JP2016003307A - Phenolic resin foam and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenolic resin foam having a low initial coefficient of thermal conductivity and maintains the low coefficient of thermal conductivity for a long term.SOLUTION: The phenolic resin foam contains cyclopentane and a high boiling point hydrocarbon with a boiling point of 190°C or more and 550°C or less, and has a density of 10 kg/mor more and 150 kg/mor less. A cyclopentane content in the phenolic resin foam is 0.25 or more and 0.85 mol or less per 22.4×10mof space volume in the phenolic resin foam. When the phenolic resin foam is pulverized in chloroform and an extraction treatment is performed, %Cof an oily component extracted in chloroform, as determined by a ring analysis n-d-M method, is 5% or less.

Description

  The present invention relates to a phenol resin foam and a method for producing the same, and in particular, a phenol resin foam having a low thermal conductivity, which can be used as a heat insulating material such as a heat insulating material for buildings, a heat insulating material for vehicles, and a heat insulating material for equipment, and the like. It relates to the manufacturing method.

The lower the thermal conductivity, the lower the thermal conductivity, the lower the thermal conductivity of the phenolic resin foam used, the heat insulation performance required with a thinner thickness can be obtained. For example, in a house, an effective living space can be widened with respect to the building area of the house.
Moreover, since a heat insulating material is used over a long period once it is constructed, it is necessary to maintain high heat insulating performance over a long period of time.
In recent years, in order to save energy and resources, the need for long-term excellent housing has increased, and heat insulation has lower initial thermal conductivity and lower thermal conductivity over a longer period than before. There is a need to maintain.

  Patent Documents 1, 2, and 3 disclose a phenol resin foam characterized by using a high-boiling foaming agent such as normal pentane or isopentane in combination with paraffin or the like. Although the phenol resin foam can improve the thermal conductivity at low temperatures, further improvement in the initial thermal conductivity and reduction in the increase in thermal conductivity over time are further required.

JP-A-11-140216 International Publication No. 99/11697 JP 2007-131803 A

  An object of the present invention is to provide a phenol resin foam having a low initial thermal conductivity and maintaining a low thermal conductivity over a long period of time, and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventor is presumed to have a cyclic structure unlike cyclopentane and isopentane. High-boiling hydrocarbons with a boiling point range of 5% are included so that the amount of cyclopentane present in the phenolic resin foam falls within a specific range, and the amount of high-boiling hydrocarbons extracted from the phenolic resin foam to chloroform is specified. as a range, and, by so has% C _a of determined by ring analysis n-d-M method oily component extracted in chloroform the following specific ratio, a low initial thermal conductivity At the same time, it has been found that a phenol resin foam that maintains a low thermal conductivity over a long period of time can be obtained, and the present invention has been made.
In other words, the present inventors, among various hydrocarbons, cyclopentane containing specified amounts, containing a specific amount of a particular high-boiling hydrocarbons, and, below a certain percentage of the% C _A of the high-boiling hydrocarbons It was found that the initial heat insulation performance and long-term heat insulation performance at 10 ° C. and 23 ° C. can be greatly improved.
That is, the present invention is as follows.

(I) a phenol resin foam containing cyclopentane and a high-boiling hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower and having a density of 10 kg / m ³ or higher and 150 kg / m ³ or lower;
The value of cyclopentane content X (unit: mol) per space volume of 22.4 × 10 ⁻³ m ^{3 in the} phenol resin foam is 0.25 or more and 0.85 or less,
The cyclopentane ratio in the hydrocarbon having 6 or less carbon atoms contained in the phenol resin foam is 60 mol% or more and 100 mol% or less,
When the phenol resin foam is pulverized in chloroform and subjected to extraction treatment, a high-boiling hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower extracted in chloroform has a spatial volume in the phenol resin foam of 22. A range in which the value of the extraction amount Y (unit: g) per 4 × 10 ⁻³ m ³ is not more than the coefficient a calculated by the following expression (1) and not less than the coefficient b calculated by the following expression (2). In
a = -11.61X + 31.57 (1)
b = 2.67X−0.46 (2)
The phenolic foam of the oil component extracted in chloroform when performing the extraction process and triturated in chloroform ring analysis n-d-M method by the determined% C _A is 5% or less, Phenolic resin foam.

  In the present specification, “pulverization” means that the phenol resin foam is crushed until the primary particle volume average particle size of the phenol resin foam becomes 30 μm or less. In addition, after pulverization, the powder may be aggregated to several hundred to several mm.

(Ii) The phenol resin foam according to (i), wherein the high-boiling hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower is liquid at a pressure of 101.325 kPa and a temperature of 30 ° C.

(Iii) The hydrocarbon having 6 or less carbon atoms contained in the phenol resin foam is selected from hydrocarbons having a cyclopentane of 60 mol% to 99.9 mol% and a boiling point of -50 ° C to 5 ° C. In addition, at least one kind is contained in an amount of 0.1 mol% to 40 mol%,
The boiling point average value of the hydrocarbon having 6 or less carbon atoms is 25 ° C. or more and 50 ° C. or less, and the content of the hydrocarbon having 6 or less carbon atoms in the phenol resin foam is the phenol resin foam. The phenol resin foam according to (i) or (ii), having a molar volume of 0.3 to 1.0 mol per space volume of 22.4 × 10 ⁻³ m ³ .

(Iv) The phenol resin foam according to any one of (i) to (iii), wherein the thermal conductivity in a 10 ° C environment and the thermal conductivity in a 23 ° C environment are both 0.0200 W / m · k or less. body.

(V) The phenol resin foam according to any one of (i) to (iv), wherein the closed cell ratio is 90% or more and the average cell diameter is 40 μm or more and 300 μm or less.

(Vi) The hydrocarbon having 6 or less carbon atoms contained in the phenol resin foam includes a hydrocarbon having a boiling point of −50 ° C. or more and 5 ° C. or less,
The phenol resin foam according to any one of (i) to (v), wherein the hydrocarbon having a boiling point of −50 ° C. or more and 5 ° C. or less contains isobutane.

(Vii) the hydrocarbon having 6 or less carbon atoms contained in the phenol resin foam includes a hydrocarbon having a boiling point of −50 ° C. or more and 5 ° C. or less,
The ratio of the total amount of cyclopentane and hydrocarbon having a boiling point of −50 ° C. to 5 ° C. contained in the substance having a boiling point of −100 ° C. to 81 ° C. contained in the phenol resin foam is 70 mol% to 100 mol%. The phenol resin foam according to any one of (i) to (vi), which is:

(Viii) The method for producing a phenol resin foam according to any one of (i) to (vii) above,
Using a mixer, at least a phenol resin, a surfactant, a high-boiling hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower, a foaming agent containing cyclopentane, and an acid curing catalyst. After mixing and discharging the foamable phenolic resin composition from the distributor of the mixer, in the process of heating and foaming and curing the foamable phenolic resin composition, pressure is applied from the top and bottom sides of the foamable phenolic resin composition. Is added to produce a phenolic resin foam molded into a plate shape.

(Ix) the boiling point was% C _A of determined by ring analysis n-d-M method of the high-boiling hydrocarbons of 550 ° C. or less 190 ° C. or higher, 5% or less, phenolic resin foam according to (viii) Manufacturing method.

(X) The manufacturing method of the phenol resin foam as described in (viii) or (ix) whose pressure of the said distribution part is 0.3 Mpa or more and 10 Mpa or less.

(Xi) The amount of water contained in the phenol resin charged into the mixer is 2% by mass or more and 20% by mass or less,
Apply pressure to the foamable phenolic resin composition using a double conveyor in the process of foaming and curing the foamable phenolic resin composition,
The manufacturing method of the phenol resin foam in any one of (viii)-(x) whose temperature in the said double conveyor is 60 degreeC or more and 100 degrees C or less.

(Xii) applying pressure to the foamable phenolic resin composition using a double conveyor in the process of foaming and curing the foamable phenolic resin composition,
The coefficient R calculated by the following formula (3) from the amount of water P (unit: mass%) contained in the phenol resin charged into the mixer and the temperature Q (unit: ° C.) in the double conveyor is 20 to 36, the method for producing a phenol resin foam according to any one of (viii) to (xi).
R = P + 0.2286Q (3)

  According to the present invention, it is possible to provide a phenol resin foam having a low initial thermal conductivity and maintaining a low thermal conductivity over a long period of time and a method for producing the same. Therefore, the phenol resin foam of this invention is preferably used as heat insulating materials, such as a heat insulating material for buildings, a heat insulating material for vehicles, and a heat insulating material for apparatuses.

It is an example of a schematic diagram of a mixer used in one embodiment of the present invention. It is an example of a schematic diagram of a molding machine using a slat type double conveyor used in one embodiment of the present invention.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

The density of the phenol resin foam in the present embodiment is 10 kg / m ³ or more and 150 kg / m ³ or less, preferably 15 kg / m ³ or more and 70 kg / m ³ or less. If the density is too low, the strength is so weak that it is difficult to handle as a foam, and since the cell membrane is thin, there is a concern that the foaming agent in the foam can be easily replaced with air, and the long-term heat insulation performance is likely to deteriorate. Moreover, when the density is too high, there is a concern that the heat conduction of the resin portion forming the bubble film increases and the heat insulation performance is lowered.

Here, the phenol resin foam in the present embodiment includes a specific amount of a high-boiling hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower, including a specific amount of cyclopentane among various hydrocarbons. It was found that the initial heat insulation performance of phenol resin foam and long-term heat insulation performance as well as long-term heat insulation performance can be greatly improved by containing and making the% C _A of high-boiling hydrocarbons below a specific ratio. It was made.
So, below, the cyclopentane and the high boiling point hydrocarbon which the phenol resin foam in this embodiment contains, and those content are demonstrated.

(Cyclopentane)
Cyclopentane functions mainly as a foaming agent when producing a phenol resin foam having the above-mentioned density, and is used to lower the thermal conductivity of the phenol resin foam and improve the heat insulation performance.

The phenolic foam of the present embodiment, a phenolic resin foamed body per spatial volume 22.4 × 10 ^-3 m ³ cyclopentane content X (unit: mol) is 0.25 or more the size of the value 0.85 or less. If the content of cyclopentane is too small, the long-term heat insulation performance tends to decrease. Moreover, when there is too much content of cyclopentane, there exists a tendency for the initial heat insulation performance of 10 degreeC and 23 degreeC to fall. The value of the cyclopentane content X is preferably 0.3 or more and 0.77 or less, more preferably 0.35 or more and 0.7 or less, and particularly preferably 0.4 or more and 0.65 or less.

