JPH10139916A - Composition for water-absorbing phenolic resin foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can give a phenolic resin foam having improved water absorptivity and water retentivity by mixing a resol phenolic resin with a specified surfactant, a specified blowing agent, and a specified curing agent. SOLUTION: This composition is prepared by mixing 100 pts.wt. resol phenolic resin with 0.2-10 pts.wt. anionic surfactant comprising a 3-50C alkylbenzenesulfonate, 0.1-5 pts.wt. anionic surfactant comprising a 10-16C alcohol ethoxylated sulfanate, 0.1-5 pts.wt. nonionic surfactant comprising a fat and oil ethoxylate and/or a long-chain fatty acid ethoxylate, 3-30 pts.wt. blowing agent such as petroleum ether or isopropyl ether and 3-20 pts.wt. curing agent such as p-toluenesulfonic acid or phenolsulfonic acid. The composition can give a foam which has excellent water absorptivity and water retentivity and therefore is suitable for especially a frog for flower arrangement, and plant cultivation, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a composition for a water-absorbing phenolic resin foam. In particular, the present invention relates to a composition for a water-absorbing phenolic resin foam suitable for sword mountain for fresh flowers and plant cultivation.

[0002]

2. Description of the Related Art Conventionally, a resole type phenolic resin foam has been prepared by stirring a resin composition comprising a resol type liquid phenolic resin, a surfactant, a foaming agent and a curing agent at a high speed.
It is manufactured by foaming and curing at a temperature of ８０80 ° C.

[0003] A phenolic resin foam is required to have a high cell openness because a uniform cell structure is required and water absorption is indispensable when used for a flower arrangement. For this purpose, nonionic surfactants are generally used. Such surfactants include, for example, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, siloxaneoxyalkylene copolymers, and castor oil ethoxylates.

[0004] However, a resol-type phenol resin foam using such a surfactant has a problem that although it has a uniform cell structure, it lacks water absorption. In order to improve the water absorption of the resol-type phenol resin foam, a method has been proposed in which an alkyl sulfonate as an anionic surfactant is used in combination with a siloxane-oxyalkylene block copolymer (Japanese Patent Publication No. 62-3175).
No.).

[0005] However, in the above method, the water absorption is not yet satisfactory, and there are problems in water absorption time as an index of water absorption speed, water absorption as an index of water absorption ability, and the like. In addition, a method using a diphenyl ether sulfonate has been proposed (JP-A-4-198335). But even with this method,
Problems remain in the water absorption time and the water absorption amount, and there are still problems to be solved such as water retention, which is an index of the water retention ability of the absorbed water.

A method has been proposed in which dodecyl diphenyl ether sulfonate is used in combination with a long-chain fatty acid ethoxylate (Czech Patent No. 258794). However, even with this method, problems remain in the water absorption time and water absorption amount,
There was a problem with water retention, which is an indicator of the water retention ability of the water that was absorbed.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a composition for a water-absorbing phenolic resin foam excellent in water absorption and water retention.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies in view of the above-mentioned circumstances, and found that, in a composition for a phenolic resin foam, alkyl benzene sulfonates (A) and alcohol ethoxy were used as surfactants. Foaming using a sulfonated compound (B) and three surfactants of fats and oils and a long-chain fatty acid ethoxylated compound (C),
It has been found that by curing, a phenolic resin foam excellent in water absorption and water retention can be obtained, and the present invention has been completed.

That is, the present invention relates to a composition for a phenolic resin foam comprising a resol type phenolic resin, a surfactant, a foaming agent and a curing agent, wherein the surfactant is
Anionic surfactants (A) composed of alkylbenzene sulfonates and anionic surfactants (B) composed of alcohol ethoxylated sulfanates and nonionic surfactants composed of ethoxylated fats and oils and long-chain fatty acids ( And C), wherein the composition for water-absorbing phenolic resin foam is characterized by using (A), (B) and (C), preferably 100 parts by weight of a resole-type phenolic resin. For (A) /
(B) / (C) = 0.2-10 / 0.1-5 / 0.1-
5 parts by weight, preferably the alkylbenzenesulfonates are dodecylbenzenesulfonates, preferably the alcohol ethoxylated sulfanates are
Oleyl alcohol ethoxylated sulfanates, preferably oils and fats and long chain fatty acid ethoxylates,
Provided is a composition for a water-absorbing phenolic resin foam which is a castor oil ethoxylate.

According to the present invention, an alkylbenzene sulfonate anionic surfactant (A), an alcohol ethoxylated sulfanate anionic surfactant (B), a non-ionic surfactant of fats and oils and long-chain fatty acid ethoxylates By changing the mixing ratio of the three surfactants of the agent (C), the water absorption and water retention of the phenol resin foam can be controlled, and a phenol resin foam having a uniform cell structure can be obtained.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The resole type phenolic resin of the present invention is prepared by preparing a phenol and an aldehyde at an equimolar ratio of aldehyde in the presence of an alkali catalyst. The phenols are not particularly limited,
For example, phenol, cresol, bisphenol A and the like can be mentioned, and these may be used alone or in combination. Aldehydes are not particularly limited, but include, for example, formaldehyde, acetaldehyde, furfural and the like, and these may be used alone or in combination. Examples of the alkaline catalyst include, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide, alkali oxides such as calcium oxide and magnesium oxide, and amines such as ammonia, triethylamine and diethylamine. And these may be used alone or in combination.

