JP2016107596A - Phenolic resin foam laminated plate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenolic resin foam laminated plate which can be produced at a low cost using simple equipment and has excellent flame retardancy.SOLUTION: There is provided a phenolic resin foam laminated plate which comprises a phenolic resin foam and a surface material having a basis weight of 30 g/mor less on at least one surface of the phenolic resin foam, wherein the area ratio of the exuding portion of the surface material is 50% or more and 80% or less and the surface closed portion area ratio of the exuding portion is 20% or more and 75% or less.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a phenolic resin foam laminate used mainly as a heat insulating material for construction and a method for producing the same.

Conventionally, polystyrene resin foams, polyurethane resin foams, phenol resin foams, and the like have been used as synthetic resin-based thermal insulation materials for buildings. Of these, the phenol resin foam is generally provided as a phenol resin foam laminate in which face materials such as paper, metal foil, glass fiber, synthetic woven fabric, and synthetic nonwoven fabric are laminated on the surface of the foam. The
Here, the cost of these face materials occupies a large part of the cost of the entire raw material. Therefore, a phenol resin foam laminate that can be manufactured at low cost using an inexpensive face material having a basis weight as low as possible is desired. However, when a face material having a low basis weight is used, in the manufacturing process of the phenol resin foam laminate, the uncured phenol resin passes through the face material and shifts to the manufacturing equipment side, thereby fouling the production equipment. There was a problem that.

For such a problem, Patent Document 1 discloses that a resin composition containing a phenol resin is mixed, continuously discharged onto a traveling lower surface material, and the upper surface is covered with an upper surface material. Is a method for producing a phenolic resin foam laminate, wherein at least a woven fabric or a non-woven fabric is used as the lower surface material, and an average surface temperature of the lower surface material at a position at which the resin composition is discharged onto the lower surface material. A method of adjusting to a range of 35 ° C. or higher and 100 ° C. or lower is disclosed. According to the method, a phenol resin foam laminate having a good appearance and without leaching of the resin composition from the face material is obtained using the face material with a low basis weight, without contaminating the production equipment. It has been reported that this is possible.
A method for producing a phenolic resin foam without using a face material has also been studied. For example, Patent Document 2 discloses a method of producing a phenolic resin foam with skin having no face material by bringing the surface into contact with a plastic film or sheet surface during foam curing of a resol type phenol resin, and According to the method, it has been reported that the manufacturing cost can be reduced.

JP 2009-262475 A Japanese Unexamined Patent Publication No. 4-67914

However, in the method described in Patent Document 1, it is necessary to control the average surface temperature of the lower surface material in a specific range in advance in order to suppress the leaching of the resin while promoting the curing of the phenol resin. Therefore, equipment for controlling the temperature of the lower surface material is required, and there is a problem that adjustment of manufacturing equipment and operating conditions thereof becomes complicated.
Furthermore, for example, many face materials used in the method described in Patent Document 1 are inferior in flame retardancy, and therefore it is difficult to sufficiently ensure the flame retardancy of the resulting phenolic resin foam laminate. was there.
Further, in the method described in Patent Document 2, since a plastic film or sheet having a flat surface is used and no face material is used, a surface film (skin) is uniformly formed on the surface of the obtained phenol resin foam. Generate. For this reason, the drying of the phenol resin foam is slow, the surface hardness immediately after molding becomes low, and as a result, it is likely to be damaged when transported in the subsequent process, which may make it difficult to handle during mass production. In addition, since the drying proceeds with time even in the air, the resulting phenolic resin foam tends to change in size. Therefore, in order to produce a foam with high dimensional accuracy, it is necessary to strictly adjust the production conditions, and thus there is a problem that the productivity is inferior. In addition, the plastic film and sheet used in the method described in Patent Document 2 are likely to be stretched and twisted when heated and cooled, particularly in a stressed state, so that stable production over a long time is possible. It was difficult.

  The present invention has been made in view of the above problems, and provides a phenolic resin foam laminate that can be produced at low cost using simple equipment and has excellent flame retardancy, and a method for producing the same. The purpose is to do.

  As a result of intensive studies on such problems, the present inventors used a face material having a basis weight of a specific value or less when producing a phenolic resin foam laminate, and at the same time specified a specific value. It has been found that by using a cloth material having properties, the surface of the phenol resin foam laminate has a specific property, and a phenol resin foam laminate having excellent flame retardancy can be produced at low cost without contaminating the production equipment. The present invention has been completed.

