JP2000119424A - Foam of phenolic resin containing inorganic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a foam having low water absorptivity in addition to a light weight, fire-proofness, and heat insulation properties by incorporating an inorganic material having a specified mean particle diameter with a phenolic resin foam having a specified means cell diameter. SOLUTION: The inorganic material is exemplified by a powder or a foam made from an inorganic component and is exemplified by a calcium carbonate powder or a silica stone powder, and has a mean particle diameter of 0.05-2.80 mm. The phenolic resin foam having a mean cell diameter of 10-400 μm is obtained by adding a blowing agent, a curing catalyst, etc., to a resol phenolic resin precondensate obtained by the condensation of a phenol with a formalin in the presence of a basic catalyst and foaming and curing the resultant mixture at 100 deg.C or below. The content of the inorganic material is suitably 50-3,000 pts.wt. per 100 pts.wt. phenolic resin foam. The foam is desirably a fiber- reinforced one. The fiber is exemplified by a glass fiber and is used in an amount of at most 500 pts.wt. par 100 pts.wt. resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various building materials such as interior materials, outer wall materials, floor materials, roof materials and the like, which are characterized by being lightweight, fire-resistant, heat-insulating and low in water absorption. The present invention relates to a phenol resin foam containing an inorganic material useful for a phenol resin.

[0002]

2. Description of the Related Art In addition to being lightweight and having excellent heat insulating properties, phenolic resin foams have characteristics such as flame retardancy and low smoke emission among resin foams. Used. In addition, phenolic resin-containing foams made of inorganic materials such as pearlite and shirasu balloons and phenolic resin foams are useful as various building materials because they have features such as light weight, fire resistance and heat insulation. Known (Japanese Patent Publication No. 5-1135,
JP-B 4-46742, etc.).

[0003] However, these conventional phenolic resin foams containing an inorganic material have a problem of high water absorption.

[0004]

The problem to be solved by the present invention is as follows.
It is to solve the above problems of the conventional inorganic material-containing phenolic resin foam, that is, lightweight and fireproof,
An object of the present invention is to provide a phenolic resin-containing foam containing an inorganic material, which is useful for various building materials and has a characteristic of low water absorption in addition to heat insulation.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to achieve the above-mentioned object, and as a result, the particle size of the contained inorganic material has been set to a specific range, and the bubbles of the phenol resin foam have been reduced. By making the size smaller than that of the conventional inorganic material-containing phenol resin foam, it was found that the water absorption was significantly reduced, and the present invention was completed.

That is, the present invention provides: 1. a phenol resin foam containing an inorganic material, comprising: an inorganic material having an average particle diameter of 0.05 mm or more and 2.80 mm or less; and a phenol resin foam having an average cell diameter of 10 μm or more and 400 μm or less. The phenol resin foam containing an inorganic material according to 1 above, wherein the phenol resin foam contains an inorganic material.

Hereinafter, the present invention will be described in detail. The inorganic material used in the present invention is, for example, a powder or foamed particles composed of an inorganic component. Specifically, calcium carbonate powder, silica powder, silica sand, talc, mica, aluminum oxide powder, aluminum hydroxide powder, calcium silicate powder, wollastonite, glass powder, glass beads, fly ash, silica fume, gypsum powder, borax And inorganic powders such as slag powder, and inorganic expanded particles such as pearlite, shirasu balloon, glass balloon, fly ash balloon, ceramic balloon, vermiculite and the like.

The inorganic material used in the present invention must have an average particle size of 0.05 mm to 2.80 mm,
It is preferably from 0.07 mm to 2.00 mm, more preferably from 0.10 mm to 1.70 mm, and particularly preferably from 0.12 mm to 1.40 mm. When the average particle size is less than 0.05 mm, a phenol resin foam containing an inorganic material having a low water absorption cannot be obtained. If the average particle size exceeds 2.80 mm, the strength of the inorganic material-containing phenol resin foam tends to decrease. One kind of the inorganic material may be used alone, or two or more kinds may be used in combination.

The average particle size of the inorganic material is JIS Z 8
It is a volume median diameter determined from the result of a sieving test performed in accordance with JIS A 1102 by selecting an appropriate sieve from standard sieves specified in 801. With this method, it is difficult to determine the average particle size as a numerical value, but it is possible to specify in which range the average particle size falls.

In this sieving test, the average particle size was 0.1
When a result of less than 50 mm is obtained, a laser diffraction particle size distribution analyzer (SALD manufactured by Shimadzu Corporation) is used for a further 0.150 mm sieve.
-3000), and the (50 / G) vol% diameter (the particle diameter at which the integrated value from the small particle diameter side becomes (50 / G) vol%) of the measurement result is the average particle size of the inorganic material. Is the diameter. Here, G is 0.1 to the total amount of the inorganic material.
It is a volume ratio occupied by a 50 mm sieve. The measurement by the laser diffraction type particle size distribution measuring apparatus is performed by using distilled water as a dispersion medium, adding 0.1 wt% of sodium hexametaphosphate as a dispersant to the dispersion medium, and using an ultrasonic wave (10%).
0 W) for 1 minute.

