium hydroxide and sulfuric acid, in addition to the addition of the salt compound.

  Examples of the acid neutralizing agent in the present invention include metal powders such as aluminum, zinc, and chromium, aluminum compounds such as aluminum oxide, aluminum hydroxide, and aluminum sulfate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, zinc carbonate, magnesium carbonate, Potassium bicarbonate, potassium carbonate, barium carbonate, ammonium carbonate, ammonium bicarbonate, calcium oxide, barium oxide, magnesium oxide, sodium oxide, potassium hydroxide, calcium hydroxide, sodium hydroxide, barium hydroxide, magnesium hydroxide, etc. There are alkali metal or alkaline earth metal carbonates, bicarbonates, oxides and hydroxides, and these can be used alone or in combination of two or more, of which barium carbonate is preferred. . The addition amount of these acid neutralizing agents is 0.5 to 30.0 parts by weight, preferably 1.0 to 20.0 parts by weight with respect to 100 parts by weight of the acid curable phenolic resin. Furthermore, in the case of barium carbonate, 15.0 parts by weight or less is particularly preferable.

In the present invention, additives that are usually used in the production of phenolic resin foams, such as foam stabilizers, fillers, diluents, curing accelerators, retarders, and flame retardants, are used as necessary. Can do.
Examples of foam stabilizers include nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate. Sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan fatty acid esters represented by polyoxyethylene sorbitan monooleate, polyoxyethylene dimethyl silicon, Castor oil ethylene oxide and propylene oxide adduct, ethylene oxide-propylene oxide block copolymer, polysiloxane-polyoxyalkylene Polymers, dimethylpolysiloxane - polyoxyalkylene copolymers, ethoxylated castor oil, epoxidized soybean oil ethoxylates, there are silicone-based surfactants may be used alone or in combination of two or more. The addition amount of these foam stabilizers is 0.1-10.0 weight part with respect to 100 weight part of acidic curable phenolic resin, Preferably it is 0.2-7.0 weight part.

  Examples of the foaming agent used in the present invention include fluorine compounds such as specific CFCs and CFC substitutes, halogen compounds such as methylene chloride, esters such as ethyl acetate, heptane, n-hexane, isohexane, cyclohexane, and 2,3-dimethyl. Low-boiling point aliphatic hydrocarbons such as butane, 2-methylpentane, 2,2-dimethylbutane, 3-methylpentane, n-pentane and cyclopentane, ethers such as isopropyl ether, alcohols such as methanol and ethanol, methyl ethyl ketone Such as ketones, cyclic ether compounds such as dioxolane, and calcium carbonate, barium carbonate, sodium hydrogen carbonate, sodium carbonate, azodicarbonamide, azo which generate gas such as carbon dioxide and nitrogen by the action of acid. Bisisobutyronitrile , There is a chemical reaction foaming agent such as p-toluenesulfonyl hydrazide, which may be used in combination alone or in combination. In addition to these, gases such as liquefied carbon dioxide, air, nitrogen, butane, and argon can be used by mixing them. The addition amount of these foaming agents is 0.2 to 20.0 parts by weight, preferably 0.5 to 15.0 parts by weight with respect to 100 parts by weight of the acid curable phenolic resin.

The acidic curing agent used in the present invention includes phenolsulfonic acid, toluenesulfonic acid, xylenesulfonic acid, benzenesulfonic acid, resorcinsulfonic acid, metaxylenesulfonic acid, ethylbenzenesulfonic acid, naphthalenesulfonic acid, naphtholsulfonic acid, anthracene. In addition to organic sulfonic acids such as sulfonic acid, orthocresol 4 sulfonic acid, and metacresol sulfonic acid, and condensates thereof with formalin, carboxylic acid esters such as γ-butyrolactone, triethylene glycol diacetate, triacetin, and methyl formate, There are cyclic alkylene carbonates such as ethylene carbonate, propylene carbonate, inorganic acids such as orthophosphoric acid, polyphosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hydrochloric acid, organic acids such as formic acid, acetic acid, oxalic acid, etc. These may be used alone, or two or more thereof. The addition amount is 1.0 to 20.0 parts by weight, preferably 2.0 to 15.0 parts by weight as an acid value of 200 to 300 mg KOH / g with respect to 100 parts by weight of the acid curable phenolic resin. is there.

