JP2018094766A - Phenol resin foam plate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenol resin foam plate which contains a foaming agent containing halogenated unsaturated hydrocarbon, is excellent in flame retardancy, and hardly causes deformation after construction.SOLUTION: A rectangular phenol resin foam plate 1 in plan view has a foam layer 10 which contains a phenol resin and halogenated unsaturated hydrocarbon, and has a density of 15-50 kg/m, a closed cell ratio of 80-99% and a limited oxygen index of 28 vol.% or more, and surface materials 12 and 14 which are laminated on both surfaces of the foam layer 10 without through an adhesive layer and contain a glass fiber, where bending elastic modulus Ex in a length direction (direction X) and bending elastic modulus Ey in a width direction (direction Y) satisfy a relationship of 1.1≤Ex/Ey≤2.5.SELECTED DRAWING: Figure 1

Description

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

Thermal insulation panels are widely used as thermal insulation materials for houses and the like. As a heat insulating panel, a phenol resin foamed board including a foamed layer of phenol resin and a face material provided on one or both sides of the foamed layer is known.
The foamed layer of phenolic resin is relatively brittle with respect to physical impact. For this reason, the foamed layer of the phenol resin is protected by providing a face material on one side or both sides of the foamed layer of the phenol resin.

Hydrocarbons that do not contain halogen atoms are foaming agents that have a zero ozone depletion coefficient and a low warming potential. However, compared to the case where halogenated hydrocarbons are used as foaming agents, the heat insulation performance and mechanical properties of phenolic resin foams The mechanical strength is inferior.
Patent Document 1 describes a method for producing a phenol resin foam using a hydrocarbon foaming agent.
Patent Document 2 proposes to use a halogenated unsaturated hydrocarbon as a foaming agent that has a zero ozone depletion coefficient and a low global warming coefficient, and that is more likely to lower the thermal conductivity than a hydrocarbon foaming agent. .

Japanese Patent No. 4711469 Japanese Patent Laying-Open No. 2015-157937

However, because hydrocarbon-based blowing agents and halogenated unsaturated hydrocarbon blowing agents have different reactivity and different foaming states, suitable conditions for phenolic resin foams using hydrocarbon-based blowing agents must be Whether it can be applied to a phenol resin foam using a hydrocarbon foaming agent cannot be predicted.
According to the knowledge of the present inventors, a halogenated unsaturated hydrocarbon foaming agent is used in place of a hydrocarbon-based foaming agent in a method for producing a phenolic resin foam board by continuously foaming on a traveling face material. And the ease of bending of a foam board changes and there exists a possibility that a deformation | transformation may arise after construction.
In addition, flame retardant properties are required for foamed plates used as building materials for houses and the like.
An object of the present invention is to provide a phenolic resin foam board that includes a halogenated unsaturated hydrocarbon, has excellent flame retardancy, and is less likely to be deformed after construction, and a method for producing the same.

The present invention has the following aspects.
[1] A foamed layer containing a phenol resin and a halogenated unsaturated hydrocarbon, having a density of 15 to 50 kg / m ³ , a closed cell ratio of 80 to 99%, and a restricted oxygen index of 28% by volume or more, and the foamed layer A phenolic resin foam plate having a rectangular shape in plan view, provided with a face material containing glass fibers, laminated on both sides without an adhesive layer, the bending elastic modulus Ex in the length direction, and the width direction The bending elastic modulus Ey is a phenolic resin foam board that satisfies the following formula (1).
1.1 ≦ Ex / Ey ≦ 2.5 (1)
[2] at 70 ° C. as measured in accordance with EN1604, the dimensional change _{D 1} of the said phenolic resin foam plate, said the amount of dimensional change _{D 10} of only the foam layer, satisfies the following equation (2), [1 ] The phenolic resin foam board of description.
0.18 ≦ D ₁ / D ₁₀ ≦ 0.9 (2)
[3] The phenolic resin foam plate according to [1] or [2], wherein the glass fiber content relative to the face material is 10% by mass or more.
[4] The phenolic resin foam plate according to any one of [1] to [3], wherein the weight of the face material is 30 g / m ² or more.
[5] The method for producing a phenolic resin foam plate according to any one of [1] to [4] above, wherein the phenolic resin, the foaming agent, and the crosslinking agent are formed on the first face material that travels at an arbitrary speed. A first step of discharging a foamable resin composition containing:
A second step of placing a second face material on the foamable resin composition discharged onto the first face material, heating, foaming and curing, a phenolic resin foam board Manufacturing method.
[6] In the first step, the foamable resin composition is discharged onto the first face material from two or more nozzles arranged in the TD direction, and the axis of the nozzle, the first face material, The method formed by the phenol resin foamed plate according to [5], in which the angle formed by is at least 60 ° and less than 90 °.