In the above sieving test, the volume of the inorganic material component remaining in each sieve and the volume of the inorganic material component passing through the 0.150 mm sieve were measured as follows. Inorganic material components remaining in each sieve and 0.1
The whole amount of the inorganic material components passed through the 50 mm sieve is individually transferred to a plastic measuring cylinder. On a firm, horizontal floor, such as a concrete floor, the graduated cylinder is dropped 50 times on the floor with its bottom level from a height of about 2 cm above the floor. Then, a measuring cylinder is placed on a horizontal floor, and the upper surface of the inorganic material is made as horizontal as possible. Then, the scale of the measuring cylinder is read to determine the volume of the inorganic material. The volume measurement is performed under the condition that a scale in a range of 50 to 100% of a measurable amount (maximum scale) of the measuring cylinder is used.

In the present invention, the content of the inorganic material in the inorganic material-containing phenolic resin foam is as follows.
The appropriate amount is 50 to 3000 parts by weight, preferably 100 to 2500 parts by weight, and
More preferably, the amount is from 0.00 to 2000 parts by weight.
It is particularly preferred that the amount is from 0 to 1500 parts by weight. If the content of the inorganic material is too small, the fire resistance of the obtained foam will be low, and if the content of the inorganic material is too large, it will be difficult to secure the necessary strength as a building material.

It is preferable that these inorganic materials are uniformly dispersed in the phenol resin foam. The phenolic resin foam in the present invention is a resol type phenolic resin initial condensate synthesized by condensing phenols and formalins in the presence of a basic catalyst, a foaming agent, a curing catalyst, and further, if necessary, are added. A foam obtained by foaming and curing a resin composition in which additives such as a foam nucleating agent and a surfactant are mixed at a relatively low temperature of 100 ° C. or less, the above-mentioned resol-type phenol resin initial condensate, a foaming agent, and if necessary Obtained by subjecting a resin composition containing an additive such as a foaming nucleating agent and a surfactant to foaming and curing at a relatively high temperature of 100 ° C. or higher, in the presence of an acidic catalyst of phenols and formalins Novolak-type phenolic resin synthesized by condensing with a premix, a foaming agent, a hardening agent, and a foamed nucleating agent to be added if necessary. A foam obtained by foaming and curing the composition at a relatively high temperature of 100 ° C. or higher, the resol-type phenol initial condensate, the novolak-type phenol initial condensate, a foaming agent, and a curing catalyst and a curing agent to be added as necessary. And foams obtained by subjecting a resin composition containing an additive such as a foam nucleating agent or a surfactant to foaming and curing at an appropriate temperature. The phenolic resin foam functions as a binder for the inorganic material.

The phenols mentioned here include cresol, xylenol, ethylphenol, propylphenol, catechol, resorcinol, hydroquinone, bisphenols and the like in addition to phenol. The formalins include formaldehyde, paraformaldehyde, hexamethylenetetramine, furfural, acetaldehyde, acetals, and the like. The resol-type phenol resin precondensate and novolak-type phenol resin precondensate may be modified by adding urea, a urea derivative, aniline, melamine, ammonia or the like during the synthesis.

The blowing agent is a volatile organic compound or a compound which decomposes by heating to generate a gas (hereinafter referred to as a decomposable compound). Specifically, as the volatile organic compound, trichlorotrifluoroethane, trichloromonofluoromethane, dichlorotrifluoroethane, dichlorofluoroethane, tetrafluoroethane, halogenated hydrocarbons such as methylene chloride and derivatives thereof, butane, pentane, Examples thereof include hydrocarbons containing no halogen, such as hexane. Examples of the decomposable compound include dizodicarbonamide, dinitrosopentamethylenetetramine, benzenesulfonylhydrazide, azobisisobutyronitrile, azodicarbonamide, paratoluenesulfonylhydrazide, ammonium carbonate, ammonium bicarbonate, and ammonium nitrite. it can. The foaming agents may be used alone or as a mixture of two or more.

The amount of the foaming agent to be added is determined mainly by the desired density of the final inorganic material-containing phenolic resin foam, but should be 3 to 40 parts by weight based on 100 parts by weight of the phenolic resin precondensate. And more preferably 5 to 30 parts by weight. In the present invention, it is also preferable to use talc, zeolite or the like as a foam nucleating agent.

