JP2017115126A - Phenol resin foam body and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenol resin foam body having low initial thermal conductivity in a wide temperature range and maintaining low thermal conductivity over long time.SOLUTION: There is provided a phenol resin foam body containing cyclopentane and a siloxane compound and having density of not less than 10 kg/mand not more than 150 kg/mas well as cyclopentane content in the phenol resin foam body of 0.25 to 0.85 mol per 22.4×10mof space volume in the phenol resin foam body.SELECTED DRAWING: None

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 and 2 disclose a phenol resin foam characterized by using a high-boiling foaming agent such as normal pentane or isopentane in combination with a siloxane compound or the like. Patent Document 3 discloses a phenolic resin foam characterized by containing a predetermined amount of silicone oil.

JP-A-11-140216 International Publication No. 99/11697 JP 2007-131801 A

Here, although the conventional phenol resin foam can improve the thermal conductivity at low temperature, further improvement in the initial thermal conductivity and reduction in the increase in thermal conductivity over time are further required. ing. In addition, the phenol resin foam is required to exhibit excellent heat insulation performance in a wide temperature range such as summer and winter in Japan.
Accordingly, an object of the present invention is to provide a phenol resin foam having a low initial thermal conductivity in a wide temperature range 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 that cyclopentane has a cyclic structure unlike normal pentane and isopentane, but cyclopentane is inherent in the phenol resin foam. First, it is possible to maintain a low thermal conductivity over a long period of time while lowering the initial thermal conductivity of the phenol resin foam by making the amount of cyclopentane present in a specific range. Inspired.
Based on the further research by the present inventors, it is assumed that cyclopentane changes from a gas state to a liquid state in the phenol resin foam, particularly in a relatively low temperature environment (for example, 10 ° C.). However, it has become clear that there is a problem that the thermal conductivity increases. In response to such problems, the present inventors have found that a phenol resin foam containing a specific siloxane compound having a structure having a high affinity for cyclopentane in addition to the above cyclopentane has an initial heat in a wide temperature range. It has been found that the conductivity is low and a low thermal conductivity can be maintained over a long period of time, and the present invention has been made.
That is, the present invention is as follows.

(I) a phenol resin foam containing a cyclopentane and a siloxane compound and having a density of 10 kg / m ³ or more and 150 kg / m ³ or less,
The siloxane compound has a methyl group and an ethyl group bonded to an Si atom as a structure A, a substituent other than a methyl group and an ethyl group bonded to an Si atom and a hydrogen atom as a structure B, and a space volume 22 of the phenol resin foam. The number (unit: mmol) of the structure A of the siloxane compound contained in 4 × 10 ⁻³ m ³ is A _m , and the space volume of the phenol resin foam is contained in 22.4 × 10 ⁻³ m ^3. the number of structure B of the siloxane compound (unit: mmol) If the set to _{B m,} the following formula (1):
S = A _m / (A _m + B _m ) (1)
The value of S calculated in the above is 0.60 or more and 1.00 or less,
The value obtained by subtracting the thermal conductivity in an environment of 10 ° C. from the thermal conductivity in an environment of 40 ° C. of the phenol resin foam is 0 W / m · K or more,
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 or less,
The phenol resin foam in which 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.

(Ii) The phenol resin foam according to (i), wherein the substituent of the structure B includes an organic group having 1 to 9 carbon atoms.

(Iii) The phenol resin foam according to (i), wherein the substituent of the structure B includes a hydrocarbon group having 1 to 9 carbon atoms.

(Iv) The phenol resin foam according to (i), wherein the substituent of the structure B includes a phenyl group.

(V) The phenol resin foam according to any one of (i) to (iv), wherein the siloxane compound has a molecular weight of 200 or more and 41000 or less.

(Vi) The phenol resin foam according to any one of claims (i) to (v), wherein the siloxane compound comprises a cyclic polysiloxane compound.

［式中、ｎは１以上５５０以下の整数を表し、Ｒ^１、Ｒ^２はそれぞれ炭素数１以上６以下の置換基を表す。］で表されるシロキサン化合物(I)、
下記式(II)：

［式中、Ｘ^１ _、Ｘ^２はそれぞれ水素原子又は炭素数１以上６以下の置換基（ｎが２以上でＸ^１が複数存在する場合、複数のＸ^１はそれぞれ同一でも異なっていてもよく、ｎが２以上でＸ^２が複数存在する場合、複数のＸ^２はそれぞれ同一でも異なっていてもよい。但し、同一のＳｉに結合したＸ^１およびＸ^２が何れもメチル基である場合は除く）を表し、Ｒ^１、Ｒ^２はそれぞれ炭素数１以上６以下の置換基を表し、ｍは０以上の整数を表し、ｎは１以上の整数を表し、そしてｍとｎの合計は１以上５５０以下である。］で表されるシロキサン化合物(II)、及び、
下記式(III):

［式中、ｎは４以上２０以下の整数を表す。］で表されるシロキサン化合物(III)からなる群から選択される少なくとも１つである、（ｉ）〜（ｖ）のいずれかに記載のフェノール樹脂発泡体。 (Vii) the siloxane compound is
Formula (I) below:

[Wherein, n represents an integer of 1 to 550, and R ¹ and R ² each represent a substituent of 1 to 6 carbon atoms. A siloxane compound (I) represented by
Formula (II) below:

Wherein, X _^1, if X ² each in which a hydrogen atom or a C 1 to 6 substituents carbon (n is X ¹ in 2 or more there is a plurality or different and each of the plurality of X ¹ are the same , when n X ² by 2 or more there are a plurality, may be different in each of the plurality of X ² are the same. However, when X ¹ and X ² bonded to the same Si are both a methyl group R ¹ and R ² each represent a substituent having 1 to 6 carbon atoms, m represents an integer of 0 or more, n represents an integer of 1 or more, and the sum of m and n is 1 550 or less. And a siloxane compound (II) represented by
Formula (III) below:

[Wherein n represents an integer of 4 or more and 20 or less. ] The phenol resin foam in any one of (i)-(v) which is at least 1 selected from the group which consists of siloxane compound (III) represented by these.

(Viii) The phenol resin foam according to (viii), wherein the siloxane compound is at least one of the siloxane compound (I) and the siloxane compound (III).

(Ix) When the phenol resin foam is crushed and extracted in chloroform, the volume of the siloxane compound extracted in chloroform is 22.4 × 10 ⁻³ m in the phenol resin foam. The value of the extraction amount Y (unit: g) per ³ is a coefficient a or less calculated by the following formula (2) using the cyclopentane content X, and the following formula using the cyclopentane content X The phenol resin foam in any one of Claims 1-8 which exists in the range more than the coefficient b calculated by (3).
a = -39.9X + 56.7 (2)
b = 0.056X (3)

(X) The hydrocarbon having 6 or less carbon atoms contained in the phenol resin foam contains 60 mol% or more and 99.9 mol% or less of cyclopentane,
The phenol resin foam according to any one of (i) to (ix), wherein the hydrocarbon having 6 or less carbon atoms has an average boiling point of 25 ° C. or more and 50 ° C. or less.

(Xi) 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 any one of (i) to (ix), having a space volume of 22.4 × 10 ⁻³ m ³ of 0.3 mol to 1.0 mol.

(Xii) The thermal conductivity in a 10 ° C environment and the thermal conductivity in a 23 ° C environment are both 0.0220 W / m · K or less, and the thermal conductivity in a 40 ° C environment is 0.0240 W / m · K. The phenol resin foam according to any one of (i) to (xi), which is:

(Xiii) The degree of deterioration of thermal conductivity under the environment of 10 ° C., 23 ° C., and 40 ° C. after the acceleration test at 110 ° C. for 14 days (the thermal conductivity after the acceleration test−the initial thermal conductivity before the acceleration test) is The phenol resin foam according to any one of (i) to (xii), which is 0.0050 W / m · K or less.

(Xiv) 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 (xiii), wherein the hydrocarbon having a boiling point of −50 ° C. or more and 5 ° C. or less contains isobutane.

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

(Xvi) The phenol resin foam according to any one of (i) to (xv), wherein the void area ratio is 1.0% or less.

(Xvii) The phenol resin foam according to any one of (i) to (xvi), further containing a hydrofluoroolefin having 3 or 4 carbon atoms,
The value of hydrofluoroolefin content (unit: mol) having 3 or 4 carbon atoms per space volume of 22.4 × 10 ⁻³ m ^{3 in the} phenol resin foam is 0.01 or more and 0.4 or less,
Total of the content of hydrocarbons having 6 or less carbon atoms per space volume of 22.4 × 10 ⁻³ m ³ and the content of hydrofluoroolefins having 3 or 4 carbon atoms (unit: mol) is 0.3 to 0.9, a phenol resin foam.

(Xviii) the phenol resin foam according to any one of (i) to (xvii), further containing a halogenated saturated hydrocarbon,
Halogenated saturated hydrocarbon content (unit: mol) per space volume of 22.4 × 10 ⁻³ m ^{3 in the} phenol resin foam is 0.01 or more and 0.35 or less,
Content of hydrocarbon having 6 or less carbon atoms per space volume of 22.4 × 10 ⁻³ m ^{3 in the} foamed phenol resin foam, content of hydrofluoroolefin having 3 or 4 carbon atoms, halogenated saturated hydrocarbon Phenolic resin foam in which the total content (unit: mol) is 0.3 or more and 1.0 or less

(Xix) A method for producing a phenol resin foam according to any one of (i) to (xvi), wherein at least the foaming agent containing the cyclopentane, the siloxane compound, the phenol resin, a surfactant, and The foamable phenol resin composition containing the acid curing catalyst is mixed using a mixer, and after the foamable phenol resin composition is discharged from the distribution section of the mixer, the foamable phenol resin composition is foamed. And in the process of hardening, pressure is applied from the up-down direction side of a foamable phenol resin composition, and the manufacturing method of a phenol resin foam which manufactures the phenol resin foam shape | molded in plate shape.

(Xx) A method for producing a phenol resin foam according to (xvii), wherein the foaming agent contains at least the cyclopentane and the hydrofluoroolefin having 3 or 4 carbon atoms, the siloxane compound, the phenol resin, and an interface. A foamable phenolic resin composition containing an activator and an acid curing catalyst is mixed using a mixer, and the foamable phenolic resin composition is discharged from the distributor of the mixer, and then heated to expand the foamable phenolic resin. In the process in which a composition foams and hardens, a pressure is applied from the up-down direction side of the foamable phenol resin composition to produce a phenol resin foam molded into a plate shape.

(Xxi) A method for producing a phenol resin foam according to (xviii), comprising at least a foaming agent containing the cyclopentane and the halogenated saturated hydrocarbon, the siloxane compound, a phenol resin, a surfactant, and The foamable phenol resin composition containing the acid curing catalyst is mixed using a mixer, and after the foamable phenol resin composition is discharged from the distribution section of the mixer, the foamable phenol resin composition is foamed. And in the process of hardening, pressure is applied from the up-down direction side of a foamable phenol resin composition, and the manufacturing method of a phenol resin foam which manufactures the phenol resin foam shape | molded in plate shape.

(Xxii) The method for producing a phenol resin foam according to any one of (xix) to (xxi), wherein the pressure in the distribution part is 0.2 MPa or more and 10 MPa or less.

(Xxiii) 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 (xix)-(xxii) whose temperature in the said double conveyor is 60 degreeC or more and 100 degrees C or less.

(Xxiv) 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 equation (4) 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 (xix) to (xxiii).
R = P + 0.2286Q (4)

  ADVANTAGE OF THE INVENTION According to this invention, the initial stage thermal conductivity is low in a wide temperature range, and the phenol resin foam which maintains a low thermal conductivity over a long period of time, and its manufacturing method can be provided. 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 phenolic foam in the present embodiment, 10 kg / ^{m 3} or more 150 kg / ^{m 3} or less, preferably 15 kg / ^{m 3} or more 70 kg / ^{m 3} or less, more preferably 15 kg / ^{m 3} or more 50 kg / ^{m 3} Hereinafter, it is more preferably 15 kg / m ³ or more and 40 kg / m ³ or less, particularly preferably 15 kg / m ³ or more and 35 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 is 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 deteriorates.

Here, the phenol resin foam in the present embodiment includes a specific siloxane compound while containing a specific amount of cyclopentane among various hydrocarbons, and optionally has 3 carbon atoms. In addition, by including a specific amount of hydrofluoroolefin of 4 and / or halogenated saturated hydrocarbon, the initial heat insulation performance of phenol resin foam at 10 ° C, 23 ° C, and 40 ° C and long-term heat insulation performance are greatly improved. It was made by finding what can be done.
Therefore, in the following, the cyclopentane, the siloxane compound, the hydrofluoroolefin having 3 or 4 carbon atoms and the halogenated saturated hydrocarbon which can be optionally contained, and the inclusion thereof, included in the phenol resin foam in the present embodiment The amount will be described.

