JP6163601B1 - Phenolic resin foam plate and method for producing the same - Google Patents

Abstract

The face material of a phenolic resin foam plate is made more difficult to peel off. A foamed layer of phenol resin and a face material provided on at least one surface of the foamed layer are provided, and the foamed layer contains a foaming agent containing a halogenated unsaturated hydrocarbon. The content of the halogenated unsaturated hydrocarbon is 40 parts by mass or more with respect to 100 parts by mass of the foaming agent, and the peel strength PM of the face material in the MD direction and the peel strength PT of the face material in the TD direction The relationship of the following formula (1) is satisfied, the difference ΔDM in the dimensional change in the MD direction and the difference ΔDT in the TD direction change satisfy the following formula (2), and the bubbles formed in the foamed layer are The length RM and the length RT in the TD direction satisfy the relationship of the following expression (3). PM / PT = 0.6 or more and 1.3 or less (1) ΔDM / ΔDT = 0.6 or more and 1.3 or less (2) RM / RT = 0.7 or more and 1.3 or less・ (3) [Selection] 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.

Conventionally, various proposals have been made to make it difficult to peel off the face material.
For example, a phenol resin foam layer having a specific density, a specific closed cell ratio, and a specific average cell diameter, and a face material disposed on both sides thereof, the face material contains paper. There has been proposed a phenolic resin foam board having a face material peel strength in a specific range (for example, Patent Document 1).
In addition, for example, a phenol resin foam board in which a synthetic fiber nonwoven fabric having a specific fiber diameter and a specific basis weight is attached to both surfaces or one surface of a foam layer of a phenol resin has been proposed (Patent Document 2).

JP 2016-47613 A International Publication No. 1999/34975

Here, since the heat insulating material is generally rectangular in plan view, when something comes into contact with the corners of the four corners of the rectangle during transportation or construction, the face material turns up from the corners, and in a diagonal direction The peeling of the face material begins.
However, the conventional technique improves only the peel strength of the face material in the longitudinal direction, and cannot be said to sufficiently prevent the face material from peeling. In the prior art, the type of face material is significantly limited.
Then, this invention aims at the phenol resin foam board from which a face material does not peel more easily.

According to the study by the present inventors, for example, in a phenol resin foam plate having a rectangular shape in plan view, in many cases, the force in the direction away from the phenol resin foam layer is applied to the face material from the corners of the four corners of the rectangle. It was found that the face material easily peeled off when applied in the diagonal direction.
As a result of diligent examination based on such knowledge, the present inventor has found that the difference between the peel strength of the face material in the MD direction and the peel strength of the face material in the TD direction becomes small, so that the face material becomes difficult to peel. The headline, the present invention has been reached.

The present invention has the following aspects.
[1] A phenolic resin foam layer and a face material provided on at least one surface of the foam layer are provided.
The foam layer comprises a foaming agent comprising a halogenated unsaturated hydrocarbon;
The content of the halogenated unsaturated hydrocarbon is 40 parts by mass or more with respect to 100 parts by mass of the blowing agent,
A peel strength P _M between the surface material and the foam layer in the MD direction, the peel strength P _T between the surface material and the foam layer in the TD direction, satisfies the following formula (1),
P _M / P _T = 0.6 or more and 1.3 or less (1)
The difference ΔD _M in the MD direction at 70 ° C. measured according to EN1604 and the difference ΔD _T in the TD direction at 70 ° C. measured according to EN1604 satisfy the following equation (2). ,
ΔD _M / ΔD _T = 0.6 or more and 1.3 or less (2)
The bubbles formed in the foam layer, and the length R _M in the MD direction, and the length R _T of the TD direction satisfies the following expression (3), a phenolic resin foam plate.
R _M / R _T = 0.7 or more and 1.3 or less (3)
[2] A first step of discharging a foamable resin composition containing a phenol resin, the foaming agent, and a crosslinking agent from two or more nozzles arranged in the TD direction onto the face material traveling at an arbitrary speed; And a second step of heating and foaming and curing the foamable resin composition discharged onto the face material, and the method for producing a phenolic resin foamed plate according to [1],
The content of the halogenated unsaturated hydrocarbon in the foamable resin composition is 40 parts by mass or more with respect to 100 parts by mass of the foaming agent,
In the first step, an angle formed between the nozzle axis and the face material in the travel direction of the face material with respect to the nozzle is set to 60 ° or more and less than 90 °, and the foamable resin composition is formed from the nozzle. A process for producing a phenolic resin foam board, which discharges the material onto the face material.