In the present invention, it is also preferable to use a surfactant. Among them, the use of nonionic surfactants is effective.Specifically, alkylene oxide, which is a copolymer of ethylene oxide and propylene oxide, a condensate of alkylene oxide and castor oil, or alkylene oxide and nonylphenol, dodecyl Examples thereof include condensates with alkylphenols such as phenol, fatty acid esters such as polyoxyethylene fatty acid esters, silicon-based compounds such as polydimethylsilioxane, and polyalcohols.

The curing catalyst is a compound capable of promoting a crosslinking reaction of a resol type phenol resin precondensate by addition, and specifically, an inorganic acid such as sulfuric acid and phosphoric acid, toluenesulfonic acid, xylenesulfonic acid, benzenesulfonic acid. Acid, phenolsulfonic acid, styrenesulfonic acid,
Examples include naphthalene sulfonic acid. The addition amount of the curing catalyst is preferably 2 to 50 parts by weight based on 100 parts by weight of the resol type phenol initial condensate.

A curing agent is a compound which can be decomposed by heating and undergo a crosslinking reaction with a novolak-type phenol resin condensate.
Hexamethylenetetramine, paraformaldehyde,
Examples include methylal, dioxane, trioxane, tetraoxane, trimethylolphosphine, S-triazine and the like. When a curing agent that generates a gas during decomposition is used, the resin composition can be foamed with the gas. That is, the curing agent may also function as a foaming agent. The addition amount of the curing agent is 3 to 2 parts by weight based on 100 parts by weight of the novolak type phenol resin precondensate.
It is preferably 0 parts by weight.

The phenolic resin foam of the present invention is preferably made of a phenolic resin having a specific crosslinked structure. In the present invention, pyrolysis gas chromatography is used as a means for indirectly measuring the crosslinked structure. Each of trimethylphenol and phenol appearing in a pattern of a pyrolysis product obtained by pyrolysis gas chromatography using a phenolic resin foam containing an inorganic material as a sample (hereinafter, referred to as a pyrogram; see FIG. 1). Although the area of the component does not directly indicate the structure of the phenolic resin constituting the phenolic resin foam,
It can be a powerful indicator that indirectly reflects the structure of the original phenolic resin. In the present invention, the area ratio C = A / B of the trimethylphenol component A to the phenol component B in the pyrogram is an index that indirectly reflects the crosslink density of the methylene structure or the methyl ether structure of the phenol resin. The C value increases when the methylene bridge or methyl ether bridge is large in the phenol resin, and the C value decreases when the methylene bridge or methyl ether bridge is small in the phenol resin.

In the present invention, the C value is preferably 0.1 or more and 4 or less, more preferably 0.1 or more and 2 or less, and particularly preferably 0.1 or more and 1 or less. By using such a crosslinked structure, a phenol resin foam containing an inorganic material having low brittleness and excellent mechanical strength can be obtained. Furthermore, the phenolic resin foam of the present invention is preferably made of a phenolic resin having a urea crosslinked structure. The index indicating the urea crosslinked structure is also determined by the area ratio of components appearing in a pyrolysis gas chromatography pyrogram of the phenol resin forming the phenol resin foam in the same manner as the C value. In the present invention, the area ratio F = D / E of the urea crosslinking component D to the phenol derivative component E in the pyrogram is used as an index reflecting the urea crosslinking density in the phenol resin.

The urea-derived component D is a component released during a retention time of 8 to 18 minutes in a pyrogram and is a compound containing a phenyl group and an isocyanate group (-NCO) in the molecule. These components are identified by a mass spectrum or the like. Specifically, for example, peaks 7 to 11 in FIG. 1 and the corresponding mass spectra are those shown in FIGS.
Phenol derivative component E includes phenol, methylphenol, dimethylphenol and trimethylpheno-
It is. These are also identified by mass spectra. Specifically, peaks 1 to 6 in FIG. 1 correspond to the mass spectra shown in FIGS. 7 to 12, respectively.

The phenolic resin foam of the present invention comprises:
The F value is preferably larger than 0, more preferably 0.03 or more and 0.3 or less, further preferably 0.035 or more and 0.2 or less, and particularly preferably 0.1 or more.
04 or more and 0.15 or less. Even with such a crosslinked structure, a phenol resin foam containing an inorganic material having low brittleness and excellent mechanical strength can be obtained.

