RU2791537C1 - Foamed phenolic resin laminated board - Google Patents

Abstract

FIELD: cold and heat insulating materials.

SUBSTANCE: cold and heat insulating materials for construction materials and industrial enterprises and relates to a laminated board made of foamed polymer resin. A foamed phenolic resin laminated board in which a flexible surface material is located on at least the top and bottom surfaces of the foamed phenolic resin. Foamed phenolic resin contains HCFO-1224yd(Z) ((Z)-1-chloro-2,3,3,3-tetrafluoropropene), has a density of not less than 20 kg/m³ and not more than 55 kg/m³, the ratio of closed mesh is 80% or more, the average cell diameter is from 60 µm to 200 µm, the seepage area ratio of the surface material is 30% or less, and the content of HCFO-1224yd(Z) in the volume of 22.4× 10-3 m³ foamed phenolic resin is from 0.06 mol to 0.35 mol.

EFFECT: obtaining a foamed phenolic resin laminated board with good appearance, in which seepage from the surface material is suppressed while reducing thermal conductivity due to the use of HCFO-1224yd(Z).

6 cl, 1 dwg, 16 ex, 1 tbl

Description

CROSS REFERENCES TO RELATED APPLICATIONS

[0001] This application claims priority to Japanese Patent Application No. 2020-019158, filed Feb. 6, 2020, and Japanese Patent Application No. 2020-089399, filed May 22, 2020, the disclosures of which are incorporated herein by reference in their entirety. .

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

[0002] The present disclosure relates to a foamed phenolic resin laminate board, and more particularly to a foamed phenolic resin laminate board with less dirt seeping from the surface material.

BACKGROUND OF THE INVENTION

[0003] Acid-cured foamed phenolic resin made from resole type phenolic resin is flame retardant, emits less smoke, and has thermal insulation properties, so it is used, for example, for exterior wall materials such as metal siding, interior wall materials such as partition panels, as well as building materials such as ceiling materials, fire doors and exterior doors. Acid-cured foamed phenolic resin is also widely used as cold and heat insulation materials for building materials and industrial plants.

[0004] With regard to the blowing agent used for the production of foamed phenolic resin, even higher thermal insulation is required in terms of environmental concerns and the growing demand for thermal insulation in buildings, and there is a need for technology to apply HCFO-1224yd(Z) (chemical name: ( Z)-1-chloro-2,3,3,3-tetrafluoropropene), which has a particularly low thermal conductivity as a blowing agent for phenolic resin foam laminate boards.

[0005] As a technology that uses HCFO-1224yd(Z), the technologies disclosed in Patent Documents 1 and 2 are known. Patent Document 1 discloses that a combination of HCFO-1224yd(Z) and another blowing agent can be used for foamed phenolic resin.

[0006] Patent Document 2 discloses that thermal conductivity can be reduced by using HCFO-1224yd(Z) in a urethane polymer foam, which is a foam of the same thermosetting resin.

LIST OF CITATIONS

PATENT LITERATURE

[0007] Patent Document 1: WO2019036049 (A1)

Patent Document 2: JP2015105343 (A)

SUMMARY OF THE INVENTION

TECHNICAL PROBLEM

[0008] However, the foamed phenolic resins disclosed in Patent Documents 1 and 2 cannot simultaneously suppress dispersion from the foaming resin composition and viscosity reduction due to plasticization caused by the characteristics of HCFO-1224yd(Z). As a result, the thermal insulation performance is reduced, and the foaming resin composition cannot be prevented from seeping onto the surface material.

[0009] Details of this are described below. Since HCFO-1224yd(Z) has a low thermal conductivity among various HCFOs, the ratio of the HCFO-1224yd(Z) component in the foam, in particular the molar amount of HCFO-1224yd(Z) in the foamed phenolic resin, affects the thermal insulation performance. In contrast, HCFO-1224yd(Z) has a lower boiling point among HCFOs, so it is likely that the foaming phenolic resin composition thrown onto the surface material will dissipate before it cures, and that the molar amount of HCFO-1224yd( Z) in foamed phenolic resin will decrease. As a result, it is difficult to take full advantage of the low thermal conductivity of HCFO-1224yd(Z). In addition, compared with an aliphatic hydrocarbon and the like, HCFO-1224yd(Z) has a higher solubility in the phenolic resin, and thus the viscosity of the foaming phenolic resin composition tends to decrease, and as a result, there is a tendency for seepage from the surface material and poor surface appearance of the phenolic resin foam laminate board. In other words, it was difficult to simultaneously achieve both low thermal conductivity and prevent seepage of material to the surface.

[0010] Thus, there has been a need for a good appearance phenolic resin foam laminate board in which seepage from a surface material can be suppressed while reducing thermal conductivity by using HCFO-1224yd(Z).

SOLUTION

[0011] Then, the present inventors carefully studied how to solve the above problem, and found a way to reduce the leakage of the foaming phenolic resin composition from the surface material along with the introduction of the required amount into the phenolic resin composition, while preventing the dispersion of HCFO-1224yd(Z), which is blowing agent with low boiling point, in the production of phenolic resin foam laminate board, and solved this problem.

[0012] In other words, the present disclosure provides the following paragraphs. [15].

[0013]

[1] A foamed phenolic resin laminate board in which a flexible surface material is disposed on at least one of two sides of the foamed phenolic resin, in which: the foamed phenolic resin contains HCFO-1224yd(Z); the foamed phenolic resin has a density of not less than 20 kg/m ³ and not more than 55 kg/m ³ , the percentage of closed cells is not less than 80%, the average cell diameter is not less than 60 μm and not more than 200 μm, and the percentage of seepage area from the surface material is 30% or less, and the content of HCFO-1224yd(Z) in a volume of 22.4×10 ^-3 m ³ foamed phenolic resin is not less than 0.06 mol and not more than 0.35 mol.

[2] The phenolic resin foam laminate board according to [1], containing at least one gas component selected from an aliphatic hydrocarbon having a carbon number of 6 or less and a chlorinated saturated hydrocarbon having a carbon number of 5 or less.

[3] The phenolic resin foam laminate board according to [1] or [2], wherein the surface material is any of non-woven fabric, woven fabric and paper.

[4] The foamed phenolic resin laminate board according to any one of paragraphs. [1] to [3] in which the 45° peel strength of the surface material is 1000 g or less.

[5] The foamed phenolic resin laminate board according to any one of paragraphs. [1] to [4], in which the thermal conductivity at 23°C is 0.0185 W/m⋅K or less.

BENEFICIAL EFFECT

[0014] According to the present invention, a high-performance phenolic resin foam laminate board having high thermal insulation performance, less seepage of the phenolic resin foam composition of the surface material, as well as good appearance can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In the accompanying drawings:

Fig. 1 is a diagram illustrating a method for measuring the 45° peel strength of a surface material.

DETAILED DESCRIPTION

[0016] The following is a detailed description of the present invention in accordance with its preferred embodiment. It should be noted that the present invention is not limited to the following embodiment, and can be modified in various ways and performed within its scope.

