JP2002338784A - Expandable phenolic resol resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an expandable phenolic resol resin composition which solves the problem concerning the separation of sheet-form facing materials established on surfaces and yields an environmentally compatible phenolic foam showing an improved resistance to water absorption or a resistance to heat insulation deterioration. SOLUTION: The expandable phenolic resol resin composition contains (A) a phenolic resol resin, (B) an acidic hardener, (C) a foaming agent essentially comprising cyclopentane, (D) a partial hydrolytic condensate of a hydrolyzable group-containing organosilicon compound and (E) a foam stabilizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an environmentally friendly phenol which mainly prevents peeling of a sheet-like face material provided on the surface, or has improved water absorption resistance or heat insulation and has resistance to thermal deterioration. The present invention relates to a foamable phenolic resole resin composition capable of providing a resinous resole resin foam.

[0002]

2. Description of the Related Art Conventionally, phenolic resole resin foams (hereinafter referred to as phenolic foams) have characteristics such as flame retardancy, heat resistance, and low smoke emission. It is used for various applications including the first. However, foam characteristics represented by heat insulation are susceptible to moisture, so that it has conventionally been necessary to deal with the structure or construction of the material.

In view of such a situation, the present inventor has sought to improve the water absorption resistance as one of the main objects. First, a phenolic resole resin, an acid curing agent, a foaming agent, a foam stabilizer, and a silicon atom Proposed a foamable phenolic resole resin composition containing an organosilicon compound having a hydrolyzable group bonded to a polymer and a partially hydrolyzed condensate thereof (Japanese Patent Application No. 2000-22).
No. 4341).

However, although the foamable phenolic resole resin composition has been improved in terms of water absorption, kraft paper and kraft paper have been added to the surface produced using a certain environmentally friendly alternative fluorocarbon foaming agent. When formed into a structure having a sheet-like surface material such as a nonwoven fabric, there are disadvantages such as that the surface material is easily peeled off when stored for a long period of time, and the heat insulating property is easily thermally degraded when exposed to high temperatures. There is still room for improvement, and further improvement in water absorption resistance is also required.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problem of peeling of a sheet-like face material provided on the surface, or to provide an environment-friendly type having improved water absorption resistance or heat insulation resistance to thermal deterioration. The purpose of the present invention is to provide a foamable phenolic resole resin composition which gives the phenolic foam of the present invention. The term “environmentally friendly” as used herein means that there is a low risk of causing ozone layer depletion and global warming.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a foamable phenolic resole resin composition having the above-mentioned properties, and as a result, a partial hydrolysis condensate of a specific organosilicon compound has been obtained. By using in combination with a blowing agent having a specific hydrocarbon as a main component, it has been found that a foamable phenolic resole resin that gives a phenolic foam that resists the above-mentioned problems, for example, heat insulation, can be obtained. The present invention has been completed based on the findings.

That is, the present invention relates to (A) a phenolic resole resin, (B) an acidic curing agent, (C) a blowing agent containing cyclopentane as a main component, and (D) an organosilicon compound having a hydrolyzable group. An object of the present invention is to provide a foamable phenolic resole resin composition containing a partially hydrolyzed condensate and (E) a foam stabilizer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a hydrocarbon-based blowing agent containing cyclopentane as a main component as a foaming agent of component (C), particularly cyclopentane alone, and an arylsulfonic acid as an acidic curing agent of component (B) It is preferable to use a glycol-based solution containing water as a main component and having a water content of less than 10% by mass.

In the foamable phenolic resole resin composition of the present invention, the phenolic resole resin used as the component (A) is, for example, a reaction catalyst such as a phenol and an aldehyde, such as a base, an acid, a divalent metal salt and In the presence of these combinations, after reacting at a temperature of from 40 ° C. to the reflux temperature for 0.5 to 24 hours, if necessary, neutralize and concentrate to produce an acid-curable resol resin or A modified resol resin obtained by mixing or reacting with an optional modifier during or after the production of the resol resin, or a mixture thereof. These resins generally have a viscosity of 5.0 to 50 P adjusted to an appropriate water content.
It is preferably used as a liquid at about a · s / 25 ° C. (JIS K-7233), but may be used in a solid state.