  According to the present invention, it is possible to obtain a phenolic resin foamed board in which the foaming agent contains a halogenated unsaturated hydrocarbon, is excellent in flame retardancy, and hardly deforms after construction.

It is a perspective view of a phenol resin foam board concerning one embodiment of the present invention. It is a fragmentary sectional view of FIG. It is a schematic diagram which shows an example of the manufacturing apparatus of a phenol resin foam board. It is a top view which shows a part of manufacturing apparatus of FIG.

The phenolic resin foam plate of the present invention includes a phenolic resin foamed layer (hereinafter sometimes simply referred to as a foamed layer) and face materials provided on both sides of the foamed layer. The face material is laminated on the foam layer without an adhesive layer.
Hereinafter, a phenol resin foam board is demonstrated with reference to drawings.

The phenol resin foam board 1 of FIG. 1 includes a flat foam layer 10, a first face material 12, and a second face material 14. The first face material 12 is provided on one surface of the foam layer 10. The second face material 14 is provided on the other surface of the foam layer 10.
The phenolic resin foam board 1 has a rectangular shape in plan view with the X direction as the length direction and the Y direction as the width direction. In the present embodiment, the X direction is an MD (Machine Direction) direction, and the Y direction is a TD (Transverse Direction) direction.

The foam layer 10 is a foam formed by foaming and curing a foamable resin composition. The foamable resin composition contains a phenol resin and a foaming agent.
As shown in FIG. 2, two or more bubbles 20 are formed in the foam layer 10. At least some of the bubbles 20 are closed cells. 2 is a partial cross-sectional view of the phenol resin foamed plate 1 of FIG. 1 divided into two equal parts in the thickness direction along the phantom line P, and the cross section observed in plan view. In FIG. 2, R _M represents the length of the bubble 20 in the MD direction, and R _T represents the length of the bubble 20 in the TD direction. R _M / R _T represents the bubble aspect ratio.

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 combined and used for it.
The use ratio of the phenol compound and the aldehyde is not particularly limited. Preferably, the molar ratio of phenol compound: aldehyde is 1: 1 to 1: 3, more preferably 1: 1.3 to 1: 2.5.

  400-3000 are preferable and, as for the weight average molecular weight Mw of a phenol resin, 700-2000 are more preferable. If a weight average molecular weight is more than the said lower limit, a closed-cell ratio will increase and it will be easy to aim at the further improvement of compressive strength and the further improvement of thermal conductivity. Moreover, it is easy to prevent formation of voids. If the weight average molecular weight Mw is not more than the above upper limit value, the viscosity of the foamable resin composition does not increase too much, and it is easy to obtain a desired expansion ratio.

The blowing agent includes a halogenated unsaturated hydrocarbon. Halogenated unsaturated hydrocarbon is preferable from the viewpoint of further enhancing the flame retardancy of the foamed layer 10 and enhancing the heat insulation.
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. The halogenated unsaturated hydrocarbon may be one in which all of the hydrogen atoms are substituted with halogen atoms, or one in which some of the hydrogen atoms are substituted with halogen atoms.
These halogenated unsaturated hydrocarbons may be used individually by 1 type, and may be used in combination of 2 or more type.
Halogenated unsaturated hydrocarbons are advantageous in that they have a small ozone depletion potential (ODP) and global warming potential (GWP), and have a small impact on the environment. As the halogenated unsaturated hydrocarbon, chlorinated fluorinated unsaturated hydrocarbon or fluorinated unsaturated hydrocarbon is preferable.

  Examples of the chlorinated fluorinated unsaturated hydrocarbon include those containing a chlorine atom, a fluorine atom 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 -Trifluoropropene (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, 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 (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.

