JP2019104226A - Phenol resin foam plate and method for producing the same, and surface material for phenol resin foam plate - Google Patents

Abstract

To make a printed part of a phenol resin foam plate more beautiful, and maintain a low conductivity over a long period of time.SOLUTION: A phenol resin foam plate includes a foam layer 10 of a phenol resin and surface materials 12 and 14 provided on both surfaces of the foam layer 10, in which a printed part 16 is formed on at least one of the surface materials 12 and 14, an area of the printed part 16 to an area of a printed surface material being a surface material formed with the printed part 16 is 5-70% or less, when a first surface layer part is represented by 10a, a central layer part is represented by 10c and a second surface layer part is represented by 10b in order from one surface when the foam layer 10 is divided into three in a thickness direction, in the first surface layer part 10a and the second surface layer part 10b, an isolated cell ratio of the surface layer part adjacent to the printed surface material is 85% or more, the printed surface material is a synthetic fiber non-woven fabric having a basis weight of 15 or more and 100 g/m, and a density of a thermal compression fixed portion of the printed surface material is 5 to 150 pieces/cm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a phenolic resin foam board, a method for producing the same, and a face material for a phenolic resin foam board.

Phenolic resin foam board is widely used as a heat insulating material in construction and other industrial fields because it is excellent in heat insulation, flame retardancy, fire resistance and the like.
As a manufacturing method of a general phenol resin foam board, the method of having a foaming hardening process, a cutting process, and a curing process is mentioned.
In the foaming and curing step, a foamable resin composition is filled between two facing sheets facing each other, and the foamable resin composition sandwiched between the two face sheets is heated to foam and cure. To form a foam layer. For this reason, a phenol resin foam board is provided with the foam layer of phenol resin, and the face material provided in the both surfaces.
The cutting step is a step of cutting the phenolic resin foam board into arbitrary dimensions.
The curing step is a step of placing a phenol resin foam board cut to any size under any temperature condition to further promote the curing of the foam layer.

Information such as a product name and a product number and a pattern for enhancing the design are printed on the face material of the phenolic resin foam board (hereinafter, the printed information and the pattern may be referred to as a printing unit). The printing part in the phenol resin foam board is formed in advance in the facing material, or is formed in the facing material after the foaming and curing process.
As a facing of a phenol resin foam board, a nonwoven fabric of synthetic fiber or natural fiber is used suitably. When the non-woven fabric is subjected to a printing process, the resin composition may exude to the surface of the facing during production of the phenolic resin foam board to produce a discolored portion on the product surface, resulting in appearance failure.
With respect to such a problem, a phenolic resin foam board has been proposed which is made of flat yarn having a specific flatness and which has a woven or non-woven fabric having a specific surface coverage as a facing material (Patent Document 1). In the invention of Patent Document 1, it is intended to suppress exudation of the foamable resin composition on the surface of the surface material and print beautifully by using a specific surface material.

Patent No. 5208563

However, the facing described in Patent Document 1 is expensive because it uses special fibers. In addition, since the face material described in Patent Document 1 uses a thread having a flat cross section, the adhesion between the foam layer and the face material is poor, and the face material is easily peeled off from the foam layer.
When a phenolic resin foam board is manufactured using a face material printed beforehand, there is a problem that a printing part gets dirty by the foamable resin composition which exudes from a face material during manufacture. Moreover, the air permeability of the face material itself is lowered by the formed printing portion, and the closed cell rate is lowered, so that the low thermal conductivity can not be maintained for a long time.
In addition, when printing on the facing after the foaming and curing step, the appearance defect of the phenolic resin foam board may occur due to the case where the closed cell rate of the surface layer is low or depending on the type of facing.
Furthermore, regardless of whether the face material on which the printing part is formed in advance is used in the foaming and curing step or the printing part is formed on the face material after the foaming and curing step, when the area of the printing part is large, The gaps are closed, and the air permeability of the facing decreases. When the air permeability of the facing decreases, the closed cell rate of the foam layer decreases. If a highly air-permeable facing material is used to avoid this, the water permeability of the foam layer is increased due to the high water permeability of the facing material, and as a result, the low thermal conductivity can not be maintained for a long time.
Then, an object of this invention is to provide the phenol resin foam board which is beautiful in a printing part and can maintain low thermal conductivity over a long period of time.

The present invention has the following aspects.
[1] A foam layer of phenol resin, and facing materials provided on both sides of the foam layer,
A printed portion is formed on at least one of the facings,
The area of the printed portion is 5% or more and 70% or less with respect to the area of the printed surface material which is the face material on which the printed portion is formed,
When the foam layer is divided into three in the thickness direction, and the first surface layer, the central layer, and the second surface layer are sequentially arranged from one side, the first surface layer and the second surface layer Among the parts, the closed cell ratio of the surface layer adjacent to the printing surface material is 85% or more,
The printing surface material is a synthetic fiber non-woven fabric having a basis weight of 15 g / m ² or more and 100 g / m ² or less,
The phenolic resin foam board characterized by the thermocompression-bonding fixed part density of the said printing surface material being five pieces / cm < ² > or more and 150 pieces / cm < ² > or less.
[2] A foamable resin composition containing a phenol resin and a foaming agent is filled between the two facing sheets facing each other, and then the foamable resin composition is foamed and cured to form the foam. Having a foam curing process to form a layer,
The said foaming hardening process is a manufacturing method of the phenol resin foam board as described in [1] which uses the said face material in which the said printing part was formed previously.
[3] A foamable resin composition containing a phenol resin and a foaming agent is filled between the two facing materials facing each other, and then the foamable resin composition is foamed and cured to form the foam. Foam curing to form a layer,
The manufacturing method of the phenol resin foam board as described in [1] which has a printing process which forms the said printing part in at least one of the said 2 surface materials after the said foaming hardening process.
[4] The fabric weight is 15 g / m ² or more and 100 g / m ² or less,
The thermocompression bonding fixed part density is 5 pieces / cm ² or more and 150 pieces / cm ² or less,
A facing material for a phenolic resin foam board, which is a synthetic fiber non-woven fabric having a raising degree of 1 / cm to 35 / cm.
[5] A printing unit is formed on at least one side,
The area of the printed portion is 5% or more and 70% or less with respect to the area of the printed surface material which is the face material on which the printed portion is formed, for a phenolic resin foam board according to [4] Facing material.

  The phenolic resin foam board of the present invention has a beautiful printed part and can maintain low conductivity for a long time.

It is a perspective view of a phenol resin foam board concerning one embodiment of the present invention. It is a side schematic diagram which shows an example of the manufacturing apparatus of a phenol resin foam board. (A) It is a perspective view which shows an example of the slit die | dye used for the manufacturing apparatus of a phenol resin foam board. (B) It is a front view of the slit die of FIG. 3 (a). It is a schematic diagram at the time of discharging a foamable resin composition from the slit die of FIG. It is a schematic diagram at the time of discharging a foamable resin composition from the slit die of another form. (A) It is a perspective view which shows an example of the slit die | dye used for the manufacturing apparatus of a phenol resin foam board. (B) It is a front view of the slit die | dye of Fig.6 (a). It is process drawing which shows the measuring method of the raising degree of a face material.

The phenol resin foam board of the present invention is provided with a foam layer of phenol resin (hereinafter sometimes referred to simply as foam layer).
Hereinafter, the phenol resin foam board of this invention is demonstrated with reference to drawings.

FIG. 1 is a perspective view of a phenolic resin foam board according to an embodiment of the present invention.
The phenol resin foam board 1 of this embodiment is provided with the flat foam layer 10, the 1st surface material 12, and the 2nd surface material 14. As shown in FIG. The first facing 12 is provided on one side of the foam layer 10. The second facing 14 is provided on the other side of the foam layer 10. A printing unit 16 is formed on the first face material 12. In the present embodiment, the first surface material 12 is a printing material.
The phenol resin foam board 1 is a plate-like thing of a planar view rectangular shape which makes an X direction long and makes a Y direction a short side. In the present embodiment, the X direction is an MD (Machine Direction) direction, and the Y direction is a TD (Transverse Direction) direction. The X direction may be the TD direction, and the Y direction may be the MD direction.
The size of the phenolic resin foam board 1 is not particularly limited, and is appropriately determined in consideration of the application and the like. The size of the phenolic resin foam board 1 is, for example, width 910 mm or more and 1000 mm or less × length 1820 mm or more and 3300 mm or less × thickness 5 mm or more and 200 mm or less.
The shape of the phenolic resin foam plate 1 may be flat, and may be rectangular, circular or the like in plan view.

(Foam layer)
The foam layer 10 is a foam board obtained by foaming and curing a foamable resin composition. The foamable resin composition contains a phenol resin and a foaming agent.
In the foam layer 10, a plurality of cells are formed. There are substantially no pores in the cell wall, and at least some of the plurality of cells are closed cells that are not in communication with one another. The cell wall is composed of a cured product of phenolic resin.
In the closed cells of the foam layer 10, a gas derived from the blowing agent is held. When the foamable resin composition contains two or more foaming agents, the composition of the gas held in the closed cells is substantially the same as the composition of the foaming agent in the foamable resin composition.

As a phenol resin, the thing of a resol type is preferable.
The resol-type phenolic resin is a phenolic resin obtained by reacting a phenolic 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, acetaldehyde and the like. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, calcium hydroxide, aliphatic amines (trimethylamine, triethylamine and the like) and the like.
However, the phenol compound, the aldehyde and the alkali catalyst are not limited to those described above. The phenol resin may be used singly or in combination of two or more.
The use ratio of the phenol compound to the aldehyde is not particularly limited. Preferably, the molar ratio of phenol compound to aldehyde is 1: 1 to 1: 3, and more preferably 1: 1.3 to 1: 2.5.

  400 or more and 3000 or less are preferable and, as for the weight average molecular weight Mw of a phenol resin, 700 or more and 2000 or less are more preferable. When the weight average molecular weight is at least the above lower limit value, the closed cell rate is increased, and it is easy to further improve the compressive strength and further reduce the thermal conductivity. Moreover, it is easy to prevent the formation of a void. When the weight average molecular weight Mw is equal to or less than the above upper limit value, the viscosity of the foamable resin composition does not increase excessively, and a desired expansion ratio can be easily obtained.

  The blowing agent is not particularly limited, but halogenated hydrocarbons such as halogenated saturated hydrocarbons and halogenated unsaturated hydrocarbons, and hydrocarbons are preferable. As a foaming agent, a halogenated hydrocarbon is preferable and a halogenated unsaturated hydrocarbon is more preferable from a viewpoint of raising the flame retardance of the foaming layer 10 more, and improving heat insulation.

As a 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 hydrocarbon, one having a cyclic molecular structure having 4 to 6 carbon atoms or a chain molecular structure having 4 to 6 carbon atoms is 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 insulating performance in a wide temperature range from a low temperature range (for example, a freezer heat insulating material of about -80 ° C.) to a high temperature range (for example, a heat insulator for a heating body of about 200 ° C.) It is relatively inexpensive and economically advantageous.

  As the halogenated hydrocarbon, those known as a foaming agent can be used. As halogenated hydrocarbons, for example, halogenated saturated hydrocarbons such as chlorinated saturated hydrocarbons and fluorinated saturated hydrocarbons; chlorinated unsaturated hydrocarbons, chlorinated fluorinated unsaturated hydrocarbons, fluorinated unsaturated hydrocarbons And halogenated unsaturated hydrocarbons such as brominated fluorinated unsaturated hydrocarbons and iodinated fluorinated unsaturated hydrocarbons. The halogenated hydrocarbon may be one in which all of hydrogen is replaced by halogen, or one in which a part of hydrogen is replaced by halogen. These halogenated hydrocarbons may be used alone or in combination of two or more.

  Preferred chlorinated saturated hydrocarbons are those having 2 to 5 carbon atoms, such as dichloroethane, propyl chloride, isopropyl chloride (2-chloropropane), butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. Be Among them, isopropyl chloride is preferable in terms of low ozone layer destruction coefficient and excellent environmental compatibility.

  Examples of chlorinated fluorinated unsaturated hydrocarbons 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) (e.g., a product made by 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, SynQuest Laboratories, product number: 1300-7-09), 3-chloro-1,2,3-trifluoropropene ( HCFO-1233ye) (E and Z isomers), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc), 3,3-dichloro-3-fluoropropene, 1,2-dichloro-3, 3,3-Trifluoropropene (HCFO-1223xd) (E and Z isomers), 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E and Z isomers), And 2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene (E and Z variants) and the like.