The pyrogram of pyrolysis gas chromatography was measured as follows. The phenolic resin-containing foam sample containing the inorganic material used for the measurement is obtained by carefully pulverizing the powder shaved by a cutter knife or the like further in a mortar, and measuring the amount of the phenolic resin in a single measurement by 0.3 to 0.4.
Adjust the sample amount to be in the range of about mg. The thermal decomposition apparatus uses PY2010D manufactured by Frontier Laboratories, which is a heating furnace type thermal decomposition apparatus, and the thermal decomposition temperature is 670 ° C.
Gas chromatography was measured using a Hewlett-Packard HP5890A model, Durabond D, a non-polar liquid phase capillary column.
B-1 (inner diameter 0.25 mm, film thickness 0.25 μm, length 3
0m), the carrier gas is helium,
Total flow rate is 100 cm ³ / min, head pressure is 10
0 kPa, the oven temperature is 50 ° C.
The temperature is raised to 340 ° C. at a rate of ° C./min and held for 15.5 minutes. The detection of each component is performed using a flame ionization detector (FI
D), the area value of each peak is normalized with respect to all the detected components, and the ratio is determined for each component. However, when the skirts of the peaks overlap, a perpendicular is drawn from the valley of the peak to the baseline, and the area surrounded by the baseline and the perpendicular is defined as the peak area.

FIG. 1 shows an example of a pyrolysis gas chromatography pyrogram of a phenolic resin foam sample according to the present invention. The structure of each component was confirmed by a mass spectrum obtained by introducing the component separated by gas chromatography into a mass spectrometer. The mass spectrum was measured by an electron impact ionization method (EI method) with an ionization voltage of 70 eV and an ionization current of 30 according to JEOL JMS AX-505H.
It was measured at 0 mA. The inorganic material-containing phenol resin foam according to the present invention has a bulk density of 0.2 to 1.2 g / c.
m ³ , preferably 0.3 to 1.0 g / m ^3.
cm ³ is more preferable, and 0.4 to
Particularly preferred is 0.8 g / cm ³ .

The average cell diameter of the phenolic resin foam in the present invention is from 10 μm to 400 μm, preferably from 10 μm to 300 μm, more preferably from 10 μm to 300 μm.
It is from 200 μm to 200 μm, particularly preferably from 10 μm to 150 μm. When the average cell diameter exceeds 400 μm, a foam having significantly lower water absorption than a conventional phenol resin foam containing an inorganic material cannot be obtained. Further, it is substantially difficult to obtain a foam having an average cell diameter of less than 10 μm.

In the present invention, the average cell diameter of the phenolic resin foam refers to a portion where the inorganic material is exposed on a 50-times enlarged photograph of the fractured surface of the inorganic material-containing phenolic resin foam (the cell structure is confirmed on the photograph). 4) A straight line having a length of 9 cm is drawn so as not to cross the portion which cannot be crossed, and the number of bubbles crossed by each straight line is determined by each straight line.
The value obtained by dividing 0 μm is a value calculated from the number of cells measured according to JIS K6402.

The foam according to the present invention is preferably fiber-reinforced by containing fibers conventionally known as reinforcing fibers. Specific examples of the fiber include glass fiber, ceramic fiber, carbon fiber, rock wool, pulp, vinylon fiber, and aramid fiber. The form of these fibers is not particularly limited, and any of those conventionally known, such as filament, roving, strand, chopped strand, mat, and cloth can be used. By including the fiber, the bending strength and impact resistance are improved, and the usefulness as a building material is further enhanced.

The content of the fiber is preferably 500 parts by weight or less based on 100 parts by weight of the phenol resin.
The content is more preferably 20 to 400 parts by weight,
It is particularly preferred that the amount is from 300 to 300 parts by weight. If the content of the fiber is too large, the water absorption of the obtained phenol resin foam containing an inorganic material increases. On the other hand, if the content is too small, the fiber reinforcing effect is not exhibited. Further, the inorganic material-containing phenol resin foam of the present invention may contain an organic material such as synthetic resin powder and synthetic resin foam particles, in addition to the phenol resin foam functioning as a binder for the inorganic material. It is preferable that the content is lower than that of the phenol resin.

In the present invention, by setting the average particle diameter of the contained inorganic material to 0.05 mm or more and the average cell diameter of the foam to 400 μm or less, water absorption is significantly higher than that of a conventional phenol resin foam containing an inorganic material. An inorganic material-containing phenolic resin foam having a low property was obtained, and the reason is presumed as follows. Generally, in a phenolic resin foam containing an inorganic material, defects such as voids are likely to occur at the interface between the inorganic material and the phenolic resin, that is, near the surface of the inorganic material, due to the familiarity between the two. And it is considered that those defects contribute to the water absorption of the foam. However, by increasing the average particle size of the inorganic material and decreasing the surface area of the inorganic material, the number of locations where these defects are likely to occur is reduced, and the number of defects in the phenolic resin foam containing the inorganic material is reduced. It is considered to be one of the factors that reduce

Reducing the average cell diameter of the foam is one of the causes of the decrease in water absorption because the reduction of the average cell diameter leads to a denser cell structure and a higher closed cell ratio. Conceivable. When both of these two conditions are satisfied, it is considered that a low-water-absorbing phenolic resin-containing foam containing an inorganic material that has not been obtained conventionally can be obtained.

