RU2792103C1 - Laminated board and composite board from foamed phenolic resin - Google Patents

Abstract

FIELD: heat-insulating composite materials.

SUBSTANCE: invention relates to a laminated board made of foamed phenolic resin. In the board, the surface material is located on at least one side of the foamed phenolic resin and on the back side of one side. The foamed phenolic resin has a density of not less than 22 kg/m³ and not more than 50 kg/m³, a cell diameter of not less than 50 mcm and not more than 170 mcm, and a percentage of closed cells of not less than 80%. When HCFO-1224yd (Z) ((Z)-1-chloro-2,3,3,3-tetrafluoropropene), aliphatic hydrocarbons with carbons of 6 or less, chlorinated saturated hydrocarbons with carbons of 5 or less and hydrofluoroolefins are gas components, the foamed phenolic resin only contains HCFO-1224yd(Z) as the gas component. The internal pressure of the air bubble in the cell is 0.20 atm or more.

EFFECT: obtaining a laminated board from a foamed phenolic resin, which has thermal conductivity and, at the same time, sufficient surface smoothness.

11 cl, 1 dwg, 3 tbl, 13 ex

Description

CROSS REFERENCES TO RELATED APPLICATIONS

[0001] This application claims priority to Japanese Patent Application No. 2020-005370, filed January 16, 2020, the entire disclosure of which is incorporated herein by reference.

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

[0002] The present disclosure relates to a phenolic resin foam laminate board.

BACKGROUND OF THE INVENTION

[0003] Foamed phenolic resin has high thermal insulation properties, fire resistance and heat resistance among foam thermal insulation materials, and in particular, in order to ensure easy handling during installation, foamed phenolic resin laminate boards with a surface material directly laminated on the surface are known.

[0004] The recent increase in demand for thermal insulation in buildings has resulted in a demand for even higher thermal insulation phenolic resin foam laminate boards, and there is a need for technology to apply HCFO-1224yd(Z) (chemical name: (Z)-1-chlorine -2,3,3,3-tetrafluoropropene), which has a particularly low thermal conductivity as a blowing agent, for phenolic resin foam laminate boards.

[0005] Patent Document (PTL) 1 discloses that a combination of HCFO-1224yd (Z) and other blowing agents can be used for foamed phenolic resin.

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

LIST OF CITATIONS

PATENT LITERATURE

[0007] Patent Document 1: WO2019/036049 (A1)

Patent Document 2: JP2015105343 (A)

SUMMARY OF THE INVENTION

TECHNICAL PROBLEM

[0008] However, HCFO-1224yd (Z) has a relatively low solubility in resole-type phenolics among many hydrofluoroolefins, and moreover has a higher volume per substance compared to blowing agents such as 2-chloropropane and cyclopentane. Therefore, HCFO-1224yd(Z) is difficult to disperse in a resole-type phenolic resin.

[0009] When the required molar amount of HCFO-1224yd (Z) is dispersed in a resole-type phenolic resin, it takes time to disperse, and furthermore, it needs to be recovered as a foaming phenolic resin composition on the surface material in a state in which the dispersion is insufficient . In addition, since HCFO-1224yd(Z) has a lower boiling point than HCFO-1233zd(E) and HFO-1336mzz(Z), if dispersion remains insufficient, HCFO-1224yd(Z) will easily disperse before the resole phenolic resin is cured. type. It was found that since the content of HCFO-1224yd (Z) in the phenolic resin decreased as a result, it was difficult to obtain sufficient internal pressure in the cell while increasing the foaming ratio.

[0010] Therefore, when HCFO-1224yd (Z) is applied with a phenolic resin, the internal pressure preventing curing shrinkage at the manufacturing stage cannot be achieved, and the foamed phenolic resin part is more likely to shrink than the surface material laminated on surfaces. As a result, there is a problem specific to HCFO-1224yd (Z) in that wrinkles may occur on the surface material and it is difficult to obtain sufficient smoothness as a phenolic resin foam laminate board.

[0011] When wrinkles occur on the surface material, the smoothness of the surface material of the phenolic foam laminated board deteriorates and workability deteriorates. Thus, in a phenolic resin foam laminate board using HCFO-1224yd(Z), both high thermal insulation and wrinkle suppression are required.

[0012] The present inventors have found a way to have HCFO-1224yd (Z) under high pressure in the bubbles of a foamed phenolic resin laminate board, that is, a way to disperse HCFO-1224yd (Z), which has a large volume per amount of substance, in a phenolic resin into the target amount and more uniformly, and thus solved the above problem.

SOLUTION

[0013] In particular, the present invention provides the following:

[1]

Phenolic resin foam laminated board, where the surface material is located on at least one of the sides of the foamed phenolic resin and on the back side of one side, in which: the foamed phenolic resin has a density of not less than 22 kg/m ³ and not more than 50 kg/ m ³ , the cell diameter is not less than 50 microns and not more than 170 microns, and the proportion of closed cells is not less than 80%; when HCFO-1224yd (Z), aliphatic hydrocarbons with carbons of 6 or less, chlorinated saturated hydrocarbons with carbons of 5 or less, and hydrofluoroolefin are gas components, only HCFO-1224yd (Z) is contained as a gas component; and the internal pressure of the air bubble in the cell is 0.20 atm or more.

[2]

Phenolic resin foam laminated board, where the surface material is located on at least one of the sides of the foamed phenolic resin and on the back side of one side, in which: the foamed phenolic resin has a density of not less than 22 kg/m ³ and not more than 50 kg/ m ³ , the cell diameter is not less than 50 microns and not more than 170 microns, and the proportion of closed cells is not less than 80%, and contains at least one gas component selected from HCFO-1224yd (Z), aliphatic hydrocarbons with a carbon number of 6 or less, chlorinated saturated hydrocarbons with a carbon number of 5 or less and hydrofluoroolefin; 20 wt.% or more of the total amount of the gas component is HCFO-1224yd (Z); and the internal pressure of the air bubble in the cell is 0.20 atm or more.

[3]

Phenolic resin foam laminated board according to [1] or [2], in which the cell internal pressure is 0.26 atm or more.

[4]

Phenolic resin foam laminated board according to any one of paragraphs. [1] to [3], in which the compressive modulus of a part of the surface layer is 4.9 MPa or more.

[5]

Phenolic resin foam laminated board according to any one of paragraphs. [1] - [4], in which the foamed phenolic resin contains 3.0 vol.% or less air.

[6]

Phenolic resin foam laminated board according to any one of paragraphs. [1] to [5], in which the thermal conductivity at 23°C is 0.0180 W/(m·K) or less.

[7]

Phenolic resin foam laminated board according to any one of paragraphs. [1] to [5], in which the thermal conductivity at 23°C is 0.0159 W/(m·K) or less.

[8]

Phenolic resin foam laminated board according to any one of paragraphs. [1] to [7], in which the thermal conductivity at 10°C is 0.0164 W/(m·K) or less.

[9]

A composite board made by coating a laminated board with foamed phenolic resin according to any one of paragraphs. [1] - [8] external element.

BENEFICIAL EFFECT

[0014] According to the present invention, a high performance phenolic resin foam laminated board having high thermal insulation performance, fewer wrinkles on the surface material, and good smoothness on the surface of the surface material can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In the accompanying drawings:

Fig. 1 is a perspective view of a phenolic resin foam laminated board according to the present embodiment.

DETAILED DESCRIPTION

[0016] The following is a detailed description of one embodiment of the present disclosure (hereinafter also referred to as "the present embodiment").

[0017] The foamed phenolic resin laminated board of the present embodiment is a foamed phenolic resin laminated board with a surface material disposed on at least one of the top and bottom surfaces of the foamed phenolic resin. The smoothness of the surface on which the surface material is placed is 0.80 mm or less. The surface smoothness is preferably 0.70 mm or less, more preferably 0.50 mm or less, even more preferably 0.41 mm or less, particularly preferably 0.37 mm or less, and most preferably 0.33 mm or less. When the surface smoothness is 0.80 mm or less, the surface has less unevenness, and sufficient machinability can be easily obtained.

