JP2018095824A - Phenol resin foam and method for producing the phenol resin foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenol resin foam to which chips do not adhere easily even when a foaming agent containing halogenated hydrocarbon is used, and to provide a method for producing the same.SOLUTION: The phenol resin foam comprises a foaming agent containing halogenated hydrocarbon, where the halogenated hydrocarbon is one or more selected from 1-chloro-3,3,3-trifluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene, a density is 25 kg/mor more and 35 kg/mor less, an average cell diameter is 50 μm or more and 150 μm or less, an average cell diameter of the surface layer is 5 μm or more and 80 μm or less, a closed cell ratio is 85% or more, thermal conductivity is 0.019 W/m K or less, and an abrasion mass in a Taber abrasion test is 0.6 g or less.SELECTED DRAWING: None

Description

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

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 is used as a synthetic resin building material, particularly a wallboard interior material.
The phenol resin foam is usually produced by foaming and curing a foamable phenol resin composition containing a phenol resin, a foaming agent, an acid catalyst (curing agent), a surfactant and the like. The phenol resin foam thus produced has closed cells, and the closed cells contain a gas generated from the blowing agent.
Known foaming agents used for phenolic resin foams include hydrocarbons such as butane and pentane, and halogenated hydrocarbons such as difluoropropene.

  Halogenated hydrocarbons and the like are suitable as phenolic resin foams because they have a substantially zero ozone depletion coefficient, a low global warming coefficient, and flame retardancy. Patent Document 1 proposes a phenol resin foam containing a predetermined amount of a blowing agent containing a halogenated hydrocarbon.

Japanese Patent Laying-Open No. 2015-157937

However, the phenol resin foam containing the foaming agent containing halogenated hydrocarbon like patent document 1 tends to become weak. For this reason, chips are easily generated when the phenol resin foam is cut. In addition, corner cracks, cracks, and dents are likely to occur due to rubbing and collision during construction of the heat insulating material. When such a malfunction occurs, there is a concern that the heat insulation performance and the air density of the portion where the phenol resin foam is applied are reduced.
Then, even if it uses the foaming agent containing a halogenated hydrocarbon, this invention aims at the phenol resin foam which is hard to produce a chip, and its manufacturing method.

In order to solve the above problems, the present invention has the following aspects.
[1] A foaming agent containing a halogenated hydrocarbon is contained, and the halogenated hydrocarbon is 1-chloro-3,3,3-trifluoropropene and 1,1,1,4,4,4-hexafluoro- It is one or more selected from 2-butene, 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 average bubble diameter of the surface layer is 5 μm or more and 80 μm or less. A phenolic resin foam having a closed cell ratio of 85% or more, a thermal conductivity of 0.019 W / m · K or less, and a wear mass in a Taber abrasion test of 0.6 g or less.

[2] A method for producing a phenol resin foam according to [1], wherein a foamable phenol resin composition containing a phenol resin, a foaming agent containing a halogenated hydrocarbon and an acid catalyst is heated to foam, A foam curing step for curing, and a curing step for drying and further curing the foamable phenolic resin composition after the foam curing step, wherein the halogenated hydrocarbon is 1-chloro-3,3,3 -One or more selected from trifluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene, and in the vicinity of the thickness direction center of the foamable phenol resin composition in the foam curing step And a cooling step of cooling the surface temperature of the foamed foamable phenol resin composition to 30 to 50 ° C. between the foam curing step and the curing step. Method for producing a phenolic resin foam characterized in that it comprises a.
[3] The method for producing a phenol resin foam according to [1], wherein the foamable phenol resin composition containing a phenol resin, a foaming agent containing a halogenated hydrocarbon, and an acid catalyst is heated to foam, A foam curing step for curing, and a curing step for drying and further curing the foamable phenolic resin composition after the foam curing step, wherein the halogenated hydrocarbon is 1-chloro-3,3,3 -One or more selected from trifluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene, and the atmospheric temperature in the foam curing step is 30 ° C or higher and 95 ° C or lower, The atmospheric temperature in the curing step is 50 ° C. or higher and 110 ° C. or lower, and the temperature difference between the atmospheric temperature in the foam curing step and the atmospheric temperature in the curing step is 5 ° C. or higher. Method for producing a phenolic foam according to symptoms.

  ADVANTAGE OF THE INVENTION According to this invention, even when the foaming agent containing a halogenated hydrocarbon is used, the phenol resin foam which does not produce cutting powder easily, and its manufacturing method can be provided.

[Phenolic resin foam]
The phenol resin foam of the present invention is obtained by foaming and curing a foamable phenol resin composition containing a phenol resin, a foaming agent and an acid catalyst.
The foamable phenol resin composition may further contain other components other than the phenol resin, the foaming agent, and the acid catalyst, as long as the effects of the present invention are not impaired.

<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.
Examples of the phenol compound include phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcinol, and modified products thereof.
Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, and acetaldehyde.
Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, calcium hydroxide, aliphatic amine (trimethylamine, triethylamine, etc.) and the like. However, the phenol compound, the aldehyde, and the alkali catalyst are not limited to those described above. A phenol resin may be used individually by 1 type, and 2 or more types may be used in combination.
The ratio of a phenol compound and an aldehyde is not specifically limited. Preferably, the molar ratio of phenol compound: aldehyde is 1: 1 to 1: 3, more preferably 1: 1.3 to 1: 2.5.

