TW202344587A - Foamed phenolic-resin object and laminate thereof - Google Patents

Abstract

A foamed phenolic-resin object containing a hydrofluoroether represented by (formula 1) in an amount of 0.03-4.3 mass%. (Formula 1): CaHbFc-O-CxHyFz (where a, b, c, x, y, and z are integers, and 2 ≤ a ≤ 7, 0 ≤ b ≤ 3, c=2a+1-b, b ≤ 2a+1, 1 ≤ x ≤ 3, 2 ≤ y ≤ 7, z=2*x+1-y, and y ≤ 2x+1).

Description

Phenolic resin foam and its laminate

The present invention relates to a phenol resin foam and a laminated board thereof.

Different from fiber-based glass wool or rock wool, foamed plastic insulation materials contain gas with lower thermal conductivity in the bubbles, thereby exhibiting higher thermal insulation performance. Therefore, in addition to exterior wall materials such as metal siding, In addition to interior wall materials such as , partition boards, etc., it is also widely used in building materials such as ceiling materials, fire doors, and window guards.

In recent years, due to concerns about global warming, there has been an urgent need to reduce greenhouse gases. Among them, as one of the methods to reduce greenhouse gases through energy conservation, high thermal insulation of buildings has attracted attention. The higher the thermal insulation performance, the greater the energy saving effect, so it is necessary to further improve the thermal insulation performance.

As a representative example of a foam with high thermal insulation performance, there is a phenol resin foam. Until now, in order to improve the thermal insulation performance, in addition to using gas with low thermal conductivity, attempts have been made to reduce the bubble diameter of the foam.

Patent Document 1 discloses that a phenol resin foam with high thermal insulation performance is obtained by reducing the bubble diameter of a phenol resin foam by adding a fluoroether that has an effect of reducing the bubble diameter. Furthermore, Patent Document 2 discloses that by adding a powdery phenol resin cured product, the bubble diameter of the phenol resin foam can be reduced, thereby achieving high thermal insulation. Prior technical literature patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 11-140217 Patent Document 2: Japanese Patent Application Publication No. 2017-210618

[Problem to be solved by the invention]

However, in Patent Document 1, Galden exemplified in the examples of fluoroethers is expensive, has a high global warming potential (GWP), and has a relatively large environmental load, so it is difficult to actively utilize it. In addition, the effect of reducing the bubble diameter is limited to the case where the foaming agent uses hydrocarbons, and is not suitable for the case where the foaming agent uses hydrofluoroolefins with low thermal conductivity.

On the other hand, Patent Document 2 is a technology that can reduce the bubble diameter even when a hydrofluoroolefin is used as a foaming agent. However, the more powdery phenolic resin cured product is added, the more heat conduction the solid has. , it is not a good method to reduce thermal conductivity. In addition, if a large amount of the powdery phenol resin cured product is added, it is likely to remain in the pipes, clogging the pipes, and causing a decrease in productivity. Furthermore, the powdery phenolic resin cured product requires not only equipment for making the powder, but also equipment for kneading the powder into the resin, which requires a high investment in equipment.

Therefore, the present inventors believe that there are three main viewpoints as the main method for improving the thermal insulation performance of the resin foam, that is, reducing the thermal conductivity. The first is "using a gas with lower thermal conductivity", the second is "making the bubble diameter of the foam smaller", and the third is "making the foam less dense". Regarding the third point of view, "lower density," since lowering density will result in the inability to maintain the independent cell ratio of the resin foam, resulting in disadvantages such as a decrease in mechanical properties, it cannot be a practical countermeasure. In addition, starting from the magnitude of the contribution to thermal conductivity, the first point of view is generally actively studied.

Based on the first point of view, in the past, CFC (chlorofluorocarbon, chlorofluorocarbon) or HFC (hydrofluorocarbon, hydrofluorocarbon) with low thermal conductivity were actively used. However, due to their high ozone depletion potential (ODP), their use is limited. Currently, as alternatives, hydrofluoroolefins with equally excellent thermal conductivity, ODP of 0 and low GWP have become mainstream. However, there is a limit to the improvement of thermal conductivity among countermeasures based only on the first viewpoint. In order to further improve thermal conductivity, the second viewpoint "refining the bubble diameter of the foam" needs to be thoroughly studied.

This second perspective is specifically based on the following idea. That is, first, it is important to create as many bubble nuclei as possible in the resin composition. Secondly, it is important that the generated bubbles grow stably and do not burst. By taking these two points into consideration, the bubbles can be miniaturized. Since the finer the bubble diameter, the more radiant heat conduction of the foam can be suppressed. Therefore, the miniaturization of the bubble diameter can be said to be a factor that contributes more to the thermal conductivity after "using a gas with a lower thermal conductivity". .

Therefore, there is a need for a technology for miniaturizing the cell diameter when using various foaming agents, which is necessary to achieve low thermal conductivity of a phenol resin foam. [Technical means to solve problems]

The inventors of the present invention conducted intensive research in order to solve the above-mentioned problems, and as a result developed a technology that adds a specific hydrofluoroether to a phenol resin composition to make the cell diameter of the phenol resin foam finer, thereby making it possible to Reduce thermal conductivity when using various blowing agents. That is, the present invention is as follows.

[1] A phenol resin foam containing a hydrofluoroether represented by the following (Formula 1) in an amount of 0.03 to 4.3% by mass relative to the phenol resin foam. Formula 1: C _a H _b F _c -OC _x H _y F _z (where a, b, c, x, y, z are integers, 2≦a≦7, 0≦b≦3, c=2a+1-b , b≦2a＋1, 1≦x≦3, 2≦y≦7, z＝2×x＋1-y, y≦2x＋1) [2] The phenolic resin foam described in [1], wherein (Formula 1) The hydrofluoroethers represented are methyl perfluoropropyl ether, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1 ,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 1,1,2,2-tetrafluoro Any of ethyl-2,2,2-trifluoroethyl ether. [3] The phenol resin foam as described in [1] or [2], which has an average cell diameter of 70 μm or more and 180 μm or less. [4] The phenolic resin foam according to any one of [1] to [3], wherein the foaming agent contains a hydrofluoroolefin. [5] The phenol resin foam according to [4], wherein the foaming agent contains hydrocarbon. [6] The phenolic resin foam according to any one of [1] to [5] has a density of 10 kg/m ³ or more and 70 kg/m ³ or less. [7] The phenolic resin foam according to any one of [1] to [6] has an independent cell ratio of 80% or more. [8] A laminated board of phenol resin foam according to any one of [1] to [7], which is provided with a surface material on at least one of one side of the phenol resin foam and the back side of the side. [Effects of the invention]

The phenol resin foam and its laminate of the present invention can refine the cell diameter of the phenol resin foam. The bubble diameter helps reduce thermal conductivity, so it can reduce thermal conductivity when using various blowing agents. In particular, when hydrofluoroether is not added, poor appearance such as pores or uneven color of the foam occurs, or the compressive strength is low, these situations can be improved. Furthermore, since the GWP of the raw material is small, it is possible to provide an environmentally friendly foam with a small environmental load.

Hereinafter, the mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. In addition, this invention is not limited to the following embodiment, It can be implemented with various changes within the scope of the summary. In addition, in this specification, a "phenol resin" to which a surfactant is added is called a "phenol resin composition", and a "phenol resin composition" to which a hydrofluoroether, a foaming agent, and a foam nucleation agent are added is called a "phenol resin composition." A "foamable phenolic resin composition" that imparts foaming properties or both foaming properties and curing properties using an agent, an acidic hardening agent, etc. Moreover, the obtained foam is called "phenol resin foam".

＜Phenolic resin foam＞ The phenolic resin foaming system of this embodiment is produced from a phenolic resin composition including hydrofluoroether, a foaming agent and an acidic hardener.