  As the fluorinated saturated hydrocarbon, for example, difluoromethane (HFC 32), 1,1,1,2,2-pentafluoroethane (HFC 125), 1,1,1-trifluoroethane (HFC 143a), 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 (HFC 227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC 365mfc) and 1,1,1,2,2,2, And hydrofluorocarbons such as 3,4,5,5,5-decafluoropentane (HFC 4310 mee).

  The fluorinated unsaturated hydrocarbon includes those containing a fluorine atom and a double bond in the molecule, and examples thereof include 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3, 3-tetrafluoropropene (HFO-1234ze) (E and Z isomers), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz) (E and Z isomers) (SynQuest) Those disclosed in JP-A-2009-513812 and the like, such as those manufactured by Laboratories, product number: 1300-3-Z6).

  The halogenated hydrocarbon is preferably a halogenated unsaturated hydrocarbon in that it has a low ozone depletion potential (ODP) and global warming potential (GWP) and little influence on the environment, and a chlorinated fluorinated unsaturated hydrocarbon is preferable. Or fluorinated unsaturated hydrocarbons are more preferred.

The foamable resin composition may contain a halogenated hydrocarbon and another foaming agent other than a hydrocarbon. As other foaming agents, for example, low boiling point gases such as nitrogen, argon, carbon dioxide gas, air and the like; ethers such as dimethyl ether; carbonates such as sodium hydrogen carbonate, sodium carbonate, calcium carbonate, magnesium carbonate etc; azodicarbonamide Chemical blowing agents such as azobisisobutyronitrile, barium azodicarboxylate, N, N'-dinitrosopentamethylenetetramine, p, p'-oxybisbenzenesulfonylhydrazide, trihydrazino triazine, etc .; Porous solid materials, etc. Can be mentioned.
These foaming agents may be used alone or in combination of two or more.

  The combination of two or more foaming agents is not particularly limited. For example, one or more chlorinated hydrocarbons or a combination of a hydrocarbon and one or more fluorinated unsaturated hydrocarbons, one or more chlorinated carbonized materials Hydrogen or a combination of a hydrocarbon and one or more fluorinated saturated hydrocarbons, a combination of one or more chlorinated hydrocarbons or hydrocarbons and one or more chlorinated fluorinated unsaturated hydrocarbons, one or more Chlorinated hydrocarbon or combination of hydrocarbon with one or more chlorinated fluorinated saturated hydrocarbon, combination of one or more chlorinated fluorinated hydrocarbon with one or more fluorinated saturated hydrocarbon, one or more Combination of at least one fluorinated unsaturated hydrocarbon and at least one fluorinated saturated hydrocarbon, combination of at least two chlorinated fluorinated hydrocarbons, combination of at least two fluorinated saturated hydrocarbons Align, fluorination of two or more unsaturated hydrocarbons in combination with each other, and the like.

As a combination of two or more kinds of halogenated hydrocarbons, a combination of a chlorinated hydrocarbon and a halogenated unsaturated hydrocarbon having a halogen atom and a carbon-carbon double bond in a molecule is preferable.
Chlorinated hydrocarbons are conventionally used as a foaming agent for a foamed layer of a phenolic resin, but when used alone, the average cell diameter of the foamed layer 10 is large, and the thermal conductivity tends to be high. By using a fluorinated unsaturated hydrocarbon in combination, the average cell diameter is small, the thermal conductivity is low, and the heat insulation of the phenolic resin foam board 1 is improved. Moreover, since the halogenated unsaturated hydrocarbon is incombustible, the flame retardance of the phenol resin foam board 1 improves.

In the combination of chlorinated hydrocarbon and halogenated unsaturated hydrocarbon, the mass ratio of chlorinated hydrocarbon to halogenated unsaturated hydrocarbon is: chlorinated hydrocarbon: halogenated unsaturated hydrocarbon = 9: 1 to 1 : 9 is preferable and 9: 1-5: 5 are more preferable.
By containing the halogenated unsaturated hydrocarbon in the range satisfying the above mass ratio, the average cell diameter is smaller, the thermal conductivity is lower, and the heat insulating property of the phenolic resin foam board 1 is more excellent. .

  The mass ratio of hydrocarbon to halogenated unsaturated hydrocarbon is preferably hydrocarbon: halogenated unsaturated hydrocarbon = 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, and 5: 5 to 5: 3: 7 is more preferred. If the ratio of the halogenated unsaturated hydrocarbon is equal to or more than the above lower limit value, the heat insulation of the phenolic resin foam board 1 can be further enhanced. If the proportion of the halogenated unsaturated hydrocarbon is not more than the above upper limit value, the foamable resin composition can be sufficiently foamed. The halogenated unsaturated hydrocarbon is highly compatible with the phenolic resin. For this reason, when the proportion of the halogenated unsaturated hydrocarbon exceeds the above upper limit value, the viscosity of the foamable resin composition is lowered, and the foaming of the phenol resin tends to be insufficient.

In the case of a chlorinated hydrocarbon or a combination of a hydrocarbon and a halogenated unsaturated hydrocarbon, the boiling point of the halogenated unsaturated hydrocarbon is preferably lower than the boiling point of the chlorinated hydrocarbon. When the boiling point of the halogenated unsaturated hydrocarbon is lower than that of the chlorinated hydrocarbon or the hydrocarbon, the cell diameter of the cell 20 in the foam layer 10 is smaller, and the number of the cells 20 per unit volume is larger, There is a tendency that the heat insulation can be further enhanced.
Moreover, it is preferable that they are 2 degreeC or more and 30 degrees C or less, and, as for the difference of those boiling points, 5 degreeC or more and 20 degrees C or less are more preferable. If the difference in boiling point is larger than the above upper limit value, the halogenated unsaturated hydrocarbon which has previously been gasified to form a bubble nucleus is removed from the bubble until the chlorinated hydrocarbon having a higher boiling point is gasified, and foaming is caused. May be insufficient. If the difference in boiling point is smaller than the above lower limit value, the chlorinated hydrocarbon may be foamed without sufficiently forming cell nuclei, and the cell diameter may become coarse.
Therefore, for example, when isopropyl chloride having a boiling point of 37.degree. C. is selected as the chlorinated hydrocarbon, as the halogenated unsaturated hydrocarbon, one having a boiling point of -7.degree. C. to 35.degree. C. is selected. It is preferable to select one having a boiling point of 17 ° C. or more and 32 ° C. or less, in terms of easy handling at around normal temperature.
When cyclopentane having a boiling point of 49 ° C. is selected as the hydrocarbon, it is preferable to select one having a boiling point of 19 ° C. or more and 47 ° C. or less. Moreover, from the viewpoint of ease of handling at around normal temperature, those having a boiling point of 29 ° C. or more and 44 ° C. or less are preferable.

As a combination of a chlorinated hydrocarbon and a halogenated unsaturated hydrocarbon, a combination of isopropyl chloride and a fluorinated unsaturated hydrocarbon, or a combination of isopropyl chloride and a chlorinated fluorinated unsaturated hydrocarbon is preferable.
As a combination of a hydrocarbon and a halogenated unsaturated hydrocarbon, a combination of cyclopentane and a fluorinated unsaturated hydrocarbon, or a combination of cyclopentane and a chlorinated fluorinated unsaturated hydrocarbon is preferable.

When the foamable resin composition contains two or more foaming agents, the composition of the gas held in the closed cells is substantially the same as the composition of the foaming agent in the foamable resin composition.
The composition of the foaming agent in the foam layer 10 can be confirmed, for example, by the following solvent extraction method.

Solvent extraction method:
The retention time under the following measurement conditions in a gas chromatograph-mass spectrometer (GC / MS) is determined in advance using a standard gas of a foaming agent. Next, 1.6 g of a sample of a phenolic resin foam plate from which the upper and lower face materials were peeled off was separated into a glass container for grinding, and 80 mL of tetrahydrofuran (THF) was added. After crushing the sample so that the sample is immersed in the solvent, the extract is ground and extracted for 1 minute and 30 seconds with a homogenizer, the extract is filtered through a membrane filter with a pore size of 0.45 μm, and the filtrate is subjected to GC / MS. The type of blowing agent is identified from the previously determined retention time and mass spectrum. In addition, other foaming agents are identified by retention time and mass spectrum. The detection sensitivity of the foaming agent component is measured by each standard gas, and the composition (mass ratio) is calculated from the detection area area and the detection sensitivity of each gas component obtained by the above GC / MS.
-GC / MS measurement conditions Working column: DB-5 ms (Agilent Technology Inc.) 60 m, internal diameter 0.25 mm, film thickness 1 μm.
Column temperature: 40 ° C (10 minutes) -10 ° C / minute-200 ° C.
Inlet temperature: 200 ° C.
Interface temperature: 230 ° C.
Carrier gas: He 1.0 mL / min.
Split ratio: 20: 1.
Measurement method: Scanning method m / Z = 11 to 550.

  1 mass part or more and 25 mass parts or less are preferable with respect to 100 mass parts of phenol resin, as for content of the foaming agent in a foamable resin composition, 3 mass parts or more and 15 mass parts or less are more preferable, and 5 mass parts or more 11 More preferably, it is at most parts by mass.

The foamable resin composition may contain an acid catalyst. An 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 alone or in combination of two or more.

  The content of the acid catalyst in the foamable resin composition is preferably 5 parts by mass or more and 30 parts by mass or less, more preferably 8 parts by mass or more and 25 parts by mass or less, and 10 parts by mass or more and 20 parts by mass. Part or less is more preferable.

The foamable resin composition may contain a surfactant. The surfactant contributes to the miniaturization of the cell diameter (cell diameter).
The surfactant is not particularly limited, and those known as a foam stabilizer and the like can be used. Examples include castor oil alkylene oxide adducts, silicone surfactants, polyoxyethylene sorbitan fatty acid esters, and the like. These surfactants may be used alone or in combination of two or more.
The surfactant preferably contains either one or both of castor oil alkylene oxide adduct and silicone surfactant in that it tends to form cells with a small cell diameter, and has a lower thermal conductivity and flame retardancy. It is more preferable to include a silicone-based surfactant in that it can be higher.

The alkylene oxide in the castor oil alkylene oxide adduct is preferably an alkylene oxide having 2 to 4 carbon atoms, and ethylene oxide (hereinafter abbreviated as "EO") and propylene oxide (hereinafter abbreviated as "PO"). More preferred is EO. The alkylene oxide added to the castor oil may be one kind or two or more kinds.
As a castor oil alkylene oxide adduct, a castor oil EO adduct and a castor oil PO adduct are preferable.
More than 20 mol and less than 60 mol are preferable, and 21 mol or more and 40 mol or less are more preferable with respect to 1 mol of castor oil with respect to the addition mole number of the alkylene oxide in a castor oil alkylene oxide adduct. In such a castor oil alkylene oxide adduct, a polyoxyalkylene group (polyoxyethylene group etc.) formed by a hydrophobic group mainly comprising long chain hydrocarbon group of castor oil and a predetermined addition mole of alkylene oxide (EO etc.) And a hydrophilic group mainly composed of H. are arranged in a well-balanced manner in the molecule to exhibit a good surface activity. Therefore, the cell diameter of the foam layer 10 is reduced. In addition, flexibility is imparted to the cell walls of the foam layer 10 so that cracking is less likely to occur.

Examples of silicone surfactants include copolymers of dimethylpolysiloxane and polyether, and organopolysiloxane compounds such as octamethylcyclotetrasiloxane. Among them, copolymers of dimethylpolysiloxane and polyether are preferred in that more uniform and finer cells can be obtained.
The structure of the copolymer of dimethylpolysiloxane and polyether is not particularly limited. For example, ABA type in which polyether chains are bonded to both ends of the siloxane chains, plural siloxane chains and plural polyether chains alternate. (AB) n type, branched type in which polyether chain is connected to each end of branched siloxane chain, and polyether chain is connected to siloxane chain as a side group (a group to be bonded to a part other than the end) A pendant type etc. are mentioned.
Examples of the copolymer of dimethylpolysiloxane and polyether include dimethylpolysiloxane-polyoxyalkylene copolymer.
The carbon number of the oxyalkylene group in polyoxyalkylene is preferably 2 or 3. The oxyalkylene group constituting the polyoxyalkylene may be one type or two or more types.
Specific examples of the dimethylpolysiloxane-polyoxyalkylene copolymer include dimethylpolysiloxane-polyoxyethylene copolymer, dimethylpolysiloxane-polyoxypropylene copolymer, and dimethylpolysiloxane-polyoxyethylene-polyoxypropylene copolymer. Polymer etc. are mentioned.
As a copolymer of dimethylpolysiloxane and polyether, one having a polyether chain whose end is -OR (R is a hydrogen atom or an alkyl group) is preferable, and the heat conductivity can be further lowered. And particularly preferably, R is a hydrogen atom.