<Foaming agent>
The phenol resin foam of the present invention contains a foaming agent containing a halogenated hydrocarbon.
Halogenated hydrocarbons can be broadly classified into halogenated saturated hydrocarbons and halogenated unsaturated hydrocarbons.
As a halogenated saturated hydrocarbon, a well-known thing can be used as a foaming agent, and a thing with a boiling point of 12-80 degreeC is mentioned typically.
The thermal conductivity of the halogenated saturated hydrocarbon is preferably 0.013 W / m · K or less, and more preferably 0.011 W / m · K or less.
2-6 are preferable and, as for carbon number of a halogenated saturated hydrocarbon, 2-5 are more preferable. Examples of the halogenated saturated hydrocarbon include chlorinated saturated hydrocarbon and fluorinated saturated hydrocarbon. The halogenated saturated hydrocarbon may be one in which all of hydrogen is substituted with halogen, or one in which a part of hydrogen is substituted with halogen.
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.
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, Examples thereof include hydrofluorocarbons such as 2,3,4,5,5,5-decafluoropentane (HFC4310mee).
Among these, isopropyl chloride is preferable because it has a low ozone depletion coefficient and is excellent in environmental compatibility.

The halogenated unsaturated hydrocarbon has a carbon-carbon double bond and a halogen atom in the molecule.
Halogenated unsaturated hydrocarbons include fluorinated unsaturated hydrocarbons, chlorinated unsaturated hydrocarbons, chlorinated fluorinated unsaturated hydrocarbons, brominated fluorinated unsaturated hydrocarbons, iodinated fluorinated unsaturated hydrocarbons, etc. Is mentioned.
As a halogenated unsaturated hydrocarbon, a well-known thing can be used as a foaming agent, and a thing with a boiling point of -28-80 degreeC is mentioned typically.
The thermal conductivity of the halogenated unsaturated hydrocarbon is preferably 0.013 W / m · K or less, and more preferably 0.011 W / m · K or less.
2-6 are preferable and, as for carbon number of a halogenated unsaturated hydrocarbon, 2-5 are more preferable.

Examples of the halogenated unsaturated hydrocarbon include, for example, a fluorinated unsaturated hydrocarbon having a carbon-carbon double bond and a halogen atom in the molecule, a chlorinated fluorinated unsaturated hydrocarbon, and a brominated fluorinated unsaturated. Examples of the halogenated unsaturated hydrocarbon include those having a fluorine atom such as a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon. The halogenated unsaturated hydrocarbon may be one in which all of hydrogen is substituted with halogen, or one in which a part of hydrogen is substituted with halogen.
These halogenated unsaturated hydrocarbons may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the fluorinated unsaturated hydrocarbon include hydrofluoroolefins having fluorine and carbon-carbon double bonds in the molecule (hereinafter also referred to as “HFO”). Examples of HFO include 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze) (E and Z isomers), 1,1 , 1, 4, 4, 4-hexafluoro-2-butene (HFO-1336mzz) (E and Z isomers) (manufactured by SynQuest Laboratories, product number: 1300-3-Z6) What is disclosed by the gazette etc. is mentioned.
Among these, 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz) is preferable because of its high boiling point and ease of handling and control of the foaming process.
These fluorinated unsaturated hydrocarbons may be used alone or in combination of two or more.

Chlorinated fluorinated unsaturated hydrocarbons include 1,2-dichloro-1,2-difluoroethene (E and Z isomers), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) ( E and Z isomers) (HoneyWell, trade name: SOLSTICE
LBA), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd) (E and Z isomers), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb) (E and Z isomer), 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) (manufactured by 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 (HCFO-1223xd) (E and Z isomers), 2-chloro-1,1,1,4 4,4-hexafluoro-2-butene (E and Z isomers), 2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene (E and Z variants), etc. Is mentioned.
Among these, 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) is preferable because of its high boiling point and ease of handling and control of the foaming process.
These chlorinated fluorinated unsaturated hydrocarbons may be used alone or in combination of two or more.

  As foaming agents other than the above-mentioned halogenated hydrocarbons, for example, cyclic or chain hydrocarbons or unsaturated hydrocarbons having 3 to 7 carbon atoms can be used as the foaming agent. Specifically, compounds such as normal butane, isobutane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, normal hexane, isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, and cyclohexane are included in the blowing agent. Can be. Of these, compounds selected from pentanes such as normal pentane, isopentane, cyclopentane and neopentane, and butanes such as normal butane, isobutane and cyclobutane are preferred.

Furthermore, the phenol resin foam of the present invention may contain other foaming agents, for example, ethers such as pdimethyl ether; carbonates such as sodium hydrogen carbonate, sodium carbonate, calcium carbonate, magnesium carbonate; azodicarboxylic acid Chemical foaming agents such as amide, azobisisobutyronitrile, barium azodicarboxylate, N, N′-dinitrosopentamethylenetetramine, p, p′-oxybisbenzenesulfonylhydrazide, trihydrazinotriazine; porous solid material Etc. These foaming agents may be used individually by 1 type, and may be used in combination of 2 or more type.
In addition, the mass of these foaming agents does not exceed 100 mass% with respect to the total mass of a foaming agent.