[0018] FIG. 1 is a perspective view of a phenolic resin foam laminated board of the present embodiment. As illustrated in FIG. 1, the phenolic resin foam laminated board 10 includes a phenolic resin foam 1 and a flexible surface material 2. Although the flexible surface material 2 is attached to at least one of the six sides of the phenolic foam plate 1 as a core material and to the reverse side, usually it is attached to the main surface of foamed phenolic resin 1. The main surface is the widest surface. In the present embodiment, each flexible surface material 2 is attached to both main surfaces. Each flexible surface material 2 is often attached by impregnating the surface material 2 with a part of the resin constituting the foamed phenolic resin 1.

[0019] The foamed phenolic resin laminated board of the present embodiment is produced by adding a surfactant to a "phenolic resin" to obtain a "phenolic resin composition", further adding a blowing agent and a curing agent including an organic acid to obtain a "foaming phenolic resin composition" capable of foaming and curing, loading the "foaming phenolic resin composition" into the mixer, withdrawing the "foaming phenolic resin composition" from the mixer after mixing it onto the surface material, and then performing foaming and curing of the "foaming phenolic resin composition" by heating.

[0020] Phenolic resin is a resole-type phenolic resin obtained by heating phenols and aldehydes in the temperature range of 40°C to 100°C in the presence of an alkali metal hydroxide or an alkaline earth metal hydroxide to synthesize a phenolic resin. The molar ratio in which phenols and aldehydes are used 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.

[0021] Examples of phenols that can preferably be used in the synthesis of a phenol resin include, in addition to phenol, resorcinol, catechol, o-, m-, and p-cresol, xylenols, ethylphenols, p-tert-butylphenol, etc. P. In addition, binuclear phenols can also be used.

[0022] Examples of aldehydes that can be preferably used in the synthesis of a phenolic resin include, in addition to formaldehyde, glyoxal, acetaldehyde, chloral, furfural, benzaldehyde, and the like, and derivatives of any of these aldehydes can also be used.

[0023] An additive such as urea, dicyandiamide, or melamine can be added to the resole-type phenolic resin during synthesis or after synthesis as needed. 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.

[0024] Since the resole-type phenolic resin obtained after synthesis usually contains an excess of water, the resole-type phenolic resin is dehydrated to obtain a viscosity suitable for foaming.

[0025] The water content of the phenolic resin is preferably not less than 2.0 mass% and not more than 20 mass%, more preferably not less than 2.0 mass% and not more than 15 mass%, even more preferably not less than 2 .0 wt.% and not more than 9 wt.%, particularly preferably not less than 3.0 wt.% and not more than 8 wt.%, and most preferably not less than 3.0 wt.% and not more than 7 wt.%. In order to make the water content of the phenol resin less than 2.0 mass%, a large amount of energy and time is required for dehydration, so a content of 2.0 mass% or more is preferable in terms of performance, and 20 mass% or less is preferred in terms of sufficient dispersion of HCFO-1224yd(Z).

[0026] Various types of additives such as an aliphatic hydrocarbon, a high boiling alicyclic hydrocarbon or a mixture thereof, viscosity adjusting diluents such as ethylene glycol or diethylene glycol or a phthalic acid compound and the like can be added to the phenolic resin as needed. The viscosity of the phenolic resin and the phenolic resin composition at 40° C. is preferably not less than 5000 mPa·s and not more than 25000 mPa·s.

[0027] Nonionic surfactants are effective as a surfactant added to a phenol resin, and preferred examples thereof include alkylene oxide, which is a copolymer of ethylene oxide and propylene oxide, an alkylene oxide-castor oil condensate, a condensation product of alkylene oxide and alkylphenol such such as nonylphenol or dodecylphenol, polyethylene oxide alkyl ester in which part of the alkyl ether has a number of carbon atoms from 14 to 22, fatty acid ester such as polyethylene oxide fatty acid ester, silicone compound such as polydimethylsiloxane, block copolymer of dimethylpolysiloxane and polyester and polyalcohol. These surfactants may be used alone or in combination of two or more of them.

[0028] The amount of surfactant that is used per 100 m.h. phenolic resin, preferably at least 0.3 m.h. and not more than 10 m.h.

[0029] The phenolic resin composition is preferably maintained for 1 hour or more under reduced pressure conditions of 15-40°C and 25-50 kPa absolute, more preferably 2 hours or more, in the step immediately before mixing with the blowing agent. Within the above-described range, defoaming can be carried out while avoiding boiling water, and air mixed with stirring the phenolic resin can be removed. As a result, the amount of air contained in the bubbles can be reduced and the thermal conductivity can be lowered.

[0030] It is preferable to mix the surfactant mixed with the blowing agent with the phenolic resin composition separately from the surfactant that is directly miscible with the phenolic resin.

[0031] The surfactant miscible with the blowing agent preferably has an HLB of 14 or less. In addition, the addition amount is preferably 70 mass% or less of the surfactant directly mixed with the phenolic resin, and preferably 1 part or more per 100 ppm. blowing agent. Within the above-described range, phase transfer emulsification from W/O emulsion to O/W emulsion promotes a fine and uniform dispersion state, whereby diffusion of HCFO-1224yd (Z) is suppressed and the internal pressure can be increased. In addition, since the generation of voids due to the coagulation of the blowing agent is suppressed, the compression modulus of a part of the surface layer of the subsequently obtained foamed phenolic resin can be increased.

[0032] The foamed phenolic resin of the present embodiment contains a blowing agent in which 20 wt.% or more of the blowing agent is HCFO-1224yd (Z), preferably 40 wt.% or more, more preferably 50 wt.% or more, even more preferably 64 wt.% or more, and most preferably 72 wt.% or more.

[0033] Since HCFO-1224yd (Z) has a low thermal conductivity among various HCFOs, the ratio of the components of HCFO-1224yd (Z) in the blowing agent affects the thermal insulation performance. In addition, since HCFO-1224yd (Z) has a low solubility in phenolic resin among various HCFOs, the hydrophobicity of the foam increases, and a decrease in the reaction rate of the resin due to water becomes unlikely. Therefore, when 20% by mass or more of the blowing agent is HCFO-1224yd (Z), the thermal insulation performance improves and the compressive modulus of the surface layer part improves.

[0034] In addition, as a blowing agent, HCFO-1224yd (Z) can be combined with other hydrofluoroolefins, hydrocarbons and chlorinated hydrocarbons.

[0035] The hydrocarbon is preferably a cyclic or chain alkane, alkene or alkine of 3 to 7 carbon atoms, and specific examples thereof include n-butane, isobutane, cyclobutane, n-pentane, isopentane, cyclopentane, neopentane, n -hexane, isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, and the like. Of these hydrocarbons, pentanes such as n-pentane, isopentane, cyclopentane and neopentane, and butanes such as n-butane, isobutane and cyclobutane can be suitably used.

[0036] Other hydrofluoroolefins include chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins.

[0037] Examples of chlorinated hydrofluoroolefins 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) from 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), etc., as well as their configurational isomers, that is, one of E and Z or a mixture of them is used. In addition to this, (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd (E)) is included.

[0038] 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 have Opteon ^TM 1100 manufactured by 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.

[0039] As the chlorinated hydrocarbon, linear or branched chlorinated aliphatic hydrocarbons having the number of carbon atoms from 2 to 5 can be preferably used. The number of bonded chlorine atoms is preferably 1-4. For example, dichloroethane, propyl chloride, 2-chloropropane, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, and the like are preferred. Of these chlorinated hydrocarbons, propyl chloride and 2-chloropropane, which are chloropropanes, are more preferably used.

[0040] It should be noted that HCFO-1224yd (Z) can be used alone or in combination with one or more types of the above blowing agent. The blowing agent that is combined with HCFO-1224yd (Z) is preferably HCFO-1233zd (E), cyclopentane, isopentane, and 2-chloropropane, more preferably cyclopentane or isopentane, and even more preferably cyclopentane. These blowing agents have a higher boiling point than HCFO-1224yd(Z) and are less likely to affect the dispersion state of HCFO-1224yd(Z) than other blowing agents. Thus, they tend to suppress the reduction in internal pressure when using HCFO-1224yd (Z).