  Further, the ratio of cyclopentane in the hydrocarbon having 6 or less carbon atoms contained in the phenol resin foam in the present embodiment is 60 mol% or more and 100 mol% or less, preferably 70 mol% or more, more preferably 75 mol%. % Or more. If the cyclopentane ratio in the hydrocarbon having 6 or less carbon atoms is too small, the excellent heat insulation performance of cyclopentane tends to be impaired.

  In addition, the hydrocarbon in this embodiment is a compound comprised only from a hydrogen atom and a carbon atom, and as a hydrocarbon having 6 or less carbon atoms, for example, methane, ethane, ethylene, propane, propylene, butane, Chain aliphatic hydrocarbons including alkanes such as butene, butadiene, pentane, pentene, hexane, and hexene, alkenes, and dienes, and cyclic aliphatic hydrocarbons including cycloalkanes such as cyclobutane, cyclopentane, and cyclohexene, and cycloalkenes. Can be mentioned.

  Furthermore, the phenol resin foam in the present embodiment comprises at least one selected from hydrocarbons having 6 or less carbon atoms contained in the foam from cyclopentane and hydrocarbons having a boiling point of −50 ° C. or more and 5 ° C. or less. It is preferable to contain. The hydrocarbon having 6 or less carbon atoms contained in the foam is selected from hydrocarbons having a cyclopentane content of 60 mol% or more and 99.9 mol% or less and a boiling point of −50 ° C. or more and 5 ° C. or less. It is preferable that at least one content is 0.1 mol% or more and 40 mol% or less, a hydrocarbon having a cyclopentane content of 70 mol% or more and 95 mol% or less and a boiling point of −50 ° C. or more and 5 ° C. or less. More preferably, the selected at least one content is 5 mol% or more and 30 mol% or less, the cyclopentane content is 75 mol% or more and 90 mol% or less, and the boiling point is −50 ° C. or more and 5 ° C. or less. It is particularly preferable that the content of at least one selected from 10 mol% to 25 mol%.

When the hydrocarbon having 6 or less carbon atoms contained in the phenol resin foam contains a hydrocarbon having a boiling point of −50 ° C. or more and 5 ° C. or less together with cyclopentane, it becomes easy to obtain a high closed cell ratio, and long-term heat insulation performance is obtained. Easy to improve. In addition, when a hydrocarbon having a boiling point of −50 ° C. or higher and 5 ° C. or lower is contained, even if the content of the high boiling hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower is small, initial thermal insulation performance good at 10 ° C. tends to be obtained. It is easy to maintain the manufacturing cost and the high flame retardancy, which is an excellent characteristic of the phenol resin foam. However, if the content of hydrocarbon having a boiling point of −50 ° C. or more and 5 ° C. or less is too large, the effect of improving the initial heat insulation performance at 10 ° C. and 23 ° C. tends to be lowered.
In addition, the boiling point in this embodiment is a normal pressure boiling point.

  Here, hydrocarbons having a boiling point of −50 ° C. or more and 5 ° C. or less include propane, propylene, isobutane, normal butane, 1-butene, cis-2-butene, trans-2-butene, 2-methylpropene, butadiene, and the like. From the viewpoint of thermal conductivity and stability, propane, normal butane, and isobutane are preferable, and isobutane is particularly preferable.

In addition, it is preferable that the boiling point average value computed by following formula (4) is 25 degreeC or more and 50 degrees C or less about the hydrocarbon with 6 or less carbon atoms contained in the phenol resin foam of this embodiment. The average boiling point is more preferably 28.5 ° C. or more and 46.5 ° C. or less, and particularly preferably 31 ° C. or more and 43 ° C. or less. If the average boiling point is too low, the thermal conductivity of the mixed gas tends to increase, and there is a concern that the initial heat insulation performance at 23 ° C. may be lowered, and the content of cyclopentane that is difficult to escape from the bubbles decreases. There is a concern that the improvement effect of long-term heat insulation performance tends to decrease because the content of hydrocarbons having a lower boiling point than cyclopentane increases. On the other hand, when the average boiling point of hydrocarbons having 6 or less carbon atoms is too high, the initial heat insulation performance at 10 ° C. tends to be lowered because the hydrocarbons are liquified at low temperatures, and the boiling point is low. When used in combination with a high boiling point hydrocarbon of 190 ° C. or more and 550 ° C. or less, there is a concern that the bubble size tends to be large, and the effect of improving the heat insulation performance is easily reduced by radiation.
Boiling point average value T _AV = a × Ta + b × Tb + c × Tc + (4)
Here, in the above formula (4), the content (molar fraction) of each hydrocarbon contained is a, b, c,..., And the boiling point (° C.) is Ta, Tb, Tc,. It is.

Furthermore, in the phenol resin foam of this embodiment, the content of hydrocarbons having 6 or less carbon atoms is 0.3 mol or more per space volume 22.4 × 10 ⁻³ m ³ (22.4 L) in the foam. It is preferable that it is 1.0 mol or less. The content of hydrocarbons having 6 or less carbon atoms per space volume of 22.4 × 10 ⁻³ m ^{3 in the} foam is more preferably 0.35 mol or more and 0.85 mol or less, further preferably 0.45 mol or more and 0.00. 7 mol or less. If the content of hydrocarbons having 6 or less carbon atoms is small, there is a concern that long-term heat insulation performance tends to decrease, and if it is too large, there is a concern that initial heat insulation performance at 10 ° C and 23 ° C tends to decrease. is there.

  The phenol resin foam of this embodiment includes carbon dioxide, nitrogen, oxygen, helium, argon and other inorganic gases, dimethyl ether, diethyl ether, methyl ethyl ether, furan and other ethers, acetone, methyl ethyl ketone and other ketones, and chloride. Halogenated hydrocarbons such as methyl, methylene chloride, ethyl chloride, 2-chloropropane may be contained. However, if many substances having foamability or volatility are contained in addition to the hydrocarbon having 6 or less carbon atoms, the initial heat insulation performance and long-term heat insulation performance may be deteriorated. Therefore, the proportion of the total amount of cyclopentane and hydrocarbons having a boiling point of −50 ° C. or more and 5 ° C. or less in a substance having a boiling point of −100 ° C. or more and 81 ° C. or less, measured by the method described later, is 70 mol% or more and 100 mol% or less is preferable, 90 mol% or more and 100 mol% or less is more preferable, and 95 mol% or more and 100 mol% or less is particularly preferable.

(High boiling point hydrocarbon)
High boiling point hydrocarbons having a boiling point of 190 ° C. or higher and 550 ° C. or lower are mainly used in combination with the above cyclopentane to lower the thermal conductivity of the foam and improve the heat insulation performance.

Here, the high boiling point hydrocarbon having a boiling point of 190 ° C. or more and 550 ° C. or less in the phenol resin foam of the present embodiment is a compound composed of only hydrogen atoms and carbon atoms, and has a linear structure, a branched structure or A compound having a cyclic structure is preferred. The high-boiling hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower in the present embodiment may be a mixture of a plurality of compounds, for example, a hydrocarbon-based synthetic oil obtained by subjecting an α-olefin to hydrogenation after polymerization, Examples include hydrocarbons contained in paraffinic base oils and naphthenic base oils obtained by subjecting components under reduced pressure distillation from crude oil to solvent washing, desulfurization, and hydrogenation treatment. Among these, hydrocarbon-based synthetic oils, and Hydrocarbons contained in highly refined paraffinic base oils are preferred.
In addition, the boiling point of the high boiling point hydrocarbon of the present invention is a normal pressure boiling point, and is a gas chromatography boiling point obtained by a gas chromatograph equipped with a nonpolar column used for analysis of crude oil or the like.

  As a commercial item of the high boiling point hydrocarbon whose boiling point is 190 degreeC or more and 550 degrees C or less, Cosmo white P series, Cosmo SP series, etc. are mentioned, for example.

The phenolic resin foam% was determined by ring analysis n-d-M method oily component extracted in chloroform when performing the extraction process and triturated in chloroform C _A is less than 5%.
When ring analysis n-d-M method by the determined% C _A of the oil component exceeds 5%, the effect of improving the thermal conductivity at low temperature affinity with high boiling hydrocarbon and cyclopentane is reduced There is a tendency to reduce. Thus, ring analysis n-d-M method by the determined% C _A of the oil component is preferably 3% or less, more preferably 1.5% or less.

Here, a ring analysis n-d-M method by the determined% C _A of the oily component as a method to 5% or less, for example, to be lower content of (i) aromatic compound Examples thereof include a method for selecting the type of the high-boiling hydrocarbon, and (ii) a method for sulfonating and extracting an aromatic ring compound from the high-boiling hydrocarbon.

The A% C _A of oily component extracted in chloroform from phenolic foam, contained in an oily component, ring analysis n-d-M method aromatic ring-containing compound calculated in (aromatic ring in a molecule Of the aromatic ring-containing compound in the oily component.
It is considered that the stabilizing ability of liquefied cyclopentane, which is an oily component acting on cyclopentane liquefied at low temperatures in the bubbles, is closely related to the content of aromatic rings, unlike linear normal pentane and isopentane. It is presumed that cyclopentane is also strongly related to the cyclic structure.

In addition, “% C _A of high-boiling hydrocarbons” means the ratio of the number of carbons derived from aromatic rings in the aromatic ring-containing compound contained in the high-boiling hydrocarbons to the total number of carbons derived from high-boiling hydrocarbons. Means.

In addition, the phenol resin foam of the present embodiment has a high boiling point hydrocarbon having a boiling point of 190 ° C. or more and 550 ° C. or less contained in the foam in the relationship with the cyclopentane content in the foam. It satisfies the conditions.
That is, the phenol resin foam of the present embodiment has a chloroform extraction amount Y (unit: high boiling point hydrocarbon having a boiling point of 190 ° C. or more and 550 ° C. or less per space volume of 22.4 × 10 ⁻³ m ^{3 in} the phenol resin foam. : G) is within the range of the coefficient a calculated by the following formula (1) or less and the coefficient b calculated by the following formula (2) or more.
a = -11.61X + 31.57 (1)
b = 2.67X−0.46 (2)
Here, the “chloroform extraction amount” is the amount extracted into chloroform when the phenol resin foam was pulverized in chloroform so that the volume average particle size of primary particles was 30 μm or less and extracted. It is. In the above formulas (1) and (2), X represents the cyclopentane content (unit: mol) per 22.4 × 10 ⁻³ m ³ of the space volume in the phenol resin foam.