Next, a method for producing the phenol resin foam containing an inorganic material of the present invention will be described. Phenolic resin precondensate, foaming agent and curing catalyst to be added if necessary,
Mix curing agent, foaming aid, foam nucleating agent, surfactant, etc.
A uniformly mixed resin composition is obtained. The mixing method is not particularly limited as long as uniform mixing can be performed, and a conventionally known method in the relevant field may be appropriately selected, but all of the blowing agent does not foam, and a curing agent is added. In this case, it is necessary to perform the reaction under the condition that the curing agent does not decompose, and it is more preferable to perform the reaction under the condition that the phenol resin initial condensate becomes liquid.

Next, an inorganic material having an average particle size satisfying the above-mentioned conditions, reinforcing fibers to be added as necessary, and the like are added to the resin composition and mixed again, and the uniformly mixed phenol resin containing the inorganic material is added. A raw material composition for a foam is obtained. There is no particular limitation on this mixing method as long as uniform mixing can be performed, and a conventionally known method in the relevant field may be appropriately selected, but again all of the blowing agent does not foam and the curing agent is used. When added, it is necessary to carry out under conditions where the curing agent does not decompose. Further, a mixing method in which the shape is changed by destroying or cutting the inorganic material is not suitable.
When a urea crosslinked structure is introduced into the phenol resin, it is preferable to add urea during the synthesis of the phenol resin precondensate to urea-modify the phenol resin precondensate.

Thereafter, the raw material composition is maintained under the condition that all the foaming agent contained in the raw material composition can foam, and the raw material composition is foamed and cured to obtain a phenol resin foam containing an inorganic material. At this time, the resin composition has an initial viscosity at the foaming temperature of the foaming agent in the range of 40 to 100 poise, and the temperature around the resin composition is maintained at the foaming temperature of the foaming agent, and is determined by a method described later. The viscosity increase coefficient is 0.10 to 0.50
Must be in the range By satisfying such conditions, it is possible to form small bubbles that could not be formed in the phenolic resin foam constituting the conventional inorganic material-containing phenolic resin foam. A resin foam is obtained. further,
Initial viscosity is 45 to 80 poise, viscosity increase coefficient is 0.30
０．４0.45 is preferred.

When the initial viscosity of the resin composition at the foaming temperature of the foaming agent is lower than 40 poise or when the ambient temperature is kept at the foaming temperature of the foaming agent, the viscosity increase coefficient of the resin composition is from 0.10. If smaller, the bubbles formed by foaming are united and become larger, and it is not possible to form bubbles of a size within the scope of the present invention, or the foam is not retained in the resin composition and the foam is It cannot be formed. When the initial viscosity of the resin composition at the foaming temperature of the foaming agent is higher than 100 poise, it becomes difficult to uniformly mix the resin composition and the inorganic filler. Also,
When the viscosity increase coefficient of the resin composition obtained by maintaining the surroundings at the foaming temperature of the foaming agent is larger than 0.50, bubbles having a size within the range of the present invention cannot be formed, May not be held in the resin composition to form a foam.

Here, the foaming temperature of the foaming agent is the boiling point when the foaming agent is a volatile organic compound, and is the decomposition temperature when the foaming agent is a decomposable compound. When two or more foaming agents are used in combination, the initial viscosity and the viscosity increase coefficient of the resin composition must satisfy the above conditions at the foaming temperature of the foaming agent having the highest foaming temperature. The initial viscosity and the viscosity increase coefficient of the resin composition at the foaming temperature of the foaming agent are measured under the following conditions.

A resin composition is obtained under the same conditions as the actual production conditions except that no foaming agent is added. Under the same conditions as when the resin composition and the inorganic material are mixed in the actual production, only this resin composition is mixed for the same time as the actual mixing time. Thereafter, an amount of the resin composition necessary for viscosity measurement is put into a rotary viscometer (R100 type viscometer RB type manufactured by Toki Sangyo Co., Ltd.) which is maintained at a foaming temperature of a foaming agent used in actual production. The viscosity immediately after the temperature of the resin composition reaches the foaming temperature of the foaming agent is measured, and this is defined as the initial viscosity V0. Further, the resin composition is held in the rotational viscometer as it is, and the viscosity is measured again 4 minutes after the initial viscosity is measured, and this viscosity is defined as V4. The viscosity increase coefficient is calculated by the following equation.