[0041] Another foamed phenolic resin of the present embodiment contains only HCFO-1224yd (Z) as a gas component when HCFO-1224yd (Z), an aliphatic hydrocarbon of 6 carbon atoms or less, a chlorinated saturated hydrocarbon of 5 carbon atoms or less and hydrofluoroolefin are the gas component.

[0042] Here, the gas component is HCFO-1224yd (Z), aliphatic hydrocarbons with carbons of 6 or less, chlorinated saturated hydrocarbons with carbons of 5 or less, and hydrofluoroolefins analyzed by gas chromatography/mass spectrometry (GC /MS) relative to the foamed phenolic resin.

[0043] When HCFO-1224yd (Z) is mixed with the phenolic resin composition, it is preferably mixed under pressure and pre-kneaded at 30-55°C before mixing with the curing catalyst. When mixed under pressure, HCFO-1224yd (Z) can be dispersed as a liquid even at elevated temperatures.

[0044] When stirred at a temperature of 30°C or higher, the solubility of HCFO-1224yd (Z) in the phenolic resin may increase, and the viscosity of the phenolic resin composition may decrease. As a result, it is possible to form a dispersed state in advance before mixing with the curing catalyst, dispersion of HCFO-1224yd (Z) can be suppressed, and the internal pressure can be easily increased. In contrast, temperatures above 55°C make it difficult to cool when mixed with a curing catalyst, and HCFO-1224yd (Z) dissipates, which tends to cause a decrease in internal pressure.

[0045] In the present embodiment, a foam nucleator may be used in the manufacture of a phenolic resin foam laminated board. As the foam nucleating agent, a gaseous foam nucleating agent such as a low boiling point substance (eg, nitrogen, helium, argon, etc.) whose boiling point is at least 50° C. lower than that of the blowing agent can be added. In addition, a solid foam nucleating agent such as an 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) can be added. , glass beads, fly ash, microsilica, gypsum powder, borax, slag powder, alumina cement or Portland cement) or organic powder (for example, crushed foamed phenolic resin powder). These foam nucleators can be used alone or in combination of two or more types without distinction between gases and solids. The addition time of the foam nucleating agent can be freely set as long as the foam nucleating agent is supplied to a mixer in which the foaming phenolic resin composition is mixed.

[0046] The amount of gaseous foam nucleating agent added relative to the blowing agent is preferably not less than 0.1 mass% and not more than 1.0 mass%, and more preferably not less than 0.1 mass% and not more than 0.5 mass% when the amount of blowing agent is taken as 100 wt.%. In addition, the amount of solid foam nucleating agent added per 100 m.h. in the amount of phenolic resin and surfactant 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.

[0047] The curing catalyst that is added to the phenolic resin composition is preferably a curing catalyst that includes an organic acid as an acid component. The organic acid is preferably an arylsulfonic acid or its anhydride. Examples of arylsulfonic acids and their anhydrides include toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, substituted phenol sulfonic acid, xylenolsulfonic acid, substituted xylenolsulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, etc., 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.

[0048] The amount of curing catalyst used differs depending on the type of curing catalyst. When a mixture of 60 wt.% p-toluenesulfonic acid monohydrate and 40 wt.% diethylene glycol is used, it is preferably used in an amount of at least 8 ppm. and not more than 20 m.h., and more preferably not less than 10 m.h. and not more than 15 m.h. per 100 m.h. total phenolic resin and surfactant.

[0049] It should be noted that the surfactant and blowing agent contained in the foaming composition of the phenolic resin may be added to the phenolic resin in advance, or may be added to the phenolic resin at the same time as the curing catalyst.

[0050] In the foamed phenolic resin of the present embodiment, the internal pressure of the blowing agent component in the cell is 0.20 atm (20.3 kPa) or more, preferably 0.23 atm (23.3 kPa) or more, more preferably 0.26 atm (26.3 kPa) or more, even more preferably 0.30 atm (30.4 kPa) or more, and most preferably 0.35 atm (35.5 kPa) or more. It should be noted that the internal pressure in the cell is the internal pressure of the bubbles of the foamed phenolic resin. The internal pressure of the blowing agent component in the cell affects the shrinkage force inside the foam and the ratio of gas to nitrogen and oxygen in the bubbles. The foamed phenolic resin laminated board is heated and cured to improve the strength of the product, but during curing, the resin softens due to high temperature and shrinks due to curing at the same time, so if the internal pressure of the cell is low, the foamed phenolic resin will shrink, and wrinkles may occur on the surface material located on the surface. When the internal pressure of the blowing agent component in the cell is 0.20 atm (20.3 kPa) or more, the shrinkage force inside the foam is weakened, wrinkling is suppressed, and the surface smoothness is improved. In addition, since the content of mixed oxygen and nitrogen is reduced, the thermal insulation performance is improved.

[0051] In order to increase the internal pressure of the blowing agent component in the cell, the increase in the volume of blowing agent due to the increase in temperature is suppressed, and instead, the amount of blowing agent remaining in the bubbles is increased to obtain the desired foam density. In particular, the internal pressure of the blowing agent component in the cell can be increased, firstly, by suppressing the diffusion of the blowing agent to increase the residual velocity of the blowing agent when a large amount of blowing agent is added, and secondly, by lowering the temperature of the foaming phenolic resin composition to suppress the vapor pressure in the calculation on the amount of blowing agent.

[0052] As a method for suppressing diffusion of the blowing agent, the blowing agent can be uniformly dispersed in the phenolic resin composition. In particular, in order to uniformly disperse HCFO-1224yd (Z), the foaming phenolic resin composition is mixed at two-stage temperature, that is, the blowing agent and surfactant are pre-mixed and then added to the phenolic resin composition.

[0053] As a method for lowering the temperature of the foaming phenolic resin composition, any of the following methods can be used: a method for lowering the temperature of the main molding step, which is the main step of the foaming and curing reactions; a method of reducing the heat of reaction of the phenolic resin per hour by increasing the residence time in the preforming stage when foaming and curing the foamable phenolic resin composition, which is extracted onto the surface material when it is coated with the surface material from above; a method for reducing the amount of added organic acid used as a curing catalyst; and a method for increasing the molecular weight of the phenolic resin to reduce the heat of reaction.

[0054] In the foamed phenolic resin of the present embodiment, the amount of air contained in the bubbles is preferably 3.0 vol% or less, more preferably 2.2 vol% or less, even more preferably 1.5 vol% or less , and most preferably 0.9 vol.% or less. Examples of the air reduction method include a method in which the phenolic resin composition is stored in a reduced pressure tank and the foam is removed. Air is mixed in while feeding and stirring the phenolic resin and is present inside in the form of small bubbles due to the high viscosity of the phenolic resin. Air is typically the starting point for voids and has a higher thermal conductivity than blowing agents, which can degrade thermal insulation performance. When the amount of air is 3.0 vol% or less, the amount of air with respect to the content of blowing agent is reduced, and as a result, excellent thermal insulation performance can be easily obtained.

[0055] The density of the foamed phenolic resin of the present embodiment is not less than 22 kg/m ³ and not more than 50 kg/m ³ , preferably not less than 22 kg/m ³ and not more than 41 kg/m ³ , and more preferably not less than 22 kg / m ³ and not more than 34 kg / m ³ . When the density is 22 kg/m ³ or more, it is possible to secure mechanical strength such as compressive strength and bending strength and avoid damage when handling the foam. In addition, when the density is 22 kg/m ³ or more, the compressive modulus of a portion of the surface layer may increase. In contrast, when the density is 50 kg/m ³ or less, it is unlikely that the heat transfer of a portion of the resin will increase, and thus the thermal insulation performance can be maintained.

[0056] The density can be adjusted to a desired value by changing the proportion of the blowing agent, the temperature of the foaming phenolic resin composition, selecting the preforming time at the stage of ejecting the mixed foaming phenolic resin composition onto the surface material, the ratio between the added amount of blowing agent and the added amount of organic acid, and the conditions curing, such as temperature and residence time, and the like.