  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 with respect to 100 parts by mass of the phenol resin. If the content of the surfactant is at least the lower limit of the above range, the cell diameter tends to be uniformly small, and if it is at the upper limit or less, the water absorption of the foam layer 10 is small, and the manufacturing cost is also suppressed.

  In the foamable resin composition, the mass ratio represented by blowing agent: surfactant is preferably, for example, 1: 1 to 6: 1. When the proportion of the foaming agent is at least the lower limit value of the above range, the foamable resin composition is easily foamed sufficiently. It is easy to fully disperse the foaming agent in a foaming resin composition as the ratio of the foaming agent is below the upper limit value of the said range. Therefore, if the mass ratio of the foaming agent to the surfactant is within the above range, the foaming agent can be uniformly dispersed in the phenol resin to form fine bubbles.

The foamable resin composition may contain conventionally known additives. Examples of the additive include urea, a plasticizer, a filler (filler), a flame retardant (such as a phosphorus-based flame retardant), a crosslinking agent, an organic solvent, an amino group-containing organic compound, a colorant and the like.
As a filler, an inorganic filler is preferable. By using the inorganic filler, the thermal conductivity of the foam layer 10 can be reduced, and the flame retardancy can be further improved.

  As the inorganic filler, for example, hydroxides or oxides of metals such as aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, titanium oxide, antimony oxide and the like; metal powders such as zinc; carbonated Carbonates of metals such as calcium, magnesium carbonate, barium carbonate and zinc carbonate; alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; alkaline earth metal hydrogencarbonates such as calcium hydrogencarbonate and magnesium hydrogencarbonate; sulfuric acid Calcium, barium sulfate, calcium silicate, mica, talc, bentonite, zeolite, silica gel and the like can be mentioned. However, when using a strong acid as an acid catalyst, it is necessary to add metal powder and carbonate in the range which does not influence adjustment of pot life. These inorganic fillers may be used alone or in combination of two or more.

As the plasticizer, conventionally known ones can be appropriately selected and used. For example, at least one selected from the group consisting of phthalic acid compounds, phosphoric acid, trimellitic acid, adipic acid, and citric acid and alcohol And the reaction product with
Examples of phthalic acid-based compounds include dioctyl phthalate, dibutyl phthalate, diethyl phthalate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate and the like, and these may be used alone, 2 More than one species may be used in combination.
As a reaction product of at least one selected from the group consisting of phosphoric acid, trimellitic acid, adipic acid and citric acid with an alcohol, for example, triamyl phosphate, tributyl phosphate, triethyl phosphate, trimethyl phosphate Phosphoric acid esters such as triphenyl phosphate and 2-ethylhexyl phosphate phosphoric acid; tris (2-ethylhexyl) trimellitate; bis (2-ethylhexyl) adipate; dioctyl adipate; diisononyl adipate; diisodecyl adipate And ester compounds such as tributyl acetyl citrate, tributyl citrate, triethyl citrate, trimethyl citrate, tripropyl citrate and other citric acid esters; and the like. These ester compounds may be used in combination of two or more as needed, and various types can be selected according to the purpose.
Among these plasticizers, phthalic acid-based compounds are highly compatible with the resole resin, and the resole resin can be plasticized (lowered in viscosity), and can be uniformly discharged from the discharge port of the discharge device in the manufacturing process described later. The closed cell rate can be further enhanced.

  The content of the filler in the foamable resin composition is preferably such that the extraction pH is 3 or more and 6 or less. 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 3 to 15 parts by mass with respect to 100 parts by mass of the phenol resin. More preferably, 5 parts by mass or more and 10 parts by mass or less are particularly preferable. When the content of the filler is less than the above lower limit value, the extraction pH of the foam layer 10 is lowered. When the extraction pH is low, the acidity is increased, and therefore, the material in contact with the phenolic resin foam plate may cause corrosion. When extraction pH exceeds the said upper limit, content of a filler will become more than the said upper limit, the curing reaction by an acid catalyst will be inhibited remarkably, and there exists a possibility that productivity may deteriorate.

  The extraction pH is measured by the following method. The foam layer 10 is ground to 250 μm (60 mesh) or less in a mortar to obtain a sample. Weigh 0.5 g of sample into a 200 mL stoppered Erlenmeyer flask. Add 100 mL of pure water to a stoppered Erlenmeyer flask, and seal tightly. Using a magnetic stirrer, stir the inside of the stoppered Erlenmeyer flask at 23 ° C. ± 5 ° C. for 7 days to prepare 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 foamable resin composition is prepared by mixing a phenolic resin and a foaming agent, and optionally, optional components (acid catalyst, surfactant, additives, etc.).
Although the order of mixing each component is not particularly limited, for example, a surfactant and optionally an additive are added to and mixed with a phenol resin, and a foaming agent and an acid catalyst are added to the obtained mixture, and this composition is The foamable resin composition can be prepared by supplying to a mixer and stirring.

  The size of the foam layer 10 is determined in consideration of the use of the phenolic resin foam board 1 and the like, and is not particularly limited. For example, the length (X direction) 500 mm or more and 4000 mm or less × width (Y direction) 500 mm or more and 1000 mm or less It may be.

  The thickness t1 of the foam layer 10 is determined in consideration of the heat insulation and the like required for the phenolic resin foam board 1 and is preferably 5 mm to 200 mm, more preferably 30 mm to 120 mm, and still more preferably 45 mm to 100 mm. . If it is more than the said lower limit, heat insulation will 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 is easy.

The density of the foam layer 10 is preferably from 10 kg / ^{m 3} or more 100 kg / ^{m 3} or less, more preferably 15~50kg / ^{m 3,} more preferably ^{20~40kg / m 3, 23~35kg / m} 3 is especially preferred. If the density is equal to or higher than the lower limit, the strength of the phenolic resin foam plate 1 can be further enhanced. If the density is equal to or lower than the upper limit, the heat insulation of the phenolic resin foam plate 1 can be further enhanced.
The density is measured in accordance with JIS A 9511: 2009.

The average cell diameter in the foam layer 10 is preferably 50 μm to 200 μm, more preferably 50 μm to 150 μm, and most preferably 50 μm to 100 μm. If the average cell diameter is within the above range, the heat insulation of the phenolic resin foam board 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 of the foam layer 10 in the thickness direction. The cut surface in the thickness direction of the test piece is photographed at a magnification of 50 times. Draw four straight lines of 9 cm in length to the captured image. At this time, a straight line is drawn so as to avoid voids (air gaps of 2 mm ² or more). The number of air bubbles crossed by each straight line (the number of cells measured according to JIS K 6400-1: 2004) is counted for each straight line, and the average value per straight line is determined. The average value of the number of bubbles is divided by 1800 μm, and the obtained value is defined as the average bubble diameter.
The average cell diameter of the foam layer 10 is controlled by the combination of the type or composition of the foaming agent, the type of surfactant, the foaming conditions (heating temperature, heating time, etc.).

The closed cell rate in the foam layer 10 is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more, and particularly preferably 95% or more. The upper limit is not particularly limited, and may be 100%. If the closed cell rate is equal to or higher than the lower limit value, low thermal conductivity can be maintained for a long time.
The closed cell rate is measured in accordance with JIS K 7138: 2006.
The closed cell rate of the foam layer 10 is controlled by the combination of the type or composition of the foaming agent, the type of surfactant, the foaming conditions (heating temperature, heating time, etc.).

The foam layer 10 is divided into three in the thickness direction, and the first surface layer portion 10a, the central layer portion 10c, and the second surface layer portion 10a are sequentially arranged from one surface (the surface on which the first surface member 12 is provided in this embodiment). In the case of the surface layer portion 10b, the closed cell ratio in the first surface layer portion 10a adjacent to the printing surface material (in the present embodiment, the first surface material 12) is 85% or more, preferably 90% or more. 95% or more is more preferable, and 100% is further preferable. If the closed cell rate of the first surface layer portion 10a adjacent to the printing surface material is equal to or more than the above lower limit, the amount of water absorption can be reduced, low thermal conductivity can be maintained over a long period, and the beauty of the printing portion is further improved. It can be done.
The closed cell rate can be measured according to JIS K 7138: 2006, measurement method 1.
Here, when the thickness of the phenolic resin foam board 1 is 45 mm or more, the first surface layer portion 10a is a thickness from one surface of the phenolic resin foam board 1 from which the surface material is peeled (that is, the foam layer 10). It is a portion up to 20 mm in the direction. The second surface layer portion 10 b is a portion up to 20 mm in the thickness direction from the other surface of the foam layer. The central layer portion 10c is a portion of a range (thickness 20 mm) 10 mm above and below from the center in the thickness direction of the phenolic resin foam plate from which the face material has been peeled off.
When the thickness of the phenolic resin foam plate is less than 45 mm, the phenolic resin foam plate is equally divided into three in the thickness direction, and the first surface layer portion, the central layer portion, and the second surface layer are sequentially arranged from one side. Be part.

  The closed cell rate of the second surface layer portion 10b is not particularly limited. The closed cell rate of the second surface layer portion 10b may be the same as or different from the closed cell rate of the first surface layer portion 10a. In addition, when a printing part is formed in the 2nd surface material 14, the closed cell rate of the 2nd surface layer part 10b adjacent to the 2nd surface material 14 is the same as the closed cell rate of the 1st surface layer part 10a. It is.

  The closed cell rate of the central layer portion 10c is not particularly limited, but is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more, and particularly preferably 100%. If the closed cell rate of the central layer portion 10c is equal to or more than the above lower limit value, the heat insulation of the phenolic resin foam board 1 can be further enhanced.

  The closed cell ratio of at least one of the first surface layer portion 10a and the second surface layer portion 10b is preferably higher than the closed cell ratio of the central layer portion 10c, and the first surface layer portion 10a and the second surface layer portion 10b More preferably, both closed cell rates are higher than the closed cell rate of the central layer portion 10c.

28 volume% or more is preferable, 30 volume% or more is more preferable, and 32 volume% or more of the limited oxygen index (hereinafter, also referred to as "LOI") of the foam layer 10 is more preferable. If the LOI of the foam layer 10 is equal to or more than the above lower limit value, the flame retardancy of the phenolic resin foam board 1 can be further improved.
LOI is measured according to JIS K 7201-2: 2007.
The LOI of the foam layer 10 is adjusted, for example, by the combination of the type or composition of the foaming agent, the type of surfactant, the type or composition of the flame retardant, and the like. For example, the lower the content of the flammable blowing agent in the blowing agent (the higher the content of halogenated hydrocarbons), the higher the LOI of the foam layer 10. In addition, if the surfactant has a silicone surfactant, particularly a polyether chain whose end is -OH, the LOI of the foam layer 10 tends to be higher than when using other surfactants. is there. Furthermore, the LOI of the foam layer 10 can be increased by containing the phosphorus-based flame retardant or the like in the foam layer 10.

(First surface material)
The first facing 12 is provided on one side of the foam layer 10. The first facing 12 can protect the foam layer 10 from physical impact or the like.
90% or more is preferable, 95% or more of the ratio of the area which the 1st surface material 12 covers with respect to the area (100%) of one side of the foam layer 10 is more preferable, and 98% or more is more preferable, 100% is particularly preferred.

The first face material 12 is a synthetic fiber non-woven fabric. In addition, it is preferable that the first facing 12 have low water absorption. In the case of a facing comprising a material having high water absorbability, shrinkage and the like occur in the facing due to the water in the foamable resin composition and the water produced upon condensation of the phenolic resin. By using a synthetic fiber non-woven fabric as the facing material, the shrinkage of the facing material due to moisture and the like can be suppressed, and the generation of wrinkles in the facing material can be suppressed.
Examples of synthetic fiber non-woven fabrics include needle punch non-woven fabrics, spun lace non-woven fabrics, thermal bond non-woven fabrics, chemical bond non-woven fabrics and the like, among which spun bond non-woven fabrics are preferred. Spunbond non-woven fabrics are easy to obtain because they have a large industrial distribution, and it is also possible to control the texture and fuzzing of the surface layer of the non-woven fabric by changing the heat-sealing point pattern between fibers by the emboss heating roll in production Easy to handle.
Examples of the fibers constituting the synthetic non-woven fabric include polypropylene fibers, polyethylene fibers, nylon fibers, polyester fibers, rayon fibers, acrylic fibers, aramid fibers and the like.