  The content of the foaming agent in the foamable phenol resin composition is preferably 1 part by mass or more and 25 parts by mass or less, more preferably 3 parts by mass or more and 15 parts by mass or less, and more preferably 5 parts by mass or more and 12 parts by mass per 100 parts by mass of the phenol resin. More preferred is less than or equal to parts by weight. When it is at least the above lower limit value, the foamable phenol resin composition is sufficiently foamed, and the heat insulation of the phenol resin foam is easily enhanced. When the amount is not more than the above upper limit value, the degree of foaming of the foamable phenol resin composition can be suppressed, and the occurrence of chips of the phenol resin foam can be easily suppressed.

<Acid catalyst>
The acid catalyst is used to initiate the polymerization of the phenolic 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 singly or in combination of two or more.

  The content of the acid catalyst in the foamable phenolic resin composition is preferably 5 to 30 parts by mass, more preferably 8 to 25 parts by mass, more preferably 10 to 20 parts by mass per 100 parts by mass of the phenol resin. More preferred is less than or equal to parts by weight. If the amount is larger than the above upper limit, the water absorption amount of the phenol resin is deteriorated. When it is less than the lower limit, the polymerization reaction of the phenol resin is slow, and the production time is long.

<Optional component>
The foamable phenol resin composition may contain components (arbitrary components) other than the phenol resin, the foaming agent, and the acid catalyst. Examples of optional components include surfactants, foam nucleating agents, urea, fillers (fillers), plasticizers, crosslinking agents, organic solvents, amino group-containing organic compounds, and colorants.

(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 singly or in combination of two or more.
The surfactant preferably contains one or both of a castor oil alkylene oxide adduct and a silicone-based surfactant because it is easy to form bubbles having a small cell diameter, and has a lower thermal conductivity and flame retardancy. It is more preferable that a silicone-based surfactant is included in that it can be made higher.

The alkylene oxide in the castor oil alkylene oxide adduct is preferably an alkylene oxide having 2 to 4 carbon atoms, more preferably ethylene oxide (hereinafter abbreviated as “EO”) or propylene oxide (hereinafter abbreviated as “PO”). Preferably, EO 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.

  The number of moles of alkylene oxide added in the castor oil alkylene oxide adduct is preferably more than 20 moles and less than 60 moles, more preferably 21 to 40 moles per mole of castor oil. In such a 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 mainly composed of is arranged in a well-balanced manner in the molecule and exhibits a good surface activity. For this reason, the bubble diameter of a phenol resin foam becomes small. Moreover, a softness | flexibility is provided to the cell wall of a phenol resin foam, and generation | occurrence | production of a crack is prevented.

Examples of the silicone surfactant include a copolymer of dimethylpolysiloxane and polyether, and an organopolysiloxane compound such as octamethylcyclotetrasiloxane. Among them, a copolymer of dimethylpolysiloxane and polyether is preferable in that more uniform and finer bubbles can be obtained.
The structure of the copolymer of dimethylpolysiloxane and polyether is not particularly limited. For example, an ABA type in which polyether chains are bonded to both ends of the siloxane chain, and a plurality of siloxane chains and a plurality of polyether chains are alternated. (AB) n-type bonded to, branched type in which a polyether chain is bonded to each end of a branched siloxane chain, and a polyether chain bonded to the siloxane chain as a side group (group bonded to a portion other than the terminal) A pendant type etc. are mentioned.

Examples of the copolymer of dimethylpolysiloxane and polyether include dimethylpolysiloxane-polyoxyalkylene copolymer.
As for carbon number of the oxyalkylene group in polyoxyalkylene, 2 or 3 is preferable.
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 favorable. In view of reduction, it is particularly preferable that R is a hydrogen atom.

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, more preferably 2 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the phenol resin. If the content of the surfactant is not less than the above lower limit value, the bubble diameter tends to be uniform and fine. If it is below the said upper limit, the water absorption of a phenol resin foam will become low and manufacturing cost will also be suppressed.
In the foamable phenol resin composition, the mass ratio represented by the foaming agent: surfactant is preferably, for example, 1: 1 to 6: 1. If the mass ratio of the foaming agent and the surfactant is within the above range, the foaming agent can be uniformly dispersed in the phenol resin to form fine bubbles. When the ratio of the foaming agent is not less than the above lower limit, the foamable phenol resin composition can be sufficiently foamed. When the ratio of the foaming agent is not more than the above upper limit value, the foaming agent in the foamable phenol resin composition is sufficiently easily dispersed.

(Foaming nucleating agent)
Examples of the foam nucleating agent include low-boiling substances such as nitrogen, helium, argon, and air. By using the foam nucleating agent, the bubbles in the phenol resin foam can be made more uniform and fine.
The content of the foam nucleating agent in the foamable phenolic resin composition is preferably 0.05 mol% or more and 5 mol% or less with respect to the foaming agent.

(urea)
Urea is used as a formaldehyde catcher agent that traps formaldehyde when foaming a foamable phenolic resin composition to produce a foam.

(filler)
As the filler, an inorganic filler is preferable in that a phenol resin foam having low thermal conductivity and acidity and improved fire resistance can be obtained.
Examples of the inorganic filler include metal hydroxides and oxides of metals such as aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, titanium oxide, and antimony oxide, and metal powders such as zinc; 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. These inorganic fillers may be used alone or in combination of two or more.

