JP6159468B1 - Phenolic resin foam and method for producing the same - Google Patents

Abstract

The present invention provides a phenolic resin foam in which the amount of warpage is suppressed and a method for producing the same. A phenolic resin foam comprising a foamed resin layer and face materials laminated on both sides thereof, wherein the foamed resin layer has 1-chloro-3,3,3- as a foaming agent. It contains trifluoropropene and hydrocarbon, the mass ratio of 1-chloro-3,3,3-trifluoropropene in the blowing agent is 30% or more, and the density is 25 kg / m3 or more and 35 kg / m3 or less. A phenol resin foam having an average cell diameter of 50 μm or more and 150 μm or less, a closed cell ratio of 90% or more, a thickness of 50 mm or less, and a warpage amount by an infrared irradiation test of less than 7 mm. [Selection figure] None

Description

  The present invention relates to a phenol resin foam and a method for producing the same.

The phenol resin foam is excellent in flame retardancy, heat resistance, chemical resistance, corrosion resistance, and the like, and thus has been adopted in various fields as a heat insulating material. For example, in the construction field, a phenol resin foam wallboard is employed as a synthetic resin building material, particularly a wallboard interior material.
The phenol resin foam is obtained by foaming a foamable phenol resin composition containing, for example, a phenol resin, at least one of fluorinated unsaturated hydrocarbon and chlorinated fluorinated unsaturated hydrocarbon as a foaming agent, and an acid catalyst. And it is manufactured by making it harden | cure (for example, refer patent document 1).

  When constructing a heat insulating material made of phenol resin foam, only one surface of the heat insulating material (the surface opposite to the building) is irradiated with sunlight, and the other surface of the heat insulating material (the surface on the building side) is irradiated. Is not exposed to sunlight. Therefore, during construction in midsummer, a temperature difference may occur between one surface and the other surface of the heat insulating material, and the heat insulating material may be warped. If the heat insulating material is warped, problems such as inability to install the heat insulating material according to the dimensions and inability to sufficiently screw the heat insulating material to the pillar may occur.

International Publication No. 2015/111670

  When a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon are used as the foaming agent, the viscosity of the foamable phenol resin composition decreases. Therefore, in the phenol resin foam obtained by foaming and curing the foamable phenol resin composition, the density in the thickness direction may be biased, the bubble diameter may be coarsened, or the shape of the bubbles may be distorted. Moreover, when the viscosity of the foamable phenol resin composition is low, the discharge amount of the foamable phenol resin composition is not uniform. Then, bubbles generated in the foamable phenol resin composition by the foaming agent flow sideways, and in the obtained phenol resin foam, the bubbles on the surface layer are easily broken (crushed) by external force. When the bubbles are crushed, the phenol resin foam is warped. Such a tendency for the bubbles to be easily broken is likely to occur in a low-density phenol resin foam or a thin phenol resin foam.

  This invention is made | formed in view of the said situation, Comprising: It aims at providing the phenol resin foam which suppressed the curvature amount, and its manufacturing method.

[1] A phenolic resin foam comprising a foamed resin layer, and a first face material and a second face material (excluding those that are metals) laminated on both surfaces thereof, the foam resin The layer contains 1-chloro-3,3,3-trifluoropropene and hydrocarbon as a blowing agent, and the mass ratio of 1-chloro-3,3,3-trifluoropropene in the blowing agent is 30%. The density is 25 kg / m ³ or more and 35 kg / m ³ or less, the average cell diameter is 50 μm or more and 150 μm or less, the closed cell ratio is 90% or more, the thickness is 35 mm or less, and the phenol The phenol resin foam characterized by the amount of curvature by the infrared irradiation test which irradiates infrared rays to the said 2nd surface material side in a resin foam being less than 7 mm.
[2] A method for producing a phenol resin foam according to [1], wherein the phenol resin, 1-chloro-3,3,3-trifluoropropene, hydrocarbon, on the first face material, A discharge step of discharging a foamable phenol resin composition containing an acid catalyst, and a second surface material bonded to the foamable phenol resin composition discharged onto the first surface material, the first surface A foaming step of foaming and curing the foamable phenolic resin composition between a material and the second face material, and in the foaming step, the first surface for conveying the first face material A method for producing a phenol resin foam, characterized in that a temperature difference between a conveyor in contact with a material and a conveyor in contact with the second surface material for conveying the second surface material is 4 ° C or more.
[3] The method for producing a phenol resin foam according to [1], wherein the phenol resin, 1-chloro-3,3,3-trifluoropropene, hydrocarbon, on the first face material, A discharge step of discharging a foamable phenol resin composition containing an acid catalyst, and a second surface material bonded to the foamable phenol resin composition discharged onto the first surface material, the first surface A foaming step of foaming and curing the foamable phenolic resin composition between the material and the second face material, and in the discharging step, a single nozzle is disposed in the running direction of the first face material. A method for producing a phenol resin foam, wherein the foamable phenol resin composition is discharged from the nozzle onto the first face material while being moved in the vertical direction.

  ADVANTAGE OF THE INVENTION According to this invention, the phenol resin foam which suppressed the curvature amount and its manufacturing method can be provided.

It is a front view which shows the infrared irradiation apparatus used for the infrared irradiation test of a phenol resin foam. It is a top view which shows the infrared irradiation apparatus used for the infrared irradiation test of a phenol resin foam. It is a side view which shows the infrared irradiation apparatus used for the infrared irradiation test of a phenol resin foam. It is a top view which shows the phenol resin foam used for the infrared irradiation test of a phenol resin foam.

Embodiments of the phenol resin foam and the method for producing the same according to the present invention will be described.
Note that this embodiment is specifically described in order to better understand the gist of the invention, and does not limit the present invention unless otherwise specified.

[Phenolic resin foam]
The phenol resin foam of this embodiment includes a foamed resin layer and a face material laminated without providing an adhesive layer on both sides thereof. The face materials are joined by the adhesiveness of the foamed resin layer itself.
In the phenol resin foam of this embodiment, the foamed resin layer contains at least one of a halogenated saturated hydrocarbon, a fluorinated unsaturated hydrocarbon, and a chlorinated fluorinated unsaturated hydrocarbon.

In other words, the phenol resin foam of this embodiment includes a phenol resin, at least one of a halogenated saturated hydrocarbon, a fluorinated unsaturated hydrocarbon, and a chlorinated fluorinated unsaturated hydrocarbon as a foaming agent, and an acid catalyst. It is obtained by a method including foaming and curing a foamable phenolic resin composition comprising: and forming a foamed resin layer.
The phenol resin foam preferably further contains a surfactant.
The phenol resin foam may further contain other components other than the phenol resin, the foaming agent, the acid catalyst, and the surfactant, as necessary, as long as the effects of the present invention are not impaired.

The phenol resin foam of the present embodiment has a density of 15 kg / m ³ or more and 50 kg / m ³ or less, preferably 20 kg / m ³ or more and 40 kg / m ³ or less, preferably 25 kg / m ³ or more and 35 kg / m ^3. The following is more preferable.
If the density of the phenol resin foam is 15 kg / m ³ or more, it is easy to further improve the compressive strength of the phenol resin foam. On the other hand, if the density of the phenol resin foam is 50 kg / m ³ or less, it is easy to further improve the heat insulation of the phenol resin foam.

  The density of the phenol resin foam of the present embodiment is a value measured according to the density measuring method defined in Japanese Industrial Standard JIS A9511: 2009.

The phenol resin foam of this embodiment has an average cell diameter of 50 μm or more and 200 μm or less, and preferably 50 μm or more and 150 μm or less.
If the average cell diameter of a phenol resin foam is 50 micrometers or more, the heat insulation of a phenol resin foam can be improved more. When the average cell diameter of the phenol resin foam is less than 50 μm, the compressive strength of the phenol resin foam decreases. On the other hand, when the average cell diameter of the phenol resin foam exceeds 200 μm, the thermal conductivity of the phenol resin foam deteriorates.

  The average cell diameter of the phenol resin foam of the present embodiment can be adjusted by the type and composition of the foaming agent, the type of surfactant, the foaming conditions (heating temperature, heating time, etc.) and the like.

  In the phenol resin foam of the present embodiment, a plurality of bubbles are formed, the bubble wall is substantially free of pores, and at least some of the plurality of bubbles are independent from each other. It is a bubble. In the closed cell, at least one gas of a halogenated saturated hydrocarbon, a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon used as a blowing agent is retained.

