KR102670604B1 - Phenol resin foam laminate plate and production method therefor - Google Patents

Abstract

An incombustible phenolic resin foam laminate is obtained that is excellent in light weight, has an improved closed cell ratio in the thickness direction, and has good smoothness, and a metal foil laminate face material is disposed on the surface layer. A phenolic resin foam laminate (1) in which a face material (4) is laminated on at least one side of the phenolic resin foam (2), wherein the phenolic resin foam (2) has a density of 20 kg/m3 or more and less than 40 kg/m3, and a central closed cell ratio. This is 85% or more, the surface layer closed cell ratio is 80% or more, the average cell diameter is 70 μm or more and 180 μm or less, the surface smoothness level is 2 mm or less, the face material 4 is made of non-woven fabric or paper, and at least one face material is A metal foil (6) is additionally laminated on (4), and a plurality of openings (7) penetrating the metal foil (6) and the face plate (4) are formed.

Description

Phenolic resin foam laminate and method of manufacturing the same {PHENOL RESIN FOAM LAMINATE PLATE AND PRODUCTION METHOD THEREFOR}

The present invention relates to a phenol resin foam laminate having metal foil laminated on the surface, excellent surface smoothness, and high thermal insulation performance.

Phenolic resin foam boards made from resor-type phenolic resins have better thermal insulation properties than inorganic insulating materials, so they are better than before, for example, in addition to exterior wall materials such as metal siding and interior wall materials such as partition panels, ceiling materials, fire doors, etc. It is widely used as building materials such as shutters and as cold and heat insulating materials for industrial plants. However, since the level of incombustibility is generally low compared to inorganic insulation materials, it is used in various fields as a highly insulating phenolic resin foam board with noncombustibility properties, especially a lightweight phenol resin foam board with a density of less than 40 kg/㎥ with excellent constructability. Non-combustible technology was required.

As a technology for incombustibility of phenol resin foam boards, a technology for manufacturing a phenol resin foam laminate made of a non-woven fabric and a gas-impermeable face material such as metal foil using foam as a core material (Patent Document 1) is known. The phenol resin foam laminate is obtained by bonding gas-impermeable metal foil using an adhesive or the like after manufacturing a phenolic resin foam laminate with a nonwoven fabric.

However, when this method is adopted, when metal foil is laminated on the phenolic resin foam laminate using an adhesive or the like, the air existing between the phenolic resin foam laminate and the metal foil does not escape and tends to remain, resulting in poor appearance. There was a problem that it was easy to become defective. In order to solve this problem of remaining air bubbles, it is necessary to apply appropriate pressure to the phenol resin foam laminate from the metal foil using equipment dedicated to laminating. However, if too much pressure is applied, it will cause the closed cell ratio of the surface layer and the center of the phenol resin foam to deteriorate, so it is necessary to manufacture it by lowering the production speed and removing the bubbles, and there is a problem that productivity does not increase. . In other words, the technology of bonding gas-impermeable metal foil using an adhesive or the like after manufacturing a phenolic resin foam laminate with a non-woven face material not only requires expensive dedicated equipment for laminating the metal foil on the phenolic resin foam laminate. In addition, there were problems such as complicated processes, decreased productivity, and excessive processing costs due to the use of adhesives.

Therefore, there has been a demand for a technology for non-flammability of phenolic resin foam boards with high thermal insulation performance that solves the above problems.

In order to solve these problems, a face material made of a base material such as metal foil and non-woven fabric is used as a face material when manufacturing a phenolic resin foam laminate, and the role of adhesion between the face material and the phenolic resin foam is made to be played by a expandable phenol resin composition. I knew there was a need.

In addition, when manufacturing a phenol resin foam laminate, it is necessary to properly dissipate and remove moisture generated along with curing of the expandable phenol resin to the outside of the system, so a face material made of a base material such as metal foil and non-woven fabric must be opened in advance. (孔) It is necessary to do so.

As a technology based on the above idea, the technology described in Patent Documents 2 and 3 is known.

Patent Document 2 describes a technique for producing a phenol resin foam having a gas-impermeable surface material (hereinafter sometimes referred to as a “metal foil laminated surface material”) in which metal foils having a large number of small holes are laminated. However, the phenol resin foam laminate obtained by the present technology has a large average cell diameter, has a low closed cell ratio, does not have high thermal insulation performance, and also has poor surface smoothness, so there are problems in practical use.

On the other hand, Patent Document 3 proposes a phenolic resin foam laminate that optimizes the opening conditions on the surface of the face material when manufacturing a phenolic resin foam laminate using a face material made of aluminum foil laminated on a base material, and the obtained product is It is said to have high insulation performance. However, it was found that the above-mentioned laminated board had poor surface smoothness of the laminated face material having aluminum foil, and furthermore, it was not possible to realize low density of the phenolic resin foam.

Additionally, in Patent Document 4, the use of metal foil as a face material is described, but the necessity of holes is not taken into consideration. Therefore, it was found that both the surface smoothness and the thermal insulation performance of the laminated face material with aluminum foil are technologies that are far from the level of practical use. In addition, although Patent Documents 5 and 6 describe that a metal film with holes formed as necessary can be used as a face material, when moisture generated along with curing of the expandable phenol resin is appropriately dissipated and removed to the outside of the system, , no consideration has been given to the difficulties in using the face material having these metal layers. In fact, it was found that the surface smoothness of the laminated face material with aluminum foil was poor and the insulation performance was also poor, so it was not at the level of practical use.

Japanese Patent Publication No. 2002-339472 Japanese Patent Publication No. 04-002097 Japanese Patent Publication No. 2009-525441 Japanese Patent Publication No. 2017-160431 International Publication No. 2016/152155 Japanese Patent Publication No. 2016-43687

In other words, there has been a demand for a phenol resin foam laminate that is excellent in light weight, has a high closed cell ratio in the thickness direction, has excellent surface smoothness, and is non-flammable.

Therefore, the present inventors conducted repeated studies to solve the above problem, and as a result, a foamable phenol resin composition was brought into contact with a previously perforated metal foil laminated face plate, and the moisture remaining in the foam generated during curing was then efficiently dissipated. By optimizing the weight average molecular weight of the phenol resin, the ambient temperature of the preforming process and the main forming process, and the wind speed of the heating gas, excellent lightweight properties, a high closed cell rate in the thickness direction, and surface smoothness are achieved. We succeeded in producing a phenol resin foam laminate that is good and non-flammable.

That is, the present invention provides the following [1] to [9].

[1] A phenolic resin foam laminate in which a face material is laminated on at least one side of the phenolic resin foam, wherein the phenolic resin foam has a density of 20 kg/m3 or more and less than 40 kg/m3, a central closed cell ratio of 85% or more, and a surface layer closed cells. The ratio is 80% or more, the average cell diameter is 70 ㎛ or more and 180 ㎛ or less, the surface smoothness level of the phenolic resin foam laminate is 2 mm or less, the face material is made of non-woven fabric or paper, and metal foil is placed on at least one face material. A phenol resin foam laminate in which these are further laminated and a plurality of openings penetrating the metal foil and the face material are formed.

[2] The phenolic resin foam laminate according to [1] above, wherein the thickness unevenness is 2 mm or less.

[3] The phenolic resin foam laminate according to [1] or [2] above, wherein a face material is laminated on both sides of the phenolic resin foam.

[4] The phenolic resin foam laminate according to any one of [1] to [3] above, wherein the hole diameter of the opening portion is 0.1 mm or more and 3 mm or less, and the number of holes is 1,000 or more and 1,000,000 or less per 1 m2.

[5] The phenol resin foam laminate according to any one of [1] to [4] above, wherein the metal foil is aluminum foil.

