JP7014566B2 - Phenol resin foam plate and its manufacturing method - Google Patents

Description

The present invention relates to a phenolic resin foam plate having good heat insulating performance and also good concentrated load bearing performance of upper and lower surface layers in the thickness direction.

Acid-curable phenolic resin foam plates made from resole-type phenolic resin are hard to burn, generate less smoke, and have good heat insulation. Therefore, for example, outer wall materials such as metal siding, partition panels, etc. In addition to inner wall materials, it is also widely used as building materials for ceiling materials, fire doors, rain doors, etc., and as cold and heat insulating materials for industrial plants. Often.

However, when the face material is peeled off and used, the phenolic resin foam plate is particularly liable to be deformed by a concentrated load. In particular, the upper and lower surfaces of the phenolic resin foam plate in the thickness direction, which have a large surface area and have many opportunities for contact with human hands and objects, have a problem that they are easily dented due to an unexpected impact or the like.

On the other hand, in Patent Document 1, an iron disk having a diameter of 50 mm and a weight of 10 kg is placed on a foam laminate sample with a face material, a weight of 100 kg is placed on the disk, and the sample is removed after 30 seconds. A phenolic resin heat insulating material that can measure the dent depth (dent amount) (mm) of the remaining trace and reduce the dent amount has been proposed. However, in this technique, a phenol resin foam having a split fiber non-woven layer made of a polyolefin resin is provided on at least one of the front and back surfaces of the phenol resin foam, and further has a split fiber non-woven layer made of a polyolefin resin. It is characterized in that a thin film layer made of a metal foil or a vapor-deposited layer of a metal or a metal oxide is provided on the outermost surface layer of at least one of the front and back surfaces. That is, it is a technique that can be achieved by devising a face material, and it is a weighted evaluation in a relatively wide area with a diameter of 50 mm, and it cannot be said that a concentrated load is applied.

On the other hand, in Patent Document 2, when a relatively low-density phenolic resin foam is compressed with a displacement of 10% in the direction perpendicular to the thickness direction, the recovery rate 1 minute after the compression is released is 96.0. A phenol resin foam having a dent amount after recovery, which is 98.5% or more and is deformed by about 10%, has been proposed. However, in this case, it can be said that the deformation factor cannot be said to be a concentrated load, and it can be said that the technique is characterized by focusing only on the plane direction perpendicular to the thickness direction.

Japanese Unexamined Patent Publication No. 2010-131848 WO2012-053493 Gazette

That is, with respect to a phenol resin foam plate that is easily deformed by a concentrated load, there has been a demand for a phenol resin foam plate that maintains excellent heat insulating properties and has a small amount of dents due to the concentrated load in the thickness direction.

Therefore, as a result of further studies to solve the above problems, the present inventor found that the amount of dents in the thickness direction and the two directions perpendicular to the thickness direction have a specific relationship, and thus the concentrated load capacity in the thickness direction. Was found to be capable of expressing. Further, in order to obtain such a foam plate, the weight average molecular weight of the phenol resin is optimized, the addition amount is optimized while adding the solid foam nucleating agent, and the preforming in the foamable phenol resin composition is performed. By raising and optimizing the temperature of Phenol formaldehyde, it was found that a tough foam plate that can withstand the concentrated load in the thickness direction can be obtained even without a face material.

That is, the present invention provides the following [1] to [4].

[1] A phenolic resin foam plate having a closed cell ratio of 85% or more and an average cell diameter of 70 μm or more and 180 μm or less, in the thickness direction, the first direction perpendicular to the thickness direction, and the thickness direction and the first. When the amount of dents when a concentrated load is applied by a columnar object having a diameter of 15 mm and a mass of 5 kg in the second direction perpendicular to the direction is Dh, Dt, and Dm, the following (1) to (3) ) Satisfying the relational expression of phenol resin foam plate.
Dh <3.0mm (1)
0.01 ≤ Dh / Dt ≤ 0.15 (2)
0.01 ≤ Dh / Dm ≤ 0.15 (3)
[2] The phenolic resin foam plate according to [1], which contains at least one selected from the group consisting of chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins.
[3] The phenolic resin foam plate according to [1] or [2], wherein the ratio of the chlorinated hydrofluoroolefin and the non-chlorinated hydrofluoroolefin in the foaming agent is 30% by mass or more.
[4] A step of mixing a foaming phenolic resin composition containing a phenolic resin, a surfactant, a foaming agent, a solid foaming nucleus, and an acidic curing agent containing an organic acid using a mixer, and the mixed foaming property. This molding is carried out by a step of discharging the phenolic resin composition onto the lower surface material, a step of preforming from the upper surface material while foaming and curing the foamable phenol resin composition discharged onto the lower surface material, and a foaming and curing reaction. The step of carrying out, including the step of performing the curing after dissipating the water in the phenol resin composition after the final molding, the weight average molecular weight of the phenol resin is 600 or more and 3000 or less, and the foamable phenol resin composition is a solid foamed nucleus. The agent is contained in a ratio of 5.0 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the total of the phenolic resin and the surfactant, and the temperature of the foamable phenolic resin composition at the time of the premolding. A method for producing a phenolic resin foam plate, characterized in that the temperature is 45 ° C. or higher and 65 ° C. or lower.

According to the present invention, it is possible to obtain a phenol resin foam plate having excellent concentrated load bearing performance in the thickness direction of the phenol resin foam plate.

It is an example of the measuring device of Dh, Dt, and Dm.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

In the phenol resin foam plate (hereinafter, may be referred to as "foam plate") in the present embodiment, a large number of bubbles are dispersed in the cured phenol resin foam which is the skeleton of the foam plate formed by the curing reaction. It is a phenol resin foam that exists in a state and is obtained in the form of a plate. The resin foam plate is generally obtained in the form of a foam laminated plate in which upper and lower face materials are laminated in the thickness direction. The foam plate of the present embodiment has a high closed cell ratio and has excellent long-term heat insulating performance. Further, since the foam plate of the present embodiment is excellent in concentrated load resistance in the thickness direction, it can be used not only as a phenol resin foam plate with upper and lower surface materials, that is, a foam laminate, but also as a foam laminate. Even in the state of a phenolic resin foam plate obtained by peeling the face material from the plate, it is easy to handle during packing, transportation, and construction, so it can be widely used as a building material with excellent flame retardancy and heat insulation.

Further, the phenol resin foam plate or the foam laminated plate can be used alone or can be used for various purposes by joining with an external member. Examples of the external member include one and a combination of a board-shaped material and a sheet-shaped / film-shaped material. Board-like materials include ordinary plywood, structural plywood, particle board, OSB, and other wood-based boards, as well as wood wool cement board, wood piece cement board, gypsum board, flexible board, medium density fiber board, and calcium silicate board. , Magnesium silicate plate, volcanic vitreous multi-layer plate and the like are suitable. The sheet-like and film-like materials include polyester non-woven fabric, polypropylene non-woven fabric, inorganic-filled glass fiber non-woven fabric, glass fiber non-woven fabric, paper, calcium carbonate paper, polyethylene-processed paper, polyethylene film, plastic moisture-proof film, asphalt waterproof paper, and aluminum. Foil (with or without holes) is suitable.