The phenol resin foam of this embodiment has a closed cell ratio of 85% or more, and more preferably 90% or more.
The upper limit value of the closed cell ratio is not particularly limited, but is substantially 99% or less. If the closed cell ratio is within the above numerical range, the phenol resin foam can maintain a low thermal conductivity over a long period of time.

  The closed cell ratio of the phenol resin foam of the present embodiment is a value measured according to the method for measuring the closed cell ratio defined in Japanese Industrial Standard JIS K7138: 2006.

The phenol resin foam of this embodiment has a warp amount of less than 7 mm and preferably 5 mm or less according to an infrared irradiation test. In addition, the curvature amount in the phenol resin foam of this embodiment is the average value of the curvature amount of the width direction of the phenol resin foam, and the curvature amount of the length direction. Moreover, the phenol resin foam of this embodiment also has a warpage amount in the width direction and a warpage amount in the length direction of less than 7 mm, and is preferably 5 mm or less.
If the amount of warpage in the infrared irradiation test of the phenol resin foam is 7 mm or more, when the heat insulating material made of the phenol resin foam is applied, the heat insulating material cannot be applied according to the dimensions. Problems such as being unable to fasten may occur.

Here, the infrared irradiation test of the phenol resin foam of this embodiment is demonstrated using FIGS.
FIG. 1 is a front view showing an infrared irradiation apparatus used for an infrared irradiation test of a phenol resin foam. FIG. 2 is a top view showing an infrared irradiation apparatus used for an infrared irradiation test of a phenol resin foam. FIG. 3 is a side view showing an infrared irradiation apparatus used for an infrared irradiation test of a phenol resin foam. FIG. 4 is a plan view showing a phenol resin foam used in an infrared irradiation test of the phenol resin foam.

The infrared irradiation device 1 is a device for irradiating the phenol resin foam 100 with infrared rays.
The infrared irradiation device 1 includes a base 2, a phosphorus tree 3, an infrared irradiation unit 5 having an infrared heater 4, and a housing 6.
The base 2 is provided 240 mm above the lower part of the housing 6 and supports the phosphorus wood 3.
The phosphorus wood 3 is provided on the upper surface 2 a of the base 2 so as to extend perpendicular to the longitudinal direction of the base 2. Further, six phosphorus trees 3 are arranged in parallel at equal intervals along the longitudinal direction of the base 2 on the upper surface 2 a of the base 2. The phosphorus wood 3 supports the phenol resin foam 100 in the infrared irradiation test.
The infrared irradiation unit 5 is suspended from the ceiling 6 a of the housing 6 and is disposed on the upper portion of the housing 6 so as to face the upper surface 2 a of the base 2. The infrared irradiation unit 5 is provided so as to extend perpendicular to the longitudinal direction of the base 2. Further, twelve infrared irradiation units 5 are arranged in parallel along the longitudinal direction of the base 2 at equal intervals. In addition, the infrared irradiation unit 5 includes a cover 7 whose shape perpendicular to the longitudinal direction forms a bowl shape, and an infrared heater 4 disposed in the center of the cover 7. As for the cover 7, the surface (lower surface) 7a on the side facing the base 2 is fully open, and the inside is hollow. Further, the infrared irradiation unit 5 is arranged such that the lower surface 7 a of the cover 7 faces the upper surface 2 a of the base 2. Thereby, infrared rays are irradiated from the infrared heater 4 of the infrared irradiation unit 5 to the upper surface 100a of the phenol resin foam 100 arranged on the upper surface 3a of the phosphorus tree 3.
The infrared heater 4 has a cylindrical shape with a diameter of 12.5 mm, and the amount of power is 1000 W.
The housing 6 is a space for housing the base 2, the phosphorus tree 3, and the infrared irradiation unit 5 and maintaining the upper surface 100 a of the phenol resin foam 100 disposed on the phosphorus tree 3 at a predetermined temperature.

1 to 3, H ₁ is the height of the casing 6 (795 mm), L ₁ is the length of the casing 6 (1878 mm), W ₁ is the width of the casing 6 (1133 mm), and L ₂ is The length of the base 2 (1878 mm), W ₂ is the width of the base 2 (1133 mm), L ₃ is the length of the phosphorus wood 3 (length in the width direction of the base 2 1100 mm), and W ₃ is the phosphorus wood 3 (100 mm), H ₂ is the height (thickness, 15 mm) of the phosphorus tree 3, D ₁ is the distance between the phosphorus trees 3 (244 mm), and L ₄ is the length of the infrared heater 4 (the width direction of the base 2). , 1050 mm), L ₅ is the length of the cover 7 (length in the width direction of the base 2, 995 mm), W ₄ is the width of the cover 7 (120 mm), D ₂ is the distance between the infrared irradiation parts 5 (30 mm) ), _{D 3} the distance between the infrared irradiation unit 5 and the casing 6 arranged at both ends (54 mm), and a ceiling 6a of _{D 4} is the housing 6 D ₆ change the thickness of the phenolic foam 100 at intervals between the top of the upper surface 7b of the bar 7 is adjustable so that the predetermined height, D ₅ is the ceiling 6a of the housing 6 The distance (270 mm) from the lower surface 7 a of the cover 7, D ₆ is the distance (235 mm) between the infrared heater 4 and the upper surface 100 a of the phenol resin foam 100, and D ₇ is the ceiling 6 a of the housing 6 and the upper surface 2 a of the base 2. , L ₆ is the length of the phenol resin foam 100 (1820 mm), and W ₅ is the width of the phenol resin foam 100 (910 mm).

A phenol resin foam 100 having a width of 910 mm and a length of 1820 mm is prepared as a test body.
About the infrared irradiation surface of the phenol resin foam 100, the position from the center of 10 mm from one end in the length direction (1820 mm), the position from the center of 10 mm from the other end in the length direction, and 3 at the center. The octopus yarn is stretched in a direction parallel to the cross section in the width direction (910 mm) at the point. After infrared irradiation, at each point, the amount of warpage (mm) of the portion with the largest amount of warpage is measured in units of 0.5 mm with a metal ruler. Next, an average value of these three warp amounts is calculated and used as the warp amount in the width direction of the phenol resin foam 100.
Moreover, about the infrared irradiation surface of the phenol resin foam 100, the position from the center of 10 mm from one end in the width direction (910 mm), the position from the center of 10 mm from the other end in the width direction, and 3 in the center. The octopus yarn is stretched in a direction parallel to the cross section in the length direction (1820 mm).
After infrared irradiation, at each point, the amount of warpage (mm) of the portion with the largest amount of warpage is measured in units of 0.5 mm with a metal ruler. Next, the average value of these three warpage amounts is calculated and used as the warpage amount in the length direction of the phenol resin foam 100.
Incidentally, in FIG. 4, [alpha] 1 is the length direction of the phenolic foam 100, [alpha] 2 is the width direction of the phenolic foam 100, _{D 9} is the distance from the longitudinal end of the phenolic foam 100 (10 mm) , _{D 8} is the distance (10 mm) from the end portion in the width direction of the phenolic foam 100.
In addition, octopus yarn is stretched at three points of the lengthwise ends of the phenolic resin foam 100, and the warp amount (mm) of the portion having the largest warp amount is measured with a metal ruler at each point.
Next, the average value of these three warpage amounts is calculated and used as the warpage amount in the length direction of the phenol resin foam 100.
The amount of warpage of the phenol resin foam 100 is the amount of change in the distance (interval) between the upper surface (irradiation surface) 100a of the phenol resin foam 100 and the octopus yarn.

The phenol resin foam 100 is installed on the upper surface 3 a of the phosphor tree 3 of the infrared irradiation device 1, and the phenol resin foam 100 is irradiated with infrared rays from the infrared heater 4 of the infrared irradiation unit 5. At this time, a thermocouple is installed at the center of the upper surface (irradiation surface) 100a of the phenol resin foam 100, and the temperature of the upper surface 100a is adjusted to 70 ° C. ± 2 ° C.
The temperature of the upper surface 100a of the phenol resin foam 100 is kept in the above range for 4 hours.
In the same manner as described above, the warpage amount in the width direction of the phenol resin foam 100 and the warpage amount in the length direction of the phenol resin foam 100 are measured again.

