JP2003183439A - Phenolic resin foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phenolic resin foam with a structure which has a high ratio of closed cells and fine cells in spite of using a low viscosity resol resin to obtain it, and a method for producing the phenolic resin foam which excels in the handling properties of a resin. <P>SOLUTION: In the method for producing a phenolic resin foam by using at least a resol resin, a blowing agent, a surface active agent, and a curing catalyst, an surface active agent having at least one kind to be selected from the group consisting of a polyethylene hydrogenated castor oil and a polyoxyethylene castor oil is used as the surface active agent. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat insulating phenolic resin foam having excellent heat insulating performance and mechanical strength.

[0002]

BACKGROUND OF THE INVENTION Phenolic resin foams are widely used as various building materials because they are excellent in flame retardancy, heat resistance, low smoke generation, dimensional stability, solvent resistance, workability, among other organic resin foams. It's being used. A general method for producing a phenol resin foam is a phenol-formaldehyde resol resin (hereinafter, referred to as a resole resin) obtained by polymerizing phenol and formalin with an alkaline catalyst,
It is produced by foaming and curing a foamable mixture in which a foaming agent, a surfactant, a curing catalyst, and other additives are uniformly mixed.

It is generally known that a relatively high initial resole resin viscosity is required as one of the requirements for producing a closed cell phenolic resin foam by using a resole resin. It is known that a high-viscosity resole resin can be achieved by removing most of free water, and that by using this resole resin, a phenol resin foam having fine closed cells can be obtained. U.S. Pat. No. 3,303,758 states that when the water content is about 0.1 to 2 wt% it produces excellent foams.

However, since the high-viscosity resole resin is extremely rich in reactivity, it becomes difficult to uniformly disperse the catalyst, foaming agent and the like required for foam production. Further, since the high-viscosity resole resin causes a large pressure loss in the pipe, there are many mechanical restrictions when handling the pump, which requires high performance of the pump and high pressure resistance of the pipe. However, since this problem is solved by using a low-viscosity resole resin, several methods for producing a closed cell phenolic resin foam using a low-viscosity resole resin have been proposed so far.

Japanese Unexamined Patent Publication (Kokai) No. 1-138244 describes a method for producing a phenol resin foam from a low-viscosity resole resin. This method, at 40 ℃, 2,
By adding a polymer gel-forming ethylene oxide-propylene oxide block copolymer surfactant to a low-viscosity resol resin having a viscosity of 000 mPa · s to 12,000 mPa · s, a closed-cell phenol resin foam is obtained. Regarding the action of the polymer gel-forming ethylene oxide-propylene oxide block copolymer surfactant, the polymer gel-forming ethylene oxide-propylene in the presence of free water existing in the resole resin and water generated in the crosslinking reaction is used. It is disclosed that the oxide block copolymer surfactant gels.
It is stated that in the presence of this surfactant, the resole resin can obtain an appropriate viscosity in an appropriate situation so that a closed cell phenolic resin foam having good properties can be produced.

However, when a polymer gel-forming ethylene oxide-propylene oxide block copolymer surfactant is added to a low-viscosity resole resin, the viscosity is about 1.5-4.
Since it will be doubled, for example, when sending the resole resin by a pump, the pressure loss of the pipe will be large, the pump motor will be required to have high performance and high functionality, or the pressure and diameter of the pipe will be restricted, and it will be handled significantly. Problems such as loss of sex have occurred. In order to solve these problems, measures such as increasing the temperature of the resol resin to lower the viscosity have been adopted, but when the temperature of the resol resin is increased, the resole resin reacts and the viscosity rises conversely during storage. New problems arise. As described above, there has been a strong demand for a method for producing a phenol resin foam having excellent various properties by using a low-viscosity resol resin without impairing the handleability of the resin.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a phenol resin foam having a high closed cell and a fine cell structure, which is obtained by using a low-viscosity resole resin, and the phenol resin. Of the form,
It is an object of the present invention to provide a manufacturing method having excellent handleability of a resin.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the use of a surfactant represented by the following formula (1) or the following formula (2), or a mixture thereof, facilitates resin handling. It was found that a phenolic resin foam having good various properties can be molded by using a low-viscosity resol resin without impairing the above-mentioned properties, and the present invention has been accomplished. That is, the present invention provides [1] polyoxyethylene hydrogenated castor oil represented by the following formula (1), polyoxyethylene castor oil represented by the following formula (2), or a mixture thereof per 100 g of phenol resin foam. Phenolic resin foam containing a total of 0.05 g or more and 1.5 g or less, a closed cell rate of 80% or more, and a bulk density of 10 kg / m ³ or more and 80 kg / m ³ or less,