The density of the phenol resin foam plate of the present embodiment as a phenol resin foam is determined according to the intended use, but is preferably 25 kg / m ³ or more and 45 kg / m ³ or less, and more preferably 25 kg / m ³ or more and 35 kg /. It is less than m ³ . When the density is 25 kg / m ³ or more, mechanical strength such as compressive strength and bending strength can be ensured, and damage can be avoided when handling the foam plate. On the other hand, when the density is 45 kg / m ³ or less, the heat transfer of the resin portion is unlikely to increase, so that the heat insulating performance can be maintained. The density of the phenol resin foam plate is mainly determined by the ratio of the foaming agent, the temperature of the foamable phenol resin composition, the timing of preforming in the step of discharging the mixed foamable phenol resin composition onto the lower surface material, and further. Can be adjusted to a desired value by changing the ratio of the amount of the foaming agent added and the amount of the organic acid used as the acidic curing agent, the curing conditions such as the temperature and the residence time, and the like.

The closed cell ratio of the phenol resin foam plate is 85% or more, preferably 90% or more, and more preferably 95% or more. If the closed cell ratio is less than 85%, there is a concern that the foaming agent in the phenolic resin foam plate may replace the air and the long-term heat insulating performance tends to deteriorate. The closed cell ratio of the phenol resin foam plate is desired, for example, by adjusting the reactivity and temperature of the phenol resin, the ratio with the amount of the organic acid used as the acidic curing agent, and changing the curing temperature conditions. Can be adjusted to a value.

The average bubble diameter of the phenol resin foam plate as a phenol resin foam is 70 μm or more and 180 μm or less, preferably 70 μm or more and 170 μm or less, and more preferably 70 μm or more and 160 μm or less. When the average cell diameter is 70 μm or more, it is possible to suppress the increase in the density of the foam and it becomes difficult to warp. As a result, the heat transfer ratio of the resin portion in the foam can be reduced, so that the heat insulating performance of the phenol resin foam plate can be ensured. On the contrary, when the average bubble diameter exceeds 180 μm, the thermal conductivity due to radiation increases, which may reduce the heat insulating performance of the foam, and also in the thickness direction and, for example, in the width direction and the longitudinal direction. As described above, the amount of each dent increases when a concentrated load is applied in the direction perpendicular to the thickness direction. The average cell diameter of the phenol resin foam plate is, for example, the reaction of the phenol resin, the adjustment of the temperature, the amount of the foam nucleating agent added, the amount of the foaming agent added, and the amount of the organic acid used as the acidic curing agent. It can be adjusted to a desired value by changing the ratio and the curing temperature conditions.

The phenolic resin foam plate contains a foaming agent, and is a foaming phenol resin composition containing, for example, a phenol resin, a surfactant, a foaming agent, a solid foaming nucleating agent, and an acidic curing agent containing an organic acid. Manufactured from. The effervescent phenol resin composition may optionally contain a component other than the above, for example, a phthalic acid-based compound or the like.

As the phenol resin, a resol type phenol resin synthesized by an alkali metal hydroxide or an alkaline earth metal hydroxide is used. The resol type phenol resin is synthesized by heating phenols and aldehydes as raw materials with an alkaline catalyst in a temperature range of 40 to 100 ° C. Further, if necessary, an additive such as urea may be added during or after the synthesis of the resol type phenol resin. When adding urea, it is more preferable to mix urea that has been methylolated with an alkaline catalyst in advance with the resol type phenol resin. Since the resol-type phenol resin after synthesis usually contains an excess amount of water, the amount of water is adjusted to be suitable for foaming at the time of foaming. In addition, the phenolic resin includes aliphatic hydrocarbons, alicyclic hydrocarbons having a high boiling point, or mixtures thereof, diluents for adjusting viscosity such as ethylene glycol and diethylene glycol, and various other additives as necessary. Can also be added.

The starting molar ratio of phenols to aldehydes during the synthesis of the phenolic resin is preferably in the range of 1: 1 to 1: 4.5, more preferably in the range of 1: 1.5 to 1: 2.5. ..

Here, the phenols preferably used in the synthesis of the phenolic resin in the present embodiment are phenol itself and other phenols, and examples of other phenols include resorcinol, catechol, o-, and m-. And p-cresol, xylenols, ethylphenols, p-tert butylphenol and the like. Also, dinuclear phenols can be used.

Further, the aldehydes may be any compound that can be an aldehyde source, and it is preferable to use formaldehyde itself, other aldehydes or derivatives thereof as the aldehydes. Examples of other aldehydes include glyoxal, acetaldehyde, chloral, furfural, benzaldehyde and the like.

Urea, dicyandiamide, melamine and the like may be added to the phenol resin as additives. In the present specification, when these additives are added, the "phenolic resin" refers to those after the additives have been added. In the present specification, a "phenol resin" to which a surfactant is added is referred to as a "phenol resin composition", and a foaming agent, a foam nucleating agent and an acidic curing agent are referred to as a "phenol resin composition". Is added to impart foamability and curability, and is referred to as a "foamable phenol resin composition". Further, as described above, the resin portion after forming the phenol resin foam plate is referred to as a "phenol resin cured product".

The weight average molecular weight of the phenol resin is 600 or more, preferably 800 or more, and more preferably 1000 or more. The weight average molecular weight described above is 3,000 or less, preferably 2,500 or less, and more preferably 2,000 or less. When the weight average molecular weight of the phenol resin is less than 600, the cured state of the obtained phenol resin foam plate becomes insufficient, and the dent amount Dh when a concentrated load is applied in the thickness direction of the foam plate increases. On the other hand, if the weight average molecular weight of the phenol resin exceeds 3000, the curing progresses too much at the time of preforming, and it becomes difficult to form a smooth plate by preforming. The weight average molecular weight of the phenol resin can be measured by using the method described in the examples of the present specification.

The viscosity of the phenol resin and the phenol resin composition at 40 ° C. is preferably 15,000 mPa · s or more and 35,000 mPa · s or less, and more preferably 20,000 mPa · s or more and 30,000 mPa · s or less. When the viscosity of the phenol resin and the phenol resin composition at 40 ° C. is lower than 15,000 mPa · s, the amount of each dent when a concentrated load is applied in the thickness direction of the foam plate increases. Further, if the viscosity of the phenol resin and the phenol resin composition at 40 ° C. is higher than 30,000 mPa · s, not only the handling of liquid feeding and the like becomes difficult, but also the foaming becomes difficult, and as a result, the thickness of the phenol resin foam plate becomes difficult. Is insufficient.

The water content of the phenol resin and the phenol resin composition is preferably 1.5% by mass or more and 3.5% by mass or less. When it is 1.5% by mass or less, the viscosity of the phenol resin and the phenol resin composition at 40 ° C. becomes high, and handling at the time of liquid feeding becomes difficult. Further, when it is 3.5% by mass or more, the amount of dent Dh when a concentrated load is applied in the thickness direction of the foam plate increases.