  The content of the filler in the foamable phenolic resin composition is preferably such that the pH is 3 or more and less than 7, more preferably 4 or more and less than 6, and even more preferably 5 or less and less than 6. For example, the content of the filler is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass per 100 parts by mass of the phenol resin. More preferred is 5 to 10 parts by mass. It becomes easy to suppress that pH of a phenol resin foam falls that content of a filler is the said lower limit or more. If the pH is suppressed to be low, the acidity can be suppressed, so that it is easy to suppress the corrosion of the material in contact with the phenol resin foam. When the filler content is not more than the above upper limit value or the pH is less than 7, the curing reaction by the acid catalyst is likely to proceed, and the productivity is likely to be improved.

[Method for producing foamable phenolic resin composition]
A foamable phenol resin composition is prepared by mixing a phenol resin, a foaming agent, an acid catalyst, and an arbitrary component as needed.
The order of mixing the components is not particularly limited. For example, optional components may be added to and mixed with the phenol resin as necessary, and a foaming agent and an acid catalyst are added to the resulting mixture, and this composition is supplied to a mixer. And stirring to prepare a foamable phenolic resin composition.

[Method for producing phenolic resin foam]
The foamed phenolic resin composition of the present invention can be produced by foaming and curing the foamable phenolic resin composition.
A phenol resin foam is manufactured by a well-known manufacturing method. For example, the phenol resin foam is obtained by heating and foaming and curing the foamable phenol resin composition, and after the foam curing process, the foamable phenol resin composition is dried and further cured. It can manufacture with the manufacturing method of the phenol resin foam which has a curing process. Furthermore, you may have the cooling process which cools the said foamable phenol resin composition between the said foam hardening process and the said curing process.
In the present embodiment, in the foam curing step, the heating time is set short in order to suppress excessive foaming of the foamable phenol resin composition. The foamable phenol resin composition after the foam curing step may not be sufficiently cured. Therefore, a curing process is provided to cure the foamable phenolic resin composition.
The foamable phenol resin composition is generally cured by heating at 80 ° C. for 60 minutes to 120 minutes, depending on the reactivity of the phenol resin and the amount of acid catalyst added.

<Foam curing process>
The foam curing step is a step of heating and foaming and curing the foamable phenol resin composition. The foam curing step is performed, for example, in a foaming furnace.
30 to 95 degreeC is preferable, as for the atmospheric temperature in a foam hardening process, 40 to 90 degreeC is more preferable, and 50 to 85 degreeC is further more preferable. By setting it as more than the said lower limit, foaming of a foamable phenol resin composition can be advanced moderately easily. By setting it to the upper limit value or less, excessive foaming of the foamable phenol resin composition can be suppressed.
At this time, the surface temperature of the foamable phenol resin composition is preferably 30 ° C. or higher and 90 ° C. or lower, more preferably 40 ° C. or higher and 85 ° C. or lower, and further preferably 50 ° C. or higher and 80 ° C. or lower. By setting it as more than the said lower limit, foaming of a foamable phenol resin composition can be advanced moderately easily. By setting it to the upper limit value or less, excessive foaming of the foamable phenol resin composition can be suppressed.
At this time, the temperature of the central portion (near the center in the thickness direction) of the foamable phenol resin composition is preferably 35 ° C. or higher and 90 ° C. or lower, more preferably 45 ° C. or higher and 85 ° C. or lower, and 55 ° C. More preferably, the temperature is 80 ° C. or lower. By setting it as more than the said lower limit, foaming of a foamable phenol resin composition can be advanced moderately easily. By setting it to the upper limit value or less, it is possible to prevent the average cell diameter of the central cell from becoming coarse.
The temperature difference between the center temperature and the surface temperature is preferably 0 ° C. or more and 10 ° C. or less, more preferably 0 ° C. or more and 8 ° C. or less, further preferably 0 ° C. or more and 6 ° C. or less, and most preferably 0 ° C. is there. If the temperature difference is within the above range, it is easy to make the average cell diameter of the cells uniform. When the average cell diameter of the cells is uniform, generation of chips of the phenol resin foam is easily suppressed.

  As a method for reducing the temperature difference between the temperature at the center and the surface temperature, a doctor blade that spreads the resin discharged from the distribution pipe in the width direction (direction perpendicular to the discharge direction of the foamable phenolic resin composition: TD direction). There is a method of discharging from a large number of discharge ports using distribution pipes that have been branched many times than before (discharge process).