  According to the phenolic resin foam plate of the present invention, the face material is more difficult to peel off.

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. It is a top view of the face material of an Example. It is a schematic diagram which shows an example of the peeling strength measuring apparatus of a face material.

The phenolic resin foam plate of the present invention includes a phenolic resin foam layer (hereinafter, simply referred to as a foam layer) and a face material provided on at least one surface of the foam 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 first face material 12 and the second face material 14 are joined to the foamed layer 10 by the adhesiveness of the phenol resin itself. That is, the first face member 12 and the second face member 14 are both joined to the foamed layer 10 without an adhesive layer interposed therebetween.
The phenolic resin foam plate 1 has a rectangular shape in plan view, with the X direction as the long side and the Y direction as the short side.
In the embodiment, the X direction is an MD (Machine Direction) direction, and the Y direction is a TD (Transverse Direction) direction. In this case, a weld line extending in parallel with the MD direction and extending in the thickness direction is visible in the cross section viewed from the MD direction. The weld line is a trace in which the foamable resin compositions discharged from each nozzle merge in the manufacturing method described later. The weld line extends substantially perpendicularly to the first face material 12 and the second face material 14, has a higher density, a smaller average cell diameter, and a deeper color tone than the periphery.
As another embodiment, the phenolic resin foam plate 1 may be manufactured such that the X direction (longitudinal) is the TD direction and the Y direction (short) is the MD direction. In this case, the weld line is formed extending in the Y direction (short 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 phenolic resin foam plate 1 of FIG. 1 divided into two equal parts in the thickness direction along the phantom line Q, and the cross section is observed in a plan view.

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.

  The weight average molecular weight Mw of the phenol resin is preferably 400 or more and 3000 or less, and more preferably 700 or more and 2000 or more. 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 is not particularly limited, but is preferably a halogenated hydrocarbon such as a halogenated saturated hydrocarbon or a halogenated unsaturated hydrocarbon, or a hydrocarbon. From the viewpoint of further improving the flame retardancy of the foamed layer 10 and enhancing the heat insulation, the foaming agent is preferably a halogenated hydrocarbon, and more preferably a halogenated unsaturated hydrocarbon.

As the hydrocarbon, those known as blowing agents can be used, and those having a boiling point of −20 ° C. or more and 100 ° C. or less are suitably used.
As the 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. And neopentane.
These hydrocarbons may be used alone or in combination of two or more. These hydrocarbons can ensure excellent heat insulation performance in a wide temperature range from a low temperature region (for example, a heat insulating material for a freezer at about −80 ° C.) to a high temperature region (for example, a heat insulating material for a heating body of about 200 ° C.), It is relatively inexpensive and economically advantageous.

As the halogenated hydrocarbon, a known blowing agent can be used. Examples of the halogenated hydrocarbon include halogenated saturated hydrocarbons such as chlorinated saturated hydrocarbons and fluorinated saturated hydrocarbons; chlorinated unsaturated hydrocarbons, chlorinated fluorinated unsaturated hydrocarbons, and fluorinated unsaturated hydrocarbons. Brominated fluorinated unsaturated hydrocarbon, iodinated fluorinated unsaturated hydrocarbon, and the like. The halogenated 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 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 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 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).

  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).

  As the halogenated hydrocarbon, a halogenated unsaturated hydrocarbon is preferable because it has a small ozone depletion potential (ODP) and a global warming potential (GWP), and has a small impact on the environment. Chlorinated fluorinated unsaturated hydrocarbons are preferable. Or a fluorinated unsaturated hydrocarbon is more preferable.

  The phenol resin foam of the present invention may contain other foaming agents, such as nitrogen, argon, carbon dioxide gas, low boiling point gas such as air; ethers such as dimethyl ether; sodium bicarbonate, sodium carbonate, Carbonates such as calcium carbonate and magnesium carbonate; azodicarboxylic acid amide, azobisisobutyronitrile, barium azodicarboxylate, N, N′-dinitrosopentamethylenetetramine, p, p′-oxybisbenzenesulfonylhydrazide, tri Examples thereof include chemical foaming agents such as hydrazinotriazine; porous solid materials. These foaming agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the foaming agent in the foamable 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, with respect to 100 parts by mass of the phenol resin, and 5 parts by mass or more and 11 parts by mass. More preferred is less than or equal to parts by weight.