[0017] Phenolic Resin Foam Laminate Board

The foamed phenolic resin laminate board of this embodiment (hereinafter, sometimes referred to as "foamed laminate board") is a laminate containing a foamed phenolic resin in which a large amount of bubbles are dispersed in a cured phenolic resin body formed by a curing reaction and a surface material on at least one of the two sides of the foamed phenolic resin. It should be noted that since the foamed laminate board in this embodiment has less seepage of the foaming phenolic resin composition of the surface material, and the top and bottom surface materials can peel off, it can be used as a building material with excellent fire retardant and heat insulation properties in the state of the base material. with surface material removed. The “thickness direction” in this embodiment refers to the dimension of the shortest side of the three sides of the foamed laminate board, and is generally the direction in which the foamable phenolic resin composition foams and grows on the bottom surface material during production of the foamed laminate board.

[0018] In addition, the phenolic resin foam laminate board is used alone or can be connected to an external member and used in various applications. Examples of external elements include one or a combination of board materials and sheet/film materials. Examples of suitable board materials include wood boards such as plywood, structural plywood, chipboard and OSB, wood fiber cement board, particle board cement board, gypsum board, flexible board, medium density fibreboard, calcium silicate board, silicate board magnesium, as well as multilayer slabs reinforced with volcanic silicate fiber. In addition, examples of suitable sheet/film materials include polyester nonwoven, polypropylene nonwoven, inorganic filled glass fiber nonwoven, glass fiber nonwoven, paper, calcium carbonate paper, polyethylene treated paper, polyethylene film, plastic waterproof film, asphalt concrete waterproof paper and aluminum foil (with or without holes).

[0019] Foamed phenolic resin

The foamed phenolic resin density of the foamed phenolic resin laminate board of this embodiment is not less than 20 kg/m ³ and not more than 55 kg/m ³ , preferably not less than 22 kg/m ³ and not more than 50 kg/m ³ , more preferably not less than 24 kg/m ³ and not more than 45 kg/m ³ , even more preferably not less than 26 kg/m ³ and not more than 40 kg/m ³ , and most preferably not less than 26 kg/m ³ and not more than 36 kg/ m ³ . When the density is 20 kg/m ³ or more, mechanical strength such as compressive strength and bending strength can be ensured and damage during foam processing can be avoided, and when the density is 55 kg/m ³ or less, an increase heat transfer in the polymer part becomes less likely, and thus the thermal insulation efficiency can be maintained. The density of the foamed phenolic resin can be controlled by controlling the amount of blowing agent added to the foamed phenolic resin. The density can be mainly controlled by changing the blowing agent proportion in the foamed phenolic resin, the temperature of the foaming phenolic resin composition, selecting the preforming time at the stage of ejecting the mixed foaming phenolic resin composition on the bottom surface material, the ratio of the added amounts of the foaming agent and the organic acid used as the acid curing agent. , as well as curing conditions such as temperature and residence time.

[0020] The closed cell ratio of the foamed phenolic resin of the foamed phenolic resin board is 80% or more, preferably 85% or more, more preferably 88% or more, even more preferably 90% or more, and most preferably 92% or more. When the percentage of closed cells is 80% or more, it is possible to suppress the long-term deterioration of thermal insulation performance due to the replacement of the blowing agent with air in the foamed phenolic resin. It should be noted that the ratio of closed cells in the foamed phenolic resin can be adjusted to a desired value by changing, for example, the addition amount of the foam nucleating agent, the addition ratio of the blowing agent and the organic acid used as the acid curing agent, and the like.

[0021] The average cell diameter of the foamed phenolic resin of the foamed phenolic resin laminate board is not less than 60 µm and not more than 200 µm, preferably not less than 65 µm and not more than 180 µm, more preferably not less than 70 µm and not more than 155 µm, and most preferably not less than 75 µm and not more than 130 µm. When the average cell diameter is 60 µm or more, high foam density can be prevented. As a result, the heat transfer coefficient of the resin portion in the foam can be reduced, and thus the thermal insulation performance of the foamed phenolic resin can be secured. On the other hand, when the average cell diameter is 200 µm or less, an increase in thermal conductivity due to radiation is suppressed, and high thermal insulation performance of the foam can be maintained. The average cell diameter of the foamed phenolic resin can be adjusted to the desired value by changing the amount of added solid foam nucleating agent, the temperature of the foaming phenolic resin composition, selecting the preforming time at the stage of ejection of the mixed foaming phenolic resin composition on the bottom surface material, the ratio between the added amount of blowing agent and the added amount an organic acid used as an acid curing agent; and curing conditions such as temperature, residence time, and the like.

[0022] The thermal conductivity of the phenolic resin foam laminate board, measured at 23°C, is preferably 0.0185 W/(m×K) or less, more preferably 0.0182 W/(m×K) or less, even more preferably 0.0178 W/(m×K) or less, particularly preferably 0.0174 W/(m×K) or less, and most preferably 0.0170 W/(m×K) or less.

[0023] Further, the foamed phenolic resin of the foamed phenolic resin laminate board contains HCFO-1224yd(Z) and is produced from a foaming phenolic resin composition that contains a phenolic resin, a surfactant, a blowing agent containing HCFO-1224yd(Z), solid a foam nucleating agent and an acid hardener containing an organic acid. It should be noted that the foamable phenolic resin composition may optionally contain a phthalic acid compound and the like in addition to the above-described components.

[0024] As the phenolic resin, a resole-type phenolic resin obtained by synthesis with an alkali metal hydroxide or an alkaline earth metal hydroxide is used. Resole-type phenolic resin is synthesized by heating phenol and aldehyde as materials with an alkali catalyst in a temperature range of 40°C to 100°C. In addition, an additive such as urea can be added, if necessary, during or after the synthesis of the resole-type phenolic resin. In the case of adding urea, it is preferable that urea previously methylolated using an alkali catalyst is mixed with a resole-type phenolic resin. Since the resole-type phenolic resin obtained after synthesis usually contains excess water, the resole-type phenolic resin is adjusted to obtain a suitable amount of water for foaming. In addition, an aliphatic hydrocarbon, a high boiling alicyclic hydrocarbon or a mixture thereof, viscosity adjusting diluents such as ethylene glycol and diethylene glycol, and additives, if necessary, can be added to the phenolic resin.

[0025] The initial molar ratio of phenol and aldehyde in the synthesis of the phenol resin is preferably in the range of 1:1 to 1:4.5, and more preferably in the range of 1:1.5 to 1:2.5.

[0026] Examples of phenols that can preferably be used in the synthesis of a phenol resin in this embodiment include phenol itself and other phenols, and examples of other phenols include resorcinol, catechol, o-, m- and p-cresol, xylenols , ethylphenols, p-tert-butylphenol, and the like. In addition, a binuclear phenol can also be used.

[0027] In addition, the aldehyde can be any compound that can be a source of aldehyde. As the aldehyde, it is preferable to use directly formaldehyde, paraformaldehyde, which can be depolymerized and used, as well as other aldehydes and their derivatives. Examples of other aldehydes include glyoxal, acetaldehyde, chloral, furfural, benzaldehyde, and the like. An additive such as urea, dicyandiamide or melamine may be added to the phenolic resin. In this specification, when these additives are added, "phenolic resin" refers to the resin after the additives have been added thereto. Further, in this specification, "phenolic resin composition" refers to compositions obtained by adding a surfactant to a "phenolic resin", and "foaming phenolic resin composition" refers to compositions obtained by adding to a "phenolic resin composition" a blowing agent, a solid a foam nucleating agent and an acid hardener, which give it foaming and curing properties. In addition, the resin portion after the foamed phenolic resin is formed is referred to as a "phenolic resin curable body".

