JP6159467B1 - Phenolic resin foam and method for producing the same - Google Patents

Abstract

A phenol resin foam excellent in resistance to stepping-through and a method for producing the same are provided. A phenolic resin foam comprising a foamed resin layer and face materials laminated on both sides thereof, the foamed resin layer containing a halogenated unsaturated hydrocarbon and a hydrocarbon as a foaming agent. The mass ratio of the halogenated unsaturated hydrocarbon to the hydrocarbon in the blowing agent is hydrocarbon: halogenated unsaturated hydrocarbon = 70: 30 to 30:70, the density is 25 kg / m 3 or more and 35 kg / m 3 or less, the average bubble diameter 50 μm or more and 150 μm or less, thermal conductivity is 0.0190 W / m · K or less, closed cell ratio is 85% or more, no yield point exists at a load of 100 kgf in stepping-through evaluation, and face material is not destroyed at 200 kgf The foamed resin layer has a central layer and two surface layers on both sides thereof, and the compressive strength of the two surface layers is 10 N / cm 2 or more, and the average value of the compressive strength is higher than the compressive strength of the central layer. A phenolic resin foam characterized by that. [Selection figure] None

Description

  The present invention relates to a phenol resin foam and a method for producing the same.

The phenol resin foam is excellent in flame retardancy, heat resistance, chemical resistance, corrosion resistance, and the like, and thus has been adopted in various fields as a heat insulating material. For example, in the construction field, a phenol resin foam wallboard is employed as a synthetic resin building material, particularly a wallboard interior material.
The phenol resin foam is obtained by foaming a foamable phenol resin composition containing, for example, a phenol resin, at least one of fluorinated unsaturated hydrocarbon and chlorinated fluorinated unsaturated hydrocarbon as a foaming agent, and an acid catalyst. And it is manufactured by making it harden | cure (for example, refer patent document 1).

  When constructing a heat insulating material made of a phenol resin foam, particularly when constructing on a roof or a floor, the installer may have to walk on the heat insulating material. When the compressive strength and bending strength of the heat insulating material are low, when the installer walks on the heat insulating material, the heat insulating material may be stepped over and fall.

International Publication No. 2015/111670

  When a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon are used as the foaming agent, the viscosity of the foamable phenol resin composition decreases. Therefore, in the phenol resin foam obtained by foaming and curing the foamable phenol resin composition, the bubble diameter may be coarsened or there may be many bubbles having a large diameter. Therefore, the obtained phenol resin foam may have low compressive strength and bending strength, and may have low resistance to stepping-through.

  This invention is made | formed in view of the said situation, Comprising: It aims at providing the phenol resin foam excellent in the tolerance with respect to stepping-through, and its manufacturing method.

[1] A phenolic resin foam comprising a foamed resin layer and face materials laminated on both sides thereof, wherein the foamed resin layer has 1-chloro-3,3,3-tri as a foaming agent. contains tetrafluoropropene and hydrocarbon, the weight ratio of 1-chloro-3,3,3-trifluoropropene and a hydrocarbon in the blowing agent, a hydrocarbon: 1-chloro-3,3,3-trifluoropropene = 70:30 to 30:70, the density is 25 kg / m ³ or more and 35 kg / m ³ or less, the average bubble diameter is 50 μm or more and 150 μm or less, and the thermal conductivity is 0.0190 W / m · K or less. The closed cell ratio is 85% or more, and in passing through evaluation, there is no yield point at a load of 100 kgf, the face material is not destroyed at 200 kgf, and the foamed resin layer has a central layer and both sides thereof. 2 on the side Two surface layers, the compressive strength of the two surface layers is 14.4 N / cm ² or more, and the average compressive strength of the two surface layers is higher than the compressive strength of the central layer Phenol resin foam (excluding those having a thickness of 40 mm or more) .
[2] The method for producing a phenol resin foam according to [1], wherein the phenol resin, the halogenated unsaturated hydrocarbon, and the hydrocarbon are formed on the first face material continuously run by the first conveyor. And a discharge step of discharging a foamable phenol resin composition containing an acid catalyst, and a second conveyor continuously run by a second conveyor to the foamable phenol resin composition discharged onto the first face material. A foaming step of bonding a face material and foaming and curing the foamable phenolic resin composition between the first face material and the second face material. In the foaming step, the first step The distance between the face material and the second face material is gradually shortened along the traveling direction of the first face material and the second face material, and is discharged onto the first face material by the first and second conveyors. The second face material to the foamed phenolic resin composition The difference between the interval between the first surface material and the second surface material at the time point and the interval between the first surface material and the second surface material at the time point when the sandwiching between the first and second conveyors is stopped is 0. method for producing a phenolic resin foam, characterized in der Rukoto than 3mm less .5mm.

  ADVANTAGE OF THE INVENTION According to this invention, the phenol resin foam excellent in the tolerance with respect to stepping-through and its manufacturing method can be provided.

Embodiments of the phenol resin foam and the method for producing the same according to the present invention will be described.
Note that this embodiment is specifically described in order to better understand the gist of the invention, and does not limit the present invention unless otherwise specified.

[Phenolic resin foam]
The phenol resin foam of this embodiment includes a foamed resin layer and a face material laminated without providing an adhesive layer on both sides thereof. The face materials are joined by the adhesiveness of the foamed resin layer itself.
In the phenol resin foam of this embodiment, the foamed resin layer contains at least one of a halogenated saturated hydrocarbon, a fluorinated unsaturated hydrocarbon, and a chlorinated fluorinated unsaturated hydrocarbon.

  In other words, the phenol resin foam of this embodiment includes a phenol resin, at least one of a halogenated saturated hydrocarbon, a fluorinated unsaturated hydrocarbon, and a chlorinated fluorinated unsaturated hydrocarbon as a foaming agent, and an acid catalyst. It is obtained by a method including foaming and curing a foamable phenolic resin composition comprising: and forming a foamed resin layer.

The phenol resin foam preferably further contains a surfactant.
The phenol resin foam may further contain other components other than the phenol resin, the foaming agent, the acid catalyst, and the surfactant, as necessary, as long as the effects of the present invention are not impaired.

The phenol resin foam of the present embodiment has a density of 15 kg / m ³ or more and 50 kg / m ³ or less, preferably 20 kg / m ³ or more and 40 kg / m ³ or less, preferably 25 kg / m ³ or more and 35 kg / m ^3. The following is more preferable.
If the density of the phenol resin foam is 15 kg / m ³ or more, it is easy to further improve the compressive strength of the phenol resin foam. On the other hand, if the density of the phenol resin foam is 50 kg / m ³ or less, it is easy to further improve the heat insulation of the phenol resin foam.