  In the phenol resin foam of the present embodiment, if the extraction amount Y of the high boiling point hydrocarbon is less than the coefficient b, the amount of the high boiling point hydrocarbon relative to the cyclopentane content in the foam is insufficient, and 10 ° C. and 23 ° C. The initial heat insulation performance tends to be reduced, and if the amount of high-boiling hydrocarbon extraction Y exceeds the coefficient a, the amount of high-boiling hydrocarbons becomes excessive, the closed cell ratio tends to deteriorate, and the long-term heat insulation performance decreases. While there is a tendency, the high flame retardance which is the outstanding characteristic of a phenol resin foam tends to fall.

In addition, from the viewpoint of suppressing long-term heat insulation performance and flame retardancy, the high-boiling hydrocarbon extraction amount Y is preferably equal to or less than the coefficient a ′ calculated by the following formula (5). It is further preferable that the coefficient is not more than the coefficient a ″ calculated in 6). Further, from the viewpoint of improving the initial heat insulation performance at 10 ° C. and 23 ° C., the extraction amount Y of the high-boiling hydrocarbon is represented by the following formula (7). It is preferably greater than or equal to the calculated coefficient b ′, and more preferably greater than or equal to the coefficient b ″ calculated by the following formula (8).
a ′ = − 9.29X + 26.23 (5)
a ″ = − 6.96X + 20.89 (6)
b ′ = 3.73X−0.43 (7)
b ″ = 4.79X−0.41 (8)

The high boiling point hydrocarbon having a boiling point of 190 ° C. or more and 550 ° C. or less is preferably liquid at a pressure of 101.325 kPa (1 atm) and a temperature of 30 ° C., more preferably a liquid at a temperature of 20 ° C., and still more preferably a temperature. It is liquid at 10 ° C., and particularly preferably liquid at a temperature of 0 ° C.
If the high-boiling hydrocarbon is solid in the temperature condition where the foam is used, the effect of improving the initial heat insulation performance at 10 ° C. and 23 ° C. tends to be insufficient, and the initial heat insulation performance at 10 ° C. and 23 ° C. Many high-boiling hydrocarbons are required to show a sufficient improvement effect. And if content of a high boiling point hydrocarbon increases, there exists a tendency for the improvement effect of long-term heat insulation performance to reduce easily. The reason why the effect of improving the initial heat insulation performance is insufficient when the high-boiling hydrocarbon is solid is not clear, but is presumed to be because it is difficult for cyclopentane and the high-boiling hydrocarbon to interact with each other. Is done.

(Properties of phenol resin foam)
The phenol resin foam in the present embodiment preferably has a thermal conductivity in a 10 ° C. environment and a thermal conductivity in a 23 ° C. environment, both described later, of 0.0200 W / m · k or less. The thermal conductivity in the environment and the thermal conductivity in a 23 ° C. environment are more preferably 0.0195 W / m · k or less, still more preferably 0.0190 W / m · k or less, and 0.0185 W / m. -It is especially preferable that it is k or less. In addition, the phenol resin foam using cyclopentane may have a high thermal conductivity at low temperatures, but it may be cyclopentane, high-boiling hydrocarbons, and optionally carbonized at a boiling point of −50 ° C. to 5 ° C. In the phenol resin foam in this embodiment containing hydrogen, the thermal conductivity in a 10 degreeC environment can be made low. The thermal conductivity in an environment of 10 ° C. is preferably 0.0185 W / m · k or less, more preferably 0.0180 W / m · k or less, and still more preferably 0.0175 W / m · k. Or less, particularly preferably 0.0170 W / m · k or less. Furthermore, the phenol resin foam in the present embodiment has a deterioration (increase) width from the initial thermal conductivity before the accelerated test of the thermal conductivity after the accelerated test described later (thermal conductivity after the accelerated test−initial thermal conductivity). , Preferably 0.0020 W / m · k or less, more preferably 0.0010 W / m · k or less, still more preferably 0.0005 W / m · k or less, particularly preferably 0.0003 W / m. -K or less. A phenol resin foam having such a thermal conductivity is preferable because it exhibits excellent heat insulation performance at both normal temperature and low temperature and maintains excellent heat insulation performance for a long period of time.

  In addition, since the closed cell ratio of the phenol resin foam in the present embodiment tends to cause a decrease in the heat insulation performance with time when it is small, it is preferably 90% or more, more preferably 93% or more, and 96% or more and 100%. The following are particularly preferred:

  If the average cell diameter of the phenol resin foam in the present embodiment is too small, the strength and the heat insulation performance tend to decrease with time, and if it is too large, the initial heat insulation performance tends to deteriorate. For this reason, the average cell diameter is preferably 40 μm or more and 300 μm or less, more preferably 50 μm or more and 170 μm or less, and particularly preferably 60 μm or more and 130 μm or less.

As described above, the average cell diameter of the phenol resin foam in the present embodiment is preferably 40 μm or more and 300 μm or less, but the foam may partially have large-diameter holes called voids. If the void area ratio of the foam is too large, the initial heat insulation performance tends to deteriorate, and the heat insulation performance tends to decrease with time. For this reason, the void area ratio is preferably 0.2% or less, and more preferably 0.1% or less. In the present embodiment, a large-diameter hole having an area of 2 mm ² or more is defined as a void, and an area of 2 mm ² in a cut surface obtained by cutting a substantially central portion in the thickness direction of the phenol resin foam in parallel with the front and back surfaces. The ratio of the area occupied by the above large-diameter holes (voids) is defined as the void area ratio.

The phenolic resin foam in the present embodiment comprises at least one of a metal hydroxide that is hardly soluble in water that releases water at 150 ° C. or higher and a phosphorus flame retardant that has a decomposition temperature of 150 ° C. or higher and is hardly soluble in water. It is preferable to contain. The total content of the metal hydroxide that is hardly soluble in water that releases water at 150 ° C. or higher and the phosphorus flame retardant having a decomposition temperature of 150 ° C. or higher that is hardly soluble in water is the phenol resin foam. On the other hand, it is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less. When the foam contains a metal hydroxide that is sparingly soluble in water that releases water at 150 ° C. or higher and / or a phosphorus flame retardant that has a decomposition temperature of 150 ° C. or higher and is sparingly soluble in water, The heat insulation performance tends to be improved, and the use of a high boiling point hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower can prevent the flame retardancy of the phenol resin foam from being lowered. The flame retardancy of the resin foam is improved. However, when there is too little content of the said metal hydroxide and phosphorus flame retardant, there exists a tendency for the initial heat insulation performance improvement effect and a flame retardance improvement effect to become inadequate. Moreover, when there is too much content of a metal hydroxide and a phosphorus flame retardant, while there exists a tendency for initial thermal conductivity to worsen, there exists a tendency for the time-dependent fall of heat insulation performance to occur easily.
In this embodiment, a compound such as a metal hydroxide or a phosphorus-based flame retardant is “insoluble in water” when the temperature is 23 ° C. and 100 g of distilled water is mixed with 100 g of distilled water. It indicates that the amount of compound to be dissolved is 15 g or less.

Here, examples of the metal hydroxide that is hardly soluble in water that releases water at 150 ° C. or higher include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and kaolin. In addition, it is preferable that the metal hydroxide having reactivity with the acid curing catalyst described later is coated on the surface to reduce or eliminate the reactivity with the acid curing catalyst. Among the above-mentioned, aluminum hydroxide is preferable because it does not have reactivity with the acid curing catalyst described later, and the effect of improving the initial heat insulation performance and flame retardancy is high.
The volume average particle diameter of the metal hydroxide that is hardly soluble in water that releases water at 150 ° C. or higher is preferably 0.5 μm to 500 μm, more preferably 2 μm to 100 μm, and particularly preferably 5 μm to 50 μm. . If the volume average particle size is too small, the initial heat insulation performance improvement effect tends to be small, and if the volume average particle size is too large, the flame retardancy improvement effect tends to be small.

Examples of the phosphorus flame retardant having a decomposition temperature of 150 ° C. or higher and hardly soluble in water include aromatic condensed esters, melamine phosphate, melamine polyphosphate, and ammonium polyphosphate. Among these, ammonium polyphosphate is preferable because of its high effect of improving the initial heat insulation performance and flame retardancy.
The volume average particle size of the phosphorus-based flame retardant that is hardly soluble in water having a decomposition temperature of 150 ° C. or higher is preferably 0.5 μm or more and 500 μm or less, more preferably 2 μm or more and 100 μm or less, and particularly preferably 5 μm or more and 50 μm or less. If the volume average particle size is too small, the initial heat insulation performance improvement effect tends to be small, and if the volume average particle size is too large, the flame retardancy improvement effect tends to be small.

In addition, the metal hydroxide that is hardly soluble in water that releases water at 150 ° C. or higher and / or the phosphorus system that is hardly soluble in water at a decomposition temperature of 150 ° C. or higher is contained in the phenol resin foam in this embodiment. The type and content of the flame retardant can be qualitatively determined by using general analytical methods as necessary and then using analytical methods such as X-ray fluorescence analysis, X-ray electron spectroscopy, atomic absorption spectroscopy, and Auger electron spectroscopy. It can be quantified.
The volume average particle size of the metal hydroxide and / or phosphorus flame retardant dispersed in the phenol resin foam is obtained by cutting the foam, expanding it with an optical microscope, Auger electron spectroscopy, etc. The location of the metal hydroxide and / or phosphorus flame retardant particles is confirmed by specifying the finely dispersed substances from the composition using elemental analysis of the micro local area of the particles, and the particle size of the dispersed particles is determined. It can be obtained by measuring and calculating an average value. In addition, it is also possible to obtain | require the content rate of a metal hydroxide and / or a phosphorus flame retardant from the occupied area of the particle | grains calculated | required as mentioned above, and the density of a composition.
Furthermore, in this embodiment, when using a metal hydroxide and / or a phosphorus flame retardant, the volume average particle size can be determined by a laser diffraction light scattering type particle size distribution measuring device.

  The phenol resin foam in the present embodiment may contain inorganic fine powders other than those described above and / or organic fine powders other than those described above. These fine powders preferably have no reactivity with the acid curing catalyst described later.

Here, when the phenol resin foam contains inorganic fine powders that are not reactive with acid curing catalysts, such as talc, silicon oxide, glass powder, and titanium oxide, the initial heat insulation performance tends to be improved. There is. However, if the amount of the inorganic fine powder contained is too large, the initial thermal conductivity tends to deteriorate and the heat insulation performance tends to decrease with time. For this reason, the inorganic fine powder that does not react with the acid curing catalyst is preferably contained in an amount of 0.1% by mass to 35% by mass with respect to the phenol resin foam, and is preferably contained in an amount of 1% by mass to 20% by mass. The content is more preferably 2% by mass or more and 15% by mass or less.
The volume average particle diameter of the inorganic fine powder not having reactivity with the acid curing catalyst is preferably 0.5 μm or more and 500 μm or less, more preferably 2 μm or more and 100 μm or less, and particularly preferably 5 μm or more and 50 μm or less.