Examples of the resole resin include a resole resin obtained by performing a base catalyzed reaction, a novolak type resole resin obtained by performing a base catalyzed reaction after the acid catalyzed reaction, and a divalent metal salt catalyzed reaction. And a mixture thereof. Above all, resole resins and novolak type resole resins excellent in acid curability are preferable, and in particular, novolak type resole resins are advantageous because they have better water absorption resistance than resole resins.

The phenols used as a raw material of the phenolic resole resin include, in addition to phenol, cresol, xylenol, p-tert-
Examples include alkylphenols such as butylphenol, resorcinol, catechol, polyphenols such as bisphenol F and bisphenol A, and mixtures thereof.

On the other hand, examples of aldehydes include formalin, paraformaldehyde, trioxane, polyoxymethylene, glyoxal, furfural, and mixtures thereof. The mixing ratio of such phenols and aldehydes is not particularly limited,
Generally, aldehydes are blended in a ratio of 0.8 to 3.0 moles per mole of phenols. As the modifier, for example, xylene resin, urea resin, epoxy compound, polyvinyl alcohol, urea, amides, starches, monosaccharides, and mixtures thereof are used.

Examples of the base catalyst used as a catalyst for the reaction between the phenols and aldehydes include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, barium hydroxide, and hydroxide. There are calcium, magnesium oxide, and ammonia. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid and the like. Examples of the divalent metal salt catalyst include zinc acetate, lead acetate, and zinc borate.

In the present invention, the acidic curing agent used as the component (B) is a component which promotes the curing of the phenolic resole resin of the component (A) or (D) a partially hydrolyzed condensate of an organosilicon compound having a hydrolyzable group. Acidic compounds having an action of accelerating the hydrolysis and condensation of the compound. Preferred examples of such acidic compounds include, for example, organic sulfonic acids, inorganic acids, and mixtures thereof, but are not limited thereto. is not. This is based on 100 parts by weight of the phenolic resole resin (A).
Usually, it is blended in a ratio of 1 to 50 parts by mass. This one is
Usually, it is used as a solution by dissolving in water or an organic solvent.

Examples of the organic sulfonic acid of such an acidic curing agent include phenolsulfonic acid, benzenesulfonic acid, ethylbenzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, styrenesulfonic acid, and naphthalenesulfonic acid. , Naphtholsulfonic acid, anthracenesulfonic acid, anthranolsulfonic acid, sulfonated phenolic resin, arylsulfonic acid such as condensation product of aromatic sulfonic acid and formaldehyde, alkylsulfonic acid such as methanesulfonic acid,
Sulfonated creosote oil, condensation products of sulfonated creosote oil and formaldehyde, and the like are used.
Examples of the inorganic acid include phosphoric acid, polyphosphoric acid, and sulfuric acid.

Among the above-mentioned acidic curing agents, arylsulfonic acids, particularly ethylbenzenesulfonic acid, p-toluenesulfonic acid, and xylenesulfonic acid are preferable in that they have good heat insulating resistance to thermal deterioration. Among these, a glycol-based solution containing p-toluenesulfonic acid as a main component and having a water content of less than 10% by mass, particularly a diethylene glycol solution, is particularly preferable in terms of heat insulation.

In the present invention, the foaming agent used as the component (C) is a gas having a foaming effect, that is, a foaming effect of (A) a phenolic resole resin which exhibits a curing reaction by the action of an acidic curing agent. Is a compound that generates physically or chemically, but from the viewpoint of preventing peeling of face materials, heat insulation performance and safety, a foaming agent containing cyclopentane as a main component, particularly a hydrocarbon compound containing cyclopentane as a main component Foaming agents are preferred. The content of cyclopentane in such a blowing agent is 50% by mass or more, preferably 7% by mass.
0 mass% or more, more preferably 80 mass% or more.
Further, cyclopentane alone is particularly preferred from the viewpoint of thermal insulation resistance to thermal degradation. The amount of the component (C) is such that the phenolic resole resin 1 (A)
It is usually 0.5 to 30 parts by mass with respect to 00 parts by mass.