As a case where a doctor blade is used, for example, in a conveyor having a length of 1000 mm in the TD direction, a plurality of discharge ports are provided in the TD direction, and a plurality of doctor blades having a V-shaped cross section are arranged behind each discharge port. . That is, the same number of doctor blades as the discharge ports are arranged. By this doctor blade, the tip of each doctor blade (V-shaped central portion) is inserted into the foamable phenolic resin composition discharged from each discharge port, and the foamable phenolic resin composition is inserted into the end of the doctor blade (V-shaped). The left and right edges of the
The temperature near the center of the foamable phenol resin composition discharged by the V-shaped doctor blade can be lowered. Note that the shape of the doctor blade is not limited to a V shape, and may be a U shape.
As the material of the doctor blade, a metal plate such as iron or stainless steel processed into a V shape can be used. However, the acid foamable phenolic resin composition does not rust and the surface is resistant to acid. It is preferable to apply the coating.
It is preferable that the plurality of doctor blades are spaced apart from each other, whereby the foamable phenol resin composition is less likely to stay in the doctor blade portion. When the conventionally known doctor blades have a plate-like shape that is continuous in the TD direction (for example, JP-A-8-216175), in the foamable phenolic resin composition having a high viscosity, the foamable phenolic resin retained by the doctor blade The amount of the composition increases, and the time until the foamable phenolic resin composition is introduced into the foam molding apparatus from the discharge port becomes non-uniform, which tends to cause poor foaming.
By using the doctor blade as described above, it is possible to suppress the increase in the temperature of the central portion where the temperature is likely to rise, thereby suppressing the coarsening of the cell in the central portion.

In addition, when using a multi-distributed distribution pipe, the number of branches is not determined because it depends on the amount of resin to be discharged and the size of the conveyor. For example, 26 pipes are used for discharging resin to a width of 1000 mm. It is preferable to use a distribution nozzle having the above discharge ports. Further, since the discharge nozzles at both ends are more easily cooled than the central discharge nozzle and the resin is likely to stay, the diameter of the discharge nozzles at both ends may be increased.
By using the multi-branch distribution pipes as described above, the discharged resin is easily cooled, and the increase in the temperature of the central portion where the temperature is likely to rise is suppressed, thereby preventing the central cell from becoming coarse.

  The heating time of the foamable phenol resin composition in the foam curing step is preferably from 200 seconds to 400 seconds, more preferably from 250 seconds to 350 seconds, and even more preferably from 280 seconds to 320 seconds. By setting it as more than the said lower limit, foaming of a foamable phenol resin composition can be advanced moderately easily. By setting it to the upper limit value or less, excessive foaming of the foamable phenol resin composition can be suppressed.

The temperature of the surface and center part of a foamable phenol resin composition is measured as follows.
When discharging the foamable phenolic resin composition, button-type temperature loggers (manufactured by KN Laboratories, Super Thermocron) are installed at the upper part, the center part, and the lower part, respectively. The upper part is affixed to the lower surface of the upper face material (the surface in contact with the foamable phenolic resin composition) with double-sided tape, and the lower part is both surfaces on the upper surface of the lower face material (the surface in contact with the foamable phenolic resin composition). Paste with tape. Install the pedestal so that the center of the foamable phenolic resin composition is at the center, attach the logger to the pedestal with double-sided tape, and place the legs of the pedestal on the upper surface of the lower face material (foamable The surface is in contact with the phenol resin composition. The maximum temperature of each part of the foamable phenol resin composition in the foam curing step is measured with a button-type temperature logger. The measurement interval is 2 seconds.

When producing a phenolic resin foam by foam molding, a face material may be provided.
The face material is not particularly limited, and glass fiber nonwoven fabric, glass fiber mixed paper, synthetic fiber nonwoven fabric made of polyester / polypropylene / nylon, spunbond nonwoven fabric, aluminum foil-clad nonwoven fabric, metal plate, metal foil, plywood, calcium silicate At least one selected from a board, a gypsum board, and a wood cement board is preferable.
The face material may be provided on one side of the phenol resin foam or may be provided on both sides. When provided on both sides, each face material may be the same or different.
As a method of providing a face material when producing a phenolic resin foam, for example, a face material is disposed on a conveyor belt that continuously runs, and a foamable phenol resin composition is discharged onto the face material, on which the face material is disposed. After laminating other face materials, a method of foam molding by passing through a foaming furnace can be mentioned. Thereby, the phenol resin foam with a face material in which the face material is laminated on both surfaces of the plate-like phenol resin foam is obtained.
After the foam molding, the face material may be provided by being bonded to the phenol resin foam using an adhesive.

<Curing process>
The curing step is a step of drying and further curing the foamable phenolic resin composition after the foam curing step. The curing process is performed, for example, in a curing cabinet.
In this embodiment, after stopping the heating in the foam curing step, the time after the heating is referred to as the curing step. Or in this embodiment, the process after a foamable phenol resin composition reaches | attains a desired expansion ratio and a polymerization degree is called a curing process.
In the present specification, the foamable phenol resin composition cured after the curing process is referred to as a phenol resin foam.
The atmosphere temperature in the curing step is preferably 50 ° C. or higher and 110 ° C. or lower, more preferably 55 ° C. or higher and 105 ° C. or lower, and further preferably 60 ° C. or higher and 100 ° C. or lower. By setting the atmospheric temperature in the curing process within the above range, a phenol resin foam having a desired density and average cell diameter can be easily obtained.
In the curing step, the curing time is preferably 2 hours or more and 18 hours or less, more preferably 2 hours or more and 15 hours or less, and further preferably 2 hours or more and 12 hours or less. By setting it to the above lower limit value or more, a sufficiently cured phenol resin foam can be easily obtained. The productivity of a phenol resin foam can be improved by setting it as the said upper limit or less.