  On the other hand, the phenol resin foam is a metal hydroxide, metal oxide, metal carbonate, metal powder, or the like that is reactive with an acid curing catalyst described later, such as calcium oxide, calcium carbonate, calcium bicarbonate, sodium carbonate, etc. When the inorganic fine powder is contained, the heat insulation performance tends to be lowered with time. Therefore, it is preferable that the phenol resin foam does not contain inorganic fine powder having reactivity with the acid curing catalyst.

In addition, when the phenol resin foam contains organic fine powder that does not have reactivity with an acid curing catalyst such as fluororesin fine powder, polypropylene fine powder, and phenol resin foam powder, the initial heat insulation performance is improved. There is a tendency to improve. However, if the amount of the organic fine powder contained is too large, the heat insulation performance tends to decrease with time. Therefore, the content of the organic fine powder having no reactivity with the acid curing catalyst is preferably 0.1% by mass or more and 35% by mass or less, and 0.5% by mass or more and 20% by mass with respect to the phenol resin foam. % Or less is more preferable, and 1% by mass or more and 10% by mass or less is particularly preferable.
The volume average particle size of the organic fine powder having no reactivity with the acid curing catalyst is preferably 0.5 μm or more and 2000 μm or less, more preferably 5 μm or more and 500 μm or less, and particularly preferably 10 μm or more and 200 μm or less. .

  On the other hand, when the phenol resin foam contains an organic fine powder having reactivity with an acid curing catalyst such as a basic ion exchange resin fine powder, there is a tendency that the heat insulation performance is likely to deteriorate with time. Therefore, it is preferable that the phenol resin foam does not contain organic fine powder having reactivity with the acid curing catalyst.

Here, the composition, average particle size, and content of the fine powder dispersed in the phenol resin foam of the present embodiment were confirmed by cutting the foam and expanding it with an optical microscope, and confirming the location of the fine powder. The location of the fine powder is confirmed by identifying the finely dispersed substance from the composition using micro local elemental analysis such as Auger electron spectroscopy, and the particle size of the fine powder dispersed is measured to determine the volume average. It can be determined using a method for calculating the value and a method for calculating the content rate from the occupied area of the fine powder to be dispersed and the density of the composition.
In addition, in this embodiment, when using fine powder, the volume average particle diameter can obtain | require an average particle diameter with the laser diffraction light scattering type particle size distribution measuring apparatus.

  The phenol resin foam in this embodiment may contain a plasticizer or the like within a range that does not affect foamability in addition to the components described above, but is a compound having reactivity with an acid curing catalyst, or acid curing. It is preferable not to contain the compound which changes with a catalyst. When the phenol resin foam contains, for example, a partially hydrolyzed condensate of an organosilicon compound having a hydrolyzable group such as a partially hydrolyzed condensate of organomethoxysilane, the thermal insulation performance tends to decrease over time. . Therefore, it is preferable that a phenol resin foam does not contain the organosilicon compound which has a hydrolysable group.

  In the phenol resin foam of this embodiment, the total amount of the content of the compound having reactivity with the acid curing catalyst and the content of the compound altered by the acid curing catalyst is 0 with respect to the phenol resin foam. 0.5 mass% or less is preferable, more preferably 0.1 mass% or less, and particularly preferably 0.01 mass% or less.

The phenol resin used for forming the phenol resin foam in this embodiment can be synthesized by polymerization of phenols and aldehydes. The starting molar ratio of phenols and aldehydes used in the polymerization (phenols: aldehydes) is preferably in the range of 1: 1 to 1: 4.5, more preferably 1: 1.5 to 1: 2. Within the range of .5.
Note that urea, dicyandiamide, melamine, or the like may be added to the phenol resin as an additive. In this embodiment, when adding these additives, a phenol resin refers to the thing after adding an additive.

  Here, the phenols preferably used in the synthesis of the phenol resin in the present embodiment include phenol, resorcinol, catechol, o-, m- and p-cresol, xylenols, ethylphenols, p-tertbutylphenol. Etc. Dinuclear phenols can also be used.

  Examples of aldehydes preferably used in the present embodiment include formaldehyde, glyoxal, acetaldehyde, chloral, furfural, benzaldehyde, paraformaldehyde and the like.

  The viscosity at 40 ° C. of the phenol resin is preferably 200 mPa · s or more and 100,000 mPa · s or less, more preferably 500 mPa · s or more and 50,000 mPa · s or less. The water content is preferably 2% by mass or more and 20% by mass or less.

  The mixing method of the fine powder and the phenol resin when adding the inorganic and / or organic fine powder is not particularly limited, and may be mixed using a mixer having a pin mixer, You may mix using a twin-screw extruder, a kneading machine, etc. The stage of mixing the fine powder with the phenol resin is not particularly limited. When the phenol resin is synthesized, it may be added to the raw material, or after the synthesis of the phenol resin is completed, before and after adding each additive. May be. It may be after the viscosity of the phenol resin is adjusted, or may be mixed with a surfactant and / or a foaming agent. However, adding the fine powder to the phenol resin increases the overall viscosity. Therefore, when adding the fine powder to the phenol resin before viscosity adjustment, the viscosity adjustment of the phenol resin is estimated based on the amount of water. Preferably it is done. Moreover, you may add a fine powder to the foamable phenol resin composition containing a phenol resin, surfactant, the foaming agent containing a hydrocarbon, and an acid curing catalyst. Furthermore, the fine powder may be mixed with a phenol resin in a necessary amount, or a phenol resin containing a high concentration of fine powder may be prepared as a master batch, and the necessary amount added to the phenol resin.

The viscosity at 40 ° C. of the phenol resin containing the fine powder is preferably 200 mPa · s or more and 300,000 mPa · s or less in consideration of the load on the apparatus due to the increase in pressure in the flowable piping of the foamable phenol resin composition. More preferably, it is 100,000 mPa * s or less, More preferably, it is 50,000 mPa * s or less.
The water content is preferably 2% by mass or more and 20% by mass or less.

  The phenolic resin foam of the present embodiment is a foamable phenolic resin comprising at least a phenolic resin, a surfactant, a high boiling point hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower, a blowing agent containing cyclopentane, and an acid curing catalyst. Obtained from the composition. The surfactant, the high-boiling hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower and the blowing agent may be added to the phenol resin in advance, or may be added simultaneously with the acid curing catalyst.

  As the surfactant used in the present embodiment, those generally used for the production of phenol resin foams can be used. Among them, nonionic surfactants are effective, for example, ethylene oxide and propylene oxide. Copolymers of alkylene oxide, condensation products of alkylene oxide and castor oil, condensation products of alkylene oxide and nonylphenol, alkylphenols such as dodecylphenol, polyoxyethylene alkyl ethers, and polyoxyethylene fatty acid esters Fatty acid esters such as ethylene oxide grafted silicone compounds such as polydimethylsiloxane, polyalcohols and the like are preferred. One type of surfactant may be used alone, or two or more types may be used in combination. Moreover, although there is no restriction | limiting in particular also about the usage-amount, It uses preferably in the range of 0.3 to 10 mass parts per 100 mass parts phenol resin.

The acid curing catalyst used in the present embodiment is not particularly limited. However, when an acid curing catalyst containing a large amount of water is used, there is a risk of destruction of the foam cell walls. Therefore, the acid curing catalyst is preferably phosphoric anhydride or aryl sulfonic anhydride. 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, dodecyl benzene sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid, and the like. One of these may be used alone, or two or more of these may be used in combination. Further, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol and the like may be added as a curing aid. Moreover, you may dilute with solvents, such as ethylene glycol and diethylene glycol.
When the acid curing catalyst is added to the phenol resin, the acid curing catalyst is uniformly dispersed as quickly as possible using a pin mixer or the like.

The use amount of the foaming agent described above varies depending on the viscosity and water content of the phenol resin and the foaming curing temperature, but preferably 1 part by mass or more and 25 parts by mass or less, more preferably 3 parts by mass with respect to 100 parts by mass of the phenol resin. It is used at a ratio of 15 parts by mass or less.
Further, the high boiling point hydrocarbon having a boiling point of 190 ° C. or more and 550 ° C. or less described above varies depending on the amount of cyclopentane used, but is 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the phenol resin. Preferably, it is used at a ratio of 0.1 parts by mass or more and 5 parts by mass or less.
The amount of the acid curing catalyst used varies depending on the type, and when phosphoric anhydride is used, it is 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 with respect to 100 parts by mass of the phenol resin. Used in the following proportions. Further, when a mixture of 60% by mass of paratoluenesulfonic acid-hydrate and 40% by mass of diethylene glycol is used, it is preferably 3 parts by mass or more and 30 parts by mass or less, more preferably 5 parts by mass with respect to 100 parts by mass of the phenol resin. It is used in a proportion of not less than 20 parts by mass.

(Method for producing phenolic resin foam)
The foamable phenolic resin composition of the present embodiment is molded by mixing the foamable phenolic resin composition described above using a mixer, ejecting it from the distributor, and then foaming and curing.

  Here, when the foaming phenol resin composition is discharged from the distributor of the mixer, if the pressure of the distributor of the mixer is too low, the tendency of increase in voids, deterioration of heat insulation performance and long-term heat insulation performance If the pressure is too high, a high pressure resistance facility is required, the facility cost increases, and the homogeneity of the foam tends to decrease. Therefore, the pressure of the distribution part of the mixer is preferably 0.3 MPa or more and 10 MPa or less, and more preferably 0.5 MPa or more and 3 MPa or less. The pressure of the distribution unit of the mixer is adjusted by a method such as controlling the temperature of the mixer and / or the distribution unit, the diameter of the tip of the distribution unit, and the diameter and length of the pipe provided before the distribution unit. Is possible.

  In this embodiment, it is preferable that moisture is contained in the foamable phenol resin composition to be charged into the mixer. Since moisture also contributes to foaming, if there is too little moisture, there is a concern that the foaming ratio will not increase and the initial heat insulation performance will be reduced. On the other hand, if there is too much moisture, the closed cell ratio tends to decrease, and there is a concern that long-term heat insulation performance will decrease. Therefore, it is preferable to control the water content of the phenolic resin charged into the mixer. The amount of water contained in the phenol resin charged into the mixer is preferably adjusted to 2% by mass or more and 20% by mass or less, more preferably 2.5% by mass or more and 13% by mass or less, and particularly preferably. It is 3 mass% or more and 10 mass% or less.