  The density of the phenol resin foam of the present embodiment is a value measured according to the density measuring method defined in Japanese Industrial Standard JIS A9511: 2009.

The phenol resin foam of this embodiment has an average cell diameter of 50 μm or more and 200 μm or less, and preferably 50 μm or more and 150 μm or less.
If the average cell diameter of a phenol resin foam is 50 micrometers or more, the heat insulation of a phenol resin foam can be improved more. When the average cell diameter of the phenol resin foam is less than 50 μm, the compressive strength of the phenol resin foam decreases. On the other hand, when the average cell diameter of the phenol resin foam exceeds 200 μm, the thermal conductivity of the phenol resin foam deteriorates.

  The average cell diameter of the phenol resin foam of the present embodiment can be adjusted by the type and composition of the foaming agent, the type of surfactant, the foaming conditions (heating temperature, heating time, etc.) and the like.

  In the phenol resin foam of the present embodiment, a plurality of bubbles are formed, the bubble wall is substantially free of pores, and at least some of the plurality of bubbles are independent from each other. It is a bubble. In the closed cell, at least one gas of a halogenated saturated hydrocarbon, a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon used as a blowing agent is retained.

The phenol resin foam of this embodiment has a closed cell ratio of 85% or more, and more preferably 90% or more.
The upper limit value of the closed cell ratio is not particularly limited, but is substantially 99% or less. If the closed cell ratio is within the above numerical range, the phenol resin foam can maintain a low thermal conductivity over a long period of time. The closed cell ratio is adjusted by a combination of the type or composition of the foaming agent, the type of surfactant, foaming conditions (heating temperature, heating time, etc.), and the like.

  The closed cell ratio of the phenol resin foam of the present embodiment is a value measured according to the method for measuring the closed cell ratio defined in Japanese Industrial Standard JIS K7138: 2006.

The phenol resin foam of this embodiment has no yield point at a load of 100 kgf and does not break the face material at 200 kgf in the step-through evaluation.
The phenomenon in which stress decreases in the process of increasing strain is called yield, and the point at which yield occurs is called the yield point. In the stress-strain curve, the yield point can be a point where the slope becomes discontinuous. Even if a load exceeding the yield point is applied, there may be no significant damage to the resin foam unless the load is removed, but the inside of the resin foam where the load is applied is broken, and the closed cell is closed. The rate decreases and the heat insulation performance decreases.
Since the yield point of the phenol resin foam of this embodiment does not exist up to a load of 100 kgf, the heat insulation performance is unlikely to deteriorate even when a load is applied.

The foamed resin layer has a central layer and two surface layers (upper layer and lower layer) on both sides thereof. The central layer and the two surface layers on both sides thereof have a uniform thickness in the thickness direction of the foamed resin layer.
Moreover, the compressive strength of two surface layers is 10 N / cm < ² > or more, and the average value of the compressive strength of two surface layers is higher than the compressive strength of a center layer.

The thermal conductivity of the phenol resin foam of this embodiment is preferably 0.0190 W / m · K or less, more preferably 0.0180 W / m · K or less, and 0.0175 W / m · K. More preferably, it is as follows.
When the thermal conductivity is 0.019 W / m · K or less, the phenol resin foam is excellent in heat insulation.

  The thermal conductivity of the phenol resin foam can be adjusted by the average cell diameter, the type and composition of the foaming agent, the type of surfactant, and the like. For example, the smaller the average cell diameter, the lower the thermal conductivity of the phenol resin foam. Further, when the surfactant is a silicone-based surfactant, particularly one having a polyether chain having a —OH end, the thermal conductivity tends to be lower than when other surfactants are used.

The phenol resin foam of the present embodiment preferably has a limiting oxygen index (hereinafter also referred to as “LOI”) of 28% or more, more preferably 30% or more, and more than 32%. More preferably it is.
LOI is the minimum oxygen concentration% (volume fraction) of the mixed gas of oxygen and nitrogen at 23 ° C ± 2 ° C required for the sample to maintain flammable combustion under specified conditions. It is an indicator. It shows that flammability is low, so that LOI is large, and when LOI is 26% or more, it is judged that it has a flame retardance.

  The LOI of the phenol resin foam can be adjusted by the type and composition of the foaming agent, the type of surfactant, the type and composition of the flame retardant and the amount thereof. For example, the lower the content of the combustible foaming agent in the foaming agent (the higher the content of at least one of fluorinated unsaturated hydrocarbon and chlorinated unsaturated fluorinated hydrocarbon), the higher the LOI. Further, if the surfactant is a silicone-based surfactant, particularly one having a polyether chain having a —OH end, the LOI tends to be higher than when other surfactants are used. Furthermore, LOI can be increased by adding a phosphorus-based flame retardant or the like.

(Phenolic resin)
As the phenol resin, a resol type resin is preferable.
The resol type phenol resin is a phenol resin obtained by reacting a phenol compound and an aldehyde in the presence of an alkali catalyst.
The phenol compound is not particularly limited, and examples thereof include phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcinol, and modified products thereof.
Although it does not specifically limit as an aldehyde, For example, formaldehyde, paraformaldehyde, furfural, acetaldehyde, etc. are mentioned.
Although it does not specifically limit as an alkali catalyst, For example, sodium hydroxide, potassium hydroxide, calcium hydroxide, an aliphatic amine (Trimethylamine, a triethylamine, etc.) etc. are mentioned.

  When synthesizing a resol type phenol resin, the blending ratio of the phenol compound and the aldehyde is not particularly limited. The mixing ratio of the phenol compound and the aldehyde is preferably a molar ratio of phenol compound to aldehyde of 1: 1 to 1: 3, and more preferably 1: 1.3 to 1: 2.5.

Moreover, the weight average molecular weight (Mw) calculated | required by the gel permeation chromatography of a phenol resin is 400-3000 normally, Preferably it is 700-2000.
When the weight average molecular weight (Mw) of the phenol resin is less than 400, the closed cell ratio of the phenol resin foam is lowered, thereby reducing the compression strength of the phenol resin foam and the long-term performance of the thermal conductivity of the phenol resin foam. There is a tendency to lead to a decline. Moreover, a phenol resin foam with many voids and a large average cell diameter is likely to be formed. On the other hand, when the weight average molecular weight (Mw) of the phenol resin exceeds 3000, the viscosity of the phenol resin raw material and the foamable phenol resin composition becomes too high. Many blowing agents are required, and when fluorinated unsaturated hydrocarbons and chlorinated fluorinated unsaturated hydrocarbons are used as blowing agents, this is expensive and not economical.