In the present invention, the blowing agent used in combination with cyclopentane is preferably a hydrocarbon-based blowing agent, but is not limited thereto. If necessary, aliphatic blowing agents such as diethyl ether and diisopropyl ether; Chemical blowing agents that generate carbon dioxide, nitrogen, and the like by the action of an acid, water, and heat, such as sodium hydrogen carbonate, calcium carbonate, hydrogen peroxide, and azodicarbonamide, as well as carbon dioxide and nitrogen gas, are used.

Examples of the hydrocarbon blowing agent include:
Aliphatic hydrocarbons such as butane, pentane and hexane; alicyclic hydrocarbons such as cyclohexane, cyclohexene and cyclopentene; dichloromonofluoroethane (HC
FC-141b), dichlorotrifluoroethane (HC
FC-123), tetrafluoroethane (HFC-13
4a), tetrafluoropropane (HFC-245f)
a), pentafluorobutane (HFC-365mf
c), halogenated hydrocarbons such as fluorohexane, fluoropentane, methylene chloride, and propyl chloride. Above all, pentane, cyclohexane, dichloromonofluoroethane, tetrafluoroethane, tetrafluoropropane and pentafluorobutane, particularly pentane and pentafluorobutane, are preferred from the viewpoint of heat resistance against thermal degradation.

In the present invention, the partially hydrolyzed condensate of an organosilicon compound having a hydrolyzable group used as the component (D) (hereinafter, referred to as a partially hydrolyzed condensate of an organosilicon compound) is By utilizing the reaction between phenolic resole resin composition and water, the water in the foamable phenolic resole resin composition is consumed to promote curing, while the water repellent function inherently present or the repellency due to the condensation of silanol generated by hydrolysis. It contributes to the improvement of water absorption resistance due to the development of the water function. Among such partially hydrolyzed condensates of organosilicon compounds, these functions are more effectively expressed and, furthermore, from the viewpoint of ease of handling, in particular, partially hydrolyzed condensates of liquid organosilicon compounds such as KC89 ( Shin-Etsu Chemical Co., Ltd., trade name, partially hydrolyzed condensate of organomethoxysilane containing organomethoxysilane monomer, AFP-1 (Shin-Etsu Chemical Co., trade name, KC8
AFP-1 is particularly preferable, for example, a partially hydrolyzed condensate of organomethoxysilane obtained by subjecting 9 to demonomerization treatment.

As the hydrolyzable group, an alkoxy group, a phenoxy group and a mercaptomethyl group are preferred in terms of good reactivity with water, but an alkoxy group, particularly a methoxy group, is preferred in terms of cost. The hydrolyzable group is
Only one kind may be present in the molecule, or two or more kinds may be mixed.

The amount of the component (D) is usually 0.1 part by mass or more, preferably 0.3 to 10 parts by mass, more preferably 0 part by mass, per 100 parts by mass of the phenolic resole resin of the component (A). It is selected within the range of 0.5 to 2 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving curability and water absorption resistance is not recognized. Since the component (D) has extremely high reactivity with water as described above, it is generally used by being previously mixed with the foaming agent of the component (C).

In the present invention, the foam stabilizer used as the component (E) is mainly composed of the phenolic resole resin (A) formed by the expansion action of the foaming agent (C) in the presence of the acidic curing agent (B). Non-ionic surfactants, which are compounds acting on uniformity and stabilization of air bubbles and having such properties, include, but are not limited to, non-ionic surfactants. Accordingly, a conventionally known anionic or cationic surfactant can be used alone or in combination with a nonionic surfactant.