  Examples of the flame retardant used in the present invention include additive brominated flame retardants such as decabromodiphenyl ether, pentabromotoluene, pentabromodiphenyl ether, and reactive bromines such as tetrabromophthalic anhydride, dibromophenol, and tribromophenol glycidyl ether. Flame retardants, triethyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tributyl phosphate, xyleryl diphenyl phosphate, phosphate esters, tris- (chloroethyl) phosphate, tris- (β-chloropropyl) phosphate , Halogen-containing phosphates such as tris- (dibromopropyl) phosphate, tris- (2,3-dibromochloropropyl) phosphate, and halogen-containing condensed phosphorus There are esters, phosphorous esters such as triphenyl phosphite, phosphoric acids such as phosphoric acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, boron compounds, aluminum hydroxide, urea, melamine, benzoguanamine, etc. Or in combination of two or more. The addition amount is 3.0 to 200 parts by weight, preferably 5.0 to 90.0 parts by weight, with respect to 100 parts by weight of the acid curable phenolic resin.

In addition to these, when producing a phenol resin foam, various additives can be added to improve the performance of the foam. For example, 1) Fibers represented by phenol fiber, carbon fiber, aramid fiber, glass fiber, rock wool fiber, etc. (improvement of mechanical strength and dimensional accuracy), 2) ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol Low molecular weight polyethylene such as tripropylene glycol and polypropylene glycols, aliphatic glycidyl ether compounds such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Or synthetic and natural polymers such as triglycidyl ether compounds, polyvinyl alcohol, carboxymethyl cellulose, methyl cellulose, starches, acrylic emulsions (modified brittleness) 3) Acetone, tetrahydrofuran, 1,3 dioxolane, etc. (decrease in viscosity) 4) Ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium chloride, ammonium phosphate, ammonium carbonate, ammonium acetate, amino groups, amide groups in the molecule , Urea having urea, urea resin, melamine, melamine resin, thiourea, dicyandiamide, benzoguanamine, sodium sulfite, sodium hydrogen sulfite, ammonium sulfite, ammonium hydrogen sulfite and the like, and bisulfites (formaldehyde trapping) It is done. In addition, inorganic fillers such as talc, mica, wollastonite, kaolin and silica, colorants such as dyes and pigments, ultraviolet absorbers and the like may be used in combination. Although there is no restriction | limiting in particular in the addition amount, Usually, it is 0.1-50.0 weight part with respect to 100 weight part of acidic curable phenolic resin, Preferably it is 0.2-40.0 weight part.

  The face material used for the acid curable phenolic resin foam in the present invention is not particularly limited, and the fibers such as kraft paper, charcoal cal paper, plywood, fiber board, and veneer, aluminum foil, galvanized steel sheet Further, metals such as galvanium steel plates, inorganic materials such as quartz plates and gypsum boards can be used.

  Next, in the present invention, as a method for producing an acid curable phenolic resin foam, a foam stabilizer, a filler, an acid neutralizing agent, a sulfate and other additives are added to the resol type phenolic resin having the above-described composition components. Conventionally known methods such as a method in which a phenolic resin composition mixed with an agent and the like, a foaming agent, and an acidic curing agent are mixed by high-speed stirring and manufactured by a batch method, and a method in which high-speed stirring is continuously manufactured are used. The mixture obtained by each of these operations is a molding method that flows out onto an endless conveyor, a method that causes spotting to flow out and partially foams, a method that throws into a cavity of a certain size to make a foam block, It is used for the method of filling and foaming while press-fitting into. Foaming by these methods, curing temperature is 30 to 100 ° C, curing time is 1 to 15 minutes, and after cutting in a semi-cured state (pre-cure), curing is further completed by post-curing (after cure) There is a way to make it. The obtained phenol-based resin foam forms a high-quality foam having high mechanical strength, excellent water absorption resistance and brittleness resistance without lowering productivity. Main applications include metal plates such as iron, stainless steel, aluminum and zinc, inorganic boards such as gypsum board and rock wool board, craft paper, asbestos paper, plywood, etc. For base materials, outer wall materials, inner wall materials, building materials such as fire doors, plant fields such as storage tanks for methane, propane, butane, etc., for cold and warm insulation such as heavy oil tanks, pipe piping, etc. Widely applied.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Example 1
(1) Preparation of phenol-based resole resin composition 4451 g of phenol and 5135 g of a 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding 25% aqueous sodium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes. Then, sulfuric acid was added to adjust the pH to 6.3, and the dehydration rate was 29.0 under reduced pressure. After dehydrating and concentrating to weight percent, 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50 was obtained. Next, 30 parts by weight of aluminum hydroxide, 30 parts by weight of clay, 1.5 parts by weight of silicone foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 100 parts by weight of the resin, and acid neutralizer A phenolic resole resin composition was prepared by adding 8 parts by weight of barium carbonate and allowed to stand for 6 hours.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of the above (1) preliminarily adjusted to 20 ° C., 18 parts by weight of n-pentane preliminarily adjusted to 20 ° C., and preliminarily adjusted to 20 ° C. After adding 60 parts by weight of 67% phenolsulfonic acid having an acid value of 260 mgKOH / g and mixing with a homodisper (trade name, mixer manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm for 30 seconds, immediately dispose the disposable cup at an angle of 60 °. After spraying (injecting) uniformly into an aluminum mold (volume: 300 mm x 300 mm x 50 mm) using double-sided kraft paper that has been temperature-controlled at 70 ° C by inclining for 10 seconds, the mold lid is fixed at four locations. After heating for 10 minutes in a dryer at 70 ° C., demolding was performed to produce an acid curable phenolic resin foam.
(3) The molded foam was allowed to stand for 5 days in an atmosphere at room temperature of 20 ° C. and humidity of 65%, and various physical properties were measured in accordance with JIS A-9511.