The surfactant, the foaming agent, and the solid foaming nucleating agent contained in the effervescent phenol resin composition may be added in advance to the phenol resin or may be added at the same time as the acid curing agent.

As the surfactant, those generally used for producing phenolic resin foams can be used, but among them, nonionic surfactants are effective, for example, alkylene which is a copolymer of ethylene oxide and propylene oxide. Oxides, condensates of alkylene oxides and castor oil, condensation products of alkylene oxides with alkylphenols such as nonylphenol and dodecylphenol, polyoxyethylene alkyl ethers with 14 to 22 carbon atoms in the alkyl ether moiety, and more. Fatty ester such as polyoxyethylene fatty acid ester, silicone compound such as polydimethylsiloxane, polyalcohol and the like are preferable. These surfactants may be used alone or in combination of two or more. The amount used is not particularly limited, but is preferably used in the range of 0.3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the phenol resin.

The foaming agent is not particularly limited, but it is preferable to use hydrocarbons (HCs), hydrofluorocarbons (HFCs), chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins, chlorinated hydrocarbons and the like. From the viewpoint of preventing the destruction of the ozone layer, it is preferable to use hydrocarbons, hydrofluorocarbons and the like. In particular, it is more preferable to use a hydrocarbon because of its small global warming potential. Further, from the viewpoint of further improving the heat insulating performance of the phenol resin foam plate, it is preferable to contain at least one of chlorinated hydrofluoroolefin and non-chlorinated hydrofluoroolefin.

As the hydrocarbon, cyclic or chain-shaped alkanes, alkanes, and alkynes having 3 to 7 carbon atoms are preferable, and specifically, normalbutane, isobutane, cyclobutane, normalpentane, isopentane, cyclopentane, neopentane, normal hexane, and the like. Examples thereof include isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, and the like. Among them, normal pentane, isopentane, cyclopentane, neopentane pentane and normal butane, isobutane, cyclobutane butane are preferably used. Examples of the hydrofluorocarbon include hydrofluoropropene, hydrochlorofluoropropene, hydrobromofluoropropene, hydrofluorobutene, hydrochlorofluorobutene, hydrobromofluorobutene, hydrofluoroethane, hydrochlorofluoroethane, and hydrobromofluoroethane. Can be mentioned.

Specific examples of the chlorinated hydrofluoroolefin include 1-chloro-3,3,3-trifluoropropene (for example, manufactured by Honeywell Japan Co., Ltd., product name: Solstice ™ LBA). Specific examples of the non-chlorinated hydrofluoroolefin include 1,3,3,3-tetrafluoro-1-propene (for example, manufactured by Honeywell Japan Co., Ltd., product name: Solstice ™ 1234ze), 2 , 3,3,3-Tetrafluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene and the like.

Here, the content ratio of the chlorinated hydrofluoroolefin and the non-chlorinated hydrofluoroolefin in the foaming agent is preferably 30% by mass or more in order to exhibit the desired heat insulating performance without increasing the environmental load. , 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more.

From the viewpoint of improving the heat insulating performance, it is preferable to use at least one selected from the group consisting of chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins as a constituent component of the foaming agent. On the other hand, in the foam plate obtained by using the foaming agent containing at least one selected from the group consisting of chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins, the affinity between the foaming agent and the resol type phenol resin is high. Because it is too high, the water generated by the curing reaction tends to remain in the foam. Therefore, it was also found that the obtained phenolic resin foam plate tends to have flexibility even if the cured state is sufficient, and is more easily deformed by a concentrated load.

As the chlorinated hydrocarbon, a linear or branched chlorinated aliphatic hydrocarbon having 2 to 5 carbon atoms can be used. The number of bonded chlorine atoms is not limited, but is preferably 1 to 4, and examples of the chlorinated aliphatic hydrocarbon include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, and pentyl. Examples include chloride and isopentyl chloride. Of these, propyl chloride and isopropyl chloride, which are chloropropanes, are more preferably used.

These foaming agents may be used alone or in combination of two or more, and may be arbitrarily selected.

The amount of the effervescent agent in the effervescent phenol resin composition varies depending on the type of effervescent agent, compatibility with the phenol resin, and effervescent / curing conditions such as temperature and residence time. It is preferably 10.0 parts by mass or less, preferably 4.5 parts by mass or more and 10.0 parts by mass or less, and 5.0 parts by mass or more and 9.0 parts by mass or less with respect to 100 parts by mass in total. Is more preferable. When the amount of the foaming agent per 100 parts by mass of the phenol resin and the surfactant is less than 4.5 parts by mass, the density of the phenol resin foam becomes too high. Further, when a foaming agent in an amount exceeding 10 parts by mass per 100 parts by mass of the phenol resin and the surfactant is added, the density becomes low, and the phenol resin foam cannot have a density having an appropriate strength, and bubbles cannot be obtained. The wall surface is liable to crack and the closed cell ratio is liable to decrease.

Further, in the present embodiment, it is necessary to use a solid effervescent nucleating agent. Solid foam nucleating agents include aluminum hydroxide powder, aluminum oxide powder, calcium carbonate powder, talc, clay (kaolin), silica stone powder, silica sand, mica, calcium silicate powder, wallastnite, glass powder, and glass beads. , Inorganic powder such as fly ash, silica fume, gypsum powder, hosand, slag powder, alumina cement, Portoland cement, and organic powder such as crushed powder of phenol resin foam can also be added. These may be used alone or in combination of two or more. The timing of addition of the solid effervescent nucleating agent may be arbitrarily determined as long as it is supplied in the mixer in which the effervescent phenol resin composition is mixed.

The amount of the solid foam nucleating agent added to the effervescent phenol resin composition in the present embodiment is 5.0 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass in total of the phenol resin and the surfactant. Yes, preferably 5.0 parts by mass or more and 8.0 parts by mass or less. When the amount of the solid foam nucleating agent per 100 parts by mass of the phenol resin and the surfactant is less than 5.0 parts by mass, the amount of dent Dh when a concentrated load is applied in the thickness direction of the foam plate increases. Further, when a solid foam nucleating agent in an amount exceeding 10 parts by mass per 100 parts by mass of the phenol resin and the surfactant is added, the viscosity of the effervescent phenol resin composition becomes high, so that heat is generated by stirring share in the mixer. It becomes easy, and the temperature of the effervescent phenol resin composition, and further, the temperature of the effervescent phenol resin composition at the time of premolding tends to rise, which is not preferable. Furthermore, it becomes difficult to send the liquid in the pipe, and the load on the equipment increases. Further, since the surface of the phenolic resin foam plate obtained in this case cures quickly, it is difficult to obtain one having good smoothness.

In the present embodiment, a gas foam nucleating agent may be further used for producing the phenol resin foam plate. As the gas foaming nucleating agent, a low boiling point substance having a boiling point of 50 ° C. or higher lower than that of the foaming agent, such as nitrogen, helium, argon, and air, can be added. The timing of adding the gas foam nucleating agent is not particularly limited, and it may be contained in the phenol resin composition in the step of mixing using a mixer.