[0009]

[Chemical 3]

(In the formula, l, m, n, x, y and z are natural numbers, and 5 ≦ l + m + n + x + y + z ≦ 150.)

[0011]

[Chemical 4]

(In the formula, p, q, r, u, v and w are natural numbers, and 5 ≦ p + q + r + u + v + w ≦ 150.) [2] At least a resole resin, a foaming agent, a surfactant and a curing catalyst. In the method for producing a phenolic resin foam using the same, the polyoxyethylene hydrogenated castor oil represented by the formula (1) and the formula (2) are used as the surfactant.
A method for producing a phenolic resin foam according to [1], which comprises using a surfactant containing at least one selected from the group consisting of polyoxyethylene castor oil represented by , Water content 0.2
The method for producing a phenolic resin foam according to [2], characterized in that the resole resin has a viscosity of 2,000 to 100,000 mPa · s at 40 ° C. in the range of wt% to 15 wt%.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The phenol resin foam of the present invention contains polyoxyethylene castor oil and / or polyoxyethylene hydrogenated castor oil, which can be detected by the method described below, in a total amount of 0.05 per 100 g of the phenol resin foam.
g or more and 1.5 g or less are contained. Since the polyoxyethylene castor oil and the polyoxyethylene hydrogenated castor oil are partially or mostly decomposed by the curing catalyst, the content of the phenol resin foam and the amount added to the resole resin do not necessarily match. As a result of producing a phenol resin foam by the method described below and measuring the content, the content was about 1/10 of the addition amount.

If the amount of polyoxyethylene hydrogenated castor oil, the amount of polyoxyethylene castor oil, or the total content of these mixtures detected per 100 g of phenol resin foam by the method described below is less than 0.05 g, a surfactant is obtained. There is a risk that it will not be effective and it will not be possible to mold the foam. On the other hand, if it exceeds 1.5 g, the resin viscosity may decrease, the average cell diameter may increase, the closed cell ratio may decrease, and the mechanical performance of the foam may decrease. Preferably, the total content of polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, or a mixture thereof detected by the method described below is 0.05 g or more and 1 g or less per 100 g of phenol resin foam.

In the production method of the present invention, the surfactant is selected from the group consisting of polyoxyethylene hydrogenated castor oil represented by the formula (1) and polyoxyethylene castor oil represented by the formula (2). A surfactant containing at least one of the following is used. Two or more kinds of polyoxyethylene hydrogenated castor oil represented by the formula (1) can be used, two or more kinds of polyoxyethylene castor oil represented by the formula (2) can be used, or a mixture thereof can be used. It is also possible to use it. Moreover, other surfactants can be mixed and used as needed.

As other surfactants, those generally used in the production of phenol resin foams can be used, but among them, nonionic surfactants are effective,
For example, alkylene oxide which is a copolymer of ethylene oxide and propylene oxide, a condensation product of alkylene oxide and nonylphenol, alkylphenol such as dodecylphenol, and fatty acid esters such as polyoxyethylene fatty acid ester, and polydimethylsiloxane. Examples thereof include silicone compounds, polyalcohols and the like.