(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 deteriorate because the performance of cyclopentane with excellent thermal conductivity cannot be sufficiently exhibited. Further, if the content of cyclopentane is too large, the pressure in the bubbles increases, and the foaming agent tends to be liquefied, so that the initial heat insulation performance tends to be deteriorated particularly in a relatively low temperature environment (for example, 10 ° C.). There are concerns that it will occur. 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 80 mol%. % Or more, more preferably 90 mol% or more, particularly preferably 95 mol% or more, and preferably 99.9 mol% or less. 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. More preferably, the hydrocarbon has a content of at least one kind of 0.1 mol% or more and 40 mol% or less, 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 content of at least one selected from 5 mol% to 30 mol% is more preferable, the carbon content of cyclopentane is 75 mol% to 90 mol%, and the boiling point is −50 ° C. to 5 ° C. The content of at least one selected from hydrogen is 10 mol% or more and 25 mol% or less, and most preferably the content of cyclopentane is 8 mol% or more 85 mol% or less and at least one content boiling point selected from the following hydrocarbons 5 ° C. or higher -50 ° C. is not more than 15 mol% or more 20 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. It is easy to improve, and since it has an appropriate dispersibility with respect to the phenol resin, it promotes bubble nucleation, tends to reduce the bubble diameter, and tends to improve the initial heat insulation performance (10 ° C. to 40 ° C.). In addition, when a hydrocarbon having a boiling point of −50 ° C. or more and 5 ° C. or less is contained, even if the content of the siloxane compound is small, excellent initial heat insulation performance tends to be obtained particularly at 10 ° C. It is easy to maintain high flame retardancy, which is an excellent characteristic of the body. However, if the content of the hydrocarbon having a boiling point of −50 ° C. or more and 5 ° C. or less is too much, the content of cyclopentane is lowered, and thus the effect of improving the initial heat insulation performance (10 ° C. to 40 ° C.) is likely to be lowered. Tend.
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 calculated by following formula (5) is 25 to 50 degreeC 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 higher and 46.5 ° C. or lower, and particularly preferably 31 ° C. or higher and 44 ° C. or lower. If the average boiling point is too low, the thermal conductivity of the mixed gas tends to be high, and the initial heat insulation performance at 23 ° C. and 40 ° C. may be deteriorated, and the content of cyclopentane that is difficult to escape from the bubbles There is a concern that the effect of improving the long-term heat insulation performance tends to decrease because of a decrease in the amount of hydrocarbon (that is, the content of hydrocarbons having a lower boiling point than cyclopentane increases). On the other hand, when the boiling point average value of the hydrocarbon having 6 or less carbon atoms is too high, the hydrocarbon tends to be liquefied at a low temperature, so that the initial heat insulation performance at 10 ° C. tends to deteriorate, and the siloxane compound When used together, the bubble size tends to be large, and there is a concern that 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 + (5)
In the above formula (5), the content (molar fraction) of each hydrocarbon contained is a, b, c,..., And the boiling point (° C.) is Ta, Tb, Tc,.

Furthermore, in the phenol resin foam of the present 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, still more preferably 0.45 mol or more, more preferably 0.85 mol or less, more preferably 0.77 mol or less, particularly preferably 0.7 mol or less, and most preferably 0.65 mol or less. If the content of hydrocarbons having 6 or less carbon atoms is small, long-term heat insulation performance deteriorates because it is more susceptible to the influence of air with high thermal conductivity that penetrates from the outside air into the bubbles of the phenol resin foam. There is a concern that it will be easy, and if it is too much, the pressure in the bubbles will increase, and the foaming agent will tend to liquefy, so that the initial heat insulation performance tends to be deteriorated particularly in an environment of relatively low temperature (for example, 10 ° C.). There are concerns.

(Hydrofluoroolefin having 3 or 4 carbon atoms)
The phenol resin foam of this embodiment may contain a hydrofluoroolefin having 3 or 4 carbon atoms (that is, 3 to 4 carbon atoms). The hydrofluoroolefin having 3 or 4 carbon atoms functions as a blowing agent together with the cyclopentane when producing a phenol resin foam having the above-mentioned density, and the fluidity of the phenol resin due to high compatibility with the phenol resin. Is used to suppress the voids of the phenol resin foam and improve the initial and long-term heat insulation performance. The phenol resin foam of the present embodiment contains only one of a hydrofluoroolefin having 3 or 4 carbons and a hydrofluoroolefin having 4 carbons as the hydroolefin having 3 or 4 carbons. In addition, both a hydrofluoroolefin having 3 carbon atoms and a hydrofluoroolefin having 4 carbon atoms may be contained.

  Here, the hydrofluoroolefin having 3 or 4 carbon atoms in the phenol resin foam of this embodiment has at least 3 carbon atoms having a fluorine atom, a hydrogen atom, and a carbon-carbon unsaturated bond (olefinic double bond). Or 4 compounds. The compound then has a substantially zero ozone depletion potential (ODP) and a zero or very low global warming potential (GWP). Here, examples of the hydrofluoroolefin having 3 or 4 carbon atoms include hydrofluoropropene, hydrochlorofluoropropene, hydrobromofluoropropene, hydrofluorobutene, hydrochlorofluorobutene, hydrobromofluorobutene, and the like. Among these, from the viewpoint of stability, tetrafluoropropene (hydrofluoropropene), chlorotrifluoropropene (hydrochlorofluoropropene), hexafluoro-2-butene (hydrofluorobutene), chlorohexafluoro-2-butene (Hydrochlorofluorobutene) is preferable, and chlorotrifluoropropene (hydrochlorofluoropropene) and hexafluoro-2-butene (hydrofluorobutene) are more preferable from the viewpoint of low toxicity, boiling point, and thermal conductivity.

The phenolic foam of the present embodiment is, when they contain hydro fluoroolefin having a carbon number 3 or 4, carbon atoms per spatial volume 22.4 × 10 ^-3 m ³ of phenolic foam body is 3 or 4 is preferably 0.01 or more and 0.4 or less, more preferably 0.05 or more and 0.35 or less, and still more preferably 0.1. It is 0.3 or less. The hydrofluoroolefin having 3 or 4 carbon atoms has a fluorine atom and has a large polarity, so that the compound has high affinity with a phenol resin. Therefore, by containing a certain amount or more due to high compatibility with the phenol resin, there is an effect of improving the fluidity of the resin, suppressing voids, and improving the initial and long-term heat insulation performance. On the other hand, if the content of the hydrofluoroolefin having 3 or 4 carbon atoms is too large, it is thought that the high affinity of the compound with the phenol resin makes it easy to scatter from the foam and easily deteriorate the closed cell ratio. However, the long-term heat insulation performance of the phenol resin foam tends to deteriorate.

  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, and acetone and methyl ethyl ketone and other ketones. , Halogenated saturated hydrocarbons such as methyl chloride, dichloromethane (methylene chloride), ethyl chloride, isopropyl chloride (2-chloropropane) may be contained. As the halogenated saturated hydrocarbon, isopropyl chloride is preferable because of its low toxicity and small influence on the environment.

The phenolic foam of the present embodiment is, when they contain halogenated saturated hydrocarbon, content of the halogenated saturated hydrocarbon per volume of space 22.4 × 10 ^-3 m ³ of phenolic foam body, Preferably it is 0.01 mol or more and 0.35 mol or less, More preferably, it is 0.20 mol or less, More preferably, it is 0.15 mol or less. If the content of the halogenated saturated hydrocarbon is too large, it is considered that due to the high affinity of the compound with the phenol resin, it is likely to be scattered from the foam and the closed cell ratio is likely to deteriorate. Long-term insulation performance tends to deteriorate.
In addition to the above-described hydrocarbons having 6 or less carbon atoms and hydrofluoroolefins having 3 or 4 carbon atoms, if many substances having foamability or volatility are contained, initial heat insulation performance and long-term heat insulation performance can be obtained. It can get worse. Therefore, cyclopentane, a hydrofluoroolefin having 3 or 4 carbon atoms, and a boiling point of −50 ° C. or higher and 5 or higher are contained in a substance having a boiling point of −100 ° C. or higher and 81 ° C. or lower as measured by the method described later. The ratio of the total amount of hydrocarbons at or below ° C is preferably 60 mol% or more and 100 mol% or less, more preferably 85 mol% or more and 100 mol% or less, and particularly preferably 95 mol% or more and 100 mol% or less.

When the phenol resin foam of the present embodiment contains a hydrofluoroolefin having 3 or 4 carbon atoms, carbonization with 6 or less carbon atoms per space volume of 22.4 × 10 ⁻³ m ^{3 in} the phenol resin foam. The total (unit: mol) of the hydrogen content and the hydrofluoroolefin content having 3 or 4 carbon atoms is preferably 0.3 or more and 0.9 or less, more preferably 0.35 or more and 0. .8 or less, more preferably 0.45 or more and 0.7 or less. If the total content of hydrocarbons having 6 or less carbon atoms and hydrofluoroolefins having 3 or 4 carbon atoms is small, there is a concern that long-term heat insulation performance is likely to deteriorate, and if too large, initial heat insulation performance (10 ° C. There is a concern that a tendency to worsen (˜40 ° C.) occurs.

When the phenol resin foam of this embodiment contains a halogenated saturated hydrocarbon, the content of hydrocarbons having 6 or less carbon atoms per space volume of 22.4 × 10 ⁻³ m ^{3 in} the phenol resin foam, The total (unit: mol) of the content of the hydrofluoroolefin having 3 or 4 carbon atoms and the content of the halogenated saturated hydrocarbon is preferably 0.3 or more and 1.0 or less, more preferably 0. .35 or more and 0.85 or less, more preferably 0.45 or more and 0.7 or less. In this case, the hydrocarbon having 6 or less carbon atoms and the hydrofluoroolefin having 3 or 4 carbon atoms excluding cyclopentane may or may not be contained in the phenol resin foam. If the total content of hydrocarbons having 6 or less carbon atoms, hydrofluoroolefins having 3 or 4 carbon atoms, and halogenated saturated hydrocarbons is small, there is a concern that long-term heat insulation performance is likely to deteriorate, There is a concern that the initial thermal insulation performance (10 ° C. to 40 ° C.) tends to decrease.

(Siloxane compound)
Siloxane compounds used in this embodiment is a compound having a SiO-Si bond (siloxane bond), for example, the formula _:-( R 2 SiO) n- [wherein, n are integers of 2 or more, R Is a linear or cyclic polysiloxane compound containing a repeating unit represented by a hydrogen atom or an arbitrary substituent. In addition, the siloxane compound used in the present embodiment may be a single compound composed of only one kind of compound or a mixture of two or more kinds of compounds.
The siloxane compound is mainly a hydrofluoroolefin having 3 or 4 carbon atoms, a hydrocarbon having 6 or less carbon atoms, and / or a halogenated saturated, which can optionally be contained in the cyclopentane and the phenol resin foam. Used in combination with hydrocarbons to lower the thermal conductivity of the foam and improve the heat insulation performance.

Here, the siloxane compound used in the present embodiment has a structure in which a methyl group and an ethyl group bonded to a Si atom constituting a siloxane bond are substituted with structures A and a methyl group and an ethyl group bonded to a Si atom constituting a siloxane bond A group and a hydrogen atom as a structure B, the number of the structure A of the siloxane compound (unit: mmol) contained in the space volume 22.4 × 10 ⁻³ m ^{3 of the} phenol resin foam is A _m , and the phenol resin When the number (unit: mmol) of the structure B of the siloxane compound contained in the space volume 22.4 × 10 ⁻³ m ^{3 of the} foam is B _m , the following formula (1):
S = A _m / (A _m + B _m ) (1)
It is necessary that the value of S calculated in the above is 0.60 or more and 1.00 or less. The value of S is preferably 0.65 or more and 1.00 or less, more preferably 0.74 or more and 1.00 or less, and further preferably 0.86 or more and 1.00 or less. . A structure in which a methyl group or an ethyl group is bonded to a Si atom (for example, a repeating unit such as a dimethylsiloxane unit or a diethylsiloxane unit) is excellent in affinity with cyclopentane. Therefore, if a siloxane compound having a value of S of 0.6 or more is used, cyclopentane in the bubbles liquefied at low temperature is stabilized, and initial heat insulation performance in a relatively low temperature (for example, 10 ° C.) environment is achieved. Can be improved.
Here, the value of _{A m} is preferably 0.8 or more, more preferably 8.0 or more, still more preferably 14.0 or more, preferably 1200 or less, 500 More preferably, it is more preferably 360 or less. When the value of A _m is 0.8 or more, further it can be improved initial heat insulating performance of the relatively low temperature (e.g. 10 ° C.). On the other hand if the value of A _m is 1200 or less, to ensure a high closed cell content of phenolic foam, it is possible to suppress the reduction of long-term thermal insulation performance and flame retardancy.
Further, the value of B _m is preferably 300 or less, more preferably 110 or less, and more preferably 10 or less from the viewpoint of securing an initial heat insulation performance at a relatively low temperature (for example, 10 ° C.). More preferably, it is particularly preferably 1 or less, and most preferably 0 (below the detection limit).
In this embodiment, the values of A _m , B _m , and S of the siloxane compound contained in the phenol resin foam can be obtained by the method described in the examples of this specification.

Here, as a substituent of the structure B mentioned above, it does not specifically limit, Arbitrary organic groups other than a methyl group and an ethyl group are mentioned. Examples of such organic groups include amino groups, epoxy groups, carbinol groups, silanol groups, mercapto groups, carboxyl groups, hydroxyl groups, methacrylic groups, polyether groups, and hydrocarbon groups (aralkyl groups, alkyl groups, Phenyl group, etc.).
And as an organic group of structure B, from a viewpoint of further improving the initial heat insulation performance in low temperature (for example, 10 degreeC) environment, the organic group which has a carbon atom is preferable, and C1-C9 organic group is an organic group. More preferred is a hydrocarbon group having 1 to 9 carbon atoms, and particularly preferred is a phenyl group.