The amount of the gas foam nucleating agent added to the foaming agent is preferably 0.2% by mass or more and 1.0% by mass or less, and 0.3% by mass or more and 0.5% by mass, with the amount of the foaming agent being 100% by mass. % Or less is more preferable. When the amount of the foam nucleating agent added is less than 0.2% by mass, non-uniform foaming tends to occur, and the average cell diameter of the obtained phenol resin foam tends to be non-uniform depending on the location. Further, when the addition amount of the effervescent nucleating agent exceeds 1.0% by mass, the average bubble diameter tends to be large, and voids are likely to occur.

The acidic curing agent may be any acidic curing agent capable of curing the phenolic resin composition, and contains an organic acid as an acid component. As the organic acid, aryl sulfonic acid or an anhydride thereof is preferable. Examples of the aryl sulfonic acid and its anhydride include toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, substituted phenol sulfonic acid, xylenol sulfonic acid, substituted xylenol sulfonic acid, dodecylbenzene sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid and the like. And their anhydrides are mentioned, and these may be used alone or in combination of two or more. In this embodiment, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol and the like may be added as a curing aid. Further, these curing agents may be diluted with a solvent such as ethylene glycol and diethylene glycol.

The amount of the acidic curing agent used varies depending on the type, and when a mixture of 60% by mass of paratoluenesulfonic acid monohydrate and 40% by mass of diethylene glycol is used, a total of 100 of the phenol resin and the surfactant. It is preferably used in an amount of 8 parts by mass or more and 20 parts by mass or less, and more preferably 10 parts by mass or more and 15 parts by mass or less with respect to parts by mass.

Then, when the amount of dent when a concentrated load is applied by a columnar object having a diameter of 15 mm and a mass of 5 kg in the thickness direction of the phenolic resin foam plate of the present embodiment is Dh, the following relational expression (1) is satisfied. It is characterized by that.
Dh <3.0mm (1)

Dh is less than 3.0 mm, preferably less than 2.0 mm, more preferably less than 1.0 mm. When Dh is 3.0 mm or more, it cannot be said that the concentrated load-bearing performance of the upper and lower surface layer portions in the thickness direction is sufficient. Dh also depends on the density of the phenolic resin foam plate, and the lower the density, the larger the Dh tends to be.

Further, when the amount of dents when a concentrated load is applied to the first direction of the phenolic resin foam plate of the present embodiment by a columnar object having a diameter of 15 mm and a mass of 5 kg is Dt, the following relational expression (2) is satisfied. It is characterized by that. The first direction is an arbitrary direction parallel to the plate surface of the phenol resin foam plate, that is, an arbitrary direction perpendicular to the thickness direction, for example, the width direction of the phenol resin foam plate. Further, the width direction of the phenol resin foam plate corresponds to, for example, a direction perpendicular to the traveling direction of the lower surface material to which the foamable phenol resin composition is discharged and the perpendicular direction of the plane of the lower surface material in the preforming step described later. It is the direction to do.
0.01 ≤ Dh / Dt ≤ 0.15 (2)

Dh / Dt is 0.01 or more and 0.15 or less, preferably 0.01 or more and 0.12 or less, and more preferably 0.01 or more and 0.10 or less. If Dh / Dt is less than 0.01, the concentrated load capacity in the first direction with respect to the thickness direction is not sufficient, and if it exceeds 0.15, the concentrated load capacity in the thickness direction with respect to the first direction is sufficient. Is not enough.

Further, when the amount of dent when a concentrated load is applied by a columnar object having a diameter of 15 mm and a mass of 5 kg in the second direction of the phenolic resin foam plate of the present embodiment is Dm, the following relational expression (3) is satisfied. It is characterized by that. The second direction is a direction parallel to the plate surface of the phenol resin foam plate and perpendicular to the first direction, that is, a direction perpendicular to the thickness direction and the first direction, for example, the longitudinal direction of the phenol resin foam plate. Is. Further, the longitudinal direction of the phenol resin foam plate is, for example, a direction corresponding to the traveling direction of the lower surface material from which the foamable phenol resin composition is discharged in the preforming step described later.
0.01 <Dh / Dm <0.15 (3)

Dh / Dm is 0.01 or more and 0.15 or less, preferably 0.01 or more and 0.12 or less, and more preferably 0.01 or more and 0.10 or less. If Dh / Dt is less than 0.01, the concentrated load capacity in the second direction with respect to the thickness direction is not sufficient, and if it exceeds 0.15, the concentrated load capacity in the thickness direction with respect to the second direction is sufficient. Is not enough.

In order to reduce the dents in the concentrated load in the thickness direction of the phenol resin foam plate, it is conceivable to increase the density of the entire phenol resin foam plate. However, increasing the density of the entire phenol resin foam plate increases the heat transfer property due to conduction in the resin portion of the phenol resin foam plate, and lowers the overall heat insulating property. On the other hand, since the phenolic resin foam plate of the present embodiment satisfies the above equations (2) and (3), it follows an arbitrary direction (first direction and second direction) parallel to the plate surface of the foam plate. Compared with the concentrated load, the strength against the concentrated load along the thickness direction is improved. Therefore, it is not necessary to increase the density of the entire phenolic resin foam plate. Therefore, the phenolic resin foam plate of the present embodiment can reduce the amount of dents with respect to the concentrated load in the thickness direction while suppressing the deterioration of the heat insulating property.

<Manufacturing method of phenol resin foam plate>
Next, the method for manufacturing the above-mentioned phenol resin foam plate will be described.

As a method for producing a phenol resin foam plate, a foaming phenol resin composition containing a phenol resin, a surfactant, a foaming agent, a solid foaming nucleating agent, and an acidic curing agent containing an organic acid is used in a mixer. Step of mixing, step of discharging the mixed effervescent phenol resin composition onto the lower surface material, step of preforming from the upper surface material while foaming and curing the effervescent phenol resin composition discharged onto the lower surface material. It is possible to adopt a continuous manufacturing method including a step of performing main molding, which is the main step of causing foaming and curing reaction, and a step of performing curing after dissipating water in the phenol resin composition after final molding. be.

In the continuous manufacturing method, the phenolic resin composition discharged onto the lower surface material is covered with the upper surface material, then preformed so as to be leveled from the vertical direction while being foamed and cured, and then plate-shaped while being foamed and cured. It will be molded into.

As a method of performing preforming and main forming in the preforming step and the main forming step in the continuous manufacturing method, a method using a slat type double conveyor, a method using a metal roll or a steel plate, and a plurality of these methods. Various methods depending on the manufacturing purpose, such as a method of using in combination, can be mentioned. Of these, for example, in the case of molding using a slat type double conveyor, the effervescent phenol resin composition coated with the upper and lower facing materials is continuously guided into the slat type double conveyor and then heated while being heated. It can be foamed and cured to form a plate while adjusting to a predetermined thickness by applying pressure from the vertical direction.