That is, the present invention provides the following [1] to [7].
[1] A phenol resin foam and a face material having a basis weight of 30 g / m ² or less on at least one surface of the phenol resin foam, and an area ratio of a leaching portion of the face material is 50% The phenol resin foam laminate, which is 80% or less and a surface blockage area ratio of the oozing out part is 20% or more and 75% or less.
[2] The phenol resin foam laminate according to [1], wherein the closed cell ratio of the phenol resin foam is 80% or more.
[3] A method for producing a phenolic resin foam laminate comprising the following steps (a) to (c):
(A) The process of arrange | positioning the face material whose fabric weight is 30 g / m < ² > or less between the cloth material which has mold release property which consists of a woven fabric or a nonwoven fabric, and a foamable phenol resin composition;
(B) a step of foam-curing the foamable phenol resin composition to obtain a phenol resin foam; and (c) a step of peeling the cloth material from the face material to obtain a phenol resin foam laminate.
[4] The cloth material is a woven or non-woven cloth made of a fluororesin fiber, or a cloth coated with a fluororesin, and the cloth is a glass cloth, an aramid cloth, a carbon cloth, a metal fiber cloth, a polyarylate cloth. [3] The method for producing a phenolic resin foam laminate according to [3], which is at least one selected from the group consisting of polybenzoxazole cloth, polyethylene cloth, polypropylene cloth, nylon cloth, polyester cloth, alumina cloth, and silica cloth.
[5] The method for producing a phenolic resin foam laminate according to [3] or [4], wherein the cloth material is used as an endless belt conveyor.
[6] The method for producing a phenolic resin foam laminate according to [3] or [4], wherein the cloth material is used by being disposed on a molding surface of a double slat conveyor.
[7] The phenol resin foam laminate according to [3] or [4], wherein the cloth material is endless, and the endless cloth material is used by covering an outer periphery on a molding surface of a double slat conveyor. A manufacturing method of a board.

  According to the present invention, it is possible to provide a phenolic resin foam laminate that can be produced at low cost using simple equipment and is excellent in flame retardancy, and a method for producing the same.

It is the image which cut out the phenol resin foam laminated board obtained in Example 1 into the magnitude | size of 210 mm x 297 mm (A4 size), and was read using the image scanner. It is a histogram of the image of FIG. FIG. 2 is a diagram in which FIG. 1 is binarized by image processing, and a bleeding portion is expressed in white, and the others are expressed in black. It is the SEM image which expanded and observed the exudation part in the phenol resin foam laminated board surface obtained in Example 1 200 times. FIG. 5 is a diagram in which FIG. 4 is binarized by image processing, and the surface blocking portion is expressed in white and the others are expressed in black. It is an example of the manufacturing equipment of the phenol resin foam laminated board of this invention which used the cloth material as an endless belt conveyor. It is an example of the manufacturing equipment of the phenol resin foam laminated board of this invention which has arrange | positioned and used the cloth material on the molding surface of a double slat conveyor. It is an example of the manufacturing equipment of the phenol resin foam laminated board of this invention which coat | covered and used the endless cloth material on the molding surface outer periphery of a double slat conveyor.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be specifically described. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

(Phenolic resin foam laminate)
The phenolic resin foam laminate in this embodiment (hereinafter sometimes abbreviated as “foam laminate”) is present in a state in which a large number of bubbles are dispersed in a phenol resin formed by a curing reaction. A laminate having a phenol resin foam and a face material having a basis weight of a specific value or less on at least one surface (preferably at least one of upper and lower surfaces) of the phenol resin foam.

<Phenolic resin foam>
The closed cell ratio of the phenol resin foam is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. By setting the closed cell ratio to 80% or more, it is possible to prevent the foaming agent in the phenolic resin foam laminate from replacing air and lowering the heat insulation performance.
The “closed cell ratio” of the phenol resin foam can be measured using the method described in the examples of the present specification.

  And the phenol resin foam of this embodiment is manufactured by foam-curing a foamable phenol resin composition containing at least a phenol resin, a surfactant, a foaming agent, and a curing catalyst. The foamable phenol resin composition may optionally contain components other than those described above.

  Examples of the phenol resin that can be used for the production of the phenol resin foam include a resol type phenol resin synthesized with an alkali catalyst, a novolac type phenol resin synthesized with an acid catalyst, an ammonia resol type phenol resin synthesized with ammonia, or lead naphthenate. Examples thereof include synthesized benzyl ether type phenol resins. Among them, resol type phenol resins are preferable from the viewpoint that foam molding is relatively easy and a foaming agent containing hydrocarbon can be used.

  The resol type phenol resin can be obtained by heating and polymerizing phenols and aldehydes as raw materials with an alkali catalyst in a temperature range of 40 ° C. or higher and 100 ° C. or lower. Moreover, you may add additives, such as urea, at the time of the synthesis | combination of a resol type phenol resin as needed, or after a synthesis | combination. When adding urea, it is more preferable to mix urea methylolated with an alkali catalyst in advance into the resol type phenol resin. Since the resol-type phenol resin after synthesis usually contains excessive moisture, it is preferable to adjust the amount of moisture suitable for foaming when foaming. Phenol resins include aliphatic hydrocarbons or high-boiling alicyclic hydrocarbons, or mixtures thereof, diluents for viscosity adjustment such as ethylene glycol and diethylene glycol, and other material recycling powders as required. It is also possible to add additives.