[0028] The weight average molecular weight of the phenolic resin is preferably 900 or more, more preferably 1000 or more, even more preferably 1150 or more, and most preferably 1300 or more. In addition, the weight average molecular weight is preferably 2500 or less, more preferably 2200 or less, even more preferably 2050 or less, and most preferably 1900 or less. When the weight average molecular weight of the phenolic resin is 900 or more, the temperature rise caused by internal heat generation of the foaming phenolic resin composition is suppressed, and dispersion of the HCFO-1224yd(Z) component can be easily suppressed. In contrast, when the weight average molecular weight of the phenolic resin is 2500 or less, the leakage of the foaming phenolic resin composition can be easily suppressed. The weight average molecular weight of the phenolic resin can be measured using the method described in the Examples of this description.

[0029] The viscosity of the phenolic resin and the phenolic resin composition at 40°C is preferably not less than 5,000 mPa⋅s and not more than 100,000 mPa⋅s, more preferably not less than 7,000 mPa⋅s and not more than 50,000 mPa⋅s, and even more preferably not less than 9000 mPa⋅s and not more than 40000 mPa⋅s. In addition, the amount of water in the phenolic resin and the phenolic resin composition is preferably not less than 1.5 mass% and not more than 30 mass%.

[0030] The surfactant, blowing agent, and solid foam nucleating agent contained in the foaming phenolic resin composition may be added to the phenolic resin in advance, or may be added simultaneously with the acid curing agent.

[0031] As a surfactant, those commonly used for the production of foamed phenolic resin can be used, and among them, a nonionic surfactant is effective, the preferred examples of which include, for example, alkylene oxide, which is a copolymer of ethylene oxide and propylene oxide. , a condensate of alkylene oxide and castor oil, a condensate of alkylene oxide and an alkylphenol such as nonylphenol or dodecylphenol, a polyoxyethylene alkyl ester in which part of the alkyl ester has 14-22 carbon atoms, a fatty acid ester such as polyethylene oxide fatty acid ester, a silicone compound such as polydimethylsiloxane; and a polyhydric alcohol. These surfactants may be used alone or in combination of two or more of them. The amount of surfactant used is not particularly limited, and is preferably within the range of 0.3 to 10 ppm (parts by mass) per 100 ppm. phenolic resin.

[0032] The blowing agent contains HCFO-1224yd(Z) as a component. In addition, it is preferable that the blowing agent contains at least one substance selected from an aliphatic hydrocarbon having a carbon number of 6 or less and a chlorinated saturated hydrocarbon having a carbon number of 5 or less as a blowing agent component other than HCFO-1224yd (Z).

[0033] As an aliphatic hydrocarbon having a carbon number of 6 or less, known porophores can be used. Examples of this include, for example, isobutane, normal butane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, and the like. These hydrocarbons may be used singly or in combination of two or more of them.

[0034] Linear or branched chlorinated saturated hydrocarbons having a carbon number of 2-5 can be used as a chlorinated saturated hydrocarbon having a carbon number of 5 or less. The number of bound chlorine atoms is not limited, but is preferably 1-4. Examples of the chlorinated aliphatic hydrocarbon include, for example, dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, and the like. Of these, propyl chloride and isopropyl chloride, which are chloropropanes, are more preferably used.

[0035] In addition, the blower may include hydrofluoroolefins other than HCFO-1224yd(Z) (at least one of a chlorinated hydrofluoroolefin and a non-chlorinated hydrofluoroolefin).

[0036] Examples of chlorinated hydrofluoroolefins other than HCFO-1224yd(Z) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd, e.g. HCFO-1233zd (E), i.e. ^Solstice® (Solstice is a registered trademark in Japan, other countries, or both) LBA (product name) manufactured by Honeywell Japan Ltd.), 1,1,2-trichloro-3,3,3-trifluoropropene (HCFO-1213xa) , 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za), 1-chloro-1,3,3,3 -tetrafluoropropene (HCFO-1224zb), 2,3,3-trichloro-3-fluoropropene (HCFO-1231xf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), 2-chloro-1,1, 3-trifluoropropene (HCFO-1233xc), 2-chloro-1,3,3-trifluoropropene (HCFO-1233xe), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-1,2 ,3-trifluoropropene (HCFO-1233yb), 3-chloro-1,1,3-trifluoropropene (HCFO-1233yc), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 3-chloro-1, 2,3-trifluoropropene (HCFO-1233ye), 3-chloro-2,3,3-trifluoropropene (HCFO-1233yf), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and the like, as well as their configurational isomers, that is, one of E and Z or a mixture thereof is used. In addition, (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)) is included.

[0037] Examples of non-chlorinated hydrofluoroolefins include 1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze, e.g. HFO-1234ze(E), product name: Solstice® (Solstice is a registered trademark in Japan, other countries, or both) manufactured by Honeywell Japan Ltd.), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz, e.g. HFO-1336mzz(Z), then has Opteon™ 1100 from Chemours Company), 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,3, 3,3-tetrafluoropropene (HFO-1234ze), 3,3,3-trifluoropropene (HFO-1243zf), 1,1,1,4,4,5,5,5-octafluoro-2-pentene (HFO-1438mzz) and the like, as well as their configurational isomers, that is, one of E and Z or a mixture thereof is used.

[0038] In addition, other porophores are not particularly limited, and examples thereof include, for example, chemical porophore such as sodium hydrogen carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, azodicarboxylic acid amide, azobisisobutyronitrile, barium azodicarboxylate, N,N '-dinitrosopentamethylenetetramine, p,p'-oxybisbenzenesulfonyl hydrazide, trihydrazinotriazine, and the like. These porophores may be used singly or in combination of two or more of them.

[0039] Although the amount of blowing agent in a foaming phenolic resin composition differs depending on the type of blowing agent, compatibility with the phenolic resin, temperature, and foaming and curing conditions such as residence time, the amount of blowing agent per 100 ppm in the amount of phenolic resin and surfactant is preferably not less than 4.0 m.h. and not more than 11.0 m.h., more preferably not less than 4.5 m.h. and not more than 10.5 m.h., and even more preferably not less than 5.0 m.h. and not more than 10.0 m.h. When the amount of blowing agent per 100 m.h. in the amount of phenolic resin and surfactant is 4.0 m.h. or more, the density increase of the foamed phenolic resin can be suppressed. In addition, when the amount of blowing agent per 100 m.h. in the amount of phenolic resin and surfactant is 11.0 m.h. or less, the low density of the foamed phenolic resin is prevented, and it can have an appropriate strength. As a result, the cell wall surface is less likely to be destroyed, and the decrease in the percentage of closed cells can be easily suppressed.

[0040] The content of HCFO-1224yd(Z) in 22.4×10 ^-3 m ³ foamed phenolic resin in this embodiment is not less than 0.06 mol and not more than 0.35 mol, preferably not less than 0.11 mol and not more than 0.35 mol, more preferably not less than 0.15 mol and not more than 0.35 mol, even more preferably not less than 0.15 mol and not more than 0.30 mol, and most preferably not less than 0.15 mol and not more than 0.25 mol. When the amount of HCFO-1224yd(Z) is 0.06 mol or more, low thermal conductivity of the foamed phenolic resin and the foamed phenolic resin laminate board is achieved. In addition, when the amount of HCFO-1224yd(Z) is 0.35 mol or less, the decrease in viscosity of the foaming phenolic resin composition along with plasticization of the resin due to the high affinity with the phenolic resin, as well as the leakage of the foaming phenolic resin composition from the surface material, can be suppressed.