The hydrofluoroether contained in the phenol resin foam of this embodiment is represented by (Formula 2). Formula 2: C _a H _b F _c -OC _x H _y F _z (where a, b, c, x, y, z are integers, 2≦a≦7, 0≦b≦3, c＝2a＋1-b , b≦2a＋1, 1≦x≦3, 2≦y≦7, z＝2×x＋1－y, y≦2x＋1)

By adding the hydrofluoroether to a phenol resin or a phenol resin composition, the effect of reducing the bubble diameter of the phenol resin foam is obtained. Generally speaking, relative to the phenol resin foam, the content is 0.03 mass% to 4.3 mass%, preferably 0.1 mass% to 3.8 mass%, more preferably 0.3 mass% to 3.3 mass%, and most preferably 0.5 mass% ~3.3% by mass. The hydrofluoroether can also be a combination of two or more molecules conforming to Formula 2. If the content of hydrofluoroether is 0.03% by mass or more, the thermal conductivity is likely to decrease. Furthermore, if the content of hydrofluoroether is 4.3% by mass or less, even when a hydrofluoroether with a higher boiling point is used, the amount of liquefied hydrofluoroether in the foam increases, resulting in an increase in thermal conductivity or There is also less concern about the decrease in rigidity of phenolic resin. In this embodiment, in order to make the content of hydrofluoroether relative to the phenolic resin foam fall within the above range (range of 0.03 mass % to 4.3 mass %), the amount of hydrofluoroether relative to 100 parts by mass of the phenol resin composition is The added amount is preferably 0.1 parts by mass to 6.8 parts by mass, but it depends on the type of hydrofluoroether, compatibility with phenolic resin, foaming temperature or residence time during foam production, and other foaming and hardening conditions. There is a difference.

Hydrofluoroether is considered to be a bubble core in the phenol resin. Since it increases the number of bubbles in the foamable phenol resin composition, it is believed to have the ability to reduce the average bubble diameter of the phenolic resin foam, inhibit radiant heat conduction, and reduce phenol The effect of thermal conductivity of resin foam. The mixing order of the phenolic resin composition, foaming agent and hydrofluoroether is not particularly limited. It is more preferable to knead the hydrofluoroether into the phenolic resin composition before kneading the foaming agent, or to mix the hydrofluoroether and the foaming agent. The foaming agent is kneaded into the phenolic resin composition at the same time. When the hydrofluoroether is kneaded into the phenol resin composition after the foaming agent, or when a mixture of the hydrofluoroether and the foaming agent in advance is kneaded into the phenol resin composition, the hydrofluoroether itself serves as It functions as a bubble nucleus, but it may be adsorbed on the bubbles that are already in the growth process and hinder the growth of the bubbles. As a result, there is concern that the independent bubble rate will decrease. The kneading method is not particularly limited as long as the hydrofluoroether can be uniformly dispersed in the phenol resin or phenol resin composition. In addition, hydrofluoroethers have oxygen atoms and alkyl groups in their molecules, so they have shorter atmospheric lifetimes than perfluoroalkanes. Therefore, they have the advantage of relatively small global warming potential and low environmental load. Furthermore, the presence of oxygen atoms in the molecule will improve the compatibility with phenol resin. Therefore, it is believed that the dispersibility of hydrofluoroether in phenol resin is improved, which has the effect of promoting the formation of fine bubble nuclei. On the other hand, if the molecular chain consisting only of carbon and fluorine in hydrofluoroether becomes longer, the atmospheric lifetime tends to become longer and the GWP may increase. Therefore, from the perspective of environmental load, the molecular chain consisting only of carbon and fluorine The molecular chain should not be too long. In addition, since hydrofluoroether is a flame-retardant substance, it is considered that the greater the content of hydrofluoroether in the phenol resin foam, the more flame retardant the phenol resin foam will be.

The hydrofluoroether of (Formula 2) needs to be an ether of a group represented by C _a H _b F _c and a group represented by C _x H _y F _z . From the viewpoint of the boiling point of hydrofluoroether, the carbon number of the group represented by C _a H _b F _c , that is, the value of a, needs to be 2 to 7, preferably 2 to 6. The group represented by C _a H _b F _c is a group in which part or all of the hydrogen of the hydrocarbon group is substituted with fluorine, preferably one with a smaller number of hydrogen atoms. The value of b needs to be 0 to 3, preferably 0 or 1. Especially preferably 0. From the viewpoint of the boiling point of hydrofluoroether, the carbon number of the group represented by C _x H _y F _z , that is, the value of x, needs to be 1 to 3, preferably 1 to 2. The group represented by C _x H _y F _z is a hydrocarbon group or a group in which a part of the hydrocarbon is substituted with fluorine, preferably one with a smaller number of fluorine atoms, and the value of z is preferably 0 to 3. When the value of hydrofluoroether a is 7 or less and the value of The resulting increase in heat conduction. It is considered that the hydrofluoroether of (Formula 2) has a group represented by C _a H _b F _c with a small number of hydrogen atoms and a C _x H _y F _z group with a small number of fluorine atoms, thereby improving the performance of the hydrofluoroether. The dispersibility in the resin promotes the formation of fine bubble nuclei. Moreover, a≧x is preferable, and a>x is more preferable.

Examples of hydrofluoroethers (formula 2) suitable for use in the present invention include: methyl perfluoropropyl ether, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, and ethyl nonafluorobutyl ether. , Ethyl nonafluoroisobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane , 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether. These hydrofluoroethers can be used alone or in combination of two or more.

The phenol resin foam of the present invention tends to have improved compressive strength compared with a phenol resin foam to which hydrofluoroether is not added. The reason for this is that the addition of hydrofluoroether makes the bubble diameter smaller. Therefore, compared with the phenol resin foam without addition, the number of bubble walls arranged in the compression direction increases, and the resistance increases. In addition, In addition, the pores that become the starting point of rupture are reduced.

Moreover, in this embodiment, the appearance is improved compared with the phenol resin foam to which hydrofluoroether is not added. The reason is that by adding hydrofluoroether, not only the bubble diameter is reduced, but also the pore generation rate is reduced, and the bubble diameter becomes uniform in the thickness direction, thus eliminating the color unevenness of the foam.

The average bubble diameter of the phenolic resin foam in the present invention is preferably 70 μm or more and 180 μm or less, more preferably 70 μm or more and 170 μm or less, further preferably 70 μm or more and 150 μm or less, most preferably 70 μm or more. Below 135 μm. If the average bubble diameter is 70 μm or more, it is possible to suppress an increase in thermal conductivity due to increased thermal conductivity of the phenol resin portion due to a smaller bubble diameter. On the other hand, if the bubble diameter is 180 μm or less, the heat conduction due to radiation becomes smaller, and the increase in thermal conductivity can be suppressed. Furthermore, the average bubble diameter of the phenolic resin foam can be determined by, for example, changing the amount of hydrofluoroether added, the amount of solid foaming nucleating agent added, the temperature of the foamable phenol resin composition, and the foaming after mixing. At the pre-forming point in the process when the phenolic resin composition is sprayed onto the lower surface material, the added amount of the foaming agent, the added amount of the acidic hardener, and the hardening conditions such as temperature or residence time are changed to adjust to the desired Expected value.

The phenol resin foam of the present invention can use a single component of hydrofluoroolefin, hydrocarbon, and chlorinated hydrocarbon, or a combination of two or more of them as a foaming agent.

Hydrofluoroolefins generally have low thermal conductivity, so when used as a foaming agent, a phenol resin foam with low thermal conductivity is obtained, so it is preferable. Hydrofluoroolefins include chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins. In the present invention, hydrochlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins can also be mixed and used.