  The siloxane compound preferably contains a cyclic polysiloxane compound. It is considered that the cyclic polysiloxane compound has a high affinity with cyclopentane having the same cyclic skeleton. However, when the cyclic polysiloxane compound is used, the initial heat insulation performance in a low temperature environment (for example, 10 ° C.) is further improved. Can be improved.

The molecular weight of the siloxane compound is preferably 200 or more and 41000 or less, more preferably 200 or more and 34000 or less, further preferably 200 or more and 27000 or less, and particularly preferably 200 or more and 19000 or less. 200 to 7600 is most preferable.
If the molecular weight is too large, the dispersibility of the siloxane compound in the foamable phenolic resin composition deteriorates due to an increase in viscosity. For this reason, it becomes difficult to make contact with cyclopentane in the bubbles of the obtained phenol resin foam, and the effect of improving the thermal conductivity is deteriorated. On the other hand, if the molecular weight is too small, the boiling point of the siloxane compound tends to be low, so that part of the vaporized siloxane compound increases the thermal conductivity. For these reasons, even if the molecular weight of the siloxane compound is too large or too small, the effect of improving the initial heat insulation performance tends to deteriorate, particularly in an environment at a relatively low temperature (for example, 10 ° C.).
In this embodiment, the “molecular weight” of the siloxane compound can be measured using the method described in the examples of the present specification.

  Here, the siloxane compound of the present embodiment can include, for example, the following siloxane compounds (I), (II), and (III). These may be used alone or in combination of two or more as long as the value of S as a siloxane compound is 0.6 or more.

式中、ｎは１以上５５０以下の整数であり、ｎの範囲は、好ましくは１以上４５０以下、より好ましくは１以上３５０以下、より一層好ましくは１以上２５０以下、更に好ましくは１以上１００以下、特に好ましくは１以上１０以下、最も好ましくは１以上９以下である。シロキサン化合物(I)は、繰り返し単位数が小さすぎると、沸点が低くなる傾向にあるため、一部の気化したシロキサン化合物(I)が熱伝導率を上昇させる。また、繰り返し単位数が大きすぎると、粘度の上昇により、発泡性フェノール樹脂組成物中におけるシロキサン化合物の分散性が悪化する。そのため、得られるフェノール樹脂発泡体の気泡内のシクロペンタンとの接触が困難となり、熱伝導率の改善効果が悪化する。これらの理由により、シロキサン化合物(I)の繰り返し単位数は、大きすぎても小さすぎても、特に比較的低温（例えば１０℃）の環境下における初期断熱性能の改善効果が悪化する傾向がある。
また式中、Ｒ^１、Ｒ^２はそれぞれ炭素数１以上６以下の置換基を表し、Ｒ^１、Ｒ^２はそれぞれ好ましくは炭素数１以上６以下の炭化水素基であり、より好ましくはメチル基である。これは、末端基が大きくなりすぎると、シロキサン化合物(I)とシクロペンタンとの親和性が低下し、気泡内の低温において液化したシクロペンタンの安定化能が低下するためである。
シロキサン化合物(I)の具体例としては、オクタメチルトリシロキサン、デカメチルテトラシロキサンが挙げられる。 <Siloxane compound (I)>
The siloxane compound (I) is a linear polysiloxane compound represented by the following formula.

In the formula, n is an integer of 1 to 550, and the range of n is preferably 1 to 450, more preferably 1 to 350, even more preferably 1 to 250, and still more preferably 1 to 100. Particularly preferably, it is 1 or more and 10 or less, and most preferably 1 or more and 9 or less. Since the boiling point of the siloxane compound (I) tends to be low when the number of repeating units is too small, a part of the vaporized siloxane compound (I) increases the thermal conductivity. On the other hand, if the number of repeating units is too large, the dispersibility of the siloxane compound in the foamable phenolic resin composition deteriorates due to an increase in viscosity. For this reason, it becomes difficult to make contact with cyclopentane in the bubbles of the obtained phenol resin foam, and the effect of improving the thermal conductivity is deteriorated. For these reasons, even if the number of repeating units of the siloxane compound (I) is too large or too small, the effect of improving the initial heat insulation performance tends to deteriorate, particularly in a relatively low temperature environment (for example, 10 ° C.). .
In the formula, each of R ¹ and R ² represents a substituent having 1 to 6 carbon atoms, and each of R ¹ and R ² is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a methyl group. It is. This is because if the terminal group becomes too large, the affinity between the siloxane compound (I) and cyclopentane decreases, and the ability to stabilize cyclopentane liquefied at low temperatures in the bubbles decreases.
Specific examples of the siloxane compound (I) include octamethyltrisiloxane and decamethyltetrasiloxane.

式中、ｍは０以上の整数を表し、ｎは１以上の整数を表す。なお、ｍの範囲は０以上３５０以下であることが好ましく、より好ましくは０以上２５０以下であり、さらに好ましくは０以上１５０以下であり、特に好ましくは０以上１００以下である。またｎの範囲は１以上２５０以下であることが好ましく、より好ましくは１以上１５０以下であり、さらに好ましくは１以上１００以下であり、特に好ましくは１以上２５以下である。なお式中、−Ｓｉ（ＣＨ_３）_２−Ｏ−の繰り返し単位が複数存在する場合（即ち、ｍが２以上の場合）、当該繰り返し単位同士は隣接して存在していてもよく、−Ｓｉ（Ｘ^１）（Ｘ^２）−Ｏ−の繰り返し単位を介して存在していてもよい。同様に、−Ｓｉ（Ｘ^１）（Ｘ^２）−Ｏ−の繰り返し単位が複数存在する場合（即ち、ｎが２以上の場合）、当該繰り返し単位同士は隣接して存在していてもよく、−Ｓｉ（ＣＨ_３）_２−Ｏ−の繰り返し単位を介して存在していてもよい。
そして、ｍおよびｎの合計（ｍ＋ｎ）の範囲は、１以上５５０以下であり、好ましくは１以上４５０以下、より好ましくは１以上３５０以下、更に好ましくは１以上２５０以下、特に好ましくは１以上１００以下、最も好ましくは１以上８０以下である。シロキサン化合物(II)は、繰り返し単位数が小さすぎると、沸点が低くなる傾向にあるため、一部の気化したシロキサン化合物(II)が熱伝導率を上昇させる。また、繰り返し単位数が大きすぎると、粘度の上昇により、発泡性フェノール樹脂組成物中におけるシロキサン化合物の分散性が悪化する。そのため、得られるフェノール樹脂発泡体の気泡内のシクロペンタンとの接触が困難となり、熱伝導率の改善効果が悪化する。これらの理由により、シロキサン化合物(II)の繰り返し単位数は、大きすぎても小さすぎても、特に比較的低温（例えば１０℃）の環境下における初期断熱性能の改善効果が悪化する傾向がある。
なお、ｍはｎの１．１倍以上であることが好ましく、１．５倍以上であることがより好ましく、２倍以上であることがさらに好ましく、３倍以上であることが特に好ましい。ｍがｎの１．１倍以上であると、シロキサン化合物(II)とシクロペンタンの親和性が確保されて、低温（例えば１０℃）の環境下での初期断熱性能を更に向上させることができる。
また式中、Ｘ^１ _、Ｘ^２はそれぞれ水素原子、又は炭素数１以上６以下の置換基（ｎが２以上でＸ^１が複数存在する場合、複数のＸ^１はそれぞれ同一でも異なっていてもよく、ｎが２以上でＸ^２が複数存在する場合、複数のＸ^２はそれぞれ同一でも異なっていてもよい。但し、同一のＳｉに結合したＸ^１およびＸ^２が何れもメチル基である場合は除く）を表し、Ｘ^１ _、Ｘ^２はそれぞれ好ましくは水素原子または炭素数１以上６以下の炭化水素基であり、より好ましくは水素原子またはフェニル基である。これは、側鎖の置換基が大きくなりすぎると、シロキサン化合物(II)とシクロペンタンとの親和性が低下し、気泡内の低温において液化したシクロペンタンの安定化能が低下するためである。
そして式中、Ｒ^１、Ｒ^２はそれぞれ炭素数１以上６以下の置換基を表し、Ｒ^１、Ｒ^２はそれぞれ好ましくは炭素数１以上６以下の炭化水素基であり、より好ましくはメチル基である。これは、末端基が大きくなりすぎると、シロキサン化合物(II)とシクロペンタンとの親和性が低下し、気泡内の低温において液化したシクロペンタンの安定化能が低下するためである。
シロキサン化合物(II)の具体例としては、メチルハイドロジェンポリシロキサンが挙げられる。 <Siloxane compound (II)>
The siloxane compound (II) is a linear polysiloxane compound represented by the following formula.

In the formula, m represents an integer of 0 or more, and n represents an integer of 1 or more. The range of m is preferably 0 or more and 350 or less, more preferably 0 or more and 250 or less, still more preferably 0 or more and 150 or less, and particularly preferably 0 or more and 100 or less. The range of n is preferably 1 or more and 250 or less, more preferably 1 or more and 150 or less, still more preferably 1 or more and 100 or less, and particularly preferably 1 or more and 25 or less. In the formula, when a plurality of repeating units of —Si (CH ₃ ) ₂ —O— are present (that is, when m is 2 or more), the repeating units may be adjacent to each other, and —Si It may exist via a repeating unit of (X ¹ ) (X ² ) —O—. Similarly, when a plurality of repeating units of —Si (X ¹ ) (X ² ) —O— are present (that is, when n is 2 or more), the repeating units may be adjacent to each other, It may exist through a repeating unit of —Si (CH ₃ ) ₂ —O—.
The range of the sum (m + n) of m and n is 1 or more and 550 or less, preferably 1 or more and 450 or less, more preferably 1 or more and 350 or less, still more preferably 1 or more and 250 or less, and particularly preferably 1 or more and 100 or less. Hereinafter, it is most preferably 1 or more and 80 or less. Since the boiling point of the siloxane compound (II) tends to be low when the number of repeating units is too small, a part of the vaporized siloxane compound (II) increases the thermal conductivity. On the other hand, if the number of repeating units is too large, the dispersibility of the siloxane compound in the foamable phenolic resin composition deteriorates due to an increase in viscosity. For this reason, it becomes difficult to make contact with cyclopentane in the bubbles of the obtained phenol resin foam, and the effect of improving the thermal conductivity is deteriorated. For these reasons, even if the number of repeating units of the siloxane compound (II) is too large or too small, the effect of improving the initial thermal insulation performance tends to deteriorate, particularly in a relatively low temperature environment (for example, 10 ° C.). .
In addition, m is preferably 1.1 times or more of n, more preferably 1.5 times or more, further preferably 2 times or more, and particularly preferably 3 times or more. When m is 1.1 times or more than n, the affinity between the siloxane compound (II) and cyclopentane is ensured, and the initial heat insulation performance in a low temperature (eg, 10 ° C.) environment can be further improved. .
Also in the formula, X _^1, X ² are each a hydrogen atom, or C 1 to 6 substituents carbon (n is X ¹ in two or more there are a plurality, be different in each of the plurality of X ¹ are the same well, when n X ² by 2 or more there are a plurality, each of the plurality of X ² may be the same or different. However, when X ¹ and X ² bonded to the same Si are both methyl X ¹ _and X ² are each preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a phenyl group. This is because if the substituent on the side chain becomes too large, the affinity between the siloxane compound (II) and cyclopentane decreases, and the ability to stabilize cyclopentane liquefied at low temperatures in the bubbles decreases.
In the formula, R ¹ and R ² each represent a substituent having 1 to 6 carbon atoms, and R ¹ and R ² are each preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a methyl group. It is. This is because if the terminal group becomes too large, the affinity between the siloxane compound (II) and cyclopentane decreases, and the ability to stabilize cyclopentane liquefied at low temperatures in the bubbles decreases.
Specific examples of the siloxane compound (II) include methyl hydrogen polysiloxane.

式中、ｎは４以上２０以下の整数を表す。 <Siloxane compound (III)>
The siloxane compound (III) is a cyclic polysiloxane compound represented by the following formula.

In the formula, n represents an integer of 4 or more and 20 or less.

Here, the cyclic polysiloxane compound may be contained in a silicone oil marketed as a linear polysiloxane compound. And as a cyclic polysiloxane compound contained in such a commercially available silicone oil, the number of repeating units (equivalent to the value of n in the said Formula (III)) is 30 using MALDI-TOF / MS measurement etc., for example. Such multimers have been confirmed. Such a multimer having a large number of repeating units also has an effect of improving the initial heat insulating performance, particularly in a relatively low temperature (for example, 10 ° C.) environment, like the linear polysiloxane compound. However, in particular, when only a cyclic polysiloxane compound is used as the siloxane compound, in consideration of the affinity between the cyclic polysiloxane compound and cyclopentane, the number of repeating units is 4 to 20 as described above. It is preferably 4 or more and 6 or less. In addition, since the cyclic polysiloxane compound (hexamethylcyclotrisiloxane) having 3 repeating units is solid at room temperature, the dispersibility in the foamable phenol resin composition is low. Therefore, contact with the cyclopentane in the bubbles of the resulting phenol resin foam becomes insufficient. Therefore, if the siloxane compound (III) having 4 or more repeating units is used, the effect of improving the thermal conductivity can be sufficiently ensured.
Specific examples of the siloxane compound (III) include octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

  Of the above-described siloxane compounds (I) to (III), the siloxane compound (I) and the siloxane compound (III) are preferable. These two are considered to be because the dimethylsiloxane unit in the siloxane structure is likely to come into contact with cyclopentane, but the initial thermal insulation performance in a low temperature (for example, 10 ° C.) environment can be easily improved. Of these two, the siloxane compound (III) is more preferable. The siloxane compound (III) is a cyclic polysiloxane compound, which is thought to be due to its high affinity with cyclopentane having the same cyclic skeleton, but further improves the initial thermal insulation performance in a low temperature environment (for example, 10 ° C.). Can be improved easily.