The phenol resin foam of this embodiment preferably has a thickness of less than 70 mm, more preferably 50 mm or less, and even more preferably 45 mm or less.
Phenol resin foams are less likely to warp as the thickness increases, so if the thickness is 70 mm or more, the foam as a whole has high bending resistance and is difficult to warp, but the production efficiency is low, especially foaming. When a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon are used as the agent, the production efficiency of the foam having a large thickness is remarkably lowered. On the other hand, if the thickness is small, warpage is likely to occur, but the warpage can be suppressed to a low level by this embodiment, so that the production efficiency is high, and particularly expensive fluorinated unsaturated hydrocarbons and chlorinated fluorinated non-reactive foams are used. Even when saturated hydrocarbons are used, production efficiency can be increased.

The thermal conductivity of the phenol resin foam of this embodiment is preferably 0.0190 W / m · K or less, more preferably 0.0180 W / m · K or less, and 0.0175 W / m · K. More preferably, it is as follows.
When the thermal conductivity is 0.019 W / m · K or less, the phenol resin foam is excellent in heat insulation.

  The thermal conductivity of the phenol resin foam can be adjusted by the average cell diameter, the type and composition of the foaming agent, the type of surfactant, and the like. For example, the smaller the average cell diameter, the lower the thermal conductivity of the phenol resin foam. Further, when the surfactant is a silicone-based surfactant, particularly one having a polyether chain having a —OH end, the thermal conductivity tends to be lower than when other surfactants are used.

The phenol resin foam of the present embodiment preferably has a limiting oxygen index (hereinafter also referred to as “LOI”) of 28% or more, more preferably 30% or more, and more than 32%. More preferably it is.
LOI is the minimum oxygen concentration% (volume fraction) of the mixed gas of oxygen and nitrogen at 23 ° C ± 2 ° C required for the sample to maintain flammable combustion under specified conditions. It is an indicator. It shows that flammability is low, so that LOI is large, and when LOI is 26% or more, it is judged that it has a flame retardance.

  The LOI of the phenol resin foam can be adjusted by the type and composition of the foaming agent, the type of surfactant, the type and composition of the flame retardant and the amount thereof. For example, the lower the content of the combustible foaming agent in the foaming agent (the higher the content of at least one of fluorinated unsaturated hydrocarbon and chlorinated unsaturated fluorinated hydrocarbon), the higher the LOI. Further, if the surfactant is a silicone-based surfactant, particularly one having a polyether chain having a —OH end, the LOI tends to be higher than when other surfactants are used. Furthermore, LOI can be increased by adding a phosphorus-based flame retardant or the like.

(Phenolic resin)
As the phenol resin, a resol type resin is preferable.
The resol type phenol resin is a phenol resin obtained by reacting a phenol compound and an aldehyde in the presence of an alkali catalyst.
The phenol compound is not particularly limited, and examples thereof include phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcinol, and modified products thereof.
Although it does not specifically limit as an aldehyde, For example, formaldehyde, paraformaldehyde, furfural, acetaldehyde, etc. are mentioned.
Although it does not specifically limit as an alkali catalyst, For example, sodium hydroxide, potassium hydroxide, calcium hydroxide, an aliphatic amine (Trimethylamine, a triethylamine, etc.) etc. are mentioned.

  When synthesizing a resol type phenol resin, the blending ratio of the phenol compound and the aldehyde is not particularly limited. The mixing ratio of the phenol compound and the aldehyde is preferably a molar ratio of phenol compound to aldehyde of 1: 1 to 1: 3, and more preferably 1: 1.3 to 1: 2.5.

Moreover, the weight average molecular weight (Mw) calculated | required by the gel permeation chromatography of a phenol resin is 400-3000 normally, Preferably it is 700-2000.
When the weight average molecular weight (Mw) of the phenol resin is less than 400, the closed cell ratio of the phenol resin foam is lowered, thereby reducing the compression strength of the phenol resin foam and the long-term performance of the thermal conductivity of the phenol resin foam. There is a tendency to lead to a decline. Moreover, a phenol resin foam with many voids and a large average cell diameter is likely to be formed. On the other hand, when the weight average molecular weight (Mw) of the phenol resin exceeds 3000, the viscosity of the phenol resin raw material and the foamable phenol resin composition becomes too high. Many blowing agents are required, and when fluorinated unsaturated hydrocarbons and chlorinated fluorinated unsaturated hydrocarbons are used as blowing agents, this is expensive and not economical.

(Foaming agent)
As a foaming agent, at least 1 sort (s) of a halogenated saturated hydrocarbon, a fluorinated unsaturated hydrocarbon (HFO), and a chlorinated fluorinated unsaturated hydrocarbon (HCFO) is included.
Examples of halogenated saturated hydrocarbons include fluorinated saturated hydrocarbons and chlorinated saturated hydrocarbons.

  Examples of the fluorinated saturated hydrocarbon include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1, 2,2-tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-hepta Fluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluobane (HFC365mfc) and 1,1,1,2,2 , 3,4,5,5,5-decafluoropentane (HFC4310mee) and the like.

  As the chlorinated saturated hydrocarbon, those having 2 to 5 carbon atoms are preferable, and examples thereof include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. Among these, isopropyl chloride is preferable because it has a low ozone depletion coefficient and is excellent in environmental compatibility.

  Examples of the fluorinated unsaturated hydrocarbon include those containing fluorine and a carbon-carbon double bond in the molecule. For example, 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3 3,3-tetrafluoropropene (HFO-1234ze) (E and Z isomers), 1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz) (E and Z isomers) (e.g. , SynQuest Laboratories, product number: 1300-3-Z6), and the like disclosed in JP-T-2009-513812.

  Examples of the chlorinated fluorinated unsaturated hydrocarbon include those containing chlorine, fluorine and a double bond in the molecule, such as 1,2-dichloro-1,2-difluoroethene (E and Z isomers), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) (E and Z isomers) (for example, Honeywell, trade name: SOLSTICE LBA), 1-chloro-2,3,3-tri Fluoropropene (HCFO-1233yd) (E and Z isomers), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb) (E and Z isomers), 2-chloro-1,3,3 -Trifluoropropene (HCFO-1233xe) (E and Z isomers), 2-chloro-2,2,3-trifluoropropene (HCFO-1233xc) 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) (for example, SynQuest Laboratories, product number: 1300-7-09), 3-chloro-1,2,3-trifluoropropene (HCFO-1233ye) (E and Z isomers), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc), 3,3-dichloro-3-fluoropropene, 1,2-dichloro-3 , 3,3-trifluoropropene (HFO-1223xd) (E and Z isomers), 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E and Z isomers) And 2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene (E and Z variants) and the like.

  Fluorinated unsaturated hydrocarbons and chlorinated fluorinated unsaturated hydrocarbons are advantageous in that they have a small ozone depletion potential (ODP) and a global warming potential (GWP) and have a small impact on the environment.

  Chlorinated saturated hydrocarbons have been conventionally used as a foaming agent for phenol resin foams. However, when one type is used alone, the average cell diameter of the phenol resin foam is large and the thermal conductivity is high. By using a fluorinated unsaturated hydrocarbon or a chlorinated fluorinated unsaturated hydrocarbon in combination, the average cell diameter is small, the thermal conductivity is lowered, and the heat insulating property of the phenol resin foam is improved. Moreover, since the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon are nonflammable, the flame retardancy of the phenol resin foam is improved.

  In a combination of a chlorinated saturated hydrocarbon and at least one of a fluorinated unsaturated hydrocarbon and a chlorinated unsaturated fluorinated hydrocarbon, the chlorinated saturated hydrocarbon, the fluorinated unsaturated hydrocarbon and the chlorinated non-fluorinated hydrocarbon The mass ratio of at least one kind of saturated hydrocarbon is chlorinated saturated hydrocarbon: at least one kind of fluorinated unsaturated hydrocarbon and chlorinated unsaturated fluorinated hydrocarbon = 9.9: 0.1 to 0.1 : 9.9 is preferable. By containing at least one kind of fluorinated unsaturated hydrocarbon and chlorinated fluorinated unsaturated hydrocarbon within a range satisfying the above-mentioned mass ratio, the average cell diameter is smaller, the thermal conductivity is lower, and the phenol resin The heat insulating property of the foam is more excellent.