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, more preferably 10 to 20 parts by mass per 100 parts by mass of the phenol resin. Part or less is more preferable.

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 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 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, 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. 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 is increased, and therefore, the material in contact with the phenol resin foam 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 phenol resin foamed plate 1, and is preferably 5 mm or more and 200 mm or less, and more preferably 30 mm or more and 120 mm or less. 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 preferably 10 kg / m ³ or more, and more preferably 20 kg / m ³ or more and 100 kg / m ³ or less. 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.

The average cell diameter in the foam layer 10 is preferably 50 μm or more and 200 μm or less, and more preferably 50 μm or more and 150 μm or less. 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.

For example, the closed cell ratio in the foamed layer 10 is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more, and most preferably 100%. 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.

Bubbles 20, and the _{R T} of length _{R M} and TD direction of the MD direction, it is preferable to satisfy the following relationship (3).
R _M / R _T = 0.7 or more and 1.3 or less (3)
R _M / R _T is more preferably from 0.8 to 1.2, and even more preferably from 0.9 to 1.1. If _RM / _RT is within the above range, the peel strength between the foam layer 10 and the first face member 12 or the second face member 14 can be further improved.

  When a halogenated hydrocarbon is used as a blowing agent, the halogenated hydrocarbon is highly polar and highly compatible with the phenol resin. In the production method described later, the foamable resin composition containing a halogenated hydrocarbon tends to spread in the TD direction after being discharged from each nozzle, but the timing of the curing reaction is slow and the elongation viscosity of the resin is conventionally increased. Will be slower. Then, bubbles that are long in the TD direction are easily formed. For this reason, when a halogenated hydrocarbon is used as the foaming agent, it is particularly preferable that the halogenated hydrocarbon is immediately expanded in the TD direction after being discharged from the nozzle as described later.

R _M / _{R T} (bubble aspect ratio) is close to 1 (i.e., the bubble 20 is close to a perfect circle) as the distance _{D M} of the bubbles 20 adjacent in the MD direction, the bubbles 20 adjacent in the TD direction The distance _DT approximates. That is, the wall thickness of the bubble 20 is approximated between the MD direction and the TD direction. When the wall thickness of the bubble 20 approximates in the MD direction and the TD direction, the contact area between the foam layer 10 and each face material approximates in the MD direction and the TD direction. Therefore, a peel strength P _M of the face material and the foam layer 10 in the MD direction, the difference between the peel strength P _T of the foamed layer 10 and the face material in the TD direction more can be reduced, the surface material is a foam layer 10 It can suppress more reliably that it peels.

The oxygen index (Limited Oxygen Index; hereinafter also referred to as “LOI”) of the foamed layer 10 is preferably 28% by volume or more, more preferably 29% by volume or more, further preferably 32% by volume or more, and particularly preferably 34% by volume or more. Preferably, 35% by volume or more is most preferable. If LOI is more than the said lower limit, the further improvement of the flame retardance of the foamed layer 10 can be aimed at.
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 material 12 covers one surface of the foam layer 10. The ratio of the area covered by the first face member 12 to the area (100%) of one surface of the foamed layer 10 is preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more, 100% is particularly preferred.

Examples of the first face material 12 include papers such as glass fiber mixed paper, aluminum hydroxide paper, calcium silicate paper, magnesium silicate paper and other inorganic materials and craft paper; woven fabric; glass Nonwoven fabrics such as fiber nonwoven fabrics, polyester fiber nonwoven fabrics, polypropylene fiber nonwoven fabrics, nylon fiber nonwoven fabrics, and aluminum foil-clad nonwoven fabrics; plywood; calcium silicate plates; gypsum boards; wood-based cement plates; And the like. Among the above, the first face material 12 is preferably paper or a synthetic fiber nonwoven fabric, more preferably a glass fiber mixed paper, a polyester fiber nonwoven fabric, or a glass fiber nonwoven fabric.
In addition, since the face material containing paper is easy to join the cellulose fiber of paper and a phenol resin, the adhesive strength of a face material and the foamed layer 10 can be improved. However, the phenolic resin foam board 1 of the present embodiment sufficiently increases the peel strength between the foamed layer 10 and the face material even if the face material does not contain cellulose fibers such as synthetic fiber nonwoven fabric and glass fiber nonwoven fabric. It is done.