[6] The phenolic resin foam laminate according to any one of [1] to [5] above, wherein the openings are filled with phenol resin foam.

[7] A mixing process of mixing a foamable phenol resin composition containing a phenol resin, a surfactant, a foaming agent, a foaming nucleating agent, and an acidic curing agent containing an organic acid, and a discharge process of discharging the mixed foamable phenol resin composition onto the bottom material. , a process of performing preforming on the upper surface material while foaming and curing the expandable phenol resin composition discharged on the lower surface material, a process of performing main molding by foaming and curing reactions, and then post-curing to dissipate moisture. Including the process to be carried out, the weight average molecular weight of the phenol resin is 300 or more and 2,000 or less, the atmospheric temperature in the process of performing preforming is 60 ℃ or more and 80 ℃ or less, and the wind speed of the heating gas in the process of performing preforming is 0.1 m/min or more, the ambient temperature in the process of performing main molding is 80°C or more and 100°C or less, the wind speed of the heating gas in the process of performing main molding is 0.25 m/min or more, and the foamable phenol of the bottom material A metal foil is laminated on at least one of the surface opposite to the side on which the resin composition is discharged and the surface on the opposite side to the side where the upper surface material is brought into contact with the expandable phenolic resin composition, and a plurality of layers penetrating the metal foil and the surface material. A method of manufacturing a phenolic resin foam laminate in which an opening is formed.

[8] The method for producing a phenolic resin foam laminate according to [7] above, wherein the hole diameter of the opening portion is 0.1 mm or more and 3 mm or less, and the number of holes is 1,000 or more and 1,000,000 or less per 1 m2.

[9] The method for producing a phenolic resin foam laminate according to [7] or [8] above, wherein the metal foil is aluminum foil.

According to the present invention, it is possible to obtain a phenolic resin foam laminate having a metal foil laminated face material disposed on the surface layer, which is excellent in light weight, has good thermal insulation performance and smoothness, and has sufficient non-combustibility performance.

1 is a diagram showing an example of a phenol resin foam laminate of the present invention.
FIG. 2A is a diagram explaining the appearance of an opening in the phenol resin foam laminate shown in FIG. 1.
FIG. 2B is a diagram explaining the appearance of an opening in the phenol resin foam laminate shown in FIG. 1.
FIG. 2C is a diagram explaining the appearance of an opening in the phenol resin foam laminate shown in FIG. 1.

Hereinafter, the present invention will be described in detail based on its preferred embodiments. In addition, the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

Figure 1 shows an example of the phenol resin foam laminate of the present invention. The phenol resin foam (hereinafter sometimes simply referred to as “foam”) (2) in the present embodiment is obtained in a plate shape in which a large number of bubbles formed by a curing reaction exist in a dispersed state. Phenolic resin foam is generally obtained in the form of a foam laminate in which top and bottom materials are laminated in the thickness direction. And, the phenolic resin foam laminate 1 of the present embodiment has a high closed cell ratio across the thickness direction and excellent thermal insulation performance. In addition, the phenolic resin foam laminate 1 of the present embodiment has a metal foil 6 further laminated on at least one face material, and a plurality of openings 7 penetrating the metal foil 6 and the face material 4. ) is formed. As a result, it can be widely used as a building material, etc., which not only has excellent thermal insulation properties but also has non-flammable properties. The phenolic resin foam laminate 1 of the present embodiment can be manufactured by the method for producing a phenolic resin foam laminate of the present invention described later.

In addition, the phenol resin foam laminate 1 of the present embodiment can be used alone or by joining it with an external member to be used for various purposes. Examples of external members include board-like materials. Board materials include wood-based boards such as ordinary plywood, structural plywood, particle board, and OSB, as well as wood wool cement board, wood cement board, gypsum board, flexible board, medium density fiber board, calcium silicate board, and magnesium silicate board. , volcanic vitreous double-layer plates, etc. are preferable.

The density of the phenol resin foam (2) in the present embodiment is determined depending on the use, but is 20 kg/m3 or more and less than 40 kg/m3, more preferably 22 kg/m3 or more and 38 kg/m3 or less, even more preferably. It is 24 kg/㎥ or more and 35 kg/㎥ or less. If the density is 20 kg/m3 or more, mechanical strengths such as compressive strength and bending strength can be secured, and damage to the phenolic resin foam laminate 1 can be avoided when handling it. On the other hand, if the density is less than 40 kg/m3, it is difficult for heat transfer in the resin portion to increase, so the thermal insulation performance can be maintained. In addition, the density of the phenolic resin foam (2) is mainly determined by changing the ratio of the foaming agent, furthermore, the ratio of the addition amount of the foaming agent to the addition amount of the organic acid used as the acidic curing agent, and the curing conditions such as temperature and residence time, etc., as desired. It can be adjusted by value.

The central closed cell ratio of the phenol resin foam (2) 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 (2) is replaced with air and the long-term thermal insulation performance tends to deteriorate. In addition, the closed cell ratio of the phenol resin foam (2) can be adjusted as desired by, for example, adjusting the reactivity or temperature of the phenol resin, the ratio with the addition amount of the organic acid used as an acidic curing agent, and further changes in the curing temperature conditions, etc. It can be adjusted by value. In particular, in the present technology, since the metal foil 6 is a gas-impermeable face material, the closed cell ratio is likely to decrease if the water generated by the curing reaction cannot be quickly dissipated to the outside of the system. The closed cell rate is determined by the diameter of the openings 7 that penetrate the metal foil 6 and the face material 4 at the time of manufacture (hereinafter referred to as “hole diameter”) and the number of openings (hereinafter referred to as “hole number”). It is easy to be influenced by

The closed cell ratio of the surface layer of the phenol resin foam (2) is 80% or more, preferably 85% or more, and more preferably 90% or more.

The average cell diameter of the phenol resin foam (2) is 70 μm or more and 180 μm or less, preferably 70 μm or more and 170 μm or less, more preferably 70 μm or more and 160 μm or less. If the average cell diameter is 70 μm or more, the density of the foam can be suppressed from increasing, so the heat transfer rate of the resin portion in the foam can be reduced, and the heat insulation performance of the phenolic resin foam laminate 1 can be secured. . Also, conversely, when the average cell diameter exceeds 180 μm, heat conductivity by radiation increases. In addition, the average cell diameter of the phenol resin foam 2 depends, for example, on the hole diameter and number of holes in the openings 7 penetrating the metal foil 6 and the face material 4 during production. It can be adjusted to a desired value by adjusting the reactivity or temperature, the ratio of the addition amount of the foaming agent to the addition amount of the organic acid used as an acidic curing agent, and further changing the curing temperature conditions, etc.

The thickness of the phenol resin foam laminate 1 is preferably 15 mm or more and 200 mm or less, more preferably 18 mm or more and 160 mm or less, and even more preferably 20 mm or more and 100 mm or less. In particular, when the thickness of the phenolic resin foam laminate 1 exceeds 200 mm, it becomes difficult to dissipate moisture in the phenol resin composition during production, the surface smoothness level is likely to decrease, and the closed cell ratio is also likely to decrease. .

And, the phenol resin foam (2) contains a foaming agent and is manufactured from a foamable phenol resin composition that includes, for example, a phenol resin, a surfactant, a foaming agent, and an acidic curing agent containing an organic acid. In addition, the foamable phenol resin composition may optionally contain components other than the above, such as phthalic acid-based compounds.