The non-woven fabric constituting the first facing 12 preferably contains titanium dioxide. By containing titanium dioxide, light resistance to ultraviolet light is improved. In addition, the non-woven fabric constituting the first facing 12 contains titanium dioxide, whereby the whiteness is enhanced and the visibility of the printing portion 16 is further enhanced.
As content of the titanium dioxide with respect to the fiber which comprises the 1st surface material 12, 0.1 mass% or more and 3 mass% or less are preferable, and 0.1 mass% or more and 1 mass% or less are more preferable. When the content of titanium dioxide is equal to or more than the above lower limit value, light resistance to ultraviolet light and whiteness can be improved. If the content of titanium dioxide is equal to or less than the above upper limit value, the strength of the first surface material 12 and the strength of the thermocompression bonding fixed part can be further improved.
In addition, titanium dioxide may be mixed in the synthetic resin which comprises the fiber of the 1st surface material 12, and may adhere to the fiber surface. Moreover, the titanium dioxide contained in the 1st face material 12 can be quantified using the ICP spectroscopy analysis based on JISH1632-1: 2014.

  The thickness of the first face material 12 is not particularly limited, but is preferably 0.06 mm or more and 1.00 mm or less, and more preferably 0.10 mm or more and 0.50 mm or less. When the thickness of the face material is equal to or more than the above lower limit value, bleeding of the foamable resin composition to the surface is easily suppressed. When the thickness of the face material is less than or equal to the above upper limit, the handleability of the face material is likely to be enhanced.

Basis weight of the first plate member 12 is not particularly limited, the basis weight of the synthetic fiber nonwoven fabric is a 15 g / ^{m 2} or more 100 g / ^{m 2} or less, preferably 15 g / ^{m 2} or more 50 g / ^{m 2} or less, 15 g / m ² or more and 40 g / m ² or less are more preferable, and 15 g / m ² or more and 30 g / m ² or less are more preferable.
If the basis weight of the first face material 12 is equal to or more than the above lower limit value, the ink to be printed does not easily penetrate the first face material 12 and does not bleed easily. Therefore, the printing unit 16 can be made more beautiful. If the fabric weight of the first face material 12 is equal to or less than the above upper limit value, the adhesion between the foam layer 10 and the first face material 12 can be enhanced. Thereby, the first face material 12 is less likely to be peeled off from the foam layer 10, and the surface can be made more beautiful.

It is preferable that a so-called embossed (thermo-compression fixed part) having a concavo-convex shape is formed on the first face material 12. By using the face material on which the emboss is formed, the adhesion between the face material and the foamable resin composition can be further enhanced.
Although it does not specifically limit as a pattern (pattern) of embossing, For example, a minus pattern, a point pattern, a crease pattern etc. are mentioned. A substantially square crease pattern or a substantially rectangular minus pattern is preferable from the viewpoint that the unevenness shape by embossing is large and the adhesiveness with the foam layer 10 can be further enhanced.
In order to emboss synthetic fiber non-woven fabric, for example, a crimped long fiber web developed under cooling conditions immediately below a spinning nozzle by a known spun bonding method is partially thermocompression-bonded with a heat embossing roll, or The crimped fiber web is produced by crimping by heat treatment and partial thermocompression bonding with a hot embossing roll.

In the thermocompression bonding fixed part formed in the case of embossing, 0.05 mm ² or more and 5.0 mm ² or less are preferable, and the area per thermo compression bonding fixed part is more preferable 0.07 mm ² or more and 3.0 mm ² or less . By using a face material within this range, it is possible to improve the adhesion between the foamable resin composition and the face material while suppressing the exudation of the foamable resin composition by the thermocompression bonding fixed part. When the above area is less than 0.05 mm ² , there is little bonding between fibers, physical strength such as frictional strength is low and the foamable resin composition tends to exude easily, and when it exceeds 5.0 mm ² , thermocompression bonding The area of the fixed portion is large, the texture is hard, and the adhesion between the foam layer 10 and the fibers of the facing is deteriorated. In addition, the ink is less likely to adhere to the surface material during printing, and the ink is likely to be peeled off or uneven in color. Furthermore, there is a possibility that the air permeability of the below-mentioned Frazier will become low, the curing time will become long, or the closed cell rate will decrease.

In general, the thermocompression-bonding fixed portion can be easily confirmed visually or by an optical microscope or the like. The area of each thermocompression-bonding fixed part is calculated | required by the following measuring methods.
<Method of measuring the area of the thermocompression bonding fixed part>
An image of a surface of the face material magnified 10 times with an optical microscope is obtained. The area of the observed thermocompression bonding fixed part is measured using an image processing software (trade name "Photoshop (registered trademark)" manufactured by Adobe Systems Incorporated), and the average value of 5 pieces of the thermocompression bonding fixed part is measured. It is the area of the crimped fixed part.

  0.05 mm or more and 5 mm or less are preferable, and, as for the minimum space | interval of a thermocompression-bonding fixed part, 0.08 mm or more and 2 mm or less are more preferable. By using a face material within this range, it is possible to improve the adhesion between the foam layer 10 and the face material while suppressing the exudation of the phenol resin. When the minimum distance is less than 0.05 mm, there are many thermocompression bonding fixed parts, the texture is hard, and the adhesiveness between the foam layer 10 and the fibers of the facing tends to be poor. When it exceeds 5 mm, there is little bonding between fibers, physical strength such as frictional strength is low, and the foamable resin composition tends to exude. Moreover, it is preferable to distribute a thermocompression-bonding fixed part equally over the whole surface of a nonwoven fabric surface.

The thermocompression bonding fixed part density is 5 pieces / cm ² or more and 150 pieces / cm ² or less, more preferably 6 pieces / cm ² or more and 100 pieces / cm ² or less, and 7 pieces / cm ² or more and 80 pieces / cm ² or less More preferable. The thermocompression bonding fixed part density means the number of the thermocompression bonding fixed parts per unit area, and is expressed by the following formula (s).
Thermocompression bonding fixed part density (pieces / cm ² ) = [number of thermocompression bonding fixed parts (pieces)] / [[surface area of facing material (cm ² )] ... (s)
If the thermocompression-bonding fixed part density is not less than the above lower limit value, bleeding of the foamable resin composition can be favorably suppressed, and the beauty of the printing portion 16 can be enhanced. If the thermocompression bonding fixed part density is below the above-mentioned upper limit, the adhesiveness of foaming layer 10 and a face material can be improved more, and the amount of water absorption can be made low. Moreover, if the thermocompression bonding fixed part density is below the above-mentioned upper limit, the Frazier air permeability mentioned later can be made high, the curing temperature can be lowered, the curing time can be shortened, the closed cell rate can be increased, and the heat conduction is low for a long time Maintain the rate.

The thermocompression bonding fixed part density is preferably adjusted by the area per one point of the thermocompression bonding fixed part. The thermocompression-bonded fixed portion is difficult to be colored because the ink does not penetrate, and the fiber portion around the thermo-compression bonded fixed portion is likely to be colored due to the ink bleeding through the capillary phenomenon. On the other hand, the thermocompression bonding fixed part has the effect of preventing the penetration of the ink and the bleeding of the resin.
Therefore, when the area of one thermocompression bonding fixing part is small, the thermocompression bonding fixing part density is increased, and when the area per one location of the thermocompression bonding fixing part is large, the thermocompression bonding fixing part density is reduced. preferable.
When the area per one portion of the thermocompression bonding fixing portion is 0.05 mm ² or more and 0.5 mm ² or less, the thermocompression bonding fixing portion density is preferably 80 pieces / cm ² or more and 150 pieces / cm ² or less. When the area per one portion of the thermocompression bonding fixing portion is 0.5 mm ² or more and 5.0 mm ² or less, the thermocompression bonding fixing portion density is preferably 5 / cm ² or more and 80 pieces / cm ² or less.
If the area per one portion of the thermocompression bonding fixed portion is equal to or less than the above upper limit, the area of the fiber portion around the thermocompression bonding fixed portion is sufficiently large even if the area of the printing portion 16 is small. Since the area to be colored with the ink (ie, the area of the fiber portion around the thermocompression bonding fixed portion) is sufficiently large, the visibility of the printing portion 16 can be further enhanced. If the area per one part of the thermocompression bonding fixed part is the above lower limit or more, the penetration of the ink and the exudation of the resin are prevented, and the water from the outside is prevented from reaching the foam layer 10 to reduce the water absorption amount it can.

Moreover, it is preferable to adjust the thermocompression bonding fixed part density according to the density of the foam layer 10.
When the density of the foam layer 10 is 27 kg / m ³ or less, the density of the thermocompression-bonding fixed portion of the first face material 12 is preferably 80 pieces / cm ² or more and 150 pieces / cm ² or less. When the density is 27 kg / m ³ or less, it is necessary to increase the expansion ratio by increasing the amount of the foaming agent or raising the curing temperature, and the viscosity of the foamable resin composition tends to decrease. For this reason, when the thermocompression-bonding fixed part density is low, there is a possibility that the low viscosity foamable resin composition may ooze to the surface of the face material. Further, if the density of the heat-bonded fixed portion of the first face material 12 is low, the tear strength is high, and a strong force is required at the time of cutting. Therefore, when the density of the foam layer 10 is low, the compressive strength of the foam layer 10 is low, and the foam layer 10 is easily crushed by the force applied at the time of cutting of the phenolic resin foam board 1.
On the other hand, when the density of the foam layer 10 exceeds 27 kg / m ³ , the thermocompression bonding fixed part density is preferably 5 pieces / cm ² or more and 80 pieces / cm ² . When the density exceeds 27 kg / m ³ , the amount of the phenol resin of the foam layer 10 is large, so that the amount of condensation water generated along with the polymerization reaction of the foamable resin composition is large. During foaming and curing of the foamable resin composition, air permeability is required so that condensation water can be removed through the facing, but if the heat-pressing fixed part density is too high, the air permeability decreases and condensation water remains and becomes independent There is a possibility that the bubble rate may decrease.

  It is preferable that the depth of the recessed part (namely, the hollow formed by thermocompression bonding by heat embossing roll processing etc.) of a thermocompression-bonding fixed part is 0.01-1.0 mm. If the depth is less than 0.01 mm, bonding of the thermocompression bonding fixed portion tends to be small, and if it exceeds 1.0 mm, processing by an embossing roll or the like tends to be difficult.

The tear strength of the first face material 12 is preferably 1.0 N or more and 6.0 N or less, more preferably 1.5 N or more and 5.0 N or less, still more preferably 2.0 N or more and 4.5 N or less, and 2.5 N or more 4.5 N or less is the most preferable. When the tear strength is less than 1.0 N, the resistance to tearing is extremely low, and during production of the phenolic resin foam board 1, it is torn during pulling out from the roll or during foaming and hardening, or the facing is torn during transportation or construction There is a high risk of When the tear strength exceeds 5 N, the resistance to tearing is extremely high, and the surface at the time of cutting after the foaming and curing step at the time of production of the phenolic resin foam board 1 and at the time of cutting at a construction site when using the phenolic resin foam board 1 The force required to cut the material may be excessively required, or the force required for the cutting may cause the cut surface of the phenolic resin foam board to be dented or crushed.
In addition, tear strength is measured according to D method (Benduram method) of JISL 1096: 1994, and measures the face material peeled off from the foaming layer 10 as it is.