Although the thickness of the 1st face material 12 is not specifically limited, For example, in the case of synthetic fiber nonwoven fabrics, such as a polyester fiber nonwoven fabric, 0.1 mm or more and 0.25 mm or less are preferable. In the case of papers such as glass fiber mixed paper, 0.1 mm to 1.0 mm is preferable. In the case of a glass fiber nonwoven fabric, it is preferably from 0.1 mm to 1.0 mm.
Basis weight of the first plate member 12 is not particularly limited, when using a synthetic fiber nonwoven fabric, is preferably at 15 g / ^{m 2} or more 200 g / ^{m 2} or less, 15 g / ^{m 2} or more 150 g / ^{m 2} more preferably less that, 15 g / ^{m 2} or more further preferably 100 g / ^{m 2} or less, particularly preferably at 15 g / ^{m 2} or more 80 g / ^{m 2} or less, 15 g / ^{m 2} or more 60 g / m Most preferably, it is ² or less.
When glass fiber mixed paper is used, the basis weight is preferably 30 g / m ² or more and 300 g / m ² or less, more preferably 50 g / m ² or more and 250 g / m ² or less, and 60 g / m ² or more. More preferably, it is 200 g / m ² or less, and particularly preferably 70 g / m ² or more and 150 g / m ² or less.
When a glass fiber nonwoven fabric is used, the basis weight is preferably 15 g / m ² or more and 300 g / m ² or less, more preferably 20 g / m ² or more and 200 g / m ² or less, and more preferably 30 g / m ² or more and 150 g. / M ² or less is more preferable.
If the basis weight is equal to or more than the above lower limit value, the foamable resin composition is difficult to ooze out on the surface of the first face member 12. If the basis weight is not more than the above upper limit value, the adhesion between the foamed layer 10 and the first face material 12 can be enhanced. Thereby, the 1st face material 12 becomes difficult to peel from the foaming layer 10, and the surface can be made beautiful. In addition, in the manufacturing method to be described later, it becomes easy to follow the irregularities on the surface of a conveying device such as a conveyor, and the productivity of the phenolic resin foam plate 1 is easily improved.

As a method of providing the first face material 12, the first face material 12 is disposed on the lower conveyor of the manufacturing system described later, and the foamable resin composition is directly discharged onto the face material, and then the top face material 12 is disposed thereon. An example is a method in which after the second face member 14 is placed, foam molding is performed by passing through a heating furnace. Thereby, a face material is provided on both surfaces of the sheet-like foam layer 10.
Moreover, the 1st face material 12 may be stuck by the adhesive agent to the foaming layer 10 foam-molded.

Peel strength _{P M} of the first flat-plate member 12 and the foamed layer 10 in the MD direction is preferably at least 300 g / 50 mm, more preferably at least 400 g / 50 mm, more 500 g / 50 mm is more preferable. If it is more than the said lower limit, it can suppress more reliably that the 1st face material 12 peels from the foaming layer 10. FIG. Upper limit of the peel strength _{P M} is not particularly limited, 1000 g / 50 mm or less. When the upper limit value is exceeded, the basis weight of the first face member 12 becomes small, and the foamable resin composition tends to ooze out on the surface of the first face member 12.
Peel strength P _T between the first flat-plate member 12 and the foamed layer 10 in the TD direction is the same as the peel strength P _M.