Moreover, in the phenol resin foam of this embodiment, even if there is too much or too little content of a siloxane compound, there exists a tendency for various characteristics, such as initial heat insulation performance (10 degreeC-40 degreeC), to deteriorate. Specifically, when the amount of the siloxane compound relative to the cyclopentane content in the foam is insufficient, the effect of improving the initial heat insulation performance under a relatively low temperature (for example, 10 ° C.) environment cannot be sufficiently obtained, and When the amount of the siloxane compound relative to the cyclopentane content in the body is excessive, the closed cell ratio tends to be poor, the long-term heat insulation performance tends to deteriorate, and the initial heat insulation performance (10 ° C. to 40 ° C.) deteriorates, High flame retardancy, which is an excellent characteristic of the phenol resin foam, tends to deteriorate.
Therefore, when the phenol resin foam is crushed and extracted in chloroform, the siloxane compound extracted in chloroform is extracted per space volume of 22.4 × 10 ⁻³ m ^{3 in} the phenol resin foam. A value Y / X (unit: g / mol) obtained by dividing the amount Y (unit: g) by the cyclopentane content X (unit: mol) per space volume of 22.4 × 10 ⁻³ m ³ in the phenol resin foam. ) Is preferably 0.38 or more and 115 or less, more preferably 0.76 or more and 76 or less.
The “extraction amount Y” means that the phenol resin foam is pulverized in chloroform so that the volume average particle size of primary particles is 30 μm or less and the extraction treatment described in the examples of the present specification is performed. The amount of siloxane compound extracted in chloroform.

In the phenol resin foam of the present embodiment, the amount of the siloxane compound contained in the foam preferably satisfies the following conditions in relation to the cyclopentane content in the foam.
That is, in the phenol resin foam of the present embodiment, the extraction amount Y (unit: g) described above is equal to or less than the coefficient a calculated by the following formula (2), and the coefficient b calculated by the following formula (3). It is preferable to be within the range.
a = -39.9X + 56.7 (2)
b = 0.056X (3)
The formula (2), in (3), X is a phenolic resin foamed body volume volume 22.4 × ¹⁰ -3 ^{m 3} per cyclopentane content X (unit: mol) refers to.

  In the phenol resin foam of this embodiment, when the extraction amount Y of the siloxane compound is less than the coefficient b, the amount of the siloxane compound relative to the cyclopentane content in the foam is insufficient, and the initial heat insulation performance at 10 ° C. and 23 ° C. When the extraction amount Y of the siloxane compound exceeds the coefficient a, the amount of the siloxane compound becomes excessive, the closed cell ratio tends to deteriorate, the long-term heat insulation performance tends to deteriorate, and the phenol resin foaming High flame retardancy, which is an excellent characteristic of the body, tends to decrease.

And when the phenol resin foam of this embodiment contains the 3 or 4 carbon fluorohydroolefin mentioned above, the quantity of the siloxane compound contained in a foam is 3 or the carbon number in a foam. It is preferable that the following conditions are satisfied in relation to the 4 hydrofluorofluoroolefin content.
That is, in the phenol resin foam of the present embodiment, it is preferable that the extraction amount Y (unit: g) described above is in the range of the coefficient c or less calculated by the following formula (6).
c = -39.2Z + 30.0 (6)
In the above formula (6), Z indicates the content of hydrofluorofluoroolefin (unit: mol) having 3 or 4 carbon atoms per space volume of 22.4 × 10 ⁻³ m ^{3 in} the phenol resin foam.

  In the phenol resin foam of this embodiment, when the extraction amount Y of the siloxane compound exceeds the coefficient c, the amount of the siloxane compound becomes excessive, the closed cell ratio tends to deteriorate, and the long-term heat insulation performance tends to be lowered.

In addition, from the viewpoint of suppressing long-term heat insulation performance and flame retardancy, the amount of siloxane compound extraction Y is preferably equal to or less than the coefficient a ′ calculated by the following formula (7). It is further preferable that the coefficient a ″ is less than or equal to the coefficient a ″ calculated by the formula (9). Further, from the viewpoint of improving the initial heat insulation performance at 10 ° C. and 23 ° C., the extraction amount Y of the siloxane compound is b ′ or more, preferably a coefficient b ″ or more calculated by the following formula (10), more preferably b ″ ′ or more calculated by the following formula (11), Most preferably, it is not less than b ″ ″ calculated by the formula (12). Furthermore, from the viewpoint of long-term heat insulation performance, the extraction amount Y of the siloxane compound is not more than the coefficient c ′ calculated by the following formula (13). More preferably, the following formula It is particularly preferred is calculated at the coefficient c "or less at 14).
a ′ = − 23.2X + 30.6 (7)
a ″ = − 11.1X + 16.9 (8)
b ′ = 0.27X (9)
b ″ = 0.55X (10)
b ″ ′ = 0.70X + 0.05 (11)
b ″ ″ = 1.01X + 0.19 (12)
c ′ = − 19.6Z + 15.0 (13)
c ″ = − 12.3Z + 9.02 (14)

(Properties of phenol resin foam)
The phenol resin foam in the present embodiment preferably has a thermal conductivity in a 10 ° C. environment described later and a thermal conductivity in a 23 ° C. environment of 0.220 W / m · K or less. The thermal conductivity in the environment and the thermal conductivity in a 23 ° C. environment are more preferably 0.0210 W / m · K or less, still more preferably 0.0200 W / m · K or less, and 0.0190 W / m. It is particularly preferably K or less, and most preferably 0.0185 W / m · K or less. In addition, in the phenol resin foam using cyclopentane, the thermal conductivity at a low temperature may be increased due to the above-mentioned liquefaction of cyclopentane, but the cyclopentane, the siloxane compound, and optionally the carbon number. In the phenol resin foam in this embodiment containing 3 or 4 hydrofluoroolefin and a hydrocarbon having a boiling point of −50 ° C. or more and 5 ° C. or less, the thermal conductivity in an environment of 10 ° C. can be lowered. 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.
In addition, in the phenol resin foam in this embodiment, the thermal conductivity in a 40 degreeC environment can also be made low. The thermal conductivity in a 40 ° C. environment is preferably 0.0240 W / m · K or less, more preferably 0.0230 W / m · K or less, and 0.0220 W / m · K or less. Is more preferable.

  Here, the value obtained by subtracting the thermal conductivity in the environment of 10 ° C. from the thermal conductivity in the environment of 40 ° C. of the phenol resin foam in the present embodiment is 0 W / m · K or more, preferably 0.8. 0010 W / m · K or more, more preferably 0.0020 W / m · K or more, still more preferably 0.0030 W / m · K or more, particularly preferably 0.0035 W / m · K or more, and most preferably 0.0040 W / m m · K or more. If the difference between the thermal conductivity in the environment of 40 ° C. and the thermal conductivity in the environment of 10 ° C. is within the above range, the initial thermal conductivity is hardly affected by the temperature, and the phenol resin foam has a wide temperature range. It can be said that stable initial thermal conductivity can be exhibited in the range. The upper limit is not particularly limited, but is preferably 0.010 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 0.0050 W / m · K or less, more preferably 0.0020 W / m · K or less, still more preferably 0.0015 W / m · K or less, particularly preferably 0.0010 W / m. -K or less, most preferably 0.0005 W / mK.
A phenol resin foam having such a thermal conductivity is preferable because it exhibits excellent heat insulation performance in a wide temperature range and maintains excellent heat insulation performance for a long period of time.

  Moreover, since the closed cell ratio of the phenol resin foam in the present embodiment tends to cause deterioration of 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 tends to deteriorate and the heat insulation performance tends to deteriorate over time, and if it is too large, the initial heat insulation performance tends to deteriorate. For this reason, the average bubble diameter is preferably 40 μm or more and 300 μm or less, more preferably 50 μm or more and 170 μm or less, and still more 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 deteriorate over time. For this reason, the void area ratio is preferably 1.0% or less, more preferably 0.5% or less, still more preferably 0.3% or less, particularly preferably 0.2% or less, and most preferably 0.1% or less. It is. 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 the 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 from 0.1% by weight to 40% by weight, more preferably from 0.5% by weight to 20% by weight, and particularly preferably from 1% by weight to 10% by weight. 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, While there exists a tendency for heat insulation performance to improve, it can prevent that the flame retardance of a phenol resin foam deteriorates by using a siloxane compound, Furthermore, the flame retardance of a phenol resin foam improves. 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 deterioration 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 flame retardant having a decomposition temperature of 150 ° C. or higher and hardly soluble in water 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. -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 deteriorate over 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 deteriorate 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, when the amount of the organic fine powder contained is too large, the heat insulation performance tends to deteriorate over 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, the heat insulation performance tends to deteriorate over 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 be calculated | required 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.

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 0.5% relative to the phenol resin foam. It is preferably at most mass%, more preferably at most 0.1 mass%, particularly preferably at most 0.01 mass%.
Note that the compound having reactivity with the acid curing catalyst and the compound altered by the acid curing catalyst do not include a phenol resin, a compound having a phenol skeleton, an aldehyde, and a nitrogen-containing compound.

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. In this embodiment, “viscosity of phenol resin at 40 ° C.” is a rotational viscometer (manufactured by Toki Sangyo Co., Ltd., R-100 type, rotor part is 3 ° × R-14), and at 40 ° C. Refers to the measured value after stabilization for 3 minutes.

  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 phenol resin foam of this embodiment includes a phenol resin, a surfactant, a siloxane compound, cyclopentane, and optionally a foaming agent containing a hydrofluoroolefin having 3 or 4 carbon atoms and a halogenated saturated hydrocarbon, and acid curing. It is obtained from a foamable phenolic resin composition containing a catalyst. The surfactant, siloxane compound and foaming agent may be added in advance to the phenol resin, 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 (except those corresponding to the above “siloxane compounds”), 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, it 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.
Moreover, although the siloxane compound mentioned above changes also with the usage-amount of cyclopentane and the usage-amount of the C3 or C4 hydrofluoroolefins used arbitrarily, it is preferably 0.1 with respect to 100 mass parts of phenol resins. 01 parts by mass or more and 15 parts by mass or less, more preferably 0.05 parts by mass or more and 10 parts by mass or less, further preferably 0.1 parts by mass or more and 5.0 parts by mass or less, particularly preferably 0.1 parts by mass or more. It is used at a ratio of 0 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. Moreover, when using the mixture of 60 mass% of paratoluenesulfonic acid monohydrate and 40 mass% of diethylene glycol, Preferably it is 3 to 30 mass parts with respect to 100 mass parts of phenol resins, More preferably, it is 5 It is used in a proportion of not less than 20 parts by mass.

  The phenol resin foam of this embodiment is a foaming phenol containing a phenol resin, a surfactant, a siloxane compound, cyclopentane, and optionally a hydrofluoroolefin having 3 or 4 carbon atoms, and an acid curing catalyst. Obtained from the resin composition. The surfactant, siloxane compound and foaming agent may be added in advance to the phenol resin, or may be added simultaneously with the acid curing catalyst. Here, it is preferable to add to a phenol resin in a state where a siloxane compound and a blowing agent containing cyclopentane and optionally a hydrofluoroolefin having 3 or 4 carbon atoms are mixed in advance. That is, in the method for producing a phenol resin foam of the present embodiment to be described later, before mixing the foamable phenol resin composition containing a phenol resin, a surfactant, a siloxane compound, a foaming agent, and an acid curing catalyst, It is preferable to mix a siloxane compound and a foaming agent in advance. By performing such premixing, it is assumed that the dispersion state of the foaming agent in the foamable phenolic resin composition and the distribution state of the foaming agent in the phenolic resin foam are improved. The heat insulation performance of the resin foam can be improved. Such premixing may be performed using the same mixer as that for mixing the foamable phenol resin composition, or may be performed using a different mixer.