Examples of phenols include resorcinol, hydroquinone, catechol, cresols, xylenols, ethylphenols, p-tertbutylphenol, saligenin and the like in addition to unsubstituted phenol. Moreover, you may use binuclear phenols. One of these may be used alone, or two or more of these may be used in combination.
Examples of aldehydes include formaldehyde, paraformaldehyde, glyoxal, acetaldehyde, chloral, furfural, and benzaldehyde. One of these may be used alone, or two or more of these may be used in combination.
The starting molar ratio of phenols: aldehydes during the production of the phenol resin is preferably 1: 1 to 1: 4.5, more preferably 1: 1.5 to 1: 2.5.

  As the surfactant that can be used for the production of the phenol resin foam, known ones that are generally used for the production of a phenol resin foam can be used. Among them, a nonionic surfactant is effective, for example, ethylene. Alkylene oxide, which is a copolymer of oxide and propylene oxide, condensation product of alkylene oxide and castor oil, condensation product of alkylene oxide and alkylphenol such as nonylphenol, dodecylphenol, polyoxyethylene alkyl ethers, and polyoxy Preference is given to fatty acid esters such as ethylene fatty acid esters, silicone compounds such as polydimethylsiloxane, polyalcohols and the like. One type of surfactant may be used alone, or two or more types may be used in combination. Moreover, there is no restriction | limiting in particular about the usage-amount of surfactant, It uses preferably in 0.3 to 10 mass parts per 100 mass parts phenol resin.

  Although it does not specifically limit as a foaming agent which can be used for manufacture of a phenol resin foam, A hydrocarbon, halogenated hydrocarbon, etc. can be mentioned. Among these, from the viewpoint of the global warming potential, the blowing agent preferably contains a hydrocarbon.

The hydrocarbon is preferably a cyclic or chain alkane, alkene or alkyne having 3 to 7 carbon atoms, and from the viewpoint of foaming performance, chemical stability and thermal conductivity of the compound itself, 4 to 6 carbon atoms. More preferred are alkanes or cycloalkanes. Specific examples of the alkane or cycloalkane having 4 to 6 carbon atoms include normal butane, isobutane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, normal hexane, isohexane, 2,2-dimethylbutane, 2, Examples include 3-dimethylbutane and cyclohexane. Among these, normal pentane, isopentane, cyclopentane, neopentane pentanes and normal butane, isobutane, cyclobutane butanes have favorable foaming characteristics in the production of phenol resin foam laminates, and thermal conductivity. Is particularly preferable since it is relatively small.
Here, one kind of hydrocarbon may be used alone, or two or more kinds of hydrocarbons may be used in combination. Specifically, a mixture composed of 5% by mass or more and 95% by mass or less of pentanes and 95% by mass or more and 5% by mass or less of butanes is preferable because it exhibits good heat insulation characteristics in a wide temperature range. Among them, the combination of normal pentane or isopentane and isobutane is preferable because the foam exhibits high heat insulation performance in a wide range from a low temperature range to a high temperature range, and these compounds are inexpensive.

Halogenated hydrocarbons include chlorinated aliphatic hydrocarbons. And as a chlorinated aliphatic hydrocarbon, a C2-C5 or less linear or branched thing is used preferably. The number of chlorine atoms bonded to the carbon atom is not limited, but is preferably in the range of 1 or more and 4 or less. Preferable chlorinated aliphatic hydrocarbons include chlorinated saturated aliphatic hydrocarbons such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. Of these, chloropropane such as propyl chloride and isopropyl chloride is more preferably used.
As halogenated hydrocarbons other than chlorinated aliphatic hydrocarbons, hydrofluorocarbons (HFCs) such as 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, and pentafluoroethane can also be used. However, it is necessary to consider that these halogenated hydrocarbons have a larger global warming potential than hydrocarbons. In addition to these, halogenated olefins having a small global warming potential as halogenated hydrocarbons such as 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2,3,3,3-tetrafluoropropene. (HFO-1234yf), 1,2,3,3-tetrafluoropropene (HFO-1234ye), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 3,3,3-trifluoro Fluoroolefins (non-chlorinated hydrofluoroolefins) such as propene (FC-1243zf), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz); 1-chloro-3, 3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene ( It is also possible to use CFO-1233xf) chlorofluorohydrocarbons olefins such as the (chlorinated hydro fluoroolefin).
Chlorinated hydrofluoroolefins and non-chlorinated hydrofluoroolefins have low thermal conductivity of the foaming agent itself, and can be preferably used for improving heat insulation and flame retardancy.
These halogenated hydrocarbons may be used alone or in combination of two or more.