Examples of the nonionic surfactant include castor oil ethylene oxide adduct and polysiloxane.
Oxyalkylene copolymer, alkylphenyl condensate ether, polyalkylene glycol alkyl ether,
Examples include glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lauric acid esters, polypropylene alkylamides, and mixtures thereof. The compounding amount of the component (E) is usually selected from the range of 0.3 to 10 parts by mass based on 100 parts by mass of the phenolic resole resin of the component (A).

Next, the foamable phenolic resole resin composition of the present invention was prepared in advance with a mixture of (A) a phenolic resole resin and (E) a foam stabilizer, and (C).
A mixture of a foaming agent containing cyclopentane as a main component and (D) a partially hydrolyzed condensate of an organosilicon compound having a hydrolyzable group is mixed with high-speed stirring to homogenize, and then (B) an acidic curing agent And uniformly high-speed stirring and mixing again, or by simultaneously performing high-pressure impingement mixing of these components.

The composition of the present invention thus obtained is
By foaming and hardening by various foaming methods such as continuous foaming method, injection foaming method, in-situ foaming method, there is no exfoliation of the surface material even during long-term storage, or excellent water absorption resistance or resistance to thermal deterioration due to heat insulation It is possible to provide an environmentally friendly phenolic foam having:

The composition of the present invention may contain, if necessary, various auxiliaries, for example, curing accelerators such as resorcin and alkylresorcin, for example, formaldehyde scavengers such as urea and melamine, for example, urea resins, melamine resins, phosphorus-containing systems.・ Halogen-containing compounds, flame retardants such as aluminum hydroxide,
For example, fiber reinforcing agents such as ceramic fibers, glass fibers, carbon fibers, phenol fibers, and aramid fibers, for example, fillers such as shirasu balloons, glass balloons, porous skeletons, and wood flour, as well as viscosity reducing agents, plasticizers, and colorings Agents, deodorants, antibacterial agents and the like can be added.

[0028]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The properties of the phenolic foams obtained in Examples and Comparative Examples were examined by the following test methods. (1) Density and water absorption: Measured according to JIS A-1412. (2) Presence or absence of face material peeling: Observed after standing at 25 ° C. for 180 days. (3) Thermal insulation (resistance to thermal degradation of thermal conductivity): After manufacturing a phenolic foam, leave it in a 25 ° C. temperature atmosphere for one day, and then adjust it to a predetermined temperature in an explosion-proof hot air circulation type incubator. After further heat treatment for 14 days, and further left for 12 hours in a temperature atmosphere of 25 ° C., the thermal conductivity was measured by a thermal conductivity measuring device (trade name “Anacon TCA Point 2” manufactured by Amco). (4) Thermal insulation (thermal conductivity): After producing the phenolic foam, it was allowed to stand in a 25 ° C. temperature atmosphere for one day, and then its thermal conductivity was measured by the thermal conductivity measuring device.

Reference Example 1 (Production of novolak type resole resin composition) In a three-necked reaction flask equipped with a reflux condenser, a thermometer, and a stirrer, 1600 g of phenol and 47 mass% of formalin 869 were prepared.
g and 1.6 g of oxalic acid, and a novolak-forming reaction was carried out at reflux temperature for 60 minutes. After cooling to 40 ° C., 1412 g of 47% by mass formalin and 41.6 g of a 50% by mass aqueous sodium hydroxide solution were charged, a resolving reaction was carried out at 80 ° C. for 80 minutes, and then cooled to 40 ° C. Next, after neutralizing with a 50% by mass aqueous solution of p-toluenesulfonic acid, 153.6 g of urea was added, and the mixture was dehydrated and concentrated to a water content of 8.0% by mass (Karl Fischer method) under reduced pressure and heating to form a liquid. (A) 2,880 g of a novolak type resole resin was obtained. Next, a novolak type resol resin composition having a viscosity of 13.5 Pa · s / 25 ° C. was added to (E) 3 parts by weight of a castor oil-based ethylene oxide adduct as a foam stabilizer with respect to 100 parts by weight of the (A) novolak type resole resin. I got