(Method for producing phenolic resin foam)
The phenolic resin foam 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 pressure of the distributor of the mixer when discharging the foamable phenolic resin composition from the distributor of the mixer is too low, the tendency of increase in voids, deterioration of heat insulation performance and deterioration of long-term heat insulation performance If it is too high, equipment with high pressure resistance is required, equipment cost increases, and the homogeneity of the foam tends to deteriorate. Therefore, the pressure in the distribution part of the mixer is preferably 0.2 MPa or more and 10 MPa or less, more preferably 0.3 MPa or more and 5 MPa or less, further preferably 0.4 MPa or more and 3 MPa or less, and particularly preferably 0.5 MPa or more and 1.5 MPa or less. It is as follows. 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 the amount of moisture is too small, there is a concern that the foaming ratio will not increase and the initial heat insulation performance will deteriorate. 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 deteriorate. 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 these, the method using a double conveyor is preferable because the smoothness of the obtained plate-like foam is good. 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 deteriorated. There is a concern that long-term 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, still more preferably 70 ° C. or higher and 95 ° C. or lower, and particularly preferably 70 ° C. or higher and 90 ° C. or lower. Hereinafter, it is most preferably 70 ° C. or higher and 85 ° 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) C), the coefficient R calculated by the following formula (4) is a hydrocarbon having a carbon number of 6 or less per space volume of 22.4 × 10 ⁻³ m ³ (22.4 L) in the phenol resin foam if it is too large. Content (when hydrofluoroolefins having 3 or 4 carbon atoms are contained, the total content of hydrocarbons having 6 or less carbon atoms and hydrofluoroolefins having 3 or 4 carbon atoms) is reduced and, there is a fear that long-term thermal insulation performance is deteriorated, the number of carbon atoms in too small phenolic foam body volume volume ^{22.4 × 10 -3 m 3 (22.4L} ) of 6 or less hydrocarbons containing The amount (the sum of the content of hydrocarbons having 6 or less carbon atoms and the content of hydrofluoroolefins having 3 or 4 carbon atoms in the case of containing hydrofluoroolefins having 3 or 4 carbon atoms), There is a concern that the initial thermal insulation performance deteriorates. 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 (4)

  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.

(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 rectangular parallelepiped specimen having a width and length of about 25 mm and a thickness equal to the thickness of the foam is cut out from the foam and has a face material. A specimen having a uniform thickness obtained by slicing the upper and lower surfaces by about 1 mm each is used. The length of each side of the specimen was measured with a vernier 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 was used according to the method described in Method A of ASTM-D-2856-94 using an air-comparing hydrometer (Tokyo Science Co., Ltd., trade name “MODEL1000”). Was measured. Further, 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 part constituting the cell wall included in the specimen is expressed by the formula VS = sample weight (W) /1.3. Calculated. And the closed cell rate was computed by following formula (15).
Closed cell ratio (%) = [(V2−VS) / (V1−VA−VS)] × 100 (15)
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 an air comparison type hydrometer (Tokyo Science company, brand name The density of the solid-containing phenol resin obtained by measuring the volume using “MODEL 1000”) was used as the density of the solid phenol resin.

(4) Void area ratio A photograph or color copy of a 100 mm × 150 mm range of a cut cross section obtained by cutting almost the center in the thickness direction of the phenol resin foam sample parallel to the front and back surfaces was taken. In a photograph or copy drawing taken, the length of each length and width is twice the actual size, and the area is four times the actual area. A transparent graph paper was overlaid on the photograph or drawing, a large diameter bubble was selected, and the cross-sectional area of the bubble was measured using the grid of the graph paper. A hole in which a 1 mm × 1 mm square continuously exists over 8 squares was defined as a void, and the observed void area was integrated to calculate an area fraction. That is, since an enlarged copy is taken, these 8 squares correspond to an area of 2 mm ^{2 in} the actual foam cross section. Measurements were made 12 times on samples with the same production conditions, and the average value was taken as the representative value of the production condition samples.

(5) Thermal conductivity in 10 ° C. environment, 23 ° C. environment, and 40 ° C. environment In accordance with JIS-A-1412-2: 1999, thermal conductivity at 10 ° C., 23 ° C., and 40 ° C. by the following method. The rate was measured.
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. When the thermal conductivity measuring device is not placed in a room controlled at 23 ± 1 ° C. and humidity 50 ± 2% where the specimen was placed, the phenol resin foam was placed at 23 ± 1 ° C. and humidity 50 ±. The bag was immediately put in a polyethylene bag under a 2% atmosphere, and the bag was closed.
For thermal conductivity measurement, the face material is peeled off so as not to damage the foamed portion, the thermal conductivity in a 10 ° C. environment is a low temperature plate 0 ° C. high temperature plate 20 ° C., and the thermal conductivity in a 23 ° C. environment is a low temperature plate. 13 ° C high temperature plate 33 ° C, 40 ° C environment thermal conductivity is low temperature plate 30 ° C high temperature plate 50 ° C, each with one specimen and symmetrical configuration type measuring device (Eihiro Seiki Co., Ltd., trade name) "HC-074 / 600").

(6) Thermal conductivity after accelerated test With reference to EN13166, the thermal conductivity after the accelerated test below was measured assuming that 25 years had passed.
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 “(5) Thermal conductivity under 10 ° C. environment, 23 ° C. environment, and 40 ° C. environment”, the thermal conductivity under 10 ° C., 23 ° C., and 40 ° C. environment was measured. .

(7) 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 3 wt% to 7 wt% of phenol resin raw material. %, The water content in the dehydrated methanol was removed from the water content of the solution, and the water content of the phenol resin raw material was determined. The moisture content of the phenol resin raw material was calculated from the measured moisture content. A Karl Fischer moisture meter (manufactured by Kyoto Electronics Co., Ltd., MKC-510) was used for the measurement. For measurement of the water content, HYDRANAL-Composite 5K manufactured by Sigma-Aldrich was used as a Karl Fischer reagent, and HAYASHI-Solvent CE dehydrated solvent (for ketones) manufactured by Hayashi Pure Chemical Industries was used for Karl Fischer titration. Further, Aquamicron standard water / methanol (water content 2 mg) manufactured by Mitsubishi Chemical was used for titer measurement of Karl Fischer reagent. The water content was measured using Method 1 set in the apparatus, and the Karl Fischer reagent titer was determined using Method 5. The ratio of the obtained water content to the mass of the phenol resin raw material was determined, and this was used as the water content of the phenol resin raw material.
(B) Moisture content in the phenolic resin foam The moisture content in the phenolic resin foam was determined by using a Karl Fischer moisture meter having a boat-type moisture vaporizer and vaporized by heating to 110 ° C with the 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.

(8) 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 was 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.

(9) The content of hydrocarbons having 6 or less carbon atoms in the foam, the content of hydrofluoroolefins having 3 or 4 carbon atoms, and the content of halogenated saturated hydrocarbons About 100 mm of phenol resin foam sample Cut into corners, prepare 6 specimens, and prepare 6 bags with heat-resistant zipper that can be sealed (hereinafter abbreviated as “bag with chuck”), and weigh each bag with a precision balance. It was measured. Place the specimen in a circulating oven controlled at 70 ° C for 24 ± 0.5 hours, disperse the contained water, immediately place it in a separate zippered bag, seal it, and cool it to room temperature. . After cooling to room temperature, remove the specimen from each zippered bag, quickly peel off the specimen surface material, measure the weight (W1) of each specimen with a precision balance, and calibrate the length of each side. The volume (V) of the specimen was calculated. Then, return each specimen to each zippered bag, seal it again leaving a part of the opening, put it between the surfaces of the hydraulic press at room temperature, and gradually compress it to a pressure of about 200 N / cm ² with the hydraulic press. Then, the bubbles of the specimen were destroyed. For the three specimens, a sample of a part of the specimen was collected, and the water content (WS1) contained was measured by the method for measuring the water content in the phenol resin foam. Subsequently, after putting the sample-filled zipper bag with some openings left in a circulating oven controlled at 81 ° C. for 30 ± 5 minutes, immediately preventing the powder from coming out of the bag. Exhaust the gas in the bag, seal the bag, and cool to room temperature. After cooling to room temperature, the weight of the bag with the sample containing the specimen not subjected to the moisture content (WS1) measurement is measured with a precision balance, and the weight of the bag with the chuck is subtracted to remove the volatile component (W2). Was measured. At the same time, a portion of the sample was taken from the bag of the three specimens whose moisture content (WS1) was measured as described above, and the moisture after being placed in a circulating oven temperature-controlled at 81 ° C. for 30 ± 5 minutes. The quantity (WS2) was measured.
Next, the difference in water content (WS1-WS2) is subtracted from the difference between W1 and W2 (W1-W2), and the solid phenol resin density is set to 1.3 g / cm ³ from the volume (V) of the specimen. The volume obtained by subtracting the calculated resin volume from W2 (space volume in the foam) and the air buoyancy weight (WF) calculated by the air density (0.00119 g / mL) are added to obtain the volatile component weight (W3). Asked. That is, W3 was calculated by the following formula (16).
W3 = (W1-W2)-(WS1-WS2) + WF (16)
In W3, the proportion of hydrocarbon components having 6 or less carbon atoms measured by the above measurement method (8), the proportion of hydrocarbon components having 3 or 4 carbon atoms, and halogenated saturated hydrocarbons. The respective content weights (W4, W4 ′, W4 ″) were calculated by multiplying the ratios in the gas components. 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 is an air comparison type hydrometer (Tokyo Science company, brand name) The density of the solid-containing phenol resin obtained by measuring the volume using “MODEL 1000”) was used as the solid phenol resin density.
The content of hydrocarbons having 6 or less carbon atoms, the content of hydrofluoroolefins having 3 or 4 carbon atoms, and the content of halogenated saturated hydrocarbons (mol / 22.4 × 10 ⁻³ m ³ ) is the measured amount and molecular weight of each substance measured by the above W4, W4 ′, W4 ″ and the above measuring method (8) in the space volume of 22.4 × 10 ⁻³ m ³ in the foam. Calculated by Similarly, the content of cyclopentane (mol / 22.4 × 10 ⁻³ m ³ ) in the foam was also calculated.

(10) Content of siloxane compound in foam (extraction amount Y)
(I) Extraction treatment of pulverized product in chloroform 0.5 g of a phenolic resin foam sample cut and divided into about 5 mm square not containing a face material and 30 g of chloroform (for Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) The mixture was mixed and the siloxane compound in the foam was extracted into chloroform while the foam was pulverized by the following procedure.
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.
First, in this treatment, the following operation was performed in order to make the cut and divided phenol resin foam conform to chloroform and perform preliminary pulverization. In other words, in a cylindrical glass container that can be sealed with a screw-type lid with an internal volume of about 100 ml, an IKA ULTRA-TURRAX (registered trademark) tube drive control dedicated member BMT-50-G (ball mill type crushing tube and glass ball) (Set of about 6 mm diameter) 25 glass balls, 0.5 g of phenol resin foam sample cut and divided into about 5 mm square, and 30 g of chloroform (for Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) After closing the lid and sealing the cylindrical glass container, hold the container in the hand so that the cylinder is in the horizontal direction, and in the longitudinal direction of the cylinder, the swing width is 20 ± 5 cm, the swing speed is 80 ± 20 times / The container was shaken at a rate of 5 minutes for 5 ± 0.5 minutes. Note that the shaking and pulverizing operation is performed once in one round trip.
Subsequently, the entire contents of the cylindrical glass container (preliminarily crushed foam, chloroform, and glass balls) were transferred to a ball mill type crushing tube of BMT-50-G, and the crushing tube was sealed. did. The crushing tube containing the contents was set in ULTRA-TURRAX (registered trademark) Tube Drive control manufactured by IKA, and the cycle of crushing treatment at 5700 rpm for 30 seconds and crushing treatment for 30 ± 5 seconds was repeated 5 times. The cylindrical glass container that had been emptied of the contents was quickly closed after the contents were taken out, and left in an atmosphere of about 23 ° C.
After crushing, transfer the entire contents in the crushing tube (crushed foam, chloroform, and glass balls) to a sealed cylindrical glass container after use, and keep it in an atmosphere of about 23 ° C. for 5 ± 0.2 minutes. Left at rest. The cylindrical glass container containing the contents was shaken 10 times by hand at a shaking speed of 80 ± 20 times / minute. Immediately after that, the entire contents in the cylindrical glass container were filtered using a hydrophobic PTFE membrane filter (ADVANTEC T050A047A) having a pore diameter of 0.5 μm, the phenol resin foam and the glass balls were removed, and the filtrate ( Chloroform extract) was obtained.
The above operation was advanced promptly so that the total contact time of the foam and chloroform in the extraction process was within the range of 16 ± 1.5 minutes. In addition, the reference | standard of the grinding | pulverization state of the foam in this process should just grind | pulverize so that the volume average particle diameter of the primary particle of a foam may be 30 micrometers or less.
A part of the filtrate was dried on a ZnSe crystal plate for infrared spectroscopic analysis (Pieroptics), and analyzed by infrared spectroscopic analysis whether impurities other than the siloxane compound were contained in chloroform. Examples of the infrared spectroscopic device and the number of integration include an infrared spectroscopic device Spectrum One (Perkin Elmer), and the number of integration four times.
Infrared spectroscopic analysis confirms the absence of methanol-soluble impurities such as phenol resin oligomer components that can adversely affect the qualitative and quantitative determination of siloxane compounds. And quantified.
On the other hand, in this extraction process, if the oligomer component contained in the phenolic resin is detected from the filtrate by infrared spectroscopic analysis and there may be impurities that affect the qualitative and quantitative determination of the siloxane compound, The following pretreatment was performed before the treatment.
(Ii) Example of pretreatment 0.5 g of phenol resin foam sample cut and divided into approximately 5 mm squares, 10 ml of distilled water (for Kanto Chemical Co., Ltd., for high performance liquid chromatography) and methanol (Kanto Chemical Co., Ltd.) , For high performance liquid chromatography) was mixed, and the hydrophilic component contained in the phenol resin foam was removed while the foam was pulverized by the following procedure. In this pretreatment, the equipment to be used and the method of collecting the phenol resin foam sample are the same as in the extraction process (i) above.
In a ball mill type crushing tube, 25 glass balls of BMT-50-G, 0.5 g of phenol resin foam sample cut and divided into about 5 mm square, 10 ml of distilled water (for Kanto Chemical Co., Inc., for high performance liquid chromatography), and 10 ml of methanol (Kanto Chemical Co., Inc., for high performance liquid chromatography) was added, and the pulverization tube was sealed. The above pulverized tube containing the contents was set in ULTRA-TURRAX (registered trademark) Tube Drive control manufactured by IKA and pulverized at 5800 rpm for 10 minutes. Subsequently, the entire content (crushed foam, glass ball, distilled water and methanol mixed solution) in the above pulverization tube was allowed to stand in an airtight container in an atmosphere of about 23 ° C. for 24 ± 0.5 hours. .
Thereafter, the glass balls removed from the above contents were centrifuged at 15000 rpm for 30 minutes using a centrifuge, and the solid matter was subjected to a hydrophilic treatment with a pore size of 0.5 μm (ADVANTEC H050A047A). And filtered to separate a solid. The solid matter remaining in the centrifuge tube in this treatment was washed out several times with 20 ml of methanol (Kanto Chemical Co., Inc., for high performance liquid chromatography) and subjected to filtration.
The total amount of the solid matter after filtration was subjected to the extraction treatment in chloroform described above (i).
(Iii) Separation by purification If impurities that affect the qualification and quantification of the siloxane compound are present even after the pretreatment in (ii) above, purification is performed by a purification method that can remove impurities such as liquid chromatography. Went. In addition, when the amount of siloxane compound is reduced due to purification loss, etc. during purification, a standard substance (siloxane compound) having a structure close to that of siloxane compound contained in chloroform (extract) is chloroform (Wako Pure Chemical Industries). The same purification treatment was performed, and the purification loss rate was calculated and corrected.
In this stage, “there is an impurity that adversely affects the qualitative and quantitative determination of the siloxane compound” means that there are a large number of impurities having peaks that cannot be distinguished from the peaks derived from the siloxane compound when the NMR and GPC measurements described below are performed. In the case where the peak position is different or the abundance ratio of impurities can be calculated from the peak intensity or the like, qualitative and quantitative determination is possible even if impurities are included. In this case, for example, peaks were distinguished from each other because the abundance ratio before and after extraction of the siloxane compound and impurities was changed, and the abundance ratio was calculated by assigning the peak derived from the siloxane compound.
(Iv) Calculation of extraction amount Y From the extraction weight of the siloxane compound per weight of the foam and the density of the foam, the extraction amount Y of the siloxane compound per space volume 22.4 × 10 ⁻³ m ^{3 in the} foam (unit: g) was calculated.
In calculating the extraction amount Y, the solid phenol resin density is usually 1.3 g / cm ³ , but the phenol resin foam containing a solid material such as an inorganic substance having a density different from that of the phenol resin, separately, The density of the solid-containing phenol resin obtained by pulverizing to a state not including a closed space, measuring the weight, and measuring the volume using an air comparison type hydrometer (Tokyo Science Co., Ltd., trade name “MODEL1000”), Used as the density of solid phenolic resin.