As the foaming agent, a mixture of hydrocarbon and halogenated hydrocarbon can be used. The hydrocarbon content in this case is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more based on the total mass of the foaming agent.
Moreover, there is no restriction | limiting in particular about the usage-amount of a foaming agent, However, Preferably it is 1 to 20 mass parts, More preferably, it is 3 to 10 mass parts per 100 mass parts phenol resin.

The curing catalyst that can be used for the production of the phenol resin foam is not particularly limited, and various organic acids and inorganic acids, or anhydrides thereof can be used, but from the viewpoint of suppressing bubble bursting during foaming, In particular, an organic acid such as aryl sulfonic acid or an anhydride thereof is preferable. Aryl sulfonic acids and their anhydrides include toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, substituted phenol sulfonic acid, xylenol sulfonic acid, substituted xylenol sulfonic acid, alkylbenzene sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid, and those The anhydride of these is mentioned. One of these may be used alone, or two or more of these may be used in combination. In this embodiment, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol or the like may be added as a curing aid. The curing catalyst may be diluted with a solvent such as ethylene glycol or diethylene glycol.
Although there is no restriction | limiting in particular about the usage-amount of a curing catalyst, Preferably it is 5 to 30 weight part per 100 mass parts of phenol resins, More preferably, it is used by 8 to 25 weight part.

In addition to the above-described phenol resin, surfactant, foaming agent and curing catalyst, the foamable phenol resin composition may contain a foam nucleating agent. Examples of the foam nucleating agent include low-boiling substances such as nitrogen, helium, argon, and air whose boiling point is 50 ° C. or lower than that of the foaming agent. As solid foam nucleating agents, aluminum hydroxide powder, aluminum oxide powder, calcium carbonate powder, talc, sand clay (kaolin), quartzite powder, quartz sand, mica, calcium silicate powder, wollastonite, glass powder, glass beads It is also possible to add inorganic powder such as fly ash, silica fume, gypsum powder, borax, slag powder, alumina cement and Portland cement, and organic powder such as phenol resin foam powder. One of these may be used alone, or two or more of these may be used in combination.
Although there is no restriction | limiting in particular about the addition amount with respect to the foaming agent of a foam nucleating agent, It is preferable that it is 0.1 to 0.6 mass% by making the quantity of a foaming agent into 100 mass%, and 0.2 mass% More preferably, it is 0.4 mass% or less.

<Face material>
The phenol resin foam laminate of this embodiment uses a face material having a basis weight of 30 g / m ² or less on at least one surface. If a face material with a basis weight exceeding 30 g / m ² is used, the effect of the present invention of cost reduction cannot be fully obtained. Moreover, the lower limit of the basis weight of the face material is not particularly limited, but is usually 5 g / m ² or more from the viewpoint of securing strength and the like. The “weight per unit area” of the face material refers to the mass per unit area of the face material.
The material constituting the face material having a basis weight of 30 g / m ² or less is not particularly limited, and examples thereof include paper, glass fiber, synthetic woven fabric, synthetic nonwoven fabric, and the like. A woven or blended one may be used. The face material having a basis weight of 30 g / m ² or less is a face material composed of at least one material selected from the group consisting of paper, glass mixed paper, glass fiber, polyester woven fabric, and polyester nonwoven fabric. Is preferred.

[Area ratio of exuded part of face material]
In the phenol resin foam laminated board of this embodiment, since the face material with a low basis weight is used as described above, the phenol resin is normally partially oozed out to the surface side of the face material. In the present application, such a surface material surface portion is referred to as a “leaching portion”, and the ratio of the “leaching portion” on the surface material surface is referred to as “the area ratio of the face material leaching portion”. .
In the present embodiment, the area ratio of the leached portion of the face material needs to be 50% or more and 80% or less, and preferably 55% or more and 75% or less. By setting it to 80% or less, adhesion of the phenol resin to the production facility side is prevented, and the production stability of the foam laminate is improved. Moreover, the flame retardance of a foam laminated board improves that it is 50% or more.