[0038]

(Equation 1)

The method for molding the phenolic resin-containing foam containing an inorganic material is not particularly limited as long as foaming is not hindered. Methods conventionally known as methods for molding resins and resin foams, for example, cast molding, Any of a press molding method, an extrusion molding method, a transfer molding method, a sandwich molding method and the like can be adopted.

[0040]

Now, the present invention will be described in further detail with reference to Examples and Comparative Examples. The measurement of the bulk density and the measurement of the water absorption in the examples and comparative examples were performed by the following methods. (1) Measurement of bulk density 100 cut out from a flat plate of 250 × 250 × 10 mm
× 100 × 10mm flat plate (all four side surfaces are cut surfaces)
Into an air dryer with a stirrer adjusted to about 105 ° C,
After heating for 24 hours, take out, put in a desiccator humidified with silica gel, cool to room temperature, and measure weight W. The density is calculated by the following equation.

[0041]

(Equation 2)

(2) Measurement of water absorption 200 cut out from a flat plate of 250 × 250 × 10 mm
× 200 × 10mm flat plate (all four side surfaces are cut surfaces)
Is allowed to stand in a room at a temperature of 20 ° C. and a relative humidity of 60% until a constant weight is obtained, and then the weight is measured to obtain a dry weight Md. Next, this flat plate was placed on a 200 × 200 mm
Place in water at ２５25 ° C. so that the upper surface is at a position 2 cm below the water surface, and leave for 24 hours. After a lapse of 24 hours, the flat plate is taken out of the water, the water adhering to the surface is wiped off with a compress, and the weight is measured immediately. The water absorption is calculated as the water absorption per 100 cm ² of the outer surface area of the flat plate by the following equation.

[0043]

(Equation 3)

[0044]

Example 1 A reactor was charged with 3,800 g of 50% formalin and 3,000 g of phenol, and the temperature was adjusted with a temperature controller while stirring with a propeller rotary stirrer, and the temperature inside the reactor (hereinafter, referred to as reaction solution) was measured. 40 ° C. Next, 66 g of a 50% aqueous sodium hydroxide solution was added, and the temperature of the reaction solution was increased stepwise from 40 ° C. to 85 ° C. to 85 ° C.
Hold for 0 minutes, then cool the reaction to 5 ° C. Then, 50 mL of paratoluenesulfonic acid monohydrate was added to the reaction solution.
% Aqueous solution was added until the pH reached 6, followed by dehydration treatment at 60 ° C. to synthesize a resol type phenol resin precondensate.

100 parts by weight of this resol type phenol resin precondensate, and normal pentane (boiling point:
36 ° C.) 12 parts by weight, 20 parts by weight of paratoluenesulfonic acid as a curing catalyst, and alkylene oxide (Pluronic P127 manufactured by BASF) 2 as a surfactant, which is a copolymer of ethylene oxide and propylene oxide.
A part by weight was put into an Aiko Chemical Mixer (manufactured by Aikosha Mfg. Co., Ltd.) and mixed at room temperature of 20 ° C. for 1 minute to obtain a resin composition. ~
600 parts by weight (within a range of 0.6 mm) were added and mixed for 2 minutes to obtain a uniformly mixed raw material composition. After spreading 300 g of this raw material composition on the bottom surface of a mold (250 × 250 × 10 mm), the mold was covered and the cover was pressed in a heating press machine (manufactured by Oji Machine Co., Ltd.) at 65 ° C. The resin composition was foamed and cured by heating in this state to obtain a phenol resin foam containing an inorganic material. The initial viscosity of the resin composition at 36 ° C. (normal pentane boiling point as a foaming agent) is 45 poise,
The viscosity increase coefficient was 0.41.

The foamed phenolic resin constituting the obtained foamed phenolic resin containing an inorganic material had an average cell diameter of 92 μm, a C value of 0.33 and an F value of 0. This inorganic material-containing phenol resin foam had a bulk density of 0.43 g / cm ³ and a water absorption of 1.5 g / 100 cm ² .

[0047]

Example 2 Novolak type phenol precondensate 100
Weight part (melting point 73 ℃ AK- manufactured by Asahi Organic Materials Industry Co., Ltd.)
5), N, N'-dinitrosopentamethylenetetramine (Cellular D, manufactured by Eiwa Chemical Industry Co., Ltd.) 1 as a blowing agent
5 parts by weight, hexamethylenetetramine 10 as a curing agent
1 part by weight of alkylene oxide (Bronon 208, manufactured by NOF Corporation) as a surfactant was mixed at 95 ° C. with a pressurized kneader (manufactured by Moriyama Co., Ltd.). Fifteen
After heating and mixing for a minute, the mixture was cooled to obtain a lump resin composition, which was pulverized into a powder. Next, 400 parts by weight of aluminum hydroxide powder (average particle size: 0.10 mm, Hygilite H-10C manufactured by Showa Denko KK) is added to the powdery resin composition, and a V-type mixer (Irie Shokai Co., Ltd.) is added. ) To obtain a uniformly mixed raw material composition. This raw material composition 35
After spreading 0 g on the bottom surface of the mold (250 × 250 × 10 mm), the mold is covered, and the resin is foamed and hardened by heating in a state where the cover is pressed in a heating press machine at 160 ° C. to form an inorganic material. A phenolic resin-containing foam was obtained.