Example 2
(1) Preparation of phenol-based resol resin composition 4451 g of phenol and 5135 g of 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous potassium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, sulfuric acid was added to adjust the pH to 6.3, and the dehydration rate was 29.0 under reduced pressure. After dehydrating and concentrating to weight percent, 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50 was obtained. Next, 30 parts by weight of aluminum hydroxide, 30 parts by weight of clay, 1.5 parts by weight of silicone foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 100 parts by weight of the resin, and acid neutralizer A phenolic resol resin composition was prepared by adding 6 parts by weight of calcium carbonate and 15 parts of a 5% aqueous sodium sulfate solution, and left for 6 hours.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of the above (1) preliminarily adjusted to 20 ° C., 7.8 parts by weight of cyclopentane preliminarily adjusted to 20 ° C., preliminarily warmed to 20 ° C. After charging 84 parts by weight of 67% phenolsulfonic acid having a prepared acid value of 260 mgKOH / g, mixing with a homodisper (trade name, a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm for 30 seconds, and then immediately placing the disposable cup at a 60 ° angle After spraying uniformly on an aluminum mold (volume: 300 mm x 300 mm x 50 mm) using a double-sided galvanized steel plate that has been temperature-controlled at 70 ° C in advance by tilting for 10 seconds, fix the lid at four locations and dry at 70 ° C The mold was heated and demolded in the machine for 10 minutes to prepare an acid curable phenolic resin foam.
(3) The molded foam was allowed to stand at room temperature of 20 ° C. and humidity of 65% for 5 days, and various physical properties were measured according to JIS A-9511.

Example 3
(1) Preparation of phenol-based resol resin composition 4451 g of phenol and 5135 g of 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous sodium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, oxalic acid was added to adjust the pH to 6.3, and the dehydration rate was 29. After dehydrating and concentrating to 0% by weight, 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50 was obtained. Next, 30 parts by weight of aluminum hydroxide, 30 parts by weight of clay, 1.5 parts by weight of silicone foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 100 parts by weight of the resin, and acid neutralizer A phenolic resole resin composition was prepared by adding 8 parts by weight of barium carbonate and 15 parts of a 5% aqueous potassium sulfate solution, and left for 6 hours.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of the above (1) preliminarily adjusted to 20 ° C., 18 parts by weight of HCHC-141b preliminarily adjusted to 20 ° C., preliminarily adjusted to 20 ° C. After adding 54 parts by weight of 67% phenolsulfonic acid having an acid value of 260 mgKOH / g, mixing with a homodisper (trade name, a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm for 30 seconds, immediately dispose the disposable cup at a 60 ° angle. After spraying uniformly on an aluminum mold (volume: 300 mm x 300 mm x 50 mm) using double-sided kraft paper that has been temperature-controlled to 70 ° C in advance by inclining for 10 seconds, the lid is fixed at four locations, and 10 minutes at 70 ° C. After drying, it was demolded to produce an acid curable phenolic resin foam.
(3) The molded foam was allowed to stand at room temperature of 20 ° C. and humidity of 65% for 5 days, and various physical properties were measured according to JIS A-9511.