[0057] The average cell diameter of the foamed phenolic resin of the present embodiment is not less than 50 µm and not more than 170 µm, preferably not less than 50 µm and not more than 150 µm, more preferably not less than 50 µm and not more than 130 µm, even more preferably not less than 50 µm and not more than 130 µm. less than 50 µm and not more than 110 µm, and most preferably not less than 50 µm and not more than 100 µm. When the average cell diameter is 50 µm or more, the bubble wall does not become too thin, and deterioration in strength due to deformation can be suppressed. In addition, when the average cell diameter is within 170 µm, heat conduction by radiation can be suppressed. The average cell diameter can be adjusted to the desired value by adjusting the reactivity and temperature of the phenolic resin, as well as by changing the added amount of foam nucleating agent, the ratio of the added amount of blowing agent and the added amount of organic acid used as a curing catalyst, and curing conditions such as temperature etc. .

[0058] The closed cell ratio of the foamed phenolic resin of the present embodiment is 80% or more, preferably 90% or more, and more preferably 95% or more. When the closed cell ratio is 80% or more, the reduction in thermal insulation performance due to diffusion of the blowing agent in the foamed phenolic resin caused by pressurization under high ambient temperature conditions during production can be easily suppressed.

[0059] It should be noted that the percentage of closed cells of the foamed phenolic resin can be adjusted to the desired value by adjusting the reactivity and temperature of the phenolic resin, as well as by changing the ratio of the amount of added blowing agent and the amount of added organic acid used as a curing catalyst, as well as curing conditions.

[0060] In the foamed phenolic resin of the present embodiment, the compressive modulus of the surface layer portion is preferably 4.9 MPa or more, more preferably 5.2 MPa or more, even more preferably 5.5 MPa or more, particularly preferably 5.8 MPa or more, and most preferably 6.0 MPa or more. Because part of the surface layer has a high resin density, the curing shrinkage tends to be smaller than that of the core layer. Therefore, with respect to the curing process of a part of the surface layer, there is an advantage that the shrinkage on the surface caused by curing can be suppressed by the shrinkage force of the inner layer, which is larger than the shrinkage caused by curing. In addition, the part of the surface layer is the part that directly contacts the surface material, and thus the part that determines the final smoothness of the surface. Therefore, when the compressive modulus of a part of the surface layer is 4.9 MPa or more, the formation of wrinkles on the surface material due to shrinkage of the foam is suppressed, and the smoothness of the surface is improved.

[0061] The compressive modulus of a portion of the surface layer increases with the progress of curing and, for example, can be increased by adding heating conditions at the beginning of the post-cure stage at a temperature higher than the temperature after it, for not less than 5 minutes and not more than 40 minutes , and for half or less of the time of the entire post-cure stage. In addition, the compressive modulus of a part of the surface layer can be increased by suppressing the diffusion of the HCFO-1224yd (Z) component and compacting the bubble structure of the surface layer. Diffusion of the HCFO-1224yd(Z) component can be suppressed by evenly dispersing HCFO-1224yd(Z) in the phenolic resin composition.

[0062] The foamed phenolic resin of the present embodiment preferably has a thermal conductivity of 0.0180 W/(m×K) or less at 23°C. The thermal conductivity is more preferably 0.0174 W/(m×K) or less, even more preferably 0.0164 W/(m×K) or less, and most preferably 0.0159 W/(m×K) or less.

[0063] The foamed phenolic resin of the present embodiment preferably has a thermal conductivity of 0.0164 W/(m×K) or less at 10°C. The thermal conductivity is more preferably 0.0160 W/(m×K) or less, even more preferably 0.0157 W/(m×K) or less, and most preferably 0.0155 W/(m×K) or less.

[0064] The thermal conductivity can be controlled, for example, by the composition of the phenolic resin, the amount of air contained, the viscosity, the type and ratio of blowing agent, the ratio of bubble nucleating agent, curing conditions, foaming conditions, and the like.

[0065] The phenolic resin foam laminated board of the present embodiment can be used alone, and furthermore, can be used in various applications as a composite board coated with an external member. Examples of external elements include at least one of board materials and sheet/film materials, as well as a combination of both. 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. 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 moisture barrier film , asphalt concrete waterproof paper and aluminum foil (with or without holes).

[0066] The following describes in detail a method for manufacturing a laminated board from the foamed phenolic resin set forth above.

[0067] The production method of foamed phenolic resin laminated board may be a continuous production method, which includes: the step of mixing a foaming phenolic resin composition that contains a phenolic resin, a surfactant, a blowing agent, and a curing catalyst containing an organic acid, with using a mixer; a step of extracting the mixed foaming phenolic resin composition onto the surface material; a step of performing preforming when coating the foamable phenolic resin composition that has been taken out onto the surface material with the surface material on top, and performing foaming and curing of the foamable phenolic resin composition; a main molding step which is a main step of performing a foaming and curing reaction; and a post-curing step that allows water to be dispersed in the phenolic resin composition.

[0068] The methods of preforming and main shaping in the preforming step and the main shaping step, respectively, of the continuous production process may be any of various methods depending on production purposes, and examples thereof include the method of using a double plate conveyor, the method of using metal roll or steel plate, as well as a combination of many of these methods. When molding using double plate conveyor, for example, the foaming phenolic resin composition, which is coated with upper and lower surface materials, is continuously sent to the double plate conveyor, pressure is sequentially applied from above and below when heated, and foaming and curing are carried out when adjusting to a certain thickness. to make it possible to form a sheet mold.

[0069] The surface materials provided on at least the top and bottom surfaces of the foamed phenolic resin may be 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. In addition, these surface materials can be mixed (or stacked) for use.

[0070] Conditions for controlling the heating temperature in the preforming step are as follows: the ambient temperature is lower than that in the main molding step by 4-12°C, and the residence time in the preforming step is 10 minutes or more. The heat of reaction of the phenolic resin can be dissipated by heating under these conditions before the main molding step, and the temperature rise of the foaming phenolic resin composition can be suppressed during the main molding step. Thus, the internal pressure of the blowing agent component in the cell can be increased. When the temperature is higher than the temperature which is 4° C. lower than the temperature of the main molding step, foaming occurs rapidly and the cell diameter increases, with the result that thermal conductivity tends to deteriorate. When the temperature is lower than the temperature of the main molding stage by more than 12°C, or the residence time is less than 10 minutes, the heat of reaction cannot be dissipated in terms of time, the temperature of the foaming phenolic resin composition rises too much in the main molding stage, and the internal pressure of the component porogen in the cell is reduced. As a result, wrinkles may appear on the surface, and the smoothness of the surface tends to decrease.

[0071] The heating temperature control condition of the main molding step following the preforming step is preferably not lower than 60°C and not higher than 80°C, and more preferably not lower than 60°C and not higher than 75°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.

[0072] The heating temperature in the main molding step affects the temperature of the foaming phenolic resin composition, and when this temperature is high, the internal pressure of the blowing agent component in the cell tends to be low. When the heating temperature in the main molding step is 80° C. or less, the vapor pressure of the blowing agent and water is suppressed, and the internal pressure of the cell tends to increase. In addition, when it is 60° C. or more, the curing of the phenolic resin is accelerated, and thus diffusion of the blowing agent tends to be suppressed.

[0073] The post-curing step is performed after the pre-molding step and the main shaping step. To prevent the foam from bursting due to the vapors inside the foam, post-curing heating is performed in two stages. It is preferable that in the first stage the foam is heated at a temperature not lower than 140°C and not higher than 150°C for not less than 5 minutes and not more than 40 minutes and not more than half of the total time of the post-curing stage. Further, in the second step, it is preferable that the foam is heated at a temperature not lower than 90°C and not higher than 120°C. When the temperature in the second stage exceeds 120° C., as in the first stage, the water vapor inside the foam tends to cause the foam to break, and at temperatures below 90° C., the time required for the reaction of the phenolic resin tends to be too long.

EXAMPLES

[0074] 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.

[0075] <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. Then, a 48 mass% aqueous sodium hydroxide solution was added until the pH reached 8.7, and then heating was carried out to 85°C to carry out the reaction. When the Ostwald viscosity of the reaction liquid reached 120 square millimeters per second (=120 mm ² /s; measurement value at 25° C.), the reaction liquid was cooled, and urea was added so that its content in the phenol resin was 4.6 wt %. %. 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 6.3. The resulting reaction liquid was then concentrated using a thin film evaporator, and the viscosity and moisture percentage were measured in the following way. As a result, a phenolic resin with a viscosity of 11,500 mPa.s at 40°C and a moisture content of 8.5% was obtained, which was phenolic resin A.