  In this embodiment, the foamable phenolic resin composition discharged from the distributor of the mixer is obtained by, for example, a method using a double conveyor, a method using a metal roll or a steel plate, or a method using a combination of these. It can be formed into a plate shape by applying pressure from the vertical direction side (upper surface direction and lower surface direction). Among them, the method using a double conveyor is preferable because the obtained flat foam has good smoothness. For example, when using a double conveyor, after discharging the foamable phenolic resin composition from the distributor of the mixer onto the bottom surface material that continuously travels, while covering with the top surface material that also travels continuously, After continuously guiding the foamable phenolic resin composition into the double conveyor, applying pressure from the up and down direction side while heating, adjusting to a predetermined thickness, foaming and curing, and forming into a plate shape A plate-like phenolic resin foam can be obtained. Here, if the temperature in the double conveyor in the process of foaming and curing the foamable phenolic resin composition is too low, there is a concern that the foaming ratio will not increase and the initial heat insulation performance will be lowered, and if it is too high, the closed cell ratio will be lowered. There is a concern that the long-term thermal insulation performance is likely to deteriorate. Therefore, the temperature in the double conveyor is preferably 60 ° C. or higher and 100 ° C. or lower, more preferably 65 ° C. or higher and 98 ° C. or lower, and further preferably 70 ° C. or higher and 95 ° C. or lower.

And in this embodiment, the water content P (unit: mass%) contained in the phenol resin put into the mixer mentioned above, and the temperature Q (unit: in the double conveyor in the process of foaming and curing described above) The coefficient R calculated by the following formula (3) from the temperature C) is too large for hydrocarbons having 6 or less carbon atoms in the space volume 22.4 × 10 ⁻³ m ³ (22.4 L) in the phenol resin foam. There is a concern that the content will decrease and the long-term heat insulation performance will decrease. If it is too small, the hydrocarbon in the space volume of 22.4 × 10 ⁻³ m ³ (22.4 L) in the phenol resin foam will have 6 or less carbon atoms. There is a concern that the content of is increased and the initial heat insulation performance is lowered. Therefore, the coefficient R is preferably in the range of 20 or more and 36 or less, more preferably 21.5 or more and 33 or less, and particularly preferably 23 or more and 29 or less.
R = P + 0.2286Q (3)

  The plate-like phenol resin foam in this embodiment can be post-cured, and the post-curing temperature is preferably 40 ° C. or higher and 130 ° C. or lower, more preferably 60 ° C. or higher and 110 ° C. or lower. Post-curing may be performed in one stage, or may be cured in several stages by changing the curing temperature according to the degree of curing.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these.
The composition, structure, and characteristics of the phenol resin and the phenol resin foam in Examples and Comparative Examples were measured and evaluated as follows.
The “boiling point average value of hydrocarbons having 6 or less carbon atoms” is a calculated value obtained by the above-described formula (4).

(1) Foam density The foam density is a value obtained by measuring the weight and apparent volume of a 20 cm square phenolic resin foam sample, removing the face material and siding material of this sample, and JIS-K. Measured according to -7222.

(2) Average bubble diameter The average bubble diameter was measured by the following method with reference to the method described in JIS-K-6402.
A photograph obtained by enlarging the cut surface obtained by cutting approximately the center in the thickness direction of the phenol resin foam in parallel with the front and back surfaces by 50 times was taken, and a length of 9 cm (actual foam cross section) was obtained on the obtained photograph. 4 lines (corresponding to 1,800 μm) were drawn, and the average value of the number of bubbles crossed by each straight line was determined. The average bubble diameter is a value obtained by dividing 1,800 μm by the average value of the number of bubbles crossed.

(3) Closed cell ratio The closed cell ratio was measured by the following method with reference to the method A of ASTM-D-2856-94 (1998).
A cube specimen of about 25 mm square was cut out from the center in the thickness direction of the foam. If the foam is thin and a specimen having a uniform thickness of 25 mm cannot be obtained, a specimen having a uniform thickness obtained by slicing the cut surface of a cube specimen of about 25 mm square by about 1 mm is used. The length of each side of the specimen was measured with a caliper, the apparent volume (V1: cm ³ ) was measured, and the weight of the specimen (W: 4 significant digits, g) was measured. Subsequently, the closed space volume (V2: cm ³ ) of the specimen is measured using an air pycnometer (Tokyo Science Co., Ltd., trade name “MODEL1000”) according to the method described in Method A of ASTM-D-2856-94. did. In addition, the bubble diameter (t: cm) was measured according to the measurement method of “(2) average bubble diameter”, and the surface area (A: cm ² ) of the specimen was measured from the length of each side already measured. From t and A, the pore volume (VA: cm ³ ) of the bubbles cut on the surface of the specimen was calculated by the formula VA = (A × t) /1.14. The density of the solid phenol resin is 1.3 g / mL, and the volume (VS: cm ³ ) of the solid portion constituting the cell wall included in the specimen is expressed by the formula VS = sample weight (W) /1.3. Calculated.
The closed cell ratio was calculated by the following formula (9).
Closed cell ratio (%) = [(V2−VS) / (V1−VA−VS)] × 100 (9)
The foam sample under the same production conditions was measured 6 times, and the average value was taken as the representative value of the production condition sample.
In addition, about the phenol resin foam containing solids, such as an inorganic substance with a density different from a phenol resin, it grind | pulverizes to the state which does not contain a closed space, measures a weight, and uses an air pycnometer (Tokyo Science company, brand name "MODEL1000"). The density of the solid-containing phenol resin obtained by measuring the volume using “)” was used as the density of the solid phenol resin.

(4) Thermal conductivity Based on JIS-A-1412-2: 1999, the thermal conductivity in 10 degreeC and 23 degreeC was measured with the following method.
A phenol resin foam sample is cut into approximately 600 mm squares, and a specimen is placed in an atmosphere of 23 ± 1 ° C. and humidity of 50 ± 2%, and the weight change over time is measured every 24 hours. Condition adjustment was carried out until it became 0.2 mass% or less. The conditioned specimen was introduced into a thermal conductivity measuring device placed in the same environment. If the thermal conductivity measurement device is not placed in a room controlled at 23 ± 1 ° C and humidity 50 ± 2% where the specimen was placed, immediately put it in a polyethylene bag and close the bag. It was taken out of the bag within the time and immediately subjected to measurement of thermal conductivity.
The thermal conductivity is measured by peeling off the face material so as not to damage the foamed portion, the thermal conductivity at 10 ° C. is the condition of the low temperature plate 0 ° C., the high temperature plate 20 ° C., and the thermal conductivity at 23 ° C. is the low temperature plate 13 ° C. high temperature plate. Under the condition of 33 ° C., one test piece and a symmetrical configuration type measuring device (Eihiro Seiki Co., Ltd., trade name “HC-074 / 600”) were used.

(5) Thermal conductivity after acceleration test With reference to EN13166, the thermal conductivity after the following acceleration test, which was assumed after 25 years, was measured.
When the phenol resin foam sample is cut into approximately 600 mm square, and the foam having the gas permeable face material has the gas impermeable face material while having the face material, the characteristics of the foam itself are evaluated. Therefore, the face material was peeled off so as not to damage the foamed part, and used as a specimen for an acceleration test.
The 600 mm square specimen was placed in a circulating oven adjusted to 110 ± 2 ° C. for 14 ± 0.05 days and subjected to an acceleration test.
Subsequently, according to the measurement method of “(4) Thermal conductivity”, the thermal conductivity at 10 ° C. and 23 ° C. was measured.

(6) Moisture content in phenolic resin and phenolic resin foam (A) Moisture content in phenolic resin Dehydrated methanol (manufactured by Kanto Chemical Co., Ltd.) whose moisture content was measured was added with 3 to 7 mass% of phenolic resin. The water content in the dehydrated methanol was subtracted from the water content of the solution to obtain the water content of the phenol resin. For the measurement, a Karl Fischer moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd., MKC-510) was used.
(B) Moisture content in the phenolic resin foam The moisture content in the phenolic resin foam is the moisture vaporized by heating to 110 ° C with a water vaporizer using a Karl Fischer moisture meter having a boat type moisture vaporizer. Was measured.
In addition, about the phenol resin foam containing the solid substance which decomposes | disassembles by high temperature heatings, such as a hydrate, and generate | occur | produces a water | moisture content, it heated at the low temperature below a decomposition temperature, the water content was vaporized, and the moisture content was measured.

(7) Composition ratio of substances having a boiling point of −100 ° C. or more and 81 ° C. or less contained in the foam 10 g of the phenol resin foam sample from which the face material has been peeled off and a metal file in a 10 L container (product name Tedlar Bag) And 5 L of nitrogen was injected. The sample was shaved from the top of the Tedlar pack using a file and finely crushed. Subsequently, it was placed in an oven adjusted to 81 ° C. for 10 minutes. 100 μL of gas generated in the Tedlar bag was sampled and measured by GC / MS, and the types and composition ratios of the generated gas components were analyzed.
Separately, the detection sensitivity of the generated gas component was measured, and the composition ratio was calculated from the detection area area and detection sensitivity of each gas component obtained by the GC / MS. And the ratio of the cyclopentane in a C6 or less hydrocarbon and the hydrocarbon whose boiling point is -50 degreeC or more and 5 degrees C or less was calculated | required.

(8) Content of hydrocarbon having 6 or less carbon atoms in foam The phenolic resin foam sample is cut into approximately 100 mm squares to prepare six specimens, and a sealed bag with heat resistance that can be sealed. Six bags (hereinafter referred to as “bags with chucks”) were prepared, and the weight of each bag was measured with a precision balance. The specimen is placed in a circulating oven adjusted to 70 ° C. for 24 ± 0.5 hours to disperse the contained water, and then immediately put in a bag with a chuck, sealed, and cooled to room temperature. After cooling to room temperature, remove the specimen from the zippered bag, quickly peel off the specimen and measure the weight (W1) of each specimen with a precision balance, and measure the length of each side with a caliper. The volume (V) of the specimen was calculated. After that, each specimen is returned to the bag with the chuck, sealed again leaving a part of the opening, put between the surfaces of the room temperature hydraulic press, and gradually compressed to a pressure of about 200 N / cm ² with the hydraulic press, The test piece bubble was destroyed. For the three specimens, a sample of a part of the specimen was taken, and the water content contained was measured by the method for measuring the water content in the phenol resin foam. For the remaining specimens, the sample-filled zippered bag with some openings left is placed in a circulating oven controlled at 81 ° C. for 30 ± 5 minutes. The gas in the bag is discharged while preventing it from coming out, the bag is sealed, and cooled to room temperature. After cooling to room temperature, the weight of the zippered bag with the specimen not subjected to moisture measurement was measured with a precision balance, the weight of the zippered bag was subtracted, and the weight (W2) from which volatile components were removed was measured. . At the same time, a sample was taken from the bag of the three specimens whose moisture content was measured as described above, and the moisture content was similarly measured.
Next, the water amount is subtracted from the difference between W1 and W2, and the volume obtained by subtracting the resin volume calculated from W2 from the volume (V) of the specimen, with the solid phenol resin density being 1.3 g / cm ^3. The air buoyancy weight calculated by the (space volume in the foam) and the air density (0.00119 g / mL) was added to measure the volatile component weight (W3), and W3 was measured by the present measurement method (7). The content weight (W4) was calculated by multiplying the proportion of hydrocarbons having 6 or less carbon atoms in the gas component. In addition, about the phenol resin foam containing solids, such as an inorganic substance with a density different from a phenol resin, it grind | pulverizes to the state which does not contain a closed space, measures a weight, and uses an air pycnometer (Tokyo Science company, brand name "MODEL1000"). The density of the solid-containing phenol resin obtained by measuring the volume using “)” was used as the density of the solid phenol resin.
The content of the hydrocarbon having 6 or less carbon atoms in the foam (mol / 22.4 × 10 ⁻³ m ³ ) is the same as the above-mentioned W4 in the space volume of 22.4 × 10 ⁻³ m ³ in the foam. And the measured amount and molecular weight of the hydrocarbon measured by the above measurement method (7). Similarly, the cyclopentane content (mol / 22.4 × 10 ⁻³ m ³ ) in the foam was also calculated.