Examples of chlorinated hydrofluoroolefins include: (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd, for example, E-body (HCFO-1233zd(E)), manufactured by Honeywell Japan Co., Ltd., product name: Solstice (trademark) LBA), 1,1,2-trichloro-3,3,3- Trifluoropropene (HCFO-1213xa), 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 1,1-dichloro-3,3,3-trifluoropropene (HCFO- 1223za), 1-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224zb), 2,3,3-trichloro-3-fluoropropene (HCFO-1231xf), 2,3-dichloro- 3,3-difluoropropene (HCFO-1232xf), 2-chloro-1,1,3-trifluoropropene (HCFO-1233xc), 2-chloro-1,3,3-trifluoropropene (HCFO-1233xe) , 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-1,2,3-trifluoropropene (HCFO-1233yb), 3-chloro-1,1,3-trifluoropropene Fluoropropene (HCFO-1233yc), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 3-chloro-1,2,3-trifluoropropene (HCFO-1233ye), 3-chloro- 2,3,3-trifluoropropene (HCFO-1233yf), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb), 1-chloro-3,3,3-trifluoropropene (HCFO- 1233zd), etc., one of the configurational isomers thereof, that is, the E-isomer or the Z-isomer, or a mixture thereof, can be used. Further examples include (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)). In the present invention, two or more types of these hydrochloric fluoroolefins may be mixed and used.

Examples of the non-chlorinated hydrofluoroolefin include: 1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze, for example, E body (HFO-1234ze(E)), manufactured by Honeywell Japan Co., Ltd. Product name: Solstice (trademark)ze), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz, for example, Z-body (HFO-1336mzz(Z)), Chemours Co., Ltd. Manufactured by the company, Opteon (trademark) 1100), 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1 ,3,3,3-tetrafluoropropene (HFO-1234ze), 3,3,3-trifluoropropene (HFO-1243zf), 1,1,1,4,4,5,5,5-octafluoro- 2-Pentene (HFO-1438mzz), etc., one of its configurational isomers, that is, E form or Z form, or a mixture thereof can be used. In the present invention, two or more types of these non-chlorinated hydrofluoroolefins may be mixed and used.

As the hydrocarbon, cyclic or chain alkanes, alkenes, and alkynes having 3 to 7 carbon atoms are preferred. Specific examples include n-butane, isobutane, cyclobutane, and n-pentane. Isopentane, cyclopentane, neopentane, n-hexane, isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, etc. Among them, pentanes such as n-pentane, isopentane, cyclopentane and neopentane and butanes such as n-butane, isobutane and cyclobutane are preferably used. In the present invention, two or more types of these hydrocarbons may be mixed and used. Examples of mixtures include: n-pentane and n-butane, isobutane and isopentane, n-butane and isopentane, isobutane and n-pentane, cyclopentane and n-butane, cyclopentane and n-pentane, etc. Pentane and isobutane, etc.

As the chlorinated hydrocarbon, it is preferable to utilize linear or branched chlorinated aliphatic hydrocarbons having 2 to 5 carbon atoms. The number of bonded chlorine atoms is preferably 1 to 4, for example: dichloroethane, 1-chloropropane, 2-chloropropane, chlorobutane, isochlorobutane, chloropentane, isochloropentane Alkane etc. Among these, 1-chloropropane and 2-chloropropane, which are chloropropanes, are more preferably used. In the present invention, these chlorinated hydrocarbons may be used in combination of two or more types.

Furthermore, other foaming agents are not particularly limited, and examples thereof include sodium bicarbonate, sodium carbonate, calcium carbonate, magnesium carbonate, azodicarboxamide, azobisisobutyronitrile, and azodicarboxylic acid. Chemical foaming agents such as barium, N,N'-dinitrosopentamethylenetetramine, p,p'-oxybibenzenesulfonyl hydrazine, and trihydrazinotrihydrazinotriamine, etc. These foaming agents may be used individually by 1 type, or in combination of 2 or more types.

The amount of the foaming agent in the phenolic resin composition varies depending on the type of foaming agent, the compatibility of the foaming agent with the phenolic resin, temperature, residence time and other foaming and hardening conditions. Therefore, it can be determined arbitrarily according to the desired density of the phenolic resin foam, foaming conditions, etc., but it is preferably 3.0 to 20 parts by mass, and more preferably 4.0 to 18 parts by mass based on 100 parts by mass of the phenolic resin composition. , more preferably 5.0 to 16 parts by mass, and most preferably 6.0 to 15 parts by mass. When the amount of the foaming agent per 100 parts by mass of the phenolic resin composition is 3.0 parts by mass or more, the density of the resin foam can be suppressed. In addition, if the amount of the foaming agent per 100 parts by mass of the phenolic resin composition is 20 parts by mass or less, it is easy to suppress the decrease in mechanical strength such as compressive strength due to the phenol resin foam becoming low-density, or the decrease in the cell wall surface. The decrease in independent bubble rate caused by easy rupture can inhibit the increase in thermal conductivity.

In this embodiment, a foaming nucleating agent can also be used in the production of phenolic resin foam. As a foaming nucleating agent, gaseous foaming nucleating agents such as nitrogen, helium, argon, and other low-boiling-point substances whose boiling points are at least 50°C lower than that of the foaming agent can be added. In addition, aluminum hydroxide powder, alumina powder, calcium carbonate powder, talc, kaolin, silica powder, silica sand, mica, calcium silicate powder, wollastonite, glass powder, glass beads, and fly ash can also be added. , silica ash, gypsum powder, borax, slag powder, alumina cement, Portland cement and other inorganic powders, and organic powders such as phenolic resin foam crushed powder and other solid foaming nucleating agents. These may be used individually or in combination of 2 or more types without distinguishing between gas and solid. The timing of adding the foaming nucleating agent can be determined arbitrarily as long as it is supplied into a mixer for mixing the phenolic resin composition.

The added amount of the solid foaming nucleating agent is preferably 3.0 mass % or more and 10.0 mass % or less, more preferably 3.0 mass % or more and 8.0 mass % or less based on 100 mass parts of the phenolic resin composition. If the added amount of the solid foaming nucleating agent is 3.0% by mass or more, the exudation of the foamable phenol resin composition from the surface material will be easily suppressed. In addition, by setting the added amount of the solid foaming nucleating agent to 10.0% by mass or less, it is easier to suppress the dissipation of the foaming agent with a lower boiling point.

The density of the phenolic resin foam of the present invention can be adjusted to the desired density according to the purpose of use of the foam, preferably 10 kg/m ³ or more and 70 kg/m ³ or less, more preferably 20 kg/m 3 ³ or more and 55 kg/m ³ or less, more preferably 22 kg/m ³ or more and 50 kg/m ^{3 or} less, most preferably 24 kg/m ³ or more and 45 kg/m ^{3 or} less. When the density is 10 kg/m ³ or more, the decrease in compressive strength or surface brittleness that is likely to occur due to the lower density is smaller, and the strength can be maintained without problems in practical use. When the density is 70 kg/m ³ or less, there is less concern that the thermal conductivity will increase due to the heat conduction of the resin part that becomes larger due to the higher density. Furthermore, regarding the density of the phenolic resin foam, it is only necessary to adjust the filling ratio of the foaming agent in the phenolic resin foam. This can mainly be achieved by changing the amount of the foaming agent added to the phenolic resin composition, the foaming ratio, and the amount of the foaming agent. The temperature of the foamable phenolic resin composition and the pre-forming point in the process of discharging and mixing the foamable phenolic resin composition can be changed, and the added amount of the foaming nucleating agent, the added amount of the acidic hardener, the temperature or the residence time can be changed. Wait for the hardening conditions, etc., and adjust to the desired value.

The independent cell ratio of the phenolic resin foam of the present invention is preferably 80% or more, more preferably 85% or more, further preferably 90% or more, most preferably 92% or more. If the closed cell ratio is 80% or more, an increase in thermal conductivity caused by the replacement of the foaming agent in the phenolic resin foam with air can be suppressed. The higher the independent bubble rate, the greater the effect. The closed cell ratio of the phenolic resin foam can be adjusted to a desired value by, for example, changing the amount of the foam nucleating agent added, the amount of the foaming agent added, the amount of the acidic hardener, etc.

