JP6927737B2 - Laminated board and its manufacturing method - Google Patents

Description

The present invention relates to a laminated board and a method for manufacturing the same.

Laminated plates provided with phenol resin foam plates are excellent in flame retardancy, heat resistance, chemical resistance, corrosion resistance, etc., and are therefore used in various fields as heat insulating materials. For example, in the construction field, the laminated board is used as a synthetic resin building material, particularly as a wall board interior material.
In a laminated board provided with a phenol resin foam board, for example, a foamable phenol resin composition containing a phenol resin, a foaming agent, an acid catalyst (curing agent), a surfactant, etc. is discharged onto a face material, and the foaming phenol resin composition is foamed. Manufactured by curing.
As such a laminated board, for example, Patent Document 1 describes a laminated board in which a phenol resin foam board and a face material made of a synthetic fiber non-woven fabric are laminated.
Patent Documents 2 and 3 describe a laminated board in which a phenol resin foam board and a face material made of a glass fiber non-woven fabric are laminated.
Patent Document 4 describes a laminated board in which a phenol resin foam board and a face material made of kraft paper or glass fiber mixed paper are laminated.

However, the laminated board described in Patent Document 1 uses only isobutane as a foaming agent for the phenol resin foam board, and has insufficient heat insulating properties. Furthermore, the flame retardancy is also insufficient.
The laminated boards described in Patent Documents 2 to 4 use halogenated unsaturated hydrocarbons as a foaming agent, and are said to have excellent heat insulating properties. However, glass fiber non-woven fabric, kraft paper, and glass fiber mixed paper are used as the face material, and these face materials easily absorb water in the phenol resin, and the face material shrinks when the water-absorbed face material dries. Wrinkles may occur, and the beauty of the surface may be impaired.

Japanese Patent No. 3523196 Japanese Patent No. 5688487 Japanese Unexamined Patent Publication No. 2015-157937 Japanese Patent No. 5795450

The synthetic fiber non-woven fabric has excellent water vapor permeability, and by using the synthetic fiber non-woven fabric as the face material, it becomes easy to suppress the occurrence of wrinkles that occur when a glass fiber non-woven fabric or the like is used as the face material.
However, when a synthetic fiber non-woven fabric is used as the face material, when the foamable phenol resin composition is discharged to the face material and the foamed and cured material is used to produce a laminated board, the foamable phenol resin composition is used as the face material. There was a problem that it oozes into the surface of the laminated board and the beauty of the surface is impaired. In particular, when a halogenated unsaturated hydrocarbon is used as the foaming agent, the viscosity of the foamable phenol resin composition decreases due to the high compatibility between the halogenated unsaturated hydrocarbon and the phenol resin, and the foamable phenol resin The composition is more likely to seep out due to the surface of the laminate.
Further, in order to suppress the exudation of the foamable phenol resin composition onto the surface of the laminated board, it is conceivable to increase the basis weight of the face material. However, in this case, the adhesive strength between the face material and the phenol resin foamed plate becomes insufficient, the face material is peeled off from the end portion of the laminated plate, and the beauty of the surface of the laminated plate is liable to be impaired.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a laminated board having excellent heat insulating properties and excellent surface beauty.

The present invention has the following aspects.
[1] A phenol resin foam plate containing a foaming agent containing a halogenated unsaturated hydrocarbon and a face material provided on at least one surface of the phenol resin foam plate are provided.
The face material is a synthetic fiber non-woven fabric ^{having a texture of 20 g / m 2} or more and 150 g / m ² or less and a heat-bonded partial density of 30 to 250 pieces / cm ^{2 represented by the following formula.}
A convex portion is formed on the surface on which the face material is provided, and a convex portion is formed.
Laminated board having an oxygen limiting index of 28% or more.
Heat-bonded part density (pieces / cm ² ) = number of heat-bonded parts (pieces) / surface area of face material (cm ² )
[2] The process of pulling out the first face material from the face material roll and
A step of discharging a foamable phenol resin composition containing a phenol resin and a foaming agent onto the first face material, and a step of discharging the foamable phenol resin composition onto the first face material.
A second face material of the same material as the first face material is pulled out from the face material roll, stacked on the foamable phenol resin composition discharged on the first face material, suppressed by a slat type double conveyor, and foamed. It is provided with a step of foaming and curing the sex phenol resin composition.
The face material is a synthetic fiber non-woven fabric ^{having a texture of 20 g / m 2} or more and 150 g / m ² or less and a heat-bonded partial density of 30 to 250 pieces / cm ^{2 represented by the following formula.}
A method for manufacturing a laminated board, wherein the pull-out tension when pulling out the first face material and the second face material from the face material roll is 0.5 to 80 N / m, respectively.
Heat-bonded part density (pieces / cm ² ) = number of heat-bonded parts (pieces) / surface area of face material (cm ² )

The laminated board of the present invention is excellent in heat insulating property and also excellent in surface beauty.

The laminated board of the present invention includes a phenol resin foam board and a face material. The face material is provided on at least one surface of the phenol resin foam plate. This face material is bonded to the phenol resin foam plate by the adhesive force when the phenol resin foam is thermoset on the surface of the face material without using an adhesive layer.
The phenolic resin foam plate contains a halogenated unsaturated hydrocarbon. A plurality of bubbles are formed in the phenol resin foam plate, there are substantially no holes in the bubble wall, and at least a part of the plurality of bubbles becomes closed cells that do not communicate with each other. There is. The bubble wall is composed of a cured product of phenol resin.
Halogenated unsaturated hydrocarbons have been used as foaming agents and are held in closed cells in the gas state. In addition to the halogenated unsaturated hydrocarbon, a gas derived from a foaming agent other than the halogenated unsaturated hydrocarbon may be held in the closed cells.

<Phenol resin foam board>
The phenolic resin foam plate of the present invention contains a halogenated unsaturated hydrocarbon. The phenol resin foam plate is preferably formed by foaming and curing a foamable phenol resin composition containing, for example, a phenol resin, a foaming agent, an acid catalyst, and a surfactant.
If necessary, the effervescent phenol resin composition may further contain components other than the phenol resin, the effervescent agent, the acid catalyst and the surfactant, as long as the effects of the present invention are not impaired.

(Phenol resin)
As the phenol resin, a resol type resin is preferable.
The resole-type phenol resin is a phenol resin obtained by reacting a phenol compound and an aldehyde in the presence of an alkaline catalyst.
Examples of the phenol compound include phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcinol and modified products thereof.
Examples of the aldehyde include formaldehyde, paraformaldehyde, furfural, acetaldehyde and the like.
Examples of the alkaline catalyst include sodium hydroxide, potassium hydroxide, calcium hydroxide, aliphatic amines (trimethylamine, triethylamine, etc.) and the like. However, the phenol compound, the aldehyde, and the alkali catalyst are not limited to the above.
The ratio of the phenol compound to the aldehyde is not particularly limited. The molar ratio of phenolic compound: aldehyde is preferably 1: 1 to 1: 3, and more preferably 1: 1.3 to 1: 2.5.