  Examples of the fluorinated unsaturated hydrocarbon include those containing a fluorine atom and a double bond in the molecule, such as 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 (HFO1336mzz) (E and Z isomers) (SynQuest Laboratories) And those disclosed in Japanese Patent Application Publication No. 2009-513812, such as product number: 1300-3-Z6).

The blowing agent may further contain a saturated hydrocarbon or a halogenated saturated hydrocarbon.
As a saturated hydrocarbon, a well-known thing can be used as a foaming agent, and a thing with a boiling point of -20 degreeC or more and 100 degrees C or less is used suitably.
As the saturated hydrocarbon, those having a cyclic molecular structure having 4 to 6 carbon atoms or a chain molecular structure having 4 to 6 carbon atoms are preferable. For example, isobutane, normal butane, cyclobutane, normal pentane, isopentane, cyclopentane Examples include pentane and neopentane.
These saturated hydrocarbons may be used individually by 1 type, and may be used in combination of 2 or more type. These saturated hydrocarbons can ensure excellent heat insulation performance in a wide temperature range from a low temperature range (for example, a heat insulating material for a freezer at about -80 ° C) to a high temperature range (for example, a heat insulating material for a heating body at about 200 ° C). It is relatively inexpensive and economically advantageous.

As the halogenated saturated hydrocarbon, a known blowing agent can be used. Examples thereof include halogenated saturated hydrocarbons such as chlorinated saturated hydrocarbons and fluorinated saturated hydrocarbons. 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.
These halogenated saturated hydrocarbons may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the chlorinated saturated hydrocarbon, those having 2 to 5 carbon atoms are preferable, and examples thereof include dichloroethane, propyl chloride, isopropyl chloride (2-chloropropane), butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. It is done. Among them, isopropyl chloride is preferable because it has a low ozone layer 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-pentafluorobutane (HFC365mfc) and 1,1,1,2,2,2 And hydrofluorocarbons such as 3,4,5,5,5-decafluoropentane (HFC4310mee).

  The foaming agent may further contain other blowing agents other than the halogenated unsaturated hydrocarbon, the halogenated saturated hydrocarbon, and the saturated hydrocarbon, if necessary. Other blowing agents include low boiling point gases such as nitrogen, argon, carbon dioxide and air; sodium bicarbonate, sodium carbonate, calcium carbonate, magnesium carbonate, azodicarboxylic acid amide, azobisisobutyronitrile, barium azodicarboxylate , N, N′-dinitrosopentamethylenetetramine, p, p′-oxybisbenzenesulfonyl hydrazide, chemical foaming agent such as trihydrazinotriazine; porous solid materials and the like.

As for content of the foaming agent in a foamable resin composition, 1-25 mass parts is preferable with respect to 100 mass parts of phenol resins, 3-15 mass parts is more preferable, and 5-11 mass parts is further more preferable.
Of the total 100 parts by mass of the blowing agent, the proportion of the halogenated unsaturated hydrocarbon is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and most preferably 30 parts by mass or more. 100 mass parts may be sufficient.

The foamable resin composition may contain an acid catalyst. The acid catalyst is used to cure 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 individually by 1 type, and may be used in combination of 2 or more type.

  The content of the acid catalyst in the foamable resin composition is preferably 5 to 30 parts by mass, more preferably 8 to 25 parts by mass, and still more preferably 10 to 20 parts by mass per 100 parts by mass of the phenol resin.

The foamable resin composition may contain a 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 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 content of the surfactant in the foamable resin composition is preferably 1 to 10 parts by mass and more preferably 2 to 5 parts by mass per 100 parts by mass of the phenol resin. If the surfactant content is not less than the lower limit of the above range, the bubble diameter tends to be uniformly small, and if it is not more than the upper limit, the amount of water absorption of the foamed layer 10 is small and the production cost can be suppressed.

The foamable resin composition may contain a conventionally known additive. Examples of the additive include urea, a plasticizer, a filler (filler), a flame retardant (for example, a phosphorus flame retardant), a crosslinking agent, an organic solvent, an amino group-containing organic compound, and a colorant.
As the filler, an inorganic filler is preferable. By using the inorganic filler, the thermal conductivity of the foamed resin laminate can be reduced and the flame retardancy can be further improved.