The thermal conductivity of the phenolic resin foam in this embodiment at 23°C is preferably 0.0211 W/(m・K) or less, more preferably 0.0200 W/(m・K) or less, and even more preferably 0.0180 W /(m・K) or less, preferably 0.0175 W/(m・K) or less.

The porosity of the phenolic resin foam of this embodiment is preferably 0.5% or less. If the porosity is less than 0.5%, it will not easily cause a decrease in the compressive strength in the thickness direction, and the appearance will be within the range where the pores are not obvious. The porosity can be adjusted by hardening conditions such as the amount of hydrofluoroether, temperature or residence time. Furthermore, in the present invention, regarding the porosity, a cross section parallel to the thickness direction of the resin foam is cut, and the voids present in the cross section are measured using the following method. For each void, the area is 2.0 mm. Those above ² are regarded as pores, and the value obtained by dividing the total area of all pores on the cross section by the cross-sectional area is regarded as the porosity.

＜Phenolic resin foamed volume laminate＞ The phenol resin foamed volume laminate in this embodiment is a laminate provided with a surface material on at least one of one side of the phenol resin foam and the back side of the side. Furthermore, the "thickness direction" in this embodiment refers to the size of the shortest side among the three sides of the phenolic resin foamed volumetric laminate, which is usually the foamability of the lower surface material when manufacturing the phenolic resin foamed volumetric laminate. The direction in which the phenolic resin composition foams and grows.

In addition to being used alone, the phenolic resin foamed volume laminate can also be used in various applications by being joined to external members. Examples of external members include plate-shaped materials, sheet-shaped and film-shaped materials, and combinations thereof. As the plate material, suitable wood-based boards such as ordinary plywood, structural plywood, plastic plywood, OSB (oriented strand board, oriented fiber board), wood wool cement board, wood chip cement board, gypsum board, flexible board, medium density fiberboard , calcium silicate board, magnesium silicate board, and volcanic silicate fiber reinforced multi-layer board, etc. Furthermore, as the sheet-like or film-like material, polyester nonwoven fabric, polypropylene nonwoven fabric, inorganic filled glass fiber nonwoven fabric, glass fiber nonwoven fabric, paper, calcium carbonate paper, polyethylene processed paper, polyethylene film, and plastic-based moisture-proof fabric are preferred. Membrane, asphalt waterproof paper, and aluminum foil (porous or non-porous), etc.

Hereinafter, the manufacturing method of the phenol resin foam is demonstrated in more detail.

＜Raw materials for phenolic resin foamed volumetric laminates＞ As the phenol resin, a soluble phenol resin synthesized from an alkali metal hydroxide or an alkaline earth metal hydroxide can be used. Soluble phenolic resin is synthesized by heating phenols and aldehydes as raw materials using an alkali catalyst in the temperature range of 40 to 100°C. In addition, if necessary, additives such as urea may be added during or after synthesis of the soluble phenol resin. When adding urea, it is more preferred to mix urea that has been methylolated with an alkali catalyst in advance into the soluble phenol resin. The synthesized soluble phenolic resin usually contains excess moisture, so the moisture content is adjusted to a suitable amount for foaming during foaming. In addition, aliphatic hydrocarbons or high-boiling alicyclic hydrocarbons or mixtures thereof, or diluents for adjusting viscosity such as ethylene glycol and diethylene glycol, and other dicyandiamide as needed can also be added to the phenol resin. Or additives such as melamine.

The initial molar ratio of phenols and aldehydes during the synthesis of phenol resin is preferably in the range of 1:1 to 1:4.5, more preferably in the range of 1:1.5 to 1:2.5.

Here, phenols suitable for use in the synthesis of phenol resin in this embodiment are phenol itself and other phenols. Examples of other phenols include: resorcinol, catechol, o-cresol, m-cresol, Cresol and p-cresol, xylenols, ethylphenols, and p-3-butylphenol, etc. Furthermore, dinuclear phenols can also be used.

In addition, the aldehyde may be a compound that can serve as an aldehyde source. As the aldehyde, formaldehyde itself, paraformaldehyde that can be used after depolymerization, other aldehydes or derivatives thereof are preferably used. Examples of other aldehydes include glyoxal, acetaldehyde, chloral, furfural, and benzaldehyde.

The mass average molecular weight of the phenol resin is preferably 300 or more, more preferably 400 or more, and still more preferably 450 or more. Moreover, the mass average molecular weight is preferably 2,500 or less, more preferably 2,200 or less, further preferably 2,050 or less, most preferably 1,900 or less. If the mass average molecular weight of the phenolic resin is 300 or more, it is less likely to cause a runaway reaction due to the reaction heat of the hardening reaction, and the reaction heat can be used for foam molding, so the energy efficiency is better. In addition, when the mass average molecular weight is 2,500 or less, the reaction heat of the polymerization reaction is less, so the bubble diameter is easy to become smaller, and the resin is less likely to harden in the equipment on the upstream side of the plate forming process, so it is less likely to contaminate the piping, and it can last for a long time. operation. In addition, the mass average molecular weight of the phenol resin can be measured using the method described in the Examples of this specification.

The viscosity of the phenolic resin composition at 40°C is preferably from 5,000 mPa·s to 100,000 mPa·s, more preferably from 7,000 mPa·s to 50,000 mPa·s, and further preferably from 9,000 mPa·s to 40,000 mPa·s. s or less. Moreover, the moisture content of the phenol resin and the phenol resin composition is preferably 1.5 mass% or more and 20 mass% or less.

The surfactant, hydrofluoroether, foaming agent and foaming nucleating agent can be added to the phenolic resin composition in advance, or can be added at the same time as the acidic hardener. However, it is preferable that the hydrofluoroether is added before the foaming agent or at the same time.

As surfactants, those commonly used in the production of phenolic resin foams can be used. Among them, nonionic surfactants are more effective. For example, a cyclic surfactant that is a copolymer of ethylene oxide and propylene oxide is preferred. Alkane oxide, or the condensate of alkylene oxide and castor oil, or the condensation product of alkylene oxide and alkylphenols such as nonylphenol and dodecylphenol, or the carbon number of the alkyl ether part is 14 to 22 Polyoxyethylene alkyl ethers, or fatty acid esters such as polyoxyethylene fatty acid esters, silicone compounds such as polydimethylsiloxane, or polyols. These surfactants can be used alone or in combination of two or more. In addition, the usage amount is not particularly limited, but it is preferably used in a range of 0.3 parts by mass to 10 parts by mass relative to 100 parts by mass of the phenol resin.

The acidic hardener only needs to be an acidic hardener capable of hardening the phenol resin composition, and contains an organic acid as an acid component. As the organic acid, arylsulfonic acid or anhydride thereof is preferred. Examples of aryl sulfonic acid and its anhydride include toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, substituted phenol sulfonic acid, xylenol sulfonic acid, substituted xylenol sulfonic acid, and dodecyl benzene sulfonate. Acid, benzenesulfonic acid, naphthalenesulfonic acid, etc., and anhydrides thereof may be used alone or in combination of two or more. Furthermore, in this embodiment, resorcinol, cresol, salinol (o-hydroxymethylphenol), p-hydroxymethylphenol, etc. may also be added as a hardening aid. In addition, these acidic hardeners can also be diluted with solvents such as ethylene glycol and diethylene glycol.

The amount of acidic hardener used varies depending on the type. When using a mixture of 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol, it is preferably 6 parts by mass relative to 100 parts by mass of the phenolic resin composition. It is used in an amount of not less than 20 parts by mass and not more than 20 parts by mass, more preferably not less than 8 parts by mass and not more than 15 parts by mass, and most preferably not less than 11 parts by mass and not more than 13 parts by mass.