Example 4
(1) Preparation of phenol-based resol resin composition 4451 g of phenol and 5135 g of 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous potassium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, sulfuric acid was added to adjust the pH to 6.3, and the dehydration rate was 29.0 under reduced pressure. After dehydrating and concentrating to weight percent, 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50 was obtained. Next, 30 parts by weight of aluminum hydroxide, 30 parts by weight of clay, 1.5 parts by weight of silicone foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 100 parts by weight of the resin, and acid neutralizer A phenolic resole resin composition was prepared by adding 8 parts by weight of calcium carbonate and allowed to stand for 6 hours.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin of the above (1) preliminarily adjusted to 20 ° C., 12 parts by weight of cyclopentane preliminarily adjusted to 20 ° C., acid value preliminarily adjusted to 20 ° C. Charge 42 parts by weight of 260 mg KOH / g 67% phenol sulfonic acid, mix for 30 seconds at 5000 rpm with a homodisper (trade name, mixer manufactured by Tokushu Kika Kogyo Co., Ltd.), and immediately tilt the disposable cup at an angle of 60 ° for 10 seconds. After spraying uniformly on an aluminum mold (volume: 300 mm x 300 mm x 50 mm, 0.5 mm galvanized steel plate on the inner bottom) preliminarily adjusted to 70 ° C, the lid is fixed at four locations, and 70 ° C It was demolded after heating in a dryer for 10 minutes to produce an acid curable phenolic resin foam.
(3) The molded foam was allowed to stand at room temperature of 20 ° C. and humidity of 65% for 5 days, and various physical properties were measured according to JIS A-9511.

Example 5
(1) Preparation of phenol-based resol resin composition 4451 g of phenol and 5135 g of 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous potassium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, sulfuric acid was added to adjust the pH to 4.5, and the dehydration rate was 5.0 under reduced pressure. After dehydrating and concentrating to weight percent, 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.65 and a viscosity of 70000 mPa · s / 23 ° C. was obtained. Next, 1.5 parts by weight of a silicone foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone) was added to 100 parts by weight of the resin to prepare a phenolic resole resin composition, which was allowed to stand for 6 hours. .
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin of the above (1) preliminarily adjusted to 20 ° C., 21 parts by weight of HCFC-141b preliminarily adjusted to 20 ° C., acid previously adjusted to 20 ° C. After charging 9 parts by weight of 67% phenolsulfonic acid with a value of 260 mgKOH / g and mixing for 30 seconds at 8000 rpm with a homodisper (trade name, a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.), immediately place the disposable cup at an angle of 60 ° for 10 seconds. After spraying uniformly on an aluminum mold (volume: 300 mm x 300 mm x 50 mm, 0.5 mm kraft paper on the inner bottom) that has been tilted and adjusted to 70 ° C in advance, the lid is fixed at four locations. The mold was removed after heating for 5 minutes in a dryer. Next, the foam after demolding was cured and molded by a hot press heated to 90 ° C. to produce an acid curable phenolic resin foam.
(3) The molded foam was allowed to stand at room temperature of 20 ° C. and humidity of 65% for 5 days, and various physical properties were measured according to JIS A-9511.

Example 6
(1) Preparation of phenol-based resole resin composition 4451 g of phenol and 5135 g of a 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding 25% aqueous sodium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes. Then, sulfuric acid was added to adjust the pH to 6.3, and the dehydration rate was 29.0 under reduced pressure. After dehydrating and concentrating to weight percent, 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50 was obtained. Next, 30 parts by weight of aluminum hydroxide, 30 parts by weight of clay, 1.5 parts by weight of silicone foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 100 parts by weight of the resin, and acid neutralizer A phenolic resole resin composition was prepared by adding 6.8 parts by weight of barium carbonate and allowed to stand for 10 minutes.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of (1) above, which was previously adjusted to 20 ° C., 18 parts by weight of cyclopentane, which was previously adjusted to 20 ° C., and was previously adjusted to 20 ° C. After charging 60 parts by weight of 67% phenolsulfonic acid having an acid value of 260 mgKOH / g and mixing at 5000 rpm for 30 seconds with a homodisper (trade name, a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.), the disposable cup was immediately adjusted to 10 at an angle of 60 °. Tilt in seconds for 7
After uniformly spraying (injecting) into an aluminum mold (volume: 300 mm x 300 mm x 50 mm) using double-sided kraft paper that has been temperature-controlled at 0 ° C, the mold lid is fixed at four locations, and a 70 ° C dryer The mixture was heated for 10 minutes and then demolded to prepare an acid curable phenolic resin foam.
(3) The molded foam was allowed to stand for 5 days in an atmosphere at room temperature of 20 ° C. and humidity of 65%, and various physical properties were measured in accordance with JIS A-9511.