The tensile strength in the longitudinal direction of the first face material 12 is preferably 45 N / 5 cm or more and 250 N / 5 cm or less, more preferably 75 N / 5 cm or more and 200 N / 5 cm or less, and still more preferably 75 N / 5 cm or more and 140 N / 5 cm or less. Moreover, 15 N / 5 cm or more and 100 N / 5 cm or less are preferable, 20 N / 5 cm or more and 80 N / 5 cm or less are more preferable, and 24 N / 5 cm or more and 40 N / 5 cm or less are more preferable. .
Furthermore, the tensile strength in the longitudinal direction is preferably higher than the tensile strength in the transverse direction. The difference in tensile strength between the longitudinal direction and the transverse direction is preferably 50 N / 5 cm or more and 150 N / 5 cm or less.
The longitudinal direction refers to the unwinding direction of the roll of the first face material 12 wound in a roll, and the lateral direction refers to the width direction of the roll of the first face material 12 wound in a roll.
It is preferable that the longitudinal direction is a direction parallel to the production direction (MD direction) of the phenolic resin foam board 1.
The face material is drawn out from a state of being rolled in a cylindrical core called a winding core, and provided for manufacturing. If the tensile strength in the longitudinal direction and the lateral direction is in the above range, the face material is unlikely to be stretched by the pulling force, so that it is difficult to cause the winding tightness of the roll due to the pulling force. Moreover, since it is hard to expand by the force at the time of drawing out, a face material does not expand-contract hard after manufacture, and the dimensional stability of the phenol resin foam board 1 can be improved.
Furthermore, if the difference in tensile strength in the longitudinal direction and in the lateral direction is within the above range, it is difficult to cause expansion and contraction at the time of drawing out and expansion and contraction of the facing caused by contraction of the phenolic resin foam board 1. Thereby, the deformation of the pattern of the printing unit can be suppressed.
The tensile strength in the longitudinal direction and the lateral direction can be adjusted by a combination of the basis weight of the face material, the shape and arrangement of the thermocompression bonding fixing portion, the thermal compression bonding fixing portion density, and the like.
Tensile strength is measured based on 6.3.1 of JIS L1913: 2010. A test piece of 5 cm × 30 cm with the long side in the longitudinal direction and a test piece of 5 cm × 30 cm with the long side in the lateral direction are prepared. Each test piece is sampled at three points per meter at equal intervals in the width direction. Each test piece is subjected to a tensile test using a constant speed elongation type tensile tester at a gripping distance of 20 cm and a tensile speed of 10 cm / min. The strength when the test piece is broken is read, and the value obtained by rounding off the first decimal place is taken as the tensile strength (N / 5 cm).

It is preferable that the synthetic fiber non-woven fabric having the thermocompression bonding fixing portion has a raised fiber in which only one end thereof is fixed at the thermocompression bonding fixing portion and the other end is not fixed at the thermocompression bonding fixing portion . Usually, the amount of raised fibers (the degree of raising) does not differ between the front and back surfaces of the synthetic fiber nonwoven fabric, but the amount of raised fibers can be made different by raising only one side.
The first face material 12 preferably has a raising degree of 1 / cm to 35 / cm, more preferably 1/30 to 30 / cm, and 3 //. More preferably, cm or more and 20 lines / cm or less. If the raising degree is within the above range, the raised fibers are embedded in the foam layer 10, the adhesion between the foam layer 10 and the first surface material 12 is improved and it becomes difficult to separate, and the ink is the first surface material 12 And the printing unit 16 is easy to form.
When the raising degree is less than 1 line / cm, it means that the thermocompression bonding fixed part density is too high or the area of the thermocompression bonding fixed part is too large, and the heat is hard to adhere to the ink on the surface of the first face material 12 Since the area occupied by the crimped fixed portion is large, it is difficult to form the printing portion 16. In addition, the adhesion between the first facing material 12 and the foam layer 10 is reduced, and it becomes easy to peel off.
On the other hand, when the raising degree exceeds 30 / cm, it means that the thermocompression bonding fixed part density is extremely low or there are few fibers connecting the adjacent thermocompression bonding fixed parts, and the machine such as the tensile strength of the surface material itself Strength is reduced. If the number of raised fibers is too large, the ink may be repelled, or the ink may not easily penetrate between the fibers constituting the first surface material 12, and the printed portion 16 may not be formed. Furthermore, the raised fibers are easily broken from the face material, and since the raised fibers broken into the printing plate are caught, it is difficult to form a continuous printing portion 16. Furthermore, since the amount of raised fibers remaining on the surface of the foam layer 10 increases after peeling the facing material, when the foam layer 10 is crushed and mixed with the foamable resin composition and recycled, viscosity is increased by the mixed raised fibers. It becomes difficult to adjust, and the closed cell rate may be reduced.
As the raised fibers amount remaining on the surface of the foam layer 10 after removal of the surface material, 0 present / cm ² 50 or more / cm ² or less, and 0.1 present / cm ² or more 30 lines / cm ^{The number} is preferably ² or less, more preferably 0.1 / cm ² or more and 10 / cm ² or less.
The amount of raised fibers remaining on the surface of the foam layer 10 after peeling the facing material can be determined by the following measurement method.
<Method of measuring the amount of raised fibers>
The facing material of 5 cm wide x 5 cm long is peeled off from the phenolic resin foam board. The surface of the foam layer 10 after peeling off the face material is enlarged by an optical microscope, SEM or the like to count the number of fibers. This is performed 3 times at an arbitrary position of the foam board, and the average value of the measured number of fibers is divided by the observed area of 25 cm ² to obtain a measurement value.

  The peel strength between the first facing material 12 and the foam layer 10 is preferably 300 g / 50 mm or more, more preferably 600 g / 50 mm or more, and still more preferably 800 g / 50 mm or more. If it is more than the said lower limit, it can suppress more reliably that the 1st face material 12 peels from the foam layer 10. As shown in FIG. Although the upper limit of peeling strength is not specifically limited, 3000 g / 50 mm or less is preferable.

Frazier air permeability of the first surface material ^12, 50 cm ^{3 /} cm preferably 2 · sec or more 1000 cm ³ / ^cm is 2 · sec or ^less, 50cm ^{3 /} cm 2 · sec or more 600cm ³ / ^cm 2 · sec or less Is more preferably 100 cm ³ / cm ² · sec or more and 500 cm ³ / cm ² · sec or less, and 200 cm ³ / cm ² · sec or more and 400 cm ³ / cm ² · sec or less Particularly preferred.
When the Frazier air permeability of the first facing 12 is less than 50 cm ³ / cm ² · sec, the curing time in the curing step is prolonged, or the water generated in the curing step remains in the foam layer 10 and remains When water is removed in the curing step, it may become pores and the closed cell rate may decrease.
The surface material of the first surface material 12 in which the Frazier air permeability of the first surface material 12 exceeds 1000 cm ³ / cm ² · sec has a very small basis weight or a very low thermocompression-bonded fixed part density. For this reason, the phenol resin composition discharged onto the face material exudes from the face material in the process of foaming and curing, which contaminates the production equipment. In addition, moisture from the outside can easily reach the foam layer 10 to increase the amount of water absorption.
In addition, Frazier air permeability is a value calculated by measuring the amount of air passing through the facing using a Fraziled tester according to JIS L 1096, and it is measured for the facing before being laminated on the foam layer 10. Be done.

  As a method of providing the first surface material 12, the second surface material 14 is disposed on the lower conveyor of the manufacturing system to be described later, and the foamable resin composition is discharged directly onto the surface material, and the second surface material 14 is discharged thereon. There is a method of heating and foaming after the first face material 12 is placed. Thereby, facings are provided on both sides of the sheet-like foam layer 10.

(Second surface material)
The second facing 14 is provided on the other side of the foam layer 10. The second facing 14 can protect the foam layer 10 from physical impact or the like.
90% or more is preferable, 95% or more of the ratio of the area which the 2nd surface material 14 covers with respect to the area (100%) of the other side of the foam layer 10 is more preferable, and 98% or more is more preferable, 100% is particularly preferred.

The type of the second facing 14 is the same as the type of the first facing 12. The type of the second facing 14 and the type of the second facing 14 may be the same or different. However, when the types of the first facing 12 and the second facing 14 are different, the phenolic resin foam board 1 is easily warped due to the difference in the amount of expansion and contraction of the both-sides. Therefore, it is preferable that the types of the first facing 12 and the second facing 14 be the same.
The thickness of the second facing 14 is the same as the thickness of the first facing 12. The thickness of the second facing 14 and the thickness of the first facing 12 may be the same or different. However, if the thickness of the first face material 12 and the second face material 14 is different, the phenolic resin foam board 1 is easily warped due to the difference in the amount of expansion and contraction of the two-sided material. For this reason, it is preferable that the thickness of the 1st surface material 12 and the 2nd surface material 14 is the same.
The basis weight of the second facing 14 is the same as the basis weight of the first facing 12. The basis weight of the second facing 14 and the basis weight of the first facing 12 may be the same or different. However, if the basis weights of the first surface material 12 and the second surface material 14 are different, the phenolic resin foam board 1 is easily warped due to the difference in the amount of expansion and contraction of the both surface materials. Therefore, it is preferable that the basis weight of the first facing 12 and the second facing 14 be the same.
The raising degree of the second facing 14 is similar to the raising degree of the first facing 12. The raising degree of the second facing 14 may be the same as or different from the raising degree of the first facing 12.
The flanged air permeability of the second facing 14 is similar to the flanged air permeability of the first facing 12. The flanged air permeability of the second facing 14 may be the same as or different from the flanged air permeability of the first facing 12.
The tensile strength of the second facing 14 is similar to the tensile strength of the first facing 12. The tensile strength of the second facing 14 may be the same as or different from the tensile strength of the first facing 12.
The peel strength between the second facing 14 and the foam layer 10 is the same as the peel strength between the first facing 12 and the foam layer 10. The peel strength between the second facing 14 and the foam layer 10 may be the same as or different from the peel strength between the first facing 12 and the foam layer 10.

(Printing department)
The printing unit 16 is provided on the surface of the first face material 12. The printing unit 16 is a symbol such as a trade name or logo of the phenolic resin foam board 1 to be manufactured, information such as a note of usage, or a pattern for enhancing the design. The printing portion 16 is formed by depositing an ink containing a dye or a pigment between the fibers of the first facing 12 or around the fibers as an ink film. The printing unit 16 refers to portions of characters and figures that are visually recognized when viewed from a distance of about 1 m from the first surface material 12.
In addition, although ink may not adhere to a thermocompression-bonding fixed part, when ink adheres to the fiber part around the thermocompression-bonding fixed part, the said thermocompression-bonding fixed part is also included in the printing part 16. FIG. Moreover, although a formaldehyde catcher agent may be apply | coated to the whole face material, this shall not be included as an area of the printing part 16. FIG.

The ink for forming the printing portion may be either an ink in which a pigment is dispersed or an ink in which a dye is dissolved.
Examples of the ink include water-based ink, oil-based ink, and curable ink such as ultraviolet curable ink and thermosetting ink. Since the phenol resin foam board 1 is used as a heat insulation material of a house wall, a floor, and a roof, the oil-based ink or hardening type ink strong against rain or moisture is preferable.

  As the pigment, any of organic and inorganic pigments may be used. For example, titanium dioxide, zinc oxide, iron oxide, chromium oxide, iron black, cobalt blue, alumina white, iron oxide yellow, viridian, zinc sulfide, lithobon, Cadmium yellow, amber, cadmium red, yellow lead, molybdate orange, zinc chromate, strontium chromate, white carbon, clay, talc, ultramarine blue, precipitated barium sulfate, barite powder, calcium carbonate, lead white, bituminous, manganese violet, carbon Black, aluminum powder, pearl pigments and the like can be mentioned.

Examples of organic pigments include quinacridone pigments, phthalocyanine pigments, graphene pigments, perylene pigments, phthalocyanine pigments, dioxazine pigments, isoindolinone pigments, methine azomethine pigments, diketopyrrolopyrrole pigments, azo lake pigments And pigments such as insoluble pigments, insoluble azo pigments, and condensed azo pigments.
These pigments may be used alone or in combination of two or more.

  In addition, although the printing part is formed only in the 1st surface material 12 in the phenol resin foam board 1 of this embodiment, this invention is not limited to this, The printing part exists only in the 2nd surface material 14 It may be formed, and the printing part may be formed in both of the first face material 12 and the second face material 14.