As the surface material arranged on at least one of one side of the phenol resin foam and the back side of the side, a flexible surface material (flexible surface material) is used. As the flexible surface material used, it is preferable that the main components include non-woven fabrics or woven fabrics such as polyester, polypropylene, and nylon, kraft paper, glass fiber mixed paper, calcium hydroxide paper, aluminum hydroxide paper, and silicon. Papers such as magnesium acid paper, or non-woven fabrics of inorganic fibers such as glass fiber non-woven fabrics, etc., can also be mixed (or laminated) for use. When the surface material is peeled off from the obtained phenolic resin foamed volume laminate and only the base material is used, it is preferable to use cheap paper that can be discarded after peeling off. These surface materials are usually provided in roll form. Furthermore, as a flexible surface material, one kneaded with additives such as a flame retardant can also be used. Furthermore, the method of bonding the surface material and the phenolic resin foam is not particularly limited, and an adhesive such as epoxy resin can be used. In terms of manufacturing costs and preventing the manufacturing process from being complicated, it is preferable to use only The adhesion of the foamable phenol resin composition when it is thermally cured on the surface of the surface material.

＜Manufacturing method of phenolic resin foamed volume laminate＞ As a manufacturing method of the phenolic resin foamed volumetric laminate, a continuous manufacturing method is used. This method includes a mixing process of mixing the above-mentioned foamable phenol resin composition using a mixer, and spraying the mixed foamable phenol resin composition to A spraying process on the lower surface material, and a foaming volumetric laminate manufacturing process for manufacturing a phenolic resin foamed volumetric laminate from the foamable phenol resin composition sprayed on the lower surface material. Alternatively, a batch method using a mold frame can be used to perform each step in stages.

In the continuous manufacturing method, after the upper surface material is coated with the phenol resin composition sprayed onto the lower surface material, it is preformed in such a way that it is foamed and hardened while being flattened from the top and bottom directions, and then foamed. and hardened, and formally formed into a plate shape. In the continuous manufacturing method, as a method for performing preforming or formal forming, there can be exemplified a method using a slat-type double conveyor belt or a method using a metal roller or a steel plate, and further examples can be exemplified by using a plurality of combinations of these. Methods, etc. Various methods corresponding to the manufacturing purpose. For example, when molding is performed using a slatted double conveyor belt, the foamable phenol resin composition coated with the upper and lower surface materials can be continuously introduced into the slatted double conveyor belt, and then heated while Pressure is applied from the top and bottom directions to adjust to a predetermined thickness, and then it is foamed and hardened to form a plate shape. The temperature of the foamable phenol resin composition when sprayed onto the lower surface material depends on the boiling point of the foaming agent, and is generally preferably 32°C or more and 45°C or less. If the temperature of the foamable phenol resin composition is 32° C. or higher, the foamable phenol resin composition will easily foam in the initial stage, so it will be easy to suppress the foamable phenol resin composition from exuding from the lower surface material. On the other hand, if the temperature of the foamable phenol resin composition is 45°C or lower, even when a foaming agent with a low boiling point is used, dissipation can be easily suppressed, and the decrease in foaming efficiency and bubble diameter can be easily prevented. The thermal conductivity increases due to the coarsening. Furthermore, the temperature of the foamable phenol resin composition sprayed onto the lower surface material can be controlled by adjusting the temperature, flow rate, and rotation speed of the temperature-controlled water of the mixer that mixes various compositions.

＜Preforming process＞ The heating and temperature adjustment conditions of the process of foaming and hardening the foamable phenol resin composition sprayed onto the lower surface material and performing preforming on the upper surface material are preferably 30°C or more and 80°C or less. If it is 30°C or above, the effect of promoting foaming during the preforming process can be easily obtained, and it can also promote hardening. In addition, if it is 80° C. or lower, the vicinity of the center portion in the thickness direction is less likely to be affected by internal heat generation, and the temperature of the center portion is less likely to increase, thereby suppressing a decrease in the independent cell ratio. When foaming and curing the foamable phenol resin composition, it is important to set up a formal structure after the preforming process in order to suppress the decrease in the closed cell ratio due to internal heat generation near the center in the thickness direction and to efficiently promote curing. The forming process and post-hardening process are heated in stages.

＜Formal forming process＞ The heating and temperature adjustment conditions for the formal forming process following the preforming process are ideally 65°C or higher and 100°C or lower. Formal forming can be carried out in this section using annular steel belt-type double conveyor belts, slat-type double conveyor belts, or rollers. In addition, since the formal forming process is the main process for foaming and hardening reactions, the residence time of this process is preferably set to 5 minutes or more and 2 hours or more. If the residence time is 5 minutes or more, foaming and hardening can be fully accelerated. If the residence time is within 2 hours, the production efficiency of phenolic resin foamed volumetric laminates can be improved. Furthermore, when using a conveyor belt, the temperature difference between the upper and lower conveyor belts should ideally be less than 4°C.

＜Post-hardening process＞ After heating and temperature adjustment in the temperature adjustment section of the preforming process and the formal forming process, a post-hardening process is applied. The temperature of the post-hardening process is preferably above 90°C and below 120°C. If it is above 90°C, the moisture in the foam board will easily dissipate. If it is below 120°C, the decrease in the independent cell ratio of the product can be suppressed and a low thermal conductivity can be maintained for a long time. By setting the temperature adjustment range of the post-hardening process, the moisture in the foamable phenolic resin composition can be dissipated after final molding. Example

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited to these.

<Synthesis of phenolic resin> Add 3,500 kg of 52 mass% formaldehyde aqueous solution (52 mass% formalin) and 2,510 kg of 99 mass% phenol (including water as an impurity) to the reactor, stir with a propeller rotary mixer, and use The temperature regulator adjusts the liquid temperature inside the reactor to 40°C. Then, while adding 48% by mass sodium hydroxide aqueous solution, the temperature was raised and the reaction was carried out. When the Oswalt viscosity of the reaction liquid reaches 110 centistokes (=110×10 ^-6 m ² /s, measured value at 25°C), the reaction liquid is cooled, and 398 kg of urea is added. Thereafter, the reaction liquid was cooled to 30°C, and the pH value was neutralized to 6.4 using a 50% by mass aqueous solution of p-toluenesulfonic acid monohydrate.

The reaction solution was concentrated at 60° C. to obtain phenol resin A. Furthermore, the mass average molecular weight and viscosity at 40°C of phenol resin A were measured using the following methods respectively. The mass average molecular weight was 1,300 and the viscosity at 40°C was 9,730 mPa·s.

<Mass average molecular weight of phenol resin> The mass of the phenolic resin was determined by gel permeation chromatography (GPC) measurement under the following conditions and based on the calibration curve obtained using the standard materials (standard polystyrene, 2-hydroxybenzyl alcohol and phenol) shown below. Average molecular weight Mw. Pre-processing: Approximately 10 mg of phenolic resin was dissolved in 1 ml of N,N dimethylformamide (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd., for high-performance liquid chromatography), and filtered with a 0.2 μm membrane filter. used as a measurement solution. Measurement conditions: Measuring device: Shodex System21 (manufactured by Showa Denko Co., Ltd.) Column: Shodex Asahipak GF-310HQ (7.5 mmI.D.×30 cm) Eluent: 0.1% by mass of lithium bromide was dissolved in N,N dimethylformamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., for high-performance liquid chromatography). Flow rate: 0.6 ml/minute Detector: RI (Refractive Index, refractive index) detector Tube string temperature: 40℃ Standard materials: Standard polystyrene ("Shodex STANDARD SL-105" manufactured by Showa Denko Co., Ltd.), 2-hydroxybenzyl alcohol (manufactured by Sigma-Aldrich Co., Ltd., 99% quality), phenol (manufactured by Kanto Chemical Co., Ltd., special grade )

＜Measurement of viscosity of phenolic resin＞ The measured value after stabilizing 0.5 ml of phenolic resin for 6 minutes at 40°C using a rotational viscometer (model DVNXHBCBG, manufactured by BrookField Metek, with a rotor part of CPA-52Z) was used as the viscosity of the phenolic resin.