As the phenol resin, a resor-type phenol resin synthesized from an alkali metal hydroxide or an alkaline earth metal hydroxide is used. Resor type phenol resin is synthesized by using phenols and aldehydes as raw materials and heating them in a temperature range of 40 to 100°C using an alkali catalyst. Additionally, if necessary, additives such as urea may be added during or after the synthesis of the resor-type phenol resin. When adding urea, it is more preferable to mix urea previously methylolated with an alkali catalyst into the resor type phenol resin. Since the synthesized resor-type phenolic resin usually contains excessive moisture, the moisture content is adjusted to be appropriate for foaming at the time of foaming. In addition, aliphatic hydrocarbons or high-boiling alicyclic hydrocarbons, or mixtures thereof, diluents for viscosity adjustment such as ethylene glycol or diethylene glycol, and various other additives may be added to the phenol resin as needed.

The starting molar ratio of phenols to aldehydes during synthesis of the phenol 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 when synthesizing the phenol resin in this embodiment are phenol itself and other phenols. Examples of other phenols include resorcinol, catechol, o-, m-, and p-cresol, xylenol, ethylphenol, and p-tert butylphenol. Additionally, dinuclear phenols can also be used.

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

Additionally, urea, dicyandiamide, melamine, etc. may be added to the phenol resin as additives. In this specification, when adding these additives, “phenol resin” refers to the product after adding the additives. In this specification, a product obtained by adding a surfactant to a “phenol resin” is referred to as a “phenol resin composition.” In addition, a foaming agent, a foaming nucleating agent, and an acidic curing agent are added to a “phenol resin composition” to provide foamability and curability, and the composition is referred to as a “foamable phenol resin composition.”

The weight average molecular weight of the phenol resin is 300 or more, preferably 400 or more, and more preferably 500 or more. Moreover, the above-mentioned weight average molecular weight is 2,000 or less, preferably 1,800 or less, and more preferably 1,600 or less. If the weight average molecular weight of the phenolic resin is less than 300, foaming progresses too much compared to curing, so the closed cell ratio in the central and surface layer portions decreases and the average cell diameter increases. On the other hand, when the weight average molecular weight of the phenol resin exceeds 2,000, it becomes difficult to promote foaming, the density increases, and the surface smoothness level deteriorates. Additionally, the weight average molecular weight of the phenol resin can be measured using the method described in the Examples of this specification.

The viscosity of the phenol resin at 40°C is preferably 7,000 mPa·s or more and 25,000 mPa·s or less, more preferably 8,000 mPa·s or more and 22,000 mPa·s or less, and even more preferably 9,000 mPa·s or more. It is less than 20,000 mPa·s.

The moisture content of the phenol resin is preferably 1.5 mass% or more and 10.0 mass% or less, more preferably 2.5 mass% or more and 8.0 mass% or less, and even more preferably 3.5 mass% or more and 6.0 mass% or less.

The surfactant and foaming agent contained in the foamable phenol resin composition may be added to the phenol resin in advance, or may be added simultaneously with the acidic curing agent.

As the surfactant, those generally used in the production of the phenol resin foam (2) can be used, but non-ionic surfactants are particularly effective. For example, alkylene oxide, which is a copolymer of ethylene oxide and propylene oxide, a condensate of alkylene oxide and castor oil, a condensation product of alkylene oxide and alkyl phenol such as nonyl phenol and dodecyl phenol, and the alkyl ether portion. Polyoxyethylene alkyl ethers having 14 to 22 carbon atoms, further fatty acid esters such as polyoxyethylene fatty acid ester, silicone compounds such as polydimethylsiloxane, and polyalcohols are preferable. These surfactants may be used individually or in combination of two or more types. There is no particular limitation on the amount used, but it is preferably used in a 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 blowing agent is not particularly limited, but it is preferable to use hydrocarbons (HCs), hydrofluorocarbons (HFCs), chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins, and chlorinated hydrocarbons. From the viewpoint of preventing destruction of the ozone layer, it is preferable to use hydrocarbons, hydrofluorocarbons, etc. In particular, since the global warming coefficient is small, it is more preferable to use hydrocarbons. Moreover, from the viewpoint of further improving the thermal insulation performance of the phenol resin foam laminate 1, it is preferable to contain at least one type of chlorinated hydrofluoroolefin and non-chlorinated hydrofluoroolefin.

As the hydrocarbon, cyclic or chain alkanes, alkenes, and alkynes having 3 to 7 carbon atoms are preferable. Specifically, n-butane, isobutane, cyclobutane, n-pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, etc. You can. Among them, pentanes such as normal pentane, isopentane, cyclopentane, and neopentane, and butanes such as normal butane, isobutane, and cyclobutane are preferably used. Additionally, hydrofluorocarbons include hydrofluoropropene, hydrochlorofluoropropene, hydrobromofluoropropene, hydrofluorobutene, hydrochlorofluorobutene, hydrobromofluorobutene, and hydrofluorocarbon. Roethane, hydrochlorofluoroethane, hydrobromofluoroethane, etc. can be mentioned.

Chlorinated hydrofluoroolefins include, specifically, 1-chloro-3,3,3-trifluoropropene (e.g., Honeywell Japan Co., Ltd., product name: Solstice (registered trademark) LBA). there is. Additionally, non-chlorinated hydrofluoroolefins include, specifically, 1,3,3,3-tetrafluoro-1-propene (e.g., Honeywell Japan Co., Ltd., product name: Solstice (registered trademark) 1234ze) , 2,3,3,3-tetrafluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene, etc.

Here, the content ratio of chlorinated hydrofluoroolefin and non-chlorinated hydrofluoroolefin in the blowing agent is preferably 30% by mass or more, and more preferably 40% by mass or more, in order to achieve the desired thermal insulation performance without increasing the environmental load. It is more preferable that it is 50 mass% or more, and it is even more preferable that it is 60 mass% or more.

Additionally, from the viewpoint of improving thermal insulation performance, it is preferable to use at least one member selected from the group consisting of chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins as a constituent of the blowing agent. On the other hand, in the case of a phenolic resin foam obtained by using a blowing agent containing at least one selected from the group consisting of chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins, the affinity between the blowing agent and the resol type phenol resin is excessively high. Therefore, water generated by the curing reaction tends to remain in the foam. Therefore, when manufacturing a phenol resin foam having a gas-impermeable surface material such as metal foil on the surface layer, it can be seen that even if the cured state is sufficient, the surface smoothness tends to be slightly lower compared to when other foaming agents are used. there was.

As the chlorinated hydrocarbon, linear or branched chlorinated aliphatic hydrocarbons 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 chlorinated aliphatic hydrocarbons include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, and pentyl chloride. , isopentyl chloride, etc. Among these, propyl chloride and isopropyl chloride, which are chloropropane, are more preferably used.

In addition, these foaming agents may be used individually, or two or more types may be combined, and may be selected arbitrarily.

The amount of foaming agent in the foamable phenol resin composition varies depending on the type of foaming agent, compatibility with the phenol resin, and foaming and curing conditions such as temperature and residence time, but for a total of 100 parts by mass of the phenol resin and surfactant, It is preferably 10.0 parts by mass or less, more preferably 4.5 parts by mass or more and 10.0 parts by mass or less, and even more preferably 5.5 parts by mass or more and 9.0 parts by mass or less. If the amount of foaming agent per 100 parts by mass of the phenol resin and surfactant is less than 4.5 parts by mass, the density of the phenol resin foam (2) becomes too high. Additionally, if a foaming agent is added in an amount exceeding 10.0 parts by mass per 100 parts by mass of the total of the phenol resin and surfactant, the density becomes excessively low, and the phenol resin foam (2) cannot be made to a density with appropriate strength, and the cell walls It becomes easy to crack, and the closed cell rate becomes easy to decrease.