(Foaming agent)
As a foaming agent, at least 1 sort (s) of a halogenated saturated hydrocarbon, a fluorinated unsaturated hydrocarbon (HFO), and a chlorinated fluorinated unsaturated hydrocarbon (HCFO) is included.

  Examples of the fluorinated unsaturated hydrocarbon include those containing fluorine and a carbon-carbon double bond in the molecule. For example, 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3 3,3-tetrafluoropropene (HFO-1234ze) (E and Z isomers), 1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz) (E and Z isomers) (e.g. , SynQuest Laboratories, product number: 1300-3-Z6), and the like disclosed in JP-T-2009-513812.

  Examples of the chlorinated fluorinated unsaturated hydrocarbon include those containing chlorine, fluorine and a double bond in the molecule, such as 1,2-dichloro-1,2-difluoroethene (E and Z isomers), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) (E and Z isomers) (for example, Honeywell, trade name: SOLSTICE LBA), 1-chloro-2,3,3-tri Fluoropropene (HCFO-1233yd) (E and Z isomers), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb) (E and Z isomers), 2-chloro-1,3,3 -Trifluoropropene (HCFO-1233xe) (E and Z isomers), 2-chloro-2,2,3-trifluoropropene (HCFO-1233xc) 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) (for example, SynQuest Laboratories, product number: 1300-7-09), 3-chloro-1,2,3-trifluoropropene (HCFO-1233ye) (E and Z isomers), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc), 3,3-dichloro-3-fluoropropene, 1,2-dichloro-3 , 3,3-trifluoropropene (HFO-1223xd) (E and Z isomers), 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E and Z isomers) And 2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene (E and Z variants) and the like.

  Fluorinated unsaturated hydrocarbons and chlorinated fluorinated unsaturated hydrocarbons are advantageous in that they have a small ozone depletion potential (ODP) and a global warming potential (GWP) and have a small impact on the environment.

  As the chlorinated saturated hydrocarbon, those having 2 to 5 carbon atoms are preferable, and examples thereof include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. Among these, isopropyl chloride is preferable because it has a low ozone depletion coefficient and is excellent in environmental compatibility.

  Examples of the fluorinated saturated hydrocarbon include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1, 2,2-tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-hepta Fluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluobane (HFC365mfc) and 1,1,1,2,2 , 3,4,5,5,5-decafluoropentane (HFC4310mee) and the like.

  Chlorinated saturated hydrocarbons have been conventionally used as a foaming agent for phenol resin foams. However, when one type is used alone, the average cell diameter of the phenol resin foam is large and the thermal conductivity is high. By using a fluorinated unsaturated hydrocarbon or a chlorinated fluorinated unsaturated hydrocarbon in combination, the average cell diameter is small, the thermal conductivity is lowered, and the heat insulating property of the phenol resin foam is improved. Moreover, since the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon are nonflammable, the flame retardancy of the phenol resin foam is improved.

  In a combination of a chlorinated saturated hydrocarbon and at least one of a fluorinated unsaturated hydrocarbon and a chlorinated unsaturated fluorinated hydrocarbon, the chlorinated saturated hydrocarbon, the fluorinated unsaturated hydrocarbon and the chlorinated non-fluorinated hydrocarbon The mass ratio of at least one kind of saturated hydrocarbon is chlorinated saturated hydrocarbon: at least one kind of fluorinated unsaturated hydrocarbon and chlorinated unsaturated fluorinated hydrocarbon = 9.9: 0.1 to 0.1 : 9.9 is preferable. By containing at least one kind of fluorinated unsaturated hydrocarbon and chlorinated fluorinated unsaturated hydrocarbon within a range satisfying the above-mentioned mass ratio, the average cell diameter is smaller, the thermal conductivity is lower, and the phenol resin The heat insulating property of the foam is more excellent.

  In this embodiment, the chlorinated saturated hydrocarbon usually has a lower molecular weight than the fluorinated unsaturated hydrocarbon or chlorinated fluorinated unsaturated hydrocarbon. If the amount is the same, the smaller the molecular weight, the larger the volume when foamed. Therefore, when the molecular weight of the chlorinated saturated hydrocarbon is smaller than the molecular weight of the fluorinated unsaturated hydrocarbon or chlorinated fluorinated unsaturated hydrocarbon, the higher the proportion of chlorinated saturated hydrocarbon, the smaller the amount of foaming agent. Sufficiently easy to foam. Further, chlorinated saturated hydrocarbons tend to be cheaper than fluorinated unsaturated hydrocarbons or chlorinated fluorinated unsaturated hydrocarbons. From these viewpoints, the mass ratio of the chlorinated saturated hydrocarbon to at least one of the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon is chlorinated saturated hydrocarbon: fluorinated unsaturated hydrocarbon and At least one chlorinated fluorinated unsaturated hydrocarbon is preferably 9.9: 0.1 to 5: 5, and more preferably 9: 1 to 7: 3. The lower the ratio of at least one of the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon within the above range, the lower the cost while maintaining excellent heat insulation.

  On the other hand, fluorinated unsaturated hydrocarbons or chlorinated unsaturated hydrocarbons tend to have lower thermal conductivity than chlorinated saturated hydrocarbons. Therefore, from the viewpoint of obtaining better heat insulation, the mass ratio of the chlorinated saturated hydrocarbon to at least one of the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon is chlorinated saturated hydrocarbon: It is preferable that at least one of a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon = 5: 5 to 0.1: 9.9. The higher the ratio of at least one of the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon within the above range, the lower the thermal conductivity and the higher the heat insulation.