(Example 1) A block copolymer containing ethylene oxide-propylene oxide and polyoxyethylene dodecyl as a surfactant in a mass ratio were mixed at a ratio of 3.0 parts by mass with respect to 100 parts by mass of the phenol resin A. A composition of 50% each of alkylphenyl ethers. This was regarded as a phenol resin composition. To the above-mentioned phenolic resin composition containing a surfactant, 4.0 mass% of phenolic resin foam powder as a foaming nucleating agent was added. The viscosity of the phenolic resin composition after kneading the phenolic resin foam powder is 22,000 mPa·s at 40°C. Furthermore, 3.0 parts by mass of 3M Novec (registered trademark) 7000 (manufactured by 3M Company) as a hydrofluoroether, 13 parts by mass of HCFO-1233zd(E) as a foaming agent were added to 100 parts by mass of the above-mentioned phenolic resin composition. 13 parts by mass of a composition of an acidic hardener containing a mixture of 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol was supplied to a variable speed mixing head whose temperature was adjusted to 17°C. In addition, the phenol resin foam powder used here is a phenol resin foam (Neoma manufactured by Asahi Kasei Building Materials Co., Ltd.) crushed according to the same procedure as Example 1 of Japanese Patent Application Laid-Open No. 2008-024868. FOAM) crushed powder (average particle size is 28 μm, bulk density is 181 kg/m ³ ), and is kneaded with the phenolic resin composition using a twin-screw extruder before adding hydrofluoroether, foaming agent and acid hardener. . Thereafter, the hydrofluoroether, the foaming agent and the acidic hardener are mixed using a mixer, and the obtained foamable phenol resin composition is distributed using a multi-pass distribution pipe and supplied to the moving lower surface material. In addition, the mixer shown in Figure 1 of Japanese Patent Application Laid-Open No. 10-225993 was used. That is, the following mixer is used: on the upper side of the mixer, the inlet of the phenolic resin composition containing the solid foaming nucleating agent, the inlet of the hydrofluoroether, and the inlet of the foaming agent are in order from top to bottom. They are arranged adjacently and have an inlet for the acidic hardener on the side near the center of the stirring part where the rotor stirs. After the stirring part, it is connected to a nozzle for spraying the foamable phenol resin composition. That is, the area up to the acid hardening agent inlet is the mixing section (front stage), the area from the acid hardening agent inlet to the stirring end section is the mixing section (rear stage), and the area from the stirring end section to the nozzle is the distribution section. The mixer includes such parts. The distributing part has a plurality of nozzles at the front end and is designed to evenly distribute the mixed foamable phenolic resin composition. Furthermore, the distribution part has a sleeve-type structure, which can fully perform heat exchange with the temperature-controlled water. The temperature of the temperature-controlled water in the distribution part is set to 17°C. Furthermore, a thermocouple was installed at the discharge port of the multi-pass distribution pipe so as to be able to detect the temperature of the foamable phenol resin composition, and the rotation speed of the mixer was set to 500 rpm. At this time, the temperature of the foamable phenol resin composition sprayed onto the lower surface material was 34°C. The foamable phenol resin composition supplied to the lower surface material was introduced into a preforming process with a temperature adjusted to 40°C. After 30 seconds, preforming was performed from above the upper surface material using a tension adjustment roller. Set the residence time of this process to 5 minutes. Thereafter, it is introduced into a slat-type double conveyor belt heated to 69°C (formal forming process) by being sandwiched between two pieces of surface material. After hardening with a retention time of 15 minutes, it is retained at 100°C for 9 minutes. , and then cured at 110°C for 2 hours (post-hardening process) to obtain a phenolic resin foamed volume laminate with a thickness of approximately 30 mm. In addition, as the surface material, polyester nonwoven fabric (Asahi Kasei Co., Ltd. ELTAS E05060, basis weight 60 g/m ² ) was used for both the upper and lower surface materials. This production method is shown as production method A in Table 2.

The characteristics of the obtained phenolic resin foam and the phenolic resin foamed volumetric laminate were evaluated by the following methods (identification and content measurement of hydrofluoroether in the phenolic resin foam, identification of the type of foaming agent, average bubbles diameter measurement, density measurement, thermal conductivity measurement at 23°C, compression strength measurement in the thickness direction, color unevenness and porosity evaluation, independent cell ratio measurement).

＜Identification and content determination of hydrofluoroether in phenolic resin foam, and identification of foaming agent types＞ First, using standard gases of hydrofluoroethers, hydrofluoroolefins, halogenated hydrocarbons, and hydrocarbons, determine the retention time under the following GC/MS (Gas chromatography/mass spectrometry) measurement conditions.

Cut a 0.25 mg sample from near the center of the phenolic resin foam and put it into a special container. Add 10 ml of chloroform and 12 crushed glass beads. The sample was pulverized using a homogenizer (IKA ULTRA-TURRAX Tube Drive) at 6000 rpm for 7 to 11 minutes, and the components were extracted in chloroform. The extract was then filtered with a 0.45 μm filter and used for GC/MS measurement. Dissolve the quantitative target component in chloroform, prepare a standard sample solution of known concentration, and use it for GC/MS measurement under the same conditions as the sample.

Hydrofluoroethers, hydrofluoroolefins, halogenated hydrocarbons, and hydrocarbons were identified based on the retention time and mass spectrum determined in advance. In addition, the detection sensitivity of the generated gas components is measured using standard gases, and the content of each substance is calculated from the detection area area and detection sensitivity of each gas component obtained by GC/MS. The hydrofluoroether content (mass % relative to the phenolic resin foam) was calculated from the content of each identified gas component, and the mass % of each foaming agent component was calculated from the content and molar mass of the foaming agent.

(GC-MS measurement conditions) GC (gas chromatography, gas chromatography) device: Agilent 6890 Column: DB1 (30 m, 0.25 mm , film thickness 0.25 μm) Column temperature: 40℃ (5 min) ~ (20℃/min. temperature rise) -200℃ Flow rate: 1 mL/min Injection port temperature: 320℃ Injection method: split flow method (1/50 ) Sample injection volume: 1 μL MS (mass spectrometry, mass spectrometry) device: JEOL AutoMass-SUN Interface temperature: 300°C Ionization method: EI (Electron Ionization, electron ionization) method 70 eV Measurement method: Scan Scan Range: m/z=20～600 Ion source temperature: 240℃

<Measurement of average bubble diameter of phenolic resin foam> The average bubble diameter is measured by the following method. Four photos were taken using a scanning electron microscope that magnified 50 times the bubbles at approximately the center of the thickness direction of the phenolic resin foamed volumetric laminate and at approximately the center relative to the center, front and back. Draw four straight lines with a length of 90 mm (equivalent to 1,800 μm in the actual foam cross-section) on the top of the screen to avoid the pores. For each straight line, calculate the number of bubbles measured based on the number of bubbles that each straight line crosses. The value obtained by dividing 1,800 μm by the average value was used as the average bubble diameter.

<Measurement of density of phenolic resin foam> A 200 mm square phenolic resin foamed volume laminate was used as a sample. After removing the surface material from the sample, the mass and apparent volume were measured in accordance with JIS K7222 to determine the mass and apparent volume.

＜Measurement of thermal conductivity of phenolic resin foamed volumetric laminates at 23°C＞ According to JIS A 1412-2:1999, the thermal conductivity in the thickness direction of the resin foamed volumetric laminate in an environment of 23°C is measured by the following method. The specific steps are as follows.

Cut the phenolic resin foam volumetric laminate into 300 mm squares, and place the test piece into an air atmosphere of 23±1°C and 50±2% humidity. Thereafter, the change in weight over time is measured every 24 hours, and the state is checked and adjusted until the weight change after 24 hours becomes 0.2 mass% or less. The state-conditioned phenolic resin foamed volumetric laminate test piece was introduced into a thermal conductivity device also placed in a gas atmosphere of 23±1°C and a humidity of 50±2%. When the thermal conductivity measuring device is not placed in a room where the phenolic resin foamed volumetric laminate test piece is placed and the humidity is controlled to 23±1% and 50±2%, the state will be carried out in the above gas atmosphere. The confirmed and adjusted test piece is quickly placed into a polyethylene bag, the bag is closed, and the thermal conductivity is measured quickly after being taken out of the bag within 1 hour.