Additionally, in this embodiment, a foaming nucleating agent is used. As the foaming nucleating agent, a gaseous foaming nucleating agent such as a low-boiling substance with a boiling point of 50°C or more lower than that of the foaming agent, such as nitrogen, helium, argon, or air, can be used. Also, aluminum hydroxide powder, aluminum oxide powder, calcium carbonate powder, talc, kaolin, silica powder, silica sand, mica, calcium silicate powder, wollastonite, glass powder, glass beads, fly ash, silica fume, gypsum powder, Solid foam nucleating agents such as inorganic powders such as borax, slag powder, alumina cement, Portland cement, and organic powders such as ground powder of phenolic resin foam may be added. These may be used individually, or may be used in combination of two or more types, regardless of gas or solid. The addition timing of the foaming nucleating agent can be determined arbitrarily as long as it is supplied into the mixer that mixes the foamable phenol resin composition.

The amount of gaseous foaming nucleating agent added to the foaming agent in this embodiment is preferably 0.2% by mass or more and 1.0% by mass or less, and more preferably 0.3% by mass or more and 0.5% by mass or less, assuming that the amount of foaming agent is 100% by mass. . If the amount of the foaming nucleating agent added is less than 0.2% by mass, nonuniform foaming tends to occur, and the average cell diameter of the obtained phenolic resin foam tends to vary depending on the location. Additionally, if the addition amount of the foaming nucleating agent exceeds 1.0% by mass, the average cell diameter tends to increase and voids also tend to occur. Additionally, the amount of solid foaming nucleating agent added to the foaming agent is preferably 3.0 parts by mass or more and 10.0 parts by mass or less, and more preferably 4.0 parts by mass or more and 8.0 parts by mass or less, based on a total of 100 parts by mass of the phenol resin and surfactant. .

The acidic curing agent may be an acidic curing agent capable of curing the phenol resin composition, and contains an organic acid as an acid component. As the organic acid, arylsulfonic acid or anhydrides thereof are preferable. Examples of arylsulfonic acid and its anhydrides include toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, substituted phenolsulfonic acid, xylenolsulfonic acid, substituted xylenolsulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, etc., and their anhydrides. These may be used as one type, or two or more types may be combined. In addition, in this embodiment, resorcinol, cresol, sarigenin (o-methylol phenol), p-methylol phenol, etc. may be added as a curing aid. Additionally, these curing agents may be diluted with solvents such as ethylene glycol and diethylene glycol.

The amount of acidic hardener used varies depending on the type, and when using a mixture of 60% by mass of p-toluenesulfonic acid monohydrate and 40% by mass of diethylene glycol, the amount is 100 parts by mass of the total of the phenol resin and the surfactant. , Preferably it is used in an amount of 8 parts by mass or more and 20 parts by mass or less, and more preferably in an amount of 10 parts by mass or more and 15 parts by mass or less.

＜Manufacturing method of phenolic resin foam laminate＞

Next, the manufacturing method of the above-mentioned phenol resin foam laminate is explained. The manufacturing method of the phenolic resin foam laminate of the present embodiment includes a mixing step of mixing a foamable phenol resin composition containing a phenol resin, a surfactant, a foaming agent, a foaming nucleating agent, and an acidic curing agent containing an organic acid, and the mixed foamable phenol. A discharging process of discharging the resin composition onto the lower surface material, a process of performing preforming on the upper surface material while foaming and curing the expandable phenol resin composition discharged on the lower surface material, and the main process of performing foaming and curing reactions. A molding process is provided, followed by a post-curing process to dissipate moisture. In this manufacturing method, a continuous manufacturing method can be adopted.

In the continuous manufacturing method, the phenol resin composition discharged on the bottom material is coated with the top material, and then preformed to be even from the top and bottom while foaming and curing, and then molded into a plate shape while foaming and curing are carried out. Here, at least one of the face materials is provided with a metal foil, and is on the surface opposite to the side on which the foamable phenol resin composition is discharged of the face material (bottom material) that discharges the foamable phenol resin composition in the discharge process, and in the preforming process. In this case, a metal foil is laminated on at least one surface of the face material (top material) disposed on the foamable phenol resin composition, opposite to the side that is in contact with the foamable phenol resin composition.

That is, the phenol resin foam and the face material are bonded by the self-adhesive properties of the expandable phenol resin composition, and between the laminated phenol resin foam and the face material, there is a coexistence portion where the phenol resin foam has penetrated into the face material.

In the continuous manufacturing method, methods of performing preforming and main forming in the preforming process and main forming process, respectively, include a method using a slat-type double conveyor, a method using a metal roll or a steel plate, and furthermore, these include: Various methods can be used depending on the manufacturing purpose, such as a method of using multiple methods in combination. Among these, for example, in the case of molding using a slat-type double conveyor, the expandable phenol resin composition coated with the upper and lower face materials is continuously guided through the slat-type double conveyor, and then pressure is applied from the up and down directions while heating to give a predetermined amount. It can be foamed and hardened while adjusting the thickness and molded into a plate shape.

The face material disposed on at least the upper and lower surfaces of the phenol resin foam is made of non-woven fabric or paper, and metal foil is laminated on at least one side of the face material. Non-woven fabrics or paper-based materials used include non-woven fabrics and woven fabrics whose main components are polyester, polypropylene, nylon, etc., and papers such as kraft paper, glass fiber mixed paper, calcium hydroxide paper, aluminum hydroxide paper, and magnesium silicate paper. , nonwoven fabrics of inorganic fibers such as glass fiber nonwoven fabrics, etc. are preferable, and these may be mixed (or laminated) for use. Among them, nonwoven fabrics made of polyester, polypropylene, nylon, etc. are more preferable because they have good gas permeability, good compatibility with the expandable phenol resin composition, and are easy to develop sufficient adhesive strength due to the anchor effect.

Additionally, these face materials are usually provided in roll form. In addition, as a face material, you may use a thing kneaded with additives such as a flame retardant. In addition, the material of the metal foil laminated on the face material is preferably aluminum, copper, iron, tin, titanium, nickel, stainless steel, etc., and its thickness is preferably 0.005 mm or more and 1.0 mm or less. In addition, the method of laminating the metal foil and the face material is not particularly limited, but can be laminated using an epoxy resin, polyethylene resin, etc. A cosmetic layer or the like may be additionally disposed on the surface of the metal foil. This cosmetic layer is a layer that constitutes the interior finish surface, and for example, a sheet (inorganic mixed paper) containing aluminum hydroxide, magnesium silicate, calcium carbonate, etc., a non-woven fabric made of polyethylene terephthalate, etc. are used. By forming such a decorative layer, the interior side finished surface becomes a surface suitable for painting, mortar processing, etc.

In the face material in which the metal foil is laminated, there is an opening part penetrating the metal foil and the face material, and the hole diameter of the opening part is 0.1 mm or more and 3 mm or less, more preferably 0.2 mm or more and 2 mm or less, even more preferably. It is 0.3 mm or more and 1 mm or less. Additionally, the shape of the hole is not particularly limited, and the hole diameter can be determined by measuring the longest diameter when considered to be approximately circular. Moreover, the number of holes is preferably 1,000 to 1,000,000 per 1 m2, more preferably 5,000 to 500,000, and still more preferably 10,000 to 250,000. In addition, when there are multiple types of hole diameters, the average hole diameter and the average number of holes per 1 m2 are measured at 5 points, and the weighted average value is taken.