The alkylbenzene sulfonates of the anionic surfactant (A) comprising the alkylbenzene sulfonates of the present invention include, for example, alkylbenzene sulfonates and alkylnaphthalene sulfonates. The alkyl group in this case is not particularly limited, but is preferably an alkyl group having 3 to 50 carbon atoms.

Examples of the alkyl group include hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl and the like. Of these, dodecylbenzenesulfonate in which the alkyl group is a dodecyl group has a water absorbing property,
It is preferable in terms of water retention. Examples of the salts of the alkylbenzene sulfonates include alkali metal salts, alkaline earth metal salts, ammonium salts, and aliphatic amine salts.
These alkylbenzene sulfonates may be used alone or in combination of two or more.

The term "water absorption" as used in the present invention means that when a phenolic resin foam is immersed in water, water is absorbed to the inside of the foam, and generally, water is completely absorbed to the inside of the foam. The time until the water is absorbed is called the water absorption time. The water-absorbing phenolic resin foam of the present invention preferably has a short absorption time. Further, the water absorption in the present invention refers to the amount of water absorbed by the phenol resin foam. Water retention means that substantially no water leakage is observed from the absorbed phenolic resin foam.

The alcohol ethoxylated sulfanate of the anionic surfactant (B) comprising the alcohol ethoxylated sulfanate is not particularly limited, but may be an aliphatic alcohol having 12 to 22 carbon atoms, or an aliphatic alcohol having 10 to 16 carbon atoms. Representative examples include ethoxylated sulfanates such as higher alcohols, and specifically, lauryl alcohol ethoxylated sulfanates, cetyl alcohol ethoxylated sulfanates, oleyl alcohol ethoxylated sulfanates, tallow alcohol ethoxylated sulfanates, oxo alcohol ethoxy. Sulfanated compounds are typical examples.
The number of moles of ethoxylated ethylene oxide is not particularly limited, but 2 to 60 moles can be used. As a sulfanate, a salt structure of sodium, potassium, calcium, barium, ammonia, an amine or the like is taken. The ratio of sulfanation is not particularly limited,
Those having a weight ratio of 20 to 100% can be used. Of these, oleyl alcohol ethoxylated sulfanate is particularly preferred in terms of water absorption and water retention. These surfactants (B) may be used alone or in combination of two or more.

The non-ionic surfactant (C) composed of a fat ethoxylate and / or an ethoxylate of a long-chain fatty acid includes a fat ethoxylate and a long-chain fatty acid ethoxylate.
Soybean oil, coconut oil, linseed oil, rapeseed oil, drill oil, castor oil, hydrogenated castor oil, ethoxylated oils such as tallow, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, sorbitan Ethoxylated fatty acids such as fatty acid esters and glycerin fatty acid esters. Particularly, the use of castor oil ethoxylate is preferable in terms of water absorption and water retention. These surfactants (C)
May be used alone or in combination of two or more.

The above surfactants (A), (B),
In addition to (C), at least one kind of known and commonly used surfactants such as polyoxyethylene-polyalkylsiloxane and polyoxypropylene-polyalkylsiloxane can be mixed and used.

According to the present invention, as the surfactant, an anionic surfactant (A) composed of the above-mentioned alkylbenzene sulfonates, an anionic surfactant (B) composed of alcohol ethoxylated sulfanates, a fat ethoxylate, By using a nonionic surfactant (C) composed of ethoxylated products of long-chain fatty acids in combination, a phenol resin foam excellent in water absorption and water retention and having a uniform cell structure can be obtained. Although the mixing ratio of these is not particularly limited, the alkyl benzene sulfonate anionic surfactant (A), the alcohol ethoxylated sulfanate anionic surfactant (B), the oil and fat and the long-chain fatty acid ethoxylate nonionic surfactant The activator (C) was used as an active ingredient with respect to 100 parts by weight of the resole type phenol resin, and (A) / (B) / (C) =
0.2 to 10 / 0.1 to 5 / 0.1 to 5 parts by weight is preferred.

When the total amount of the above (A), (B) and (C) is less than the above range, the water absorption time becomes extremely long, the water absorption performance is poor, and when the total amount is more than the above range. The cells are liable to become large and non-uniform, and are liable to cause poor foaming such as crushing, and are preferably used in the above range.

Within the above range, the more preferable ratio of the balance between water absorption and water retention is the ratio of the resol type phenol resin 10
0.5 to 5 / 0.2 to 0 parts by weight of the active ingredient
It is in the range of 3 / 0.2-3.

As the foaming agent, known and commonly used ones can be used, and examples thereof include petroleum ether, isopropyl ether, carbon tetrachloride, trichloroethane, pentane, hexane and the like. I do not care. The use amount thereof is preferably 3 to 30 parts by weight based on 100 parts by weight of the resole type phenol resin.