  In this embodiment, the chlorinated saturated hydrocarbon usually has a lower molecular weight than the fluorinated unsaturated hydrocarbon or chlorinated fluorinated unsaturated hydrocarbon. If the amount is the same, the smaller the molecular weight, the larger the volume when foamed. Therefore, when the molecular weight of the chlorinated saturated hydrocarbon is smaller than the molecular weight of the fluorinated unsaturated hydrocarbon or chlorinated fluorinated unsaturated hydrocarbon, the higher the proportion of chlorinated saturated hydrocarbon, the smaller the amount of foaming agent. Sufficiently easy to foam. Further, chlorinated saturated hydrocarbons tend to be cheaper than fluorinated unsaturated hydrocarbons or chlorinated fluorinated unsaturated hydrocarbons. From these viewpoints, the mass ratio of the chlorinated saturated hydrocarbon to at least one of the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon is chlorinated saturated hydrocarbon: fluorinated unsaturated hydrocarbon and At least one chlorinated fluorinated unsaturated hydrocarbon is preferably 9.9: 0.1 to 5: 5, and more preferably 9: 1 to 7: 3. The lower the ratio of at least one of the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon within the above range, the lower the cost while maintaining excellent heat insulation.

  On the other hand, fluorinated unsaturated hydrocarbons or chlorinated unsaturated hydrocarbons tend to have lower thermal conductivity than chlorinated saturated hydrocarbons. Therefore, from the viewpoint of obtaining better heat insulation, the mass ratio of the chlorinated saturated hydrocarbon to at least one of the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon is chlorinated saturated hydrocarbon: It is preferable that at least one of a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon = 5: 5 to 0.1: 9.9. The higher the ratio of at least one of the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon within the above range, the lower the thermal conductivity and the higher the heat insulation.

In the combination of a chlorinated saturated hydrocarbon and at least one of a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon, the boiling point of the fluorinated unsaturated hydrocarbon or the chlorinated fluorinated unsaturated hydrocarbon is: It is preferably lower than the boiling point of the chlorinated saturated hydrocarbon. When the boiling point of fluorinated unsaturated hydrocarbon or chlorinated fluorinated unsaturated hydrocarbon is lower than the boiling point of chlorinated saturated hydrocarbon, the bubble diameter of the bubbles in the phenol resin foam is small, and the bubbles per unit volume There is a tendency that the number of is increased and the heat insulation is more excellent.
Moreover, it is preferable that the difference of those boiling points is 2 degreeC or more and 30 degrees C or less, and 5 degreeC or more and 20 degrees C or less are more preferable. If the difference in boiling points is larger than the above upper limit, fluorinated unsaturated hydrocarbons or chlorinated fluorinated unsaturated hydrocarbons previously gasified to form bubble nuclei will be gasified, and chlorinated saturated hydrocarbons with higher boiling points will be gasified. By doing so, it may escape from the bubbles and foaming may be insufficient. If the difference in boiling points is smaller than the above lower limit, the chlorinated saturated hydrocarbon may foam without sufficiently forming bubble nuclei, and the bubble diameter may become coarse.
Therefore, for example, when isopropyl chloride having a boiling point of 36 ° C. is selected as a chlorinated saturated hydrocarbon, a halogenated unsaturated hydrocarbon having a boiling point of 6 ° C. or higher and 34 ° C. or lower is selected. It is preferable to select one having a boiling point of 14 ° C. or higher and 34 ° C. or lower from the viewpoint of easy handling near normal temperature.

  As a combination of a chlorinated saturated hydrocarbon and at least one of a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon, a combination of isopropyl chloride (2-chloropropane) and a fluorinated unsaturated hydrocarbon, Alternatively, a combination of isopropyl chloride and chlorinated fluorinated unsaturated hydrocarbon is preferred. In these combinations, each of the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon may be one type or two or more types.

The blowing agent may contain a hydrocarbon as a blowing agent other than halogenated saturated hydrocarbons, fluorinated unsaturated hydrocarbons and chlorinated fluorinated unsaturated hydrocarbons.
It does not specifically limit as hydrocarbon, For example, it is preferable that a C3-C7 hydrocarbon (Butane, isobutane, pentane, isopentane, cyclopentane, hexane, heptane, etc.) is included.

  In addition to the above blowing agents, low boiling point gases such as nitrogen, argon, carbon dioxide and air; sodium hydrogen carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, azodicarboxylic amide, azobisisobutyronitrile, azodicarboxylic Chemical foaming agents such as barium acid, N, N′-dinitrosopentamethylenetetramine, p, p′-oxybisbenzenesulfonyl hydrazide, trihydrazinotriazine; porous solid materials and the like may be included.

  The content of the foaming agent in the phenol resin foam (or foamable phenol resin composition) is preferably 1 part by mass or more and 25 parts by mass or less per 100 parts by mass of the phenol resin, and 3 parts by mass or more and 15 parts by mass. More preferably, it is more preferably 5 parts by mass or more and 11 parts by mass or less.

Composition (mass ratio) of at least one kind of halogenated saturated hydrocarbon, fluorinated unsaturated hydrocarbon and chlorinated unsaturated unsaturated hydrocarbon in the foaming agent in the foamable phenol resin composition used for producing the phenol resin foam ) Substantially matches the composition of at least one of a halogenated saturated hydrocarbon, a fluorinated unsaturated hydrocarbon and a chlorinated fluorinated unsaturated hydrocarbon contained in the phenol resin foam.
The composition of at least one of the halogenated saturated hydrocarbon, the fluorinated unsaturated hydrocarbon and the chlorinated fluorinated unsaturated hydrocarbon contained in the phenol resin foam can be confirmed, for example, by the following solvent extraction method.

Solvent extraction method:
Using a standard gas of halogenated saturated hydrocarbon, fluorinated unsaturated hydrocarbon or chlorinated fluorinated unsaturated hydrocarbon in advance, the retention time under the following measurement conditions with a gas chromatograph-mass spectrometer (GC / MS) Ask.
Next, 1.6 g of a phenol resin foam sample from which the upper and lower face materials have been peeled is taken into a glass container for grinding, and 80 mL of tetrahydrofuran (THF) is added.
After crushing the sample so that it is immersed in the solvent, it is pulverized and extracted for 1 minute and 30 seconds with a homogenizer, the extract is filtered with a membrane filter having a pore size of 0.45 μm, and the filtrate is subjected to GC / MS.
The type of halogenated saturated hydrocarbon, fluorinated unsaturated hydrocarbon or chlorinated fluorinated unsaturated hydrocarbon is identified from the retention time and mass spectrum determined in advance. The types of gases other than halogenated saturated hydrocarbons, fluorinated unsaturated hydrocarbons or chlorinated fluorinated unsaturated hydrocarbons are identified by the retention time and mass spectrum.
The detection sensitivity of each blowing agent component is measured with a standard gas, and the composition (mass ratio) is calculated from the detection area area and detection sensitivity of each gas component obtained by the GC / MS.
GC / MS measurement conditions Column used: DB-5ms (Agilent Technology) 60m, inner diameter 0.25mm, film thickness 1μm
Column temperature: 40 ° C (10 minutes)-10 ° C / min-200 ° C
Inlet temperature: 200 ° C
Interface temperature: 230 ° C
Carrier gas: He 1.0 mL / min Split ratio: 20: 1
Measuring method: scanning method m / Z = 11 to 550

(Acid catalyst)
The acid catalyst is contained in the foamable phenol resin composition in order to cure the phenol resin.
Examples of the acid catalyst include organic acids such as benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, and phenolsulfonic acid, and inorganic acids such as sulfuric acid and phosphoric acid. These acid catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the acid catalyst in the foamable phenolic resin composition is preferably 5 parts by mass or more and 30 parts by mass or less, more preferably 8 parts by mass or more and 25 parts by mass or less per 100 parts by mass of the phenol resin. More preferably, they are 10 to 20 mass parts.

(Surfactant)
The surfactant contributes to the refinement of the cell diameter (cell diameter).
The surfactant is not particularly limited, and those known as foam stabilizers can be used. For example, castor oil alkylene oxide adduct, silicone surfactant, polyoxyethylene sorbitan fatty acid ester and the like can be mentioned. These surfactants may be used alone or in combination of two or more.
The surfactant preferably contains at least one of a castor oil alkylene oxide adduct and a silicone-based surfactant in terms of easily forming bubbles having a small cell diameter, and has a lower thermal conductivity and a higher flame retardancy. It is more preferable that a silicone type surfactant is included at the point which can do.