(11) Value of S of Siloxane Compound A siloxane compound was extracted with chloroform from 0.5 g of the phenol resin foam in the same procedure as (10) above. The resulting filtrate from _{A m} and _{B m} (Unit: mmol) (chloroform extracts siloxane compound) to identify the value of the following formula (1):
S = A _m / (A _m + B _m ) (1)
The value of S was calculated.
Here, the value of _{A m} and _{B m} were identified by NMR as follows.
(I-1) NMR (Nuclear Magnetic Resonance Spectrum) Measurement The terminal or side chain substituent of the siloxane compound can be identified from the chemical shift or coupling of the peak derived from the substituent. Also, the abundance ratio and abundance of each substituent in the siloxane compound can be obtained from the peak derived from the substituent of the terminal or side chain, the methyl group or ethyl group on the Si atom, and the integration ratio of the added standard substance. it can.
(I-2) NMR measurement example All or part of a sample (dry sample, mass W _d g) obtained by blowing nitrogen to the obtained filtrate (chloroform extract of siloxane compound) and drying it, It was dissolved in 0.6 mL CDCl ₃ containing DMSO (110 ppm) as an internal standard substance, and NMR measurement was performed under the following measurement conditions.
Measuring device: ECS400 manufactured by JEOL RESONANCE
Observation nucleus: 1H
Integration count: 256 times Solvent: CDCl ₃
Internal standard substance: DMSO (110ppm)
Chemical shift standard: CHCl ₃ (7.26ppm)
Peaks were assigned to the obtained spectra from chemical shift simulations and spectral data of known siloxane compounds. In particular, in the case of a siloxane compound which is a partially substituted structure of a dimethylsiloxane polymer, a proton peak derived from the methyl group of —O—Si (CH ₃ ) ₂ — in the main chain skeleton and a side chain or terminal substituent The abundance ratio of the substituent was determined by the integration ratio. Furthermore, the integration ratio (area ratio) between these substituent peaks and DMSO peaks of known concentrations used as internal standard substances was determined. The concentration of structure A and the concentration of structure B were determined from this integration ratio, and the number of structures A (A ′ mmol) and the number of B (B ′ mmol) in the above-mentioned dry sample were calculated. Next, from A ′ and B ′ and the following formula using the extraction amount Y of the siloxane compound per space volume 22.4 × 10 ⁻³ m ^{3 in the} foam obtained in the above (10), The values of A _m and B _m were determined.
A _m = A ′ × Y / W _d (17)
B _m = B ′ × Y / W _d (18)
(12) Molecular Weight of Siloxane Compound Using the filtrate (chloroform extract of siloxane compound) obtained in the same manner as (11) above, the molecular weight of the siloxane compound was specified as follows.
(Ii-1) GPC (gel permeation chromatography) measurement First, the number average molecular weight of the siloxane compound was measured using GPC.
A sample obtained by blowing nitrogen to the obtained filtrate (chloroform extract) was dried and dissolved in THF, and GPC measurement was performed under the following conditions.
Data processing: Tosoh EcoSEC-WS
Equipment: Tosoh EcoSEC
Column: 1 TSKgel SuperHZM-M (4.6mmID x 15cm) +
1 TSKgel SuperHZ2000 (4.6mmID × 15cm) Oven temperature: 40 ℃
Eluent: THF 0.35ml / min Sample volume: 20μl
Detector: RI
Calibration curve: polystyrene conversion The peak before the solvent peak at an elution time of about 10 minutes was divided for each peak, and the number average molecular weight was calculated.
When the obtained number average molecular weight was 1100 or more, the number average molecular weight was defined as the molecular weight of the siloxane compound. On the other hand, when the obtained number average molecular weight was less than 1100, the molecular weight was measured by GC / MS measurement described later, and the molecular weight obtained by GC / MS measurement was defined as the molecular weight of the siloxane compound.
(Ii-2) GC / MS (Gas Chromatography / Mass Spectrum) Measurement The obtained filtrate (chloroform extract of siloxane compound) was accurately adjusted to 10 mL, and GC / MS measurement was performed under the following conditions.
GC device: Agilent Technologies 7890
Column: DB-5MS (30m × 0.25mmφ) Film thickness 0.25μm
Column temperature: 40 ° C (5 minutes) → (10 ° C / minute temperature increase) → 320 ° C (5 minutes)
Column flow rate: 1 ml / min Inlet temperature: 320 ° C
Injection method: Split 1:10
Injection volume: 1μl
MS equipment: JEOL Q1000
Ionization: EI 70eV
Voltage: -1300V
Scan range: m / z = 10-800
Ion source: 250 ° C
Interface: 300 ℃
In addition, about 1% by mass of octamethyltrisiloxane / chloroform solution (0.1002g / 10mL) was prepared for quantification, and further diluted with chloroform appropriately to prepare standard solutions of 1μg / mL, 10μg / mL, and 100μg / mL. . This standard solution was subjected to GC / MS measurement under the same conditions as the sample solution.
Mass spectrum measurement was performed on each detected and separated peak component to identify the siloxane compound from the database and to specify the molecular weight. In addition, a calibration curve was created from the measurement results of the octamethyltrisiloxane sample, and the detected peak was quantitatively calculated using this calibration curve.

Example 1
The reactor was charged with 3500 kg of a 52% by weight aqueous formaldehyde solution 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 65 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.
The obtained reaction solution was dehydrated at 60 ° C. And when the moisture content of the reaction liquid after dehydration was measured, the moisture content was 3.7 mass%.
An ethylene oxide-propylene oxide block copolymer (manufactured by BASF, Pluronic F-127) was mixed in a proportion 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.

  1.0 part by mass of dimethylpolysiloxane (equivalent to siloxane compound (I), 10 ≦ n ≦ 550), 7.5 parts by mass of cyclopentane as a blowing agent, and xylenesulfone as an acid curing catalyst with respect to 100 parts by mass of phenol resin A 11 parts by mass of a mixture of 80% by mass of acid and 20% by mass of diethylene glycol are mixed, and the resulting foamable phenolic resin composition is supplied to a mixing head whose temperature is adjusted to 25 ° C., and moves through a multiport distribution pipe. Fed on. 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 introduction port for the phenol resin 1, the siloxane compound 2, and the foaming agent 3 in which a surfactant is added to the phenol resin on the upper side surface, and is located near the center of the stirring unit that the rotor d stirs. An inlet for the curing catalyst 4 is provided on the side surface. 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 42.5 ° C., and the pressure measured by this distributor pressure sensor was 0.71 MPa.

As the face material, a polyester nonwoven fabric (“Spunbond E05030” manufactured by Asahi Kasei Fibers Co., Ltd., weighing 30 g / m ² , thickness 0.15 mm) was used.
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 at 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 78 ° 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. The foamable phenolic resin composition coated with the upper and lower surface materials was molded into a plate shape by appropriately applying pressure from above and below through the surface material with a slat type double conveyor.
Then, the foam obtained in the above and having not been cured was heated in an oven at 110 ° C. for 2 hours to obtain a phenol resin foam having a thickness of 46.7 mm.

(Example 2)
For 100 parts by mass of phenol resin, instead of dimethylpolysiloxane, methylphenylpolysiloxane (corresponding to siloxane compound (II), m + n = about 10 (where m is 3 or more times n), and a multimer having dispersity, X ¹ and X ² are both phenyl groups, R ¹ and R ² are both methyl groups) 0.9 parts by mass, and the amount of cyclopentane as a blowing agent is 7.3 parts by mass, measured with a conveyor temperature sensor A phenol resin foam having a thickness of 47.9 mm was obtained in the same manner as in Example 1 except that the double conveyor temperature was changed to 81 ° C. The temperature measured by the distributor temperature sensor was 41.2 ° C., and the pressure measured by the distributor pressure sensor was 0.70 MPa.

(Example 3)
Except for the dehydration conditions of the reaction solution, except that the water content was 6.0% by mass, octamethyltrisiloxane (siloxane compound) was used instead of dimethylpolysiloxane with respect to 100 parts by mass of the phenol resin as in Example 1. (Equivalent to (I)) was 0.9 parts by mass, the amount of cyclopentane as a blowing agent was 7.1 parts by mass, and the double conveyor temperature measured by the conveyor temperature sensor was changed to 83 ° C. 1 to obtain a phenolic resin foam having a thickness of 52.1 mm. The temperature measured by the distributor temperature sensor was 41.4 ° C., and the pressure measured by the distributor pressure sensor was 0.65 MPa.

Example 4
Except for the dehydration conditions of the reaction solution, except that the water content was 6.0% by mass, octamethylcyclotetrasiloxane (siloxane) instead of dimethylpolysiloxane with respect to 100 parts by mass of the phenol resin as in Example 1. Corresponding to compound (III), n = 4) was 0.9 parts by mass, the amount of cyclopentane as a foaming agent was 6.0 parts by mass, and the double conveyor temperature measured by the conveyor temperature sensor was changed to 85 ° C. Except for the above, a phenol resin foam having a thickness of 50.7 mm was obtained in the same manner as in Example 3. The temperature measured by the distributor temperature sensor was 42.1 ° C., and the pressure measured by the distributor pressure sensor was 0.68 MPa.

(Example 5)
The amount of octamethylcyclotetrasiloxane (equivalent to siloxane compound (III), n = 4) is 0.5 parts by mass with respect to 100 parts by mass of the phenol resin, and a mixture of 62 mol% cyclopentane and 38 mol% isobutane as a blowing agent. A phenol resin foam with a thickness of 52.2 mm was obtained in the same manner as in Example 4 except that 5.4 parts by mass were used. The temperature measured by the distributor temperature sensor was 40.2 ° C., and the pressure measured by the distributor pressure sensor was 0.97 MPa.

(Example 6)
Except for the dehydration conditions of the reaction solution, except that the water content was 11.2% by mass, the equivalent of octamethylcyclotetrasiloxane (corresponding to the siloxane compound (III)) with respect to 100 parts by mass of the phenol resin as in Example 1. N = 4), 0.5 parts by mass, 4.1 parts by mass of a mixture of 85 mol% cyclopentane and 15 mol% isobutane as a blowing agent, and the double conveyor temperature measured by the conveyor temperature sensor to 99 ° C. A phenol resin foam having a thickness of 57.7 mm was obtained in the same manner as in Example 4 except that the change was made. The temperature measured by the distributor temperature sensor was 40.3 ° C., and the pressure measured by the distributor pressure sensor was 0.65 MPa.