[0041] In this embodiment, a solid foam nucleator is preferably used as a foam nucleator for the production of a foamed phenolic resin. As a solid foam nucleating agent, inorganic powder such as aluminum hydroxide powder, aluminum oxide powder, calcium carbonate powder, talc, kaolin, quartz stone powder, quartz sand, mica, calcium silicate powder, wollastonite, glass powder, glass beads, fly ash, microsilica, gypsum powder, borax, slag powder, alumina cement, Portland cement, and the like; and organic powder such as pulverized phenolic resin foam powder. These foam nucleators may be used alone or in combination of two or more of them.

[0042] The solid foam nucleating agent need only be present in the foaming phenolic resin composition, and the timing of its addition is not particularly limited. In most cases, it is added to the phenolic resin composition, or added at the same time as the blowing agent, in a mixing step which will be described later.

[0043] Added amount of solid foam nucleating agent per 100 m.h. composition of the phenolic resin is preferably not less than 3.0 m.h. and not more than 10.0 m.h., and more preferably not less than 4.0 m.h. and not more than 8.0 m.h. When the added amount of solid foam nucleating agent is 3.0 m.h. or more, it becomes less likely that the seepage of the foaming phenolic resin composition from the surface material will be suppressed. In addition, when the added amount of solid foam nucleating agent is 10.0 m.h. or less, diffusion of HCFO-1224yd(Z), which is a low boiling point porophore, can be easily suppressed.

[0044] The acid hardener must be capable of curing the phenolic resin composition and include an organic acid as the acid component. Examples of the preferred organic acid include arylsulfonic acid or its anhydride. Examples of arylsulfonic acids and their anhydrides include toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, substituted phenolsulfonic acid, xylenolsulfonic acid, substituted xylenolsulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, as well as anhydrides of any of the previous examples. These organic acids may be used alone or in combination of two or more of them. Note that, in the present embodiment, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol, and the like can be added as a co-curing agent. In addition, these hardeners can be diluted with a solvent such as ethylene glycol or diethylene glycol.

[0045] The amount of acid hardener used differs depending on its type, and when a mixture of 60 wt.% p-toluenesulfonic acid monohydrate and 40 wt.% diethylene glycol is used, preferably not less than 8 m.h. and not more than 20 m.h., and more preferably not less than 10 m.h. and not more than 15 m.h. acid hardener is used per 100 m.h. in the amount of phenolic resin and surfactant.

[0046] The surface materials provided on at least one of the top and bottom sides of the foamed phenolic resin are surface materials having flexibility (flexible surface materials). Preferred examples of flexible surface materials that can be used include non-woven fabric and woven fabric containing polyester, polypropylene, nylon, and the like. as the main component, paper such as kraft paper, blended glass fiber paper, calcium hydroxide paper, aluminum hydroxide paper or magnesium silicate paper, and inorganic fiber nonwoven fabric such as glass fiber nonwoven fabric. They can be mixed (or laminated). In the case where the surface materials are to be peeled from the resulting phenolic resin foam laminate board in order to use only the base material, it is preferable to use a cheap paper that can be discarded after peeling. Such surface materials are usually provided in the form of a roll. In addition, materials mixed with additives such as fire retardants can be used as flexible surface materials. It should be noted that the surface material and the foamed phenolic resin may be bonded in various ways, and adhesives such as epoxy resin may be used. However, they are preferably only bonded by the force of adhesion when the foamed phenolic resin is thermally cured on the surface material from the point of view of production cost and simplification of the production process.

[0047] The percentage of seepage from the surface material can be estimated using a measurement method to be described later, and is 30% or less, preferably 25% or less, more preferably 20% or less, even more preferably 15% or less, and most preferably 10% or less. When it is 30% or less, a phenolic resin foam laminate board with good appearance can be obtained, and the 45° peel strength of the surface material is reduced. As a result, the surface material is easily removed from the board, and it can be used as a foamed phenolic resin.

[0048] The 45° peel strength of the surface material for the phenolic resin foam laminate board of this embodiment is preferably 1000 g or less, more preferably 900 g or less, even more preferably 800 g or less, and most preferably 700 g or less. less. When the 45° peel strength of the surface material for the phenolic foam laminate board is 1000 g or less, the surface material is easily removed from the board and it is easily used without the surface material. Here, the 45° peel strength of the surface material can be adjusted to a desired value by varying the amount of HCFO-1224yd(Z) added, the amount of solid foam nucleating agent used and added, the weight average molecular weight of the phenolic resin, and the temperature of the foaming phenolic resin composition. It should be noted that the 45° peel strength of a surface material for a phenolic foam laminate board can be measured by the method described in the Examples of this specification.

[0049] Method for manufacturing a foamed phenolic resin laminate board

Next, the production method of the above-described phenolic resin foam laminate board will be explained.

[0050] As a manufacturing method for the foamed phenolic resin laminate board, a continuous manufacturing process can be used, which includes: a step of mixing the above-described foaming phenolic resin composition with a mixer; a step of ejecting the mixed foaming phenolic resin composition onto the bottom surface material; and a step of producing a foamed phenolic resin laminate board from the phenolic resin composition that has been thrown onto the bottom surface material.

[0051] In a continuous production process, the phenolic resin composition thrown onto the bottom surface material is coated with the top surface material, then preformed so that it is aligned at the top and bottom in the foamed state, and is cured and completely molded into a plate shape while foaming is continued. and affirmations.

[0052] In a continuous manufacturing process, examples of the method for performing preforming and main shaping include various methods depending on the production purpose, such as the method of using a double plate conveyor, the method of using a metal roll or a steel plate, and a combination of both. When molding is performed using a double plate conveyor, for example, the foamable phenolic resin composition coated with the top and bottom surface materials is continuously sent to the double plate conveyor, then pressure is applied to it in the vertical direction while heating to obtain a predetermined thickness, and it is foamed, cured and molded into a slab shape.

[0053] The temperature of the foaming phenolic resin composition when it is thrown onto the bottom surface material is preferably not lower than 35°C and not higher than 45°C. When the temperature of the foamable phenolic resin composition is 35° C. or higher, the foamable phenolic resin composition tends to foam at an early stage, and as a result, leakage of the foamable phenolic resin composition from the bottom surface material can be easily suppressed. In contrast, when the temperature of the foamable phenolic resin composition is 45° C. or lower, the diffusion of HCFO-1224yd(Z), which is a low boiling point blowing agent, can be easily suppressed. It should be noted that, the temperature of the foaming phenolic resin composition thrown onto the bottom surface material can be changed by adjusting the temperature or the water flow to control the temperature of the mixing head for mixing different compositions, the number of revolutions, and the like.

[0054] The step of preforming the foaming phenolic resin composition thrown onto the bottom surface material on top of the top surface material in the foaming and curing process is preferably performed in a temperature range of not lower than 40°C and not higher than 80°C. When the temperature is 40° C. or higher, the effect of promoting foaming in the preforming step can be easily obtained, and the curing can be accelerated. In addition, when the temperature is 80° C. or lower, it is unlikely to be affected by internal heat generation near the center in the thickness direction. Thus, it is unlikely that the temperature at the center will rise easily, and the decrease in the proportion of closed cells can be suppressed.