Example 7
(1) Preparation of phenol-based resole resin composition 4451 g of phenol and 5135 g of a 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous sodium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, and then 50% paratoluenesulfonic acid was added to adjust the pH to 6.3. A dehydration rate of 29.0% by weight was obtained by dehydration and concentration to obtain 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50. Next, 92.7 parts by weight of aluminum hydroxide, 1.5 parts by weight of silicone-based foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 12 parts by weight of 9% aqueous potassium sulfate solution with respect to 100 parts by weight of the resin Then, 6.8 parts by weight of barium carbonate as an acid neutralizing agent was added to prepare a phenolic resole resin composition, which was allowed to stand for 10 minutes.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of the above (1) preliminarily adjusted to 20 ° C., 7.8 parts by weight of cyclopentane preliminarily adjusted to 20 ° C., preliminarily warmed to 20 ° C. After charging 60 parts by weight of 67% phenolsulfonic acid having a prepared acid value of 260 mgKOH / g, mixing with a homodisper (trade name, a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm for 30 seconds, and then immediately placing the disposable cup at a 60 ° angle Was sprayed (injected) uniformly into an aluminum mold (volume: 300 mm x 300 mm x 50 mm) using double-sided kraft paper that had been temperature-controlled at 70 ° C by inclining for 10 seconds, and then fixed at four locations on the mold lid Then, after heating for 10 minutes in a dryer at 70 ° C., the mold was removed to produce an acid curable phenolic resin foam.
(3) The molded foam was allowed to stand for 5 days in an atmosphere at room temperature of 20 ° C. and humidity of 65%, and various physical properties were measured in accordance with JIS A-9511.

Example 8
(1) Preparation of phenol-based resole resin composition 4451 g of phenol and 5135 g of a 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous sodium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, and then 50% paratoluenesulfonic acid was added to adjust the pH to 6.3. A dehydration rate of 29.0% by weight was obtained by dehydration and concentration to obtain 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50. Next, 92.7 parts by weight of aluminum hydroxide and 1.5 parts by weight of silicone foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 100 parts by weight of the resin, 9 prepared in advance. A phenolic resole resin composition was prepared by adding a mixed solution of 12 parts by weight of an aqueous potassium sulfate solution and 6.8 parts by weight of barium carbonate, and allowed to stand for 10 minutes.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of (1) above, which was previously adjusted to 20 ° C., 18 parts by weight of cyclopentane, which was previously adjusted to 20 ° C., and was previously adjusted to 20 ° C. After charging 60 parts by weight of 67% phenolsulfonic acid having an acid value of 260 mgKOH / g and mixing at 5000 rpm for 30 seconds with a homodisper (trade name, a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.), the disposable cup was immediately adjusted to 10 at an angle of 60 °. After uniformly spraying (injecting) into an aluminum mold (volume: 300 mm x 300 mm x 50 mm) using a double-sided kraft paper that has been temperature-controlled to 70 ° C in advance by tilting for 2 seconds, the mold lid is fixed at four locations, After heating for 10 minutes in a 70 ° C. dryer, the mold was removed to produce an acid curable phenolic resin foam.
(3) The molded foam was allowed to stand for 5 days in an atmosphere at room temperature of 20 ° C. and humidity of 65%, and various physical properties were measured in accordance with JIS A-9511.

The results of Examples 1 to 5 are shown in Table 1, and the results of Examples 6 to 8 are shown in Table 2. In the table, pH change indicates the amount of change in pH of the phenolic resin composition.

Comparative Example 1
(1) Preparation of phenol-based resol resin composition 4451 g of phenol and 5135 g of 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous sodium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, and then PTS was added to adjust the pH to 6.3.
To 69.0 g of a liquid phenolic resol resin having a molar ratio (formaldehyde / phenol) of 1.50. Next, 30 parts by weight of aluminum hydroxide, 30 parts by weight of clay, 1.5 parts by weight of silicone foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 100 parts by weight of the composition, acid neutralizer As a result, 5 parts by weight of barium carbonate was added to prepare a phenolic resole resin composition, which was allowed to stand for 6 hours.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of the above (1) preliminarily adjusted to 20 ° C., 18 parts by weight of n-pentane preliminarily adjusted to 20 ° C., and preliminarily adjusted to 20 ° C. After adding 66 parts by weight of 67% phenolsulfonic acid having an acid value of 260 mgKOH / g and mixing with a homodisper (trade name, a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm for 30 seconds, the carbonate immediately decomposes. Formula: Y = Foam was not obtained because it was not within the range of 0.0034X + 2.167 or less and was not cured.