Regarding the thermal conductivity measurement, the thermal conductivity at 23°C was measured using a measuring device (Eiko Seiki Co., Ltd., trade name "HC-074/ FOX304").

<Measurement of compressive strength in thickness direction of phenolic resin foam> After removing the face material from the obtained phenolic resin foamed volumetric laminate, the compressive strength of the phenolic resin foam in the thickness direction was measured in accordance with JIS K7220. Among them, the size of the foam is set to 100 mm×100 mm×30 mm.

<Evaluation of color unevenness of phenolic resin foam> Visually observe the foam cross section of the phenolic resin foam in the thickness direction. As a result, if, in addition to pores, differences in bubble diameters that can be visually confirmed appear in strips or are localized, causing the color of the foam to appear uneven, it will be evaluated as having color unevenness. If not, then the color unevenness will be evaluated. If this situation is met, it is evaluated as "none" color unevenness.

<Evaluation of Porosity of Phenolic Resin Foam> Cut the approximate center of the thickness direction of the phenolic resin foam parallel to the front and back surfaces, and enlarge the area of 100 mm × 150 mm by 200% (area 4.0 times) for coloring. Copy, use transparent graph paper to accumulate the area of 1 mm×1 mm squares with more than 8 (2.0 mm2 ^or more) gaps, calculate the area fraction as porosity (%) (average of 4 measurements), and The porosity of the phenolic resin foam was evaluated as "low" when it was 0.5% or less, and it was evaluated as "high" when it exceeded 0.5%.

<Measurement of the independent cell ratio of the phenolic resin foam> Use a cutting tool such as a band saw at the center of the phenol resin foam in the thickness direction to cut out 25 mm when the thickness of the resin foam is 25 mm or more. mm square cube as the sample. In addition, when the thickness of the resin foam is less than 25 mm, cut it to a thickness after removing the face material (when the fiber body derived from the face material remains or when there is a face material on the back side) And a rectangular parallelepiped with a length and width of 25 mm was used as the sample. Then, the sample volume V (cm ³ ) was measured using the standard method of using an air comparative hydrometer (Model 1000, manufactured by Tokyo-Science Co., Ltd.). As shown in the following formula, the volume of the bubble wall (W/ρ) calculated from the sample mass W (g) and the density ρ of the resin composition constituting the resin foam is subtracted from the above sample volume V, and the result is The difference is divided by the apparent volume Va (cm ³ ) calculated from the dimensions outside the sample. The value obtained is the independent cell ratio of the resin foam, and is measured in accordance with ASTM D 2856 (C method). The density of the phenolic resin composition was calculated as 1.27 kg/L. Independent bubble rate (%) = ((V-W/ρ)/Va)×100

(Example 2) A resin foam was produced in exactly the same manner as in Example 1, except that the hydrofluoroether was changed to 3M Novec (registered trademark) 7100 high-functional liquid (manufactured by 3M Company).

(Example 3) A resin foam was produced in exactly the same manner as in Example 1, except that the hydrofluoroether was changed to 3M Novec (registered trademark) 7200 high-functional liquid (manufactured by 3M Company).

(Example 4) A resin foam was produced in exactly the same manner as in Example 1, except that the hydrofluoroether was changed to 3M Novec (registered trademark) 7300 high-functional liquid (manufactured by 3M Company).

(Example 5) A resin foam was produced in exactly the same manner as in Example 1, except that the hydrofluoroether was changed to Asahiklin (registered trademark) AE-3000 (manufactured by AGC, purity 99% or more).

(Example 6) The same procedure as in Example 1 was performed except that the hydrofluoroether was changed to Novec (registered trademark) 7200 (manufactured by 3M Company) and the amount of hydrofluoroether added was 0.1 part with respect to 100 parts by mass of the phenolic resin composition. method to produce resin foam.

(Example 7) The same procedure as in Example 1 was carried out except that the hydrofluoroether was changed to Novec (registered trademark) 7200 (manufactured by 3M Company) and the amount of hydrofluoroether added was 6.5 parts per 100 parts by mass of the phenolic resin composition. method to produce resin foam.

(Example 8) It was completely the same as Example 1 except that the hydrofluoroether was changed to Novec (registered trademark) 7200 (manufactured by 3M Company) and HCFO-1224yd(Z) (manufactured by AGC Company) as the foaming agent was set to 14 parts by mass. method to produce resin foam.

(Example 9) The hydrofluoroether was changed to Novec (registered trademark) 7200 (manufactured by 3M Company), and a mixture of 80 mass% HCFO-1224yd (Z) (manufactured by AGC Company) and 20 mass% cyclopentane was used as a foaming agent. A resin foam was produced in exactly the same manner as in Example 1 except that the added amount of the foaming agent was 12 parts by mass.

(Example 10) A resin foam was produced in exactly the same manner as in Example 1, except that the hydrofluoroether was changed to Novec (registered trademark) 7200 (manufactured by 3M Company) and the cyclopentane used as the foaming agent was 6.3 parts by mass.

(Example 11) The hydrofluoroether was changed to Novec (registered trademark) 7200 (manufactured by 3M Company), HCFO-1224yd (Z) (manufactured by AGC Company) was used as the foaming agent, the foaming agent addition amount was set to 14 parts by mass, and the hydrofluoroether was A resin foam was produced in exactly the same manner as in Example 1 except that the ether inlet was provided on the downstream side of the mixer and the hydrofluoroether was kneaded after the foaming agent. This production method is shown in Table 2 as production method B.

(Example 12) A block copolymer containing ethylene oxide-propylene oxide and polyoxyethylene dodecyl as a surfactant were mixed at a ratio of 3.0 parts by mass with respect to 100 parts by mass of phenol resin A. A mixture of 50% each of alkylphenyl ethers. This was regarded as a phenol resin composition. 3M Novec (registered trademark) 7200 (manufactured by 3M Company), which is a hydrofluoroether, was placed in a polyethylene cup so that it became 3.0 parts by mass relative to 100 parts by mass of the phenolic resin composition containing the surfactant. The stirring rod is installed in a cordless drill batch (Hi-Koki DS 10DAL) for kneading, and then the polyethylene cup is cooled while using the cordless drill batch so that HCFO-1233zd(E) as a foaming agent becomes 12 parts by mass. Practice. Here, no foaming nucleating agent is added, but the air entrained during mixing acts as a foaming nucleating agent. From the change in the weight of the resin composition, it was confirmed that the predetermined amount was kneaded. Next, the polyethylene cup containing the foamable phenol resin composition was cooled in a refrigerator for 1 hour. After confirming that the foamable phenol resin composition was 12° C. or lower, xylene sulfonic acid containing xylene sulfonic acid was added as an acidic hardener. 13 parts by mass of a mixture of 80% by mass and 20% by mass of diethylene glycol was kneaded for 2 minutes using a cordless drill while bathing in ice. Next, the foamable phenol resin composition was applied to the bottom surface of the metal metal frame (mold frame) using a scraper in an environment of 13°C. The coating amount of the foamable phenol resin composition should be appropriately adjusted to prevent the thickness from protruding from the metal frame (mold frame) after foaming. The metal frame (mold frame) used here consists of metal with a thickness of 2.0 mm, an inner diameter of 300 mm × 300 mm × a height of 30 mm. Holes with a diameter of 5 mm are drilled at 1 mm intervals on the bottom surface, and polyethylene is laid on the bottom surface. Ester nonwoven fabric (Asahi Kasei Co., Ltd. ELTAS E05060, weight per unit area 60 g/m ² ) was used as the surface material. The working time from kneading the foamable phenol resin composition and the acidic hardener to completion of coating was set to 5 minutes. After that, a board larger than 300 mm × 300 mm with the same hole size and bottom surface and a surface material that is the same as the bottom surface of the metal frame (mold frame) is pasted as the top board, with the surface material facing the foaming phenolic resin side. The top plate is covered and fixed to the metal frame (mold frame) using clamps. Put the metal frame (mold frame) into an oven heated to 85°C. Place a 25 kg weight heated to 85°C in the center of the top plate of the metal frame (mold frame). After heating for 1 hour, further heat at 105°C. After curing for 1 hour, a phenolic resin foamed volume laminate with a thickness of 30 mm was obtained. This production method is shown in Table 2 as production method C.