[0055] In order to effectively promote curing while suppressing the decrease in the closed cell ratio due to internal heat generation near the center in the thickness direction when foaming and curing the foamable phenolic resin composition, it is important to provide a main molding step and a post-curing step after the pre-molding step to incrementally increase temperature. The heating temperature control conditions in the main molding step after the preforming step are preferably not lower than 65°C and not higher than 100°C. At this stage, the main shaping may be carried out using a steel belt type double endless conveyor, a plate type double conveyor, a roller, or the like. In addition, the residence time in the main molding step is preferably not less than 5 minutes and not more than 2 hours, since this is the main stage in which foaming and curing reactions are carried out. When the residence time is 5 minutes or more, foaming and curing can be performed sufficiently. When the residence time does not exceed 2 hours, the production efficiency of the foamed phenolic resin laminate board can be increased. It should be noted that when a conveyor is used, the difference in temperature between the upper and lower conveyors is preferably less than 4°C.

[0056] The post-curing step is applied after temperature control by heating after the temperature control section in the pre-forming step and the main shaping step. The post-curing temperature is preferably not lower than 90°C and not higher than 120°C. When the temperature is 90°C or more, water in the foam board easily diffuses, and when the temperature is 120°C or less, the decrease in the proportion of closed cells of the product is suppressed and the thermal insulation performance is high. When a temperature control section is provided at the post-curing stage, water in the foaming phenolic resin composition may diffuse after final molding.

EXAMPLES

[0057] The following is a more detailed description of the present disclosure with the help of examples and a comparative example, but the present disclosure is not limited to this.

[0058] Synthesis of phenolic resin A

3500 kg of an aqueous solution of formaldehyde with a concentration of 52 wt.% (formalin 52 wt.%) and 2510 kg of 99 wt.% phenol (containing water as an impurity) were loaded into the reactor, these materials were mixed with a propeller stirrer, and the internal temperature of the liquid in the reactor was brought to up to 40°C with temperature controller. Thereafter, the temperature was raised simultaneously with the addition of 48 wt.% aqueous sodium hydroxide solution to continue the reaction. When the Ostwald viscosity of the reaction liquid reached 110 centistokes (=110×10 ⁻⁶ m ² /s; measured at 25° C.), the reaction liquid was cooled and 398 kg of urea was added thereto. Thereafter, the reaction liquid was cooled to 30° C., and a 50 mass% aqueous solution of p-toluenesulfonic acid monohydrate was added until the pH reached 6.4.

[0059] The resulting reaction liquid was then concentrated at 60°C to obtain a phenolic resin A. The weight average molecular weight and viscosity at 40°C of the phenolic resin A were measured using the following methods, and the weight average molecular weight was 1300 and the viscosity at 40°C was 9700 mPa⋅s.

[0060] Viscosity

The viscosity of phenolic resin A was taken as the measurement value obtained with a rotational viscometer (R-100 manufactured by Toki Sangyo Co., Ltd.; rotary part: 3°×R-14) after 3 minutes of stabilization at 40°C.

[0061] Weight average molecular weight

Gel permeation chromatography (GPC) measurement was performed under the following conditions, and the weight average molecular weight Mw of the phenol resin was obtained from the calibration curve obtained with the standard substance (standard polystyrene, 2-hydroxybenzyl alcohol and phenol) shown below.

Preliminary processing:

Approximately 10 mg of phenolic resin was dissolved in 1 ml of N,N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography), and the solution filtered through a 0.2 µm membrane filter was used as a measuring solution.

Measurement conditions:

Measuring device: Shodex System 21 (manufactured by Showa Denko K. K)

Column: Shodex asahipak GF-310HQ (inner diameter 7.5 mm 30 cm)

Eluent: 0.1 mass% of lithium bromide was dissolved in N,N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) and used.

Flow rate: 0.6 ml/min.

Detector: RI detector

Column temperature: 40°C

Standard substance: Standard polystyrene ("Shodex standard SL-105" manufactured by Showa Denko K. K), 2-hydroxybenzyl alcohol (manufactured by Sigma-Aldrich Co. LLC, 99%), phenol (manufactured by Kanto Chemical Co., Inc. ., Special)

[0062] Synthesis of Phenolic Resin B

Phenolic resin B with a weight average molecular weight of 900 and a viscosity at 40°C of 9800 mPa⋅s was obtained by synthesis using the same procedure as phenol resin A, except that when the Ostwald viscosity of the reaction liquid reached 80 centistokes ( = 80×10 ^-6 m ² /s; measured at 25°C), the reaction liquid was cooled, and 430 kg of urea was added, as well as by adjusting the concentration conditions of the reaction liquid.

[0063] Synthesis of Phenolic Resin C

Phenolic resin C with a weight average molecular weight of 2500 and a viscosity at 40°C of 9300 mPa⋅s was synthesized by the same procedure as phenol resin A, except that when the Ostwald viscosity of the reaction liquid reached 240 centistokes ( = 160×10 ^-6 m ² /s; measured at 25°C), the reaction liquid was cooled, and 310 kg of urea was added, as well as by adjusting the concentration conditions of the reaction liquid.

[0064] Synthesis of phenolic resin D

Phenolic resin D with a weight average molecular weight of 800 and a viscosity at 40°C of 9500 mPa⋅s was obtained by synthesis using the same procedure as phenol resin A, except that when the Ostwald viscosity of the reaction liquid reached 75 centistokes ( = 75×10 ^-6 m ² /s; measured at 25°C), the reaction liquid was cooled, and 450 kg of urea was added, as well as by adjusting the concentration conditions of the reaction liquid.