(Example 7)
Except for the dehydration conditions of the reaction solution, except that the water content was 3.7% by mass, octamethylcyclotetrasiloxane (corresponding to the siloxane compound (III)) with respect to 100 parts by mass of the phenol resin as in Example 1. , N = 4) in an amount of 0.5 parts by mass, as a blowing agent, 51 mol% of cyclopentane, HFO1233zd (trans-1-chloro-3,3,3-trifluoropropene, manufactured by Honeywell, trade name Solstice (registered) (Trademark) LBA) (hereinafter referred to as HFO1233zd) 45 mol% and isobutane 4 mol% 9.8 parts by mass, except that the double conveyor temperature measured by the conveyor temperature sensor was changed to 77 ° C. Similarly, a phenolic resin foam having a thickness of 44.1 mm was obtained. The temperature measured by the distributor temperature sensor was 37.0 ° C., and the pressure measured by the distributor pressure sensor was 0.63 MPa.

(Example 8)
Except for the dehydration conditions of the reaction solution, except that the water content was 6.0% by mass, octamethylcyclotetrasiloxane (corresponding to the siloxane compound (III)) with respect to 100 parts by mass of the phenol resin as in Example 1. , N = 4) in an amount of 0.5 parts by mass, as a blowing agent, 76 mol% of cyclopentane, hydrofluoroolefin HFO1234ze ((E) -1,3,3,3-tetrafluoroprop-1-ene, Honeywell) (Trade name: Solstice (registered trademark) GBA or less, abbreviated as “HFO1234ze”) 10 mol% and isobutane 14 mol% in 4.3 parts by mass, and the double conveyor temperature measured by the conveyor temperature sensor is changed to 93 ° C. A phenol resin foam with a thickness of 53.8 mm was obtained in the same manner as in Example 4 except that. The temperature measured by the distributor temperature sensor was 40.5 ° C., and the pressure measured by the distributor pressure sensor was 0.66 MPa.

Example 9
The amount of octamethylcyclotetrasiloxane (corresponding to siloxane compound (III), n = 4) is 0.9 parts by mass with respect to 100 parts by mass of the phenol resin, and 94 mol% of cyclopentane and 6 mol% of isopropyl chloride are used as a blowing agent. A phenol resin foam with a thickness of 49.4 mm was obtained in the same manner as in Example 4 except that 5.9 parts by mass of the above mixture was used. The temperature measured by the distributor temperature sensor was 41.6 ° C., and the pressure measured by the distributor pressure sensor was 0.67 MPa.

(Example 10)
The amount of octamethylcyclotetrasiloxane (corresponding to siloxane compound (III), n = 4) is 0.5 parts by mass with respect to 100 parts by mass of the phenol resin, and 75 mol% of cyclopentane and 20 mol% of isopropyl chloride are used as blowing agents. And the phenol resin foam of thickness 50.5mm was obtained like Example 4 except having used 5.9 mass parts of mixtures of 5 mol% of isobutane. The temperature measured by the distributor temperature sensor was 39.5 ° C., and the pressure measured by the distributor pressure sensor was 0.65 MPa.

(Example 11)
The amount of octamethylcyclotetrasiloxane (corresponding to siloxane compound (III), n = 4) is 0.5 parts by mass with respect to 100 parts by mass of the phenol resin, and the foaming agent is 75 mol% cyclopentane, 10 mol% HFO1233zd, isopropyl. A phenol resin foam having a thickness of 51.4 mm was obtained in the same manner as in Example 4 except that 6.5 parts by mass of a mixture of 10 mol% of chloride and 5 mol% of isobutane was used. The temperature measured by the distributor temperature sensor was 39.9 ° C., and the pressure measured by the distributor pressure sensor was 0.67 MPa.

(Example 12)
The amount of decamethylcyclopentasiloxane (equivalent to siloxane compound (III), n = 5) is 3.1 parts by mass, and cyclopentane is 57 mol% as a blowing agent, based on 100 parts by mass of the phenol resin. A thickness of 53.8 mm was obtained in the same manner as in Example 1 except that 6.5 parts by mass of a mixture of 35 mol% of isopropyl chloride and 8 mol% of isobutane was used and the double conveyor temperature measured by the conveyor temperature sensor was changed to 93 ° C. A 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 0.67 MPa.

(Example 13)
The amount of octamethylcyclotetrasiloxane (corresponding to siloxane compound (III), n = 4) is 0.5 parts by mass with respect to 100 parts by mass of the phenol resin, and as a foaming agent, 80 mol% of cyclopentane, hydrofluoroolefin HFO 1336mzz. (Cis-1,1,1,4,4,4-hexafluoro-2-butene, manufactured by DuPont, trade name Formacel® 1100) 6.8 parts by mass of a mixture of 15 mol% and isobutane 5 mol% were used. A phenol resin foam having a thickness of 51.6 mm was obtained in the same manner as in Example 4 except that. The temperature measured by the distributor temperature sensor was 40.4 ° C., and the pressure measured by the distributor pressure sensor was 0.77 MPa.

(Example 14)
Except for the dehydration conditions of the reaction solution, except that the water content was 11.0% by mass, octamethylcyclotetrasiloxane (corresponding to the siloxane compound (III)) with respect to 100 parts by mass of the phenol resin as in Example 1. n = 4) was 0.02 parts by mass, and 4.5 parts by mass of a mixture of 85 mol% cyclopentane and 15 mol% isobutane was used as a foaming agent, and the double conveyor temperature measured by the conveyor temperature sensor was changed to 96 ° C. Except for the above, a phenol resin foam having a thickness of 57.7 mm was obtained in the same manner as in Example 4. The temperature measured by the distributor temperature sensor was 41.4 ° C., and the pressure measured by the distributor pressure sensor was 0.66 MPa.

(Example 15)
Except for the dehydrating conditions of the reaction solution, except that the water content was 9.3 mass%, octamethylcyclotetrasiloxane (corresponding to the siloxane compound (III)) was equivalent to 100 parts by mass of the phenol resin as in Example 1. A phenol resin foam having a thickness of 57.2 mm was obtained in the same manner as in Example 14 except that n = 4) was changed to 0.2 parts by mass. The temperature measured by the distributor temperature sensor was 41.1 ° C., and the pressure measured by the distributor pressure sensor was 0.69 MPa.

(Example 16)
Except for the dehydration conditions of the reaction solution, except that the water content was 10.0% by mass, 100 parts by mass of the phenol resin, which was the same as in Example 1, was equivalent to octamethylcyclotetrasiloxane (corresponding to siloxane compound (III), n = 4) A phenol resin foam having a thickness of 57.4 mm was obtained in the same manner as in Example 14 except that 0.3 part by mass was used. The temperature measured by the distributor temperature sensor was 41.2 ° C., and the pressure measured by the distributor pressure sensor was 0.68 MPa.

(Example 17)
With respect to 100 parts by mass of the phenol resin as in Example 1, 0.03 parts by mass of octamethylcyclotetrasiloxane (corresponding to siloxane compound (III), n = 4) is used instead of dimethylpolysiloxane, and the conveyor temperature. A phenol resin foam having a thickness of 47.4 mm was obtained in the same manner as in Example 1 except that the double conveyor temperature measured by the sensor was changed to 80 ° C. The temperature measured by the distributor temperature sensor was 43.0 ° C., and the pressure measured by the distributor pressure sensor was 0.72 MPa.

(Example 18)
Except for the dehydration conditions of the reaction solution, except that the water content was set to 4.0% by mass, 100 parts by mass of the phenol resin was the same as in Example 1, and octamethylcyclotetrasiloxane (equivalent to the siloxane compound (III), n = 4) was 0.3 parts by mass, and a phenol resin foam having a thickness of 48.6 mm was obtained in the same manner as in Example 17 except that the double conveyor temperature measured by the conveyor temperature sensor was changed to 82 ° C. 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.

(Example 19)
Except for the dehydration conditions of the reaction solution, except that the water content was 3.8% by mass, octamethylcyclotetrasiloxane (corresponding to siloxane compound (III), n = 4) was 0.5 parts by mass, and a phenol resin foam having a thickness of 47.3 mm was obtained in the same manner as in Example 17 except that the double conveyor temperature measured by the conveyor temperature sensor was changed to 81 ° C. The temperature measured by the distributor temperature sensor was 43.5 ° C., and the pressure measured by the distributor pressure sensor was 0.69 MPa.

(Example 20)
Except for the dehydration conditions of the reaction solution, except that the water content was 7.2% by mass, the octamethylcyclotetrasiloxane (siloxane compound) instead of octamethyltrisiloxane was used in the same manner as in Example 1 except for 100 parts by mass of the phenol resin. Corresponding to (III), n = 4) is 0.03 part by mass, and the double conveyor temperature measured by the conveyor temperature sensor is changed to 88 ° C. A resin foam was obtained. The temperature measured by the distributor temperature sensor was 42.8 ° C., and the pressure measured by the distributor pressure sensor was 0.66 MPa.

(Example 21)
Except for the dehydration conditions of the reaction solution, except that the water content was 5.3% by mass, 100 parts by mass of the phenol resin was the same as in Example 1, and octamethylcyclotetrasiloxane (corresponding to siloxane compound (III), n = 4) was set to 0.25 parts by mass, and a phenol resin foam having a thickness of 50.5 mm was obtained in the same manner as in Example 4 except that the double conveyor temperature measured by the conveyor temperature sensor was changed to 83 ° C. The temperature measured by the distributor temperature sensor was 42.5 ° C., and the pressure measured by the distributor pressure sensor was 0.70 MPa.

(Example 22)
Except for the dehydrating conditions of the reaction solution, except that the water content was 5.7% by mass, 100 parts by mass of the phenol resin was the same as in Example 1, and octamethylcyclotetrasiloxane (corresponding to the siloxane compound (III), n = 4) A phenol resin foam having a thickness of 51.6 mm was obtained in the same manner as in Example 4 except that 0.45 parts by mass was used. The temperature measured by the distributor temperature sensor was 42.6 ° C., and the pressure measured by the distributor pressure sensor was 0.68 MPa.

(Example 23)
Except for the dehydration conditions of the reaction solution, except that the water content was 10.3 mass%, 100 parts by mass of the phenol resin was the same as in Example 1, but instead of octamethylcyclotetrasiloxane, methylphenylpolysiloxane (siloxane compound) Corresponding to (II), m + n = about 15 (where m is at least 1.2 times n), X ¹ and X ² are both phenyl groups, and R ¹ and R ² are both methyl The phenolic resin foam having a thickness of 57.6 mm was obtained in the same manner as in Example 6 except that the base was 15 parts by mass and the double conveyor temperature measured by the conveyor temperature sensor was changed to 96 ° C. The temperature measured by the distributor temperature sensor was 40.3 ° C., and the pressure measured by the distributor pressure sensor was 0.68 MPa.

(Example 24)
Except for the dehydration conditions of the reaction solution, except that the water content was 11.1% by mass, 100 parts by mass of the phenol resin was the same as in Example 1, and methylphenylpolysiloxane (corresponding to the siloxane compound (II), m + n = A polymer having a dispersity of about 70 (where m is 3 times or more of n), X ¹ and X ² are all phenyl groups, and R ¹ and R ² are both methyl groups. Otherwise, a phenol resin foam with a thickness of 57.4 mm was obtained in the same manner as in Example 23. The temperature measured by the distributor temperature sensor was 40.1 ° C., and the pressure measured by the distributor pressure sensor was 0.64 MPa.

(Example 25)
The decamethylcyclopentasiloxane (siloxane compound) was replaced with methylphenylpolysiloxane with respect to 100 parts by mass of the phenolic resin as in Example 1 except that the dehydrating conditions of the reaction solution differed and the water content was 9.4% by mass. A phenol resin foam having a thickness of 57.0 mm was obtained in the same manner as in Example 23, except that the equivalent of (III) and n = 5) was 4.4 parts by mass. The temperature measured by the distributor temperature sensor was 40.7 ° C., and the pressure measured by the distributor pressure sensor was 0.69 MPa.

(Example 26)
For 100 parts by mass of the phenolic resin as in Example 1, instead of dimethylpolysiloxane, methylphenylpolysiloxane (equivalent to siloxane compound (II), m + n = about 350 (where m is at least twice n)) Multimers with dispersity, X ¹ and X ² are all phenyl groups, R ¹ and R ² are both methyl groups) and the double conveyor temperature measured by the conveyor temperature sensor is 82 ° C. A phenol resin foam having a thickness of 48.1 mm was obtained in the same manner as in Example 1 except that the change was made to. The temperature measured by the distributor temperature sensor was 43.3 ° C., and the pressure measured by the distributor pressure sensor was 0.73 MPa.

(Example 27)
Double measured by a conveyor temperature sensor with dimethylpolysiloxane (equivalent to siloxane compound (I), 10 ≦ n ≦ 550) being 3.1 parts by mass with respect to 100 parts by mass of the phenol resin as in Example 1. A phenol resin foam having a thickness of 47.1 mm was obtained in the same manner as in Example 1 except that the conveyor temperature was changed to 80 ° C. The temperature measured by the distributor temperature sensor was 43.1 ° C., and the pressure measured by the distributor pressure sensor was 0.74 MPa.