(Foaming agent)
The foaming agent contains a halogenated unsaturated hydrocarbon.
Halogenated unsaturated hydrocarbons have a lower thermal conductivity than non-halogenated hydrocarbons such as isopentane. When the phenol resin foam plate contains a halogenated unsaturated hydrocarbon, the thermal conductivity of the foam plate is lowered and the heat insulating property is enhanced.
In addition, halogenated unsaturated hydrocarbons have a small ozone depletion potential (ODP) and global warming potential (GWP), and have a small impact on the environment. Further, since the halogenated unsaturated hydrocarbon is nonflammable, the flame retardancy of the phenol resin foam plate is enhanced.
Halogenated unsaturated hydrocarbons have high compatibility with phenol resins, and the use of a foaming agent containing halogenated unsaturated hydrocarbons tends to reduce the viscosity of the foamable phenol resin composition.

Halogenated unsaturated hydrocarbons have double bonds and halogen atoms in the molecule.
As the halogenated unsaturated hydrocarbon, a known foaming agent can be used, and typically has a boiling point of −28 to 80 ° C.
The thermal conductivity of the halogenated unsaturated hydrocarbon is preferably 0.013 W / m · K or less, more preferably 0.011 W / m · K or less.
The halogenated unsaturated hydrocarbon preferably has 2 to 6 carbon atoms, more preferably 2 to 5 carbon atoms.

Examples of halogenated unsaturated hydrocarbons include fluorinated unsaturated hydrocarbons, chlorinated unsaturated hydrocarbons, chlorinated fluorinated unsaturated hydrocarbons, brominated fluorinated unsaturated hydrocarbons, and iodide fluorinated unsaturated hydrocarbons. Can be mentioned. The halogenated unsaturated hydrocarbon may be one in which all of hydrogen is substituted with halogen, or one in which part of hydrogen is substituted with halogen.
As the halogenated unsaturated hydrocarbon, those having a fluorine atom such as a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon are preferable.
These halogenated unsaturated hydrocarbons may be used alone or in combination of two or more.

Examples of the fluorinated unsaturated hydrocarbon include hydrofluoroolefins having a fluorine and a double bond in the molecule (hereinafter, also referred to as “HFO”). Examples of the HFO include 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze) (E and Z isomers), 1,1. , 1,4,4,4-hexafluoro-2-butene (HFO-1336mzz) (E and Z isomers) (manufactured by SynQuest Laboratories, product number: 1300-3-Z6), etc. Examples are those disclosed in publications and the like.
These fluorinated unsaturated hydrocarbons may be used alone or in combination of two or more.

Chlorinated fluorinated unsaturated hydrocarbons include 1,2-dichloro-1,2-difluoroethane (E and Z isomers), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) (HCFO-1233zd). E and Z isomers) (manufactured 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) (manufactured by SynQuest Laboratories, product number: 1300-7-09), 3 -Chloro-1,2,3-trifluoropropene (HCFO-1233ye) (E and Z isomers), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc), 3,3-dichloro- 3-Fluoropropene, 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd) (E and Z isomers), 2-chloro-1,1,1,4,4,4-hexa Fluoro-2-butene (E and Z isomers), 2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene (E and Z isomers) and the like can be mentioned.
These chlorinated fluorinated unsaturated hydrocarbons may be used alone or in combination of two or more.

The foaming agent may further contain a foaming agent other than the halogenated unsaturated hydrocarbon.
Other foaming agents are not particularly limited, and are, for example, hydrocarbons; saturated hydrocarbons halogenated; sodium hydrogen carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, azodicarboxylic acid amide, azobisisobutyronitrile, azodicarboxylic. Chemical foaming agents such as barium acid, N, N'-dinitrosopentamethylenetetramine, p, p'-oxybisbenzenesulfonylhydrazide, trihydrazinotriazine; porous solid materials and the like. These foaming agents may be used alone or in combination of two or more.

As the hydrocarbon, a known foaming agent can be used, and a hydrocarbon having a boiling point of -20 to 50 ° C. is preferably used.
The hydrocarbon preferably has a cyclic molecular structure having 4 to 6 carbon atoms or a chain molecular structure having 4 to 6 carbon atoms, and examples thereof include isobutane, normal butane, cyclobutane, normal pentane, isopentane, cyclopentane, and neopentane. Can be mentioned. These hydrocarbons can ensure excellent heat insulating performance in a wide temperature range from a low temperature range (for example, a heat insulating material for a freezer at about -80 ° C) to a high temperature range (for example, a heat insulating material for a heating body at about 130 ° C). It is relatively inexpensive and economically advantageous.
These hydrocarbons may be used alone or in combination of two or more.

As the halogenated saturated hydrocarbon, a known foaming agent can be used, and examples thereof include chlorinated saturated hydrocarbons and fluorinated saturated hydrocarbons. The halogenated saturated hydrocarbon may be one in which all of hydrogen is substituted with halogen, or one in which part of hydrogen is substituted with halogen.
The chlorinated saturated hydrocarbon preferably has 2 to 5 carbon atoms, and examples thereof include dichloroethane, propyl chloride, 2-chloropropane (isopropyl chloride), butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. ..
Examples of the fluorinated saturated hydrocarbon include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1,1. 2,2-Tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-hepta Fluoropropane (HFC227ea), 1,1,1,3,3-pentafluopropane (HFC245fa), 1,1,1,3,3-pentafluobtan (HFC365mfc), and 1,1,1,2, Hydrofluorocarbons such as 2,3,4,5,5,5-decafluoropentane (HFC4310mee) can be mentioned.
Among the above, 2-chloropropane is preferable because it has a low ozone depletion potential and is excellent in environmental compatibility.

In the present invention, the foaming agent preferably further contains hydrocarbons and / or halogenated saturated hydrocarbons. That is, it is preferable that the phenol resin foam plate contains a halogenated unsaturated hydrocarbon and a hydrocarbon and / or a halogenated saturated hydrocarbon.

When the foaming agent contains a hydrocarbon, it is possible to prevent the viscosity of the effervescent phenol resin composition from becoming too low, and it becomes easy to suppress exudation to the surface.
When the foaming agent contains hydrocarbons, the mass ratio of halogenated unsaturated hydrocarbons to hydrocarbons is preferably halogenated unsaturated hydrocarbons: hydrocarbons = 1: 9 to 9: 1. It is more preferably ~ 7: 3, and even more preferably 4: 6 to 6: 4.
When the ratio of the halogenated unsaturated hydrocarbon is at least the above lower limit value, the heat insulating property of the phenol resin foam plate can be further enhanced. When the ratio of the halogenated unsaturated hydrocarbon is not more than the above upper limit value, the viscosity of the effervescent phenol resin composition does not become too low, and the ability to suppress exudation to the surface is likely to be enhanced. Further, the effervescent phenol resin composition has good foamability and can be sufficiently foamed even if the amount of the foaming agent is small.

When the foaming agent contains a halogenated saturated hydrocarbon, the mass ratio of the halogenated unsaturated hydrocarbon to the halogenated saturated hydrocarbon is as follows: halogenated unsaturated hydrocarbon: halogenated saturated hydrocarbon = 1: 9 to 9. It is preferably 1: 1, more preferably 3: 7 to 7: 3, and even more preferably 4: 6 to 6: 4.
The halogenated saturated hydrocarbon has high compatibility with the phenol resin composition, and the effervescent phenol resin composition containing the halogenated saturated hydrocarbon tends to have a lower viscosity. By adjusting, it is possible to suppress exudation to the surface.