Cellular D, which is a foaming agent, is a decomposable compound and has a foaming temperature of 125 ° C. in the novolak type phenol resin precondensate. The initial viscosity at 125 ° C. of the resin composition was 63 poise, and the viscosity increase coefficient was 0.45. The phenol resin foam constituting the obtained inorganic material-containing phenol resin foam has an average cell diameter of 156 μm.
The m and C values were 0.14 and the F value was 0. This inorganic material-containing phenol resin foam has a bulk density of 0.52 g /
cm ³ , and the water absorption was 2.1 g / 100 cm ² .

[0049]

Example 3 A reactor was charged with 3800 g of 50% formalin and 3000 g of phenol, and the temperature was adjusted with a temperature controller while stirring with a propeller rotary stirrer, and the temperature inside the reactor (hereinafter, referred to as reaction solution) was measured. 40 ° C. Next, 66 g of a 50% aqueous sodium hydroxide solution was added, and the temperature of the reaction solution was increased stepwise from 40 ° C. to 85 ° C. to 85 ° C.
Hold for 0 minutes, then cool the reaction to 5 ° C. This is designated as reaction liquid R.

On the other hand, separately from the reaction solution R, 50%
After 1080 g of formalin, 1000 g of water, and 100 g of a 50% aqueous sodium hydroxide solution were charged and stirred with a propeller-type stirrer, 1600 g of urea was further added, and the temperature was adjusted with a temperature controller while stirring. Next, the temperature of the reaction solution was raised to 70 ° C. and maintained for 60 minutes, and then cooled to room temperature. This is designated as reaction solution U. next,
5000 g of the reaction solution R and 770 g of the reaction solution U were mixed, and the temperature of the solution was raised to 60 ° C. and maintained at 60 ° C. for 80 minutes, and then the reaction solution was cooled to 30 ° C. Then, a 50% aqueous solution of paratoluenesulfonic acid monohydrate was added to the reaction solution at pH.
Was reduced to 6 and then dehydrated at 60 ° C. to synthesize a urea-modified resol type phenol resin precondensate.

100 parts by weight of this resol type phenol resin precondensate, and cyclopentane (boiling point: 4
9 ° C), 8 parts by weight, 20 parts by weight of paratoluenesulfonic acid as a curing catalyst, and 2 parts by weight of an alkylene oxide (Pluronic P127 manufactured by BASF) which is a copolymer of ethylene oxide and propylene oxide as a surfactant. (Manufactured by Aikosha Seisakusho Co., Ltd.), and mixed at room temperature of 20 ° C. for 1 minute to obtain a resin composition. Then, 800 parts by weight of No. 5 silica sand is further added, mixed for 2 minutes, and uniformly mixed. The obtained raw material composition was obtained. 400 g of this raw material composition is placed in a mold (250 × 250 × 10 m
m) After spreading on the bottom surface, the mold is covered and heated in a heating press machine (manufactured by Oji Kikai Co., Ltd.) at 65 ° C. with the cover pressed to heat and foam and harden the resin, containing inorganic materials. A phenolic resin foam was obtained. The initial viscosity of the resin composition at 49 ° C. (boiling point of cyclopentane as a foaming agent) was 71 poise, and the viscosity increase coefficient was 0.30.

The foamed phenolic resin constituting the obtained foamed phenolic resin containing an inorganic material had an average cell diameter of 185 μm, a C value of 0.32 and an F value of 0.10. This inorganic material-containing phenol resin foam has a bulk density of 0.59 g / cm ³ and a water absorption of 2.0 g / 100.
cm ² .

[0053]

Example 4 Glass fiber (chopped strand 6 mm in length, RCS- manufactured by Nippon Sheet Glass Co., Ltd.) together with No. 5 silica sand
No. 06) was added in the same manner as in Example 1 except that 100 parts by weight of phenol resin foam containing an inorganic material was obtained. The foamed phenolic resin constituting the obtained inorganic material-containing phenolic resin foam had an average cell diameter of 109 μm, a C value of 0.35, and an F value of 0. This inorganic material-containing phenol resin foam has a bulk density of 0.44 g / cm ³ and a water absorption of 1.7 g / 100.
cm ² .