  The filler content in the foamable resin composition is preferably such that the extraction pH is 3 or more. For example, the content of the filler is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, further preferably 3 to 15 parts by mass, and more preferably 5 to 10 parts by mass per 100 parts by mass of the phenol resin. Particularly preferred. When the content of the filler is less than the lower limit, the extraction pH of the foam layer 10 is lowered. When the extraction pH is lowered, the acidity increases, and therefore the material that comes into contact with the foamed phenol resin may be corroded. When the content of the 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. The foam layer 10 is ground to 250 μm (60 mesh) or less with a mortar 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 thickness t1 of the foamed layer 10 is determined in consideration of the heat insulating property required for the phenolic resin foamed plate 1, and is, for example, preferably 5 to 200 mm, more preferably 20 to 120 mm. If it is more than the said lower limit, heat insulation can be improved more. If thickness t1 is below the said upper limit, the thickness of the phenol resin foam board 1 will not become thick too much, and handling will be easy.

The density of the foam layer 10 is a 15~50kg / ^{m 3,} preferably ^{20~40kg / m 3, 25~35kg / m} 3 and more preferably. If a density is more than the said lower limit, intensity | strength will be raised more, and if it is below the said upper limit, the heat insulation of the phenol resin foamed board 1 can be improved more.
The density of the foam layer 10 is a value measured according to JIS A 9511: 2009.

50-200 micrometers is preferable and, as for the average bubble diameter in the foaming layer 10, 50-150 micrometers is more preferable. When the average cell diameter is within the above range, the heat insulating property of the phenolic resin foam plate 1 can be further enhanced.
The average bubble diameter is measured, for example, by the following measurement method.
First, a test piece is cut out from approximately the center in the thickness direction of the foam layer 10. Photograph the cut surface in the thickness direction of the specimen 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 K6400-1: 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.
The average cell diameter of the foamed layer 10 is adjusted by a combination of the type or composition of the foaming agent, the type of surfactant, the foaming conditions (heating temperature, heating time, etc.) and the like.

The closed cell ratio in the foamed layer 10 is 80% to 99%, more preferably 85 to 99%, and still more preferably 90 to 99%. If the closed cell rate is equal to or higher than the lower limit, the heat insulating property of the phenolic resin foam plate 1 can be further improved.
The closed cell ratio is measured according to JIS K 7138: 2006.
The closed cell ratio of the foamed layer 10 is adjusted by a combination of the type or composition of the foaming agent, the type of surfactant, the foaming conditions (heating temperature, heating time, etc.) and the like.

The restricted oxygen index (hereinafter also referred to as “LOI”) of the foam layer 10 is 28% by volume or more, preferably 30% by volume or more, and more preferably 32% by volume or more. If LOI is more than the said lower limit, the foamed layer 10 is excellent in flame retardance.
LOI is a value measured according to JIS K7201-2: 2007.
The LOI of the foam layer 10 is adjusted by a combination of the type or composition of the foaming agent, the type of surfactant, the type or composition of the flame retardant and the amount thereof. For example, the lower the content of combustible foaming agent in the foaming agent (the higher the content of halogenated 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.

The first face member 12 includes glass fibers. Examples of the material of the first face member 12 include glass fiber mixed paper, glass fiber woven fabric, and glass fiber nonwoven fabric.
The glass fiber content in the first face member 12 is preferably 10% by mass or more, more preferably 30% by mass or more, and may be 100% by mass. When the content of the glass fiber is equal to or higher than the lower limit, the flame retardancy of the phenolic resin foam plate 1 can be further improved.

Although the thickness of the 1st face material 12 is not specifically limited, For example, 0.1-1.0 mm is preferable.
The basis weight of the first face member 12 is preferably 30 g / m ² or more, and more preferably 50 g / m ² or more. If the basis weight is not less than the above lower limit value, the foamed layer 10 can be better protected. Although the upper limit of a fabric weight is not specifically limited, 200 g / m < ² > or less is preferable and 150 g / m < ² > or less is more preferable from the viewpoint of weight reduction of the phenol resin foam board 1.

The material of the second face material 14 is the same as the material of the first face material 12. In the phenolic resin foam plate 1, the material of the second face material 14 and the material of the first face material 12 may be the same or different.
The glass fiber content of the second face material 14 is the same as the glass fiber content of the first face material 12. In the phenolic resin foam plate 1, the glass fiber content of the second face material 14 and the glass fiber content of the first face material 12 may be the same or different.
The thickness of the second face material 14 is the same as the thickness of the first face material 12. In the phenolic resin foam plate 1, the thickness of the second face material 14 and the thickness of the first face material 12 may be the same or different.