Reference Example 2 (Production of resol resin composition) In a three-necked reaction flask equipped with a reflux condenser, a thermometer, and a stirrer, 1600 g of phenol and 47% by mass of formalin 228 were prepared.
2 g and 41.6 g of a 50% by mass aqueous sodium hydroxide solution
And a resolving reaction was carried out at 80 ° C. for 80 minutes.
After cooling to 40 ° C., the mixture was neutralized with a 50% by mass aqueous solution of p-toluenesulfonic acid, 153.6 g of urea was added, and the mixture was dehydrated and concentrated to a water content of 8.0% by mass under reduced pressure and heating to obtain a liquid (A).
2830 g of a resole resin was obtained. Next, (E) 3.0 parts by mass of a castor oil-based ethylene oxide adduct as a foam stabilizer was added to 100 parts by mass of the resole resin (A) to give a viscosity of 2
A resole resin composition at 5.2 Pa · s / 25 ° C. was obtained.

Example 1 In a 500 ml disposable cup, 100 parts by mass of the novolak type resole resin composition prepared in Reference Example 1, 5 parts by mass of cyclopentane as the component (C), and AFP-1 as the component (D)
(Partial hydrolysis condensate of organomethoxysilane obtained by demonomerizing KC89, manufactured by Shin-Etsu Chemical Co., Ltd.) and a mixture with 0.1 part by mass, and further adjusted to a temperature of 25 ° C. . Next, 18 parts by mass of a 60% by mass p-toluenesulfonic acid diethylene glycol solution of the component (B), which was previously adjusted to a temperature of 25 ° C., was added, and immediately a high-speed stirrer (trade name “Homodisper” manufactured by Tokushu Kika Kogyo Co., Ltd.) For 10 seconds to produce a foamable phenolic resole resin composition. The resulting composition was treated with 80
ク ラ フ ト 上 素 早 く 素 早 く 素 早 く 素 早 く 素 早 く 素 早 く 素 早 く 素 早 く 素 早 く 素 早 く 素 早 く 素 早 く 素 早 く 素 早 く さ ら に さ ら に ８０ 、 、 、 ８０
A phenol foam having a density of 40.1 kg / cm ³ was produced by heat-treating in an explosion-proof specification hot air circulation type thermostat for 5 minutes to foam and harden. The obtained phenol-based foam was examined by the above-mentioned test method for water absorption, thermal conductivity, resistance to thermal deterioration of thermal conductivity, and the presence or absence of peeling of the face material. Table 1 shows the results.

Examples 2 to 4 Three kinds of phenolic foams were prepared in the same manner as in Example 1 except that the amount of component (D) AFP-1 was changed to the amount shown in Table 1. Further, the density, water absorption, thermal conductivity of the obtained phenolic foam, resistance to thermal degradation of thermal conductivity, and the presence or absence of peeling of the face material were examined.
Table 1 shows the results.

Example 5 In Example 1, 0.1 part by mass of AFP-1 as the component (D) was partially hydrolyzed and condensed with KC89 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., an organomethoxysilane containing an organomethoxysilane monomer). Product) except that 0.5 parts by mass was used.
A phenolic foam was prepared in the same manner as in Example 1,
Furthermore, the density, water absorption,
The thermal conductivity, the resistance to thermal degradation of the thermal conductivity, and the presence or absence of peeling of the face material were examined. Table 1 shows the results.

Example 6 In Example 1, the novolak type resole resin composition prepared in Reference Example 1 was replaced with the resole resin composition prepared in Reference Example 2, and the amount of component (D) AFP-1 was changed to 0. .1
A phenolic foam was prepared in the same manner as in Example 1 except that the mass was changed from 0.5 part by mass to 0.5 part by mass, and the density, water absorption, thermal conductivity and heat conductivity of the obtained phenolic foam were further measured. The resistance to deterioration and the presence / absence of peeling of the face material were examined. Table 1 shows the results.