When the temperature difference between the atmospheric temperature in the foam curing step and the ambient temperature in the curing step is 5 ° C. or more, it is easy to suppress warping of the phenol resin foam, and a phenol resin foam having a desired density and average cell diameter is obtained. This is preferable because it is easily formed.
At this time, the atmospheric temperature in the foam curing step and the atmospheric temperature in the curing step may be higher in the former or higher in the latter.

<Cooling process>
The cooling step is a step of cooling the foamable phenol resin composition to suppress foaming.
In the present embodiment, the time from when the heating in the foam curing process is stopped and the cooling is started to the time before the heating is again referred to as the cooling process. Alternatively, in the present embodiment, after reaching the desired expansion ratio and degree of polymerization, until the time of heating again is referred to as a cooling step.
In the present embodiment, the cooling step may or may not be provided, but the cooling step is provided from the viewpoint of easily obtaining a phenol resin foam having a desired density and average cell diameter. Is preferred.
In the cooling step, it is preferable to cool the foamed phenolic resin composition foamed over 120 to 300 seconds until the surface temperature of the foamable phenolic resin composition reaches 30 to 50 ° C.
By cooling, it is possible to suppress the bubble diameter of the cell at the center from becoming coarser, so that the bubble diameter can be made uniform easily. By making the cell diameter uniform, it becomes easy to suppress the generation of chips of the phenol resin foam.
A cooling process may be provided in a foaming furnace, and may be provided in a curing warehouse. Moreover, you may provide in the place different from a foaming furnace and a curing warehouse.
After the cooling step, the foamable phenol resin composition is sent to the curing step, dried and further cured to obtain a phenol resin foam.

The density of the phenolic foam of the present invention is less 15 kg / ^{m 3} or more 50 kg / ^{m 3,} preferably 20 kg / ^{m 3} or more 40 kg / ^{m 3} or less, more preferably 25 kg / ^{m 3} or more 35 kg / ^{m 3} or less . If it is more than the said lower limit, it will be easy to suppress generation | occurrence | production of the chip of a phenol resin foam, and if it is below the said upper limit, it will be easy to aim at the heat insulation improvement of a phenol resin foam.
The density can be measured according to JIS A 9511: 2009.
The density of the phenol resin foam 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.

The average cell diameter in the phenol resin foam of the present invention is 50 μm or more and 200 μm or less, preferably 50 μm or more and 150 μm or less, and more preferably 50 μm or more and 100 μm or less. If the average cell diameter is not less than the above lower limit, it is easy to further improve the compressive strength of the phenol resin foam. If the average cell diameter is less than or equal to the above upper limit value, convection and radiation within the cell are suppressed, and the thermal conductivity of the phenol resin foam is lowered, so that the heat insulation of the phenol resin foam can be further improved.
The average cell diameter can be measured by the following method.

<Measurement method of average bubble diameter>
A test piece is cut out from approximately the center in the thickness direction of the phenol resin foam. The cross section (thickness direction cross section) in the width direction of the test piece is photographed at 50 times magnification. Draw four straight lines with a length of 9 cm on the captured image. At this time, a straight line is drawn so as to avoid voids (voids of 2 mm ² or more). The number of bubbles crossed by each straight line (the number of cells measured according to JIS K 6400-1: 2004) is counted for each straight line, and the average value per straight line is obtained. 1800 μm is divided by the average value of the number of bubbles, and the obtained value is defined as the average bubble size.

In the present invention, the average cell diameter of the surface layer of the phenol resin foam is preferably 5 μm or more and 100 μm or less, more preferably 5 μm or more and 90 μm or less, and further preferably 5 μm or more and 80 μm or less. If the average cell diameter is not less than the above lower limit, it is easy to further improve the compressive strength of the phenol resin foam. If an average cell diameter is below the said upper limit, it will be easy to suppress generation | occurrence | production of the cutting powder of a phenol resin foam.
In addition, in this invention, a surface layer shall mean the layer to the distance of 3 mm in the thickness direction from the foam surface which peeled off the face material with respect to the thickness of a phenol resin foam.
The average cell diameter of the surface layer is measured by performing the measurement method of the average cell diameter on the surface layer.
In the foam curing step, the foamable phenolic resin composition is excellent in heat insulation, and tends to be hotter as it is closer to the center, and foaming is easily promoted. Therefore, the average cell diameter in the center is larger than the average cell diameter in the surface layer. . By making the distribution of the average cell diameter uniform, it becomes easy to suppress the generation of chips of the phenol resin foam.
The average cell diameter of the phenol resin foam 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.
Further, the ratio of the average cell diameter of the center layer and the surface layer of the foam (average cell diameter of the center layer / (average value of the average cell diameter of the top and bottom surfaces of the foam)) is preferably 8 or less, and 6 or less. It is more preferable that it is 4 or less.
If it is below the said upper limit, it means that the coarsening of the bubble of a center layer can be suppressed, and the fall of the brittleness of a center layer part can be suppressed.

In the phenol resin foam of the present invention, a plurality of bubbles are formed, the bubble wall is substantially free of pores, and at least some of the plurality of bubbles are closed cells that are not in communication with each other. It has become. In the closed cells, a halogenated hydrocarbon gas used as a blowing agent is held. The closed cell ratio is usually 85% or more, and more preferably 90% or more. The upper limit value is not particularly limited, but is substantially 99% or less. If it is in the said numerical range, low thermal conductivity can be maintained over a long period of time.
The closed cell ratio is measured according to JIS K 7138: 2006.