(Comparative example 1) A resin foam was produced in exactly the same manner as in Example 1, except that the fluorine compound AMOLEA (registered trademark) AS-300 (manufactured by AGC, purity 99% or more) that does not conform to Formula 1 was changed.

(Comparative example 2) The same procedure as in Example 1 was carried out except that the hydrofluoroether was changed to Novec (registered trademark) 7200 (manufactured by 3M Company) and the amount of hydrofluoroether added was 7 parts with respect to 100 parts by mass of the phenolic resin composition. method to produce resin foam.

(Comparative example 3) A resin foam was produced in exactly the same manner as in Example 1 except that no hydrofluoroether was added.

(Comparative example 4) A resin foam was produced in exactly the same manner as in Example 8 except that no hydrofluoroether was added.

(Comparative example 5) A resin foam was produced in exactly the same manner as in Example 9 except that no hydrofluoroether was added.

(Comparative example 6) A resin foam was produced in exactly the same manner as in Example 10 except that no hydrofluoroether was added.

(Comparative Example 7) A resin foam was produced in exactly the same manner as in Example 12 except that no hydrofluoroether was added.

Table 1 shows the types of hydrofluoroethers used in Examples 1 to 12 and Comparative Examples 1 and 2. In addition, the above-mentioned measurement and evaluation tests were performed on Examples 1 to 12 and Comparative Examples 1 to 7. The measurement results and evaluation results are shown in 2.

[Table 1] Types of hydrofluoroether Product name Compound name a 2≦a≦7 b 0≦b≦3 c c=2a+1-b x 1≦x≦3 y 2≦y≦7 z z＝2×x＋1－y Boiling point [℃] A 3M Novec (registered trademark) 7000 Methyl perfluoropropyl ether 3 0 7 1 3 0 34 B 3M Novec (registered trademark) 7100 Mixture of methyl nonafluorobutyl ether and methyl nonafluoroisobutyl ether 4 0 9 1 3 0 61 C 3M Novec (registered trademark) 7200 Compounds of ethyl nonafluorobutyl ether and ethyl nonafluoroisobutyl ether 4 0 9 2 5 0 76 D 3M Novec (registered trademark) 7300 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane 6 0 13 1 3 0 98 E Asahiklin (registered trademark) AE-3000 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether 2 1 4 2 2 3 56 F AMOLEA (registered trademark) AS-300 Mixture of (E)-1-chloro-2,3,3-trifluoropropene and (Z)-1-chloro-2,3,3-trifluoropropene Does not comply with formula 1 54

[Table 2] Preparation method Types of hydrofluoroether Amount of hydrofluoroether added relative to 100 parts by mass of phenolic resin composition [g] Hydrofluoroether content (relative to phenolic resin foam mass [%]) Average bubble diameter [μm] Foaming agent Density [kg/m ³ ] Thermal conductivity at 23℃[W/(m・K)] Compressive strength in thickness direction [N/cm ² ] uneven color Porosity assessment Independent bubble rate [%] Example 1 A A 3 2.0 148 HCFO-1233zd(E) 29 0.0170 14 without few 90 Example 2 A B 3 2.0 129 HCFO-1233zd(E) 30 0.0169 16 without few 92 Example 3 A C 3 2.0 125 HCFO-1233zd(E) 32 0.0169 17 without few 92 Example 4 A D 3 2.0 125 HCFO-1233zd(E) 31 0.0169 14 without few 91 Example 5 A E 3 2.0 165 HCFO-1233zd(E) 28 0.0174 14 without few 89 Example 6 A C 0.1 0.07 180 HCFO-1233zd(E) 30 0.0173 16 without few 93 Example 7 A C 6.5 4.3 143 HCFO-1233zd(E) 30 0.0174 14 without few 89 Example 8 A C 3 2.0 121 HCFO-1224yd(Z) 32 0.0166 18 without few 92 Example 9 A C 3 2.0 118 HCFO-1224yd(Z)/cyclopentane=80 mass%/20 mass% 28 0.0172 14 without few 93 Example 10 A C 3 2.0 146 cyclopentane 30 0.0211 14 without few 91 Example 11 B C 3 2.0 132 HCFO-1224yd(Z) 32 0.0176 17 without few 78 Example 12 C C 3 2.5 167 HCFO-1233zd(E) 29 0.0172 13 without few 93 Comparative example 1 A F 3 2.0 193 HCFO-1233zd(E) 26 0.0177 11 without many 82 Comparative example 2 A C 7 4.7 198 HCFO-1233zd(E) 31 0.0179 11 without few 88 Comparative example 3 A - 0 0 215 HCFO-1233zd(E) 30 0.0175 13 have many 87 Comparative example 4 A - 0 0 184 HCFO-1224yd(Z) 32 0.0172 17 without few 89 Comparative example 5 A - 0 0 181 HCFO-1224yd(Z)/cyclopentane=80 mass%/20 mass% 28 0.0176 13 without few 89 Comparative example 6 A - 0 0 211 cyclopentane 30 0.0216 12 without few 91 Comparative example 7 C - 0 0 227 HCFO-1233zd(E) 28 0.0177 12 have many 87 [Industrial availability]

The phenolic resin foam and its laminate according to the present embodiment have small cell diameters, so they may have excellent thermal insulation properties, and may have improved appearance defects such as pores or uneven color of the foam, or improved compressive strength. Therefore, for example, they can be used in Used in various places that require heat insulation. In addition, compared with the previous technology, the raw materials are cheap, the equipment investment is small, and the GWP is small, so it can provide an environmentally friendly foam with a small environmental load. [Cross-reference of related applications]

This application claims priority to Japanese Patent Application No. 2022-071172 filed in Japan on April 22, 2022, and the entire disclosure of the previous application is incorporated herein by reference.

Claims (9)

A phenol resin foam containing a hydrofluoroether represented by the following (Formula 1) in an amount of 0.03 to 4.3% by mass relative to the phenol resin foam, (Formula 1): C _a H _b F _c -OC _x H _y F _z (where a, b, c, x, y, z are integers, 2≦a≦7, 0≦b≦3, c＝2a＋1-b, b≦2a＋1, 1≦x≦3, 2 ≦y≦7, z＝2×x＋1-y, y≦2x＋1). The phenol resin foam of claim 1, wherein the hydrofluoroether represented by (Formula 1) is methyl perfluoropropyl ether, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl Nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether. For example, the phenolic resin foam of claim 1 or 2 has an average bubble diameter of 70 μm or more and 180 μm or less. The phenolic resin foam of claim 1 or 2, wherein the foaming agent contains hydrofluoroolefin. The phenol resin foam of claim 4, wherein the blowing agent contains hydrocarbons. For example, the density of the phenolic resin foam in claim 1 or 2 is not less than 10 kg/ ^m3 and not more than 70 kg/ ^m3 . For example, the phenolic resin foam of claim 1 or 2 has an independent cell rate of more than 80%. For example, the phenolic resin foam of claim 3 has an independent cell rate of more than 80%. A laminated board of phenol resin foam according to claim 1 or 2, which is provided with a surface material on at least one of one side of the phenol resin foam and the back side of the side.