[0076] <Synthesis of Phenolic Resin B>

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. Then, a 48 mass% aqueous sodium hydroxide solution was added until the pH reached 8.7, and then heating was carried out to 85°C to carry out the reaction. When the Ostwald viscosity of the reaction liquid reached 80 square millimeters per second (=80 mm ² /s; measurement value at 25° C.), urea was added while cooling the reaction liquid so that its content in the phenol resin was 4.6 mass% . 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 6.3. The resulting reaction liquid was then concentrated using a thin film evaporator, and the viscosity and moisture percentage were measured in the following way. As a result, a phenolic resin with a viscosity of 12,000 mPa.s at 40°C and a moisture content of 6.9% was obtained, which was the phenolic resin B.

[0077] <Moisture Percentage of Phenolic Resin>

Moisture Percentage of Phenolic Resin Material

The phenolic resin material was dissolved in the range of 3-7 mass% in dehydrated methanol (manufactured by Kanto Chemical Co., Inc.) whose moisture content was measured, and the water content of the phenolic resin material was determined by subtracting the water content of the dehydrated methanol from the water content of the solution. The moisture percentage of the phenolic resin material was calculated based on the measured moisture content. The measurement was performed using a Karl-Fischer moisture meter (MKC-510 manufactured by Kyoto Electronics Manufacturing Co., Ltd.). HYDRANAL-Composite 5K from Sigma-Aldrich was used as a Karl-Fischer reagent for water measurement, and HAYASHI-Solvent CE dehydrating solvent (for ketones) from Hayashi Pure Chemical Industry was used for Karl-Fischer titration. In addition, the standard water/methanol solution AQUAMICRON (2 mg water) manufactured by Mitsubishi Chemical Co. was used to measure the titer of the Karl-Fischer reagent. The water content was measured using Method 1 installed in the device, and the Karl-Fischer reagent titer was determined using Method 5. The ratio of the obtained water content to the weight of the phenolic resin material was determined, and this ratio was used as the percent moisture content of the phenolic resin material.

[0078] <Viscosity measurement>

The viscosity of the phenolic resin 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.

[0079] (Example 1)

<Production of Phenolic Resin Foam Laminated Board>

The phenolic resin composition was obtained by mixing Pluronic® F-127 block copolymer of ethylene oxide and propylene oxide as a surfactant in a proportion of 2.0 ppm. per 100 m.h. phenolic resin A. As a blowing agent for 100 m.h. phenolic resin was added to 12.1 m.h. a mixture of 34 wt.% HCFO 1224yd (Z), 62 wt.% HCFO-1233 zd (E) and 4 wt.% isobutane, then the first stage of mixing was carried out at an ambient temperature of 40°C and a pressure of 7 bar, which was then maintained equal to 7 bar or more, and the resulting mixture was fed into a mixing head with adjustable rotation speed, the temperature of which was maintained at 15°C.

[0080] After that, 14 m.h. composition of a mixture of 80 wt.% xylene sulfonic acid and 20 wt.% diethylene glycol as a curing catalyst per 100 m.h. the phenolic resin compositions (that is, the amount obtained by subtracting the blowing agent from the mixture is defined as 100 ppm) were fed into the mixing head for the second mixing stage with a mixer. The rotation speed of the mixing head was set to 450 rpm. The resulting foaming phenolic resin composition was distributed by a multi-way distribution pipeline and applied to the moving material of the lower surface. It should be noted that the mixer disclosed in JP H10-225993 A was used as the mixer (mixer). Specifically, the mixer used included an opening for supplying a phenolic resin composition and a foaming agent containing a foam nucleating agent on the upper side surface of the mixer. , and included a curing catalyst supply port on the side surface near the center of the mixing portion in which the mixing was carried out by the rotor. After the mixing part, nozzles were attached to eject the foaming phenolic resin composition. In addition, the mixer included the part up to the curing catalyst supply pipe as the mixing part (preceding stage), the part from the curing agent supply pipe 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. The temperatures of the mixer and nozzles were controlled using water for temperature control, and the temperature of the water was 25°C. In addition, a thermocouple was installed at the outlet of the multi-way distribution pipe to enable the temperature of the foamable phenolic resin composition to be detected, and the foamable phenolic resin composition that was taken out onto the surface material had a temperature of 45°C. The foamable phenolic resin composition that was applied to the surface material was introduced into the preforming step, and the temperature of the equipment in this preforming step was set to 74°C. The residence time at this stage was 11 minutes. It should be noted that preforming was performed with a free roll on top of the top surface material.

[0081] Thereafter, the foamable phenolic resin composition was fed to a double plate-type conveyor with a room temperature heated to 79°C, while the foamable phenolic resin composition was placed between the two surface materials (main molding step). In the main molding step, curing was performed at a residence time of 11 minutes, and then the composition was cut in a direction perpendicular to the direction of travel to obtain an intermediate phenolic resin foam board 1820 mm long. Thereafter, the composition was heated for three hours in an oven at 110° C. (post-curing step) to obtain a foamed phenolic resin board. Table 1 shows the conditions of the stages of pre-forming, main molding and post-curing. It should be noted that a polyester nonwoven fabric (Asahi Kasei ELTAS E05060) having a weight per unit area of 60 g/m ² was used as both the upper and lower surface material.

[0082] [Table 1]

Temperature of preforming stage [°C] Residence time of the preforming stage [min] Temperature of the main molding stage [°C] Post-curing stage: First stage temperature
[°C] Post-curing stage: First stage time
[min] Post-curing stage: Second stage temperature
[°C] Post-curing stage: Second stage time
[min] Example 1 74 eleven 79 No No 110 180 Example 2 74 eleven 79 140 10 110 180 Example 3 74 eleven 79 140 10 110 180 Example 4 74 eleven 79 140 10 110 180 Example 5 74 eleven 79 140 10 110 180 Example 6 74 eleven 79 140 10 110 180 Example 7 74 eleven 79 140 10 110 180 Example 8 74 eleven 79 140 10 110 180 Example 9 74 eleven 79 140 10 110 180 Example 10 69 12 74 140 10 110 180 Example 11 69 12 74 140 10 110 180 Example 12 62 12 70 140 10 110 180 Example 13 74 eleven 79 No No 110 180 Comparative Example 1 63 3 79 No No 110 180

[0083] Density, average cell diameter, percentage of closed cells, full thickness compressive modulus, surface layer compressive modulus, identification of blowing agent type and composition ratio, internal pressure of blowing agent component in the cell, amount of air contained, surface smoothness, thermal conductivity (23°C) and thermal conductivity (10°C) of the foamed phenolic resin were measured by the method described below for the resulting foamed phenolic resin. Table 2 shows the results of measurements of density, average cell diameter, percentage of closed cells, compressive modulus of the foam, compressive modulus of a part of the surface layer of the foam, internal pressure of the blowing agent component in the cell, the amount of air contained, surface smoothness, thermal conductivity (23°C) and thermal conductivity (10°C). Table 3 shows the blowing agent type identification and composition ratio measurement results.