Comparative Example 2
(1) Preparation of phenol-based resol resin composition 4451 g of phenol and 5135 g of 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous sodium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, then xylene sulfonic acid was added to adjust the pH to 6.3, and the dehydration rate was 29 under reduced pressure. It was dehydrated and concentrated to 0.0% by weight to obtain 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50. Next, 30 parts by weight of aluminum hydroxide, 30 parts by weight of clay, 1.5 parts by weight of silicone foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 100 parts by weight of the resin, and acid neutralizer A phenolic resole resin composition was prepared by adding 6 parts by weight of calcium carbonate and allowed to stand for 6 hours.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of the above (1) preliminarily adjusted to 20 ° C, 9.0 parts by weight of cyclopentane preliminarily adjusted to 20 ° C, preliminarily warmed to 20 ° C 60 parts by weight of 67% phenolsulfonic acid with a prepared acid value of 260 mgKOH / g was charged, and decomposition of carbonate occurred suddenly during mixing for 30 seconds at 5000 rpm with a homodisper (trade name, mixer manufactured by Tokushu Kika Kogyo Co., Ltd.) : Since it did not enter into the range of Y = 0.0034X + 2.167 or less and was not cured, a foam was not obtained.

Comparative Example 3
(1) Preparation of phenol-based resol resin composition 4451 g of phenol and 5135 g of 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous sodium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, then formic acid was added to adjust the pH to 6.3, and the dehydration rate was 29.0 under reduced pressure. After dehydrating and concentrating to weight percent, 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50 was obtained. Next, 30 parts by weight of aluminum hydroxide, 30 parts by weight of clay, 1.5 parts by weight of silicone foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 100 parts by weight of the resin, and acid neutralizer A phenolic resole resin composition was prepared by adding 8 parts by weight of barium carbonate and allowed to stand for 6 hours.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of the above (1) preliminarily adjusted to 20 ° C., 18 parts by weight of HCFC-141b preliminarily adjusted to 20 ° C., preliminarily adjusted to 20 ° C. After charging 42 parts by weight of 67% phenolsulfonic acid with an acid value of 260 mgKOH / g and mixing with a homodisper (trade name, a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.) for 30 seconds at 5000 rpm, the disposable cup was immediately put at an angle of 60 °. After spraying uniformly on an aluminum mold (volume: 300 mm x 300 mm x 50 mm) that has been preliminarily adjusted to 70 ° C by inclining for 10 seconds, the lid is fixed at four places, heated in a 70 ° C dryer for 10 minutes, and then demolded However, a foam could not be obtained due to insufficient curing.

Comparative Example 4
(1) Preparation of phenol-based resole resin composition 4451 g of phenol and 5135 g of a 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous sodium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, and then 50% paratoluenesulfonic acid was added to adjust the pH to 6.3. A dehydration rate of 29.0% by weight was obtained by dehydration and concentration to obtain 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50. Next, 92.7 parts by weight of aluminum hydroxide, 1.5 parts by weight of silicone-based foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 12 parts by weight of 9% aqueous potassium sulfate solution with respect to 100 parts by weight of the resin Then, 12 parts by weight of barium carbonate as an acid neutralizer was added to prepare a phenol-based resole resin composition, which was allowed to stand for 10 minutes.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of the above (1) preliminarily adjusted to 20 ° C., 7.8 parts by weight of cyclopentane preliminarily adjusted to 20 ° C., preliminarily warmed to 20 ° C. 60 parts by weight of 67% phenolsulfonic acid having a prepared acid value of 260 mgKOH / g was charged and mixed with homodisper (trade name, a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm for 30 seconds. The amount of barium carbonate relative to the phenol resin solid content Because of the excess, carbonate decomposed rapidly during mixing, and no foam was obtained.
(3) The molded foam was allowed to stand for 5 days in an atmosphere at room temperature of 20 ° C. and humidity of 65%, and various physical properties were measured in accordance with JIS A-9511.

Comparative Example 5
(1) Preparation of phenol-based resole resin composition 4451 g of phenol and 5135 g of a 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous sodium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, and then 50% paratoluenesulfonic acid was added to adjust the pH to 6.3. A dehydration rate of 29.0% by weight was obtained by dehydration and concentration to obtain 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50. Next, 92.7 parts by weight of aluminum hydroxide, 1.5 parts by weight of silicone-based foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 12 parts by weight of 9% aqueous potassium sulfate solution with respect to 100 parts by weight of the resin Then, 6.8 parts by weight of barium carbonate as an acid neutralizer was added to prepare a phenol-based resol resin composition, which was allowed to stand for 1 minute.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of the above (1) preliminarily adjusted to 20 ° C., 7.8 parts by weight of cyclopentane preliminarily adjusted to 20 ° C., preliminarily warmed to 20 ° C. 60 parts by weight of 67% phenolsulfonic acid having a prepared acid value of 260 mgKOH / g was charged and mixed with a homodisper (trade name, a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm for 30 seconds, but the standing time was 1 minute. During mixing, carbonate decomposition suddenly occurred and no foam was obtained.
(3) The molded foam was allowed to stand for 5 days in an atmosphere at room temperature of 20 ° C. and humidity of 65%, and various physical properties were measured in accordance with JIS A-9511.