(9) Content of high-boiling hydrocarbons having a boiling point of 190 ° C. or more and 550 ° C. or less 100 parts by mass of chloroform and 1.7 parts by mass of phenol resin foam sample cut and divided into a plurality not including a face material Place in a solvent-resistant fine pulverizer and pulverize the foam intermittently for 15 minutes until the volume average particle size is 30 μm or less. After extraction treatment, the chloroform extract is measured by GC / MS. The types of extracted high-boiling hydrocarbons were analyzed. In addition, the pulverized phenol resin foam may aggregate, and the volume average particle diameter is a primary particle diameter.
In addition, the phenol resin foam sample was extract | collected from the thickness part of 10 mm of center parts of the thickness direction of a foam, and the extraction process was started within 10 minutes after foam cutting.
Examples of the solvent-resistant pulverizer include ULTRA-TURRAX (registered trademark) Tube Trive manufactured by IKA.
A calibration curve for high boiling point hydrocarbons was prepared by GC using stearic acid as an internal standard substance and Cosmo White Lubricants Cosmo White P120 as high boiling point hydrocarbons. Note that a flame ionization detector (FID) was used as the detector.
Place 100 parts by mass of chloroform containing stearic acid at the same concentration as the calibration curve, and 1.7 parts by mass of phenol resin foam sample that was cut and divided into multiple parts that did not contain face material, and placed in a sealed solvent-resistant grinder. The foam is pulverized intermittently for 15 minutes until the volume average particle size of the particles becomes 30 μm or less, and after the extraction treatment, the chloroform extract is subjected to GC analysis to determine the amount of high-boiling hydrocarbons extracted from the foam. It was measured.
In the flame ionization detector (FID), there is almost no difference in the sensitivity due to the boiling point difference and the molecular weight of the high boiling point hydrocarbon. However, strictly speaking, the high boiling point hydrocarbon amount in this specification is the Cosmo Oil Lubricants. Cosmo white P120 equivalent amount.
Furthermore, if the extraction amount is small and the detection sensitivity is very low, the foam is introduced into the pulverizer several times as appropriate, and the ratio of the foam to chloroform is increased, or both the calibration curve solution and the extraction solution are the same. The amount extracted from the foam was measured by, for example, analyzing after concentration to magnification.
From the extraction amount per foam weight and the density of the foam, the high boiling point hydrocarbon extraction amount (g) per space volume 22.4 × 10 ⁻³ m ^{3 in the} foam was calculated.
In calculating the extraction amount, the density of the solid phenol resin is usually 1.3 g / cm ³ , but the phenol resin foam containing a solid such as an inorganic substance having a density different from that of the phenol resin includes a closed space. The density of the solid-containing phenol resin determined by measuring the volume and measuring the volume using an air pycnometer (trade name “MODEL1000”) using an air pycnometer is used as the density of the solid phenol resin. Using.

(10)% C _{A of} oily component extracted in chloroform
Phenol resin foam sample, from which the face material was peeled off and the surface layer was cut and removed by 3 mm or more and 5 mm or less, was placed between the surfaces of a hydraulic press at room temperature and gradually compressed to a pressure of about 200 N / cm ² with a hydraulic press. A piece of air bubbles was broken and compressed.
Subsequently, after 100 parts by mass of the phenol resin foam sample subjected to the compression treatment and 1000 parts by mass of chloroform were put into a solvent-resistant fine pulverizer and subjected to extraction treatment while finely pulverizing the foam for 15 minutes. The phenol resin fine powder was filtered by suction filtration to obtain a chloroform extract.
The obtained chloroform extract was concentrated by a rotary evaporator to a mass ratio of 1/10, and the concentrate was sufficiently washed with purified water to extract and remove water-soluble components.
The concentrated chloroform extract, which was sufficiently washed with purified water, was concentrated with a rotary evaporator until no chloroform was present.
The concentrated oily component was filtered through a membrane filter to obtain a solid and an oily substance. The oily substance extracted from this phenol resin foam sample does not contain chloroform used for extraction.
The% C _A of the resulting oil was determined by ring analysis ndM method according to ASTM D-3238.

(11) Viscosity of phenol resin The viscosity of the phenol resin is stabilized at 40 ° C. for 3 minutes using a rotational viscometer (manufactured by Toki Sangyo Co., Ltd., R-100 type, rotor part is 3 ° × R-14). It was set as the measured value after. In addition, the viscosity of the foamable phenolic resin composition at the time of forming into a plate is evaluated by eliminating the influence of the increase in viscosity due to curing of the resin as much as possible. The measured value was used.

(12) Volume average particle diameter of powder The volume average particle diameter of the powder was measured using a laser diffraction light scattering type particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., Microtrac HRA; 9320-X100). In order to uniformly disperse the body in water, it was measured after being treated with ultrasonic waves for 1 minute.

(Example 1)
The reactor was charged with 3500 kg of 52% by weight formaldehyde and 2510 kg of 99% by weight phenol, stirred with a propeller rotating stirrer, and the temperature inside the reactor was adjusted to 40 ° C. with a temperature controller. Next, the reaction was carried out by raising the temperature while adding a 50 mass% aqueous sodium hydroxide solution. When the Ostwald viscosity reached 60 centistokes (measured value at 25 ° C.), the reaction solution was cooled, and 570 kg of urea (corresponding to 15 mol% of the charged amount of formaldehyde) was added. Thereafter, the reaction solution was cooled to 30 ° C., and the pH was neutralized to 6.4 with a 50 mass% aqueous solution of paratoluenesulfonic acid monohydrate.
When the obtained reaction solution was dehydrated at 60 ° C. and the water content was measured, the water content was 5.7% by mass.
An ethylene oxide-propylene oxide block copolymer (manufactured by BASF, Pluronic F-127) was mixed at a ratio of 2.5 parts by mass with respect to 100 parts by mass of the reaction solution after dehydration. This was designated as phenol resin A.

  Highly refined paraffinic oil Cosmo White P120 (hereinafter abbreviated as “P120”) manufactured by Cosmo Oil Lubricants Co., Ltd., 3.0 parts by mass with respect to 100 parts by mass of phenol resin A, and 6.0 parts by mass of cyclopentane as a blowing agent A foamable phenol resin composition comprising 11 parts by mass of a mixture of 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as an acid curing catalyst is supplied to a mixing head whose temperature is adjusted to 25 ° C., and moves through a multiport distribution pipe. Supplied on the bottom material. The mixer (mixer) to be used is shown in FIG. This mixer is obtained by enlarging the mixer disclosed in JP-A-10-225993 and increasing the number of nozzles. That is, the mixer has an inlet for the phenol resin 1, the high boiling point hydrocarbon 2, and the foaming agent 3 in which a surfactant is added to the phenol resin on the upper side surface, and the center of the stirring unit where the rotor d stirs. An inlet for the curing catalyst 4 is provided on the side surface in the vicinity. The part after the stirring part is connected to a nozzle e for discharging the foamable phenol resin composition 5. That is, the mixer is composed of the mixing part a up to the catalyst inlet, the mixing part b from the catalyst inlet to the stirring end part, and the distributing part c from the stirring end to the discharge nozzle. The distribution part c has a plurality of nozzles e at the tip, and is designed so that the mixed foamable phenolic resin composition is uniformly distributed. In addition, a distribution unit temperature sensor and a distribution unit pressure sensor are set in the distribution unit c (not shown) so that the temperature and pressure in the system can be measured. Furthermore, each mixing part and the distribution part are each provided with the jacket for temperature control for enabling temperature adjustment. The temperature measured by this distributor temperature sensor was 42.3 ° C., and the pressure measured by this distributor pressure sensor was 0.75 MPa.

A polyester nonwoven fabric (“Spunbond E05030” manufactured by Asahi Kasei Fibers Co., Ltd., weighing 30 g / m ² , thickness 0.15 mm) was used as the face material.
The foamable phenolic resin composition supplied on the lower surface material was coated with the upper surface material, and at the same time, sandwiched between the upper and lower surface materials, sent to a slat type double conveyor, and cured with a residence time of 20 minutes. A slat type double conveyor to be used is shown in FIG. This conveyor is a slat type double conveyor disclosed in Japanese Patent Application Laid-Open No. 2000-218635, and is located in the center between the upper and lower plates of the upper slat conveyor at a position where it passes 3 minutes after the foamable phenolic resin composition is discharged. In addition, a conveyor temperature sensor is set (not shown) so that the double conveyor temperature in the process of foaming and curing can be measured. The temperature measured by this conveyor temperature sensor was 85 ° C. In FIG. 2, 6 is a face material, 10 is a lower slat conveyor, 20 is an upper slat conveyor, 30 is a heat insulating material, 31 is an air supply fan, 32 is an exhaust fan, 33 is a mixer, 34 is a cutting device, 40 Is a panel-like phenol resin foam, and 41 is a molding apparatus.
Then, it cured for 2 hours in 110 degreeC oven, and obtained the phenol resin foam of thickness 50.6mm. The slat type double conveyor used at this time is designed to release moisture generated during curing to the outside. And the foamable phenol resin composition coat | covered with the upper and lower surface material was shape | molded in plate shape by applying a moderate pressure through a surface material from the up-down direction with a slat type double conveyor.