[0084] [Table 2]

Internal pressure of the blowing agent component in the cell
[atm] Compressive modulus of foam [MPa] Compressive modulus of foam surface layer [MPa] The amount of air contained
[about.%] Density
[kg/ ^m3 ] Average cell diameter
[µm] Share of closed cells
[%] Thermal conductivity (23°C)
[W/(mK)] Thermal conductivity (10°C)
[W/(mK)] Surface smoothness
[mm] Example 1 0.22 8.5 4.9 3.1 30.7 126 84 0.0179 0.0169 0.67 Example 2 0.22 8.5 5.2 3.2 30.7 126 84 0.0179 0.0169 0.61 Example 3 0.25 9.4 5.2 3.1 30.4 115 87 0.0177 0.0166 0.57 Example 4 0.25 9.2 5.2 1.8 30.7 115 87 0.0175 0.0164 0.57 Example 5 0.22 8.1 5.4 1.8 30.8 111 87 0.0173 0.0161 0.57 Example 6 0.25 8.0 5.4 1.8 30.6 115 85 0.0183 0.0172 0.49 Example 7 0.26 9.1 5.4 1.8 30.1 109 90 0.0179 0.0172 0.46 Example 8 0.31 8.7 5.4 1.8 30.5 101 92 0.0177 0.0177 0.38 Example 9 0.31 9.1 5.6 1.8 30.2 99 91 0.017 0.0163 0.35 Example 10 0.36 9.3 5.6 1.8 30.3 96 93 0.0169 0.0168 0.32 Example 11 0.36 9.5 5.9 1.8 30.4 95 93 0.0165 0.0156 0.30 Example 12 0.37 8.6 6.1 0.9 30.7 95 95 0.0157 0.0147 0.27 Example 13 0.22 8.5 4.7 3.1 30.4 132 84 0.0179 0.0168 0.72 Comparative Example 1 0.18 8.4 4.5 3.1 30.7 153 84 0.0187 0.0175 0.82

[0085] [Table 3]

Phenolic resin material Amount of surfactant used
[parts] Holding time in the decompression tank [h] Pre-mixing foam and phenolic resin HLB surfactant miscible with blowing agent Surfactant miscible with blowing agent [parts relative to blowing agent] Curing catalyst
[parts] blowing agent [parts] Proportion HCFO-1224yd(Z)
[wt%] Other blowing agent 1 Share of other blowing agent 1
[wt%] Other blowing agent 2 Share of other blowing agent 2
[wt%] Example 1 A 2 0 pre-mixed - - 14 12.1 34 HCFO-1233zd(E) 62 isobutane 4 Example 2 A 2 0 pre-mixed - - 14 12.1 34 HCFO-1233zd(E) 62 isobutane 4 Example 3 B 2 0 pre-mixed - - 14 12 34 HCFO-1233zd(E) 62 isobutane 4 Example 4 B 2 1 pre-mixed - - 14 12 34 HCFO-1233zd(E) 62 isobutane 4 Example 5 B 2 1 pre-mixed - - 14 12.3 46 HCFO-1233zd(E) 50 isobutane 4 Example 6 B 2 1 pre-mixed - - 14 9.3 46 2-chloropropane 50 isopentane 4 Example 7 B 2 1 pre-mixed - - 14 8.7 46 cyclopentane 54 - - Example 8 B 2 1 pre-mixed 13.1 4 14 8.7 46 cyclopentane 54 - - Example 9 B 2 1 pre-mixed 13.1 4 14 10.2 68 cyclopentane 32 - - Example 10 B 2 1 pre-mixed 13.1 4 14 eleven 68 cyclopentane 32 - - Example 11 B 2 1 pre-mixed 13.1 4 14 12.3 81 cyclopentane 19 - - Example 12 B 2 2 pre-mixed 13.1 4 14 15.2 100 - - - - Example 13 B 2 0 pre-mixed - - 14 12.1 22 HCFO-1233zd(E) 78 - - Comparative Example 1 A 2 0 No - - 14 12.3 34 HCFO-1233zd(E) 62 isobutane 4

[0086] <Density of Foamed Phenolic Resin>

A 200 mm square phenolic resin foam board was taken as a sample, and its mass and apparent volume were measured in accordance with JIS K7222.

[0087] <Average Phenolic Resin Foam Cell Diameter>

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 at about the center of its thickness. On the resulting photograph, four straight lines 9 cm long (equivalent to 1800 µm in the actual foam cross section) were drawn so that there were no 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 value obtained by dividing the average number of cells by 1800 µm. Note that this method is based on the method described in JIS K6402.

[0088] <Proportion of closed cells of foamed phenolic resin>

At the position of the center in the thickness direction of the foamed phenolic resin, a cube with a side of 25 mm was cut as a sample when the thickness of the foamed resin was 25 mm or more using a cutting tool such as a band saw. In addition, when the thickness of the foamed phenolic resin was less than 25 mm, a rectangular body with a length and a width of 25 mm was cut as a sample with a thickness after removing the surface material (when the fibrous material obtained from the surface material remains, or when there is a surface material on the back surface side ). Then, the volume of the sample (cm ³ ) was measured by the standard method using an air comparative pycnometer (Type 1000 manufactured by Tokyo Science Co., Ltd.). The closed cell ratio of the foamed phenolic resin is the value obtained by dividing the value obtained by subtracting the bubble wall volume (W/ρ) calculated from the mass of the sample W (g) and the density ρ of the polymer composition constituting the foam from the volume V of the sample by apparent volume Va (cm ³ ) calculated from the outer diameter of the sample, which was measured in accordance with ASTM D 2856 (Method C).

Share of closed cells (%)=((V - W/ρ)/Va) × 100

[0089] <Compressive Modulus of Foam Surface Part Part>

A test piece with a length of 100 mm, a width of 100 mm, and a thickness from the outermost layer of 10 mm was cut from the phenolic resin foam laminated board obtained in Examples and Comparative Example, and the surface material was removed to obtain a test piece. A compressive strength of 10% was measured according to JIS K 7220 with a test sample thickness of 10 mm. The compressive modulus was the maximum value of e obtained from the following equation in the range from 0% strain to yield strength.

e=(b2 - b1)/{(a2 + Δx) - a2}

Where

b1: Compressive stress (MPa) at a2

b2： Compressive stress (MPa) at a2 + Δx

a2: Any strain (%) (less than yield strain)

Δx： Any deformation (%) not less than 0.0001 and not more than 0.0002

[0090] Typically, the compressive modulus is calculated for the portion of the load versus strain curve where a linear relationship is evident. However, in foamed phenolic resin, the force-strain curve may not have a clear straight section (the curve smoothly changes from convex downwards to convex upwards), so the maximum slope in a small area before the yield point was determined as the compressive modulus.

[0091] <Foam Compressive Modulus>

A test piece 100 mm long and 100 mm wide was cut from the phenolic resin foam laminated board obtained in Examples and Comparative Example, and the surface material was removed to obtain a test piece.

The 10% compressive strength was measured according to JIS K 7220 without changing the thickness of the test piece. The compressive modulus was the maximum value obtained from the following equation, as in the above equation, from 0% strain to yield strength.

e=(b2 - b1)/{(a2 + Δx) - a2}

Where

b1: Compressive stress (MPa) at a2

b2： Compressive stress (MPa) at a2 + Δx

a2: Any strain (%) (less than yield strain)

Δx： Any deformation (%) not less than 0.0001 and not more than 0.0002

The result of measuring the compressive modulus of a part of the surface layer is usually lower than that of a full thickness sample. It should be noted that when part of the surface layer is cut out, one side of the sample does not have a surface layer, so these two sides are evaluated under different assumptions.

[0092] <Identification of blowing agent types in foamed phenolic resin and composition ratios>

First, standard gases of chlorinated hydrofluoroolefin, non-chlorinated hydrofluoroolefin, halogenated hydrocarbon, and hydrocarbon are used to determine the retention time under the following GC/MS measurement conditions.

[0093] The surface material was separated from the foamed phenolic resin laminated board obtained in Examples and Comparative Example, and 100 mg of the sample was cut from the foamed phenolic resin using a utility knife. This sample was placed in a Tedlar bag, degassed with a pump, and then minced by hand. Next, the sample in a Tedlar bag was placed in a temperature controller, the temperature of which was brought to 81°C for 10 min. 100 µl of the gas generated in the Tedlar bag was taken and GC/MS analysis was performed under the measurement conditions shown below to determine the types of blowing agent in the foamed phenolic resin.

[0094] The presence of hydrofluoroolefins, halogenated hydrocarbons and hydrocarbons was confirmed by the results of GC/MS analysis. Types of hydrofluoroolefins, halogenated hydrocarbons and hydrocarbons were identified by predetermined retention times and mass spectra. The detection sensitivity of each generated gas component was measured separately for each standard gas, and composition ratios were calculated based on the detection area and detection sensitivity of each gas component obtained by GC/MS. The mass fraction of each gas component was calculated from the composition ratio and the molar mass of each identified gas component.