  As a method of providing the first face material 12 and the second face material 14, the first face material 12 is disposed on the lower conveyor of the manufacturing system described later, and the foamable resin composition is discharged onto the face material. And after mounting the 2nd face material 14 on it, the method of letting a heating furnace pass and foam-molding is mentioned. Thereby, a face material is laminated and integrated on both surfaces of the plate-like foam layer 10 without an adhesive layer interposed therebetween.

The bending elastic modulus Ex in the length direction of the phenol resin foam board 1 and the bending elastic modulus Ey in the width direction satisfy the following expression (1).
1.1 ≦ Ex / Ey ≦ 2.5 (1)
Ex / Ey (ratio of flexural modulus) is more preferably 1.2 ≦ Ex / Ey ≦ 2.3, and further preferably 1.3 ≦ Ex / Ey ≦ 2.0. When Ex / Ey is within the above range, the phenolic resin foam plate 1 is hardly deformed after construction, and the handleability is also good.

In the phenolic resin foam plate 1, the dimensional change amount D ₁ of the phenol resin foam plate 1 at 70 ° C. measured according to EN 1604 and the dimensional change amount D _{10 of} only the foam layer 10 at 70 ° C. measured according to EN 1604. Preferably satisfies the following formula (2).
0.18 ≦ D ₁ / D ₁₀ ≦ 0.9 (2)
_{D 1} / D ₁₀ (the ratio of dimensional change) is more preferably _{0.19 ≦ D 1 / D 10 ≦} 0.9, more preferably _{0.20 ≦ D 1 / D 10 ≦} 0.9. Within D 1 _/ D ₁₀ is within the above range, deformation after application of the phenol resin foam plate 1 is further suppressed.

The thermal conductivity of the phenolic resin foam board 1 is preferably 0.022 W / m · K or less, more preferably 0.020 W / m · K or less, still more preferably 0.019 W / m · K or less, and 0.018 W / Particularly preferred is m · K or less. If thermal conductivity is below the said upper limit, the further improvement of the heat insulation of the phenol resin foam board 1 can be aimed at.
The thermal conductivity of the phenolic resin foam plate 1 is adjusted by a combination of the average cell diameter in the foamed layer 10, the type or 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 phenolic resin foam plate 1. 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 thermal conductivity is a value measured according to JIS A 1412-2.

The phenol resin foam board 1 of the present embodiment is a first step of discharging a foamable resin composition containing a phenol resin, a foaming agent, and a crosslinking agent onto a first face material that travels at an arbitrary speed. And a second step of placing the second face material on the foamable resin composition discharged onto the first face material, heating, foaming and curing the second face material. .
Hereinafter, the manufacturing method of a phenol resin foam board using a manufacturing system provided with a discharge device and a foam molding device located downstream of the discharge device will be described as an example.

The manufacturing system 40 illustrated in FIG. 3 includes a discharge device 60 and a foam molding device 70.
The discharge device 60 includes a mixing unit 62 for mixing raw materials such as phenol resin, and two or more nozzles 64 for discharging the mixed raw material (foamable resin composition). The two or more nozzles 64 are arranged in a direction orthogonal to the flow direction of the foamable resin composition 80.

  The foam molding apparatus 70 includes a frame portion 71 and heating means (not shown). The frame portion 71 includes conveyors (a lower conveyor 72 and an upper conveyor 74) arranged vertically so that a space corresponding to the cross-sectional shape of the phenolic resin foam plate 1 is formed.

The lower conveyor 72 is a conveyor having an endless belt that runs in the W1 direction. The upper conveyor 74 is a conveyor having an endless belt that runs in the W2 direction.
Examples of the heating means include a heating furnace surrounding the frame portion 71, a heater provided in contact with an endless belt of the lower conveyor 72 or the upper conveyor 74, and the like.
Examples of the foam molding apparatus 70 include those described in JP 2000-218635 A.