In the production method of the present invention, the polyoxyethylene hydrogenated castor oil represented by the formula (1) and / or the polyoxyethylene castor oil represented by the formula (2) is added in an amount of 0. 1 part by mass or more, 15
Add not more than part by weight. Preferably 0.3 parts by mass or more, 1
Add 0 parts by mass or less. The molecular weight of polyoxyethylene hydrogenated castor oil and polyoxyethylene castor oil used in the present invention can be selected by the number of polyoxyethylene chains. In the present invention, 5 ≦ l + m + n + x + y + z, 5 ≦ p + q + r +
u + v + w. 5 ≦ l + m + n + x + y + z, 5 ≦
If it is p + q + r + u + v + w, it has an affinity with the resole resin and can be mixed well, so that the effect as a surfactant can be exhibited. Polyoxyethylene chain is l + m +
n + x + y + z = 150, p + q + r + u + v + w = 1
When it exceeds 50, it becomes very expensive, which is disadvantageous in terms of cost. Preferably 10 ≦ l + m + n + x + y + z ≦ 12
0, 10 ≦ p + q + r + u + v + w ≦ 120, more preferably 30 ≦ l + m + n + x + y + z ≦ 100,
30 ≦ p + q + r + u + v + w ≦ 100.

The closed cell ratio of the phenol resin foam in the present invention is 80% or more, preferably 90% or more and less than 98.5%. If the closed cell ratio is less than 80%, the foaming agent in the phenolic resin foam may be replaced with air and the heat insulation performance may be significantly deteriorated. In addition, the surface embrittlement of the phenolic resin foam may be increased, resulting in mechanical practical use. There is a concern that performance will not be satisfied. The bulk density of the phenolic resin foam in the present invention is 10 kg / m ^3.
80 kg / m ³ or less, preferably 20 kg / m ³
m ³ or more and 50 kg / m ³ or less. Bulk density is 10 kg /
If it is less than m ³ , the mechanical strength such as compressive strength becomes small, the foam tends to be damaged during handling, and the surface brittleness also increases. On the other hand, if the bulk density exceeds 80 kg / m ³ , the heat transfer in the resin part may increase and the heat insulating performance may deteriorate.

The average cell diameter of the phenol resin foam in the present invention is preferably 10 μm or more and 200 μm or less,
It is more preferably 20 μm or more and 150 μm or less. When the average cell diameter is less than 10 μm, the foam density is inevitably increased because the thickness of the cell wall is limited, and as a result, the heat transfer rate of the resin portion in the foam increases and the phenol resin foam Insulation performance may be insufficient. On the other hand, when it exceeds 200 μm, the heat conductivity due to radiation increases, and the heat insulating performance of the foam deteriorates.

Usually, the starting molar ratio of phenols to aldehydes of the resole resin used in the present invention is preferably 1: 1 to 1: 4.5, more preferably 1: 1.5 to 1: 2.5. Is the range. Phenols preferably used in the present invention when synthesizing the resole resin include phenol itself and other phenols, and the amount thereof is about 10
Mention may be made of phenol substituted up to wt%. Examples of other phenols include resorcinol,
Catechol, o-, m- and p-cresol, xylenols, ethylphenols, p-tert-butylphenol and the like can be mentioned. Dinuclear phenols can also be used. Aldehydes preferably used in the synthesis of the resole resin include formaldehyde itself and formaldehyde substituted by other aldehydes up to about 10 wt%. Examples of other aldehydes include glyoxal, acetaldehyde, chloral, furfural, benzaldehyde and the like.

Urea, methylol urea, melamine and the like may be added to the resol resin as an additive. In the present invention, the one to which the additive is added is also called a resol resin.
The resol resin used in the present invention has a water content of 0.2 to
It is 15 wt%, preferably 2 to 10 wt%, more preferably 3 to 8 wt%. The viscosity of the resole resin used in the present invention is preferably 40 because of the handling property of the resin.
It is 2,000 to 100,000 mPa · s at ℃, preferably 3,000 to 50,000 mPa · s, more preferably 5,000 to 20,000 mPa · s. urea,
When an additive such as methylol urea or melamine is added, the viscosity of the resole resin is the viscosity of the resole resin after the addition of the additive.