A peel strength _{P M,} the peel strength _{P T,} satisfies the following formula (1).
P _M / P _T = 0.6 or more and 1.3 or less (1)
P _M / P _T (peel strength ratio) is more preferably 0.7 or more and 1.2 or less, and further preferably 0.8 or more and 1.1 or less. If P _M / P _T is within the above range, the first face member 12 is difficult to peel from the foamed layer 10. As P _M / P _T approaches 1 (that is, the closer the peel strength P _M and the peel strength _PT are), the degree of force applied to pull the first face member 12 away from the foamed layer 10 is MD. The direction and the TD direction are the same. For this reason, the force which separates the 1st face material 12 from the foaming layer 10 is disperse | distributed, and the 1st face material 12 becomes difficult to peel from the foaming layer 10. FIG.
When P _M / P _T is less than the above lower limit value or exceeds the upper limit value, there is a difference in the peel strength of the face material, so that it is directed from the corner of the rectangular phenolic resin foam plate 1 to the diagonal line during transportation or construction. When the face material is peeled, peeling in the longitudinal direction or the short side direction where the peel strength is low proceeds and the peeling width increases. For this reason, it becomes easy to peel also in the direction with high peeling strength, and as a result, it cannot endure use.

The type of the second face material 14 is the same as the kind of the first face material 12. The type of the second face material 14 and the type of the second face material 14 may be the same or different. However, if the types of the first face member 12 and the second face member 14 are different, the phenol resin foam 1 is likely to warp due to the difference in the amount of expansion / contraction between the two face members. For this reason, it is preferable that the kind of the 1st face material 12 and the 2nd face material 14 is the same.
The thickness of the second face material 14 is the same as the thickness of the first face material 12. The thickness of the second face material 14 and the thickness of the first face material 12 may be the same or different. However, if the thicknesses of the first face member 12 and the second face member 14 are different, the phenol resin foam 1 is likely to warp due to the difference in the amount of expansion and contraction of the double face members. For this reason, it is preferable that the thickness of the 1st face material 12 and the 2nd face material 14 is the same.
The basis weight of the second face member 14 is the same as the basis weight of the first face member 12. The basis weight of the second face member 14 and the basis weight of the first face member 12 may be the same or different. However, if the basis weights of the first face material 12 and the second face material 14 are different, the phenol resin foam 1 is likely to warp due to the difference in the amount of expansion and contraction of the double face materials. For this reason, it is preferable that the fabric weight of the 1st face material 12 and the 2nd face material 14 is the same.
The peel strength between the second face material 14 and the foam layer 10 is the same as the peel strength between the first face material 12 and the foam layer 10. The peel strength between the second face member 14 and the foam layer 10 and the peel strength between the first face member 12 and the foam layer 10 may be the same or different.
_P M / _{P T} in the second plate member 14 is similar to _P M / _{P T} in the first plate member 12. And _P M / _{P T} in the second plate member 14, and the _P M / _{P T} in the first plate member 12, may be the same or different.

In the phenolic resin foamed plate 1, the difference ΔD _M in the MD direction at 70 ° C. measured according to EN 1604 and the difference ΔD _T in the TD direction at 70 ° C. measured according to EN 1604 are: It is preferable to satisfy the following formula (2).
ΔD _M / ΔD _T = 0.6 or more and 1.3 or less (2)
ΔD _M / ΔD _T (dimensional change ratio) is more preferably 0.7 or more and 1.2 or less, and further preferably 0.8 or more and 1.1 or less. If ΔD _M / ΔD _T is within the range, the difference in dimensional change between the MD direction and the TD direction becomes small and shrinks uniformly, so that the face material becomes more difficult to peel from the foamed layer 10. When ΔD _M / ΔD _T is less than the above lower limit value or exceeds the upper limit value, there is a difference in the shrinkage amount in the TD direction and the MD direction at the time of shrinkage, so the joint between the first face material 12 and the foam layer 10, or A force is applied non-uniformly to the joint between the second face member 14 and the foamed layer 10, and a difference in the peel strength between the TD direction and the MD direction tends to occur.

The thermal conductivity of the phenolic resin foam board 1 is preferably 0.0190 W / m · K or less, more preferably 0.0185 W / m · K or less, and further preferably 0.0175 W / 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 this embodiment is manufactured according to the conventionally well-known manufacturing method of a phenol resin foam board.
For example, the manufacturing method of the phenol resin foam board 1 has the process of foaming and hardening a foamable resin composition.
Hereinafter, a phenol resin foam production method using a production system including 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 that mixes raw materials such as phenol resin, and a plurality of 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. A nozzle having a single discharge port such as a slit die and having a wide width in the TD direction is not preferable because the flow rate or pressure does not become uniform in the nozzle, and the discharge amount differs between the central portion and the end portion.