The abrasion mass in the Taber abrasion test of the phenol resin foam of the present invention is 0.6 g or less, preferably 0.5 g or less, and more preferably 0.4 g or less.
When the abrasion mass in the Taber abrasion test is less than or equal to the above upper limit value, it is easy to suppress the generation of chips, and it is easy to suppress the occurrence of corner chipping, cracking, and dents due to rubbing and collision during construction of the heat insulating material. The lower limit value is not particularly limited, but may be 0 g or more.
The Taber abrasion test can be performed by the following method.

<Taber abrasion test>
A disk-shaped test piece having a width and length of about 150 mm and a thickness of about 10 mm is cut out from approximately the center in the thickness direction of the phenol resin foam, and the test piece is kept at 23 ° C. and a relative humidity of 50% until just before the test. Heal for at least 16 hours below. After curing, measure the mass of the test piece before the test, and use a Taber ablation tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd .: No. 101 TABER TYPE ABRATIONION TESTER) to fix a pair of wear wheels on the rotating test piece. The specimen is worn by pressing with a load. The shavings adhering to the test piece are removed with a vacuum cleaner, and the mass of the test piece after the test is measured. The mass difference between the test pieces before and after the test is calculated and used as the wear mass.
The file used for the test is CS17, the weight of the file is 250 g, the rotation number of the test piece is 50 rotations, and the rotation speed is 60 rpm.
The abrasion mass in the Taber abrasion test of the phenol resin foam 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.

The compressive strength of the phenolic resin foam of the present invention is preferably 10 N / cm ² or more, more preferably 12 N / cm ² or more, and further preferably 14 N / cm ² or more. It is easy to suppress generation | occurrence | production of the dent at the time of heat insulation construction as it is more than the said lower limit.
The compressive strength is measured according to JIS K 7220.
The compressive strength of the phenol resin foam 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.

The thermal conductivity of the phenol resin foam is preferably 0.0195 W / m · K or less, more preferably 0.0185 W / m · K or less, and still more preferably 0.0180 W / m · K or less. When the thermal conductivity is 0.0195 W / m · K or less, the heat insulation is excellent.
The thermal conductivity can be measured according to JIS A 1412-2.
The thermal conductivity of the phenol resin foam 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.

As above-mentioned, the phenol resin foam of this embodiment is excellent by heat insulation by using a specific foaming agent. For this reason, the phenol resin foam of this embodiment is particularly useful as a heat insulating material for buildings such as apartment houses, built houses, and warehouses that require high heat insulation.
In addition, the phenol resin foam of this embodiment can suppress the generation of chips, and can suppress the occurrence of corner chipping, cracking, and dents due to rubbing and collision during construction of the heat insulating material.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

[Example 1]
Liquid resol type phenolic resin (Asahi Organic Materials Co., Ltd., trade name: PF-339) 100 parts by mass, surfactant (castor oil EO adduct (added mole number 30)) 4 parts by mass, formaldehyde catcher agent ( After mixing 4 parts by mass of urea), it was left at 20 ° C. for 8 hours.
108 parts by mass of the obtained mixture, 16 parts by mass of a foaming agent having the composition shown in Table 1, and 16 parts by mass of an acid catalyst (a mixture of paratoluenesulfonic acid and xylenesulfonic acid) were mixed to obtain a foamable phenol resin composition. Prepared.
This foamable phenolic resin composition was discharged onto a first face material (material: glass fiber mixed paper) that was continuously run from 18 nozzles arranged in the width direction at equal intervals. At this time, 18 V-shaped doctor blades (width 45 mm, V-shaped angle 120 °) were installed immediately after the nozzle outlet, and the foamable phenolic resin composition was widened in the TD direction. At this time, each doctor blade was installed 11 mm apart. A second face material (material: glass fiber mixed paper) is overlaid on the slat-type double conveyor to suppress the thickness to 45 mm, and this is foamed by heating at 70 ° C. for 300 seconds (foam curing process). ). After the foam curing step, the product was dried at 65 ° C. for 10 hours (curing step) to prepare 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 45 mm thick phenol resin foam plate (plate-like phenol resin foam).

[Example 2]
A phenol resin foam board was produced in the same manner as in Example 1 except that the foaming agent was changed to the composition shown in Table 1 and the heating temperature in the curing process was 60 ° C. and the time was 12 hours.

[Example 3, Reference Example 1]
A phenolic resin foam board was produced in the same manner as in Example 1 except that the foaming agent was changed to the composition shown in Table 1.

[Examples 4 to 5]
A phenol resin foam board was produced in the same manner as in Example 1 except that the foaming agent was changed to the composition shown in Table 1 and the heating temperature in the curing process was 70 ° C. and the time was 8 hours.

[Reference Example 2]
The same as in Example 1 except that the foaming agent was changed to the composition shown in Table 1 and a cooling step of cooling at 30 ° C. for 300 seconds was introduced, and the heating temperature of the curing step was 80 ° C. and the time was 6 hours. Thus, a phenolic resin foam plate was produced.