In the combination of a chlorinated saturated hydrocarbon and at least one of a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon, the boiling point of the fluorinated unsaturated hydrocarbon or the chlorinated fluorinated unsaturated hydrocarbon is: It is preferably lower than the boiling point of the chlorinated saturated hydrocarbon. When the boiling point of fluorinated unsaturated hydrocarbon or chlorinated fluorinated unsaturated hydrocarbon is lower than the boiling point of chlorinated saturated hydrocarbon, the bubble diameter of the bubbles in the phenol resin foam is small, and the bubbles per unit volume There is a tendency that the number of is increased and the heat insulation is more excellent.
Moreover, it is preferable that the difference of those boiling points is 2 degreeC or more and 30 degrees C or less, and 5 degreeC or more and 20 degrees C or less are more preferable. If the difference in boiling points is larger than the above upper limit, fluorinated unsaturated hydrocarbons or chlorinated fluorinated unsaturated hydrocarbons previously gasified to form bubble nuclei will be gasified, and chlorinated saturated hydrocarbons with higher boiling points will be gasified. By doing so, it may escape from the bubbles and foaming may be insufficient. If the difference in boiling points is smaller than the above lower limit, the chlorinated saturated hydrocarbon may foam without sufficiently forming bubble nuclei, and the bubble diameter may become coarse.
Therefore, for example, when isopropyl chloride having a boiling point of 36 ° C. is selected as a chlorinated saturated hydrocarbon, a halogenated unsaturated hydrocarbon having a boiling point of 6 ° C. or higher and 34 ° C. or lower is selected. It is preferable to select one having a boiling point of 14 ° C. or higher and 34 ° C. or lower from the viewpoint of easy handling near normal temperature.

  As a combination of a chlorinated saturated hydrocarbon and at least one of a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon, a combination of isopropyl chloride (2-chloropropane) and a fluorinated unsaturated hydrocarbon, Alternatively, a combination of isopropyl chloride and chlorinated fluorinated unsaturated hydrocarbon is preferred. In these combinations, each of the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon may be one type or two or more types.

The blowing agent may contain a hydrocarbon as a blowing agent other than fluorinated unsaturated hydrocarbons, chlorinated fluorinated unsaturated hydrocarbons and chlorinated saturated hydrocarbons.
It does not specifically limit as hydrocarbon, For example, it is preferable that a C4-C7 hydrocarbon (butane, isobutane, pentane, isopentane, cyclopentane, hexane, heptane etc.) is included.

  In addition to the above blowing agents, low boiling point gases such as nitrogen, argon, carbon dioxide and air; sodium hydrogen carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, azodicarboxylic amide, azobisisobutyronitrile, azodicarboxylic Chemical foaming agents such as barium acid, N, N′-dinitrosopentamethylenetetramine, p, p′-oxybisbenzenesulfonyl hydrazide, trihydrazinotriazine; porous solid materials and the like may be included.

  The content of the foaming agent in the phenol resin foam (or foamable phenol resin composition) is preferably 1 part by mass or more and 25 parts by mass or less per 100 parts by mass of the phenol resin, and 3 parts by mass or more and 15 parts by mass. More preferably, it is more preferably 5 parts by mass or more and 11 parts by mass or less.

Composition (mass ratio) of at least one kind of halogenated saturated hydrocarbon, fluorinated unsaturated hydrocarbon and chlorinated unsaturated unsaturated hydrocarbon in the foaming agent in the foamable phenol resin composition used for producing the phenol resin foam ) Substantially matches the composition of at least one of a halogenated saturated hydrocarbon, a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon contained in the phenol resin foam.
The composition of at least one of the halogenated saturated hydrocarbon, the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon contained in the phenol resin foam can be confirmed, for example, by the following solvent extraction method.

Solvent extraction method:
Using a standard gas of halogenated saturated hydrocarbon, fluorinated unsaturated hydrocarbon or chlorinated fluorinated unsaturated hydrocarbon in advance, the retention time under the following measurement conditions with a gas chromatograph-mass spectrometer (GC / MS) Ask.
Next, 1.6 g of a phenol resin foam sample from which the upper and lower face materials have been peeled is taken into a glass container for grinding, and 80 mL of tetrahydrofuran (THF) is added.
After crushing the sample so that it is immersed in the solvent, it is pulverized and extracted for 1 minute and 30 seconds with a homogenizer, the extract is filtered with a membrane filter having a pore size of 0.45 μm, and the filtrate is subjected to GC / MS.
The type of halogenated saturated hydrocarbon, fluorinated unsaturated hydrocarbon or chlorinated fluorinated unsaturated hydrocarbon is identified from the retention time and mass spectrum determined in advance. The types of gases other than halogenated saturated hydrocarbons, fluorinated unsaturated hydrocarbons or chlorinated fluorinated unsaturated hydrocarbons are identified by the retention time and mass spectrum.
The detection sensitivity of each blowing agent component is measured with a standard gas, and the composition (mass ratio) is calculated from the detection area area and detection sensitivity of each gas component obtained by the GC / MS.
GC / MS measurement conditions Column used: DB-5ms (Agilent Technology) 60m, inner diameter 0.25mm, film thickness 1μm
Column temperature: 40 ° C (10 minutes)-10 ° C / min-200 ° C
Inlet temperature: 200 ° C
Interface temperature: 230 ° C
Carrier gas: He 1.0 mL / min Split ratio: 20: 1
Measuring method: scanning method m / Z = 11 to 550

(Acid catalyst)
The acid catalyst is contained in the foamable phenol resin composition in order to cure the phenol resin.
Examples of the acid catalyst include organic acids such as benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, and phenolsulfonic acid, and inorganic acids such as sulfuric acid and phosphoric acid. These acid catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

 The content of the acid catalyst in the foamable phenolic resin composition 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 or less per 100 parts by mass of the phenol resin. More preferably, they are 10 to 20 mass parts.

(Surfactant)
The surfactant contributes to the refinement of the cell diameter (cell diameter).
The surfactant is not particularly limited, and those known as foam stabilizers can be used. For example, castor oil alkylene oxide adduct, silicone surfactant, polyoxyethylene sorbitan fatty acid ester and the like can be mentioned. These surfactants may be used alone or in combination of two or more.
The surfactant preferably contains at least one of a castor oil alkylene oxide adduct and a silicone-based surfactant in terms of easily forming bubbles having a small cell diameter, and has a lower thermal conductivity and a higher flame retardancy. It is more preferable that a silicone type surfactant is included at the point which can do.

The alkylene oxide in the castor oil alkylene oxide adduct is preferably an alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide (hereinafter abbreviated as “EO”), propylene oxide (hereinafter abbreviated as “PO”). Is more preferable. The alkylene oxide added to the castor oil may be one type or two or more types.
As the castor oil alkylene oxide adduct, castor oil EO adduct and castor oil PO adduct are preferable.