The content of the foaming agent in the effervescent phenol resin composition is preferably 1 to 25 parts by mass, more preferably 3 to 15 parts by mass, and even more preferably 5 to 12 parts by mass per 100 parts by mass of the phenol resin. If it is less than the above lower limit, the degree of foaming of the foamable phenol resin composition may be insufficient, and the heat insulating property of the phenol resin foam plate may be lowered. If it exceeds the above upper limit, the degree of foaming of the foamable phenol resin composition may be too high, and the strength of the phenol resin foam plate may decrease.

The viscosity of the effervescent phenol resin composition obtained by mixing a phenol resin, a surfactant, and a foaming agent containing a halogenated unsaturated hydrocarbon at 10 ° C. is preferably 20000 mPa · s or more and 100,000 mPa · s or less. More preferably, it is 30,000 mPa · s or more and 80,000 mPa · s or less.
The viscosity referred to here is a measured value after stabilizing at 10 ° C. for 3 minutes using a rotational viscometer (manufactured by Toki Sangyo Co., Ltd., R-100 type, rotor part is 3 ° × R-14). Is. When the acid catalyst is added, the phenol resin starts to harden and the viscosity cannot be measured. Therefore, the effervescent phenol resin composition has the viscosity before the acid catalyst is mixed.

When the foaming agent is a mixture of two or more kinds of foaming agents, the composition (mass ratio) of the foaming agent contained in the foamable phenol resin composition is the composition of the foaming agent contained in the foam-cured phenol resin foam plate. The composition of two or more types of halogenated hydrocarbons contained in the phenol resin foaming plate can be confirmed, for example, by the following solvent extraction method.

Solvent extraction method:
Using a standard gas of halogenated unsaturated hydrocarbon in advance, the holding time under the following measurement conditions with a gas chromatograph-mass spectrometer (GC / MS) is determined. Next, 1.6 g of a sample of a phenol resin foam plate from which the upper and lower face materials have been peeled off is separated into a glass container for crushing, and 80 mL of tetrahydrofuran (THF) is added. After crushing the sample to the extent that it is immersed in a solvent, the sample is pulverized and extracted with a homogenizer for 1 minute and 30 seconds, the extract is filtered through a membrane filter having a pore size of 0.45 μm, and the filtrate is subjected to GC / MS. The type of halogenated unsaturated hydrocarbon is identified from the retention time and mass spectrum obtained in advance. In addition, other types of halogenated hydrocarbons are identified by retention time and mass spectrum. The detection sensitivity of the foaming agent component is measured with a 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 GC / MS: Shimadzu Corporation GCMS-QP2010 Plus
Column used: DB-5ms (Agilent Technologies) 60m, inner diameter 0.25mm, film thickness 1μm
Column temperature: 40 ° C (10 minutes) -10 ° C / min-200 ° C
Injection port temperature: 200 ° C
Interface temperature: 230 ° C
Carrier gas: He 1.0 mL / min Split ratio: 20: 1
Measuring method: Scanning method m / Z = 11-550

(Acid catalyst)
The acid catalyst is used to initiate the polymerization of the phenolic resin.
Examples of the acid catalyst include organic acids such as benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid and phenolsulfonic acid, and inorganic acids such as sulfuric acid and phosphoric acid. These acid catalysts may be used alone or in combination of two or more.

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

(Surfactant)
The surfactant is not particularly limited, and known surfactants and the like can be used. For example, castor oil alkylene oxide adduct, silicone-based surfactant, polyoxyethylene sorbitan fatty acid ester and the like can be mentioned. These surfactants may be used alone or in combination of two or more.
The surfactant preferably contains one or both of the castor oil alkylene oxide adduct and the silicone-based surfactant in that it easily forms bubbles having a small bubble diameter, has a lower thermal conductivity, and is flame-retardant. It is more preferable to include a silicone-based surfactant in that the amount can be increased.

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

The number of moles of alkylene oxide added in the castor oil alkylene oxide adduct is preferably more than 20 mol and less than 60 mol, more preferably 21 to 40 mol, with respect to 1 mol of castor oil. In such a castor oil alkylene oxide adduct, a polyoxyalkylene group (polyoxyethylene group, etc.) formed by a hydrophobic group mainly composed of a long-chain hydrocarbon group of castor oil and a predetermined addition molar alkylene oxide (EO, etc.) Hydrophilic groups mainly composed of the above are arranged in a well-balanced manner in the molecule, and good surface activity is exhibited. Therefore, the bubble diameter of the phenol resin foam plate becomes small. In addition, flexibility is imparted to the bubble wall of the phenolic resin foam plate, and the occurrence of cracks is prevented.

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

Examples of the copolymer of dimethylpolysiloxane and polyether include a dimethylpolysiloxane-polyoxyalkylene copolymer.
The number of carbon atoms of the oxyalkylene group in the polyoxyalkylene is preferably 2 or 3. The oxyalkylene group constituting the polyoxyalkylene may be one kind or two or more kinds.
Specific examples of the dimethylpolysiloxane-polyoxyalkylene copolymer include dimethylpolysiloxane-polyoxyethylene copolymer, dimethylpolysiloxane-polyoxypropylene copolymer, and dimethylpolysiloxane-polyoxyethylene-polyoxypropylene. Examples include polymers.

The copolymer of dimethylpolysiloxane and polyether is preferably one having a polyether chain having a terminal -OR (in the formula, R is a hydrogen atom or an alkyl group), and has a higher thermal conductivity. It is particularly preferable that R is a hydrogen atom in that it can be lowered.

The content of the surfactant in the foamable phenol resin composition is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass, per 100 parts by mass of the phenol resin. When the content of the surfactant is at least the above lower limit value, the bubble diameter tends to be uniform and fine. When it is not more than the above upper limit value, the water absorption of the phenol resin foam plate is lowered, and the manufacturing cost can be suppressed.

In the effervescent phenol resin composition, the mass ratio represented by (foaming agent): (surfactant) is preferably, for example, 1: 1 to 6: 1. When the mass ratio of the foaming agent and the surfactant is within the above range, the foaming agent can be uniformly dispersed in the phenol resin to form fine bubbles. If the ratio of the foaming agent is less than the above lower limit, the content of the foaming agent in the foaming phenol resin composition may be too small, and the foaming of the foaming phenol resin composition may be insufficient. If the ratio of the foaming agent exceeds the above upper limit, the amount of the surfactant may be too small and the dispersibility of the foaming agent in the foamable phenol resin composition may be lowered.

(Other ingredients)
As the effervescent phenol resin composition, those known as additives for the effervescent phenol resin composition can be used, for example, a foam nucleating agent, a glycol-based compound, urea, a filler (filler), a flame retardant (for example). Phosphoric flame retardants, etc.), cross-linking agents, organic solvents, amino group-containing organic compounds, colorants, etc. can be mentioned.