As the face material arranged on at least the upper and lower surfaces of the phenol resin foam, a flexible face material (flexible face material) is used. The flexible surface materials used include non-woven fabrics and woven fabrics whose main components are polyester, polypropylene, nylon, etc., kraft paper, glass fiber mixed paper, calcium hydroxide paper, aluminum hydroxide paper, magnesium silicate paper, etc. Papers, non-woven fabrics of inorganic fibers such as non-woven fabrics of glass fibers, and the like are preferable, and these may be mixed (or laminated) and used. Above all, when the face material is peeled off from the obtained phenol resin foam laminated board and only the foam board is used, inexpensive papers that can be discarded after the peeling are preferable. These facing materials are usually provided in the form of rolls. Further, as the flexible surface material, a material kneaded with an additive such as a flame retardant may be used. The method of adhering the face material to the phenol resin foam is not particularly limited, and the adhesive force of the phenol resin foam when it is thermally cured on the surface of the face material or an adhesive such as epoxy resin is used. It doesn't matter what you do.

In the present invention, the amount of the solid foam nucleating agent added and the temperature of the effervescent phenol resin composition at the time of preforming are extremely important. During premolding, a plurality of effervescent phenolic resin compositions are continuously discharged onto the lower surface material in the flow direction, but in the production method according to the present embodiment, the effervescent phenolic resin composition is exposed to the outside air. It is characterized in that the foaming agent at a portion close to the surface layer in contact with the foaming agent is dissipated and the content of the foaming agent at the portion concerned is reduced. It is presumed that the above-mentioned characteristics are exhibited by promoting foaming by the solid effervescent nucleating agent in the effervescent phenol resin composition while raising the temperature of the effervescent phenol resin composition during premolding. To. By reducing the foaming agent content at the site, the density of the surface of the obtained phenol resin foam plate is increased, and as a result, the strength of the surface is improved and the durability against concentrated load in the thickness direction is improved. Presumed.

In the step of preforming, the temperature of the effervescent phenol resin composition at the time of first preforming is 45 ° C. or higher and 65 ° C. or lower.

When the temperature of the effervescent phenol resin composition at the time of preforming is less than 45 ° C., the surface temperature of the effervescent phenol resin composition is low, and the foaming agent is not sufficiently released from the effervescent resin composition. Since it is not possible to increase the density of the surface of the phenolic resin foam plate, the amount of dent Dh when a concentrated load is applied in the thickness direction of the foam plate increases, which is not preferable.

On the other hand, if the temperature of the effervescent phenol resin composition at the time of preforming exceeds 65 ° C., the closed cell ratio of the obtained phenol resin foam plate decreases, the average cell diameter increases, which is not preferable, and there are many voids. Therefore, you need to be careful.

The temperature of the effervescent phenol resin composition at the time of preforming can be adjusted by adjusting the temperature control temperature and flow rate of the mixing head, the rotation speed of the mixing head, and the like, and further adjusting the preforming position. .. The temperature of the effervescent phenolic resin composition at the time of preforming can be measured by a thermometer installed at the preforming position or a thermometer measuring each time at the preforming position.

Following the premolding step, it is important to provide a main molding step and a post-curing step to raise the temperature stepwise. It is desirable that the heating temperature control condition of the main molding step following the premolding step is 65 ° C. or higher and 100 ° C. or lower. In this section, the main molding can be performed using an endless steel belt type double conveyor, a slat type double conveyor, a roll or the like. Further, the residence time of this molding step is preferably 5 minutes or more and 2 hours or less because it is the main step of causing the foaming and curing reaction. When the residence time is 5 minutes or more, foaming and curing can be sufficiently promoted. Further, when the foaming and curing of the phenol resin composition is completed to some extent, the characteristics of the obtained phenol resin foam plate hardly change. Therefore, if the residence time is within 2 hours, the production efficiency of the phenol resin foam plate can be improved.

The post-curing step is performed after the pre-molding step and the main molding step. The temperature of the post-curing step is preferably 90 ° C. or higher and 120 ° C. or lower. If the temperature is lower than 90 ° C, the moisture in the foam plate is less likely to be dissipated, and if the temperature is higher than 120 ° C, the closed cell ratio of the product is lowered and the heat insulating performance of the product is lowered. By providing the temperature control section in the post-curing step, the water content in the phenol resin composition can be dissipated after the final molding.

That is, as a result of diligent studies, a step of mixing a foaming phenol resin composition containing a phenol resin, a surfactant foaming agent, a solid foaming nucleating agent, and an acidic curing agent containing an organic acid using a mixer. , A step of discharging the mixed foamable phenol resin composition onto the lower surface material, a process of preforming from the upper surface material while foaming and curing the foamable phenol resin composition discharged onto the lower surface material, foaming and curing. It includes a step of performing main molding, which is the main step of carrying out the reaction, and a step of performing curing after dissipating water in the phenol resin composition after final molding, and the molecular weight of the phenol resin is 600 or more and 3000 or less, and it is effervescent. The phenol resin composition contains a solid foaming nucleating agent in a proportion of 5% by mass or more and 10% by mass or less with respect to the phenol resin, and the temperature of the foamable phenol resin composition at the time of preforming is 40 ° C. or more and 60 ° C. By doing the following, it was found that a tough foam plate that can withstand the concentrated load in the thickness direction can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Synthesis of phenol resin A>
Charge the reactor with 3500 kg of 52 mass% formaldehyde aqueous solution (52 mass% formalin) and 2510 kg of 99 mass% phenol (including water as impurities), stir with a propeller rotary stirrer, and adjust the temperature of the internal liquid of the reactor with a temperature controller. The temperature was adjusted to 40 ° C. Then, a 48 mass% sodium hydroxide aqueous solution was added until the pH reached 8.7, and then the temperature was raised to 85 ° C. to carry out the reaction. When the Ostwald viscosity of the reaction solution reached 160 square meters per second (= 160 × 10 ^-6 m ² / s, measured value at 25 ° C.), the reaction solution was cooled and the urea content in the phenol resin was 4.6. Urea was added so as to be by mass%. Then, the reaction solution was cooled to 30 ° C., and a 50% by mass aqueous solution of p-toluenesulfonic acid monohydrate was added until the pH reached 6.3. The obtained reaction solution was concentrated by a thin film evaporator, and the viscosity and water content were measured by the following methods. As a result, a phenol resin A having a weight average molecular weight of 1800 and a viscosity at 40 ° C. of 19,800 mPa · s was obtained. This is referred to as phenol resin A.