The ratio of the total area of the printing unit 16 to the total area of the first face material 12 (hereinafter also referred to as “printing area ratio”) is preferably 5% to 70%, and more preferably 10% to 60%. 15% or more and 50% or less is most preferable. If the printing area ratio is less than 5%, depending on the cut area of the phenolic resin foam board 1, almost no printed portion remains, and there is a risk of losing the identification ability such as the brand name. If the printing area ratio exceeds 70%, the air permeability of the first surface material 12 may be reduced by the ink forming the printing unit 16, and the curing step may require a long time. If the printing area ratio exceeds 70%, the drying speed of the ink is slower than the production speed of the phenolic resin foam board 1, and the ink may adhere to other phenolic resin foam boards 1 and production lines . In addition, the total area of the 1st surface material 12 is the area of the whole surface material including the printing part 16 and a non-printing part.
A printing area ratio shall be calculated about the rectangular phenol resin foam board 1 whose area of the whole surface material is 7000 cm < ² > or more at least, and whose at least one side is 400 mm or more. The area of the phenolic resin foam board that generally circulates is 16562 cm ² (91 cm wide x 182 cm long), and the size of the rectangular space between the pillars and beams that constitute the wall and floor of the building It is cut and used at the construction site according to Moreover, the space | interval of pillars etc. is 400 mm or more normally, and an area is 7000 cm < ² > or more normally. For this reason, in the phenol resin foam board 1 after a cutting | disconnection, it is because the area of the printing part 16 which exhibits identifiability in an aspect with an area of 7000 cm < ² > or more at least 400 mm of one side is required.

500 cm < ² > or less is preferable and, as for the area per one place of the printing part 16, 300 cm < ² > or less is more preferable. By setting the print area per part to 500 cm ² or less, it is possible to suppress the deterioration of air permeability due to printing and the generation of wrinkles on the surface material.
Note that “area per location” is the area of a region that is recognized as a group of information such as a series of product names, description of usage, patterns, and the like.

Basis weight is preferably from 0.01 g / ^{m 2} or more 1.5 g / ^{m 2} or less of the printing unit 16, 0.01g / ^{m 2} or more 1.0 g / ^{m 2} or less is more preferable. The basis weight of the printing unit 16 refers to the mass of the printing unit 16 with respect to the entire area of the first surface material 12 including the area of the surface material where the printing unit 16 is not formed.

(Characteristics of phenolic resin foam board)
0.0200 W / mK or less is preferable, as for the initial stage thermal conductivity of the phenol resin foam board 1, 0.0190 W / m * K or less is more preferable, and 0.0185 W / m * K or less is especially preferable. If the initial thermal conductivity is equal to or less than the above upper limit value, the heat insulation of the phenolic resin foam board 1 can be further improved.
The initial thermal conductivity is a value at 23 ° C., and is measured in accordance with JIS A 1412-2: 1999.
The initial thermal conductivity of the phenolic foam plate 1 is adjusted by the thermal conductivity of the foam layer 10. The thermal conductivity of the foam layer 10 is adjusted by the combination of the average cell diameter, the type or composition of the foaming agent, the type of surfactant, and the like. For example, the thermal conductivity of the foam layer 10 tends to be lower as the average cell diameter is smaller. When the surfactant is a silicone surfactant, particularly one having a polyether chain whose end is -OH, the thermal conductivity tends to be low as compared with the case where other surfactants are used.

0.0210 W / m · K or less is preferable, the long-term thermal conductivity of the phenolic resin foam board 1 is more preferably 0.0200 W / m · K or less, and particularly preferably 0.0190 W / m · K or less.
The long-term thermal conductivity is an estimated value after 25 years of thermal conductivity measured after leaving a phenolic resin foam board sample of 300 mm square in the vertical direction at 70 ° C. for 25 weeks, and conforms to ISO 11561 Annex B Measured.

28 volume% or more is preferable, as for LOI of the phenol resin foam board 1, 30 volume% or more is more preferable, and 32 volume% or more is more preferable. If LOI is more than the said lower limit, the further improvement of the flame retardance of the phenol resin foam board 1 can be aimed at.
The LOI of the phenolic resin foam board 1 is adjusted by the LOI of the foam layer 10, the content of the phosphorus-based flame retardant in the facing material, and the like. For example, the LOI can be increased by increasing the content of the phosphorus-based flame retardant in the facing material.

3.5 g / 100 cm ² or less is preferable, 3.0 g / 100 cm ² or less is more preferable, 2.5 g / 100 cm ² or less is more preferable, and 2.0 g / 100 cm ² or less of the water absorption amount of the phenol resin foam board 1 is preferable. Most preferred. The lower limit is not particularly limited. As the amount of water absorption is smaller, the hygroscopicity of the phenolic resin foam board 1 is lowered, and the corrosion of the phenolic resin foam board 1, the corrosion of the material in contact with the phenolic resin foam board 1, the generation of mold and the like can be prevented.

(Manufacturing method of phenol resin foam board)
The phenol resin foam board 1 of this embodiment is manufactured according to the manufacturing method of the conventionally well-known 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, the method for producing phenolic resin foam is described as an example using a production system including a discharge device, a foam molding device located downstream of the discharge device, and a printing device located downstream of the foam molding device. Do.

The manufacturing system 40 illustrated in FIG. 2 includes a discharge device 60, a foam molding device 70, a printing device 90, and a cutting device 80. The foam molding device 70 is located downstream of the discharge device 60, the printing device 90 is located downstream of the foam molding device 70, and the cutting device 80 is located downstream of the printing device 90.
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 the direction orthogonal to the flow direction of the foamable resin composition. The mixing unit 62 and the two or more nozzles 64 are connected via a distribution pipe 66.
As the discharge device 60, one in which a distribution pipe having a plurality of branch parts (for example, WO2014 / 133023) is disposed in the TD direction can be mentioned.

The foam molding apparatus 70 includes a frame portion 71 and heating means (not shown).
The frame portion 71 is a conveyor (lower conveyor 72, upper conveyor 74, left conveyor (not shown), right conveyor (the lower conveyor 72, upper conveyor 74, and the like) which are arranged vertically and horizontally so as to form a space corresponding to the cross sectional shape of the phenolic resin foam board 1. Not shown)).
The lower conveyor 72 is a conveyor having an endless belt traveling in the MD1 direction. The upper conveyor 74 is a conveyor having an endless belt traveling in the MD2 direction.
As a heating means, for example, 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, etc. may be mentioned.
In addition, the foam molding apparatus 70 does not need to be equipped with the left side conveyor and the right side conveyor. The foam molding apparatus 70 may be an apparatus having a slat conveyor as described in JP-A-2000-218635, instead of the conveyor having an endless belt. On the surface of the phenolic resin foam plate 1 manufactured using the slat conveyor, marks of joints between the slats called slat marks in the direction parallel to the TD direction are formed across the width direction of the phenolic resin foam plate.

  The printing apparatus 90 includes, for example, a letterpress printing apparatus, a gravure printing apparatus, a gravure offset printing apparatus, a lithographic printing apparatus, a reverse printing apparatus, a screen printing apparatus, an ink jet apparatus, etc., among which a letterpress printing apparatus, a gravure printing apparatus, a gravure printing apparatus Offset printing devices are preferred.

Next, an example of the manufacturing method of the phenol resin foam board 1 using this manufacturing system 40 is demonstrated.
First, a phenolic resin and a foaming agent, and optionally, optional components (acid catalyst, surfactant, additives, etc.) are introduced into the mixing section 62 and mixed to prepare a foamable resin composition.
Next, the second facing 14 is drawn onto the lower conveyor 72. The foamable resin composition is supplied from the mixing unit 62 to the nozzle 64 through the distribution pipe 66 and discharged from the nozzle 64 onto the second surface material 14.

Usually, the facing is drawn out from a state of being wound in a roll shape with respect to a cylindrical core called a winding core and provided for manufacturing. The face material is wound around the core under winding tension. Therefore, if the drawing tension applied to the surface material is too large when drawing the surface material from the roll, winding and tightening of the roll may damage the emboss pattern or uneven pattern of the surface material, or the thermocompression bonding fixed part and the fibers may peel The fibers may be torn off to increase brushing, making it difficult to print. Moreover, in the face material in which the printing part was previously formed, there exists a possibility that a printing part may peel. If the draw-out tension is too small, in the case of a slat type double conveyor, the face material may be caught between the slats and wrinkled, or the face material may meander and have a crease.
Therefore, the drawing tension of the surface material is preferably 0.3 N / m to 50 N / m, more preferably 0.5 N / m to 30 N / m, and further preferably 0.5 N / m to 20 N / m. Is more preferred.
The drawing tension of the surface material can be adjusted by moving the position of the tension adjustment roller when drawing the surface material from the roll through the tension adjustment roller. Alternatively, the tension adjustment roller may be provided with a motor or a powder type clutch or the like, and the rotation of the roller may be controlled by the tension controller to adjust the draw-out tension to a desired value. The draw-out tension can be measured by converting the torque itself generated at the time of adjustment of the draw-out tension or a voltage necessary for controlling the motor or the clutch into a torque.

  Next, the first face material 12 is drawn out, and the first face material 12 is placed on the foamable resin composition discharged onto the second face material 14. Thus, the foamable resin composition is filled between the two facing materials facing each other. The foamable resin composition sandwiched between the two facings is introduced into the frame portion 71 and heated at an arbitrary temperature. 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 10 minutes or less. As a result, the foamable resin composition foams between the first facing 12 and the second facing 14 and hardens to form the foam layer 10, and the foam layer 10 and the first facing 12 The phenol resin foam board 1 provided with the 2nd face material 14 is obtained (foaming hardening process).

This phenolic resin foam board 1 is derived | led-out from the foam molding apparatus 70, and printing parts, such as printing and a logo, are formed on the 1st surface material 12 with the printing apparatus 90 (printing process).
Thereafter, the printed phenolic resin foam board 1 is cut into an arbitrary length by a cutting device 80, and a post curing / drying step (curing step) is performed in a hot air curing furnace (curing chamber). The structure of the hot air curing furnace is not particularly limited, and may be a single structure or a composite structure. Also, a hot air curing furnace may be used as the curing furnace. In this case, the speed of the hot air is not particularly limited, but is preferably 0.5 m / min to 500 m / min, more preferably 1 m / min to 300 m / min, and still more preferably 10 m / min to 200 m / min. If the air velocity is less than 0.5 m / min, it takes too long for the post-curing treatment, and the productivity is poor, and it is difficult to obtain the phenolic resin foam board 1 having predetermined physical properties. On the other hand, if it exceeds 500 m / min, the drying progresses too much, and the moisture content becomes too low, so that chips are easily generated when the phenolic resin foam board 1 is cut.
In particular, when the density of the thermocompression-bonding fixed part of the first surface material 12 and the second surface material 14 is 5 pieces / cm ² or more and 100 pieces / cm ² or less, the wind speed of hot air is 1 m / min or more and 150 m / min or less preferable. When the thermocompression bonding fixed part density is 100 pcs / cm ² or more and 150 pcs / cm ² or less, the wind speed of the hot air is preferably more than 150 m / min and 300 m / min or less. In the case where the thermocompression bonding fixed part density is low, the drying progresses too much if the wind speed of the hot air exceeds 150 m / min. On the other hand, when the thermocompression bonding fixed part density is high, if the wind speed of the hot air is 150 m / min or less, the drying does not proceed and the curing time becomes long.

  In the manufacturing method of the present embodiment, the foamable resin composition discharged onto the second face material 14 foams to a certain extent before being introduced into the foam molding apparatus. When the foamable resin composition is discharged onto the second surface member 14, it is preferable to spread in the width direction of the phenol resin foam plate (direction orthogonal to the discharge direction of the foamable resin composition: TD direction) . Thereafter, in the foamable resin composition discharged onto the second surface member 14, the bubbles which are being cured by heating and the acid catalyst are broken by the movement of the foamable resin composition, and the closed cell rate is lowered. is there. By spreading the foamable resin composition in the TD direction, the amount of movement of the foamable resin composition in the TD direction in the foam molding apparatus 70 can be reduced, and a decrease in the closed cell rate can be suppressed. In particular, since the surface layer side of the foamable resin composition is pushed and spread by the upper and lower conveyors, the open cell ratio of the first surface layer portion and the second surface layer portion can be improved by spreading the resin composition in the TD direction. .

In the phenolic resin foam board 1 manufactured by the above manufacturing method, the first surface material 12 and the foam layer 10 are thermally cured on the surface of the first surface material 12 of the foamable resin composition without the adhesive layer. It is pasted together by the adhesion power at the time of doing. Similarly, the second face material 14 and the foam layer 10 are bonded by the adhesive force when the foamable resin composition is thermally cured on the surface of the second face material 14 without the adhesive layer. .
Generally, in the foam layer 10, a weld line extending in the MD direction and extending in the thickness direction is formed. The weld line is a boundary where the foamable resin compositions discharged from the plurality of nozzles join together, and has a higher density than the other parts of the foam layer 10 and a higher density. Transparency is low compared to the other parts (the color tone is dark).