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

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 the endless belt of the lower conveyor 72 or the upper conveyor 74, and the like.
In addition, as the foam molding apparatus 70, it may replace with the conveyor which has an endless belt, and the apparatus which has a slat conveyor of Unexamined-Japanese-Patent No. 2000-218635 may be sufficient.

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 °. Is preferably 60 ° or more and less than 85 °. 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 above lower limit value, the bubble aspect ratio (R _M / R _T ) of the bubbles 20 formed in the foam layer 10 can be easily set within a desired range, and the peel strength ratio (P _M / P _T ). Can be controlled to 0.6 or more and 1.3 or less. For this reason, the face material is difficult to peel from the foamed layer 10.
The reason why the face material is difficult to peel from the foamed layer 10 when the nozzle angle is in the above range 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 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.
Further, when the nozzle angle θ is set to 90 ° or more (the nozzle 64 is set up with respect to the face material), the resin is also discharged outside the direction opposite to the conveying direction of the first face material 12, and around the nozzle outlet. The cured resin accumulates and the nozzle is likely to be clogged.
On the other hand, when the nozzle angle θ is 60 ° or more and less than 90 °, the foamable resin composition 80 discharged onto the first face material 12 is applied to the first face material 12 by the discharge pressure from the nozzle 64. It is pressed and spreads 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.
For this reason, the bubble aspect ratio (R _M / R _T ) of the formed bubbles 20 approaches 1 and the peel strength ratio (P _M / P _T ) easily approaches 1.
Note that the closer the discharge port of the nozzle 64 and the first face material 12 from which the resin is discharged are, the easier it is to spread the foamable resin composition in the TD direction, but the discharge port is likely to be clogged. If the discharge port and the first face member 12 are too far apart, it is difficult to spread the foamable resin composition in the TD direction, but it can be adjusted by the traveling speed of the first face member 12 and the viscosity of the resin.
Moreover, you may incline so that the lower conveyor 72 and the upper conveyor 74 itself may climb toward a running direction. By combining the inclination angle of the conveyor and the nozzle angle θ, the foamable resin composition can be easily spread.

  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 ° C. or more and 95 ° C. or less. The heating time is, for example, 1 minute or more and 15 minutes or less. 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.
Although the shape of the phenolic resin foam board 1 is not specifically limited, For example, the board of planar view rectangle which makes MD direction a long side and makes TD direction short is mentioned.
Moreover, the magnitude | size of the phenol resin foam board 1 is although it does not specifically limit, The thing of length 500mm or more and 2000mm or less x width 500mm or more and 1000mm or less x thickness 5mm or more and 200mm or less is mentioned.

As described above, according to the phenolic foam resin plate of the present embodiment, the face material peel strength ratio P _M / P _T is in a specific range, and thus the face material is difficult to peel from the foam layer.

The present invention is not limited to the above-described embodiment.
In the above-described embodiment, the three-layer structure of the foam layer, the first face material, and the second face material is used, but the present 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 1-11, Comparative Examples 1-2)
According to the composition shown in Table 1, liquid resol type phenol resin (Asahi Organic Materials Co., Ltd., trade name: PF-339), surfactant (castor oil ethylene oxide adduct (addition mole number 30)), formaldehyde catcher agent (Urea) was added, mixed and left at 20 ° C. for 8 hours. A foaming agent and an acid catalyst (a mixture of p-toluenesulfonic acid and xylenesulfonic acid) were added to this mixture, and the mixture was stirred and mixed to prepare a foamable resin composition.
Using a manufacturing system similar to the manufacturing system 40 shown in FIG. 3, a phenolic resin foam plate having face materials on both sides of the foam layer was obtained. 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 manufacturing system used for manufacturing this phenolic resin foam plate includes a discharge device in which 18 nozzles are arranged at equal intervals in the TD direction. Table 1 shows the nozzle angle θ when the phenolic resin foam plate of each example was manufactured.
The foamable resin composition was discharged from 18 nozzles onto the face material described in Table 1, and a face material was newly placed on the discharged foamable resin composition. The distance between the upper and lower face materials was 45 mm and heated at 70 ° C. for 300 seconds to obtain a phenolic resin foam plate.
The obtained phenolic resin foam board was cut into a width of 910 mm and a length of 1820 mm. Next, the cut phenol resin foam plate was allowed to stand at 85 ° C. for 5 hours to obtain a phenol foam plate of each example.
For each example of the phenolic resin foam plate, the density of the foam layer, average cell diameter, closed cell rate, thermal conductivity, cell aspect ratio, peel strength of the face material, and difference in dimensional change were measured, and the results are shown in the table. Shown in