Examples of the blowing agent used in the present invention include CFCs such as trichlorotrifluoroethane (CFC-113) and trichloromonofluoroethane (CFC-11), dichlorofluoroethane (HCFC-123) and dichlorofluoroethane. HC such as (HCFC-141b)
FCs, or HFCs such as 1,1,1,2-tetrafluoroethane (HFC-134a) and 1,1-difluoroethane (HFC-152a), or HCs such as cyclohexane, cyclopentane, and normal pentane,
There are carbon dioxide, etc. Even if this foaming agent is used in one type,
It may be a combination of two or more kinds. Further, a low boiling point substance such as nitrogen, helium, argon or air may be added to the foaming agent as a foam nucleating agent.

The curing catalyst used in the present invention is not particularly limited, but if an acid containing water is used, the foam cell wall may be destroyed. Therefore, it is considered that phosphoric anhydride or aryl sulfonic anhydride is preferable. Examples of the aryl sulfonic anhydride include toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, substituted phenol sulfonic acid, xylenol sulfonic acid, substituted xylenol sulfonic acid, dodecylbenzene sulfonic acid, benzene sulfonic acid and naphthalene sulfonic acid. May be used alone or in combination of two or more. Further, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol and the like may be added as a curing aid. Further, these curing catalysts may be diluted with a solvent such as diethylene glycol or ethylene glycol.

Phenolic resin foam is obtained by adding a surfactant, a foaming agent and a curing catalyst to at least a resole resin, uniformly dispersing these, and curing them using an oven or the like. The surfactant and the foaming agent may be added to the resole resin in advance, or may be added simultaneously with the curing catalyst. The catalyst-added resole resin is uniformly dispersed and cured as quickly as possible using a pin mixer or the like.

The amount of the foaming agent used varies depending on its type, but when HFC-134a is used as the foaming agent, it is preferably 3 per 100 parts by mass of the resole resin.
It is used in an amount of 30 parts by mass or more and 30 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less. Normal pentane 50
When a mixture of wt% and isobutane of 50 wt% is used, the amount is preferably 3 parts by mass or more and 20 parts by mass or less, more preferably 5 parts by mass or more and 17 parts by mass or less.

The amount of the curing catalyst used also differs depending on its type. For example, when phosphoric anhydride is used, the resol resin 1
It is used in an amount of preferably 5 parts by mass or more and 30 parts by mass or less, more preferably 8 parts by mass or more and 25 parts by mass or less with respect to 00 parts by mass. Paratoluenesulfonic acid monohydrate 60 wt
% And diethylene glycol 40 wt% are used, preferably 3 parts by mass or more and 30 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less.
The curing temperature is preferably 40 ° C or higher and 120 ° C or lower, more preferably 60 ° C or higher and 95 ° C or lower. The curing may be performed in one step, or the curing temperature may be changed according to the degree of curing and the curing may be performed in several steps.

Next, the method for evaluating the composition, structure and properties of the resole resin and phenol resin foam in the present invention will be described. The viscosity of the resole resin in the present invention is measured by a rotational viscometer (R-100 type manufactured by Toki Sangyo Co., Ltd .;
The measurement was carried out at 40 ° C. by using ° × R-14). The water content of the resol resin was measured as follows. The resol resin was dissolved in dehydrated methanol (manufactured by Kanto Chemical Co., Inc.) whose water content was measured in the range of 3 wt% to 7 wt%, and the water content of the solution was measured to obtain the water content in the resol resin. . A Karl Fischer moisture meter (MKC-510 manufactured by Kyoto Electronics Manufacturing Co., Ltd.) was used for the measurement.

The closed cell ratio was obtained by hollowing a cylindrical sample having a diameter of 35 mm to 36 mm from a phenol resin foam with a cork borer and cutting it to a height of 30 mm to 40 mm, and then using an air comparison type hydrometer (Tokyo Science Co. 1,000.
The sample volume is measured by the standard use method of (type). The value obtained by subtracting the volume of the cell wall calculated from the sample weight and the resin density from the sample volume was divided by the apparent volume calculated from the outer dimensions of the sample, and was measured according to ASTM D2856. Here, the density of the phenol resin is 1.3 kg /
It was set to l.