Comparative Example 6
(1) Preparation of phenol-based resole resin composition 4451 g of phenol and 5135 g of a 41.5 wt% formalin aqueous solution are charged into a reflux tube and a reactor equipped with a stirrer, and stirring is started. After adding a 25% aqueous sodium hydroxide solution as a catalyst, the temperature was raised to 85 ° C. and reacted at the same temperature for 70 minutes, and then 50% paratoluenesulfonic acid was added to adjust the pH to 6.3. A dehydration rate of 29.0% by weight was obtained by dehydration and concentration to obtain 6800 g of a liquid phenolic resole resin having a molar ratio (formaldehyde / phenol) of 1.50. Next, 92.7 parts by weight of aluminum hydroxide, 1.5 parts by weight of silicone-based foam stabilizer SH-193 (manufactured by Toray Dow Corning Silicone), 12 parts by weight of 9% aqueous potassium sulfate solution with respect to 100 parts by weight of the resin Then, 11 parts by weight of barium carbonate as an acid neutralizing agent was added to prepare a phenolic resole resin composition, which was allowed to stand for 10 minutes.
(2) In a 1000 ml disposable cup, 600 parts by weight of the phenolic resole resin composition of the above (1) preliminarily adjusted to 20 ° C., 7.8 parts by weight of cyclopentane preliminarily adjusted to 20 ° C., preliminarily warmed to 20 ° C. 24 parts by weight of 67% phenol sulfonic acid with a prepared acid value of 260 mgKOH / g was added and mixed for 30 seconds at 5000 rpm with a homodisper (trade name, a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.). There was little, and the cream by decomposition | disassembly of carbonate occurred during mixing, and the foam was not obtained.
(3) The molded foam was allowed to stand for 5 days in an atmosphere at room temperature of 20 ° C. and humidity of 65%, and various physical properties were measured in accordance with JIS A-9511.
The results of Comparative Examples 1 to 3 are shown in Table 3, and the results of Comparative Examples 4 to 6 are shown in Table 4. In the table, pH change indicates the amount of change in pH of the phenolic resin composition.

注）
・ 硫黄(Ｓ)、カリウム（Ｋ）、ナトリウム（Na）の各元素は蛍光Ｘ線分析にて測定し
た。
・ フォーム物性の密度はＪＩＳ Ａ−９５１１に準拠して測定した。
・ フォームｐＨは室温２０℃、湿度６５％に５日間放置した後、フォーム中央部から
カッターナイフで３〜５mm角にフォームをカットし０．１ｇを２００ｍｌビーカーに
秤り取った。次いで蒸留水１００ｍｌを入れ、１５分間マグネティックスターラーに
て攪拌した。(攪拌は浮いているフォームを巻き込むぐらいに激しく行なった) 攪拌
終了後、ろ過を行い、ろ液をｐHメーター計にて測定した。
・ 鋼鈑の腐蝕性及び鋼鈑表面の変色試験は両面０．５ｍｍ厚の亜鉛鋼鈑で接着された
発泡体をポリ袋へ入れ密閉した。次いで、８０℃の乾燥機内に1ヶ月間放置後、腐蝕
の進行及び鋼鈑表面の変色を目視にて観察した。

note)
• Each element of sulfur (S), potassium (K), and sodium (Na) was measured by fluorescent X-ray analysis.
-The density of the physical properties of the foam was measured according to JIS A-9511.
The foam pH was left at room temperature of 20 ° C. and humidity of 65% for 5 days, then the foam was cut into 3 to 5 mm square from the center of the foam with a cutter knife, and 0.1 g was weighed into a 200 ml beaker. Next, 100 ml of distilled water was added and the mixture was stirred with a magnetic stirrer for 15 minutes. (Stirring was carried out vigorously enough to involve the floating foam.) After completion of stirring, filtration was performed and the filtrate was measured with a pH meter.
・ In the corrosion test of the steel plate and the discoloration test on the surface of the steel plate, a foam bonded with a 0.5 mm thick zinc steel plate on both sides was placed in a plastic bag and sealed. Next, after standing in a dryer at 80 ° C. for 1 month, the progress of corrosion and the discoloration of the steel plate surface were visually observed.

  From the results of Table 1, Table 2, Table 3, and Table 4, it can be seen that the phenolic resin foam produced by the production method of the present invention has good cell and cured conditions and excellent foam properties.