[Reference Example 3]
The foaming agent was changed to the composition shown in Table 1, and a cooling step for cooling at 30 ° C. for 200 seconds was introduced, and the heating temperature in the curing step was set to 80 ° C. and the time was set to 6 hours. Thus, a phenolic resin foam plate was produced.

[Example 6]
A phenolic resin foam plate was produced in the same manner as in Example 1 except that the heating temperature in the foam curing step was 65 ° C., the time was 320 seconds, the heating temperature in the curing step was 80 ° C., and the time was 6 hours.

[Example 7]
Example 1 except that the foaming agent was changed to the composition shown in Table 1, the heating temperature in the foam curing step was 65 ° C., the time was 350 seconds, the heating temperature in the curing step was 80 ° C., and the time was 6 hours. A phenolic resin foam board was produced in the same manner as described above.

[Comparative Example 1]
A phenolic resin foam plate was produced in the same manner as in Example 1 except that the heating temperature in the curing process was 80 ° C., the time was 6 hours, and the doctor blade was not used.

[Comparative Examples 2 to 8]
The foaming agent was changed to the composition shown in Table 2, the heating temperature in the curing process was set to 80 ° C., the time was set to 6 hours, and the doctor resin foam plate was prepared in the same manner as in Example 1 except that the doctor blade was not used. Produced.

  The phenol resin foam of each example was measured for density, average cell diameter, closed cell rate, wear mass, compressive strength, and thermal conductivity in a Taber abrasion test. Each test was performed in an environment of 23 ° C. and 50% humidity. The results are shown in Tables 1-2. In the foaming agent compositions in Tables 1-2, IPC refers to isopropyl chloride. HCFO-1233zd refers to (E) -1-chloro-3,3,3-trifluoropropene. HFO-1336mzz refers to (Z) -1,1,1,4,4,4-hexafluoro-2-butene. IP refers to isopentane. A numerical value is the mass% with respect to the gross mass of a foaming agent. Among the foamable phenolic resin composition temperatures in Tables 1 and 2, the temperature difference is the difference between the temperature at the center and the average value of the upper and lower temperatures.

When the phenol resin foam board of each example was cut | disconnected with the cutter knife, in Examples 1-10 which applied this invention, it was hard to produce a chip.
Moreover, since Examples 1-10 to which the present invention is applied all have a thermal conductivity of 0.0195 W / m · K or less, it was found that the heat insulation is also excellent.
On the other hand, in Comparative Example 2 that does not contain a halogenated hydrocarbon as a foaming agent, no improvement in heat insulation was observed, and in Comparative Examples 1 and 3 to 8 that contain a halogenated hydrocarbon, the generation of chips was suppressed. I knew it was n’t there.

  According to the present invention, it has been found that even when a foaming agent containing a halogenated hydrocarbon is used, it is possible to provide a phenol resin foam that hardly generates chips and a method for producing the same.

[Example 3, Reference Example 1]
A phenolic resin foam board was produced in the same manner as in Example 1 except that the foaming agent was changed to the composition shown in Table 1. Example 3 is a reference example.

[Example 7]
Example 1 except that the foaming agent was changed to the composition shown in Table 1, the heating temperature in the foam curing step was 65 ° C., the time was 350 seconds, the heating temperature in the curing step was 80 ° C., and the time was 6 hours. A phenolic resin foam board was produced in the same manner as described above. Example 7 is a reference example.

Claims (3)

Containing a blowing agent containing a halogenated hydrocarbon,
The halogenated hydrocarbon is at least one selected from 1-chloro-3,3,3-trifluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene;
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 average cell diameter of the surface layer is 5 μm or more and 80 μm or less,
The closed cell rate is 85% or more,
The thermal conductivity is 0.019 W / m · K or less,
A phenol resin foam having a wear mass in the Taber abrasion test of 0.6 g or less. It is a manufacturing method of the phenol resin foam of Claim 1, Comprising:
A foam curing step of heating, foaming and curing a phenolic resin, a foaming phenol resin composition containing a foaming agent containing a halogenated hydrocarbon and an acid catalyst,
After the foam curing step, the foaming phenol resin composition is dried and further cured.
The halogenated hydrocarbon is at least one selected from 1-chloro-3,3,3-trifluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene;
In the foam curing step, the temperature in the vicinity of the center in the thickness direction of the foamable phenol resin composition is 35 ° C. or more and 90 ° C. or less,
The method for producing a phenol resin foam further comprising a cooling step of cooling the surface temperature of the foamable foamable phenol resin composition to 30 to 50 ° C. between the foam curing step and the curing step. . It is a manufacturing method of the phenol resin foam of Claim 1, Comprising:
A foam curing step of heating, foaming and curing a phenolic resin, a foaming phenol resin composition containing a foaming agent containing a halogenated hydrocarbon and an acid catalyst,
After the foam curing step, the foaming phenol resin composition is dried and further cured.
The halogenated hydrocarbon is at least one selected from 1-chloro-3,3,3-trifluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene;
The atmospheric temperature in the foam curing step is 30 ° C. or higher and 95 ° C. or lower,
The atmospheric temperature in the curing process is 50 ° C. or higher and 110 ° C. or lower,
The manufacturing method of the phenol resin foam characterized by the temperature difference of the atmospheric temperature in the said foam hardening process and the atmospheric temperature in the said curing process being 5 degreeC or more.