[0065] Method for manufacturing a foamed phenolic resin laminate board

Example 1

A composition containing a block copolymer of ethylene oxide-propylene oxide and polyoxyethylenedecylphenyl ether in a mass ratio of 50% each was mixed as a surfactant in a proportion of 3.0 m.h. per 100 m.h. phenolic resin A, which was provided as a phenolic resin composition. Then to 100 m.h. the composition of the phenolic resin containing the above surfactant was added to 4.0 m.h. foamed phenolic resin as a solid foam nucleating agent, 7.2 m.h. a mixture of 40 wt.% HCFO-1224yd(Z) and 60 wt.% cyclopentane as a blowing agent, and 12.0 m.h. composition of a mixture of 80 wt.% xylenesulfonic acid and 20 wt.% diethylene glycol as an acid hardener, and these materials were then fed into a mixing head with a variable speed rotation, the temperature of which was maintained at 18°C. The phenolic resin foam powder used here was a phenolic resin foam powder (Neoma Foam manufactured by Asahi Kasei Construction Materials Co.) (average particle size: 28.0 µm, bulk density: 181 kg/m ³ ), ground according to the same the same procedure as in Example 1 disclosed in JP 2008-024868(A), and its kneading was carried out with a twin screw extruder before adding the blowing agent and the acid curing agent. After that, the blowing agent and the acid curing agent were mixed, and the resulting foaming phenolic resin composition was distributed through a multi-way distribution pipeline and supplied to the moving material of the lower surface. Note that, as the mixer (mixer), the mixer disclosed in JP H10-225993(A) was used. In other words, the mixer included an opening for supplying a phenolic resin composition including a solid foam nucleating agent and a blowing agent on the upper side surface of the mixer, and included an opening for supplying an acid curing agent on a side surface near the center of the mixing portion in which mixing was performed. rotor. After the mixing part, nozzles were attached to eject the foaming phenolic resin composition. In other words, the mixer comprised the part up to the acid hardener supply port as the mixing part (preceding stage), the part from the acid hardener supply port to the mixing end part as the mixing part (following stage), and the part from the mixing end part. , up to the injectors as a distribution part. The distribution part included a plurality of nozzles at its end and was designed so that the mixed phenolic resin foaming composition was evenly distributed. In addition, the distribution part has a jacket that provides sufficient heat exchange with the temperature-controlled water, and the temperature of the temperature-controlled water in the distribution part was set at 23°C. In addition, a thermocouple was installed at the outlet of the multi-way distribution pipe to enable the temperature of the foaming phenolic resin composition to be detected, and the rotation speed of the mixing head was set to 300 rpm. The temperature of the foaming phenolic resin composition thrown onto the bottom surface material was 39°C. The foamable phenolic resin composition applied to the bottom surface material was introduced at the preforming stage, the temperature of which was maintained at 65°C, and after 30 seconds, preforming was performed on top of the upper surface material with a free roll. Pre-shaping was controlled by setting the roll at a height that was 2/3 of the strand height at the time of ejection. Then, the foaming phenolic resin composition was fed to a double plate-type conveyor heated to 83°C and placed between the two surface materials (main molding stage), curing was carried out at a residence time of 15 minutes, and then another 2 hours, curing was performed in an oven at 110°C. C (post-curing step) to obtain a foamed phenolic resin laminate board with a thickness of 50mm. It should be noted that a polyester non-woven fabric (Asahi Kasei ELTAS E05060 having a basis weight of 60 g/m ² ) was used as both the upper and lower surface material.

[0066] Then characteristics (density, closed cell ratio and average cell diameter of foamed phenolic resin, content of HCFO-1224yd(Z) in 22.4×10 ^-3 m ³ of foamed phenolic resin, percentage of seepage area from material surface, strength of surface material peeling at 45° and thermal conductivity at 23°C) of the obtained foamed phenolic resin and the foamed phenolic resin laminate board were evaluated by the following methods.

[0067] Density of foamed phenolic resin

A 200 mm square phenolic resin foam board was taken as a sample, the surface material was removed from the sample, and the mass and apparent volume were measured according to JIS K7222.

[0068] Phenolic Resin Foam Closed Cell Percentage

The proportion of closed cells of the foamed phenolic resin was measured in accordance with ASTM-D-2856 (Method C). Specifically, after the surface materials were removed from the foamed phenolic resin laminate board, a plug drill was used to obtain a cylindrical sample with a diameter of 35-36 mm. This sample was cut and flattened to a height of 30-40 mm, and then the typical volume of the sample was measured using a standard method using an air comparative pycnometer (Type 1000 manufactured by Tokyo Science Co., Ltd.). The volume of the walls (parts other than cells and voids) calculated from the mass of the sample and the density of the curable phenolic resin body was subtracted from the volume of the sample. The resulting value was then divided by the apparent volume of the sample, calculated from its external dimensions, and was determined as the proportion of closed cells. It should be noted that the density of the phenolic resin curable body was taken to be 1.3 kg/L.

[0069] Phenolic Resin Foam Average Cell Diameter

The average cell diameter of the foamed phenolic resin was measured by the method described in JIS K6402. A 50x magnification photograph was taken of a cross section of a sample obtained by cutting this board parallel to the front and back surfaces of the foamed phenolic resin laminate board at about the center of its thickness. On the resulting photograph, four straight lines 90 mm long (equivalent to 1800 µm in the actual foam cross section) were drawn in such a way as to avoid voids, the number of cells intersected by each of the straight lines was determined for each of these lines, and the average cell diameter was taken as the value obtained by dividing the average value of the number of cells by 1800 μm.

[0070] Percentage of seepage area from surface material

After marking with a pen the area where the foamable phenolic resin composition leaked onto the top and bottom surface materials of the foamed phenolic resin laminate board, a 300 mm × 300 mm section of the foamed phenolic resin laminate board was photographed with a digital camera. After color tone correction, the number of pixels at the resin composition bleed-through and the number of pixels in a 300 mm × 300 mm area were counted by the pixel counting software, and the leakage area percentage was calculated using the following equation (1).

Percentage of the seepage area of the surface material (%)=(number of pixels in the seepage area/number of pixels in an area of 300 mm × 300 mm) × 100 (1)

[0071] 45° Peel Strength of Surface Material

The strength of the surface material of the foamed phenolic resin laminate board at 45° was calculated based on the measurements described below (see FIG. 1). First, the phenolic resin foam laminate board was cut into a width of 50 mm and a length of 120 mm (the length direction is the same as the direction of product movement), and one of the surface materials (a) and (b) located on the upper and lower surfaces, namely (b ), peeled off. Then, the phenolic resin foam laminate board, after peeling off the surface material (b), was cut in a direction parallel to the top and bottom surfaces, and as a result, a sample for evaluation 1 was prepared having a width of 50 mm, a length of 120 mm, and a thickness of 25 mm with the surface material (a ). Then, at a position of 20 mm from one end of the sample for evaluation 1 in the length direction, a cut was made with a cutter 20 mm deep in the thickness direction from the side without surface material (a). At the notching position, the base material 2 of the evaluation sample was carefully divided in the thickness direction. Meanwhile, care has been taken that no force in the length direction is applied to prevent peeling of the surface material (a) (corresponding to surface material 3 in Fig. 1) from the base material 2. Then, the portion of the evaluation specimen 1 in which the base metal was separated on the side where the base material was longer, was held by the clamp 7 at an angle of 45° to the horizontal plane, as shown in Fig. 1. Then, the container 6, connected by the metal wire 5, was installed at the end of the section on the side where the base material was shorter, using a paper clip 4. Thereafter, water was continuously supplied to the empty container 6 by means of a pump (not shown) at a rate of 100 g/min. The mass of water in the container 6 was measured when the surface material 3 was separated from the position of the notch by 50 mm in the direction of the length of the sample for evaluation 1. The same operation was performed twice, and the average value of the total mass of the clamp 4, metal wire 5, container 6 and water was taken as surface material strength (a) for peeling. In addition, an evaluation specimen having a surface material (b), a width of 50 mm, a length of 120 mm, and a thickness of 25 mm, was prepared separately, and the peel strength of the surface material (b) was obtained in the same manner as that of the surface material. material (a) for peeling. Then, the smaller of the peel strength values of the surface material (a) and the surface material (b) was taken as the 45° peel strength of the surface material (in g) of the phenolic foam laminate board.

[0072] Solid water content

The amount of water evaporated when heated to a temperature of 110°C was measured using a Karl-Fischer moisture meter having a boat-type evaporator.