During foam molding, the expandable phenol resin composition penetrates into the openings and hardens. It is preferable that the hole diameter of the opening is 3 mm or less because it becomes difficult for the expandable phenol resin composition to seep out from the opening and contaminates the equipment, making continuous production possible for a long period of time. Therefore, it is important that it is designed to conform to FIGS. 2A to 2C. As described above, the phenol resin foam and the face material are bonded by the self-adhesive properties of the expandable phenol resin composition, and a coexistence zone where the phenol resin foam has penetrated into the face material exists between the laminated phenol resin foam and the face material. Here, an opening is formed that penetrates the metal foil and face material laminated on the phenol resin foam. Therefore, only the foamable phenol resin composition penetrates into the opening and hardens without coexisting with the face material, and as a result, it is filled as a phenol resin foam. Three types of configuration states can be obtained depending on the difference in the state of charge. That is, when the expandable phenol resin composition is foamed and cured, the outermost layer in the thickness direction of the obtained phenol resin foam stays at the thickness direction position in the coexistence area of the phenol resin foam and the face material (Figure 2A), and stays at the position of the adhesive layer. In this case (Figure 2B), it stays in the position within the metal foil (Figure 2C). In either case, this is a configuration that can achieve this technology.

If the hole diameter of the opening is 0.1 mm or more or the number of holes is 1,000 or more per 1 m2, moisture generated by curing is likely to be dissipated, and the closed cell rate in the center and the closed cell rate in the surface layer are unlikely to decrease, and the surface The smoothness level is also improved. In addition, it is preferable that the number of holes is less than 1,000,000 per 1 m2 because it becomes difficult to break when tension is applied to the metal foil laminated face material.

Non-combustible phenolic resin foam laminates are expected to be in demand as laminates in various applications such as building materials, most of which require thickness precision. Therefore, it has been strongly desired to improve the smoothness of the surface on which the metal foil is laminated, that is, for practical purposes, to be within 2 mm in the measurement of the surface smoothness level described later. Additionally, in addition to surface smoothness, it is desirable to have small thickness unevenness throughout the laminate.

In the present invention, the weight average molecular weight of the phenolic resin, the atmospheric temperature of the process for performing preforming and the wind speed of the heating gas for the process, and further, the atmospheric temperature for the process for performing main molding and the heating gas for the process are Wind speed becomes very important. In particular, in the prior art, the wind speed of the heating gas in the process of performing preforming was generally set to less than 0.10 m/min, and the wind speed of the heating gas in the process of performing main forming was set to less than 0.15 m/min. In examining the present invention, the necessity of optimizing this wind speed condition became clear.

During preforming, a plurality of expandable phenol resin compositions are continuously discharged on the bottom material in the flow direction and coated with the top material. At that time, it is important to adjust the ambient temperature to 60°C or more and 80°C or less, and to set the heating gas at a wind speed of 0.1 m/min or more with respect to the sheet material on which the metal foil is laminated.

Here, air, nitrogen, argon, etc. can be used as the heating gas, but air is preferably used.

If the ambient temperature of the preforming process is less than 60°C, it becomes difficult to dissipate moisture in the phenol resin composition, and the surface smoothness level tends to decrease. On the other hand, if the ambient temperature is higher than 80°C, curing cannot keep up with foaming, the average cell diameter tends to increase, and the surface smoothness level decreases, which is not preferable.

In addition, in the preforming process, when the heating gas is used at a wind speed of less than 0.1 m/min for the face material on which the metal foil is laminated, it becomes difficult to dissipate moisture in the phenol resin composition, and the surface smoothness level decreases. Not desirable.

Following the preforming process, it is important to form a main forming process and a post-curing process and raise the temperature in stages. The heating temperature control conditions for this molding process are important to adjust the ambient temperature to 80°C or more and 100°C or less, and to set the heating gas to a wind speed of 0.25 m/min or more with respect to the face material on which the metal foil is laminated.

If the ambient temperature of the main molding process is less than 80°C, it becomes difficult to dissipate moisture in the phenol resin composition, and the surface smoothness level tends to decrease. On the other hand, if the ambient temperature exceeds 100°C, curing cannot keep up with foaming, the closed cell ratio in the center and surface layer tends to decrease, the average cell diameter tends to increase, and the surface smoothness level decreases. , is not desirable.

In addition, in this molding process, when the heating gas is used at a wind speed of less than 0.25 m/min for the face material on which the metal foil is laminated, it becomes difficult to dissipate moisture in the phenolic resin composition, and the surface smoothness level decreases. Not desirable.

In that section, the main forming can be performed using an endless steel belt type double conveyor, a slat type double conveyor, or a roll. In addition, the residence time in this molding process is preferably 5 minutes or more and 2 hours or less, since it is a main process that causes foaming and hardening reactions. If the residence time is 5 minutes or more, foaming and curing can be sufficiently promoted. Additionally, if the residence time is less than 2 hours, the production efficiency of the phenol resin foam laminate can be increased.

The post-cure process is performed after the main molding process. The ambient temperature of the post-cure process is preferably 90°C or higher and 120°C or lower. If the temperature is 90°C or higher, moisture in the foam laminate becomes easily dissipated, and if it is 120°C or lower, the closed cell rate of the product improves and the thermal insulation performance of the product improves. By forming a temperature control section for the post-curing process, much of the remaining moisture can be dissipated. In addition, in the post-curing process, it is preferable to set the heating gas at a wind speed of 0.1 m/min or more with respect to the face material on which the metal foil is laminated. The residence time of the post-cure process is preferably 1 hour or more and 8 hours or less. If the residence time is 1 hour or more, moisture dissipation can be sufficiently promoted. Moreover, if the residence time is less than 8 hours, the production efficiency of the phenol resin foam laminate can be increased.

In addition, in order to improve the surface smoothness level of a phenol resin foam laminate having a density of 20 kg/m3 or more and less than 40 kg/m3, the weight average molecular weight of the phenol resin is optimized, the atmospheric temperature of the preforming process, and the It is very important to optimize the wind speed of the heating gas to the face material on which the metal foil is laminated, the ambient temperature of the main molding process, and further, the wind speed of the heating gas to the face material on which the metal foil is laminated in the main molding process.

The non-flammable performance requirement is that a heat generation test (heating) using a cone calorimeter is conducted for 20 minutes, and the total calorific value is 8 MJ/m2 or less. However, the phenolic resin foam laminate obtained by this technology meets these standards. Satisfies.

In addition, the cone calorimeter is a device for measuring the amount of heat generated during combustion of a sample, and the evaluation of non-combustible materials, etc. in the Building Standards Act includes the item of heat generation test using the cone calorimeter.

The phenolic resin foam laminate obtained by the present invention has openings penetrating the metal foil and the face material. However, whether the openings exist is determined by peeling the face material on which the metal foil is laminated from the phenolic resin foam laminate. This can be easily confirmed with the naked eye by observing the peeling surface on the side (the interface in contact with the phenolic resin foam).

Furthermore, as a result of careful study by the present inventors, a foamable phenol resin composition with an optimized weight average molecular weight of the phenol resin was discharged onto a previously perforated metal foil laminated face plate, and the moisture remaining in the foam generated during curing was efficiently removed. I found out that it needs to be removed. That is, the present inventors have optimized the weight average molecular weight of the phenol resin, and the atmospheric temperature and wind speed of the heating gas in the preforming process and molding process, thereby obtaining a non-combustible, lightweight phenol resin foam laminate with a good level of surface smoothness. found out

Example

Below, the present invention will be described in more detail through Examples and Comparative Examples, but the present invention is not limited to these.