  Although the manufacturing system 40 of the present embodiment includes the printing device, the present invention is not limited thereto, and the manufacturing system 40 may not include the printing device 90. In this case, it is possible to manufacture a phenolic resin foam board in the same manner as the present embodiment except that the first surface material 12 or the second surface material 14 in which the printing portion is formed in advance is used.

In a general method of manufacturing a foamed foam of phenol resin, a discharge device is used which includes a distribution pipe having a plurality of branch portions and in which a plurality of nozzles are arranged in the TD direction. According to this discharge device, the foamable resin composition discharged from the nozzle can be spread in the TD direction. However, since it is difficult to discharge uniformly from all the nozzles in a distribution pipe having a plurality of branch parts, it is necessary to use a special distribution pipe. In addition, a foamable resin composition having a high viscosity is likely to be clogged at a branch portion.
In addition, a method using a slit die having a discharge part long in the TD direction is known (WO2009 / 066621). In this method, the foamable resin composition does not flow at a uniform speed in the die, and a difference occurs in the flow velocity and the discharge amount between the slow and fast flow portions, and the properties (viscosity etc.) of the resin after discharge It is different. As described above, if the flow velocity and the discharge amount in the TD direction are not uniform, the foamable resin composition moves in the TD direction in the foam molding apparatus 70, and the closed cell rate on the surface layer side decreases.

Therefore, in the present invention, the slit die 100 of FIG. 3 can be used in place of the nozzle 64.
FIG. 3A is a plan perspective view of the slit die 100, and FIG. 3B is a front view of the discharge port of the slit die 100.
The slit die 100 is a quadrangle in plan view, in which a flow path in the X direction (MD direction) is formed, and a discharge port 110 whose longitudinal direction is the Y direction (TD direction) is formed.
The discharge port 110 is formed with a main discharge port 112 having a square shape in a front view whose longitudinal direction is the Y direction, and sub-discharge ports 114 which extend the main discharge port 112 on both sides of the main discharge port 112. The auxiliary discharge port 114 is substantially circular in a front view, and is formed wider than the main discharge port 112.
As shown in FIG. 5, in a general slit die (die having a square square shaped discharge port in front view) 120, the foamable resin composition is more likely to be cooled and the viscosity is likely to increase compared to the center in the TD direction near both ends. . For this reason, when the foamable resin composition is discharged in the Z direction, the flow velocity and the discharge amount of the foamable resin composition 122 are smaller at the both ends of the slit die 120 than in the center, and the discharge port is formed in the subsequent foam curing step. The foamable resin composition 122 at the center of the above tends to flow in the TD direction, and the closed cell rate of the surface layer portion tends to decrease.
In the slit die 100 of the present embodiment, since the sub-discharge port 114 is formed wide, the temperature of the foamable resin composition on both sides in the TD direction is unlikely to be cooled. For this reason, as shown in FIG. 4, when the foamable resin composition is discharged in the Z direction by the slit die 100, the difference in the viscosity of the foamable resin composition at the center and at both ends is reduced. And as for the foamable resin composition 102 discharged, the quantity of TD direction becomes uniform, and the closed cell rate in a surface layer part is raised more.

The size of the discharge port 110 is appropriately determined according to the size of the desired phenolic resin foam plate.
For example, in the case of obtaining a phenolic resin foam plate having a width of 910 mm, the length L1 of the discharge port 110 is preferably 930 mm or more and less than 1200 mm. In addition, in the case of obtaining a phenolic resin foam plate having a width of 910 mm, the length L2 of the main discharge port 112 is preferably 910 mm or more.
For example, in the case of obtaining a phenolic resin foam plate having a thickness of 10 mm or more and 200 mm or less, the width W1 of the main discharge port 112 is preferably 5 mm or more and 30 mm or less. In this case, the width W2 of the auxiliary discharge port 114 is preferably the width W1 + 5 mm or more and 20 mm or less.

Also, for example, instead of the nozzle 64, a slit die 200 shown in FIG. 6 may be used. 6 (a) is a plan perspective view of the slit die 200, and FIG. 6 (b) is a front view of the discharge port of the slit die 200.
The slit die 200 is formed with the discharge port 210 whose longitudinal direction is the Y direction in a front view. The discharge port 210 is wider in width from the center toward both ends in the TD direction.
By using the slit die 200, as in the slit die 100, the closed cell rate of the surface layer portion of the foam layer can be further enhanced.
That is, in the present invention, the first surface layer is provided by using a slit die having a discharge port whose longitudinal direction is in the TD direction in the front view and the width of both ends of the discharge port in the TD direction is larger than the width of the center. It is easy to increase the closed cell rate of the portion 10a or the second surface portion 10b.

In the present invention, since the closed cell rate of the surface layer portion of the foam layer 10 is high, the substitution of the blowing agent gas in the foam layer 10 is possible even if a high air permeability of the flange and high water permeability is used as the facing material. It is hard to happen. In addition, it is possible to keep the thermal conductivity low over a long period of time because the foam layer 10 hardly absorbs moisture that has permeated through the facing material.
In addition, when printing is performed on the first facing material 12 laminated on the foam layer 10, the closed cell rate of the first surface layer portion 10a adjacent to the first facing material 12 is high, so that completely before curing. Even in the foamed layer 10 before curing, the pressure of the printing roll does not cause the first surface layer portion 10a to be recessed.

  In the phenolic resin foam board 1 manufactured by the slit die 100 or the slit die 200, a weld line is not formed. For this reason, the phenol resin foam board 1 manufactured by the slit die 100 or the slit die 200 is preferable in terms of product appearance.

  As described above, in the phenolic resin foam board of the present embodiment, since the specific face material is adjacent to the surface layer portion of the specific closed cell ratio and the printing area ratio is within the specific range, the printing area becomes beautiful and long-term Low thermal conductivity can be maintained over the

The phenol resin foam board of this invention is suitable as a heat insulation material of a house wall, a floor, and a roof.
Therefore, other layers, such as an interior base material and a structural material, may be provided on the first face material and / or the second face material. It is preferable that the said other layer is located on the face material in which the printing part is not formed. As said other layer, interior base materials, such as a gypsum board (thickness 9.5 mm or 12.5 mm), floor plywood (thickness 12 mm-24 mm), a calcium-silicate board, a wood cement board, a structural panel, a particle A board, a sheathing board, a medium density fiber board (MDF), a hard board, a laminated fiber board, a wood-based board such as structural plywood, a rock wool sound absorbing board, etc. may be mentioned. These are previously bonded to the first or second face material via the adhesive layer. The adhesive layer may be provided on the entire surface of the phenolic resin foam board, or may be partially provided.

  In the phenol resin foam board of the present invention, since the density of the thermocompression-bonding fixed part of the first or second face material is within a specific range, the adhesive constituting the adhesive layer can easily penetrate the face material. Furthermore, when the first or second facing material has a specific raising degree, the raising of the facing material is entangled with the adhesive layer applied to the surface of the other layer to exert an anchor effect. For this reason, the other layer and the phenolic resin are combined by combining the other layer and the first or second face material firmly through the adhesive layer and bonding the face material and the foam layer firmly joined together. It is hard to separate from the foam layer of the foam board during transportation or construction.

  EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

(Raw material used)
<Bubbling agent>
The composition of the blowing agent used was as follows.
Blowing agent A: cyclopentane (CP).
Foaming agent B: isopentane (IP): a mixture of trans-1-chloro-3,3,3-trifluoropropene (HCFO 1233 zdE) = 50: 50 (mass ratio).
· Foaming agent C: A mixture of HCFO 1233 zd: isopropyl chloride (IPC) = 20: 80 (mass ratio).
· Mixture of blowing agent D: CP: HCFO-1233zdE = 50: 50 (mass ratio).
· Mixture of blowing agent E: CP: HCFO-1233zdE = 20: 80 (mass ratio).
Foaming agent F: IP.
· Foaming agent G: Mixture of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO 1336 mzz Z) = 50: 50 (mass ratio).
Foaming agent H: CP: HCFO-1233zdE: Mixture of cis-1-chloro-3,3,3-trifluoropropene (HCFO1233zdZ) = 40: 50: 10 (mass ratio).

(Evaluation method)
<Measurement of closed cell rate>
-Examples 1-1 to 1-6, comparative examples 1-1 to 1-5
From the center part of the phenol resin foam board, three test specimens were prepared by cutting with a cutter knife into a width of 30 mm × length 30 mm × thickness 45 mm. First, about the 1st test piece, it cut out with a cutter knife from the one surface (upper surface side) which peeled the face material to the place of 20 mm in the thickness direction, and made this the test piece of the 1st surface layer part. Next, a second test piece was cut out with a cutter knife from the other surface (lower surface side) from which the face material was peeled off to a point of 20 mm in the thickness direction, and this was used as a test piece of the second surface layer. Furthermore, for the third test piece, a portion from 12.5 to 32.5 mm from one side of the test piece cut into width 30 mm × length 30 mm × thickness 45 mm is cut with a cutter knife, It was a test piece.
-Examples 2-1 to 2-7, comparative examples 2-1 to 2-3
From the center part of the phenol resin foam board, three test pieces which were cut out with a cutter knife in width 30 mm × length 30 mm × thickness 60 mm were prepared.
First, for the first test piece, a portion from the one surface (upper surface side) from which the face material was peeled off to a position of 20 mm in the thickness direction was cut with a cutter knife to obtain a test piece of the first surface layer.
Next, a second test piece was cut out with a cutter knife from the other surface (lower surface side) from which the face material was peeled off to the position of 20 mm in the thickness direction to obtain a test piece of the second surface layer.
Furthermore, for the third test piece, the test piece cut into a width of 30 mm × length 30 mm × thickness 60 mm from the one surface to a portion of 20 to 40 mm was cut with a cutter knife to obtain a test piece of the central layer portion .

Since the air bubbles on the surface of the test piece are broken by cutting out the test piece with a cutter knife, and it is not possible to accurately measure the closed cell rate, in order to remove the test piece surface where the air bubbles are broken, The surface (6 faces) of each test piece was thinly cut with a razor.
At this time, it is preferable to cut with a razor as thin as possible, and the width 25 mm ± 1 mm, the length 25 mm ± 1 mm, and the thickness 19 mm ± 1 mm. The independent cell rate of each test piece of which the surface was cut with a razor was measured and calculated as follows according to JIS K 7138: 2006, measurement method 1.
Closed cell rate = (volume measurement result with dry density meter) / (volume measurement result with wet density meter) × 100

«Dry density meter»
Product name: Tokyo Science Co., Ltd. Air comparison type hydrometer 1000 type.
Model number: 1000.
«Wet density meter»
Product name: Shimadzu LIBROR EB-330H.
Model number: 63572.

<Measuring method of napping degree>
The napping degree is measured on a surface of the first face material 12 which is not in contact with the foam layer 10 and where the printed portion is not formed.
First, the first face material 12 was peeled off from the phenolic resin foam plate 1 having a length of 200 mm × 200 mm, to obtain a measurement piece of 200 mm × 200 mm. In addition, the part in which the printing part is formed may be included in this measurement piece. As shown in FIG. 7A, the measurement sample 204 was formed by mountain-folding at a fold line B extending in the direction passing through the plurality of heat-sealed portions on the surface of the measurement piece raised. At this time, a portion where the printed portion is not formed is included in the mountain-folded portion by 1 cm or more. Next, this measurement sample 204 was placed on an A4 size black backing sheet 211a. As shown in FIG. 7B, an A4-sized black backing sheet 211b having a hole 207 of 1 cm long × 1 cm wide was placed on the measurement sample 204. At this time, as shown in FIG. 7B, the black mount 211b is disposed so that the portion of the measurement sample 204 where the printing portion is not formed can be seen through the hole 207 of the upper black mount 211b. . For both mounts, “Kenran (black) continuous weight 265 g” of Fuji Kyowa Paper Co., Ltd. was used.
After that, a weight of 50 g was placed on each side of the hole 207 of the upper mount 211 b at a position 5 cm outward along the fold line 205, and the measurement sample 204 was folded. Next, as shown in FIG. 7C, the inside of the hole 207 of the black backing sheet 211b is observed at a magnification of 30 times using a microscope (VHX-900 manufactured by KEYENCE Corporation), and printing of the measurement sample 204 is performed. Measure the number of fibers protruding upward from the imaginary line 208 formed at a position translated 0.2 mm upward from the fold line 205 of the portion where the part is not formed, and count the number of raised fibers per 1 cm And It measured nine places and made the amount of the fiber which is raising the average value (rounded off the 2nd decimal place) the raising degree.