As the curing agent, known and commonly used curing agents can be used, and p-toluenesulfonic acid, phenolsulfonic acid,
Examples thereof include organic acids such as xylene sulfonic acid, and inorganic acids such as sulfuric acid and phosphoric acid. The amount of the active ingredient is preferably 3 to 20 parts by weight based on 100 parts by weight of the resole type phenol resin.

The above-mentioned resol-type phenolic resin, a mixture of various surfactants, a foaming agent, a curing agent and the like are stirred at a high speed and cured and foamed at 30 to 80 ° C. to obtain a phenolic resin foam. . The foaming method is not particularly limited, and examples include continuous slab foaming, mold foaming, and spray foaming.

The obtained phenolic resin foam has excellent water absorbency and water retention, and has a uniform cell structure, and can be used for applications such as flower sculpture, flower sculpture, and plant cultivation. Can be.

[0025]

The present invention will be described below with reference to Synthesis Examples and Examples. All parts and percentages in the examples are on a weight basis.

Synthesis Example In a four-necked 3-liter flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 940 parts of phenol, 4
1000 parts of 2% formalin and 9.4 parts of 48% caustic soda as a catalyst are added, reacted at 90 ° C. for 3 hours, neutralized with formic acid, adjusted to pH 6 to 7, dehydrated under reduced pressure, and resole-type phenol. A resin was obtained. (Viscosity: 4000 cp
s, nonvolatile content: 70%) Examples 1 to 6 To 100 parts of the resol-type phenol resin obtained in Synthesis Example 1, 9 parts by weight of a surfactant shown in Table 1 and 9 parts by weight of pentane as a foaming agent were added. And mixed with high speed stirring. 65% p-toluenesulfonic acid 7.5 as curing agent
The mixture was stirred at a high speed, put in a cardboard container, and foamed and cured at 50 ° C. Table 1 shows the physical properties of these foams.

Comparative Examples 1 to 9 With respect to 100 parts of the resole type phenol resin, 9 parts by weight of a surfactant shown in Table 2 and 9 parts of pentane as a foaming agent were used.
Parts by weight were added and mixed with high-speed stirring. 65 as hardener
% Paratoluenesulfonic acid (7.5 parts by weight) was added, and the mixture was stirred at a high speed, placed in a cardboard container, and foamed and cured at 50 ° C. The physical properties of these foams are shown in Table 2.

[0028]

[Table 1]

Foam size: 2000 cm ³ Water absorption time: Place the foam in water at 25 ° C. and time until water is immersed in all the foam Water absorption: Water immersion Water retention: Retention of immersed water Rate (after 60 minutes)

[0030]

[Table 2]

Foam size: 2000 cm ³ Water absorption time: The foam is placed in water at 25 ° C., and the time until water is immersed in the whole foam Water absorption: Water immersion Water retention: Retention of immersed water Rate (after 60 minutes) As can be seen from Tables 1 and 2, the composition for a water-absorbing phenolic resin foam of the present invention comprises, as surfactants, an anionic surfactant (A) composed of an alkylbenzene sulfonate and an alcohol. By using, as essential components, three types of surfactants, an anionic surfactant (B) composed of ethoxylated sulfanated compounds and a nonionic surfactant (C) composed of ethoxylated fatty acids and long-chain fatty acids. It is possible to produce a phenolic foam having excellent water absorbency and water retention and having a uniform cell structure, which cannot be obtained by mixing two types alone.

[0032]

The foam obtained from the composition for a phenolic resin foam according to the present invention is excellent in water absorbency and water retention, and thus is particularly suitable for uses such as flower sculpture for sword mountain and plant cultivation.

Continued on the front page (72) Inventor Akira Sasakura Exhibition 62-3 Azaka Nakamachi, Taka-gun, Hyogo Prefecture

Claims (5)

[Claims] 1. A resol type phenol resin, a surfactant,
In a composition for a phenolic resin foam containing a foaming agent and a curing agent, as a surfactant, an anionic surfactant (A) comprising an alkylbenzene sulfonate and an anionic surfactant comprising an alcohol ethoxylated sulfanate A composition for a water-absorbing phenolic resin foam, comprising using an agent (B) and a nonionic surfactant (C) comprising an ethoxylated oil or fat and / or an ethoxylated long-chain fatty acid. 2. An anionic surfactant (A) comprising an alkylbenzene sulfonate, an anionic surfactant (B) comprising an alcohol ethoxylated sulfanate, and a nonionic surfactant comprising an oil or fat and a long-chain fatty acid ethoxylate. Surfactant (C) was added to (A) / (B) /
The composition for a phenolic resin foam according to claim 1, wherein (C) = 0.2 to 10 / 0.1 to 5 / 0.1 to 5 parts by weight is used. 3. The composition for a phenolic resin foam according to claim 1, wherein the alkylbenzenesulfonate is dodecylbenzenesulfonate. 4. The composition for a phenolic resin foam according to claim 1, wherein the alcohol ethoxylated sulfanate is oleyl alcohol ethoxylated sulfanate. 5. The composition for a phenolic resin foam according to claim 1, wherein the ethoxylated oil or fat and / or the ethoxylated long-chain fatty acid is a castor oil ethoxylated product.