Examples 7 and 8 In Example 1, 5 parts by mass of the component (C) cyclopentane was added to 70% by mass of cyclopentane and 30% by mass of pentane.
And 5 parts by mass of a mixture of 70% by mass of cyclopentane and 30% by mass of pentafluorobutane (HFC-365mfc), respectively, and the compounding amount of AFP-1 of the component (D) is 0.1%. Two types of phenolic foams were prepared in the same manner as in Example 1 except that the amount was changed from 0.5 parts by mass to 0.5 parts by mass, and the density, water absorption, thermal conductivity, and thermal conductivity of the obtained phenolic foam were further obtained. The resistance to thermal degradation of the rate and the presence or absence of peeling of the face material were examined. Table 1 shows the results.

COMPARATIVE EXAMPLE 1 In Example 1, the component (C) cyclopentane was replaced with AK
-141b (manufactured by Asahi Glass Co., trade name, HCFC-141b
Phenolic foam was prepared in the same manner as in Example 1 except that the blending amount of AFP-1 as the component (D) was changed from 0.1 part by mass to 0.5 part by mass. The density, water absorption, thermal conductivity, resistance to thermal degradation of thermal conductivity, and the presence or absence of peeling of the face material of the obtained phenol foam were examined. Table 1 shows the results.

Comparative Example 2 In Example 1, 0.1 parts by mass of AFP-1 as the component (D) was replaced with 0.5 parts by mass of KBPH-13 (trade name, methyltriphenoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.). A phenolic foam was prepared in the same manner as in Example 1, and the density, water absorption, thermal conductivity and resistance to thermal degradation of the thermal conductivity and the presence or absence of peeling of the face material were determined in the same manner as in Example 1. Examined. Table 1 shows the results.

Comparative Example 3 A phenolic foam was prepared in the same manner as in Example 1 except that the component (D) was not added, and the density and water absorption of the obtained phenolic foam were also measured. The thermal conductivity, the resistance to thermal degradation of the thermal conductivity, and the presence or absence of peeling of the face material were examined. Table 1 shows the results.

[0040]

[Table 1]

[0041]

According to the present invention, (C) a blowing agent containing cyclopentane as a main component and (D) a partially hydrolyzed condensate of an organosilicon compound having a hydrolyzable group are used in combination to obtain ( The effects of 1) improved water absorption resistance, (2) no peeling of face materials even after long-term storage, and (3) improved heat insulation (thermal conductivity) resistance to thermal degradation, alone or An environmentally friendly phenolic resole resin foam having a low risk of causing ozone layer destruction and global warming problems can be provided. Further, the phenolic resole resin foam obtained by the composition of the present invention has an advantage that it has good heat insulating properties, in other words, low thermal conductivity.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yasuhiro Ueda 26, Niitsu, Minamiyama, Fuso-cho, Fuwa-cho, Niwa-gun, Aichi Prefecture F-term in the Aichi Plant of Asahi Organic Materials Industry Co., Ltd. 4J002 CC041 CH052 CP032 DG046 DH026 EA017 EA027 EB067 EB077 EH049 EV236 EX038 FD156 FD312 FD319 FD327

Claims (4)

[Claims] (A) a phenolic resole resin,
(B) an acidic curing agent, (C) a foaming agent containing cyclopentane as a main component, (D) a partially hydrolyzed condensate of an organosilicon compound having a hydrolyzable group, and (E) a foam stabilizer. Characteristic foamable phenolic resole resin composition. 2. The foamable phenolic resole resin composition according to claim 1, wherein the component (C) is a hydrocarbon foaming agent containing cyclopentane as a main component. 3. The foamable phenolic resole resin composition according to claim 2, wherein the component (C) is cyclopentane. 4. The foamable phenolic resol resin composition according to claim 1, wherein the component (B) is a glycol-based solution having an arylsulfonic acid as a main component and a water content of less than 10% by mass. object.