Examples of the effervescent nucleating agent include low boiling point substances such as nitrogen, helium, argon, carbon dioxide, and air. By using the foam nucleating agent, the bubbles in the phenol resin foam plate can be made more uniform and fine.
The content of the effervescent nucleating agent in the effervescent phenol resin composition is preferably 0.05 to 5 mol% with respect to the effervescent agent.
However, the effervescent nucleating agent is usually dispersed in the effervescent agent in advance and blended in the effervescent phenol resin composition. In order to disperse the foaming nucleating agent in the foaming agent, it is necessary to inject the foaming nucleating agent into the foaming agent under pressurized conditions, which complicates the manufacturing process. In the present invention, since uniform and fine bubbles can be formed without using a foaming nucleating agent, a phenol resin foaming plate can be easily manufactured without the need for equipment for dispersing the foaming nucleating agent in the foaming agent or complicated steps. can.

Glycol compounds are used as plasticizers. By using the glycol-based compound, the filler described later can be uniformly dispersed in the effervescent phenol resin composition.
As the glycol-based compound, alkylene glycol ether is preferable. Examples of the alkylene glycol ether include alkylene glycol alkyl ethers such as ethylene glycol methyl ether and propylene glycol methyl ether.

Urea is used as a formaldehyde catcher agent that traps formaldehyde when foam-molding an effervescent phenol resin composition to produce a foam plate.

As the filler, an inorganic filler is preferable because a phenol resin foam plate having low thermal conductivity and acidity and improved fire resistance can be obtained.
Examples of the inorganic filler include hydroxides and oxides of metals such as aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, titanium oxide and antimony oxide, and metal powders such as zinc; carbon dioxide. Metal carbonates such as calcium, magnesium carbonate, barium carbonate, zinc carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkaline earth metal hydrogen carbonates such as calcium hydrogen carbonate and magnesium hydrogen carbonate; sulfuric acid Examples thereof include calcium, barium sulfate, calcium silicate, mica, talc, bentonite, zeolite, silica gel and the like. However, when a strong acid is used as an acid catalyst, metal powder and carbonate must be added within a range that does not affect the adjustment of pot life. These inorganic fillers may be used alone or in combination of two or more.

The filler also functions as a protective agent for capturing hydrogen fluoride. It is known that the halogenated unsaturated hydrocarbon used as a foaming agent generates hydrogen fluoride by decomposition and contains hydrogen fluoride used as a raw material for its production as an impurity (Special Table 2014-). 511930). This hydrogen fluoride reacts with the siloxane bond constituting the hydrophobic portion of the silicone-based surfactant to reduce the surface-active action. Therefore, the filler may be added to the effervescent phenol resin composition as a protective agent.

(Characteristics of phenol resin foam plate)
The closed cell ratio of the phenolic resin foam plate of the present invention is usually 85% or more, more preferably 90% or more.
The closed cell ratio is measured according to JIS K 7138: 2006.

The average cell diameter of the phenolic resin foam plate of the present invention is preferably 150 μm or less, more preferably 40 to 120 μm, and even more preferably 50 to 100 μm. When the average bubble diameter is not more than the above upper limit value, convection and radiation in the bubbles are suppressed, the thermal conductivity of the phenol resin foam plate is low, and the heat insulating property is more excellent.

The average cell diameter of the phenol resin foam plate is the type and composition of the foaming agent, the ratio of phenol to formaldehyde when synthesizing the resol type phenol resin, and the amount of acid catalyst (curing rate, degree of cross-linking, extensional viscosity after cross-linking). , The type of surfactant, foaming conditions (heating temperature, heating time, etc.) can be adjusted.

The thermal conductivity of the phenolic resin foam plate of the present invention is preferably 0.020 W / m · K or less, more preferably 0.019 W / m · K or less. If the thermal conductivity is the above upper limit value, the heat insulating property is excellent.

The average cell diameter and closed cell ratio greatly contribute to the thermal conductivity of the phenol resin foam plate. The thermal conductivity can be adjusted by the type and composition of the foaming agent, the ratio of phenol to formaldehyde when synthesizing the resole-type phenol resin, the amount of acid catalyst, the type of surfactant, and the like. For example, as described above, the smaller the average cell diameter, the lower the thermal conductivity of the phenolic resin foam plate tends to be. Further, when the surfactant is a silicone-based surfactant, particularly one having a polyether chain having a −OH terminal, the thermal conductivity tends to be lower than when other surfactants are used.

The phenolic resin foam plate of the present invention preferably has a Limited Oxygen Index (hereinafter, also referred to as “LOI”) of 28% or more, more preferably 30% or more.
LOI is the minimum oxygen concentration% (volume fraction) of a mixed gas of 23 ° C ± 2 ° C oxygen and nitrogen required for the sample to maintain flame combustion under specified conditions, and is flammable. It is an index. The larger the LOI, the lower the flammability. Generally, if the LOI is 26% or more, it is judged to have flame retardancy.

The LOI of the phenol resin foam plate can be adjusted by the type and composition of the foaming agent, the type of the surfactant, the type and composition of the flame retardant, and the amount thereof. For example, the lower the content of the flammable foaming agent in the foaming agent (the higher the content of halogenated hydrocarbons), the higher the LOI. Further, if the surfactant is a silicone-based surfactant, particularly one having a polyether chain having a −OH terminal, the LOI tends to be higher than when other surfactants are used. Further, the LOI can be increased by adding a phosphorus-based flame retardant or the like.

The density of the phenolic resin foam plate of the present invention (JIS A 9511: 2009) is preferably at 10 kg / ^{m 3} or more, 20 and 100 kg / ^{m 3} and more preferably.
The brittleness of the phenolic resin foam plate of the present invention (JIS A 9511: 2006) is preferably 20% or less, more preferably 10 to 18%.

<Lumber>
Face materials are provided on one or both sides of the phenolic resin foam plate. When the face materials are provided on both sides, each face material may be the same or different.
A non-woven fabric is used as the face material. Examples of the non-woven fabric include needle punched non-woven fabric, spunlace non-woven fabric, thermal bonded non-woven fabric, chemical bonded non-woven fabric, etc. An easy-to-manage spunbonded non-woven fabric, which can control the texture and fluffing of the surface layer of the non-woven fabric by changing the fusion point pattern, can be mentioned. Examples of the constituent materials include synthetic resin fibers such as polypropylene fibers, polyethylene fibers, nylon fibers, polyester fibers, rayon fibers, acrylic fibers and aramid fibers, mineral fibers such as glass fibers, and natural fibers such as cotton and hemp. However, synthetic resin fibers are preferable from the viewpoints of dimensional stability, economy, and handleability during humidification and water absorption. By using a synthetic fiber non-woven fabric as the face material, the face material shrinks and wrinkles are generated due to the moisture in the foamable phenol resin composition and the water generated during the condensation of the phenol resin. Can be suppressed.

The face material preferably does not contain cellulose fibers. If the face material contains hygroscopic fibers such as cellulose fibers, the face material may shrink due to the moisture in the phenol resin and the condensed water during the curing reaction.
Further, when unevenness is formed on the surface of the foam in which the face material containing the cellulose fiber is laminated, the surface area of the face material is increased due to the formation of the unevenness. For this reason, the expansion and contraction of the face material due to the absorption and release of the surrounding moisture after manufacturing is larger than that in the case where the unevenness is not formed, and the difference in the moisture absorption of the face materials on both sides causes a difference in the expansion and contraction of the face material. , The foam warps. Therefore, it is more preferable that the face material does not contain cellulose fibers, especially when forming irregularities.