The average cell diameter of the phenol resin foam in the present invention means 9c on a 50 times enlarged photograph of the foam cross section.
This is a value obtained by dividing 1,800 μm by the average value of the number of bubbles that the straight line that is drawn crosses four straight lines of length m.
It is an average value calculated from the number of cells measured according to K6402. The thermal conductivity of the phenol resin foam is 200mm square of the phenol resin foam sample, low temperature plate 5 ℃,
The measurement was performed according to the flat plate heat flow meter method of JIS A1412 at a high temperature plate of 35 ° C.

The density is a value obtained by using a 20 cm square phenol resin foam as a sample, removing the face material and siding material of the sample, and measuring the weight and apparent volume.
It was measured according to JIS K7222. The compressive strength of the phenol resin foam was measured according to JIS K7220 with a specified strain of 0.05. The quantification of polyoxyethylene hydrogenated castor oil and polyoxyethylene castor oil in phenol resin foam was performed as follows. Phenol resin foam is crushed, and the powder is kept at standard temperature class 3 (temperature 23 ± 5 ° C) and standard humidity class 3 (relative humidity 40 to 60%) specified for JIS K7100 for 16 hours or more, and then chloroform is added. Soxtech extraction using (using 200 ml of chloroform for 2.4 g of sample.
Extracted overnight at 150 ° C.). The extract was JAIGEL on a column using Nippon Analytical Industry LC-908 type GPC.
-2H-1H (20 mmφ × 600 mm / piece) was used, the solvent was chloroform, and the flow rate was 3.3 ml / min for purification. Quantitative GPC is Tosoh GPC-8020
It was used. Column is TSKgel SuperHZ
MM (4.6 mmφ x 15 cm) + TSKgel S
upperHZ2000 (4.6 mmφ × 15 cm) was used. When the oven temperature was 40 ° C., tetrahydrofuran (THF) (0.35 ml / min) was used as the eluent, the sample concentration was 0.1 wt%, and the detector was a differential refractometer (RI). A peak was obtained in the range of 13.2 minutes. The peak area was converted according to a calibration curve to calculate the concentrations of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil per 100 g of phenol resin foam.

The qualities of the polyoxyethylene hydrogenated castor oil and the polyoxyethylene castor oil were quantified by the ¹ H-NMR measurement and IR measurement of the eluate collected by the column by GPC. ^{For 1} H-NMR, JNM λ40 manufactured by JEOL Ltd.
0 was used. The solution is deuterated chloroform and the temperature is 4
The temperature was 5 ° C. When using polyoxyethylene hydrogenated castor oil, 0.8, 1.3, 1.4, 1.5, 1.6,
Peaks were obtained at 2.3, 3.6, 3.7, 4.2 and 4.8 ppm. The peaks at 4.8 ppm and 3.6 ppm were obtained in the ratio range of 1:15 to 1: 525.
0.8 when using polyoxyethylene castor oil,
1.3, 1.4, 1.5, 1.6, 2.3, 3.6,
Peaks were obtained at 3.7, 4.2, 4.8 and 5.6 ppm. The peaks at 4.8 ppm and 3.6 ppm were obtained in the ratio range of 1:15 to 1: 525.

For IR, 160 made by PERKINE LMER
It was measured at a resolution of 4 cm ⁻¹ by the transmission method using KBr tablets using 0 Series FTIR. 723, 84 when using polyoxyethylene castor oil
8,852,1110,1260,1297,134
9, 1489, 1735, 2888, 2926, 334
A peak was obtained at 6 cm ^-1 . 723, 848, 852, 96 when using polyoxyethylene castor oil
0, 1110, 1260, 1297, 1349, 148
9, 1650, 1735, 2888, 2926, 334
A peak was obtained at 6 cm ^-1 . Next, the present invention will be described with reference to Examples and Reference Examples.