<Synthesis of phenol resin A>

3,500 kg of 52 mass% formaldehyde aqueous solution (52 mass% formalin) and 2,510 kg of 99 mass% phenol (including water as an impurity) are charged into the reactor, stirred by a propeller-type stirrer, and stirred inside the reactor by a temperature controller. The liquid temperature was adjusted to 40°C. Next, a 48% by mass aqueous solution of sodium hydroxide was added until the pH reached 8.7, and then the temperature was raised to 85°C to carry out the reaction. At the stage when the Ostwald viscosity of the reaction solution reaches 120 square millimeters per second (=120 mm2/s, measured value at 25°C), the reaction solution is cooled, and urea is added so that the urea content in the phenol resin is 4.6% by mass. Added. After that, 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 liquid was concentrated using a thin film evaporator, and the weight average molecular weight and viscosity were measured by the following methods. As a result, a phenol resin was obtained with a weight average molecular weight of 1,800 and a viscosity of 12,000 mPa·s at 40°C. This was used as phenol resin A.

＜Weight average molecular weight＞

Gel permeation chromatography (GPC) measurement was performed under the following conditions, and the weight average molecular weight Mw of the phenol resin was determined from a calibration curve obtained using the standard substances shown below.

Pretreatment :

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

Measuring conditions :

Measuring device: Shodex System21 (manufactured by Showa Electric Co., Ltd.)

Column: Shodex asahipak GF-310HQ (7.5 ㎜I.D. × 30 ㎝)

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 chromatography) and used.

Flow rate: 0.6 ml/min

Detector: RI detector

Column temperature: 40℃

Standard materials: standard polystyrene (“Shodex standard SL-105” manufactured by Showa Electric Co., Ltd.), 2-hydroxybenzyl alcohol (manufactured by Sigma-Aldrich Co., Ltd., 99% product), phenol (manufactured by Kanto Chemical Co., Ltd., special grade)

＜Viscosity＞

A rotational viscometer (manufactured by Toki Sangyo Co., Ltd., type R-100, rotor section: 3°

<Synthesis of phenol resin B>

At the stage when the Ostwald viscosity of the reaction solution reaches 30 square millimeters per second (=30 mm2/s, measured value at 25°C), the reaction solution is cooled, and urea is added so that the urea content in the phenol resin is 6.0 mass%. Except for the addition, phenol resin B was synthesized in the same manner as phenol resin A, and the concentration conditions of the reaction solution were adjusted to obtain phenol resin B with a weight average molecular weight of 610 and a viscosity of 12,000 mPa·s at 40°C.

<Synthesis of phenol resin C>

At the stage when the Ostwald viscosity of the reaction solution reaches 300 square millimeters per second (=300 mm2/s, measured value at 25°C), the reaction solution is cooled, and urea is added so that the urea content in the phenol resin is 3.3% by mass. Except for the addition, it was synthesized in the same manner as the phenol resin A, and the concentration conditions of the reaction solution were adjusted to obtain phenol resin C, which had a weight average molecular weight of 2,000 and a viscosity of 12,000 mPa·s at 40°C.

＜Synthesis of phenol resin D＞

At the stage when the Ostwald viscosity of the reaction solution reaches 450 square millimeters per second (=450 mm2/s, measured value at 25°C), the reaction solution is cooled, and urea is added so that the urea content in the phenol resin is 3.3% by mass. Except for addition, it was synthesized in the same manner as the phenol resin A, and the concentration conditions of the reaction solution were adjusted to obtain phenol resin D, which had a weight average molecular weight of 2,900 and a viscosity of 12,000 mPa·s at 40°C.

＜Synthesis of phenol resin E＞

3,500 kg of 52 mass% formaldehyde aqueous solution (52 mass% formalin) and 2,510 kg of 99 mass% phenol (including water as an impurity) are charged into the reactor, stirred by a propeller-type stirrer, and stirred inside the reactor by a temperature controller. The liquid temperature was adjusted to 40°C. Next, 50% by mass aqueous sodium hydroxide solution was added until the pH of the reaction solution reached 8.7. The reaction solution was heated to 85°C over 1 hour, and then, at the stage when the Ostwald viscosity reached 200 square millimeters per second (=200 mm2/s, measured value at 25°C), the reaction solution was cooled, and urea 400 kg was added. After that, 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 6.4. The obtained reaction liquid was concentrated using a thin film evaporator to obtain a phenol resin with a weight average molecular weight of 1,510 and a viscosity of 20,000 mPa·s. This was used as phenol resin E.

<Synthesis of phenolic resin F>

3,500 kg of 52 mass% formaldehyde aqueous solution (52 mass% formalin) and 2,510 kg of 99 mass% phenol (including water as an impurity) are charged into the reactor, stirred by a propeller-type stirrer, and stirred inside the reactor by a temperature controller. The liquid temperature was adjusted to 40°C. Next, the temperature was raised while adding 50% by mass aqueous sodium hydroxide solution, and the reaction was performed. At the stage where the Ostwald viscosity reached 60 square millimeters per second (=60 mm2/s, measured value at 25°C), the reaction liquid was cooled and 570 kg of urea was added. Thereafter, the reaction solution was cooled to 30°C, and the pH was neutralized to 6.4 with a 50% by mass aqueous solution of p-toluenesulfonic acid monohydrate. This reaction liquid was concentrated at 60°C to obtain a phenol resin with a weight average molecular weight of 750 and a viscosity of 5,300 mPa·s. This was designated as phenol resin F.

(Example 1)

A composition containing 50% by mass of a block copolymer of ethylene oxide-propylene oxide and polyoxyethylene dodecylphenyl ether as a surfactant is mixed at a ratio of 3.0 parts by mass with respect to 100 parts by mass of phenol resin A. The composition was obtained. With respect to 100 parts by mass of the phenol resin composition, 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, and nitrogen as a gaseous foaming nucleating agent are added to the foaming agent. 0.35% by mass, and 10 parts by mass of a composition consisting of a mixture of 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as an acidic curing agent was added, and the mixture was supplied to a mixing head with a variable rotation speed whose temperature was adjusted to 30°C. did. After mixing, the obtained foamable phenol resin composition was distributed through a multi-port distribution pipe and supplied onto the moving bottom material. In addition, the mixer (mixer) disclosed in Japanese Patent Application Publication No. Hei 10-225993 was used. That is, a mixer was used that had an inlet for a foaming agent containing phenol resin A and a foaming nucleating agent on the upper side of the mixer, and an inlet for an acidic curing agent on the side near the center of the stirring section where the rotor stirs. After the stirring part, it is connected to a nozzle for discharging the foamable phenol resin composition. Additionally, the mixer is composed of a mixing section (front stage) from the acid curing agent introduction port, a mixing section (back stage) from the acid curing agent introduction port to the end of stirring, and a distribution section from the end of stirring to the nozzle. The distribution unit has a plurality of nozzles at the tip and is designed to uniformly distribute the mixed foamable phenol resin composition. Here, the temperature of the mixer and the nozzle can be adjusted using temperature control water, and the temperature of the temperature control water is all set to 25°C. Additionally, a thermocouple was installed at the discharge port of the multi-port distribution pipe to detect the temperature of the expandable phenol resin composition, and the rotation speed of the mixing head was set to 600 rpm. The foamable phenolic resin composition supplied on the bottom material was introduced into the preforming process. At this time, the equipment temperature of the preforming process was 70°C and the wind speed of heated air was 0.20 m/min. In addition, preforming was performed with a free roller from above the upper surface material. After that, it was held between two sheets of face material and introduced into a slat-type double conveyor heated to 90°C (main molding process). The wind speed of the heated air in this molding process was set to 0.35 m/min. In the main molding process, the expandable phenol resin composition was cured for a residence time of 15 minutes, and then cured in an oven at 110°C for 3 hours (post-curing process) to obtain a phenol resin foam laminate with a thickness of 50 mm. In addition, as the face material, for both the upper and lower surfaces, aluminum foil (7 ㎛ thick) was integrally laminated on a polyester nonwoven fabric (Asahi Chemical Co., Ltd. Eltas E05060, weight per square meter of 60 g/m2) through a polyethylene resin layer. The one that had been perforated (hole diameter: 1 mm, number of holes: 10,000/m2) was used.