The nozzle 64 has a cylindrical shape or a rectangular tube shape. An angle (nozzle angle) θ between the axis O of the nozzle 64 and the imaginary line Q extending in the W1 direction which is the traveling direction of the lower conveyor 72 in the surface direction of the first face member 12 is 60 ° or more and 90 °. Less than is preferable. The angle θ is an angle formed by the axis O and the virtual line Q, and is an angle formed behind the nozzle 64 with respect to the traveling direction of the lower conveyor 72. If the nozzle angle θ is equal to or greater than the lower limit value, the flexural modulus ratio (Ex / Ey) can be easily controlled within the above range. For this reason, the phenolic resin foam board 1 is hardly deformed after construction, and the handleability is also improved.
The reason why the ratio of the flexural modulus (Ex / Ey) can be controlled by setting the nozzle angle in the above range is considered as follows. This will be described with reference to FIG.
FIG. 4 is a partial plan view schematically showing a part of the manufacturing system 40. FIG. 4 schematically shows a state where the foamable resin composition is discharged from the nozzle 64. In addition, illustration of the mixing part 62 grade | etc., Was abbreviate | omitted for convenience of explanation.
As shown in FIG. 4, the adjacent nozzles 64 are arranged at an arbitrary interval. When the nozzle angle θ is less than 60 ° (the nozzle 64 is laid on the face material), the foamable resin composition 80 is discharged in accordance with the speed of the traveling first face material 12. The foamable resin composition 80 discharged onto the first face material 12 expands in the width direction of the first face material 12 (that is, the TD direction of the foam layer 10) as it advances in the W1 direction. The agent gradually foams. At this time, the bubbles 20a generated by foaming of the foaming agent in the foamable resin composition 80 swell while becoming longer in the TD direction. In particular, when a halogenated unsaturated hydrocarbon is used as a foaming agent, the viscosity of the foamable resin composition 80 becomes low, and the discharged foamable resin composition 80 tends to spread in the TD direction. When bubbles 20 that are long in the TD direction are thus formed, the bending elastic modulus in the TD direction is reduced, and the bending elastic modulus ratio (Ex / Ey) is increased.
On the other hand, when the nozzle angle is 60 ° or more and less than 90 °, the foamable resin composition 80 discharged onto the first face material 12 is pressed against the first face material 12 by the discharge pressure from the nozzle 64. And spread in the MD direction and the TD direction. For this reason, the air bubbles 20a generated in the discharged foamable resin composition 80 extend in the MD direction and the TD direction. Thus, by bringing the bubble aspect ratio (R _M / R _T ) of the bubbles 20 close to 1, the flexural modulus ratio (Ex / Ey) can be lowered.

  The interval between the nozzles 64 is not particularly limited, but is preferably as narrow as possible. If the interval between the nozzles 64 is narrow, the foamable resin composition 80 discharged from each nozzle 64 immediately contacts each other. For this reason, the foamable resin composition 80 is difficult to spread in the TD direction, and the bubble aspect ratio is likely to approach 1.

Next, an example of the manufacturing method of the phenol resin foam board 1 using this manufacturing system 40 is demonstrated. First, the first face material 12 is fed out on the lower conveyor 72. The foaming resin composition is prepared by mixing the raw materials in the mixing unit 62. The foamable resin composition is discharged onto the first face member 12 from two or more nozzles 64 (first step). The 2nd face material 14 is mounted on the discharged foamable resin composition 80, these are introduce | transduced into the flame | frame part 71, and it heats at arbitrary temperature (2nd process). The heating temperature is, for example, 30 to 95 ° C. The heating time is, for example, 1 to 15 minutes. As a result, the foamable resin composition foams and cures between the first face member 12 and the second face member 14, and the foam layer 10, the first face member 12, and the second face member 14. A phenolic resin foam board 1 is obtained.
Next, the phenolic resin foam plate 1 is cut into an arbitrary length by a cutting device.
The shape of the phenol resin foam board 1 is a rectangular shape in plan view in which the MD direction is the length direction and the TD direction is the width direction.
Although the magnitude | size of the phenol resin foam board 1 is not specifically limited, The thing of length 500-4000 mm x width 500-1000 mm x thickness 20-150 mm is mentioned.

  In the present embodiment, a weld line extending in the MD direction and extending in the thickness direction is formed in the foam layer 10. The weld line is a joint between the foamable resin compositions discharged from two or more nozzles 64.