The basis weight of the face material is 20 g / m ² or more. The effervescent phenolic resin composition of the present invention has a low viscosity by containing a foaming agent containing a halogenated unsaturated hydrocarbon. When the viscosity of the composition is lowered, the composition easily seeps into the face material, and the composition easily seeps out to the surface of the laminated board. When the basis weight of the face material is 20 g / m ² or more, it is possible to suppress the composition from seeping out to the surface.
The basis weight of the face material ^{is preferably 50 g / m 2} or more, and more preferably 80 g / m ² or more.
In particular, when a halogenated unsaturated hydrocarbon and a halogenated saturated hydrocarbon such as 2-chloropropane are used in combination as a foaming agent, the viscosity of the effervescent phenol resin composition tends to be lower. When the texture of the face material is equal to or higher than the above lower limit, exudation to the surface of the laminated board is suppressed even when a halogenated unsaturated hydrocarbon and a halogenated saturated hydrocarbon are used in combination as a foaming agent. It will be easier.
Also, the basis weight of the surface material is at 150 g / ^{m 2} or less, 100 g / ^{m 2} or less. When the basis weight of the face material is not more than the above upper limit value, the adhesiveness between the face material and the phenol resin foam plate is enhanced, the face material can be suppressed from peeling from the surface of the laminated plate, and the beauty of the surface is enhanced.
Further, it is easy to follow the uneven shape provided on the transport surface of the slat type double conveyor, which will be described later, and the productivity of the phenol resin foam plate and the handleability of the face material are improved.

The face material and the phenol resin foam plate are bonded together by the adhesive force when the phenol resin foam is thermoset on the surface of the face material without going through an adhesive layer, and when the face material is peeled off, the cured phenol resin is surfaced. Since it adheres to the lumber, the texture of the face material peeled from the foam is larger than that of the face material itself.
And the basis weight of the peeled surface material from the foam, the difference between the basis weight of the surface material used is preferably 2 g / ^{m 2} or more 12 g / ^{m 2} or less, 4g / ^m, more preferably ² or more 10 g / ^{m 2} or less, 6 g / ^{m 2} or more 10 g / ^{m 2} or less is most preferred.
If the difference between the basis weight of the face material peeled from the foam and the basis weight of the face material used ^{is less than 2 g / m 2} , it means that the bonding between the fibers of the face material and the surface of the phenol resin foam plate is weak. The face material is easily peeled off. On the other hand, if the difference between the basis weight of the face material peeled from the foam and the basis weight of the used face material ^{exceeds 12 g / m 2} , the phenol resin often exudes to the face material, and the conveyor surface of the manufacturing equipment is conveyed. Is likely to be contaminated with exuded phenolic resin.
The basis weight of the peeled face material shall be the basis weight of the face material peeled by the same method as the peeling method used in the measurement / evaluation of the adhesive strength of the face material.

Examples of the material of the synthetic fiber non-woven fabric include synthetic resins such as polyester, polypropylene, nylon and polyethylene. As the material of the synthetic fiber non-woven fabric, polyester, polypropylene, and nylon are preferable.
One of these synthetic resins may be used alone, or two or more thereof may be used in combination.
The fiber diameter of the synthetic fiber of the synthetic fiber non-woven fabric is preferably 0.5 to 4.0 denier, more preferably 1.5 to 3.0 denier.
When the fiber diameter of the synthetic fiber is not more than the upper limit value, it becomes easy to suppress the exudation to the surface of the laminated board.
When the fiber diameter of the synthetic fiber is at least the above lower limit value, the handleability of the synthetic fiber is enhanced and the non-woven fabric is easily manufactured.

The thickness of the face material is not particularly limited, but is preferably 0.06 to 1.00 mm, more preferably 0.10 to 0.50 mm. When the thickness of the face material is at least the above lower limit value, the exudation to the surface of the laminated board is likely to be suppressed. When the thickness of the face material is not more than the upper limit value, the handleability of the face material is likely to be improved.

It is preferable that the face material is formed with so-called embossing having an uneven shape. By using the embossed face material, the adhesiveness between the face material and the foamable phenol resin composition is further enhanced.
The embossing pattern (pattern) is not particularly limited, and examples thereof include a minus pattern, a point pattern, and a crease pattern. A crease pattern is preferable because the uneven shape due to embossing is large and the adhesiveness to the phenol resin foam plate is further enhanced.
To emboss the synthetic fiber non-woven fabric, for example, by using a known spunbond method, the crimped long fiber web developed under the cooling conditions directly under the spun is partially heat-bonded with a thermal embossing roll, or latently wound. It is manufactured by crimping a crimped fiber web by heat treatment and partially heat-bonding it with a thermal embossing roll.

Incidentally, it is preferable that the area per one place of the thermocompression bonding part is 0.05～5.0Mm ^2, more preferably 0.07~3.0mm ^2. By using the face material within this range, it is possible to improve the adhesiveness with the phenol resin foam plate while suppressing the exudation of the phenol resin by the thermocompression bonding portion. When the above area is ^{less than 0.05 mm 2} , the fibers are less bonded to each other, the physical strength such as frictional strength is low, and the phenol resin tends to exude. When ^{the area exceeds 5.0 mm 2} , the area of the thermocompression bonding portion is large. There is a tendency for the texture to be hard and the adhesiveness between the phenolic resin and the fibers of the face material to be poor. The minimum distance between the heat-bonded portions is preferably 0.05 to 5 mm, more preferably 0.08 to 2 mm. By using the face material within this range, it is possible to improve the adhesiveness with the phenol resin foam plate while suppressing the exudation of the phenol resin. When the minimum distance is less than 0.05 mm, there are many thermocompression-bonded portions and the texture is hard, and the adhesiveness between the phenol resin and the fibers of the face material tends to be poor. Physical strength such as frictional strength is low, and phenolic resin tends to seep out easily. Further, it is preferable that the thermocompression bonding portions are evenly distributed over the entire surface of the non-woven fabric.
The heat-bonded partial density is preferably 30 to 250 pieces / cm ² , and more preferably 80 to 150 pieces / cm ^2. The heat-bonded part density means the number of heat-bonded parts per unit area, and is expressed by the following equation.
Heat-bonded part density (pieces / cm ² ) = number of heat-bonded parts (pieces) / surface area of face material (cm ² )
When the thermocompression bonding portion density is within the above range, it is possible to improve the adhesiveness with the phenol resin foam plate while suppressing the exudation of the phenol resin by the thermocompression bonding portion.
The depth of the recess (that is, the recess formed by thermal crimping by thermal embossing roll processing or the like) of the thermal crimping portion is preferably 0.01 to 1.0 mm. If the depth is less than 0.01 mm, the heat-bonded portion tends to be less bonded, and if it exceeds 1.0 mm, it tends to be difficult to process by embossing roll or the like.

A preferred combination of the effervescent phenolic resin composition and the face material is an effervescent phenolic resin composition containing a halogenated unsaturated hydrocarbon and a foaming agent containing a hydrocarbon, and a synthetic fiber of either polyester, polypropylene or nylon. A combination of face materials made of the non-woven fabric of the above is preferable. The basis weight of the face material is preferably ^{20 to 80 g / m 2.} The fiber diameter of the synthetic fiber is preferably 1.0 to 3.0 denier.