[0073] Composition ratio of HCFO-1224yd(Z) and other blowing gas contained in the foam

Ten grams of the foam sample from which the surface material was removed, as well as the metal file, were placed in a 10 liter container (product name: Tedlar bag), sealed, and the container was filled with 5 liters of nitrogen. The sample was scraped off from all over bag of Tedlar with a file and finely chopped. Then the sample was placed in a thermostat, the temperature of which was brought to 81°C, for 10 min. 100 µl of the gas generated in the Tedlar bag was sampled, measured by GC/MS, and the type and compositional ratio of the generated gas component were analyzed. The type of gas was identified by retention time and mass spectrum. Separately, the detection sensitivity of the formed gas component was measured, and the composition ratio was calculated from the detection area of each gas component obtained by GC/MS and the detection sensitivity.

Measurement conditions with GC/MS

The GC/MS measurement was performed under the following conditions.

Gas chromatography: "Agilent 7890" from Agilent Technology Inc.

Column: DB-5MS (0.25 mm ϕ × 30 m, film thickness 1 µm)

Carrier Gas: Helium

Flow rate: 1 ml/min.

Inlet temperature: 150°C

Injection method: Crushing method (1:10)

Injection amount of sample: 1 µl of solution (for a gas sample, 100 µl is injected using a gas-tight syringe)

Column temperature: After 40°C (5 min), the temperature was increased to 150°C at a rate of 50°C/min and held for 4.8 min.

Mass spectrometric analysis: "Q1000GC" manufactured by JEOL Ltd.

Ionization method: Electron ionization (70 eV)

Scan range: m/Z=10-500

Voltage: -1300V

Ion source temperature: 230°C

Border temperature: 150°C

[0074] The content of HCFO-1224yd(Z) in foamed phenolic resin

A sample of phenolic resin foam laminate board was cut into approximately 100 mm squares and six test pieces were prepared. Then, six sealed heat-resistant zipper bags (hereinafter referred to as "zipper bags") were prepared, and the weight of each bag was measured using a precision balance. The samples were placed in an internal air circulation oven, in which the temperature was maintained at 70°C, for 24±0.5 hours in order to evaporate the moisture contained in them. The samples were then immediately placed in zippered bags, sealed, and cooled to room temperature. After cooling to room temperature, each sample was removed from the bag with a zipper. Then, the surface material of each sample was immediately separated, the mass (W1) of each sample was measured with a precision balance, and the length of each side was measured with a caliper to calculate the volume (V) of the sample. Each sample was then returned to the zippered bag, placed between the plates of the hydraulic press at room temperature, leaving the zipper of the bag partially open, and progressively compressed by the hydraulic press to a pressure of approximately 200 N/cm.²to destroy the cells in the sample. For three of these six samples, a portion of the sample was taken, the amount of moisture contained was measured using the method described above for measuring the amount of moisture in a solid, and the amount of moisture (WS1) averaged over three points was determined. The remaining three samples were left in the partially open bag. with a zipper and placed in an internal air circulation oven, in which the temperature was maintained at 81°C, for 30 ± 5 minutes. Immediately after this, the gas was released from the bag, preventing the powder from escaping from the bag, the bag was sealed and cooled to room temperature. After cooling to room temperature, the weight of the zipper bag containing the sample for which no moisture was measured was measured using a precision balance, the weight of the zipper bag was subtracted from it, and the weight (W2) with volatile components removed was measured in three points. At the same time, a part of the samples were taken from the bags of three samples, for which the water content was measured as described above, and the average water content (WS2) was determined for three points. In other words, the amount of moisture in the measurement of each of W1 and W2 in this test corresponds to WS1 and WS2 in Equation (2) shown below.

[0075] For the masses of HCFO-1224yd(Z) and other blowing gas in the foam, the mass of the volatile component (W3) was measured by subtracting the difference between WS1 and WS2 from the difference between W1 and W2 described above, and adding the mass of air buoyancy (WF). Air buoyancy mass (WF) was calculated by subtracting the resin volume from the volume (V) of the sample (volume of space in the foam), and using the air density (0.00119 g/ml), with the resin volume calculated from W2 and the density of the solid phenolic resin , and the density of the solid phenolic resin was taken to be 1.3 g/cm ³ , which is the well-known density of the phenolic resin. The resulting W3 value was multiplied by the measured ratio of HCFO-1224yd(Z) and other blowing gas components to calculate the mass (W4) of HCFO-1224yd(Z). W3 and WF are expressed by the following equations, respectively.

W3=(W1 - W2) - (WS1 - WS2) + WF (2)

WF=(V - W2/1.3) × 0.00119 (3)

The content (mol/22.4×10 ^-3 m ³ ) of HCFO-1224yd(Z) in the foam was calculated using the molecular weight of HCFO-1224yd(Z).

[0076] Thermal conductivity at 23°C

Thermal conductivity of the foamed phenolic resin laminate board in the thickness direction was measured at 23° C. by the following method according to JIS 1412-2:1999. Specific procedures are described below.

[0077] A 300 mm square was cut from a phenolic resin foam laminate board, the sample was placed in an atmosphere with a temperature of 23 ± 1°C and a humidity of 50 ± 2%, and its change in weight over time was measured every 24 hours. This continued until the change in weight was 0.2 mass% or less. A sample of the foamed phenolic resin laminate board in this state was placed in a thermal conductivity measuring device placed in an atmosphere with a temperature of 23±1°C and a humidity of 50±2%. If the thermal conductivity measuring device in which the foamed phenolic resin laminate board was placed was not located in a temperature controlled room of 23±1°C and a humidity of 50±2%, the sample, which was adjusted in the above atmosphere, was immediately placed in a polyethylene plastic bag. Then the bag was closed, the sample was taken out of the bag for one hour, and its thermal conductivity was immediately measured.

[0078] The thermal conductivity was measured using one sample and measuring device (EKO Instruments Co., Ltd.; product name: HC-074/FOX304) using the symmetrical configuration method. The thermal conductivity at 23°C was measured under conditions of a low temperature plate temperature of 13°C and a high temperature plate temperature of 33°C.

[0079] Example 2

The foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that the controlled temperature of the water in the distribution portion of the mixer was set to 16°C.

[0080] Example 3

A foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that the controlled temperature of the water in the distribution portion of the mixer was set to 28°C.

[0081] Example 4

A phenolic resin foamed laminate board was obtained in the same manner as in Example 1, except that phenolic resin B was used instead of phenolic resin A.

[0082] Example 5

A phenolic resin foam laminate board was obtained in the same manner as in Example 1, except that phenolic resin C was used instead of phenolic resin A.

[0083] Example 6

A foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that 7.6 m.h. a mixture of 65 wt.% HCFO-1224yd(Z) and 35 wt.% cyclopentane was added as a blowing agent, and 13.0 m.h. a composition consisting of a mixture of 80 wt.% xylene sulfonic acid and 20 wt.% diethylene glycol was added as an acid hardener.

[0084] Example 7

A foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that 7.7 m.h. a mixture of 40 wt.% HCFO-1224yd(Z) and 60 wt.% isopentane was added as a blowing agent, and 13.2 m.h. a composition consisting of a mixture of 80 wt.% xylene sulfonic acid and 20 wt.% diethylene glycol was added as an acid hardener.

[0085] Example 8

A foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that 8.3 m.h. a mixture of 40 wt.% HCFO-1224yd(Z) and 60 wt.% 2-chloropropane was added as a blowing agent, and 13.3 m.h. a composition consisting of a mixture of 80 wt.% xylene sulfonic acid and 20 wt.% diethylene glycol was added as an acid hardener.