In the above-described embodiment, the X direction is the MD direction and the Y direction is the TD direction, but the X direction may be the TD direction and the Y direction may be the MD direction.
Moreover, although it is set as the three-layer structure of a foam layer, a 1st face material, and a 2nd face material, this invention is not limited to this. For example, another layer may be further provided on the first face material. Examples of other layers include a decorative layer and a waterproof film layer. Further, for example, another layer may be provided on the second face material. The other layers on the second face material are the same as the other layers on the first face material.

  The phenolic resin foam board of the present invention is suitable as a heat insulating material for a house wall, floor, or roof.

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

(Examples 1-9)
According to the composition described in Table 1, a foamable resin composition was prepared.
100 parts by mass of liquid resol type phenolic resin (Asahi Organic Materials Co., Ltd., trade name: PF-339), 4 parts by mass of surfactant (castor oil ethylene oxide adduct (addition mole number 30)), formaldehyde catcher agent ( (Urea) 4 parts by mass was added, mixed and allowed to stand at 20 ° C. for 8 hours.
To 108 parts by mass of the obtained mixture, the foaming agent described in Table 1 (the blending amount is shown in the table) and 16 parts by mass of an acid catalyst (a mixture of paratoluenesulfonic acid and xylenesulfonic acid) were added and stirred. A foamable resin composition was prepared by mixing.
Using a manufacturing system similar to the manufacturing system 40 shown in FIG. 3, a foam resin foam plate was obtained by providing face materials on both sides of the foam layer. The phenolic resin foam plate was a plate body having a rectangular shape in plan view of length (MD direction) 1820 mm × width (TD direction) 910 mm × thickness 45 mm.
The face material I in the table is a glass fiber nonwoven fabric (glass fiber content 90 mass%), the face material II is a glass fiber mixed paper (glass fiber content 20 mass%), the face material III is a polyester nonwoven fabric, and the face material IV is a craft. It is paper. The basis weight of the face material is shown in the table.
The manufacturing system used for manufacturing this phenolic resin foam plate was provided with a discharge section in which 18 nozzles were arranged at equal intervals in the TD direction, and the nozzle angle θ was 65 °. The foamable resin composition was discharged onto the face material from 18 nozzles, and the face material was newly placed on the discharged foamable resin composition, and heated at 70 ° C. for 300 seconds to cause foaming. Subsequently, after being kept at 85 ° C. for 15 minutes, it was left in a heating furnace at 110 ° C. for 2 hours to obtain a phenol resin foam.
The obtained phenolic resin foam was cut into a width of 910 mm and a length of 1820 mm, left in a heating furnace at 110 ° C. for 2 hours, and cured to obtain a phenolic resin foamed board of each example.
About the obtained phenolic resin foam board, the density of the foamed layer, the average cell diameter, the closed cell rate, the thermal conductivity, and the limiting oxygen index (LOI) were measured. Moreover, the ratio of the bending elastic modulus and the ratio of dimensional change of the phenol resin foamed plate were measured. The results are shown in the table (hereinafter the same).

(Composition of foaming agent)
The composition of the blowing agent in the table is as follows.
-Foaming agent A ... HCFO-1233zd: cyclopentane = 80: 20 (mass ratio) mixture.
-Blowing agent B ...... mixture of HCFO-1233zd: cyclopentane = 60:40 (mass ratio).
-Foaming agent C ... HCFO-1233zd: cyclopentane = 40:60 (mass ratio) mixture.
-Foaming agent D ... HCFO-1233zd: isopropyl chloride = 60:40 (mass ratio) mixture.
-Foaming agent E ... HCFO-1233zd: Isopropyl chloride = 80:20 (mass ratio) mixture.
-Foaming agent F ... HCFO-1233zd: isopentane = 70:30 (mass ratio) mixture.
-Foaming agent G ... HCFO-1233zd.

(Comparative Example 1)
In Example 1, a phenolic resin foam plate was produced in the same manner as in Example 1 except that the nozzle angle θ was changed from 65 ° to 20 °.
(Comparative Example 2)
In Example 1, a phenolic resin foam plate was produced in the same manner as in Example 1 except that the type of the face material was changed from the face material I to the face material III.
(Comparative Example 3)
In Example 1, a phenolic resin foam plate was produced in the same manner as in Example 1 except that the type of the face material was changed from the face material I to the face material IV.