<Weight average molecular weight>
Measurement was performed under the following conditions by gel permeation chromatography (GPC) measurement, and the weight average molecular weight Mw of the phenol resin was obtained from the calibration curve obtained by the standard substances (standard polystyrene, 2-hydroxybenzyl alcohol and phenol) shown later. I asked.
Preprocessing:
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 chromatograph), and the solution filtered through a 0.2 μm membrane filter was used as a measurement solution.
Measurement condition:
Measuring device: Shodex System21 (manufactured by Showa Denko KK)
Column: Shodex asahipak GF-310HQ (7.5 mm ID x 30 cm)
Eluent: 0.1% by mass of lithium bromide was dissolved in N, N dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) and used.
Flow rate: 0.6 ml / min Detector: RI detector Column temperature: 40 ° C
Standard material: Standard polystyrene (Showa Denko KK "Shodex standard"
SL-105 "), 2-hydroxybenzyl alcohol (manufactured by Sigma-Aldrich, 99% product), phenol (manufactured by Kanto Chemical Co., Inc., special grade)

<Viscosity>
Using a rotational viscometer (manufactured by Toki Sangyo Co., Ltd., R-100 type, rotor part is 3 ° x R-14), the measured value after stabilizing at 40 ° C for 3 minutes was taken as the viscosity of phenol resin A. ..

<Synthesis of phenol resin B>
When the Ostwald viscosity of the reaction solution reached 65 square meters per second (= 65 × 10 ^-6 m ² / s, measured value at 25 ° C.), the reaction solution was cooled and the urea content in the phenol resin was 6.0. The viscosity was 19,800 mPa at a weight average molecular weight of 610 and 40 ° C. by synthesizing in the same procedure as that of phenol formaldehyde A except that urea was added so as to be by mass% and adjusting the concentration conditions of the reaction solution. The phenolic resin B, which is s, was obtained.

<Synthesis of phenol resin C>
When the Ostwald viscosity of the reaction solution reached 450 square meters per second (= 450 × 10 ^-6 m ² / s, measured value at 25 ° C.), the reaction solution was cooled and the urea content in the phenol resin was 3.3. By synthesizing in the same procedure as that of phenol formaldehyde A except that urea was added so as to be mass%, and adjusting the concentration conditions of the reaction solution, the weight average molecular weight was 2900 and the viscosity at 40 ° C. was 19,800 mPa. The phenolic resin C, which is s, was obtained.

<Synthesis of phenol resin D>
The weight average molecular weight was increased by synthesizing in the same procedure as that of phenol resin A except that urea was added so that the urea content in the phenol resin was 3.8% by mass, and the concentration conditions of the reaction solution were adjusted. A phenol formaldehyde D having a viscosity at 1800 and 40 ° C. of 19,800 mPa · s was obtained.

<Synthesis of phenol resin E>
Charge the reactor with 3500 kg of 52% by mass formaldehyde aqueous solution (52% by mass formalin) and 2510 kg of 99% by mass phenol (including water as impurities), stir with a propeller rotary stirrer, and adjust the temperature of the liquid inside the reactor with a temperature controller. The temperature was adjusted to 40 ° C. Then, the temperature was raised while adding a 50% by mass sodium hydroxide aqueous solution to carry out the reaction. When the Ostwald viscosity reaches 60 square meters per second (= 60 x 10 ^-6 m ² / s, measured value at 25 ° C), the reaction solution is cooled and urea is added to 570 kg (equivalent to 15 mol% of the amount of formaldehyde charged). Added. Then, the reaction solution was cooled to 30 ° C., and a 50% by mass aqueous solution of p-toluenesulfonic acid monohydrate was neutralized until the pH reached 6.4. When this reaction solution was dehydrated at 60 ° C. and the viscosity was measured, a phenol resin E having a viscosity at 40 ° C. of 5,800 mPa · s was obtained. The weight average molecular weight was 500.

(Example 1)
3.0 parts by mass of a composition containing 50% each of a block copolymer of ethylene oxide-propylene oxide and polyoxyethylene dodecylphenyl ether as a surfactant with respect to 100 parts by mass of phenol resin A. In addition, 8 parts by mass of the phenol formaldehyde foam fine powder obtained by the method shown in JP-A-2008-024868 was added and kneaded with a twin-screw extruder (manufactured by Technobel Co., Ltd.). Phenol resin foam A phenol resin containing fine powder was obtained. The phenolic resin foam fine powder was a solid foam nucleating agent, and its bulk density was 182 kg / m ³ , and the average particle size measured by the laser diffractive light scattering type particle size distribution measuring device was 26.6 μm. Then, 6.3 parts by mass of a mixture of 40% by mass of isopropyl chloride and 60% by mass of 1-chloro-3,3,3-trifluoropropene as a foaming agent with respect to 100 parts by mass of the phenol resin containing fine powder of the phenol resin foam. A composition consisting of a mixture of 0.40% by mass of nitrogen as a gas foaming nucleating agent and 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol was added as an acidic curing agent at 30 ° C. It was supplied to a variable rotation speed mixing head whose temperature was adjusted to. The mixture was mixed, and the obtained effervescent phenol resin composition was distributed by a multi-port pipe and supplied onto a moving lower surface material. As the mixer (mixer), the one disclosed in Japanese Patent Application Laid-Open No. 10-225993 was used. That is, the mixing has an introduction port for a foaming agent containing phenol resin A and a foaming nucleating agent on the upper side surface of the mixer, and an introduction port for an acidic curing agent on the side surface near the center of the stirring portion where the rotor stirs. I used the machine. After the stirring part, it is connected to a nozzle for discharging the effervescent phenol resin composition. Further, the mixer is composed of a mixing section (front stage) up to the acid curing agent introduction port, a mixing section (second stage) from the acid curing agent introduction port to the stirring end section, and a distribution section from the stirring end section to the nozzle. There is. The distribution unit has a plurality of nozzles at the tip and is designed so that the mixed effervescent phenol resin composition is uniformly distributed. Here, the temperature of the mixer and the nozzle can be adjusted by temperature control, and the temperature control temperature is 25 ° C. Further, a thermocouple was installed at the discharge port of the multi-port distribution pipe so that the temperature of the effervescent phenol resin composition could be detected, and the rotation speed of the mixing head was set to 700 rpm. The temperature of the effervescent phenolic resin composition discharged onto the lower surface material at this time was 52 ° C. The foamable phenol resin composition supplied on the bottom surface material was introduced into the preforming step, and the temperature of the phenol resin foam plate at the time of preforming was 55 ° C. The equipment temperature in the preforming process at this time was 68 ° C. The preforming was performed with a free roller from above the upper surface material. After that, it was introduced into a slat type double conveyor heated to 83 ° C. (main molding step) so as to be sandwiched between two face materials, cured with a residence time of 15 minutes, and then placed in an oven at 110 ° C. for 2 After time curing (post-curing step), a phenol resin foam laminated board having a thickness of 50 mm was obtained. As the face material, glass fiber mixed papermaking (weight: 140 g / m ² ) was used for both the upper and lower face materials, which are flexible face materials. The upper surface material and the lower surface material were carefully peeled off from the phenol resin foam laminated plate to obtain a phenol resin foam plate.

Then, the characteristics of the obtained phenol resin foam plate (density of phenol resin foam, closed cell ratio, average cell diameter, concentrated load evaluation, and surface smoothness evaluation of phenol resin foam plate) were evaluated by the following methods. ..