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

  As the castor oil alkylene oxide adduct, one obtained by adding alkylene oxide, particularly EO, more than 20 moles and less than 60 moles to 1 mole of castor oil, and more preferably 21 moles or more and 40 moles or less is added. In the castor oil alkylene oxide adduct, a polyoxyalkylene group (polyoxyethylene group or the like) formed by a hydrophobic group mainly composed of a long chain hydrocarbon group of castor oil and a predetermined addition mole of alkylene oxide (EO or the like). The hydrophilic group as a main component is arranged in a well-balanced manner in the molecule, and good surface activity is exhibited. Therefore, the cell diameter of the phenol resin foam is reduced. In addition, the bubble wall is given flexibility, and the generation of cracks is prevented.

Examples of silicone surfactants include copolymers of dimethylpolysiloxane and polyether, and organopolysiloxane compounds such as octamethylcyclotetrasiloxane. A copolymer of dimethylpolysiloxane and polyether is preferable in that the surface tension can be easily adjusted by changing the polymerization degree of each of the hydrophobic part and the hydrophilic part.
The copolymer of dimethylpolysiloxane and polyether is preferably a block copolymer of dimethylpolysiloxane and polyether. The structure of the block copolymer is not particularly limited. For example, an ABA type in which a polyether chain A is bonded to both ends of the siloxane chain B, and a plurality of siloxane chains B and a plurality of polyether chains A are alternately bonded. (AB) _n- type, branched type in which a polyether chain is bonded to each end of a branched siloxane chain, pendant type in which a polyether chain is bonded as a side group (group bonded to a portion other than the terminal) to the siloxane chain Can be mentioned.

Examples of the copolymer of dimethylpolysiloxane and polyether include dimethylpolysiloxane-polyoxyalkylene copolymer.
The number of carbon atoms of the oxyalkylene group in polyoxyalkylene is preferably 2 or 3.
The oxyalkylene group constituting the polyoxyalkylene may be one type or two or more types.
Specific examples of the dimethylpolysiloxane-polyoxyalkylene copolymer include dimethylpolysiloxane-polyoxyethylene copolymer, dimethylpolysiloxane-polyoxypropylene copolymer, dimethylpolysiloxane-polyoxyethylene-polyoxypropylene copolymer. A polymer etc. are mentioned.

  As the copolymer of dimethylpolysiloxane and polyether, those having a polyether chain whose terminal is -OR (wherein R is a hydrogen atom or an alkyl group) are preferred, and the thermal conductivity is more enhanced. A compound in which R is a hydrogen atom is particularly preferable because it is low and flame retardancy can be further increased.

When the phenol resin foam contains a surfactant, the content of the surfactant in the foamable phenol resin composition is preferably 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the phenol resin. It is more preferable that the amount is not less than 5 parts by mass.
If the content of the surfactant is not less than the lower limit of the above range, the cell diameter tends to be uniformly small, and if it is not more than the upper limit, the water absorption of the phenol resin foam is low and the production cost can be suppressed. .

(Other ingredients)
As another component, what is known as an additive of a phenol resin foam can be added to a foamable phenol resin composition. Examples of other components include urea, plasticizers, fillers, flame retardants (for example, phosphorus flame retardants), crosslinking agents, organic solvents, amino group-containing organic compounds, and colorants.

Urea is used as a formaldehyde catcher agent that captures formaldehyde when foaming a foamable phenolic resin composition to produce a foam.
Examples of the plasticizer include polyester polyol and polyethylene glycol which are reaction products of phthalic acid and diethylene glycol.

  Here, it is known to add a plasticizer having high compatibility with a hydrophilic phenol resin, for example, a plasticizer containing a polyester polyol (for example, Patent No. 4761446). Publication). However, fluorinated unsaturated hydrocarbons and chlorinated fluorinated unsaturated hydrocarbons are highly compatible with phenolic resins due to their high polarities in the molecule, and fluorinated unsaturated hydrocarbons and chlorinated fluorinated unsaturated hydrocarbons. When a foaming agent containing a large amount of a plasticizer and a plasticizer are used in combination, the viscosity of the phenol resin is too low, and foaming may not sufficiently occur, or the phenol resin may ooze out from the face material. Therefore, when using fluorinated unsaturated hydrocarbons or chlorinated fluorinated unsaturated hydrocarbons as the foaming agent, it is preferable not to include a plasticizer.

Examples of the filler include basic fillers. As the basic filler, an inorganic filler is preferable in that a phenol resin foam having low acidity and improved fire resistance can be provided.
Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, titanium oxide, metal oxide such as antimony oxide, metal powder such as zinc, carbonic acid Metal carbonates such as calcium, magnesium carbonate, barium carbonate, zinc carbonate, alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkaline earth metal hydrogen carbonates such as calcium hydrogen carbonate and magnesium hydrogen carbonate, sulfuric acid Examples include calcium, barium sulfate, calcium silicate, mica, talc, bentonite, zeolite, silica gel, and the like. However, when a strong acid is used as the acid catalyst, it is necessary to add the metal powder and carbonate within a range that does not affect the adjustment of the pot life. These inorganic fillers may be used alone or in combination of two or more.

When the foamable phenol resin composition contains a basic filler, the content of the basic filler in the foamable phenol resin composition is preferably such that the extraction pH is 5 or more. For example, the content of the basic filler is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, per 100 parts by mass of the phenol resin. It is more preferably 3 parts by mass or more and 15 parts by mass or less, and particularly preferably 5 parts by mass or more and 10 parts by mass or less.
If content of a basic filler is less than the said lower limit, the extraction pH of a phenol resin foam will become low. When the extraction pH is lowered, the acidity increases, so that the material in contact with the phenol resin foam may be corroded. When the content of the basic filler exceeds the above upper limit, the curing reaction by the acid catalyst is remarkably inhibited, and the productivity may be deteriorated.

The extraction pH is measured by the following method.
A phenol resin foam is pulverized in a mortar to 250 μm (60 mesh) or less to prepare a sample. Weigh 0.5 g of sample into a 200 mL Erlenmeyer flask with a stopper. Add 100 mL of pure water to a conical stoppered Erlenmeyer flask and seal tightly. Using a magnetic stirrer, the inside of the conical stoppered flask is stirred at 23 ° C. ± 5 ° C. for 7 days to obtain a sample solution. The pH of the obtained sample solution is measured with a pH meter, and the value is taken as the extraction pH.

  The basic filler also functions as a protective agent that captures hydrogen fluoride. It is known that the halogenated unsaturated hydrocarbon used as the blowing agent generates hydrogen fluoride by decomposition or contains hydrogen fluoride used as a raw material for its production as an impurity (see Table 2014). No. 511930). This hydrogen fluoride is not only highly reactive and extremely harmful to the human body, but also reacts with the siloxane bond constituting the hydrophobic part of the silicone surfactant to reduce the surface active action. Therefore, the above basic filler may be added to the foamable phenol resin composition as a hydrogen fluoride scavenger or a surfactant protective agent. In particular, among the above fillers, it is preferable to use a basic inorganic filler such as calcium carbonate because the extraction pH can be increased.

  On the other hand, as a result of examination by the inventors of the present application, it has been found that the smaller the content of the inorganic filler, the lower the thermal conductivity of the phenol resin foam. Therefore, from the viewpoint of heat insulation, the content of the inorganic filler in the foamable phenolic resin composition is preferably less than 0.1 parts by mass and 0 parts by mass with respect to 100 parts by mass of the phenolic resin. Particularly preferred. That is, it is preferable that the foamable phenol resin composition does not contain an inorganic filler.

The foamable phenol resin composition can be prepared by mixing the above-described components.
The mixing order of each component is not particularly limited. For example, a surfactant is added to a phenol resin, and other components are added as necessary, and the whole is mixed. A foaming agent and an acid catalyst are added to this mixture, and this composition is added. Is supplied to a mixer and stirred to prepare a foamable phenolic resin composition.

The face material is not particularly limited, and glass paper, glass fiber woven fabric, glass fiber nonwoven fabric, glass fiber mixed paper, kraft paper, synthetic fiber nonwoven fabric made of polyester, polypropylene, nylon, etc., spunbond nonwoven fabric, aluminum foil-clad nonwoven fabric At least one selected from the group consisting of aluminum foil-clad kraft paper, metal plate, metal foil, plywood, calcium silicate plate, gypsum board, and wood-based cement plate is preferable.
Each face material provided on both surfaces of the foamed resin layer may be the same or different.