(Example 2)
Example, except that the amount of the high-boiling hydrocarbon P120 is 3.2 parts by mass with respect to 100 parts by mass of the phenol resin, and 5.7 parts by mass of a mixture of 93 mol% cyclopentane and 7 mol% isobutane is used as a blowing agent. In the same manner as in No. 1, a 49.3 mm thick phenol resin foam was obtained. The temperature measured by the distributor temperature sensor was 42.0 ° C., and the pressure measured by the distributor pressure sensor was 0.75 MPa.

(Example 3)
A phenol resin foam having a thickness of 51.4 mm was obtained in the same manner as in Example 1 except that 5.6 parts by mass of a mixture of 87 mol% cyclopentane and 13 mol% isobutane was used as a foaming agent with respect to 100 parts by mass of the phenol resin. Obtained. The temperature measured by the distributor temperature sensor was 41.7 ° C., and the pressure measured by the distributor pressure sensor was 0.83 MPa.

Example 4
Except for the dehydration conditions of the reaction solution, except that the water content was 11% by mass, the amount of P120 was 2.5 parts by mass with respect to 100 parts by mass of the phenolic resin as in Example 1, and cyclohexane was used as the blowing agent. Phenol having a thickness of 52.6 mm was used in the same manner as in Example 1 except that 4.1 parts by mass of a mixture of 85 mol% of pentane and 15 mol% of isobutane was used and the double conveyor temperature measured by the conveyor temperature sensor was changed to 99 ° C. A resin foam was obtained. The temperature measured by the distributor temperature sensor was 40.3 ° C., and the pressure measured by the distributor pressure sensor was 0.76 MPa.

(Example 5)
The amount of the high-boiling hydrocarbon P120 is 2.5 parts by mass with respect to 100 parts by mass of the phenol resin, and 4.7 parts by mass of a mixture of 85 mol% of cyclopentane and 15 mol% of isobutane is used as a foaming agent. A phenol resin foam having a thickness of 50.1 mm was obtained in the same manner as in Example 1 except that the measured double conveyor temperature was changed to 90 ° C. The temperature measured by the distributor temperature sensor was 41.6 ° C., and the pressure measured by the distributor pressure sensor was 0.92 MPa.

(Example 6)
Only the dehydrating conditions of the reaction solution are different, except that the amount of water is 3.5% by mass, the amount of P120 is 2.5 parts by mass with respect to 100 parts by mass of the phenolic resin as in Example 1, and the foaming agent As in Example 1, except that 6.4 parts by mass of a mixture of 85 mol% of cyclopentane and 15 mol% of isobutane was used and the double conveyor temperature measured by the conveyor temperature sensor was changed to 80 ° C. Of a phenolic resin foam was obtained. The temperature measured by the distributor temperature sensor was 40.9 ° C., and the pressure measured by the distributor pressure sensor was 0.87 MPa.

(Example 7)
The amount of the mixture of 85 mol% cyclopentane and 15 mol% isobutane as a blowing agent is 7.2 parts by mass with respect to 100 parts by mass of the phenol resin, the double conveyor temperature measured by the conveyor temperature sensor is 73 ° C, and the slat type double A phenol resin foam having a thickness of 47.3 mm was obtained in the same manner as in Example 6 except that the residence time on the conveyor was changed to 30 minutes. The temperature measured by the distributor temperature sensor was 40.3 ° C., and the pressure measured by the distributor pressure sensor was 0.85 MPa.

(Example 8)
Except that the amount of the high-boiling hydrocarbon P120 is 6.3 parts by mass with respect to 100 parts by mass of the phenol resin, and 5.6 parts by mass of a mixture of 80 mol% of cyclopentane and 20 mol% of isobutane is used as a blowing agent. In the same manner as in Example 1, a 48.5 mm thick phenolic resin foam was obtained. The temperature measured by the distributor temperature sensor was 42.4 ° C., and the pressure measured by the distributor pressure sensor was 0.83 MPa.

Example 9
A phenol resin foam having a thickness of 50.8 mm was obtained in the same manner as in Example 8 except that the amount of the high-boiling hydrocarbon P120 was changed to 4.0 parts by mass with respect to 100 parts by mass of the phenol resin. The temperature measured by the distributor temperature sensor was 41.9 ° C., and the pressure measured by the distributor pressure sensor was 0.88 MPa.

(Example 10)
A phenol resin foam having a thickness of 51.5 mm was obtained in the same manner as in Example 8, except that the amount of the high-boiling hydrocarbon P120 was changed to 0.6 parts by mass with respect to 100 parts by mass of the phenol resin. The temperature measured by the distributor temperature sensor was 41.2 ° C., and the pressure measured by the distributor pressure sensor was 0.87 MPa.

(Example 11)
Example, except that the amount of the high-boiling hydrocarbon P120 is 2.0 parts by mass with respect to 100 parts by mass of the phenol resin, and 5.6 parts by mass of a mixture of 78 mol% of cyclopentane and 22 mol% of isobutane is used as a blowing agent. In the same manner as in Example 1, a phenol resin foam having a thickness of 50.6 mm was obtained. The temperature measured by the distributor temperature sensor was 41.3 ° C., and the pressure measured by the distributor pressure sensor was 0.88 MPa.

(Example 12)
A thickness of 50 in the same manner as in Example 11 except that 2.0 parts by mass of highly refined paraffinic oil Cosmo SP10 manufactured by Cosmo Oil Lubricants Co., Ltd. was used instead of P120 with respect to 100 parts by mass of the phenol resin. An 8 mm phenolic resin foam was obtained. The temperature measured by the distributor temperature sensor was 41.2 ° C., and the pressure measured by the distributor pressure sensor was 0.88 MPa.

(Example 13)
Using 100 parts by mass of phenol resin, instead of P120, 3.0 parts by mass of highly refined paraffinic oil Cosmo White P260 manufactured by Cosmo Oil Lubricants Co. is used, and 72 mol% of cyclopentane and 28 mol of isobutane are used as blowing agents. A phenol resin foam having a thickness of 51.1 mm was obtained in the same manner as in Example 1 except that 5.4 parts by mass of the mixture of 5% was used. The temperature measured by the distributor temperature sensor was 41.2 ° C., and the pressure measured by the distributor pressure sensor was 0.92 MPa.

(Example 14)
A phenol resin foam having a thickness of 50.5 mm was obtained in the same manner as in Example 1 except that 5.9 parts by mass of a mixture of 62 mol% cyclopentane and 38 mol% isobutane was used as a foaming agent with respect to 100 parts by mass of the phenol resin. Obtained. The temperature measured by the distributor temperature sensor was 40.8 ° C., and the pressure measured by the distributor pressure sensor was 1.08 MPa.

(Comparative Example 1)
A phenol resin foam having a thickness of 51.3 mm was obtained in the same manner as in Example 1 except that the amount of P120 was changed to 0 parts by mass (that is, P120 was not blended). The temperature measured by the distributor temperature sensor was 41.5 ° C., and the pressure measured by the distributor pressure sensor was 0.80 MPa.

(Comparative Example 2)
A phenol resin having a thickness of 49.7 mm was obtained in the same manner as in Example 1 except that 6.0 parts by mass of normal pentane was used as a foaming agent with respect to 100 parts by mass of the phenol resin (that is, cyclopentane was not used). A foam was obtained. The temperature measured by the distributor temperature sensor was 41.6 ° C., and the pressure measured by the distributor pressure sensor was 0.84 MPa.

(Comparative Example 3)
For 100 parts by mass of phenol resin, in place of P120, 3.0 parts by mass of Cosmo Oil Safety Cosmo Pure Safety 46 manufactured by Cosmo Oil Lubricants Co., Ltd. was used, and 6.0 parts by mass of isopentane was used as a blowing agent (ie, A phenol resin foam having a thickness of 50.8 mm was obtained in the same manner as in Example 1 except that no cyclopentane was used. The temperature measured by the distributor temperature sensor was 41.4 ° C., and the pressure measured by the distributor pressure sensor was 0.86 MPa.

(Comparative Example 4)
A phenol resin foam having a thickness of 49.8 mm was prepared in the same manner as in Comparative Example 3 except that 5.7 parts by mass of a mixture of 85 mol% of cyclopentane and 15 mol% of isobutane was used as a foaming agent with respect to 100 parts by mass of the phenol resin. Obtained. The temperature measured by the distributor temperature sensor was 42.3 ° C., and the pressure measured by the distributor pressure sensor was 0.93 MPa.

(Comparative Example 5)
The same procedure as in Example 1 was performed except that the amount of P120 was 9.0 parts by mass with respect to 100 parts by mass of the phenol resin, and 6.0 parts by mass of a mixture of 85 mol% of cyclopentane and 15 mol% of isobutane was used as a foaming agent. Thus, a phenol resin foam having a thickness of 50.1 mm was obtained. The temperature measured by the distributor temperature sensor was 40.6 ° C., and the pressure measured by the distributor pressure sensor was 0.76 MPa.

(Comparative Example 6)
Only the dehydrating conditions of the reaction solution are different, except that the amount of water is 15.0% by mass, the amount of P120 is 2.0 parts by mass with respect to 100 parts by mass of the phenolic resin as in Example 1, and the foaming agent As in Example 1 except that 3.1 parts by mass of a mixture of 85 mol% cyclopentane and 15 mol% isobutane was used and the double conveyor temperature measured by the conveyor temperature sensor was changed to 101 ° C. Of a phenolic resin foam was obtained. The temperature measured by the distributor temperature sensor was 39.8 ° C., and the pressure measured by the distributor pressure sensor was 0.78 MPa.

(Comparative Example 7)
Except for the dehydration conditions of the reaction solution, except that the water content was 3.5% by mass, the amount of P120 was 2.0 parts by mass with respect to 100 parts by mass of the phenol resin as in Example 1, and the blowing agent 10.5 parts by mass of a mixture of 85 mol% of cyclopentane and 15 mol% of isobutane was used, the double conveyor temperature measured by the conveyor temperature sensor was changed to 68 ° C, and the residence time on the slat type double conveyor was changed to 30 minutes A phenol resin foam with a thickness of 47.5 mm was obtained in the same manner as in Example 1 except that. The temperature measured by the distributor temperature sensor was 41.5 ° C., and the pressure measured by the distributor pressure sensor was 0.98 MPa.

(Comparative Example 8)
A phenol resin foam having a thickness of 50.5 mm was obtained in the same manner as in Example 1 except that 5.4 parts by mass of a mixture of cyclopentane 40 mol% and isobutane 60 mol% was used as a foaming agent with respect to 100 parts by mass of the phenol resin. Obtained. The temperature measured by the distributor temperature sensor was 40.7 ° C., and the pressure measured by the distributor pressure sensor was 0.91 MPa.