And, the properties of the obtained phenolic resin foam laminate (density, closed cell ratio in the center, closed cell ratio in the surface layer, average cell diameter, analysis of chlorinated hydrofluoroolefin and non-chlorinated hydrofluoroolefin in the phenolic resin foam, and the properties of the phenolic resin foam laminate) The surface smoothness level and incombustibility by exothermic test using a cone calorimeter were evaluated by the following methods.

＜Density＞

A 20 cm x 20 cm phenol resin foam was used as a sample, and the mass and apparent volume were measured and determined according to JIS K7222.

＜Central independent cell rate＞

Measurements were made according to ASTM-D-2856. Specifically, after removing the face material from the phenol resin foam laminate, a cylindrical sample with a diameter of 30 mm to 32 mm was cut out with a cork bore. Next, the phenolic resin foam was cut to a height of 9 mm to 13 mm and aligned so that the center of the thickness direction was the center, and then the sample volume was measured using a standard air comparison hydrometer (Tokyo Science, Type 1,000). . From the measured sample volume, subtract the volume of the wall (part other than the cells) calculated from the sample mass and the density of the phenolic resin, divide it by the apparent volume calculated from the outer dimensions of the sample, and multiply by 100 to obtain the independent cells. It was obtained as a rate. The same operation was performed on all 10 points at a distance of 50 mm or more from each measurement site, and the lowest measured value was taken as the central layer closed cell ratio. Additionally, the density of the phenol resin was set to 1.3 kg/l. In addition, when the thickness of the phenolic resin foam is 30 mm or less, cut out a cylindrical sample with a diameter of 30 mm to 32 mm with a cork bore and cut it into pieces with a height of 4 mm to 6 mm so that the center of the thickness direction of the phenol resin foam is the center. After doing so, the same evaluation was performed.

＜Surface closed cell ratio＞

After removing the face material from the phenolic resin foam laminate, a cylindrical sample with a diameter of 30 mm to 32 mm was cut out with a cork bore. Next, the phenolic resin foam was cut to a height of 9 mm to 13 mm and aligned so that one surface in the thickness direction was one side of the circular surface of the cylinder, and then used as a standard method of using an air-comparative hydrometer (manufactured by Tokyo Science, Type 1,000). The sample volume was measured by . From the measured sample volume, the volume of the wall (part other than the bubbles) calculated from the sample mass and the density of the phenolic resin was subtracted, divided by the apparent volume calculated from the outer dimensions of the sample, and the value was obtained by multiplying by 100. . The same operation was performed to measure a total of 10 points at sites 50 mm or more away from each measurement site, and the lowest measured value was taken as (a). Additionally, the density of the phenol resin was set to 1.3 kg/l. Additionally, for the same sample cut out with a cork bore, cut it to a height of 9 mm to 13 mm and align it so that the other surface in the thickness direction of the foam is one side of the circular surface of the cylinder, and then measure a total of 10 points in the same manner. And the lowest measured value was set as (b). Thereafter, among the measured values (a) and (b), the lower measured value was defined as the skin layer closed cell ratio. In addition, when the thickness of the phenolic resin foam is 30 mm or less, a cylindrical sample with a diameter of 30 mm to 32 mm is cut out with a cork bore and cut into pieces with a height of 4 mm to 6 mm so that one surface of the phenol resin foam is one side. After doing so, the same evaluation was performed.

＜Average cell diameter＞

The average cell diameter was measured by the following method with reference to the method described in JIS K6402.

Almost the center of the thickness direction of the phenolic resin foam laminate was cut parallel to the front and back surfaces, and the cut surface of the obtained test piece was photographed magnified 50 times. Then, on the obtained photograph, four straight lines with a length of 9 cm (equivalent to 1,800 ㎛ in the actual foam cross section) were drawn avoiding voids, and the number of cells measured based on the number of bubbles crossed by each straight line was counted for each straight line. was obtained, and the average value divided by 1,800 ㎛ was taken as the average bubble diameter. In addition, voids refer to bubbles having a cell diameter corresponding to an approximately circular diameter of 1.5 cm or more in the photograph enlarged 50 times.

<Analysis of chlorinated and non-chlorinated hydrofluoroolefins in phenol resin foam>

Whether chlorinated hydrofluoroolefin and non-chlorinated hydrofluoroolefin were contained in the phenol resin foam of the phenol resin foam laminate 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. Next, a 10 g sample of the phenol resin foam obtained from the phenol resin foam laminate and a metal string were placed in a 10 L container (product name: Tedrabac), sealed, and 5 L of nitrogen was injected. Then, the sample was cut from the Tedra bag using a file, and the sample was finely pulverized. Subsequently, the Tedra bag was placed in a temperature controller whose temperature was adjusted to 81°C for 10 minutes. 100 μl of gas generated in the Tedra bag was collected and analyzed under the GC/MS measurement conditions shown below. The types of chlorinated hydrofluoroolefin and non-chlorinated hydrofluoroolefin were identified from the retention time and mass spectrum determined in advance.

[GC/MS measurement conditions]

GC/MS measurement was carried out as follows.

The gas chromatograph used was an Agilent 7890 model manufactured by Agilent Technologies, Inc., and the column used was an InertCap 5 manufactured by GL Science (inner diameter 0.25 mm, film thickness 5 µm, length 30 m). Helium was used as a 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 sample injection volume was 100 μl. The column temperature was first maintained at -60°C for 5 minutes, then raised to 150°C at 50°C/min and maintained for 2.8 minutes.

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

<Evaluation of surface smoothness level of phenolic resin foam laminate>

The thickness of the phenolic resin foam laminate was measured using a nozzle. Five cubic samples with one side having the measured thickness were prepared. With respect to the width direction of the cubic sample, the thickness was measured at 5 mm intervals, and the difference Δh between the maximum and minimum values was determined. In the same manner, the thickness of the cubic sample was measured at 5 mm intervals in the longitudinal direction, and the difference Δh between the maximum and minimum values was determined. Among Δh in each of the width and length directions, the larger value was taken as ΔH. The surface smoothness level was evaluated as A if ΔH was more than 0 mm and 1 mm or less, B if ΔH was more than 1 mm and 2 mm or less, and C if ΔH was more than 2 mm. Additionally, ΔH is preferably A and B.

＜Non-uniform thickness of phenolic resin foam laminate＞

The thickness of the phenolic resin foam laminate was measured using a nozzle. First, the length of one side of the phenolic resin foam laminate was measured and the center position was determined. Then, marking was performed on both sides at 10 mm intervals from this center position toward the end, and the thickness at the marked position was measured using a nozzle. Next, for one side in the direction perpendicular to the side on which the measurement was performed, the thickness at all marking positions was similarly measured using a nozzle at 10 mm intervals, and at all measurement points on the two sides, the maximum values and The minimum difference ΔHa was obtained. Thickness unevenness was evaluated as A when ΔHa was greater than 0 mm and 1 mm or less, B when ΔHa was greater than 1 mm and 2 mm or less, and C when ΔHa was greater than 2 mm. Additionally, ΔHa is preferably A and B.

＜Exothermic test evaluation using a cone calorimeter; Non-flammable>

A sample of (99 ± 1) mm × (99 ± 1) mm was cut from the phenolic resin foam laminate, and the total calorific value when heated at a radiation intensity of 50 kW/m 2 for 20 minutes was measured in accordance with ISO-5660. In the exothermic test under the above conditions, non-flammability evaluation was conducted by assigning A if the total calorific value was 8 MJ/m2 or less, and B if the total calorific value was more than 8 MJ/m2. Additionally, the evaluation is preferably A.