  In addition, when counting the number of fibers raised, for example, as in the case of the fiber 206 shown in FIG. 7C, there is a fiber crossing the imaginary line 208 0.2 mm above the crease 205 twice , The fiber counts with two. Specifically, in the example shown in FIG. 7C, there are four fibers that cross the virtual line 208 once, and one fiber 206 that crosses the virtual line 208 twice. Counting as a book, the amount of raised fibers is 6 / cm.

<Measurement of water absorption>
The amount of water absorption was measured according to JIS A 9511.

<Measurement of long-term thermal conductivity>
In accordance with ISO 11561 Annex B, the thermal conductivity after leaving the sample of the phenolic resin foam board of 300 mm by 300 mm for 25 weeks for 25 weeks after the maximum temperature which can be generated in the building is 70 ° C. Measured as an estimated value.

<Face material peel strength>
The surface material peel strength of the phenolic resin foam board was measured and determined as follows.
First, a phenol resin foam board is cut into a width of 50 mm and a length of 120 mm (the length direction coincides with the product flow direction), and one of the surface materials (a) and (b) located on the upper and lower surfaces The material (b) was peeled off. Thereafter, the laminated sheet after peeling of the face material (b) was cut in a direction parallel to the upper and lower surfaces to prepare a sample for evaluation including the face material (a) and having a width of 50 mm, a length of 120 mm, and a thickness of 25 mm.
Next, using a cutter, a cut having a depth of 20 mm was made in the thickness direction from the surface not having the surface material (a) at a position of 20 mm from one end of the evaluation sample in the longitudinal direction. At the cut position, the base material 2 of the evaluation sample was carefully divided in the thickness direction. At this time, the force in the lengthwise direction was not applied so as to prevent the face material (a) from peeling off from the base material.
Then, the portion of the sample for evaluation in which the base material is divided is held by the clamp 7 so as to form an angle of 45 ° with the horizontal plane by the clamp 7, and the length of the base material is short. The container 6 connected with the metal wire 5 was set via the clamp 4 at the end of the side part.
Thereafter, water was continuously introduced into the empty container 6 at an injection rate of 100 g / min using a pump. The mass of water in the container was measured when the face material peeled 50 mm from the cut position in the longitudinal direction of the evaluation sample. The same operation was performed twice, and the average value of the sum of the mass of the clamp, the metal wire, the container, and the obtained water was taken as the surface material peel strength (a).
Separately, a sample for evaluation having a surface material (b), width 50 mm, length 120 mm, thickness 25 mm was prepared, and the surface material peel strength (b) was determined in the same manner as the surface material peel strength (a). The lower value of the face material peel strength (a) and the face material peel strength (b) was taken as the face material peel strength (unit: g) of the phenolic resin foam plate.

<Continuous productivity>
In the process of producing the phenolic resin foam board, the stains and printing defects due to the exudation of the phenolic resin, the breakage of the facing material, etc. are visually confirmed, and the following is the elapsed time from the start of production to the judgment that production continuation is difficult Evaluated.
Less than 0.5 hours: No.
0.5 hours or more and less than 1 hour: defective.
1 hour or more: good.

<Appearance evaluation>
The surface material was visually observed, and it was judged as "good" that there were no wrinkles, dents, bleeding of resin in the surface material itself, blur of the printed part, color loss and the like. When abnormalities such as wrinkles and dents in the face material itself, dents, resin exudation, blur of the printed part and color loss were observed, the state is described in the table.

(Examples 1-1 to 1-6, comparative examples 1-1 to 1-5)
100 parts by mass of liquid resol type phenol resin (Asahi Organic Material Industry Co., Ltd., trade name: PF-339), 4 parts by mass of surfactant (castor oil EO adduct (additional number of moles 30)), formaldehyde catcher agent ( After mixing with 4 parts by mass of urea), the mixture was allowed to stand at 20 ° C. for 8 hours.
According to Table 2, 108 parts by mass of the obtained mixture, 15 parts by mass of a foaming agent, and 17 parts by mass of an acid catalyst (a mixture of para-toluenesulfonic acid and xylene sulfonic acid) were mixed to prepare a foamable resin composition .
The phenolic resin foam board of each example was obtained using the manufacturing system similar to the manufacturing system 40 shown in FIG. This manufacturing system comprises a slat type double conveyor. A manufacturing system provided with a slit die A similar to the slit die 100 of FIG. 3 was used to manufacture the phenolic resin foam board of each example. The slit die had a discharge portion length L1 of 1000 mm, a main discharge portion length L2 of 910 mm, a discharge portion width W1 of 30 mm, and a main discharge portion width W2 of 20 mm.
The second face material (width in the direction of TD: 1150 mm, with a surface material described in Table 2, no printed part, see Table 1). The foamable resin composition was discharged onto the above. The first surface material (width in the TD direction: 1150 mm, surface material described in Table 2, printing, drawn out from the roll and continuously run on the foamed resin composition discharged onto the second surface material There is a portion, and the material of the facing is see Table 1), which is heated at 70 ° C. for 300 seconds for foam molding to obtain a foamed foam of phenol resin having a thickness of 45 mm (foaming and curing step). At this time, as the first face material, one on which a printing portion (weight of ink: 0.7 g / m ² ) was formed in advance was used. The printed portion of the first face material was a printed portion formed of the design area ratio of Table 2 consisting of symbols and characters.
The phenolic resin foam board thus obtained was cut into a width 910 mm and a length 1820 mm. Subsequently, the cut phenolic resin foam board was heated for a time described in Table 2 in a curing cabinet with an atmosphere temperature of 95 ° C. and a wind speed of 100 m / min to obtain a phenol foam board of each example.
The closed cell rate, the amount of water absorption, the long-term thermal conductivity and the appearance were evaluated for the phenolic resin foam board of each example, and the results are shown in the table.
In Table 1, PET represents polyethylene terephthalate, and PP represents polypropylene.

(Examples 2-1 to 2-6)
As the first facing material, using the facing material on which the printed portion is not formed, 3 parts by mass of a plasticizer (di-n-octyl phthalate) is added to the foamable resin composition, and the thickness of the foam layer is The foaming and curing step was performed in the same manner as in Example 1 except that the size was made to be 60 mm and the production conditions in Table 3 were used, to obtain a phenolic resin foam board. After that, the first surface material (without a printing portion) of the obtained phenolic resin foam board was formed of a pattern and characters using a printing apparatus to form a printing portion having a printing area ratio described in Table 3 .
In the printing unit, a plate-like relief plate made of resin and having a convex portion formed of a predetermined pattern and characters formed on the surface is wound around a cylindrical plate cylinder, and the relief plate is made of Example 1 of JP2009-149859A. The ink is transferred to the plate-like relief plate using the anilox roll in which the concave portion is formed from the ink pan in which the curable flexographic ink described in claim 1 is stored, and then the ink is used for the second surface of the phenol resin foam plate obtained from the relief plate The printing part was formed by transferring to a material. The concave portions of the anilox roll were adjusted so that the basis weight of the ink transferred onto the face material was 0.8 g / m ² .
The phenolic resin foam board thus obtained was cut into a width of 910 mm and a length of 1820 mm. Next, the cut phenolic resin foam board was heated for 2 hours in a aging chamber at an atmosphere temperature of 100 ° C. and a wind speed of 50 m / min to obtain a phenol foam board of each example.
The closed cell rate, the amount of water absorption, the long-term thermal conductivity and the appearance were evaluated for the phenolic resin foam board of each example, and the results are shown in the table.

(Example 2-7)
A phenolic resin foam board was produced in the same manner as in Example 2-2 except that the face material II was subjected to a raising process and the raising degree was 15 / cm and the foaming agent B was a foaming agent H. This was evaluated.

(Comparative example 2-1)
A phenolic resin foam board was obtained and evaluated in the same manner as in Example 2-3 except that the facing material III was changed to the facing material VII.

(Comparative Example 2-2)
A phenolic resin foam board was obtained and evaluated in the same manner as in Example 2-1 except that 16 nozzles arranged in the TD direction were used instead of the slit die A.

(Comparative example 2-3)
Instead of the slit die A, a slit die (slit die B) provided with a rectangular discharge part having a discharge length L1 and a length L2 both being 1000 mm and a width W1 and a width W2 both being 25 mm A phenolic resin foam board was obtained and evaluated in the same manner as in Example 2-1 except for the above.

As shown in Table 2, in Examples 1-1 to 1-6 to which the present invention was applied, the appearance evaluation was good. In addition, Examples 1-1 to 1-6 had low water absorption and low long-term thermal conductivity.
On the other hand, in Comparative Example 1-1, since the printing area ratio is high, the closed cell rate is low, the amount of water absorption is high, and the long-term thermal conductivity is high. In Comparative Example 1-2, since the curing temperature was too high, the closed cell rate was low, the amount of water absorption was high, and the long-term thermal conductivity was high. In Comparative Example 1-3, since the density of the thermocompression-bonding fixed part of the face material was low, the phenol resin oozed out during the production, and the continuous productivity was poor. In Comparative Example 1-4, the density of the thermocompression-bonding fixed part of the face material is high, the fine printed parts such as characters are difficult to identify, and the tear strength of the face material is low, so breakage of the face material occurs. Continuous productivity was bad. In Comparative Example 1-5, the draw tension was high, breakage of the facing occurred, and continuous production could not be performed.

As shown in Table 3, in Examples 2-1 to 2-6 to which the present invention was applied, the appearance evaluation was good. In addition, Examples 2-1 to 2-6 had low amounts of water absorption and low long-term thermal conductivity.
On the other hand, in Comparative Example 2-1, as in Comparative Example 1-3, in addition to the problem due to the exudation of the phenol resin, the raising degree is high relative to the printing area, and the printing portion is blurred and it is difficult to form an appropriate pattern. Met. In Comparative Examples 2-2 and 2-3, the closed cell ratio of the surface layer was low, and a dent was generated on the surface by printing.

  1 Phenolic resin foam board; 10 foam layer; 10a first surface layer portion; 10b second surface layer portion; 10c central layer portion; 12 first surface material; 14 second surface material;

Claims (5)

A foam layer of phenol resin, and facings provided on both sides of the foam layer,
A printed portion is formed on at least one of the facings,
The area of the printed portion is 5% or more and 70% or less with respect to the area of the printed surface material which is the face material on which the printed portion is formed,
When the foam layer is divided into three in the thickness direction, and the first surface layer, the central layer, and the second surface layer are sequentially arranged from one side, the first surface layer and the second surface layer Among the parts, the closed cell ratio of the surface layer adjacent to the printing surface material is 85% or more,
The printing surface material is a synthetic fiber non-woven fabric having a basis weight of 15 g / m ² or more and 100 g / m ² or less,
The phenolic resin foam board characterized by the thermocompression-bonding fixed part density of the said printing surface material being five pieces / cm < ² > or more and 150 pieces / cm < ² > or less. A foamable resin composition containing a phenol resin and a foaming agent is filled between the two facing sheets facing each other, and then the foamable resin composition is foamed and cured to form the foamed layer. Have a foaming and curing process
The manufacturing method of the phenol resin foam board of Claim 1 using the said face material in which the said printing part was previously formed at the said foaming hardening process. A foamable resin composition containing a phenolic resin and a foaming agent is filled between the two facing sheets facing each other, and then the foamable resin composition is foamed and cured to form the foamed layer Foam curing process,
The manufacturing method of the phenol resin foam board of Claim 1 which has a printing process which forms the said printing part in at least one of the said 2 surface materials after the said foaming hardening process. The basis weight is 15 g / m ² or more and 100 g / m ² or less,
The thermocompression bonding fixed part density is 5 pieces / cm ² or more and 150 pieces / cm ² or less,
A facing material for a phenolic resin foam board, which is a synthetic fiber non-woven fabric having a raising degree of 1 / cm to 35 / cm. A printing unit is formed on at least one side,
The area of the printed portion is 5% or more and 70% or less with respect to the area of the printed surface member which is the face member on which the printed portion is formed. Facing material.

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