  As the castor oil alkylene oxide adduct, one obtained by adding alkylene oxide, particularly EO, more than 20 moles and less than 60 moles to 1 mole of castor oil, and more preferably 21 moles or more and 40 moles or less is added. In the castor oil alkylene oxide adduct, a polyoxyalkylene group (polyoxyethylene group or the like) formed by a hydrophobic group mainly composed of a long chain hydrocarbon group of castor oil and a predetermined addition mole of alkylene oxide (EO or the like). The hydrophilic group as a main component is arranged in a well-balanced manner in the molecule, and good surface activity is exhibited. Therefore, the cell diameter of the phenol resin foam is reduced. Further, flexibility is imparted to the bubble wall, thereby preventing the occurrence of cracks.

Examples of silicone surfactants include copolymers of dimethylpolysiloxane and polyether, and organopolysiloxane compounds such as octamethylcyclotetrasiloxane. A copolymer of dimethylpolysiloxane and polyether is preferable in that the surface tension can be easily adjusted by changing the polymerization degree of each of the hydrophobic part and the hydrophilic part.
The copolymer of dimethylpolysiloxane and polyether is preferably a block copolymer of dimethylpolysiloxane and polyether. The structure of the block copolymer is not particularly limited. For example, an ABA type in which a polyether chain A is bonded to both ends of the siloxane chain B, and a plurality of siloxane chains B and a plurality of polyether chains A are alternately bonded. (AB) _n- type, branched type in which a polyether chain is bonded to each end of a branched siloxane chain, pendant type in which a polyether chain is bonded as a side group (group bonded to a portion other than the terminal) to the siloxane chain Can be mentioned.

Examples of the copolymer of dimethylpolysiloxane and polyether include dimethylpolysiloxane-polyoxyalkylene copolymer.
The number of carbon atoms of the oxyalkylene group in polyoxyalkylene is preferably 2 or 3.
The oxyalkylene group constituting the polyoxyalkylene may be one type or two or more types.
Specific examples of the dimethylpolysiloxane-polyoxyalkylene copolymer include dimethylpolysiloxane-polyoxyethylene copolymer, dimethylpolysiloxane-polyoxypropylene copolymer, dimethylpolysiloxane-polyoxyethylene-polyoxypropylene copolymer. A polymer etc. are mentioned.

  As the copolymer of dimethylpolysiloxane and polyether, those having a polyether chain whose terminal is -OR (wherein R is a hydrogen atom or an alkyl group) are preferred, and the thermal conductivity is more enhanced. A compound in which R is a hydrogen atom is particularly preferable because it is low and flame retardancy can be further increased.

When the phenol resin foam contains a surfactant, the content of the surfactant in the foamable phenol resin composition is preferably 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the phenol resin. It is more preferable that the amount is not less than 5 parts by mass.
If the content of the surfactant is not less than the lower limit of the above range, the cell diameter tends to be uniformly small, and if it is not more than the upper limit, the water absorption of the phenol resin foam is low and the production cost can be suppressed. .

(Other ingredients)
As another component, what is known as an additive of a phenol resin foam can be added to a foamable phenol resin composition. Examples of other components include urea, plasticizers, fillers, flame retardants (for example, phosphorus flame retardants), crosslinking agents, organic solvents, amino group-containing organic compounds, and colorants.

Urea is used as a formaldehyde catcher agent that captures formaldehyde when foaming a foamable phenolic resin composition to produce a foam.
Examples of the plasticizer include polyester polyol and polyethylene glycol which are reaction products of phthalic acid and diethylene glycol.

  Here, it is known to add a plasticizer having high compatibility with a hydrophilic phenol resin, for example, a plasticizer containing a polyester polyol (for example, Patent No. 4761446). ). However, fluorinated unsaturated hydrocarbons and chlorinated fluorinated unsaturated hydrocarbons are highly compatible with phenolic resins due to their high polarities in the molecule, and fluorinated unsaturated hydrocarbons and chlorinated fluorinated unsaturated hydrocarbons. When a foaming agent containing a large amount of and a plasticizer are used in combination, the viscosity of the phenol resin is too low, and there is a possibility that the foam may not be sufficiently foamed or the phenol resin may ooze out from the face material. Therefore, when using fluorinated unsaturated hydrocarbons or chlorinated fluorinated unsaturated hydrocarbons as the foaming agent, it is preferable not to include a plasticizer.

Examples of the filler include basic fillers. As the basic filler, an inorganic filler is preferable in that a phenol resin foam having low acidity and improved fire resistance can be provided.
Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, titanium oxide, metal oxide such as antimony oxide, metal powder such as zinc, carbonic acid Metal carbonates such as calcium, magnesium carbonate, barium carbonate, zinc carbonate, alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkaline earth metal hydrogen carbonates such as calcium hydrogen carbonate and magnesium hydrogen carbonate, sulfuric acid Examples include calcium, barium sulfate, calcium silicate, mica, talc, bentonite, zeolite, silica gel, and the like. However, when a strong acid is used as the acid catalyst, it is necessary to add the metal powder and carbonate within a range that does not affect the adjustment of the pot life. These inorganic fillers may be used individually by 1 type, and may be used together 2 or more types.

When the foamable phenol resin composition contains a basic filler, the content of the basic filler in the foamable phenol resin composition is preferably such that the extraction pH is 5 or more. For example, the content of the basic filler is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, per 100 parts by mass of the phenol resin. It is more preferably 3 parts by mass or more and 15 parts by mass or less, and particularly preferably 5 parts by mass or more and 10 parts by mass or less.
If content of a basic filler is less than the said lower limit, the extraction pH of a phenol resin foam will become low. When the extraction pH is lowered, the acidity increases, so that the material in contact with the phenol resin foam may be corroded. When the content of the basic filler exceeds the above upper limit, the curing reaction by the acid catalyst is remarkably inhibited, and the productivity may be deteriorated.

The extraction pH is measured by the following method.
A phenol resin foam is pulverized in a mortar to 250 μm (60 mesh) or less to prepare a sample. Weigh 0.5 g of sample into a 200 mL Erlenmeyer flask with a stopper. Add 100 mL of pure water to a conical stoppered Erlenmeyer flask and seal tightly. Using a magnetic stirrer, the inside of the conical stoppered flask is stirred at 23 ° C. ± 5 ° C. for 7 days to obtain a sample solution. The pH of the obtained sample solution is measured with a pH meter, and the value is taken as the extraction pH.