(Example 15)
Only the dehydrating conditions of the reaction solution are different, except that the amount of water is 3.5% by mass, and the amount of P120 is 3.7 parts by mass with respect to 100 parts by mass of the phenol resin as in Example 1, and the foaming agent A phenol resin foam having a thickness of 47.4 mm was prepared in the same manner as in Example 1 except that the amount of cyclopentane was 7.5 parts by mass and the double conveyor temperature measured by the conveyor temperature sensor was changed to 78 ° C. Obtained. The temperature measured by the distributor temperature sensor was 43.1 ° C., and the pressure measured by the distributor pressure sensor was 0.71 MPa.

(Example 16)
Only the dehydration conditions of the reaction solution were different, except that the water content was 3.5% by mass, and the amount of P120 was 1.2 parts by mass with respect to 100 parts by mass of the phenol resin as in Example 1, and the foaming agent A phenol resin foam having a thickness of 49.6 mm was prepared in the same manner as in Example 1 except that the amount of cyclopentane was 7.5 parts by mass and the double conveyor temperature measured by the conveyor temperature sensor was changed to 78 ° C. Obtained. The temperature measured by the distributor temperature sensor was 43.4 ° C., and the pressure measured by the distributor pressure sensor was 0.76 MPa.

(Example 17)
Double that was measured with a conveyor temperature sensor, using 5.1 parts by mass of P120 with respect to 100 parts by mass of phenol resin, and using 4.1 parts by mass of a mixture of 72 mol% cyclopentane and 28 mol% propane as a blowing agent. A phenol resin foam having a thickness of 50.5 mm was obtained in the same manner as in Example 1 except that the conveyor temperature was changed to 90 ° C. The temperature measured by the distributor temperature sensor was 41.5 ° C., and the pressure measured by the distributor pressure sensor was 0.95 MPa.

(Example 18)
Double measured by a conveyor temperature sensor using 100 parts by weight of phenolic resin with P120 being 0.4 parts by weight and using 4.1 parts by weight of a mixture of cyclopentane 72 mol% and propane 28 mol% as a blowing agent. A phenol resin foam having a thickness of 51.1 mm was obtained in the same manner as in Example 1 except that the conveyor temperature was changed to 90 ° C. The temperature measured by the distributor temperature sensor was 41.1 ° C., and the pressure measured by the distributor pressure sensor was 0.97 MPa.

(Comparative Example 9)
Only the dehydrating conditions of the reaction solution were different, except that the water content was 3.5% by mass, and the amount of P120 was 6.5 parts by mass with respect to 100 parts by mass of the phenol resin as in Example 1, and the foaming agent A phenol resin foam having a thickness of 47.1 mm was obtained in the same manner as in Example 1 except that the amount of cyclopentane was 7.5 parts by mass and the double conveyor temperature measured by the conveyor temperature sensor was changed to 78 ° C. It was. The temperature measured by the distributor temperature sensor was 43.4 ° C., and the pressure measured by the distributor pressure sensor was 0.69 MPa.

(Comparative Example 10)
Only the dehydrating conditions of the reaction solution were different, except that the water content was 3.5% by mass, and the amount of P120 was 0.5 parts by mass with respect to 100 parts by mass of the phenol resin as in Example 1, and the foaming agent A phenol resin foam having a thickness of 47.4 mm is obtained in the same manner as in Example 1 except that the amount of cyclopentane is 7.5 parts by mass and the double conveyor temperature measured by the conveyor temperature sensor is changed to 78 ° C. It was. The temperature measured by the distributor temperature sensor was 43.7 ° C., and the pressure measured by the distributor pressure sensor was 0.77 MPa.

(Comparative Example 11)
Double measured by a conveyor temperature sensor using PSA amount of 8.5 parts by mass and 100 parts by mass of phenol resin and using 4.1 parts by mass of a mixture of 72 mol% cyclopentane and 28 mol% propane as a blowing agent. A phenol resin foam having a thickness of 50.9 mm was obtained in the same manner as in Example 1 except that the conveyor temperature was changed to 90 ° C. The temperature measured by the distributor temperature sensor was 41.6 ° C., and the pressure measured by the distributor pressure sensor was 0.97 MPa.

(Comparative Example 12)
Double measured by a conveyor temperature sensor using 100 parts by mass of P120 and 0.2 parts by mass of P120, and using 4.1 parts by mass of a mixture of 72 mol% cyclopentane and 28 mol% propane as a blowing agent. A phenol resin foam having a thickness of 51.9 mm was obtained in the same manner as in Example 1 except that the conveyor temperature was changed to 90 ° C. The temperature measured by the distributor temperature sensor was 40.6 ° C., and the pressure measured by the distributor pressure sensor was 1.03 MPa.

  According to the present invention, it is possible to provide a phenol resin foam having a low initial thermal conductivity and maintaining a low thermal conductivity over a long period of time and a method for producing the same. Therefore, the phenol resin foam of this invention is preferably used as heat insulating materials, such as a heat insulating material for buildings, a heat insulating material for vehicles, and a heat insulating material for apparatuses.

DESCRIPTION OF SYMBOLS 1 ... Phenolic resin, 2 ... High boiling point hydrocarbon whose boiling point is 190 degreeC or more and 550 degrees C or less, 3 ... Foaming agent, 4 ... Curing catalyst, 5 ... Foamable phenol resin composition, 6 ... Face material, 10 ... Lower slat conveyor, 20 ... Upper slat conveyor, 30 ... Thermal insulation material, 31 ... Air supply fan, 32 ... Exhaust fan, 33 ... Mixing 34 ... cutting device, 40 ... panel-shaped phenol resin foam, 41 ... molding device, a ... mixing unit, b ... mixing unit, c ... distribution unit, d ... rotor for stirring, e ... nozzle for discharge.

Claims (12)

A phenolic resin foam containing cyclopentane and a high-boiling hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower and having a density of 10 kg / m ³ or higher and 150 kg / m ³ or lower;
The value of cyclopentane content X (unit: mol) per space volume 22.4 × 10 ⁻³ m ^{3 in the} phenol resin foam is 0.25 or more and 0.85 mol or less,
The cyclopentane ratio in the hydrocarbon having 6 or less carbon atoms contained in the phenol resin foam is 60 mol% or more and 100 mol% or less,
When the phenol resin foam is pulverized in chloroform and subjected to extraction treatment, the space volume in the phenol resin foam of the high-boiling hydrocarbons having a boiling point of 190 ° C. or higher and 550 ° C. or lower extracted in chloroform is 22.4. The value of the extraction amount Y (unit: g) per × 10 ⁻³ m ³ is within the range of the coefficient a calculated by the following formula (1) and the coefficient b calculated by the following formula (2). And
a = -11.61X + 31.57 (1)
b = 2.67X−0.46 (2)
The phenolic foam of the oil component extracted in chloroform when performing the extraction process and triturated in chloroform ring analysis n-d-M method by the determined% C _A is 5% or less, Phenolic resin foam.   The phenol resin foam according to claim 1, wherein the high-boiling hydrocarbon having a boiling point of 190 ° C or higher and 550 ° C or lower is liquid at a pressure of 101.325 kPa and a temperature of 30 ° C. The hydrocarbon having 6 or less carbon atoms contained in the phenol resin foam is at least one selected from hydrocarbons having a cyclopentane of 60 mol% to 99.9 mol% and a boiling point of -50 ° C to 5 ° C. Containing 0.1 mol% to 40 mol% of seeds,
The boiling point average value of the hydrocarbon having 6 or less carbon atoms is 25 ° C. or more and 50 ° C. or less, and the content of the hydrocarbon having 6 or less carbon atoms in the phenol resin foam is the phenol resin foam. The phenol resin foam according to claim 1, wherein the foam volume is 0.3 mol or more and 1.0 mol or less per 22.5 × 10 ⁻³ m ³ of the space volume.   The phenol resin foam according to any one of claims 1 to 3, wherein both the thermal conductivity in a 10 ° C environment and the thermal conductivity in a 23 ° C environment are 0.0200 W / m · k or less.   The phenol resin foam according to any one of claims 1 to 4, wherein the closed cell ratio is 90% or more and the average cell diameter is 40 µm or more and 300 µm or less. The hydrocarbon having 6 or less carbon atoms contained in the phenol resin foam includes a hydrocarbon having a boiling point of −50 ° C. or more and 5 ° C. or less,
The phenol resin foam according to any one of claims 1 to 5, wherein the hydrocarbon having a boiling point of -50 ° C to 5 ° C contains isobutane. The hydrocarbon having 6 or less carbon atoms contained in the phenol resin foam includes a hydrocarbon having a boiling point of −50 ° C. or more and 5 ° C. or less,
The ratio of the total amount of cyclopentane and hydrocarbon having a boiling point of −50 ° C. to 5 ° C. contained in the substance having a boiling point of −100 ° C. to 81 ° C. contained in the phenol resin foam is 70 mol% to 100 mol%. The phenol resin foam according to any one of claims 1 to 6, which is the following. It is a manufacturing method of the phenol resin foam in any one of Claims 1-7,
Using a mixer, at least a phenol resin, a surfactant, a high-boiling hydrocarbon having a boiling point of 190 ° C. or higher and 550 ° C. or lower, a foaming agent containing cyclopentane, and an acid curing catalyst. After mixing and discharging the foamable phenolic resin composition from the distributor of the mixer, in the process of heating and foaming and curing the foamable phenolic resin composition, pressure is applied from the top and bottom sides of the foamable phenolic resin composition. Is added to produce a phenolic resin foam molded into a plate shape. The boiling point was% C _A of determined by ring analysis n-d-M method of the high-boiling hydrocarbons of 550 ° C. or less 190 ° C. or higher, 5% or less, the production method of the phenolic foam according to claim 8 .   The manufacturing method of the phenol resin foam of Claim 8 or 9 whose pressure of the said distribution part is 0.3 Mpa or more and 10 Mpa or less. The amount of water contained in the phenol resin charged into the mixer is 2% by mass or more and 20% by mass or less,
Apply pressure to the foamable phenolic resin composition using a double conveyor in the process of foaming and curing the foamable phenolic resin composition,
The manufacturing method of the phenol resin foam in any one of Claims 8-10 whose temperature in the said double conveyor is 60 degreeC or more and 100 degrees C or less. Apply pressure to the foamable phenolic resin composition using a double conveyor in the process of foaming and curing the foamable phenolic resin composition,
The coefficient R calculated by the following formula (3) from the amount of water P (unit: mass%) contained in the phenol resin charged into the mixer and the temperature Q (unit: ° C.) in the double conveyor is The method for producing a phenol resin foam according to any one of claims 8 to 11, which is 20 or more and 36 or less.
R = P + 0.2286Q (3)

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