(Example 2)

A phenol resin foam laminate was obtained in the same manner as in Example 1, except that phenol resin B was used.

(Example 3)

A phenol resin foam laminate was obtained in the same manner as in Example 1, except that phenol resin C was used.

(Example 4)

A phenol resin foam laminate was obtained in the same manner as in Example 1, except that the ambient temperature in the preforming process was 60°C.

(Example 5)

A phenolic resin foam laminate was obtained in the same manner as in Example 1, except that the ambient temperature in the preforming process was 80°C.

(Example 6)

A phenolic resin foam laminate was obtained in the same manner as in Example 1, except that the wind speed of the heated air in the preforming step was 0.1 m/min.

(Example 7)

A phenol resin foam laminate was obtained in the same manner as in Example 1, except that the ambient temperature in the main molding process was set to 80°C.

(Example 8)

A phenol resin foam laminate was obtained in the same manner as in Example 1, except that the ambient temperature in the main molding process was 100°C.

(Example 9)

A phenol resin foam laminate was obtained in the same manner as in Example 1, except that the wind speed of the heated air in the main molding process was set to 0.25 m/min.

(Example 10)

For both the upper and lower materials, aluminum foil (thickness 7 ㎛) is integrally laminated on kraft paper (65 g/㎡) with a polyethylene resin layer interposed, and holes are formed (hole diameter 1 mm, number of holes 10,000 per ㎡). ), a phenol resin foam laminate was obtained in the same manner as in Example 1, except that the face material subjected to ) was used.

(Comparative Example 1)

Similarly to Example 5 in Patent Document 2 (Japanese Patent Publication No. 04-002097), aluminum foil with a thickness of 0.050 mm was laminated on kraft paper (65 g/m2) using an adhesive, and then a hole diameter of 0.6 mm was added. , a face plate opened with 200 holes/m2, and phenol resin D are used, there is no preforming process, the ambient temperature of the main forming process is set to 70°C, and the wind speed of the heated air in the main forming process is set to 0.12. A phenolic resin foam laminate with a thickness of 30 mm was obtained in the same manner as in Example 1, except that it was set at m/min.

(Comparative Example 2)

Similarly to Example 1 in Patent Document 3 (Japanese Patent Publication No. 2009-525441), an aluminum foil with a thickness of 0.050 mm was laminated on a glass fiber face plate (140 g/m2) using an adhesive, and then the hole diameter was 0.7. ㎜, a face plate perforated with a number of holes of 210/㎡, and phenol resin D are used, there is no preforming process, the ambient temperature of the main forming process is set to 70°C, and the wind speed of the heated air in the main forming process is set to A phenolic resin foam laminate with a thickness of 50 mm was obtained in the same manner as in Example 1 except that the speed was set to 0.12 m/min.

(Comparative Example 3)

For both the upper and lower surfaces, aluminum foil (7 ㎛ thick) is laminated on glass fiber mixed paper (apparent weight 70 g/㎥) with a polyethylene resin layer interposed, and holes are formed (hole diameter 1 mm, number of holes 10,000/). ㎡) was used, except that phenol resin A was used as the phenol resin, and the same procedure as Example 1 in Patent Document 4 (Japanese Patent Application Publication No. 2017-160431) was carried out to produce a phenol resin foam with a thickness of 50 mm. A laminated board was obtained. That is, there is no preforming process.

(Comparative Example 4)

The face material corresponding to Example 1 of the present application, that is, both the upper and lower surfaces, was made of aluminum foil (7 ㎛ thick) interposed between a polyethylene resin layer and a polyester nonwoven fabric (Asahi Chemical Co., Ltd. Eltas E05060, weight per square meter of 60 g/㎥) The thickness was the same as Example 1 in Patent Document 5 (International Publication 2016/152155), except that a hole was added (hole diameter: 1 mm, number of holes: 10,000/m2) to the integrally laminated layer. A 50 mm phenol resin foam laminate was obtained. That is, phenol resin E is used as the phenol resin, and there is no preforming process.

(Comparative Example 5)

For both the upper and lower surfaces, aluminum foil (7 ㎛ thick) was laminated on a polyester nonwoven fabric (Asahi Kasei Co., Ltd. Eltas E05030, weight 30 g/㎥) with a polyethylene resin layer interposed thereon, and an aperture (hole diameter) was formed. A phenolic resin foam laminate with a thickness of 50 mm was prepared in the same manner as in Example 1 in Patent Document 6 (Japanese Patent Application Publication No. 2016-43687), except that a face plate with 1 mm (1 mm, number of holes: 10,000 holes/m2) was used. got it That is, phenol resin F is used as the phenol resin, and there is no preforming process.

(Comparative Example 6)

A preforming process was performed in the same manner as in Comparative Example 5, except that the preforming conditions were that the equipment temperature was 70°C and the wind speed of the heated air was 0.08 m/min, and a phenol resin foam laminate with a thickness of 50 mm was obtained. .

The evaluation results of the properties of the phenol resin foam laminates obtained in Examples 1 to 10 and Comparative Examples 1 to 6 are summarized in Table 1.

From Table 1, compared to the phenolic resin foam laminates obtained in Examples 1 to 10, the phenolic resin foam laminates obtained in Examples 1 to 10 are superior in light weight, have a high closed cell ratio in the thickness direction, and have smoothness. It can be seen that it is a good, non-flammable phenol resin foam laminate.

1: Phenolic resin foam laminate
2: Phenolic resin foam
3: Coexistence area of phenol resin foam and face material
4: Face plate
5: Adhesive layer
6: Metal foil (aluminum foil)
7: Gaegongbu
8: Phenolic resin foam penetrated into the opening

Claims (11)

A phenolic resin foam laminate in which a face material is laminated on at least one side of the phenolic resin foam, wherein the phenolic resin foam has a density of 20 kg/m3 or more and less than 40 kg/m3, a central closed cell rate of 85% or more, and a surface layer closed cell rate of 80%. % or more, the average cell diameter is 70 ㎛ or more and 180 ㎛ or less, the thickness unevenness of the phenolic resin foam laminate is 2 mm or less, the face material is made of non-woven fabric or paper, and a metal foil is additionally laminated on at least one face material. A phenolic resin foam laminate in which a plurality of openings penetrating the metal foil and the face material are formed. According to claim 1,
A phenolic resin foam laminate containing at least one of chlorinated hydrofluoroolefin and non-chlorinated hydrofluoroolefin. The method of claim 1 or 2,
A phenolic resin foam laminate in which a face material is laminated on both sides of the phenolic resin foam. The method of claim 1 or 2,
A phenol resin foam laminate wherein the hole diameter of the opening portion is 0.1 mm or more and 3 mm or less, and the number of holes is 1,000 or more and 1,000,000 or less per 1 m2. According to claim 3,
A phenol resin foam laminate wherein the hole diameter of the opening portion is 0.1 mm or more and 3 mm or less, and the number of holes is 1,000 or more and 1,000,000 or less per 1 m2. According to claim 5,
A phenolic resin foam laminate whose metal foil is aluminum foil. The method of claim 1 or 2,
A phenolic resin foam laminate, characterized in that the opening is filled with phenol resin foam. According to claim 3,
A phenolic resin foam laminate, characterized in that the opening is filled with phenol resin foam. According to claim 4,
A phenolic resin foam laminate, characterized in that the opening is filled with phenol resin foam. According to claim 5,
A phenolic resin foam laminate, characterized in that the opening is filled with phenol resin foam. According to claim 6,
A phenolic resin foam laminate, characterized in that the opening is filled with phenol resin foam.