Here, the following method is used as a method of calculating the area ratio of the oozing portion of the face material.
First, a phenol resin foam laminate is cut into a size of 210 mm × 297 mm (A4 size). The surface of the cut phenol resin foam laminate on which the target face material is present is read as an image using an image scanner. As an example, the image in Example 1 is shown in FIG.
This image is binarized by using a known image processing software at the exudation portion and other portions. Here, FIG. 2 is a histogram when the image of FIG. 1 is read by image processing software (product name “Photoshop (registered trademark)” manufactured by Adobe Systems Incorporated). Since the presence or absence of the surface of the face material can be clearly discriminated on the histogram in this way, the image shown in FIG. 1 is processed by a known method based on the histogram, and the seepage portion (white, figure 2 (right mountain on the histogram) and other parts (black, left mountain on the histogram in FIG. 2) can be binarized (see FIG. 3). Note that, depending on the relationship between the color of the phenol resin and the color of the face material, the relationship between whether or not it is a oozing portion and the brightness on the histogram may be reversed from the above example.
By calculating the ratio of the number of pixels of the white portion to the total number of pixels in the image of FIG. 3 processed in this way, it is possible to calculate the area ratio of the exuded portion of the face material (for example, FIG. 3). 3 is 59.5%).
In addition, the area ratio of the oozing-out portion of the face material can be adjusted by changing the basis weight of the face material and the foam curing conditions when producing the phenol resin foam laminate.

[Area ratio of the surface blockage in the exuded part]
Here, when the microscopic structure of the portion treated as a oozing portion in the face material in the above-described method is observed in more detail with a scanning electron microscope (SEM) or the like, the face material surface is blocked with resin. It can be seen that there are locations (surface blocking portions), but there are also locations where the face material surface is not blocked with resin (see FIG. 4). In the present embodiment, when the area of the oozing portion is 100%, the area ratio of the surface blocking portion in the leaching portion (surface blocking portion area ratio of the leaching portion) is 20% or more and 75%. It is necessary to be below, and it is preferable that they are 30% or more and 60% or less. Thus, it becomes possible to improve the flame retardance of a phenol resin foam laminated board by forming the surface obstruction | occlusion part of a predetermined ratio in the oozing part. And when the area ratio of the surface obstruction | occlusion part which occupies for the oozing-out part is 20% or more, the above-mentioned flame retardance improves, In addition, the shift | transfer to the manufacturing equipment side of a phenol resin is suppressed, and the dirt of manufacturing equipment A decrease in production stability can be prevented. On the other hand, when the area ratio is 75% or less, the drying rate during production is improved, and the dimensional stability of the phenolic resin foam laminate tends to be improved. In addition, this surface obstruction | occlusion part may be substantially parallel with respect to the main surface of a phenol resin foam laminated board, and may be curving.

Here, the following method can be used as a method of calculating the area ratio of the surface blocking portion in the leaching portion.
First, using SEM or the like, an image obtained by enlarging the oozing portion of the face material surface of the phenol resin foam laminate to 200 times is obtained (see FIG. 4). Here, on the image, the surface blocking portion can be easily discriminated visually, and the ratio of the area of the surface blocking portion to the entire image area is calculated using a known image processing software. Obtained. FIG. 5 reads the image of FIG. 4 with image processing software (product name “Photoshop (registered trademark)” manufactured by Adobe Systems Incorporated), and uses an automatic selection function and a color gamut designation selection function, ) And other parts (black).
The ratio of the number of pixels of the white portion to the total number of pixels of the image processed in this way is calculated (for example, 91.7% in FIG. 5). The above operation is performed for a total of 10 randomly selected locations, and the average value is defined as the surface blockage area ratio (%) of the leaching portion. In addition, when the vicinity of the surface of the phenol resin foam laminate is destroyed and the presence of the surface blocking portion cannot be confirmed, the area ratio of the surface blocking portion is set to 0%.
In addition, the area ratio of the surface obstruction | occlusion part which occupies for the oozing-out part can be adjusted by changing the conditions of the foaming hardening at the time of manufacturing the kind of below-mentioned cloth material, or manufacturing a phenol resin foam laminated board.

<Surface layer flammability evaluation level>
In the phenol resin foam laminated board of this embodiment, it is excellent in the flame retardance of a surface layer part by contribution of the above-mentioned surface obstruction | occlusion part. Specifically, in this embodiment, the surface layer portion combustibility evaluation level of the phenolic resin foam laminate is preferably 21% or more, more preferably 22% or more, and 23% or more. Is more preferable. When the surface layer combustibility evaluation level is 21% or more, there is no possibility of continuous combustion in air.
Here, the “surface layer combustibility evaluation level” of the phenol resin foam laminate can be derived using the method described in the examples of the present specification.

The density of the phenolic resin laminate can be selected according to conditions such as the amount of foaming agent used and the temperature during curing, but is preferably 10 kg / m ³ or more and 100 kg / m ³ or less. preferably less 15 kg / m ³ or 60 kg / m ^3, more preferably not more than 20 kg / m ³ or 50 kg / m ^3. By setting the density to 10 kg / m ³ or more, there is a tendency that mechanical strength such as compressive strength can be ensured, damage during handling can be prevented, and surface brittleness can also be suppressed. On the other hand, by setting the density to 100 kg / m ³ or less, there is a tendency that the heat transfer of the resin portion of the phenolic resin foam laminate can be suppressed, the heat insulation performance can be suppressed, and the cost can be reduced.
The “density” of the phenol resin foam laminate is a value obtained by measuring the mass and the apparent volume of the material using a 20 cm square phenol resin foam laminate with a face material as a sample. , And can be measured according to JIS-K-7222.