(Measuring method)
<Ratio of flexural modulus>
The flexural modulus was measured according to JIS K 7221-2.
The ratio of bending elastic modulus (Ex / Ey) was calculated from the obtained Ex and Ey.

<Ratio of dimensional change>
From the central part in the TD direction of the phenolic resin foam plate of each example, two sections having a rectangular shape in a plan view of 200 mm in the MD direction and 200 mm in the TD direction were cut out and used as the first evaluation sample and the second evaluation sample, respectively. initial MD direction length _D M0 of use sample and (mm), was measured TD direction length _D T0 (mm).
For the first evaluation sample, the dimensional change difference ΔD _M (mm) in the MD direction and the dimensional change difference ΔD _T (mm) in the TD direction were determined according to the following procedure according to the test method of EN1604.
Immediately after the sample for evaluation was allowed to stand at 70 ° C. for 48 hours, the length D _M (mm) in the MD direction and the length D _T (mm) in the TD direction of the sample for evaluation were measured. The dimensional change amount ΔD _M in the MD direction and the dimensional change amount ΔD _T in the TD direction were calculated by the following equations.
ΔD _M = | Length D _M -D _M0 |
ΔD _T = | Length D _T -D _T0 |
Of the obtained ΔD _M and ΔD _T , the larger value was taken as the dimensional change D ₁ of the first evaluation sample.
For the second evaluation sample from which the face materials on both sides were peeled, the dimensional change amount ΔD _M in the MD direction and the dimensional change amount ΔD _T in the TD direction were measured in the same manner as in the first evaluation sample. the value was dimensional change D ₁₀ of the second evaluation sample.
The ratio (D ₁ / D ₁₀ ) of the dimensional change was calculated from the determined D ₁ and D ₁₀ .

  The phenolic resin foam plates obtained in Examples 1 to 9 have a foam layer having a LOI of 28% by volume or more and excellent flame retardancy, and have a specific flexural modulus in the length direction and a specific flexural modulus in the width direction. It had a balance and was difficult to deform after construction. Moreover, the handleability at the time of constructing by gripping both ends in the width direction was also good.

  DESCRIPTION OF SYMBOLS 1 Phenolic resin foam board; 10 Foam layer; 12 1st face material; 14 2nd face material; 64 nozzle; 80 Foamable resin composition

Claims (6)

A foamed layer containing a phenolic resin and a halogenated unsaturated hydrocarbon, having a density of 15 to 50 kg / m ³ , a closed cell ratio of 80 to 99%, and a restricted oxygen index of 28% by volume or more;
A phenolic resin foam plate having a rectangular shape in plan view, provided with a face material containing glass fibers laminated on both sides of the foam layer without an adhesive layer,
The bending elastic modulus Ex in the length direction and the bending elastic modulus Ey in the width direction are phenolic resin foam boards that satisfy the following formula (1).
1.1 ≦ Ex / Ey ≦ 2.5 (1) At 70 ° C. as measured in accordance with EN1604, the dimensional change D ₁ of the said phenolic resin foam plate, said the amount of dimensional change D ₁₀ of only the foam layer, satisfies the following expression (2), according to claim 1 Phenolic resin foam board.
0.18 ≦ D ₁ / D ₁₀ ≦ 0.9 (2)   The phenolic resin foam board according to claim 1 or 2, wherein the glass fiber content relative to the face material is 10% by mass or more. The phenol resin foam board as described in any one of Claims 1-3 whose fabric weights of the said face material are 30 g / m < ² > or more. It is a manufacturing method of the phenolic resin foam board as described in any one of Claims 1-4,
A first step of discharging a foamable resin composition containing a phenolic resin, a foaming agent, and a crosslinking agent onto the first face material traveling at an arbitrary speed;
A second step of placing the second face material on the foamable resin composition discharged onto the first face material, heating, foaming and curing;
A process for producing a phenolic resin foam board. In the first step, the foamable resin composition is discharged onto the face material from two or more nozzles arranged in the TD direction.
The method for producing a phenolic resin foamed plate according to claim 5, wherein an angle formed between the axis of the nozzle and the face material is 60 ° or more and less than 90 °.

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