[0054]

[Comparative Example 1] An average particle size of 0.028 m instead of No. 5 silica sand
A phenol resin foam containing an inorganic material was obtained in the same manner as in Example 1 except that m silica powder was used. The phenol resin foam constituting the obtained inorganic material-containing phenol resin foam has an average particle size of 129 μm and a C value of 0.3.
1, F value was 0. This inorganic material-containing phenol resin foam had a bulk density of 0.43 g / cm ³ and a water absorption of 8.1 g / 100 cm ² .

[0055]

Comparative Example 2 A resol-type phenolic resin initial condensate was synthesized in the same manner as in Example 1 except that the time of maintaining the temperature at 85 ° C. was changed to 100 minutes, and an inorganic material-containing material was used using the initial condensate. A phenolic resin foam was obtained. 36 ° C. of resin composition (boiling point of normal pentane as blowing agent)
Has an initial viscosity of 23 poise and a viscosity increase coefficient of 0.3.
It was 4. The foamed phenolic resin constituting the obtained inorganic material-containing phenolic resin foam had an average cell diameter of 450 μm, a C value of 0.34, and an F value of 0.
This inorganic material-containing phenol resin foam had a bulk density of 0.41 g / cm ³ and a water absorption of 9.8 g / 100 cm ² .

[0056]

[Comparative Example 3] Charge the reactor to obtain the reaction liquid R 5
The amount of 0% formalin was changed to 3200 g, and the mixing ratio of the reaction solution R and the reaction solution U was changed to 6000 g of the reaction solution R and the reaction solution U.
A urea-modified resol type phenol resin initial condensate was synthesized in the same manner as in Example 3 except that the amount was changed to 910 g, and a phenol resin foam containing an inorganic material was obtained using the initial condensate. The initial viscosity of the resin composition at 49 ° C. (boiling point of cyclopentane as a blowing agent) was 52 poise, and the viscosity increase coefficient was 0.05. The foamed phenolic resin constituting the obtained inorganic material-containing phenolic resin foam had an average cell diameter of 480 μm, a C value of 0.31, and an F value of 0.12. This phenol resin foam containing an inorganic material has a bulk density of 0.58 g / cm.
^{3. The} water absorption was 10.6 g / 100 cm ² .

[0057]

Industrial Applicability According to the present invention, an inorganic-containing phenol resin foam useful for various building materials having features of being lightweight, fire-proof, heat-insulating, and low-water-absorbing can be obtained.

[Brief description of the drawings]

FIG. 1 is an example of a pyrolysis gas chromatography pyrogram of a phenolic resin foam molded article sample. The vertical axis indicates the relative intensity.

FIG. 2 is a mass spectrum of one structural component derived from a urea crosslink in a pyrogram of a pyrolysis gas chromatography of a phenolic resin foam molded article sample.

FIG. 3 is a mass spectrum of one structural component derived from a urea crosslink in a pyrogram of a pyrolysis gas chromatography of a phenolic resin foam molded article sample.

FIG. 4 is a mass spectrum of one structural component derived from a urea crosslink in a pyrogram of a pyrolysis gas chromatography of a phenolic resin foam molded article sample.

FIG. 5 is a mass spectrum of one structural component derived from a urea crosslink in a pyrogram of a pyrolysis gas chromatography of a phenolic resin foam molded article sample.

FIG. 6 is a mass spectrum of one structural component derived from a urea crosslink in a pyrogram of a pyrolysis gas chromatography of a phenolic resin foam molded article sample.

FIG. 7 is a mass spectrum of a phenol component of a pyrogram of a phenolic resin foam molded article sample obtained by pyrolysis gas chromatography.

FIG. 8 is a mass spectrum of a trimethylphenol component in a pyrogram of a pyrolysis gas chromatography of a phenolic resin foam molded article sample.

FIG. 9 is a mass spectrum of an o-methylphenol component in a pyrogram of a pyrolysis gas chromatography of a phenolic resin foam molded article sample.

FIG. 10 is a mass spectrum of a p-methylphenol component in a pyrogram of a pyrolysis gas chromatography of a phenolic resin foam molded article sample.

FIG. 11 is a mass spectrum of a 2,4-dimethylphenol component in a pyrolysis gas chromatography pyrogram of a phenolic resin foam molded article sample.

FIG. 12 is a mass spectrum of a 2,6-dimethylphenol component in a pyrolysis gas chromatography pyrogram of a phenolic resin foam molded article sample.

Claims (2)

[Claims] 1. An average particle size of 0.05 mm or more and 2.80 m
m and an average bubble diameter of 10 μm or more and 40 μm or less.
A phenol resin foam containing an inorganic material, comprising a phenol resin foam of 0 μm or less. 2. A phenol resin foam containing an inorganic material according to claim 1, wherein the phenol resin foam contains an inorganic material.