<Thermal conductivity>
In addition, the thermal conductivity at 23 ° C. of the phenolic resin foam laminate is preferably 0.023 W / m · K or less, more preferably 0.015 W / m · K or more and 0.023 W / m · K or less, 0 It is more preferably not less than .015 W / m · K and not more than 0.021 W / m · K, particularly preferably not less than 0.015 W / m · K and not more than 0.019 W / m · K.
In addition, "the heat conductivity in 23 degreeC" of a phenol resin foam laminated board can be measured with the following method based on JIS-A-1412-2: 1999.
A phenolic resin foam laminate sample is cut into approximately 300 mm squares, and a specimen is placed in an atmosphere of 23 ± 1 ° C. and humidity of 50 ± 2%, and the mass change over time is measured every 24 hours. Condition is adjusted until the change is 0.2 mass% or less. The conditioned specimen is introduced into a thermal conductivity measuring device placed in the same environment. If the thermal conductivity measuring device is not placed in a room controlled at 23 ± 1 ° C and humidity of 50 ± 2% where the test piece was placed, immediately put it in a polyethylene bag and close the bag. Take it out of the bag within a short time, and promptly measure the thermal conductivity.
The thermal conductivity is measured using a test piece (one specimen and a symmetrical configuration type measuring device, trade name “HC-074 / 600”, manufactured by Eihiro Seiki Co., Ltd.) under conditions of a low temperature plate of 13 ° C. and a high temperature plate of 33 ° C. Do.

(Method for producing phenolic resin foam laminate)
Although the method of manufacturing the phenol resin foam laminate described above is not particularly limited, it is preferable to use the method of manufacturing a phenol resin foam laminate of the present embodiment described in detail below.

Specifically, the manufacturing method of the phenol resin foam laminate of this embodiment includes the following steps (a) to (c) in this order. In addition, you may provide another arbitrary process between each process.
(A) The process of arrange | positioning the face material whose areal weight is 30 g / m < ² > or less between the cloth material which has mold release property which consists of a woven fabric or a nonwoven fabric, and a foamable phenol resin composition.
(B) A step of foam-curing the foamable phenol resin composition to obtain a phenol resin foam.
(C) The process of peeling the said cloth material from the said face material, and obtaining a phenol resin foam laminated board.

  By producing the phenolic resin foam laminate by the production method of the present embodiment, the migration of the phenol resin to the production equipment side is suppressed, and contamination of the production equipment can be prevented, resulting in cost reduction and production stability. It is possible to achieve both improvement.

<Cloth material>
First, the cloth material which has the releasability which consists of a woven fabric or a nonwoven fabric used for the manufacturing method of this embodiment is demonstrated. Here, the cloth material has “releasing properties” means that the mass increase rate of the cloth material when the cloth material is peeled from the phenol resin foam laminate (phenol resin foam and face material) is 5% or less. It means that. By using the cloth material having such releasability, the cloth material can be used repeatedly, and the cost required for manufacturing the phenol resin foam laminate can be reduced.
In addition, when a cloth material having poor releasability (that is, the mass increase rate exceeds 5%) is used, the surface blockage portion of the foam laminate is peeled off together with the cloth material, and the surface blockage occupies the leaching portion. The area ratio of the part may be less than 20%. The cloth material peeled off together with the surface blocking portion is difficult to reuse, and is not preferable because the manufacturing cost becomes higher compared to the case where reuse is possible.

  Here, examples of the cloth material having releasability made of woven fabric or nonwoven fabric include woven fabric or nonwoven fabric made of resin fibers having releasability, cloth coated with a resin having releasability, and the like.

The resin fiber having releasability is preferably a fluororesin fiber or a silicone resin fiber from the viewpoint of releasability and heat resistance, and more preferably a fluororesin fiber. That is, as the cloth material, a woven fabric or a nonwoven fabric made of fluororesin fibers can be preferably exemplified. Examples of the fluororesin constituting the fluororesin fiber include polytetrafluoroethylene (PTFE), poly (tetrafluoroethylene-co-hexafluoropropylene) (PFE), poly (tetrafluoroethylene-co-perfluoroalkyl vinyl ether) (PFA). ), Poly (ethylene-co-tetrafluoroethylene) (ETFE), polyvinylidene fluoride (PVdF), polychlorotrifluoroethylene (PCTFE), and the like. Among these, PTFE, PFE, and PFA are more preferable. From the viewpoint of releasability and cost, PTFE is particularly preferable, and from the viewpoint of wear resistance, PFA is particularly preferable.
In addition, the woven fabric or the nonwoven fabric may use a single fiber as a raw material, or may use a mixture of a plurality of fibers, a mixed woven fabric, or a blended fabric.