(Measurement conditions with GC/MS)

- Gas chromatography: "Agilent 7890" manufactured by 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)

- Sample injection method: 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 is 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: - 1300 V

- Ion source temperature: 230°C

- Border temperature: 150°C

[0095] <Internal pressure of blowing agent component in the cell>

Similar to the density measurement of foamed phenolic resin, a 20 cm square foamed phenolic resin board was used as a sample, and the density obtained by measuring mass and apparent volume according to JIS K7222 was defined as I (g/m ³ ). The density of the phenolic resin was determined as 1.27×10 ⁶ (g/m ³ ), and the ratio of bubble volume J to sample volume and bubble volume K (m ³ /g) per unit weight of sample were determined.

J=1 - {I/1.27 × 10 ⁶ }

K \u003d I ^-1 × J (m ³ / g)

[0096] Then approximately 0.25 g was cut from the vicinity of the center of the sample with a utility knife. A homogenizer (ULTRA-TURRAX® tubular drive manufactured by IKA Japan Co., Ltd.) was used to extract the blowing agent from the sample. The cut sample was placed in a sealed container attached to the device, 10 ml of chloroform and 12 glass beads for grinding were additionally placed there, after which the sample was hermetically sealed. The sample was crushed for 3 min at a rotation speed of 6000 rpm to extract the blowing agent. The extract was filtered through a 0.45 µm PTFE disc filter and GC/MS measurements were made under the same conditions as above.

[0097] Then, for the pore-forming component detected by the GC/MS analysis, a calibration curve of the area value versus the solution concentration of each component was built. For the blowing agent, which is liquid at room temperature, samples were prepared diluted with chloroform to various concentrations. For the blowing agent, which is a gas at room temperature, samples diluted with nitrogen gas to various concentrations were prepared in a polyvinyl fluoride sample bag (Tedlar® bag). Thereafter, GC/MS measurement was performed under the same conditions as above.

[0098] From each mass of the blowing agent component obtained from the ratio with the calibration curve, the amount of substance of each blowing agent component per unit mass of the sample was determined. The value was obtained based on the total amount M of each blowing agent component per unit mass of the sample (mol/g), the internal pressure of the blowing agent component P (atm) in the bubble, and the standard atmospheric pressure of 101325 (Pa), and then substituting the previous bubble volume K into the following equation.

P=[(M × 8.314 × 273.15)/K]/101325 (atm)

[0099] <The amount of air contained in the foamed phenolic resin>

Procedure 1: When the thickness of the resin foam was 20 mm or more, at the center position in the thickness direction of the foamed phenolic resin laminated board, a cube with a side of 20 mm was cut as a sample using a utility knife. In addition, when the thickness of the foamed phenolic resin was less than 20 mm, a rectangular body both in length and 20 mm in width with a thickness was cut as a sample after removing the surface material (when the fibrous material obtained from the surface material remains, or when there is a surface material with back side). Then the volume A (in liters) of the cut sample was measured.

Procedure 2: The cut foam and grinder, 6 crushing glass beads, glove bag, oxygen concentration meter and utility knife were placed in the front chamber of the glove box.

Procedure 3: The front chamber of the glove box was evacuated to an oxygen concentration of 0.0%. The contents of the anterior chamber have been transferred to the glove box body.

Procedure 4: Using the utility knife in the glove box, the specimen was cut into 4 equal pieces crosswise in the direction of its thickness.

Procedure 5: All samples cut into 4 pieces and 6 glass beads were placed in a sealed container and the container was closed.

Procedure 6: The sealed container was attached to the crusher and the sample was ground at 6000 rpm for 15 minutes.

Procedure 7: The sealed container was removed and placed in the glove bag, after which the glove bag was closed.

Procedure 8: When measuring with an air pump installed in the glove box, 30 L of nitrogen gas from the glove box was supplied to the glove bag.

Procedure 9: The sealed container was opened in the glove bag and left to stand so that the entire glove bag was filled with gas from the sealed container.

Procedure 10: An oxygen meter was connected to the glove bag and the basal oxygen concentration was recorded as B0 at this time.

Procedure 11: Suction was then performed at 0.5 L/min for 2 minutes with an air pump, and a stable oxygen concentration B (ppm) was recorded.

Procedure 12: The amount of oxygen C in 30 L was calculated using the following equation.

C=30 × (B - B0) (in liters)

Procedure 13: The oxygen concentration D in the foamed phenolic resin was determined from the following equation.

D=C/A (vol.%)

A: sample volume

C: amount of oxygen in 30 liters of gas in a glove bag

D: Oxygen concentration of foamed phenolic resin

The calculation was made with an oxygen concentration in the air of 20.95% and an air concentration in the foamed phenolic resin 4.77 times the oxygen concentration.

The crusher used was a disposable tube-type dry mill manufactured by IKA Japan Co., Ltd.

[0100] <Thermal Conductivity of Phenolic Resin Foam Laminated Board>

The thermal conductivity at 10°C was measured in accordance with JIS 1412-2: 1999. In particular, a sample of foamed phenolic resin laminated board was cut into squares with a side of 600 mm, the sample was placed in an atmosphere with a temperature of 23±1°C and a humidity of 50 ±2%, and the change in weight over time was measured every 24 hours. The condition was adjusted until the weight change in 24 hours was 0.2 mass% or less. The resulting sample was introduced into a device for measuring thermal conductivity, placed in an atmosphere with a temperature of 23±1°C and a humidity of 50±2%.

[0101] One sample and a measuring device of symmetrical configuration ("HC-074/600" from EKO Instruments Inc.) was used to measure thermal conductivity at 10°C under the conditions of a low temperature plate of 0°C and a high temperature plate of 20°C, and thermal conductivity at 23°C under 13°C low temperature plate and 33°C high temperature plate conditions.

[0102] <Smoothness>

A phenolic resin foam laminated board of any thickness, cut into pieces 65 cm wide and 65 cm long, was placed on a flat surface of the board, and a surface of 50 cm in the center was used as the measurement object. In this range, measurements were made at 50 cm at a scanning speed of 1.0 cm/s in the longitudinal direction using a laser displacement meter. The difference between the maximum value and the minimum value of the heights of the obtained 50 points was calculated. Further, the measurement was carried out by changing the position twice, and the average value of the difference between the maximum value and the minimum value for these three measurement cycles was taken as the smoothness of the surface of one side. Then the surface material was turned over and the surface smoothness of the other side was determined in the same way. The largest of the surface smoothness on both sides was defined as the surface smoothness of the foamed phenolic resin laminated board.

[0103] The length direction is the direction in which the surfaces (welding lines) by which the strip-shaped expandable resin compositions are connected to each other are continuous. The direction in which the indented bands are visible on the surface from which the surface material is peeled off can be considered as the length direction. Alternatively, when looking at the cut surface, the direction in which the dark portion exists near the middle layer, and that portion continues on the opposite surface, can be considered as the length direction. The width direction is the direction orthogonal to the length direction.

[0104] (Example 2)

The phenolic resin foam laminated board was produced in the same manner as in Example 1, except that, in the post-curing step, the laminate board was heated at 140°C in an oven for 10 minutes before being cured in an oven at 110°C. within 3 hours, after which it was evaluated.

[0105] (Example 3)

Phenolic resin foam laminated board was produced in the same manner as in Example 2, except that phenolic resin A was changed to phenolic resin B, and the amount of blowing agent added to the phenolic resin was 12 ppm, after which it was evaluated.

[0106] (Example 4)

The foamed phenolic resin laminated board was produced in the same manner as in Example 3, except that the blowing agent was added after storing the phenolic resin composition obtained by mixing the surfactant in a tank whose pressure was reduced to 30 kPa for one hour, after which it was evaluated.

[0107] (Example 5)

The phenolic resin foam laminated board was produced in the same manner as in Example 4, except that the amount of blowing agent added to the phenolic resin was 12.3 ppm. a mixture of 46 wt.% HCFO-1224yd(Z), 50 wt.% HCFO-1233zd(E) and 4 wt.% isobutane, after which it was evaluated.

[0108] (Example 6)

The phenolic resin foam laminated board was produced in the same manner as in Example 5, except that the amount of blowing agent added to the phenolic resin was 9.3 ppm. a mixture of 46 wt.% HCFO-1224yd(Z), 50 wt.% 2-chloropropane and 4 wt.% isopentane, after which it was evaluated.