According to the phenol resin foam of the present embodiment, the phenol resin foam includes a foam resin layer and face materials provided on both sides of the foam resin layer, and the foam resin layer is a fluorinated unsaturated hydrocarbon. And a density of 15 kg / m ³ or more and 50 kg / m ³ or less, an average cell diameter of 50 μm or more and 200 μm or less, and a closed cell ratio of 85% or more And the amount of warpage in the infrared irradiation test is less than 7 mm. Therefore, when installing a heat insulating material made of phenol resin foam, even if only one surface of the heat insulating material (the surface on the opposite side of the building) is exposed to sunlight, the heat insulating material cannot be applied according to the dimensions. There is no problem that the material cannot be sufficiently screwed to the pillar.

[Production method]
(First embodiment)
The manufacturing method of the phenol resin foam of this embodiment is a manufacturing method of the phenol resin foam of this embodiment, Comprising: On the 1st face material, a phenol resin, a halogenated saturated hydrocarbon, a fluorinated unsaturated carbonization A discharge step of discharging a foamable phenol resin composition containing at least one of hydrogen and a chlorinated fluorinated unsaturated hydrocarbon and an acid catalyst; and a foamable phenol resin composition discharged on a first face material And a foaming step in which the foamable phenolic resin composition is foamed and cured between the first face material and the second face material by bonding the second face material, and in the foaming step, the first face material The temperature difference between the conveyor in contact with the first surface material for conveying the second surface material and the conveyor in contact with the second surface material for conveying the second surface material is 4 ° C. or more.

As a method of providing the first face material and the second face material when manufacturing the phenol resin foam, for example, the first face material is arranged on a conveyor that runs continuously, and the foamable phenol is formed on the first face material. After discharging the resin composition (discharge process) and laminating (bonding) the second face material on the foamable phenolic resin composition discharged on the first face material by a conveyor, the first face material, There is a method in which foaming molding is performed by passing through a heating furnace in a state where a laminate composed of the foamable phenolic resin composition and the second face material is sandwiched between a pair of conveyors (foaming step). Thereby, the phenol resin foam with a face material which the 1st face material and the 2nd face material laminated | stacked on both surfaces of the plate-shaped phenol resin foam is obtained, respectively.
Examples of the conveyor include a slat conveyor and a conveyor belt. The slat conveyor is an integrated conveyor formed by connecting a plurality of plates called slats next to each other. The conveyor belt uses an endless belt as a conveyor.
As the first face material and the second face material, the same face materials as those described above are used.

  In the discharging step, the method for discharging the foamable phenol resin composition onto the first face material is not particularly limited. For example, a method of discharging the foamable phenol resin composition from a plurality of nozzles is used.

In the foaming step, the foamable phenol resin composition of the present embodiment can be produced by foaming and curing the foamable phenol resin composition between the first face material and the second face material.
The phenol resin foam can be produced by a known method. For example, a phenol resin foam can be produced by heating and foaming and curing a foamable phenol resin composition at 30 ° C. or more and 95 ° C. or less.

  As described above, in the foaming step, the laminate comprising the first face material, the foamable phenolic resin composition, and the second face material is sandwiched between a pair of conveyors, and the laminate is passed through a heating furnace. And foam molding. In the manufacturing method of the phenol resin foam of this embodiment, the temperature of the conveyor which contacts a 1st surface material and the temperature of the conveyor which contacts a 2nd surface material are adjusted, and the temperature difference shall be 4 degreeC or more. Thereby, in the foamed resin layer formed between the first face material and the second face material by foaming and curing of the foamable phenol resin composition, the moisture content of the layer on the first face material side and the second A difference occurs in the moisture content of the face material side layer. In this way, the laminate composed of the first face material, the foamed resin layer, and the second face material is cured in a state where the moisture content of the layer on the first face material side and the moisture content of the layer on the second face material side are different. When dried (cured) and the laminate is a phenol resin foam, the water content of the entire phenol resin foam becomes uniform. Therefore, in the phenol resin foam, stress is generated on the layer side where the moisture content is high. Thereby, when the heat insulating material which consists of a phenol resin foam is constructed by making the layer side where the moisture content was low into the surface, the heat insulating material becomes difficult to warp to the surface side.

In the foaming step, the temperature difference between the conveyor in contact with the first face material and the conveyor in contact with the second face material is 4 ° C. or higher, preferably 4 ° C. or higher and 30 ° C. or lower, preferably 5 ° C. or higher and 20 ° C. or lower. More preferably, it is more preferably 5 ° C. or more and 15 ° C. or less.
If the temperature difference between the conveyor in contact with the first face material and the conveyor in contact with the second face material is less than 4 ° C., in the foamed resin layer formed between the first face material and the second face material, Since the difference between the moisture content of the layer and the moisture content of the layer on the second face material side is not sufficient, warping of the phenol resin foam cannot be suppressed.
In the foamed resin layer, the difference in moisture content between the first face material side and the second face material side is preferably 1.5% or more and 5% or less, and 2.0% or more and 4.5% or less. Is more preferable.

  According to the method for producing a phenol resin foam of the present embodiment, the first face material and the second face material are bonded to the foamable phenol resin composition discharged onto the first face material by bonding the second face material. In the foaming step of foaming and curing the foamable phenolic resin composition between, a conveyor in contact with the first face material for conveying the first face material and a second face material for conveying the second face material The temperature difference of the conveyor in contact with is set to 4 ° C. or more. Therefore, the curvature amount of a phenol resin foam can be suppressed.

[Production method]
(Second Embodiment)
The manufacturing method of the phenol resin foam of this embodiment is a manufacturing method of the phenol resin foam of this embodiment, Comprising: On the 1st face material, a phenol resin, a halogenated saturated hydrocarbon, a fluorinated unsaturated carbonization A discharge step of discharging a foamable phenol resin composition containing at least one of hydrogen and a chlorinated fluorinated unsaturated hydrocarbon and an acid catalyst; and a foamable phenol resin composition discharged on a first face material And a foaming step in which the foamable phenolic resin composition is foamed and cured between the first face material and the second face material by laminating the second face material, and in the discharge process, a single nozzle The foamable phenolic resin composition is discharged onto the first face material from the nozzle while moving in a direction perpendicular to the running direction of the first face material.

  As a method of providing the first face material and the second face material when manufacturing the phenol resin foam, the same method as in the first embodiment is used.

In the discharging step, a method of discharging the foamable phenolic resin composition from a single nozzle is used as a method of discharging the foamable phenolic resin composition onto the first face material.
As a method of discharging the foamable phenolic resin composition from a single nozzle, a single nozzle is moved in a direction perpendicular to the traveling direction of the first face material (longitudinal direction of the first face material). A method of discharging the foamable phenolic resin composition onto the first face material from one nozzle is used.

Moreover, when discharging a foamable phenol resin composition on a 1st face material from a single nozzle, moving a single nozzle to the orthogonal | vertical direction with respect to the running direction of a 1st face material, the 1st face material It is preferable that the traveling speed of the nozzle is equal to the moving speed of the nozzle.
Moreover, it is preferable that the width | variety which moves a single nozzle to the orthogonal | vertical direction with respect to the running direction of a 1st face material is 50 to 80% of the width | variety of a 1st face material.

In the foaming step, the foamable phenol resin composition of the present embodiment can be produced by foaming and curing the foamable phenol resin composition between the first face material and the second face material.
The phenol resin foam can be produced by a known method.

  According to the method for producing a phenol resin foam of the present embodiment, a single nozzle is moved while moving a single nozzle in a direction perpendicular to the traveling direction of the first face material (longitudinal direction of the first face material). Since the foamable phenol resin composition is discharged on the first face material in order to discharge the foamable phenol resin composition on the first face material, the foamable phenol resin composition is foamed and cured. In the phenol resin foam obtained by the above, stress is generated almost uniformly in the width direction and the length direction. Thereby, the curvature amount of a phenol resin foam can be suppressed.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.
Measurement methods used in Examples and Comparative Examples described later are shown below.