From the viewpoint of strength and dimensional stability, the cloth material is preferably a cloth coated with a resin having releasability. Examples of the cloth include glass cloth, aramid cloth, carbon cloth, metal fiber cloth, polyarylate cloth, polybenzoxazole cloth, polyethylene cloth, polypropylene cloth, nylon cloth, polyester cloth, alumina cloth, and silica cloth. Among these, glass cloth, aramid cloth, carbon cloth, and metal fiber cloth are preferable, and glass cloth is more preferable from the viewpoint of durability and cost.
In addition, what used the single fiber as a raw material may be used for cloth, and what mixed several fibers, the mixed woven fabric, or the mixed spinning may be used.
And as resin which has the mold release property which coat | covers these cloth | cross, it is preferable to use what was mentioned above as a fluororesin which comprises a fluororesin fiber. That is, as a cloth material, a cloth coated with a fluororesin can be preferably exemplified. In addition, a well-known method can be used for the method of coat | covering cloth | cross using resin which has mold release property.

  Since the cloth coated with the resin having releasability is particularly excellent in dimensional stability and strength, the cloth is hardly deteriorated such as elongation and twist during repeated use, and can be used for a long time. By using such a cloth material, it is possible to further enjoy one of the effects of the present invention, namely cost reduction.

  The term “cross” is used in the field of woven and non-woven fabrics. In this embodiment, “cross” refers to all woven and non-woven fabrics.

  The cloth material that can be used in the manufacturing method of the present embodiment may be subjected to antistatic processing. In order to further improve the releasability, a known release agent such as silicone, fluorine or oil may be applied.

<Process (a)>
In the step (a), a face material having a basis weight of 30 g / m ² or less is positioned between the cloth material having releasability composed of the woven fabric or the nonwoven fabric described above and the foamable phenol resin composition. A cloth material, a foamable phenol resin composition, and a face material are disposed. As a specific implementation method, there is mainly a method in which a foamable phenol resin composition is continuously discharged onto a cloth material and a face material which are laminated and run. There is no particular limitation as long as the face material is disposed in contact with both of the materials. As such an implementation method, it is particularly preferable that the cloth material is used as an endless belt conveyor (see FIG. 6), and the cloth material is used on the molding surface of a double slat conveyor (see FIG. 7). ), A method of using an endless cloth material by covering the outer periphery of the double slat conveyor on the molding surface (see FIG. 8). These methods are selected in consideration of various items such as the type of cloth material to be used and the maintainability of the manufacturing equipment.

<Step (b)>
Next, in the step (b), the foamable phenol resin composition is foam-cured to obtain a phenol resin foam. The method for foam curing is not particularly limited, and examples thereof include known methods such as hot air, infrared rays, induction heating, and microwaves. By passing through the process, a laminate including a cloth material, a face material, and a phenol resin foam (for example, a thickness of 5 to 300 mm) in this order is obtained.