  The basic filler also functions as a protective agent that captures hydrogen fluoride. It is known that the halogenated unsaturated hydrocarbon used as the blowing agent generates hydrogen fluoride by decomposition or contains hydrogen fluoride used as a raw material for its production as an impurity (see Table 2014). No. 511930). This hydrogen fluoride is not only highly reactive and extremely harmful to the human body, but also reacts with the siloxane bond constituting the hydrophobic part of the silicone surfactant to reduce the surface active action. Therefore, the above basic filler may be added to the foamable phenol resin composition as a hydrogen fluoride scavenger or a surfactant protective agent. In particular, among the above fillers, it is preferable to use a basic inorganic filler such as calcium carbonate because the extraction pH can be increased.

  On the other hand, as a result of examination by the inventors of the present application, it has been found that the smaller the content of the inorganic filler, the lower the thermal conductivity of the phenol resin foam. Therefore, from the viewpoint of heat insulation, the content of the inorganic filler in the foamable phenolic resin composition is preferably less than 0.1 parts by mass and 0 parts by mass with respect to 100 parts by mass of the phenolic resin. Particularly preferred. That is, it is preferable that the foamable phenol resin composition does not contain an inorganic filler.

The foamable phenol resin composition can be prepared by mixing the above-described components.
The mixing order of each component is not particularly limited. For example, a surfactant is added to a phenol resin, and other components are added as necessary, and the whole is mixed. A foaming agent and an acid catalyst are added to this mixture, and this composition is added. Is supplied to a mixer and stirred to prepare a foamable phenolic resin composition.

The face material is not particularly limited, and glass paper, glass fiber woven fabric, glass fiber nonwoven fabric, glass fiber mixed paper, kraft paper, synthetic fiber nonwoven fabric made of polyester, polypropylene, nylon, etc., spunbond nonwoven fabric, aluminum foil-clad nonwoven fabric At least one selected from the group consisting of aluminum foil-clad kraft paper, metal plate, metal foil, plywood, calcium silicate plate, gypsum board, and wood-based cement plate is preferable.
Each face material provided on both surfaces of the foamed resin layer may be the same or different.

According to the phenol resin foam of the present embodiment, the phenol resin foam includes a foam resin layer, and the foam resin layer is at least one of a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon. The density is 15 kg / m ³ or more and 50 kg / m ³ or less, the average bubble diameter is 50 μm or more and 200 μm or less, the closed cell ratio is 85% or more, and the yield point is measured at a load of 100 kgf in the step-through evaluation. Does not exist, and the face material is not destroyed at 200 kgf. Therefore, it has excellent resistance to stepping through.

[Production method]
The manufacturing method of the phenol resin foam of this embodiment is a manufacturing method of the phenol resin foam of this embodiment, Comprising: On the 1st face material, a phenol resin, a halogenated saturated hydrocarbon, a fluorinated unsaturated carbonization A discharge step of discharging a foamable phenol resin composition containing at least one of hydrogen and a chlorinated fluorinated unsaturated hydrocarbon and an acid catalyst; and a foamable phenol resin composition discharged on a first face material And a foaming step in which the foamable phenolic resin composition is foamed and cured between the first face material and the second face material by bonding the second face material, and in the foaming step, the first face material The distance between the first face material and the second face material is gradually shortened along the traveling direction of the first face material and the second face material.

As a method of providing the first face material and the second face material when manufacturing the phenol resin foam, for example, the first face material is arranged on a conveyor that runs continuously, and the foamable phenol is formed on the first face material. After discharging the resin composition (discharge process) and laminating (bonding) the second face material on the foamable phenolic resin composition discharged on the first face material by a conveyor, the first face material, There is a method in which foaming molding is performed by passing through a heating furnace in a state where a laminate composed of the foamable phenolic resin composition and the second face material is sandwiched between a pair of conveyors (foaming step). Thereby, the phenol resin foam with a face material which the 1st face material and the 2nd face material laminated | stacked on both surfaces of the plate-shaped phenol resin foam is obtained, respectively.
Examples of the conveyor include a slat conveyor and a belt conveyor. The slat conveyor is an integrated conveyor formed by connecting a plurality of plates called slats next to each other. The belt conveyor uses an endless belt as a conveyor.
As the first face material and the second face material, the same face materials as those described above are used.

  In the discharging step, the method for discharging the foamable phenol resin composition onto the first face material is not particularly limited. For example, a method of discharging the foamable phenol resin composition from a plurality of nozzles is used.

In the foaming step, the foamable phenol resin composition of the present embodiment can be produced by foaming and curing the foamable phenol resin composition between the first face material and the second face material.
The phenol resin foam can be produced by a known method. For example, a phenol resin foam can be produced by heating and foaming and curing a foamable phenol resin composition at 30 ° C. or more and 95 ° C. or less.

In the foaming step, the distance in the thickness direction of the phenol resin foam, that is, the distance between the first face material and the second face material is gradually shortened along the running direction of the first face material and the second face material. . The interval between the first face material and the second face material when the second face material is bonded to the foamable phenolic resin composition discharged onto the first face material (the starting point of the foaming process), and the end point of the foaming process. The difference between the distance between the first face material and the second face material at the time when the sandwich of the first face material, the foamable phenolic resin composition and the second face material is stopped between the pair of conveyors is 0. It is preferably 5 mm or more and 3 mm or less, more preferably 0.5 mm or more and 2 mm or less, and further preferably 0.5 mm or more and 1 mm or less.
When the difference between the first face material and the second face material at the start point and the end point of the foaming process is less than 0.5 mm, the effect of improving the compressive strength of the phenol resin foam cannot be obtained. On the other hand, if the difference between the first face material and the second face material at the start and end points of the foaming process exceeds 3 mm, the foaming pressure applied to the conveyor is high, the meandering occurs in the conveyor and the face material, and the thickness is constant. Cannot be produced continuously.

  According to the method for producing a phenol resin foam of the present embodiment, the first face material and the second face material are bonded to the foamable phenol resin composition discharged onto the first face material by bonding the second face material. In the foaming step of foaming and curing the foamable phenolic resin composition, the distance between the first face material and the second face material is gradually shortened along the running direction of the first face material and the second face material. To do. Therefore, a phenol resin foam excellent in resistance to stepping through is obtained.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.
Measurement methods used in Examples and Comparative Examples described later are shown below.

(1) Density The density of the phenol resin foam was measured in accordance with the density measurement method specified in Japanese Industrial Standards JIS A9511: 2009.