(Example 28)
Except for the dehydration conditions of the reaction solution, except that the water content was 4.4% by mass, 100 parts by mass of the phenol resin was the same as in Example 1, but instead of dimethylpolysiloxane, decamethylcyclopentasiloxane (siloxane compound ( A phenol resin foam having a thickness of 47.7 mm was obtained in the same manner as in Example 1 except that it was equivalent to III) and n = 5) was changed to 2.0 parts by mass. 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.

(Example 29)
Methylphenylpolysiloxane (siloxane compound) was used instead of octamethylcyclotetrasiloxane with respect to 100 parts by mass of the phenol resin as in Example 1 except that the dehydrating conditions of the reaction solution were different and the water content was 5.2% by mass. Corresponding to (II), m + n = about 280 (where m is 2 or more times n) and a dispersity, X ¹ and X ² are both phenyl groups, and R ¹ and R ² are both methyl groups) Was 8.8 parts by mass, and a phenol resin foam having a thickness of 49.7 mm was obtained in the same manner as in Example 4 except that the double conveyor temperature measured by the conveyor temperature sensor was changed to 81 ° C. The temperature measured by the distributor temperature sensor was 42.1 ° C., and the pressure measured by the distributor pressure sensor was 0.66 MPa.

(Example 30)
Except for the dehydration conditions of the reaction solution, except that the water content was 6.0% by mass, 100 parts by mass of the phenol resin was the same as in Example 1, and methylphenylpolysiloxane (corresponding to siloxane compound (II), m + n = A multimer having a dispersity of about 200 (where m is 3 or more times n), X ¹ and X ² are all phenyl groups, R ¹ and R ² are both methyl groups, and 4.9 parts by mass, A phenol resin foam having a thickness of 51.7 mm was obtained in the same manner as in Example 29 except that the double conveyor temperature measured by the conveyor temperature sensor was changed to 84 ° C. The temperature measured by the distributor temperature sensor was 41.5 ° C., and the pressure measured by the distributor pressure sensor was 0.68 MPa.

(Example 31)
Decamethylcyclopentasiloxane (siloxane compound) was used instead of octamethyltrisiloxane for 100 parts by mass of the phenolic resin as in Example 1 except that the dehydrating conditions of the reaction solution differed and the water content was 6.0% by mass. Equivalent to (III), n = 5) 1.75 parts by mass and methylphenylpolysiloxane (equivalent to siloxane compound (II), m + n = 70 (where m is at least 3 times n) and a large amount having a degree of dispersion. Body, X ¹ and X ² are all phenyl groups, R ¹ and R ² are all methyl groups) and 0.75 parts by mass (a total of 2.5 parts by mass of siloxane compounds) are measured by a conveyor temperature sensor. A phenol resin foam having a thickness of 53.3 mm was obtained in the same manner as in Example 3 except that the double conveyor temperature was changed to 89 ° C. The temperature measured by the distributor temperature sensor was 42.9 ° C., and the pressure measured by the distributor pressure sensor was 0.67 MPa.

(Comparative Example 1)
The amount of octamethylcyclotetrasiloxane was changed to 0 parts by mass with respect to 100 parts by mass of the phenol resin (that is, octamethylcyclotetrasiloxane was not blended), and 6.0 parts by mass of cyclopentane was used as a foaming agent. A phenol resin foam having a thickness of 50.0 mm was obtained in the same manner as in Example 4 except that it was used (that is, the hydrofluoroolefin having 3 or 4 carbon atoms was not used). The temperature measured by the distributor temperature sensor was 41.5 ° C., and the pressure measured by the distributor pressure sensor was 0.69 MPa.

(Comparative Example 2)
100 parts by mass of phenol resin, instead of octamethylcyclotetrasiloxane, methylphenylpolysiloxane (equivalent to siloxane compound (II), m + n = 10 (where m is less than 1 times n)) Body, X ¹ and X ² are all phenyl groups, and R ¹ and R ² are both methyl groups). Got the body. The temperature measured by the distributor temperature sensor was 41.8 ° C., and the pressure measured by the distributor pressure sensor was 0.67 MPa.

Water content in the phenol resin charged into the mixer of the above Examples and Comparative Examples, cyclopentane content per space volume of 22.4 × 10 ⁻³ m ^{3 in} the obtained phenolic resin foam, 3 or 4 carbon atoms Hydrofluoroolefin (HFO) content, total content of hydrocarbons having 6 or less carbon atoms and hydrofluoroolefin having 3 or 4 carbon atoms, content of hydrocarbons having 6 or less carbon atoms, halogenated saturated hydrocarbons Tables 1 and 2 show the cyclopentane ratio in hydrocarbons having 6 or less carbon atoms, the hydrocarbon ratio having a boiling point of −50 to 5 ° C., and the average boiling points of hydrocarbons having 6 or less carbon atoms. Table 3 shows the analysis results of the siloxane compound, and Table 4 shows the evaluation results of the characteristics and thermal conductivity of the obtained phenol resin foam.

  ADVANTAGE OF THE INVENTION According to this invention, the initial stage thermal conductivity is low in a wide temperature range, and the phenol resin foam which maintains a low thermal conductivity over a long period of time, and its manufacturing method can be provided. 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 ... Siloxane compound, 3 ... Foaming agent, 4 ... Curing catalyst, 5 ... Foamable phenol resin composition, 6 ... Face material, 10 ... Lower slat conveyor, 20 ... upper slat conveyor, 30 ... heat insulation material, 31 ... air supply fan, 32 ... exhaust fan, 33 ... mixer, 34 ... cutting device, 40 .. Panel-shaped phenolic resin foam, 41... Molding device, a... Mixing unit, b... Mixing unit, c.・ Discharge nozzle.

Claims (24)

A phenol resin foam containing a cyclopentane and a siloxane compound and having a density of 10 kg / m ³ or more and 150 kg / m ³ or less,
The siloxane compound has a methyl group and an ethyl group bonded to an Si atom as a structure A, a substituent other than a methyl group and an ethyl group bonded to an Si atom and a hydrogen atom as a structure B, and a space volume 22 of the phenol resin foam. The number (unit: mmol) of the structure A of the siloxane compound contained in 4 × 10 ⁻³ m ³ is A _m , and the space volume of the phenol resin foam is contained in 22.4 × 10 ⁻³ m ^3. the number of structure B of the siloxane compound (unit: mmol) If the set to _{B m,} the following formula (1):
S = A _m / (A _m + B _m ) (1)
The value of S calculated in the above is 0.60 or more and 1.00 or less,
The value obtained by subtracting the thermal conductivity in an environment of 10 ° C. from the thermal conductivity in an environment of 40 ° C. of the phenol resin foam is 0 W / m · K or more,
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 or less,
The phenol resin foam in which 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.   The phenol resin foam of Claim 1 in which the substituent of the said structure B contains a C1-C9 organic group.   The phenol resin foam of Claim 1 in which the substituent of the said structure B contains a C1-C9 hydrocarbon group.   The phenol resin foam according to claim 1, wherein the substituent of the structure B includes a phenyl group.   The phenol resin foam according to any one of claims 1 to 4, wherein the siloxane compound has a molecular weight of 200 or more and 41,000 or less.   The phenol resin foam according to any one of claims 1 to 5, wherein the siloxane compound includes a cyclic polysiloxane compound. The siloxane compound is
Formula (I) below:

[Wherein, n represents an integer of 1 to 550, and R ¹ and R ² each represent a substituent of 1 to 6 carbon atoms. A siloxane compound (I) represented by
Formula (II) below:

Wherein, X _^1, if X ² each in which a hydrogen atom or a C 1 to 6 substituents carbon (n is X ¹ in 2 or more there is a plurality or different and each of the plurality of X ¹ are the same , when n X ² by 2 or more there are a plurality, may be different in each of the plurality of X ² are the same. However, when X ¹ and X ² bonded to the same Si are both a methyl group R ¹ and R ² each represent a substituent having 1 to 6 carbon atoms, m represents an integer of 0 or more, n represents an integer of 1 or more, and the sum of m and n is 1 550 or less. And a siloxane compound (II) represented by
Formula (III) below:

[Wherein n represents an integer of 4 or more and 20 or less. The phenol resin foam according to any one of claims 1 to 5, which is at least one selected from the group consisting of siloxane compounds (III) represented by the formula:   The phenol resin foam according to claim 7, wherein the siloxane compound is at least one of the siloxane compound (I) and the siloxane compound (III). When the phenol resin foam was pulverized and extracted in chloroform, the siloxane compound extracted in chloroform per space volume of 22.4 × 10 ⁻³ m ^{3 in the} phenol resin foam. The value of the extraction amount Y (unit: g) is equal to or less than the coefficient a calculated by the following formula (2) using the cyclopentane content X, and the following formula (3) using the cyclopentane content X The phenol resin foam in any one of Claims 1-8 which exists in the range more than the coefficient b calculated by (1).
a = -39.9X + 56.7 (2)
b = 0.056X (3) The hydrocarbon having 6 or less carbon atoms contained in the phenolic resin foam contains 60 mol% or more and 99.9 mol% or less of cyclopentane,
The phenol resin foam in any one of Claims 1-9 whose boiling point average value of the said C6 or less hydrocarbon is 25 to 50 degreeC. 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 any one of claims 1 to 9, wherein the foam volume is 0.3 mol or more and 1.0 mol or less per 22.4 × 10 ⁻³ m ^{3 of the} following.   The thermal conductivity in a 10 ° C environment and the thermal conductivity in a 23 ° C environment are both 0.0220 W / m · K or less, and the thermal conductivity in a 40 ° C environment is 0.0240 W / m · K or less. The phenolic resin foam according to any one of claims 1 to 11.   110 ° C., 14-day accelerated test, and 10 ° C., 23 ° C., and 40 ° C. thermal conductivity deterioration width (thermal conductivity after accelerated test−initial thermal conductivity before accelerated test) The phenol resin foam according to any one of claims 1 to 12, which is 0.0050 W / m · K 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 13, wherein the hydrocarbon having a boiling point of -50 ° C or higher and 5 ° C or lower contains isobutane.   The phenol resin foam according to any one of claims 1 to 14, which has a closed cell ratio of 90% or more and an average cell diameter of 40 µm to 300 µm.   The phenol resin foam according to any one of claims 1 to 15, wherein a void area ratio is 1.0% or less. The phenol resin foam according to any one of claims 1 to 16, further comprising a hydrofluoroolefin having 3 or 4 carbon atoms,
The value of hydrofluoroolefin content (unit: mol) having 3 or 4 carbon atoms per space volume of 22.4 × 10 ⁻³ m ^{3 in the} phenol resin foam is 0.01 or more and 0.4 or less,
Total of the content of hydrocarbons having 6 or less carbon atoms per space volume of 22.4 × 10 ⁻³ m ³ and the content of hydrofluoroolefins having 3 or 4 carbon atoms (unit: mol) is 0.3 to 0.9, a phenol resin foam. The phenol resin foam according to any one of claims 1 to 17, further comprising a halogenated saturated hydrocarbon,
Halogenated saturated hydrocarbon content (unit: mol) per space volume of 22.4 × 10 ⁻³ m ^{3 in the} phenol resin foam is 0.01 or more and 0.35 or less,
Content of hydrocarbon having 6 or less carbon atoms per space volume of 22.4 × 10 ⁻³ m ^{3 in the} foamed phenol resin foam, content of hydrofluoroolefin having 3 or 4 carbon atoms, halogenated saturated hydrocarbon A phenol resin foam in which the total content (unit: mol) is 0.3 or more and 1.0 or less.   It is a manufacturing method of the phenol resin foam in any one of Claims 1-16, Comprising: The foaming agent containing the said cyclopentane, the said siloxane compound, a phenol resin, surfactant, and an acid curing catalyst are included at least. In the process in which the foamable phenol resin composition is mixed using a mixer, and after the foamable phenol resin composition is discharged from the distributor of the mixer, the foamable phenol resin composition is heated and heated. The manufacturing method of a phenol resin foam which applies a pressure from the up-down direction side of a foamable phenol resin composition, and manufactures the phenol resin foam shape | molded in plate shape.   The method for producing a phenol resin foam according to claim 17, wherein the foaming agent contains at least the cyclopentane and the hydrofluoroolefin having 3 or 4 carbon atoms, the siloxane compound, the phenol resin, a surfactant, In addition, the foamable phenol resin composition containing the acid curing catalyst is mixed using a mixer, and after the foamable phenol resin composition is discharged from the distributor of the mixer, the foamable phenol resin composition is heated. In the process of foaming and curing, a method for producing a phenol resin foam, wherein pressure is applied from the up and down direction side of the foamable phenol resin composition to produce a phenol resin foam molded into a plate shape.   19. The method for producing a phenol resin foam according to claim 18, wherein the foaming agent contains at least the cyclopentane and the halogenated saturated hydrocarbon, the siloxane compound, the phenol resin, the surfactant, and the acid curing catalyst. The foamable phenolic resin composition containing is mixed using a mixer, and after the foamable phenolic resin composition is discharged from the distributor of the mixer, the foamable phenolic resin composition is foamed and cured by heating. In the process, a method for producing a phenol resin foam, wherein pressure is applied from the vertical direction side of the foamable phenol resin composition to produce a phenol resin foam molded into a plate shape.   The method for producing a phenol resin foam according to any one of claims 19 to 21, wherein the pressure of the distribution part is 0.2 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 19-22 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 equation (4) 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 19 to 23, which is 20 or more and 36 or less.
R = P + 0.2286Q (4)

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