[0033]

[Examples] <Synthesis of resole resin> 5,000 37wt formaldehyde (manufactured by Wako Pure Chemical Industries, special grade reagent) in a reactor
g and 99% phenol (manufactured by Wako Pure Chemical Industries, special grade reagent) 3,
000 g is charged and stirred by a propeller rotating stirrer, and the temperature of the liquid inside the reactor is adjusted to 40 ° C. by a temperature controller. Then, add 60 wt% of 50 wt% sodium hydroxide aqueous solution.
g, and the temperature of the reaction solution was raised from 40 ° C to 85 ° C.
Hold for minutes. Then, the reaction solution is cooled to 5 ° C. This is called resol resin A.

On the other hand, in another reactor, 1,080 g of 37 wt% formaldehyde, 1,000 g of water and 78 g of 50 wt% aqueous sodium hydroxide solution were added, and 1,600 g of urea (manufactured by Wako Pure Chemical Industries, special grade reagent) was charged, and a propeller was used. Stir with a rotary stirrer, and adjust the temperature of the liquid inside the reactor to 40 ° C. with a temperature controller. Then, the reaction solution is heated at 40 ° C to 70 ° C.
The temperature was raised to ℃ and kept for 60 minutes. This is methylol urea U. Next, 1,350 g of methylol urea U was mixed with the resole resin A, and the liquid temperature was raised to 60 ° C. and kept for 1 hour. Then, the reaction solution was cooled to 30 ° C. and adjusted to pH 6 with a 50 wt% aqueous solution of paratoluenesulfonic acid monohydrate.
Neutralized. The reaction solution was dehydrated at 60 ° C. and the viscosity was measured. The viscosity at 40 ° C. was 5,700 m.
It was Pa · s. This is called resol resin A-U.

[0035]

Example 1 A resole resin composition was prepared by adding 3.5 parts by mass of polyoxyethylene hydrogenated castor oil (manufactured by Nikko Chemicals Co., Ltd., HCO-100) as a surfactant to 100 parts by mass of the resole resin A-U. did. Paratoluenesulfonic acid monohydrate 60 wt% (manufactured by Wako Pure Chemical Industries, purity 95% or more) and diethylene glycol 40 wt% (manufactured by Wako Pure Chemical Industries, purity 98%) as a curing catalyst with respect to 100 parts by mass of the resole resin composition. 13 parts by mass of a mixture of 50 parts by weight of normal pentane (manufactured by Wako Pure Chemical Industries, purity 99% or more) and isobutane (manufactured by SK Sangyo Co., Ltd.).
Purity 99% or more) 0.3 parts by mass of nitrogen dissolved in 100 parts by mass of a mixture of 50 wt% was used as a foaming agent at a ratio of 10 parts by mass, and was continuously applied to a pin mixer whose temperature was controlled at 15 ° C. And stirred uniformly. The mixture that came out of the mixer was designed so that the water generated during the curing reaction can be released to the outside, and the thickness is 30 mm × 300 mm × 3
75 g was poured into a 00 mm mold and kept in an oven at 80 ° C. for 2 hours to produce a phenol resin foam. A polyester non-woven fabric (manufactured by Asahi Kasei Co., Ltd., Spunbond E1040) was previously attached to the inside of the mold so that the phenol resin foam could be easily removed from the mold after foaming and curing.

[0036]

Example 2 Except that 3.5 parts by mass of polyoxyethylene hydrogenated castor oil (manufactured by Nikko Chemicals Co., Ltd., HCO-80) was used as a surfactant with respect to 100 parts by mass of the resole resin AU. A phenolic resin foam was prepared as in 1.

[0037]

[Example 3] Polyoxyethylene hydrogenated castor oil (HCO-60, manufactured by Nikko Chemicals Co., Ltd.) as a surfactant
A phenol resin foam was produced in the same manner as in Example 1 except that 3.5 parts by mass was used with respect to 100 parts by mass of the resol resin A-U.

[0038]

Example 4 Except that 3.5 parts by mass of polyoxyethylene hydrogenated castor oil (manufactured by Nikko Chemicals Co., Ltd., HCO-40) was used as a surfactant with respect to 100 parts by mass of the resole resin AU. A phenolic resin foam was prepared as in 1.