<Density of phenolic resin foam>
Using a 20 cm square phenol resin foam plate as a sample, the mass and apparent volume were measured and determined according to JIS K7222.

<Phenol resin foam closed cell ratio>
Measured according to ASTM-D-2856. Specifically, a phenolic resin foam plate is cut through a cylindrical sample with a diameter of 35 mm to 36 mm with a cork borer, cut to a height of 30 mm to 40 mm, and then an air comparison hydrometer (manufactured by Tokyo Science Co., Ltd., 1, The sample volume was measured by the standard usage method of 000 type). Independently divided the value obtained by subtracting the volume of the wall (parts other than bubbles and voids) calculated from the sample mass and the density of the cured phenolic resin from the sample volume by the apparent volume calculated from the outer dimensions of the sample. The bubble ratio was used. Here, the density of the cured phenolic resin was 1.3 kg / L.

<Average cell diameter of phenolic resin foam>
The average bubble diameter was measured by the following method with reference to the method described in JIS K6402.
A 50-fold magnified photograph of the cut surface of the test piece obtained by cutting the center of the phenolic resin foam plate in the thickness direction parallel to the front and back surfaces was taken, and a length of 9 cm was taken on the obtained photograph to avoid voids. Draw four straight lines (corresponding to 1,800 μm in the actual foam cross section), calculate the number of cells measured according to the number of bubbles crossed by each straight line, and calculate the average value of each straight line. The value obtained by dividing 800 μm was taken as the average bubble diameter.

<Analysis of chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins in phenol resin foams>
Whether or not chlorinated hydrofluoroolefin and non-chlorinated hydrofluoroolefin were contained in the phenol resin foam of the phenol resin foam plate was confirmed by the following method.

First, the retention time under the following GC / MS measurement conditions was determined using the standard gas of the compound to be analyzed. Subsequently, 10 g of a cured phenol resin sample obtained from a phenol resin foam plate and a metal resin were placed in a 10 L container (product name: Tedlarbag), sealed, and injected with 5 L of nitrogen. Then, the sample was scraped from the top of the tedler bag using a file, and the sample was finely crushed. Subsequently, the tedler bag was placed in a temperature controller whose temperature was adjusted to 81 ° C. for 10 minutes. 100 μL of the gas generated in the tedler bag was sampled and analyzed under the GC / MS measurement conditions shown below. The types of chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins were identified from the retention time and mass spectrum obtained in advance.

[GC / MS measurement conditions]
The GC / MS measurement was performed as follows.
An Agilent 7890 type manufactured by Agilent Technologies was used as the gas chromatograph, and an InertCap 5 (inner diameter 0.25 mm, film thickness 5 μm, length 30 m) manufactured by GL Sciences was used as the column. Helium was used as the carrier gas, and the flow rate was 1.1 mL / min. The temperature of the injection port was 150 ° C., the injection method was the split method (1:50), and the injection amount of the sample was 100 μL. The column temperature was first held at −60 ° C. for 5 minutes, then raised to 150 ° C. at 50 ° C./min and held for 2.8 minutes.

The mass spectrometer used was a Q1000GC type manufactured by JEOL Ltd. Mass spectrometry was performed under the conditions of ionization method: electron ionization method (70 eV), scan range: m / Z = 10 to 500, voltage: -1300 V, ion source temperature: 230 ° C., and interface temperature: 150 ° C.

<Measurement of Dh, Dt, Dm>
The thickness of the phenolic resin foam plate was measured using a caliper. Six cubic samples with the measured thickness as one side were prepared. Samples were prepared so that the length accuracy in the width and longitudinal directions was within 5% of the thickness. Then, the cubic sample was placed on the smooth surface so that the thickness direction was up and down. Further, as shown in FIG. 1, a diameter suspended from above by a wire 3 that can be moved up and down by rotating a columnar object position adjusting handle 5 from above the sample 1 using a pulley 4. A columnar object 2 having a diameter of 15 mm and a mass of 5 kg was arranged, and the columnar object 2 was slowly lowered onto the cubic sample 1 from above. Then, after the columnar object 2 became independent on the cubic sample 1 and the wire 3 was loosened, it was held for 30 seconds. Then, the wire 3 was pulled up, and the amount of dents in the cubic sample 1 was measured using a caliper. In the six samples 1, the upper surface side was measured in three samples, and the lower surface side was measured in the remaining three samples, and measurements were made at a total of six points, and the average value was determined as Dh. Similarly, the amount of dents was measured with a caliper for the six samples in the width direction and the longitudinal direction, and the average values were obtained as Dt and Dm, respectively.

<Evaluation of surface smoothness of phenolic resin foam plate>
The thickness of the phenolic resin foam plate was measured using a caliper. Five cubic samples with the measured thickness as one side were prepared. The thickness was measured at intervals of 5 mm in the width direction, and the difference Δh between the maximum value and the minimum value was obtained. Similarly, in the length direction, the thickness was measured at intervals of 5 mm, and the difference Δh between the maximum value and the minimum value was obtained. Let ΔH be the larger value of Δh in each of the width direction and the length direction. The surface smoothness was evaluated as A when ΔH was 0 mm or more and less than 1 mm, B when ΔH was 1 mm or more and less than 2 mm, and C when ΔH was 2 mm or more. In addition, ΔH is preferably A and B.

<Measurement of thermal conductivity>
According to JIS A 1412-: 1999, the thermal conductivity of the phenolic resin foam plate was measured in an environment of 23 ° C. by the following method.
The phenolic resin foam laminated board was cut into 600 mm squares. The specimen obtained by cutting was placed in an atmosphere of 23 ± 1 ° C. and humidity of 50 ± 2%, and the change over time of the mass was measured every 24 hours, and the rate of change from the latest mass was 0.2% by mass or less. I kept that state until it became. The heat conductivity of a 600 mm square phenol resin foam laminated board with a rate of change from the latest mass of 0.2% by mass or less was placed in the same environment after the face material was peeled off so as not to damage it. Introduced to the measuring device of. The thermal conductivity was measured using one test piece and a measuring device of the target configuration method (Hideko Seiki Co., Ltd., trade name "HC-074 / 600"). The thermal conductivity in an environment of 23 ° C. was measured under the conditions of 13 ° C. for the low temperature plate and 33 ° C. for the high temperature plate.

(Example 2)
A phenol resin foam plate was obtained in the same manner as in Example 1 except that the phenol resin B was used. The rotation speed of the mixing head of the mixer (mixer) at the time of preforming was the same as in Example 1, and the temperature of the foamable phenol resin composition discharged onto the lower surface material was 46 ° C.

(Example 3)
A phenol resin foam plate was obtained in the same manner as in Example 1 except that the phenol resin C was used. The rotation speed of the mixing head of the mixer (mixer) at the time of preforming was the same as in Example 1, and the temperature of the foamable phenol resin composition discharged onto the lower surface material was 64 ° C.