(2) Average cell diameter A test piece was cut out from approximately the center in the thickness direction of the phenol resin foam. The cut surface in the thickness direction of the test piece was photographed at 50 times magnification. Four straight lines 9 cm in length were drawn on the photographed image.
At this time, a straight line was drawn so as to avoid voids (voids of 2 mm ² or more). The number of bubbles crossed by each straight line (based on the method for measuring the number of cells defined in Japanese Industrial Standards JIS K6400-1: 2004) was counted for each straight line, and the average value per straight line was obtained. 1800 μm was divided by the average value of the number of bubbles, and the obtained value was defined as the average cell diameter.

(3) Closed cell ratio The closed cell ratio of the phenol resin foam was measured in accordance with the closed cell ratio measurement method specified in Japanese Industrial Standards JIS K7138: 2006.

(4) Thermal conductivity The thermal conductivity of the phenol resin foam was measured based on the measurement method of thermal conductivity defined in Japanese Industrial Standards JIS A 1412-2. The measurement was performed twice on the same sample.

(5) Limiting oxygen index The limiting oxygen index of the phenol resin foam was measured in accordance with the measuring method of limiting oxygen index (LOI) defined in Japanese Industrial Standards JIS K7201-2: 2007.

(6) Step-through evaluation On the universal testing machine, assumed rafters having a length of 910 mm were installed at intervals of 455 mm.
The size of the assumed rafter was 89 mm high x 38 mm wide.
A phenol resin foam of 500 mm × 910 mm was placed on the assumed rafter, and a pseudo foot mold of 100 mm long × 270 mm wide was placed on the center of the phenol resin foam. At this time, the pseudo foot mold was installed in a universal testing machine (Shimadzu Corporation “Autograph AG-50KNE”). This universal testing machine automatically measures the stress-strain curve based on the applied load.
A load was applied and stopped in the thickness direction of the phenol resin foam through the pseudo-foot mold until the load reached 200 kgf at 10 mm / second. After stopping, the presence or absence of a yield point at 100 kgf or less was confirmed by a stress-strain curve. Further, it was visually confirmed whether or not the surface of the phenol resin foam after the test was broken.

(7) Compressive strength of phenol resin foam A phenol resin foam was cut into 100 mm x 100 mm.
The compressive strength of the phenol resin foam was measured in accordance with a measurement method defined in Japanese Industrial Standard JIS K7220.

(8) Compressive strength of the center layer and the surface layer (upper layer, lower layer) of the foamed resin layer A phenol resin foam was cut into 100 mm × 100 mm.
The face material was peeled off from the phenol resin foam, and the foamed resin layer was cut evenly (thickness 10 mm) in the thickness direction, and each was used as a test piece for the center layer, the upper layer, and the lower layer.
Based on the measurement method prescribed | regulated to Japanese Industrial Standards JISK7220, the compressive strength of each test piece (a center layer, an upper layer, a lower layer) was measured.

[Reference Example 1]
100 parts by mass of a liquid resol type phenolic resin (trade name: PF-339, manufactured by Asahi Organic Materials Co., Ltd.), 4 parts by mass of castor oil EO adduct (addition mole number 30) as a surfactant, and urea 4 as a formaldehyde catcher agent A part by mass was added and mixed, and left at 20 ° C. for 8 hours.
As a foaming agent, 14 parts by mass of the foaming agent A shown in Table 1 was added to 108 parts by mass of the mixture thus obtained, and 16 parts by mass of a mixture of paratoluenesulfonic acid and xylenesulfonic acid was added as an acid catalyst. The foamable phenol resin composition was prepared by stirring and mixing. In Table 1, “HCFO-1233zd” represents “E-1-chloro-3,3,3-trifluoropropene”, “CP” represents “cyclopentane”, and “IP” represents “isopentane”. “IPC” indicates “isopropyl chloride”.
On the first face material, the foamable phenolic resin composition is continuously run by a conveyor from 18 nozzles arranged in parallel at equal intervals in a direction perpendicular to the running direction of the first face material. Was discharged.
Subsequently, the 2nd face material was laminated | stacked with the conveyor on the foamable phenol resin composition discharged on the 1st face material. At this time, by adjusting the temperature in the heating and curing furnace in which the conveyor is stored, the previous stage temperature from the heating and curing furnace to the vicinity of the center is 70 ° C., the middle stage temperature near the center of the heating and curing furnace is 65 ° C., and the center of the heating and curing furnace The post-stage temperature from the vicinity to the outlet was set to 60 ° C., and the foamable phenolic resin composition was foamed and cured by being conveyed at a constant speed so as to be heated for about 100 seconds at each temperature from the pre-stage to the post-stage.
Further, when the foamable phenol resin composition is foamed and cured between the first face material and the second face material, the second face material is applied to the foamable phenol resin composition discharged on the first face material. The interval between the first face material and the second face material at the time of bonding (the start point of the foaming process), and the end point of the foaming process (the laminate comprising the first face material, the foamable phenolic resin composition, and the second face material) The difference between the distance between the first face material and the second face material (at the time of stopping the sandwiching between the pair of conveyors) (inlet interval-outlet interval shown in Table 2) was the length shown in Table 1.
Glass fiber mixed paper was used as the first face material and the second face material.
After foaming and curing of the foamable phenol resin composition were completed, the laminate composed of the first face material, the foamed resin layer and the second face material was cured and dried (cured) to obtain a phenol resin foam.
The obtained phenol resin foam was cut into a width of 910 mm and a length of 1820 mm to prepare a phenol resin foam of Reference Example 1 having a thickness of 20 mm.
About the obtained phenol resin foam, it evaluated about the item of said (1)-(8). The results are shown in Table 2. The evaluation results regarding the phenol resin foams of the following Reference Examples 2 to 6 and Examples 2 to 8 are also shown in Table 2.

[Example 1]
A phenol resin foam of Example 1 was produced in the same manner as in Reference Example 1 except that the former stage temperature was 70 ° C, the middle stage temperature was 65 ° C, and the latter stage temperature was 65 ° C.

[Reference Example 2]
A phenol resin foam of Reference Example 2 was produced in the same manner as in Reference Example 1 except that 12 parts by mass of the foaming agent B shown in Table 1 was added as a foaming agent to prepare a foamable phenol resin composition.

[Reference Example 3]
A phenol resin foam of Reference Example 3 was produced in the same manner as Reference Example 2 except that the front-stage temperature was 70 ° C, the middle-stage temperature was 65 ° C, and the rear-stage temperature was 65 ° C.

[Example 2]
As a foaming agent, 14 parts by mass of a foaming agent C shown in Table 1 was added to prepare a foamable phenol resin composition.
Using this foamable phenolic resin composition, the phenol resin foam of Example 2 was prepared in the same manner as in Reference Example 1 except that the former temperature was 75 ° C., the middle temperature was 65 ° C., and the latter temperature was 60 ° C. did.