(1) Measuring method of moisture content of phenol resin foam before curing In a continuous production using a conveyor belt, a laminate composed of a pair of face materials and a foamed resin layer that have undergone a foaming process is extracted, and the width is 200 mm × length is 200 mm. A test piece was cut out.
When both of the face materials of the test piece are peeled off and the thickness of the foamed resin layer is less than 30 mm, it is cut into two equal parts in the vertical direction and the thickness of the foamed resin layer is 30 mm or more. Was cut into three equal parts in the direction perpendicular to the thickness direction, and the mass of each piece was measured. The difference in the thickness of the fragments was set to be within 0.5 mm.
The operation up to this point was performed within 20 minutes after the laminate was extracted.
Each piece was placed in an oven at 104 ° C. and dried. After 48 hours, the mass of each fragment was measured.
The mass before drying was m ₀ and the mass after drying was m _1, and the moisture content α (%) of each fragment was calculated from the following formula.
Water content α (%) = (m ₀ −m ₁ ) / m ₀ × 100

(2) Density The density of the phenol resin foam was measured in accordance with the density measurement method specified in Japanese Industrial Standards JIS A9511: 2009.

(3) Average cell diameter A test piece was cut out from approximately the center in the thickness direction of the phenol resin foam. The cut surface in the thickness direction of the test piece was photographed at 50 times magnification. Four straight lines 9 cm in length were drawn on the photographed image.
At this time, a straight line was drawn so as to avoid voids (voids of 2 mm ² or more). The number of bubbles crossed by each straight line (based on the method for measuring the number of cells defined in Japanese Industrial Standards JIS K6400-1: 2004) was counted for each straight line, and the average value per straight line was obtained. 1800 μm was divided by the average value of the number of bubbles, and the obtained value was defined as the average cell diameter.

(4) Aspect ratio of bubbles The phenol resin foam of each example was divided into two equal parts in the thickness direction, and a photograph in which the cross section was magnified 50 times with an electron microscope was taken. In the photographed image, two straight lines (corresponding to a length of 1800 μm) were drawn in the length direction of the foam layer, and two straight lines (corresponding to a length of 1800 μm) were drawn in the width direction of the foam layer. The diameter on the straight line of the bubbles crossed by the straight line in the length direction was measured, and the average diameter was calculated from the result to obtain the bubble diameter (RM) in the length direction. Moreover, the diameter on the straight line of the bubble which the straight line of the width direction crossed was measured, the average diameter was computed from the result, and it was set as the bubble diameter (RT) in the width direction.
The bubble aspect ratio was calculated from the obtained RM and RT.

(5) Closed cell ratio The closed cell ratio of the phenol resin foam was measured in accordance with the closed cell ratio measurement method defined in Japanese Industrial Standards JIS K7138: 2006.

(6) Thermal conductivity The thermal conductivity of the phenol resin foam was measured based on the measurement method of thermal conductivity defined in Japanese Industrial Standards JIS A 1412-2. The measurement was performed twice on the same sample.

(7) Limiting oxygen index The limiting oxygen index of the phenol resin foam was measured in accordance with the measuring method of limiting oxygen index (LOI) defined in Japanese Industrial Standards JIS K7201-2: 2007.

(8) Compressive strength Based on Japanese Industrial Standard JIS K 7220: 2006, the compressive strength of the phenol resin foam was measured.

(9) Infrared irradiation test The above-described infrared irradiation apparatus was used.
A phenol resin foam was installed on the upper surface of the phosphorous tree of the infrared irradiation device, and the phenol resin foam was irradiated with infrared rays from the infrared heater of the infrared irradiation section. At this time, the thermocouple was installed in the center part of the upper surface of a phenol resin foam, and the temperature of the upper surface was set to 70 degreeC +/- 2 degreeC.
The temperature of the upper surface of the phenol resin foam was continuously heated for 4 hours while maintaining the above temperature.
Thereafter, the amount of warpage in the width direction of the phenol resin foam and the amount of warpage in the length direction of the phenol resin foam were immediately measured by the method described in paragraph 0024, and the average values in the length direction and the width direction were calculated.

[Reference Example 1]
100 parts by mass of a liquid resol type phenolic resin (trade name: PF-339, manufactured by Asahi Organic Materials Co., Ltd.), 4 parts by mass of castor oil EO adduct (addition mole number 30) as a surfactant, and urea 4 as a formaldehyde catcher agent A part by mass was added and mixed, and left at 20 ° C. for 8 hours.
As a foaming agent, 14 parts by mass of the foaming agent A shown in Table 1 was added to 108 parts by mass of the mixture thus obtained, and 16 parts by mass of a mixture of paratoluenesulfonic acid and xylenesulfonic acid was added as an acid catalyst. The foamable phenol resin composition was prepared by stirring and mixing. In Table 1, “HCFO-1233zd” represents “E-1-chloro-3,3,3-trifluoropropene”, “IP” represents “isopentane”, and “IPC” represents “isopropyl chloride”. Indicates.
The first face material in which this foamable phenol resin composition is continuously run by a conveyor belt from 18 nozzles arranged in parallel at equal intervals in a direction perpendicular to the running direction of the first face material. It was discharged on the top.
Next, the second face material was laminated (bonded) onto the foamable phenolic resin composition discharged onto the first face material by a conveyor belt. At this time, the temperature of the conveyor belt in contact with the first face material is adjusted, and the first face material (the lower surface side of the laminate composed of the first face material, the foamable phenol resin composition and the second face material) is used. The temperature of the lower conveyor belt to be conveyed is adjusted to 60 ° C., the temperature of the conveyor belt in contact with the second face material is adjusted, and the second face material (first face material, foamable phenolic resin composition) And the upper conveyor belt that conveys the laminate comprising the second face material) is heated for 300 seconds in a furnace adjusted so that the temperature of the upper conveyor belt is 70 ° C., and the foamable phenolic resin composition is foamed and cured. did.
As the first face material and the second face material, the face materials described in the table were used.
After foaming and curing of the foamable phenol resin composition were completed, the laminate composed of the first face material, the foamed resin layer and the second face material was cured and dried (cured) to obtain a phenol resin foam.
The obtained phenol resin foam was cut into a width of 910 mm and a length of 1820 mm to prepare a phenol resin foam plate of Reference Example 1 having a thickness of 20 mm.
About the obtained phenolic resin foam board, it evaluated about the item of said (1)-(9). The results are shown in Table 2. Table 2 or Table 3 also shows the evaluation results regarding the phenolic resin foam plates of Reference Examples 2 to 10 and Examples 2 to 7 below.

[Example 1]
A phenolic resin foam board of Example 1 was produced in the same manner as Reference Example 1 except that the thickness was 35 mm.

[Example 2]
A phenolic resin foam plate of Example 2 was produced in the same manner as Reference Example 1 except that the thickness was 50 mm.

[Reference Example 2]
As a foaming agent, 14 parts by mass of foaming agent B shown in Table 1 was added to prepare a foamable phenolic resin composition.
Using this foamable phenolic resin composition, the temperature of the lower conveyor belt that conveys the first face material is adjusted to 65 ° C., and the temperature of the upper conveyor belt that conveys the second face material becomes 70 ° C. A phenolic resin foam board of Reference Example 2 was produced in the same manner as Reference Example 1 except that the amount was adjusted to.

[Reference Example 3]
A phenolic resin foam board of Reference Example 3 was produced in the same manner as Reference Example 2 except that the thickness was 35 mm.

[Reference Example 4]
A phenolic resin foam plate of Reference Example 4 was produced in the same manner as Reference Example 2 except that the thickness was 50 mm.

[Reference Example 5]
As a foaming agent, 12 parts by mass of a foaming agent C shown in Table 1 was added to prepare a foamable phenolic resin composition.
Using this foamable phenolic resin composition, the temperature of the lower conveyor belt that conveys the first face material is adjusted to 65 ° C., and the temperature of the upper conveyor belt that conveys the second face material becomes 75 ° C. A phenolic resin foam board of Reference Example 5 was produced in the same manner as Reference Example 1 except that the amount was adjusted.

[Reference Example 6]
A phenolic resin foam board of Reference Example 6 was produced in the same manner as Reference Example 5 except that the thickness was 35 mm.

[Reference Example 7]
A phenolic resin foam board of Reference Example 7 was produced in the same manner as Reference Example 5 except that the thickness was 50 mm.