(Example 4)
A phenolic resin foam plate was obtained in the same manner as in Example 1 except that the foaming core composition was 5.0 parts by mass of a mixture of 70% by mass of cyclopentane and 30% by mass of isobutane. The rotation speed of the mixing head of the mixer (mixer) at the time of preforming was the same as in Example 1, and the temperature of the foamable phenol resin composition discharged onto the lower surface material was 53 ° C.

(Example 5)
A phenol resin foam plate was obtained in the same manner as in Example 1 except that 5.0 parts by mass of a phenol resin foam fine powder as a solid foam nucleating agent was added to the phenol resin. The rotation speed of the mixing head of the mixer (mixer) at the time of preforming was the same as in Example 1, and the temperature of the foamable phenol resin composition discharged onto the lower surface material was 47 ° C.

(Example 6)
A phenol resin foam plate was obtained in the same manner as in Example 1 except that 10.0 parts by mass of a phenol resin foam fine powder as a solid foam nucleating agent was added to the phenol resin. The rotation speed of the mixing head of the mixer (mixer) at the time of preforming was the same as in Example 1, and the temperature of the foamable phenol resin composition discharged onto the lower surface material was 64 ° C.

(Example 7)
Phenol resin foam plate in the same manner as in Example 1 except that the temperature of the effervescent phenol resin composition at the time of preforming was adjusted to 45 ° C. by setting the mixing head rotation speed of the mixer (mixer) to 300 rpm. Got

(Example 8)
Phenol resin foam plate in the same manner as in Example 1 except that the temperature of the effervescent phenol resin composition at the time of preforming was adjusted to 65 ° C. by setting the mixing head rotation speed of the mixer (mixer) to 1200 rpm. Got

(Example 9)
A phenolic resin foam plate was obtained in the same manner as in Example 1 except that the upper and lower face materials were changed to Eltus E05030 (weight: 30 g / m ² ), which is a polyester (PET) non-woven fabric manufactured by Asahi Kasei Corporation. .. The rotation speed of the mixing head of the mixer (mixer) at the time of preforming was the same as in Example 1, and the temperature of the foamable phenol resin composition discharged onto the lower surface material was 51 ° C.

(Example 10)
A phenol resin foam plate was obtained in the same manner as in Example 1 except that the phenol resin D was used. The rotation speed of the mixing head of the mixer (mixer) at the time of preforming was the same as in Example 1, and the temperature of the foamable phenol resin composition discharged onto the lower surface material was 48 ° C.

(Example 11)
Examples of the example except that aluminum hydroxide powder (manufactured by Tomoe Kogyo Co., Ltd., B-325, average particle size 23.0 μm) was used as the solid foam nucleating agent and 8.0 parts by mass was added to the phenol resin. A phenolic resin foam plate was obtained in the same manner as in 1. The rotation speed of the mixing head of the mixer (mixer) at the time of preforming was the same as in Example 1, and the temperature of the foamable phenol resin composition discharged onto the lower surface material was 50 ° C.

(Comparative Example 1)
A phenol resin foam plate was obtained in the same manner as in Example 1 except that the solid foam nucleating agent was not added. The rotation speed of the mixing head of the mixer (mixer) at the time of preforming was the same as in Example 1, and the temperature of the foamable phenol resin composition discharged onto the lower surface material was 43 ° C.

(Comparative Example 2)
A phenol resin foam plate was obtained in the same manner as in Example 1 except that the phenol resin E was used. The rotation speed of the mixing head of the mixer (mixer) at the time of preforming was the same as in Example 1, and the temperature of the foamable phenol resin composition discharged onto the lower surface material was 39 ° C.

(Comparative Example 3)
By using phenol resin E, the temperature control temperature of the mixer and nozzle is set to 30 ° C, and the mixing head rotation speed of the mixer (mixer) is set to 1250 rpm, the temperature of the effervescent phenol resin composition at the time of preforming. A phenol resin foam plate was obtained in the same manner as in Example 1 except that the temperature was adjusted to 52 ° C.

(Comparative Example 4)
No solid foaming nucleating agent is added, 2.2 parts by mass of a mixture of 40% by mass of isopropyl chloride and 60% by mass of 1-chloro-3,3,3-trifluoropropene as a foaming agent, and nitrogen as a gas foaming nucleating agent. A phenol resin foam plate was obtained in the same manner as in Example 1 except that the density of the phenol resin foam was adjusted to 60 kg / m ³ by adjusting the content to 0.20% by mass with respect to the agent. The rotation speed of the mixing head of the mixer (mixer) at the time of preforming was the same as in Example 1, and the temperature of the foamable phenol resin composition discharged onto the lower surface material was 67 ° C.

The evaluation results of the characteristics of the phenolic resin foam plates obtained in Examples 1 to 11 and Comparative Examples 1 to 4 are summarized in Table 1.

From Table 1, the phenolic resin foam plates obtained in Examples 1 to 11 have better heat insulating performance than the phenol resin foam plates obtained in Comparative Examples 1 to 4, and further, the upper and lower surface layers in the thickness direction. It can be seen that the concentrated load resistance performance of the part is good.

1 Cube-shaped sample 2 Cylindrical object (diameter 15 mm, mass 5 kg)
3 Wire 4 Pulley 5 Columnar object position adjustment handle

Claims (4)

A phenolic resin foam plate having a closed cell ratio of 85% or more and an average cell diameter of 70 μm or more and 180 μm or less, in a thickness direction, a first direction perpendicular to the thickness direction, and perpendicular to the thickness direction and the first direction. When the amount of dents when a concentrated load is applied by a columnar object having a diameter of 15 mm and a mass of 5 kg in each of the second directions is Dh, Dt, and Dm, the following relationships (1) to (3) A phenolic resin foam plate characterized by satisfying the formula.
Dh <3.0mm (1)
0.01 ≤ Dh / Dt ≤ 0.15 (2)
0.01 ≤ Dh / Dm ≤ 0.15 (3) The phenolic resin foam plate according to claim 1, wherein the phenol resin foam plate contains at least one selected from the group consisting of chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins. The phenolic resin foam plate according to claim 1 or 2, wherein the ratio of the chlorinated hydrofluoroolefin and the non-chlorinated hydrofluoroolefin in the foaming agent is 30% by mass or more. A step of mixing a foaming phenolic resin composition containing a phenolic resin, a surfactant, a foaming agent, a solid foaming nucleus, and an acidic curing agent containing an organic acid using a mixer, a mixed foaming phenolic resin composition. A step of discharging an object onto the bottom surface material, a step of preforming from the top surface material while foaming and curing the foamable phenolic resin composition discharged onto the bottom surface material, a step of performing main molding by foaming and curing reaction, A step of performing curing after releasing water in the phenolic resin composition after the final molding is included, the weight average molecular weight of the phenolic resin is 600 or more and 3000 or less, and the efferent phenolic resin composition is a solid foaming nucleating agent. The temperature of the efferent phenolic resin composition at the time of premolding is 45 ° C., which contains 5.0 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the total of the phenolic resin and the surfactant. A method for producing a phenolic resin foam plate, characterized in that the temperature is 65 ° C. or higher.

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