[Example 3]
A phenol resin foam of Example 3 was produced in the same manner as in Example 2 except that the front temperature was 70 ° C, the middle temperature was 60 ° C, and the rear temperature was 60 ° C.

[Example 4]
A phenol resin foam of Example 4 was prepared in the same manner as in Reference Example 1 except that 14 parts by mass of the foaming agent D shown in Table 1 was added as a foaming agent to prepare a foamable phenol resin composition.

[Example 5]
A phenol resin foam of Example 5 was produced in the same manner as in Example 4 except that the former stage temperature was 70 ° C., the middle stage temperature was 65 ° C., and the latter stage temperature was 65 ° C.

[Example 6]
A phenol resin foam of Example 6 was produced in the same manner as in Reference Example 1 except that 14 parts by mass of the foaming agent E shown in Table 1 was added as a foaming agent to prepare a foamable phenol resin composition.

[Example 7]
A phenol resin foam of Example 7 was produced in the same manner as in Example 6 except that the former stage temperature was 75 ° C, the middle stage temperature was 65 ° C, and the latter stage temperature was 60 ° C.

[Reference Example 4]
A foaming phenol resin composition was prepared by adding 14 parts by mass of a foaming agent F shown in Table 1 as a foaming agent.
Using this foamable phenolic resin composition, the phenol resin foam of Reference Example 4 was prepared in the same manner as in Reference Example 1 except that the former temperature was 75 ° C., the middle temperature was 65 ° C., and the latter temperature was 60 ° C. did.

[Example 8]
A phenol resin foam of Example 8 was produced in the same manner as in Reference Example 4 except that the former stage temperature was 70 ° C, the middle stage temperature was 60 ° C, and the latter stage temperature was 60 ° C.

[Reference Example 5]
A phenol resin foam of Reference Example 5 was produced in the same manner as in Reference Example 1 except that 14 parts by mass of the foaming agent G shown in Table 1 was added as a foaming agent to prepare a foamable phenol resin composition.

[Reference Example 6]
A phenol resin foam of Reference Example 6 was produced in the same manner as Reference Example 5 except that the former stage temperature was 65 ° C, the middle stage temperature was 65 ° C, and the latter stage temperature was 60 ° C.

[Comparative Example 1]
A phenol resin foam of Comparative Example 1 was produced in the same manner as in Example 1 except that the former stage temperature was 75 ° C, the middle stage temperature was 75 ° C, and the latter stage temperature was 75 ° C.

[Comparative Example 2]
A phenol resin foam of Comparative Example 2 was produced in the same manner as in Example 11 except that the former stage temperature was 70 ° C., the middle stage temperature was 70 ° C., and the latter stage temperature was 70 ° C.

From the results of Table 2, it was found that the phenol resin foams of Examples 1 to 6 had no yield point at a load of 100 kgf and the face material was not destroyed at 200 kgf in the step-through evaluation.
On the other hand, the phenol resin foam of Comparative Example 1 was found to have a yield point at a load of 100 kgf in the step-through evaluation. Moreover, the phenol resin foam of Comparative Example 2 was found to have a yield point at a load of 100 kgf and to destroy the face material at 200 kgf in the step-through evaluation.
From the above results, it was confirmed that the phenol resin foams of Examples 1 to 6 were excellent in resistance to stepping through.

The phenolic resin foam of the present invention includes a foamed resin layer, and the foamed resin layer contains a halogenated unsaturated hydrocarbon and a hydrocarbon as a foaming agent, and the halogenated unsaturated hydrocarbon and the hydrocarbon in the foaming agent. Is a hydrocarbon: halogenated unsaturated hydrocarbon = 70: 30 to 30:70, a density is 25 kg / m ³ or more and 35 kg / m ³ or less, and an average bubble diameter is 50 μm or more and 150 μm or less. The thermal conductivity is 0.0190 W / m · K or less, the closed cell ratio is 85% or more, and in the step-through evaluation, there is no yield point at a load of 100 kgf, and the face material is not destroyed at 200 kgf. The foamed resin layer has a central layer and two surface layers on both sides thereof, the compressive strength of the two surface layers is 10 N / cm ² or more, and the average value of the compressive strength of the two surface layers is Middle layer pressure Since it is higher than the compression strength, it has excellent resistance to stepping through. Therefore, it is very useful industrially.

Claims (2)

A phenolic resin foam comprising a foamed resin layer and face materials laminated on both sides thereof,
The foamed resin layer contains 1-chloro-3,3,3-trifluoropropene and hydrocarbon as a foaming agent,
The mass ratio of 1-chloro-3,3,3-trifluoropropene to hydrocarbon in the blowing agent is hydrocarbon: 1-chloro-3,3,3-trifluoropropene = 70: 30 to 30:70. Yes,
The density is 25 kg / m ³ or more and 35 kg / m ³ or less,
The average bubble diameter is 50 μm or more and 150 μm or less,
The thermal conductivity is 0.0190 W / m · K or less,
The closed cell rate is 85% or more,
In the step-through evaluation, there is no yield point at a load of 100 kgf, the face material is not destroyed at 200 kgf,
The foamed resin layer has a central layer and two surface layers on both sides thereof, and the compressive strength of the two surface layers is 14.4 N / cm ² or more,
A phenol resin foam characterized in that an average value of the compressive strengths of the two surface layers is higher than the compressive strength of the central layer (excluding those having a thickness of 40 mm or more) . It is a manufacturing method of the phenol resin foam of Claim 1, Comprising:
A discharge step of discharging a foamable phenol resin composition containing a phenol resin, a halogenated unsaturated hydrocarbon, a hydrocarbon, and an acid catalyst on the first face material continuously run by the first conveyor ;
A second surface material continuously run by a second conveyor is bonded to the foamable phenolic resin composition discharged on the first surface material, and the space between the first surface material and the second surface material. And a foaming step of foaming and curing the foamable phenolic resin composition,
In the foaming step, an interval between the first face material and the second face material is gradually shortened along a traveling direction of the first face material and the second face material ,
The interval between the first face material and the second face material when the second face material is bonded to the foamable phenolic resin composition discharged onto the first face material by the first and second conveyors, first, phenolic resin foam difference in at the time to stop the pinching in the second conveyor and the first surface member and the spacing of the second surface material is characterized der Rukoto than 3mm less 0.5mm Manufacturing method.