[Example 3]
While the single nozzle is moved in the direction perpendicular to the traveling direction of the first face material, the foamable phenol resin composition is discharged from the single nozzle onto the first face material, and the first face material is Implemented in the same manner as in Reference Example 1 except that the temperature of the lower conveyor belt to be conveyed is adjusted to 70 ° C. and the temperature of the upper conveyor belt to convey the second face material is adjusted to 70 ° C. The phenolic resin foam board of Example 3 was produced.

[Example 4]
A phenolic resin foam plate of Example 4 was produced in the same manner as Example 3 except that the thickness was 50 mm.

[Reference Example 8]
5 parts by mass of calcium carbonate was added as an additive to prepare a foamable phenolic resin composition.
Using this foamable phenolic resin composition, the temperature of the lower conveyor belt that conveys the first face material is adjusted to 65 ° C., and the temperature of the upper conveyor belt that conveys the second face material becomes 70 ° C. A phenolic resin foam board of Reference Example 8 was produced in the same manner as Reference Example 1 except that it was adjusted to.

[Example 5]
A phenolic resin foam plate of Reference Example 8 was produced in the same manner as in Example 5 except that the thickness was 50 mm.

[Example 6]
As a foaming agent, 14 parts by mass of foaming agent D shown in Table 1 was added to prepare a foamable phenol resin composition.
Using this foamable phenolic resin composition, the temperature of the lower conveyor belt that conveys the first face material is adjusted to 65 ° C., and the temperature of the upper conveyor belt that conveys the second face material becomes 75 ° C. A phenolic resin foam board of Example 6 was produced in the same manner as in Reference Example 1 except that the amount was adjusted.

[Reference Example 9]
A foaming phenol resin composition was prepared by adding 14 parts by mass of a foaming agent E shown in Table 1 as a foaming agent.
Using this foamable phenolic resin composition, the temperature of the lower conveyor belt that conveys the first face material is adjusted to 65 ° C., and the temperature of the upper conveyor belt that conveys the second face material becomes 75 ° C. A phenolic resin foam board of Reference Example 9 was produced in the same manner as Reference Example 1 except that the amount was adjusted to.

[Reference Example 10]
A foaming phenol resin composition was prepared by adding 14 parts by mass of a foaming agent F shown in Table 1 as a foaming agent.
Using this foamable phenolic resin composition, the temperature of the lower conveyor belt that conveys the first face material is adjusted to 65 ° C., and the temperature of the upper conveyor belt that conveys the second face material becomes 75 ° C. A phenolic resin foam board of Reference Example 10 was produced in the same manner as in Reference Example 1 except that the amount was adjusted.

[Example 7]
A foaming phenol resin composition was prepared by adding 14 parts by mass of a foaming agent G shown in Table 1 as a foaming agent.
Using this foamable phenolic resin composition, the temperature of the lower conveyor belt that conveys the first face material is adjusted to 65 ° C., and the temperature of the upper conveyor belt that conveys the second face material becomes 75 ° C. A phenolic resin foam board of Example 7 was produced in the same manner as in Reference Example 1 except that the amount was adjusted.

[Comparative Example 1]
Example 1 except that the temperature of the lower conveyor belt that conveys the first face material is adjusted to 70 ° C. and the temperature of the upper conveyor belt that conveys the second face material is adjusted to 70 ° C. Similarly, a phenolic resin foam board of Comparative Example 1 was produced.
About the obtained phenolic resin foam board, it evaluated about the item of said (1)-(9). The results are shown in Table 4. Table 4 also shows the evaluation results regarding the phenol resin foam boards of Comparative Examples 2 to 6 below.

[Comparative Example 2]
A phenolic resin foam board of Comparative Example 2 was produced in the same manner as Comparative Example 1 except that the thickness was 50 mm.

[Comparative Example 3]
As a foaming agent, 18 parts by mass of a foaming agent H shown in Table 1 was added to prepare a foamable phenolic resin composition.
Using this foamable phenolic resin composition, the temperature of the lower conveyor belt that conveys the first face material is adjusted to 70 ° C., and the temperature of the upper conveyor belt that conveys the second face material becomes 70 ° C. A phenolic resin foam board of Comparative Example 3 was produced in the same manner as in Example 1 except that the adjustment was made.

[Comparative Example 4]
A phenol resin foamed plate of Comparative Example 4 was produced in the same manner as Comparative Example 3 except that the thickness was 50 mm.

[Comparative Example 5]
Example 4 except that the temperature of the lower conveyor belt that conveys the first face material is adjusted to 70 ° C. and the temperature of the upper conveyor belt that conveys the second face material is adjusted to 70 ° C. Similarly, a phenolic resin foam board of Comparative Example 5 was produced.

[Comparative Example 6]
A phenol resin foamed plate of Comparative Example 6 was produced in the same manner as Comparative Example 5 except that the thickness was 50 mm.

From the results of Tables 2 and 3, the phenolic resin foam plates of Examples 1 to 7 have a warp amount in the width direction of 3.5 mm or less, a warp amount in the length direction of 5.5 mm or less, and a warp in the width direction. It turned out that the average value of quantity and the amount of curvature of a length direction is 4.3 mm or less.
On the other hand, from the results in Table 4, the phenolic resin foam plates of Comparative Examples 1 to 6 have a warpage amount in the width direction of 6 mm or more, a warpage amount in the length direction of 7 mm or more, a warpage amount in the width direction and a length direction. It was found that the average value of the warpage amount was 7 mm or more.
From the above results, it was confirmed that the phenolic resin foam plates of Examples 1 to 7 had a small amount of warpage.

The phenolic resin foam of the present invention comprises a foamed resin layer and face materials provided on both sides thereof, and the foamed resin layer comprises 1-chloro-3,3,3-trifluoropropene as a foaming agent. It contains hydrocarbons, the mass ratio of 1-chloro-3,3,3-trifluoropropene in the blowing agent is 30% or more, the density is 25 kg / m ³ or more and 35 kg / m ³ or less, and the average bubbles When the diameter is 50 μm or more and 150 μm or less, the closed cell ratio is 90% or more, the thickness is 50 mm or less, and the warpage amount by the infrared irradiation test is less than 7 mm, the warpage amount is small. Therefore, it is very useful industrially.

DESCRIPTION OF SYMBOLS 1 ... Infrared irradiation apparatus, 2 ... Base, 3 ... Phosphorus wood, 4 ... Infrared heater, 5 ... Infrared irradiation part, 6 ... Case, 7 ... Cover, 100: Phenol resin foam.

Claims (3)

A phenolic resin foam comprising a foamed resin layer, and a first face material and a second face material (excluding those that are metals) laminated on both sides thereof,
The foamed resin layer contains 1-chloro-3,3,3-trifluoropropene and hydrocarbon as a foaming agent,
The mass ratio of 1-chloro-3,3,3-trifluoropropene in the blowing agent is 30% or more,
The density is 25 kg / m ³ or more and 35 kg / m ³ or less,
The average bubble diameter is 50 μm or more and 150 μm or less,
The closed cell rate is 90% or more,
The thickness is 35 mm or less,
The phenol resin foam, wherein the amount of warpage in an infrared irradiation test in which infrared light is irradiated to the second face material side of the phenol resin foam is less than 7 mm. It is a manufacturing method of the phenol resin foam of Claim 1, Comprising:
A discharge step of discharging a foamable phenol resin composition containing a phenol resin, 1-chloro-3,3,3-trifluoropropene, a hydrocarbon, and an acid catalyst on the first face material;
The foamable phenol resin composition is bonded between the first face material and the second face material by bonding a second face material to the foamable phenol resin composition discharged onto the first face material. A foaming process for foaming and curing the object,
In the foaming step, a temperature difference between a conveyor in contact with the first surface material for conveying the first surface material and a conveyor in contact with the second surface material for conveying the second surface material is 4 ° C. or more. A method for producing a phenolic resin foam characterized by comprising: It is a manufacturing method of the phenol resin foam of Claim 1, Comprising:
A discharge step of discharging a foamable phenol resin composition containing a phenol resin, 1-chloro-3,3,3-trifluoropropene, a hydrocarbon, and an acid catalyst on the first face material;
The foamable phenol resin composition is bonded between the first face material and the second face material by bonding a second face material to the foamable phenol resin composition discharged onto the first face material. A foaming process for foaming and curing the object,
In the discharging step, the foamable phenol resin composition is discharged from the nozzle onto the first face material while moving a single nozzle in a direction perpendicular to the traveling direction of the first face material. The manufacturing method of the phenol resin foam characterized.

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