Further, a combination of a foamable phenol resin composition containing a halogenated unsaturated hydrocarbon and a foaming agent containing a halogenated saturated hydrocarbon and a face material made of a non-woven fabric of synthetic fibers of either polyester, polypropylene or nylon can be used. preferable. The basis weight of the face material is preferably ^{50 to 120 g / m 2.} The fiber diameter of the synthetic fiber is preferably 1.0 to 3.0 denier. The thickness of the face material is preferably 0.1 to 1 mm.
If the foamable phenol resin composition is combined with the face material, it becomes easy to suppress exudation of the laminated board to the surface when the laminated board is manufactured.

As the synthetic fiber non-woven fabric, those obtained by a known manufacturing method can be used, for example, a wet method, a chemical bond method, a needle punch method, a stitch bond method, a thermal bond method, a spunlace method, a melt blow method, and a spunbond. A non-woven fabric obtained by law or the like is used. Among these, a non-woven fabric produced by the spunbond method is preferable because of its excellent productivity and strength.

[Manufacturing method of effervescent phenol resin composition]
The effervescent phenol resin composition is prepared, for example, by supplying a phenol resin, a foaming agent, an acid catalyst and, if necessary, an arbitrary component to a mixer or the like and mixing them.
The mixing order of each component is not particularly limited, but is, for example, an order in which an arbitrary component is added to the phenol resin as necessary and mixed, and a foaming agent and an acid catalyst are added to the obtained mixture.

[Manufacturing method of laminated board]
The laminated board of the present invention can be produced by foaming and curing the foamable phenol resin composition on a face material.
The laminated board of the present invention can be produced by using a known foam molding method. An example is given below.

In this example, a manufacturing system including a discharge device, a foam molding device arranged on the downstream side of the discharge device, and a cutting device arranged on the downstream side of the foam molding device is used.
The discharge device includes a mixing unit for mixing raw materials such as phenol resin, and a plurality of nozzles arranged along a direction orthogonal to the flow direction for discharging the mixed raw materials (foamable phenol resin composition). To be equipped with.
The foam molding apparatus includes a frame portion and heating means. The frame portion includes conveyors (lower conveyor, upper conveyor, left conveyor, right conveyor) arranged vertically and horizontally so as to form a space corresponding to the cross-sectional shape of the phenol resin foam plate. The lower and upper conveyors regulate vertical foaming, and the left and right conveyors regulate horizontal foaming. The effervescent phenol resin composition that passes through the frame portion is heated, foamed, and cured by the heating means. Examples of such a foam molding apparatus include those described in JP-A-2000-218635.

In this manufacturing system, first, the first face material is continuously supplied between the discharge device and the foam molding device. In the discharge device, the effervescent phenol resin composition is discharged from a plurality of nozzles onto the first face material. A second face material is placed on it, introduced into the frame portion of the foam molding apparatus, and heated at 30 to 95 ° C. As a result, the foamable phenol resin composition is foamed and cured between the first face material and the second face material to form a laminated board. This laminated board is taken out from the foam molding apparatus and cut to an arbitrary length by the cutting apparatus. As a result, a laminated board in which the first face material is provided on one surface and the second face material is provided on the other surface is obtained.

The laminated board may have irregularities formed on the surface provided with the face material. By forming the unevenness, the adhesiveness between the phenolic resin foam plate and the face material is further enhanced, and the integrity of the laminated plate is further improved. Further, if the texture of the face material is increased, the exudation of the phenol resin is suppressed, while the adhesiveness between the face material and the phenol resin foam plate is also lowered. Even if the amount is increased, the adhesiveness between the face material and the phenol resin foam plate does not decrease, and the exudation of the phenol resin can be suppressed. Further, so-called slat marks caused by the step between the slat of the slat type double conveyor can be made inconspicuous.

As a method for forming irregularities on the laminated board, for example, an apparatus provided with a slat type double conveyor described in Japanese Patent No. 3837226 and Japanese Patent Application Laid-Open No. 2000-218635 as a foam molding apparatus is used, and the slat type double conveyor is used. An example is a method in which unevenness is provided on the transport surface and the uneven surface is used to form unevenness on the surface of the laminated plate. Further, a method of pressing a plate having irregularities on the surface of a laminated plate that has not been completely solidified immediately after being discharged from the foam molding apparatus (for example, providing irregularities on the transport surface of the second double conveyor described in Japanese Patent No. 3837226. , A method of forming unevenness on the surface of the laminated plate by this uneven surface). Further, for example, in the manufacturing method including the foam curing step and the post-curing step described in Japanese Patent Application Laid-Open No. 2015-151484, unevenness is provided on the surface of the spacer that separates the laminated plates in the post-curing step, and the laminated plates are laminated by the uneven surface. Unevenness may be formed on the surface of the plate.
Further, a method of laminating a face material having irregularities in advance on the surface of the phenol resin foam plate may be used.

The size of the unevenness is not particularly limited, but for example, the height from the bottom surface of the concave portion to the apex of the convex portion is preferably 0.01 to 3 mm, and the width of the convex portion is preferably 1 to 20 mm. The height of the convex portion is preferably larger than the thickness of the face material.
The plan view shape of the convex portion (the plan view shape of the region surrounded by the rising portion (outer edge) of the convex portion) is not particularly limited, but is a polygonal shape such as a quadrangle or a hexagon, a perfect circle shape, or an elliptical shape. , It can be a circular shape such as an oval shape. Here, the shape of the convex portion in a plan view means a case where the line of sight is perpendicular to the surface on which the face materials of the laminated boards are laminated. Further, the rising portion of the convex portion means a set of points where the ridge line from the bottom surface of the concave portion to the apex of the convex portion is substantially separated from the bottom surface of the concave portion. Such points are formed by the ridgeline of the central convex portion (the line formed by the surface of the laminated board) and the central convex portion when cut in the thickness direction so as to pass through the vertices of the three adjacent convex portions. This is the point where the bottom surfaces of the recesses existing on the left and right (the surface formed by the interface between the face material and the phenol resin foam plate) come into contact with each other. Since the bottom surface of the recess has irregularities derived from the fibers of the face material and the heat-bonded portion, irregularities lower than the thickness of the face material to be used shall be ignored.
The apex of the convex portion can be the apex when the laminated plate is placed on a horizontal Tokiwa and the height is measured by a laser displacement meter. Alternatively, the surface of the laminated board can be observed with an optical microscope and then depth-analyzed, and the highest portion in the observed portion can be set as the apex.
As the cutting tool, it is preferable to use a sharp tool such as a razor or a heat insulating material cutter (manufactured by Kanzawa Iron Works Co., Ltd., K-470, blade thickness 0.8 mm).
The width of the convex part means the longest part of the distance between the two points of the straight line intersecting the shape of the convex part in a plan view. For example, in the case of a perfect circle shape, it means the diameter and is a regular quadrangle. In the case of, it means a diagonal line. When the shape of the convex portion in a plan view is a perfect circle in a plan view, the diameter is preferably 1 mm or more and 10 mm or less, and more preferably 5 mm or more and 8 mm or less.
As described above, the convex portion has, for example, a height of 0.05 mm to 1 mm and a diameter of 5 mm from the bottom surface of the concave portion (the portion between the rising portion of the convex portion to the rising portion of the adjacent convex portion) to the apex of the convex portion. Can be columnar.
Further, the width of the concave portion formed between the adjacent convex portions (distance from the rising portion of the convex portion to the rising portion of the adjacent convex portion) is preferably 0.01 to 4.00 mm. By reducing the distance between the adjacent convex portions, the face material bites into the concave portion between the adjacent convex portions, and the adhesiveness between the face material and the phenol resin foam plate can be further improved.