(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.
-Foaming agent B ... HCFO-1233zd: isopropyl chloride = 80:20 (mass ratio) mixture.
-Foaming agent C ... HFO-1336mzz: a mixture of cyclopentane = 60:40 (mass ratio).
-Foaming agent D ... HFO-1336mzz: isopropyl chloride = 60:40 (mass ratio) mixture.
-Foaming agent E ... HCFO-1233zd: cyclopentane = 60:40 (mass ratio) mixture.
-Foaming agent F ... HCFO-1233zd: isopentane = 60:40 (mass ratio) mixture.
-Mixture of foaming agent G ...... HCFO-1233zd: cyclopentane = 40: 60 (mass ratio).
-Mixture of foaming agent H ...... HCFO-1233zd: isopropyl chloride = 40: 60 (mass ratio).
-Foaming agent I ... cyclopentane.

(Type of face material)
The composition of the face material in the table is as follows.
-Face material I ... Glass fiber nonwoven fabric (weight per unit: 70 g / m < ² >).
-Face material II: polyester nonwoven fabric (weight per unit: 30 g / m ² ).

(Measuring method)
<Bubble aspect ratio>
About the phenolic resin foam board of each example, the photograph which image | photographed it equally in the thickness direction and expanded the cross section 50 times with the electron microscope was image | photographed. On the photographed image, two straight lines (corresponding to a length of 1800 μm) were drawn in the MD direction of the foam layer, and two straight lines (corresponding to a length of 1800 μm) were drawn in the TD direction of the foam layer. The diameter on the straight line of bubbles crossed by the straight line in the MD direction was measured, and the average value was calculated from the result to obtain the bubble diameter (R _M ) in the MD direction. Moreover, the diameter on the straight line of the bubble which the straight line of TD direction crossed was measured, the average value was computed from the result, and it was set as the bubble diameter ( _RT ) in TD direction.
From _{R M} and _{R T} obtained was calculated bubbles aspect ratio.

<Surface peel strength>
With reference to FIGS. 5-6, the measuring method of face material peeling strength is demonstrated.
As shown in FIG. 5, from the central portion of the phenolic resin foam plate of each example in the Y direction (TD direction), cut into a rectangle of 50 mm in the X direction (MD direction) and 120 mm in the Y direction, and peel off one face material. Te gave the sections _{S T.} The sections _{S T} was cut in the thickness direction, comprising a face material on one side, and a width of 50 mm, length 120 mm, the evaluation sample T having a thickness of 25 mm.
Next, a 20 mm depth incision was made in the thickness direction from the surface having no face material at a position 20 mm from one end in the length direction of the evaluation sample T having a thickness of 25 mm. At the cutting position, the foam layer was divided in the thickness direction (reference numeral 100 in FIG. 6). At this time, the face material was not peeled off from the foamed layer.
A portion 102 having a long foam layer in the evaluation sample T was held by a clamp 107. At this time, the portion 102 was held at an angle of 45 ° with respect to the horizontal direction. A portion 103 having a short foam layer length was held by a clamp 104. The container 106 was suspended by a metal wire 105 below the clamp 104.
Thereafter, water was continuously charged into the container 106 at a charging rate of 100 g / min using a pump (not shown). When the face material 101 peeled 50 mm from the cut position in the length direction of the evaluation sample T, the introduction of water into the container 106 was stopped. The mass of water in the container 106 was measured. The same operation was performed twice, and the average value of the total mass of the water in the clamp 104, the metal wire 105, the container 106, and the container 106 was defined as the face material peel strength _{PT in the} TD direction.

Subsequently, from the central portion of the phenolic resin foam plate from which the sample T for evaluation was collected in the Y direction (TD direction), it was cut into a rectangle of 50 mm in the Y direction and 120 mm in the X direction. was S _M (Fig. 1). Bisecting the sections S _M in the thickness direction, and the evaluation sample M with a thickness of 25 mm. For evaluation sample M, it was determined surface material peeling strength P _M in the MD direction in the same manner as in the evaluation sample T.
The peel strength ratio was calculated from the obtained _PM and _PT .