Claims (15)

When a phenolic resin composition is blended with a foaming agent and an acidic curing agent, and foamed and cured to produce a phenolic resin foam, the pH value of the composition obtained by adding the acidic curing agent to the phenolic resin composition is Formula: Y = 0.0034X + 2.167 (Formula 1) It exists in the range below the value shown by these. The manufacturing method of the acid curable phenolic resin foam characterized by the above-mentioned.
Formula 1 shown here is a phenolic resin composition in which pH change caused by consumption of an acidic curing agent over time by an acid neutralizing agent, a filler, etc. in a phenolic resin composition is adjusted to a constant temperature. The relationship between the elapsed time (X: seconds, 0 ≦ X ≦ 120) after adding the acidic curing agent to the product and the pH value (Y) is measured under a certain condition.   The method for producing an acid curable phenolic resin foam according to claim 1, comprising a sulfate.   2. The acid neutralizing agent according to claim 1, wherein at least one member selected from the group consisting of metal powder, aluminum compound, alkali metal or alkaline earth metal carbonate, bicarbonate, oxide, and hydroxide is blended. Or the manufacturing method of the acid curable phenolic resin foam of 2.   The method for producing an acidic curable phenolic resin foam according to any one of claims 1 to 3, wherein the sulfate is potassium sulfate and / or sodium sulfate.   The method for producing an acid curable phenolic resin foam according to claim 4, wherein the acid neutralizer is barium carbonate and the foaming agent is cyclopentane.   The content of potassium sulfate and / or sodium sulfate with respect to 100 parts by weight of the solid content of the phenolic resin is 2.0 parts by weight or less, and the content of barium carbonate is 15.0 parts by weight or less. The manufacturing method of the acidic curable phenol-type resin foam of description. A foaming agent and an acidic curing agent are added to the phenolic resin composition, and the gelation time (Y ¹ ) and the amount of the curing agent (X ¹ ) after mixing are represented by the formula: Y ¹ = −X ¹ +16 (Formula 2) It exists in the range below a value, The manufacturing method of the acid-curable phenolic resin foam of any one of Claims 4-6 characterized by the above-mentioned.
Formula 2 shown here is a gelling time (Y ¹ minute) measured under conditions of a liquid temperature of 20 ° C. and a drying temperature of 65 ° C., and the amount of curing agent (X ¹ part by weight) relative to 100 parts by weight of the solid content of the phenol resin. ).   8. The foaming agent and the acidic curing agent are added and mixed after 10 minutes or more have elapsed after adding and mixing potassium sulfate and / or sodium sulfate and barium carbonate to the phenolic resin composition. Of producing an acid-curable phenolic resin foam. Gelation time (Y ² ) after adding and mixing foaming agent and acidic curing agent after 10 minutes or more after adding and mixing potassium sulfate and / or sodium sulfate and barium carbonate to phenolic resin composition And the amount of the curing agent (X ² ) is in the range of the value represented by the formula: Y ² = −0.75X ² +14.5 (Formula 3) Of producing a resin-based resin foam.
Equation 3 shown here is the gelling time (Y ² minutes) and the amount of curing agent (X ² weights) with respect to 100 parts by weight of the solid content of the phenolic resin, measured under conditions of a liquid temperature of 20 ° C. and a drying temperature of 65 ° C. Part)). The method for producing an acid curable phenolic resin foam according to claim 9, wherein potassium sulfate and / or sodium sulfate is added as an aqueous solution or a hydrous alcohol solution. 6. The method for producing an acidic curable phenolic resin foam according to claim 5, wherein an aqueous solution or a hydrous alcohol solution of potassium sulfate and / or sodium sulfate and barium carbonate are added after being mixed in advance. The acid curable mold according to any one of claims 4, 5, 10, or 11, wherein a cream time after adding and mixing a foaming agent and an acidic curing agent to the phenol resin composition is 10 seconds or more. A method for producing a phenolic resin foam. Foam characteristics with a density of 10 to 500 kg / m ³ , a pH of 4 or more, and a water absorption of 1 to 15 g.
/ 100 cm ² , and an acidic curable phenolic resin foam characterized by containing sulfur element and potassium element and / or sodium element in the foam. It is manufactured with the manufacturing method in any one of Claims 1-12, A foam characteristic is a density of 10-500 kg / m < ³ >, pH is 4 or more, and a water absorption is 1-15 g / 100cm < ² >, In foam An acidic curable phenolic resin foam characterized by containing sulfur element and potassium element and / or sodium element. The acid-curable phenolic resin foam according to claim 13 or 14, wherein both surfaces or one surface are coated with one or more kinds of face materials selected from the group consisting of fibers, metals, and inorganic substances.