The convex area ratio on the surface of the foam is 15% or more and 80% or less.
Here, the convex area ratio is the ratio of the total area of the convex portion to the total area of the surface having the face material in the plate-shaped foam in which the face material is laminated on at least one surface, and is expressed by the following equation. expressed. The area of the convex portion means the area in a plan view of the region surrounded by the rising portion of the convex portion. As the unit area in the formula, the area of the laminated board cut out from an arbitrary position of the laminated board to a length of 5 cm and a width of 5 cm is 25 cm ^2, and the convex area ratio per unit area is the convex area of the entire laminated board. Let it be a percentage.
Convex area ratio (%) = {(Area of multiple convex parts existing per unit area) / (Unit area)} x 100 [%]
In order to reduce the distance between adjacent convex portions and improve the adhesiveness of the face material, the convex portion area ratio is preferably 20% or more, more preferably 25%, and particularly preferably 30% or more. On the other hand, if the distance between the convex portions is too small, the adhesiveness of the face material is lowered, so that it is preferably 75% or less, more preferably 70% or less, and particularly preferably 60% or less.
Further, in order to allow the face material to bite between the convex portions, the convex portions are preferably discontinuous, and the area per convex portion is preferably 0.5 mm ² or more and 80 mm ² or less, and 10 mm ² or more and 65 mm ² or less. More preferably, 15 mm ² or more and 50 mm ² or less is particularly preferable.

The face material is used by being pulled out from a state in which it is wound in a roll shape with respect to a cylindrical core called a winding core, and is wound by applying a winding tension when winding. Therefore, if the pull-out tension applied to the face material when it is pulled out and used is too large, the embossed pattern or uneven pattern of the non-woven fabric may be damaged due to the winding of the non-woven fabric roll, or the heat-bonded portion may be peeled off or the fibers may be torn off. On the other hand, if the pull-out tension is too small, in the case of a slat type double conveyor, the face material may be caught between the slats and become wrinkled, or the face material may meander and crease.
Therefore, the pull-out tension of the face material is preferably 0.5 to 80 N / m, more preferably 1 to 60 N / m.
To adjust the pull-out tension of the face material, the face material is pulled out from the non-woven roll via the tension adjusting roller, and the position of the tension adjusting roller is moved, or a motor or powder clutch is used on the tension adjusting roller. The pull-out tension can be adjusted to a desired value by controlling the roller rotation with a tension controller, and the torque itself generated during these adjustments and the voltage required to control the motor and clutch are converted into torque. By doing so, the pull-out tension can be measured.

As described above, the laminated board of the present embodiment is lightweight, and is excellent in heat insulating property and flame retardancy by providing a phenol resin foam board containing a specific foaming agent and a face material having a specific basis weight. In addition, exudation to the surface is suppressed, and the beauty of the surface is further enhanced. Therefore, the laminated board of the present embodiment is particularly useful as a heat insulating material for buildings such as apartment houses, detached houses, and warehouses, which require high heat insulating properties.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. However, Examples 13 to 16 are reference examples.

<Measurement method>
The measurement methods used in Examples and Comparative Examples described later are shown below.

(Thermal conductivity)
The thermal conductivity of the phenolic resin foam plate was measured according to JIS A 9511: 2009. The same sample was measured twice, and the average value was calculated.

(Limited Oxygen Index (LOI))
The oxygen limiting index (LOI) of the phenolic resin foam plate was measured according to JIS K 7201-2: 2007.

(Metsuke of face material)
The measurement was performed according to the "mass per unit area" of JIS L 1906 "general long fiber non-woven fabric test method".

(Fiber diameter of face material)
Among the means for measuring the denier of elastic fibers and multifilament fibers, multifilament fibers are in accordance with JIS-L-1013. For elastic fibers, denier (D) is measured by hanging the elastic fibers in a standard atmosphere with no load, measuring the yarn length (L: unit m), and measuring the weight (W: unit g). ) Can be calculated from D = (W / L) × 9000, and this is performed 30 times, and the average value is taken as denier.
When measuring the denier of the elastic fiber, the length of the yarn length L is not particularly limited, but in order to obtain a numerical value with high accuracy, a length that is not affected by the elongation due to the own weight effect of the elastic fiber is preferable, for example, 20 denier or more. For a yarn having a yarn length of about 40 denier, the yarn length L is preferably about 1 m.

<Evaluation method for suppressing exudation to the surface>
In the evaluation of the inhibitory property of exudation to the surface of the laminated board, the surface of the laminated board was visually observed for 20 laminated boards having a thickness of 45 mm, a width of 1000 mm, and a length of 910 mm manufactured in Examples and Comparative Examples described later. , Evaluated according to the following evaluation criteria.
≪Evaluation criteria≫
◯: No exudation to the surface of the laminated board was observed for 20 of the 20 laminated boards.
Δ: Exudation to the surface of the laminated board was observed for at least one laminated board out of 20 sheets.
X: The effervescent phenol resin composition exudes significantly, causing a problem that the exuded phenol resin sticks to the transport surface of the conveyor.

<Measurement / evaluation of face material adhesive strength>
The adhesive strength was measured by the following procedure. First, in the central part of the end of the laminated board having a width of 60 cm and a length of 120 cm, six strip-shaped cuts of 3 cm in the width direction and 30 cm in the longitudinal direction are provided, and the end of the strip is peeled off by about 3 cm to form a paper clip. Then, connect it to a force gauge and peel it off at a speed of about 1 cm / sec while keeping the peeling angle between the face material and the core material (phenol resin foam plate) at 90 degrees. Record the maximum value at that time, and use the average value of the measured values of 10 points excluding the lowest value and the highest value out of the total of 12 measured values on the front and back of the laminated board, and use the face material of the laminated board. The adhesive strength between the core material and the core material (g / 3 cm width). A force gauge having a maximum load of 500 g and a minimum scale of 0.1 g was used, and the measured value was rounded off to the nearest whole number. As the value of the adhesive strength, the average of the measured values of the five laminated boards was calculated, and the value rounded off to the first digit was adopted, and the value was evaluated according to the following evaluation criteria.
≪Evaluation criteria≫
◯: Excellent adhesive strength (120 g / 3 cm width or more)
Δ: Medium adhesive strength (80 g / 3 cm width or more and less than 120 g / 3 cm width)
X: Adhesive strength is inferior (less than 80 g / 3 cm width)

<Metsuke of face material after peeling>
The basis weight of the peeled face material was measured by the above-mentioned measurement and evaluation of the face material adhesive strength.