<Difference in dimensional change>
From the central part in the TD direction of the phenolic resin foam plate in each example, a rectangular section in plan view with an MD direction of 200 mm and a TD direction of 200 mm was cut out and used as an evaluation sample. For this 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.
First, it cut out into 200 mm x 200 mm, this was cured according to EN1604, and it was set as the sample for evaluation. The length D _M0 (mm) in the MD direction and the length D _T0 in the TD direction of the sample for evaluation were measured.
Next, 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 difference ΔD _M in the MD direction and the dimensional change difference ΔD _T in the TD direction were calculated according to the following equations.
ΔD _M = length D _{M0 −length} D _M
ΔD _T = length D _{T0 -length} D _T
The dimensional change ratio was calculated from the obtained ΔD _M and ΔD _T.

<Evaluation of continuous productivity>
When the phenolic resin foam plate was continuously produced, the periphery of the nozzle outlet was observed, and the frequency of cleaning the nozzle outlet was evaluated.
≪Evaluation criteria≫
○: When the phenolic resin foam plate was continuously produced for 5 hours, almost no resin was observed around the nozzle outlet (nozzle cleaning frequency was low).
(Triangle | delta): When a phenol resin foamed board was manufactured continuously for 5 hours, a small amount of resin adhered to the nozzle discharge port periphery (nozzle cleaning frequency).
X: When a phenol resin foam board was manufactured continuously for 5 hours, a large amount of resin adhered to the periphery of the nozzle outlet (nozzle cleaning frequency was high). Or production was stopped due to clogging at the nozzle outlet.

<Evaluation of peeling of face material>
About five phenolic resin foam boards of each example, it cut | disconnected in the TD direction, the corner | angular part in the both ends of a cut surface was observed, and the following references | standards evaluated.
≪Evaluation criteria≫
○: The face material is not peeled off from any corner.
(Triangle | delta): There was one sheet | seat from which the face material peeled 0.5 cm or more from the corner | angular part.
X: There were two or more pieces of the face material peeled from the corner by 0.5 cm or more.

  As shown in Table 1, Examples 1 to 11 to which the present invention was applied had sufficient peel strength. In Examples 1 to 11, the evaluation of continuous productivity was “◯” or “Δ”.

  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 (2)

A foam layer of phenol resin having a thickness of 30 mm to 120 mm and a face material provided on both surfaces of the foam layer;
The foam layer comprises a foaming agent comprising a halogenated unsaturated hydrocarbon;
The content of the halogenated unsaturated hydrocarbon is 40 parts by mass or more with respect to 100 parts by mass of the blowing agent,
The halogenated unsaturated hydrocarbon is 1-chloro-3,3,3-trifluoropropene or 1,1,1,4,4,4-hexafluoro-2-butene;
A peel strength P _M between the surface material and the foam layer in the MD direction, the peel strength P _T between the surface material and the foam layer in the TD direction, satisfies the following formula (1),
P _M / P _T = 0.6 or more and 1.3 or less (1)
The difference ΔD _M in the MD direction at 70 ° C. measured according to EN1604 and the difference ΔD _T in the TD direction at 70 ° C. measured according to EN1604 satisfy the following equation (2). ,
ΔD _M / ΔD _T = 0.6 or more and 1.3 or less (2)
The bubbles formed in the foam layer, and the length R _M in the MD direction, and the length R _T of the TD direction satisfies the following expression (3), a phenolic resin foam plate.
R _M / R _T = 0.7 or more and 1.3 or less (3) A first step of discharging a foamable resin composition containing a phenol resin, the foaming agent, and a crosslinking agent from two or more nozzles arranged in the TD direction onto the face material traveling at an arbitrary speed; It has a second step of heating and foaming and curing the foamable resin composition discharged above, and a method for producing a phenolic resin foam board according to claim 1,
The content of the halogenated unsaturated hydrocarbon in the foamable resin composition is 40 parts by mass or more with respect to 100 parts by mass of the foaming agent,
In the first step, an angle formed between the nozzle axis and the face material behind the nozzle in the running direction of the face material is 65 ° or more and less than 90 °, and the foamable resin composition is formed from the nozzle. A process for producing a phenolic resin foam board, which discharges the material onto the face material.

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