[0109] (Example 7)

The phenolic resin foam laminated board was produced in the same manner as in Example 5, except that the amount of blowing agent added to the phenolic resin was 8.7 ppm. a mixture of 46 wt.% HCFO-1224yd(Z)46 and 54 wt.% cyclopentane, after which it was evaluated.

[0110] (Example 8)

The phenolic resin composition was obtained by mixing Pluronic® F-127 block copolymer of ethylene oxide and propylene oxide as a surfactant in a proportion of 2.0 ppm. per 100 m.h. Phenolic Resin B. The phenolic resin composition was held in a tank whose pressure was reduced to 20 kPa for one hour.

[0111] To 8.7 m.h. a mixture of 46 wt.% HCFO-1224yd(Z) and 54 wt.% cyclopentane was added to the surfactant nonylphenyl ether polyethylene oxide (HLB13.1) in the amount of 4 m.h. per 100 m.h. blowing agent, and the resulting mixture was added to the phenolic resin composition while mixing using a static mixer. At the same time, the first stage of mixing was carried out in an environment with a pressure of 7 bar and a temperature of 40°C. This solution was then fed, while maintaining a pressure of 7 bar or higher, into a variable speed mixing head which was kept at a temperature of 15°C. The phenolic resin foam laminated board was produced in the same manner as in Example 2 except for the above, after which it was evaluated.

[0112] (Example 9)

The phenolic resin foam laminated board was produced in the same manner as in Example 8, except that the amount of blowing agent added to the phenolic resin was 10.2 ppm. a mixture of 68 wt.% HCFO-1224yd(Z)68 and 32 wt.% cyclopentane, after which it was evaluated.

[0113] (Example 10)

Phenolic resin foam laminated board was produced in the same manner as in Example 9, except that the amount of blowing agent added to the phenolic resin was 11 ppm, the temperature of the preforming step was 69°C, the residence time was 12 minutes, and the temperature of the main molding step was 74°C, after which it was evaluated.

[0114] (Example 11)

The phenolic resin foam laminated board was produced in the same manner as in Example 10, except that the amount of blowing agent added to the phenolic resin was 12.3 ppm. a mixture of 81 wt.% HCFO-1224yd(Z) and 19 wt.% cyclopentane, after which it was evaluated.

[0115] (Example 12)

The phenolic resin foam laminated board was produced in the same manner as in Example 10, except that: the holding time in the tank, the pressure of which was reduced to 30 kPa, was changed to 2 hours; the amount of blowing agent added to the phenolic resin was 15.2 ppm. HCFO-1224yd(Z); the temperature of the preforming step was 62°C; residence time was 12 minutes; and the temperature of the main molding step was 70°C, after which it was evaluated.

[0116] (Example 13)

The phenolic resin foam laminated board was produced in the same manner as in Example 1, except that the amount of blowing agent added to the phenolic resin was 12.1 ppm. a mixture of 22 wt.% HCFO-1224yd(Z) and 78 wt.% HCFO-1233zd(E), after which it was evaluated.

[0117] (Comparative example 1)

In Example 1, mixing of the blowing agent at two temperature stages was stopped and the mixture was fed into the mixing head simultaneously with the curing catalyst. In other words, the phenolic resin composition was obtained by mixing Pluronic® F-127 block copolymer of ethylene oxide and propylene oxide as a surfactant in a proportion of 2.0 ppm. per 100 m.h. phenolic resin A. K 100 m.h. the composition of the phenolic resin was added to 12.3 m.h. a mixture of 34 wt.% HCFO-1224yd(Z), 62 wt.% HCFO-1233zd(E) and 4 wt.% isobutane as a blowing agent, and an additional 14 m.h. a composition consisting of a mixture of 80 wt.% xylenesulfonic acid and 20 wt.% diethylene glycol was added as a curing catalyst, and all this was fed into a mixing head with adjustable speed, the temperature of which was maintained at 15°C. In addition, the phenolic resin foam laminated board was produced in the same manner as in Example 1, except that the temperature of the preforming step was changed to 63°C and the residence time was changed to 3 minutes, after which it was appreciated.

INDUSTRIAL APPLICABILITY

[0118] According to the present invention, a phenolic resin foam laminated board having no wrinkles on the surface material and having both a smooth surface and high thermal conductivity can be obtained.

LIST OF REFERENCES

[0119] 1 - Foamed phenolic resin (core material)

2 - Flexible surface material

10 - Phenolic resin foam laminated board

Claims (23)

1. Phenolic resin foam laminated board, where the surface material is located on at least one of the foamed phenolic resin sides and on the back side of one side, in which: the foamed phenolic resin has a density of not less than 22 kg/m ³ and not more than 50 kg/m ³ , a cell diameter of not less than 50 µm and not more than 170 µm, and a percentage of closed cells of not less than 80%; when (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd (Z)), aliphatic hydrocarbons with carbons of 6 or less, chlorinated saturated hydrocarbons with carbons of 5 or less, and hydrofluoroolefins are gas components, only HCFO-1224yd (Z) is contained as a gas component; And the internal pressure of the air bubble in the cell is 0.20 atm or more. 2. Phenolic resin foam laminated board, where the surface material is located on at least one of the foamed phenolic resin sides and on the back side of one side, in which: the foamed phenolic resin has a density of not less than 22 kg/m ³ and not more than 50 kg/m ³ , a cell diameter of not less than 50 µm and not more than 170 µm, and a percentage of closed cells of not less than 80%; and contains at least one gas component selected from (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd (Z)), aliphatic hydrocarbons with a carbon number of 6 or less, chlorinated saturated hydrocarbons with the number of carbon atoms of 5 or less and hydrofluoroolefin; 20 wt.% or more is HCFO-1224yd (Z) from the total amount of the gas component; And the internal pressure of the air bubble in the cell is 0.20 atm or more. 3. Phenolic resin foam laminated board, where the surface material is located on at least one of the foamed phenolic resin sides and on the back side of one side, in which: the foamed phenolic resin has a density of not less than 22 kg/m ³ and not more than 50 kg/m ³ , a cell diameter of not less than 50 µm and not more than 170 µm, and a percentage of closed cells of not less than 80%; when (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd (Z)), aliphatic hydrocarbons with carbons of 6 or less, chlorinated saturated hydrocarbons with carbons of 5 or less, and hydrofluoroolefins are gas components, only HCFO-1224yd (Z) is contained as a gas component; And the smoothness of the surface on which the surface material is placed is 0.80 mm or less. 4. Phenolic resin foam laminated board, where the surface material is located on at least one of the foamed phenolic resin sides and on the back side of one side, in which: the foamed phenolic resin has a density of not less than 22 kg/m ³ and not more than 50 kg/m ³ , a cell diameter of not less than 50 µm and not more than 170 µm, and a percentage of closed cells of not less than 80%; and contains at least one gas component selected from (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd (Z)), aliphatic hydrocarbons with a carbon number of 6 or less, chlorinated saturated hydrocarbons with the number of carbon atoms of 5 or less and hydrofluoroolefin; 20 wt.% or more is HCFO-1224yd (Z) from the total amount of the gas component; And the smoothness of the surface on which the surface material is placed is 0.80 mm or less. 5. Laminated board made of foamed phenolic resin according to any one of paragraphs. 1-4, in which the internal pressure in the cell is 0.26 atm or more. 6. Laminated board made of foamed phenolic resin according to any one of paragraphs. 1-5, in which the compressive modulus of a part of the surface layer is 4.9 MPa or more. 7. Laminated board made of foamed phenolic resin according to any one of paragraphs. 1-6, in which the foamed phenolic resin contains 3.0% vol. or less air. 8. Laminated board made of foamed phenolic resin according to any one of paragraphs. 1-7, in which the thermal conductivity at 23°C is 0.0180 W/(m⋅K) or less. 9. Laminated board made of foamed phenolic resin according to any one of paragraphs. 1-7, in which the thermal conductivity at 23°C is 0.0159 W/(m⋅K) or less. 10. Laminated board made of foamed phenolic resin according to any one of paragraphs. 1-5, in which the thermal conductivity at 10°C is 0.0164 W/(m⋅K) or less. 11. Composite board made by coating a laminated board of foamed phenolic resin according to any one of paragraphs. 1-10 external element.

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