[0086] Example 9

A foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that 9.7 m.h. a mixture of 40 wt.% HCFO-1224yd(Z), 35 wt.% HCFO-1233zd (E) and 25 wt.% cyclopentane was added as a blowing agent, and 13.5 m.h. a composition consisting of a mixture of 80 wt.% xylene sulfonic acid and 20 wt.% diethylene glycol was added as an acid hardener.

[0087] Example 10

A foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that 9.7 m.h. a mixture of 40 wt.% HCFO-1224yd(Z), 35 wt.% HCFO-1233zd (E) and 25 wt.% isopentane was added as a blowing agent, and 13.6 m.h. a composition consisting of a mixture of 80 wt.% xylene sulfonic acid and 20 wt.% diethylene glycol was added as an acid hardener.

[0088] Example 11

A phenolic resin foam laminate board was obtained in the same manner as in Example 1, except that 3.0 mass% of aluminum hydroxide powder (B-325 manufactured by TOMOE Engineering Co., Ltd., average particle size : 23.0 µm) was added as a solid foam nucleating agent to the phenolic resin composition.

[0089] Example 12

A foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that 7.9 m.h. a mixture of 85 wt.% HCFO-1224yd(Z) and 15 wt.% cyclopentane was added as a blowing agent, and 13.2 m.h. a composition consisting of a mixture of 80 wt.% xylene sulfonic acid and 20 wt.% diethylene glycol was added as an acid hardener.

[0090] Comparative Example 1

A foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that phenolic resin D was used instead of phenolic resin A.

[0091] Comparative Example 2

A foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that no solid foam nucleator was used, and nitrogen was added as a foam nucleating gas in an amount of 1 wt.% per 100 ppm. porophore.

[0092] Comparative Example 3

The foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that the controlled temperature of the water in the distribution portion of the mixer was set to 14°C.

[0093] Comparative Example 4

A foamed phenolic resin laminate board was obtained in the same manner as in Example 1, except that the controlled temperature of the water in the distribution portion of the mixer was set to 30°C.

[0094] Table 1 shows the production conditions specific to Examples 1-12 and Comparative Examples 1-4, as well as the performance evaluation results of the obtained foamed phenolic resin laminate boards.

[0095]

[Table 1] Phenolic resin Porofor The proportion of added HCFO1224yd (wt.%) Foam nucleator Temperature of the foaming phenolic resin composition thrown onto the bottom surface material (°C) Density (kg/ ^m3 ) Share of closed cells (%) Average cell diameter (µm) Percentage of seepage area from surface material (%) The content of HCFO-1224yd(Z) per 22.4×10 ^-3 m ³ in foamed phenolic resin (mol) Surface material peel strength at 45° (g) Thermal conductivity at 23°C (W/m⋅K) Example 1 A HCFO1224yd/cyclopentane 40 Foamed Phenolic Resin Powder 39 31 93 95 4 0.11 687 0.0177 Example 2 A HCFO1224yd/cyclopentane 40 Foamed Phenolic Resin Powder 35 29 94 90 29 0.35 992 0.0164 Example 3 A HCFO1224yd/cyclopentane 40 Foamed Phenolic Resin Powder 45 33 90 115 0 0.07 589 0.0185 Example 4 B HCFO1224yd/cyclopentane 40 Foamed Phenolic Resin Powder 44 32 91 107 0 0.07 612 0.0185 Example 5 C HCFO1224yd/cyclopentane 40 Foamed Phenolic Resin Powder 37 29 92 102 29 0.18 989 0.0174 Example 6 A HCFO1224yd/cyclopentane 65 Foamed Phenolic Resin Powder 36 29 94 89 26 0.17 936 0.0172 Example 7 A HCFO1224yd/isopentane 40 Foamed Phenolic Resin Powder 37 32 92 104 4 0.11 650 0.0180 Example 8 A HCFO1224yd/2-chloropropane 40 Foamed Phenolic Resin Powder 39 31 93 109 15 0.15 828 0.0176 Example 9 A HCFO1224yd/HFO1233zd/cyclopentane 40 Foamed Phenolic Resin Powder 39 31 94 95 28 0.20 989 0.0168 Example 10 A HCFO1224yd/HFO1233zd/isopentane 40 Foamed Phenolic Resin Powder 39 31 93 98 13 0.20 807 0.0171 Example 11 A HCFO1224yd/cyclopentane 40 Aluminum hydroxide powder 38 31 92 96 6 0.11 662 0.0177 Example 12 A HCFO1224yd/cyclopentane 85 Foamed Phenolic Resin Powder 38 32 94 91 29 0.22 965 0.0165 Comparative Example 1 D HCFO1224yd/cyclopentane 40 Foamed Phenolic Resin Powder 45 36 90 139 0 0.05 522 0.0190 Comparative Example 2 A HCFO1224yd/cyclopentane 40 Nitrogen 36 38 90 146 0 0.05 554 0.0193 Comparative Example 3 A HCFO1224yd/cyclopentane 40 Foamed Phenolic Resin Powder 34 28 93 90 31 0.36 1010 0.0164 Comparative Example 4 A HCFO1224yd/cyclopentane 40 Foamed Phenolic Resin Powder 46 40 84 151 0 0.05 534 0.0194

[0096] From Table 1 comparing the foamed phenolic resin laminate boards obtained in Comparative Examples 1-4 and the foamed phenolic resin laminate boards obtained in Examples 1-12, it can be seen that the foamed phenolic resin laminate boards obtained in Examples 1-12, can satisfactorily prevent seepage of the foaming resin composition onto the surface material of the laminate board while achieving low thermal conductivity without reducing the amount of blowing agent in the laminate board.

LIST OF REFERENCES

[0097] 1 - evaluation sample

2 - piece of sample foam for evaluation

3 - material of the lower surface of the sample for evaluation

4 - paper clip

5 - metal wire

6 - container

7 - clamp.

Claims (6)

1. A foamed phenolic resin laminate board in which a flexible surface material is located on at least one of two sides of the foamed phenolic resin, in which: the foamed phenolic resin contains HCFO-1224yd(Z) (Z-1-chloro-2,3 ,3,3-tetrafluoropropene) and has a density of not less than 20 kg/m ³ and not more than 55 kg/m ³ , the percentage of closed cells is not less than 80%, the average cell diameter is not less than 60 microns and not more than 200 microns, and the content of HCFO -1224yd(Z) (Z-1-chloro-2,3,3,3-tetrafluoropropene) in a volume of 22.4×10 ^-3 m ³ foamed phenolic resin is not less than 0.06 mol and not more than 0.35 mol . 2. The phenolic resin foam laminate board according to claim 1, wherein the seepage area ratio of the surface material is 30% or less. 3. Phenolic resin foam laminate board according to claim 1 or 2, comprising at least one gas component selected from an aliphatic hydrocarbon having a carbon number of 6 or less and a chlorinated saturated hydrocarbon having a carbon number of 5 or less. 4. Laminate board made of foamed phenolic resin according to any one of paragraphs. 1-3, wherein the surface material is any of nonwoven fabric, fabric, and paper. 5. Laminate board made of foamed phenolic resin according to any one of paragraphs. 1-4, wherein the 45° peel strength of the surface material is 1000 g or less. 6. Laminate board made of foamed phenolic resin according to any one of paragraphs. 1-5, in which the thermal conductivity at 23°C is 0.0185 W/m⋅K or less.

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