[0039]

Example 5 Except that 3.5 parts by mass of polyoxyethylene hydrogenated castor oil (manufactured by Nikko Chemicals Co., Ltd., HCO-30) was used as a surfactant with respect to 100 parts by mass of the resole resin AU. A phenolic resin foam was prepared as in 1.

[0040]

Example 6 Except that 3.5 parts by mass of polyoxyethylene hydrogenated castor oil (manufactured by Nikko Chemicals Co., Ltd., HCO-20) was used as a surfactant with respect to 100 parts by mass of the resole resin AU. A phenolic resin foam was prepared as in 1.

[0041]

Example 7 Example 1 except that polyoxyethylene castor oil (manufactured by Nikko Chemicals Co., Ltd., CO-60TX) was used as a surfactant in an amount of 3.5 parts by mass based on 100 parts by mass of the resole resin AU. A phenolic resin foam was prepared in the same manner as in.

[0042]

Example 8 Example 1 except that polyoxyethylene castor oil (manufactured by Nikko Chemicals Co., Ltd., CO-40TX) was used as a surfactant in an amount of 3.5 parts by mass based on 100 parts by mass of the resole resin AU. A phenolic resin foam was prepared in the same manner as in.

[0043]

Example 9 Example 1 except that polyoxyethylene castor oil (manufactured by Nikko Chemicals Co., Ltd., CO-20TX) was used as a surfactant in an amount of 3.5 parts by mass relative to 100 parts by mass of the resole resin AU. A phenolic resin foam was prepared in the same manner as in.

[0044]

[Example 10] Polyoxyethylene hydrogenated castor oil (HCO-40, manufactured by Nikko Chemicals Co., Ltd.) as a surfactant
Example 1 except that a mixture of 50 wt% and 50 wt% of polyoxyethylene hydrogenated castor oil (manufactured by Nikko Chemicals Co., Ltd., HCO-10) was used in 3.5 parts by mass with respect to 100 parts by mass of the resole resin AU. Similarly, a phenolic resin foam was produced.

[0045]

[Example 11] Polyoxyethylene hydrogenated castor oil as a surfactant (HCO-40, manufactured by Nikko Chemicals Co., Ltd.)
Same as Example 1, except that a mixture of 50 wt% and polyoxyethylene castor oil (Nikko Chemicals Co., Ltd., CO-10) 50 wt% was used in 3.5 parts by mass with respect to 100 parts by mass of the resole resin AU. A phenolic resin foam was manufactured.

[0046]

[Example 12] Polyoxyethylene hydrogenated castor oil as a surfactant (HCO-40, manufactured by Nikko Chemicals Co., Ltd.)
A phenol resin foam was produced in the same manner as in Example 1 except that 0.1 part by mass was used with respect to 100 parts by mass of the resol resin A-U.

[0047]

Example 13 Polyoxyethylene hydrogenated castor oil (HCO-40, manufactured by Nikko Chemicals Co., Ltd.) as a surfactant
A phenol resin foam was produced in the same manner as in Example 1 except that 10 parts by mass was used for 100 parts by mass of the resole resin AU.

[0048]

Comparative Example 1 A block copolymer of ethylene oxide-propylene oxide (made by BASF,
Pluronic F-127) with resol resin A-U100
Although 3.5 parts by mass was used with respect to parts by mass, the resin liquid supply pump could not be operated due to overpressure, and liquid could not be continuously supplied to the pin mixer. Therefore, the phenol resin foam could not be manufactured.

[0049]

Comparative Example 2 A block copolymer of ethylene oxide-propylene oxide (manufactured by BASF,
Pluronic F-127) with resol resin A-U100
3.5 parts by mass were used with respect to parts by mass. By controlling the temperature of the resin tank, the liquid feed pump, and the pipe to 70 ° C., the liquid could be continuously fed to the pin mixer, and thus a phenol resin foam was produced in the same manner as in Example 1.