<Appearance of face material>
In the evaluation of the appearance of the face material as seen from the surface of the laminated board, the face material on the surface of the laminated board was visually evaluated for 20 laminated boards having a thickness of 45 mm, a width of 1000 mm, and a length of 910 mm manufactured in Examples and Comparative Examples described later. It was observed and evaluated according to the following evaluation criteria.
≪Evaluation criteria≫
○: No exuding stains, wrinkles, or creases ×: Exuding stains, wrinkles, or creases

[Example 1]
100 parts by mass of liquid resol type phenol resin (manufactured by Asahi Organic Materials Industry Co., Ltd., trade name: PF-339), surfactant (silicone-based surfactant, "Product No. SH193" manufactured by Toray Dow Corning Co., Ltd., polyether chain After mixing 4 parts by mass of −OH) and 4 parts by mass of a formaldehyde catcher (urea), the mixture was left at 20 ° C. for 8 hours.
108 parts by mass of the obtained mixture, 15 parts by mass of a foaming agent (HCFO-1233 zd-E: mixture of isopentane = 40: 60 (mass ratio)), and an acid catalyst (mixture of paratoluenesulfonic acid and xylenesulfonic acid). A foaming phenol resin composition was prepared by mixing with 15.0 parts by mass.
The first face material (material: polyester, grain) in which this effervescent phenol resin composition is continuously run from 16 nozzles (discharge port diameter: length 10 mm, width 30 mm) arranged in the TD direction. : 30 g / m ² , fiber diameter: 2.0 denier, heat-bonded partial density: 100 pieces / cm ² ), and a second face material of the same material as the first face material is layered on top of it. The thickness was 45 mm and the width was 1000 mm with a slat type double conveyor so as to be sandwiched between the first and second face materials, and this was heated at 70 ° C. for 300 seconds for foam molding. At this time, the first and second face materials were pulled out from the face material rolls so that the tension applied to the first and second face materials was 4 N / m.
Of the upper and lower conveyors of the slat conveyor, the transport surface in contact with the phenol resin foam plate is provided with unevenness cut into a hemispherical shape, and the unevenness causes the surface of the phenol resin foam plate to have a circular diameter of 5 mm. Then, the convex portions having a height of 0.5 mm at the central portion were provided in a staggered arrangement, and the distance between the convex portions (concave portions) was adjusted so that the convex portion area ratio was 40%.
The obtained sheet was cut to a length of 910 mm to prepare a laminated board of Example 1.

[Examples 2 to 6]
Laminated plates of Examples 2 to 6 were prepared in the same manner as in Example 1 except that the foaming agent was changed to the composition shown in Table 1.

[Examples 7 to 12, Comparative Examples 1 to 3]
Except that the foaming agent was changed to the composition shown in Table 1, the face material was changed to the basis weight shown in Table 1, the diameter of the convex portion was set to 4 mm, and the convex portion on the surface was changed so that the convex area ratio was shown in Table 1. Made laminated plates of Examples 7 to 12 and Comparative Examples 1 to 3 in the same manner as in Example 1.

[Comparative Examples 4 and 5]
Laminated plates of Comparative Examples 4 and 5 were prepared in the same manner as in Example 5 except that the heat-bonded partial density of the face material was changed as shown in Table 1.

[Examples 13 and 14]
Example 13 in the same manner as in Example 1 except that the foaming agent was changed to the composition shown in Table 1 and the face material was changed to the basis weight shown in Table 1 and the upper and lower transport surfaces of the slat conveyor were not uneven. , 14 laminated boards were prepared.

[Examples 15 and 16]
A face material having a convex portion shown in Table 1 in advance as the first and second face materials having a foaming agent having the composition shown in Table 1 (material: polyester, texture: 50 g / m ² , fiber diameter: 2.0 denier, Use a heat-bonded partial density: 100 pieces / cm ² ), and use a slat conveyor with no irregularities on the upper and lower transport surfaces so that the tension applied to the first and second surface materials is 2 N / m. The laminated boards of Examples 15 and 16 were prepared in the same manner as in Example 1 except that the first and second face materials were pulled out from the face material rolls.

[Comparative Examples 6 and 7]
Laminated plates of Comparative Examples 6 and 7 were prepared in the same manner as in Example 15 except that the tension applied to the first and second face materials was changed as shown in Table 1.

The thermal conductivity and LOI of the phenolic resin foamed plates of the laminated plates of each example were measured. Table 1 shows the measurement results such as thermal conductivity, LOI, and basis weight of the face material used.
In addition, the ability to suppress exudation of the laminated board to the surface, the adhesive strength of the face material, and the appearance of the face material were evaluated. The evaluation results are shown in Table 1.
In the table, the content of each component in the foaming agent means the ratio (mass%) to the total mass of the foaming agent.

As shown in the above results, the laminated boards of Examples 1 to 16 to which the present invention is applied have a sufficiently low thermal conductivity, excellent heat insulating properties, and are suppressed from seeping out to the surface and peeling of the face material on the surface. It was excellent in beauty.
On the other hand, in the laminated boards of Comparative Examples 1, 3 and 4, the exuding of the foamable phenol resin composition to the surface is remarkable, and the exuded phenol resin adheres to the transport surface of the conveyor during manufacturing. Trouble has occurred. In the laminated boards of Comparative Examples 2, 5 and 7, the adhesive strength between the face material and the phenol resin foam board was insufficient, and the face material was peeled off at the end of the laminated board. In the laminated board of Comparative Example 6, wrinkles and creases were formed on the surface material of the surface, and the surface beauty was inferior.
From these results, it was confirmed that by applying the present invention, a laminated board having excellent heat insulating properties and excellent surface beauty can be obtained.

Claims (2)

A phenol resin foam plate containing a foaming agent containing a halogenated unsaturated hydrocarbon and a face material provided on at least one surface of the phenol resin foam plate are provided.
The face material is a synthetic fiber non-woven fabric ^{having a texture of 20 g / m 2} or more and 150 g / m ² or less and a heat-bonded partial density of 30 to 250 pieces / cm ^{2 represented by the following formula.}
A convex portion is formed on the surface on which the face material is provided, and a convex portion is formed.
Laminated board having an oxygen limiting index of 28% or more.
Heat-bonded part density (pieces / cm ² ) = number of heat-bonded parts (pieces) / surface area of face material (cm ² ) The process of pulling out the first face material from the face material roll,
A step of discharging a foamable phenol resin composition containing a phenol resin and a foaming agent containing a halogenated unsaturated hydrocarbon onto the first face material, and
A second face material of the same material as the first face material is pulled out from the face material roll, stacked on the foamable phenol resin composition discharged on the first face material, suppressed by a slat type double conveyor, and foamed. It is provided with a step of foaming and curing the sex phenol resin composition.
The face material is a synthetic fiber non-woven fabric ^{having a texture of 20 g / m 2} or more and 150 g / m ² or less and a heat-bonded partial density of 30 to 250 pieces / cm ^{2 represented by the following formula.}
A method for manufacturing a laminated board, wherein the pull-out tension when pulling out the first face material and the second face material from the face material roll is 0.5 to 80 N / m, respectively.
Heat-bonded part density (pieces / cm ² ) = number of heat-bonded parts (pieces) / surface area of face material (cm ² )