[0050]

Comparative Example 3 Polyoxyethylene alkylphenyl formaldehyde (Nikko Chemicals Co., Ltd.) as a surfactant
R-1020) was used in an amount of 3.5 parts by mass with respect to 100 parts by mass of the resol resin A-U, but an attempt was made to manufacture a phenol resin foam in the same manner as in Example 1, but the phenol resin foam was not foamed, and thus the phenol resin was used. No foam was obtained.

[0051]

Comparative Example 4 Polyglycerin fatty acid ester (Hexaglyn manufactured by Nikko Chemicals Co., Ltd.) as a surfactant
1-L) was used in the same manner as in Example 1 except that 3.5 parts by mass was used with respect to 100 parts by mass of the resole resin A-U, but the phenol resin foam was not foamed because it did not foam. I couldn't get it. Table 1 shows the respective resole resin viscosities, water contents, closed cell ratios when the phenol resin foam was produced, average cell diameters, thermal conductivity, density and compressive strength.

Table 2 shows the quantitative results of polyoxyethylene hydrogenated castor oil or polyoxyethylene castor oil contained in the phenolic resin foam. Phenol resin foam 100 is described by converting the peak area according to the calibration curve.
The calculated concentration of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil per g was expressed as a converted concentration (g / 100 g).

[0053]

[Table 1]

Since Comparative Examples 1, 3 and 4 could not be foamed, the closed cell ratio, average cell diameter, thermal conductivity, density and compressive strength could not be measured. Further, in Comparative Example 2, the resin gradually reacted in the pipe and the pressure became high, so that the operation for a predetermined time could not be performed.

[0055]

[Table 2]

Extracted components of Comparative Examples 1, 2, 3 and 4 are GPC
Showed different peaks, and ¹ H-NMR and IR also showed different peaks.

[0057]

Industrial Applicability According to the present invention, it has become possible to produce a high-quality closed-cell phenol resin foam even with a low-viscosity resol resin which has been difficult to produce. By using the low-viscosity resol resin, for example, the pressure loss due to the piping is reduced, the load on the liquid delivery pump is reduced, and the cost for equipment can be reduced. Further, since the liquid transfer is facilitated, it becomes possible to stably produce a good quality closed-cell phenol resin foam.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F074 AA60 AA76 AB01 AB05 AC31                       AD15 AG20 BA32 BA35 BA39                       BA53 BA54 BA58 BA60 BB01                       BB05 BB10 BC02 CA23 DA02                       DA12                 4J002 CC041 CC051 CC061 CH022                       DH027 EA016 EA026 EB066                       EV237 FD147 FD150 FD312                       FD326                 4J005 AA04 AA12

Claims (3)

[Claims] 1. A polyoxyethylene hydrogenated castor oil represented by the following formula (1), a polyoxyethylene castor oil represented by the following formula (2), or a mixture thereof is added in a total amount of 0. 05g or more 1.
Contains 5 g or less, closed cell ratio of 80% or more, bulk density of 1
Phenolic resin foam characterized by being 0 kg / m ³ or more and 80 kg / m ³ or less. [Chemical 1] (In the formula, l, m, n, x, y, and z are natural numbers, and 5
≦ l + m + n + x + y + z ≦ 150. ) [Chemical 2] (In the formula, p, q, r, u, v, w are natural numbers, and
≦ p + q + r + u + v + w ≦ 150. ) 2. A method for producing a phenolic resin foam using at least a resole resin, a foaming agent, a surfactant and a curing catalyst, wherein the surfactant is represented by the formula (1):
A surfactant containing at least one selected from the group consisting of polyoxyethylene hydrogenated castor oil represented by: and polyoxyethylene castor oil represented by formula (2) is used. 1. The method for producing a phenolic resin foam according to 1. 3. The resole resin has a water content of 0.2 wt% or more and 15 wt% or less and a viscosity at 40 ° C. of 2,000.
The method for producing a phenolic resin foam according to claim 2, which is a resole resin of 100,000 mPa · s.