<Step (c)>
In step (c), the cloth material is peeled from the face material to obtain a phenol resin foam laminate. By reusing the peeled cloth material, the manufacturing cost can be reduced.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these examples. In addition, the physical property evaluation in the following Examples and Comparative Examples was performed as follows.
<Moisture content>
The amount of water in the phenolic resin was measured using a Karl Fischer moisture meter MKA-510 (manufactured by Kyoto Electronics Industry Co., Ltd.).
<Viscosity>
Using a rotational viscometer (manufactured by Toki Sangyo Co., Ltd., R-100 type, rotor portion 3 ° × R-14), the measured value after stabilizing at 40 ° C. for 3 minutes was taken as the viscosity of the phenol resin.
<Closed cell ratio>
Measured according to ASTM-D-2856. Specifically, after removing the face material from the phenolic resin foam laminate, a cylindrical sample having a diameter of 35 mm to 36 mm is pierced with a cork borer and trimmed to a height of 30 mm to 40 mm, and then an air comparison specific gravity meter The sample volume was measured by the standard usage method (manufactured by Tokyo Science Co., Ltd., type 1,000). The value obtained by subtracting the volume of the wall (parts other than bubbles and voids) calculated from the sample mass and the density of the phenol resin from the sample volume, and dividing the value by the apparent volume calculated from the outer dimensions of the sample is the closed cell ratio It was. Here, the density of the phenol resin was 1.3 kg / L.
<Area ratio of exuded part>
First, the phenol resin foam laminate was cut into a size of 210 mm × 297 mm (A4 size). A surface corresponding to the lower surface material side of the cut phenolic resin laminate was manufactured as an image using an image scanner (product name “iR-ADV C5250F” manufactured by Canon Inc.).
For this image, image processing software (manufactured by Adobe Systems Inc., product name “Photoshop (registered trademark)”) was used to binarize the exudation part (white) and the other part (black). . By calculating the ratio of the number of pixels of the white part to the total number of pixels of the image processed in this way, the area ratio of the exuded part of the face material was calculated.
<Area ratio of the surface blocking part in the oozing part>
First, an SEM was used to obtain an image in which a oozing portion existing on a surface corresponding to the lower surface material side at the time of manufacturing a phenol resin foam laminate was magnified 200 times. Read the image with image processing software (manufactured by Adobe Systems Incorporated, product name “Photoshop (registered trademark)”), and use the automatic selection function and the color gamut designation selection function to block the surface (white) and other parts Binarized to (black).
The ratio of the number of pixels of the white portion to the total number of pixels of the image processed in this way was calculated. The above operation was performed for a total of 10 randomly selected locations, and the average value was defined as the surface blockage area ratio (%) of the leached portion. When the vicinity of the surface of the phenolic resin foam laminate was destroyed and the presence of the surface blocking portion could not be confirmed, the area ratio of the surface blocking portion was set to 0%.
<Surface layer flammability evaluation level>
Thirty samples (sample size; thickness 10 mm, width 10 mm, length 150 mm) of the surface layer portion of the foam laminate including all face materials were prepared as test pieces. Next, the test piece was placed vertically in a combustion cylinder (made of glass; height 500 mm, inner diameter 100 mm, upper lid with a 40 mm diameter hole in the upper part), and the sample atmosphere was set to a predetermined oxygen concentration (23 ° C., 1 atm). Volume%) and was stabilized at the oxygen concentration (the oxygen concentration was 21 vol% as the initial value). Next, the gas burner is lowered vertically from the top cover hole at the top of the combustion cylinder, and after applying a gas burner to the sample surface (surface material surface) for 3 seconds, the burner flame is released to confirm the presence of combustion (for combustion) The distance from the top of the cylinder to the sample surface is 100 mm). Determination of the presence or absence of combustion was performed as follows. When the combustion distance (maximum length of the combustion part) was less than 75 mm, it was judged as “no combustion”, and the test was repeated while the oxygen concentration was sequentially increased by 0.1%. When the combustion distance was 75 mm or more, it was determined that “there was combustion”, and the test was repeated while the oxygen concentration was sequentially reduced by 0.1%. The oxygen concentration was changed depending on the combustion state, the above operation was repeated, and the minimum value of the oxygen concentration determined to be “combustion” was set as the surface layer portion flammability evaluation level of the phenol resin foam laminate.
<Continuous operation time>
At the time of manufacturing the phenolic resin foam laminate, the degree of phenol resin adhesion to the manufacturing facility and the degree of damage to the cloth material were visually checked, and the elapsed time from the start of manufacturing was determined to be difficult to continue manufacturing. . In addition, even if it exceeded 4 hours from the start of manufacture, it was judged that continuous operation for a long time was possible if the degree of adhesion of the phenol resin to the production facility and the degree of breakage of the cloth material were sufficiently small.
<Shrinkage evaluation>
In the present technology, the foamable phenolic resin composition supplied onto the lower surface material is coated with the upper surface material, and at the same time, sandwiched between the upper and lower surface materials and sent to the slat type double conveyor. Is peeled off and cured for a predetermined residence time, and then cured in a final curing oven to obtain a phenol resin foam. The dimension in the longitudinal direction was measured as follows between the step of peeling the cloth material from the face material and the final curing step.
A length of 1000 mm is placed on the surface of the foam, and one line perpendicular to the longitudinal direction of the foam laminate corresponding to the long end corresponding to 1000 mm (two lines in total) is noted.
Next, the distance (Amm) between the two lines on the foam surface after the final curing step is measured.
The shrinkage rate (%) is obtained by the following formula 1.
Shrinkage rate (%) = A / 1000 × 100 (Formula 1)

Example 1
<Synthesis of phenolic resin>
The reactor was charged with 3500 kg of a 52% by weight aqueous formaldehyde solution and 2510 kg of 99% by weight phenol, stirred with a propeller rotating stirrer, and the temperature inside the reactor was adjusted to 40 ° C. with a temperature controller. Next, the temperature was raised while adding a 50 mass% aqueous sodium hydroxide solution to advance the reaction. When the Ostwald viscosity reached 60 centistokes (measured value at 25 ° C.), the reaction solution was cooled, and 570 kg of urea (corresponding to 15 mol% of the charged amount of formaldehyde) was added. Thereafter, the reaction solution was cooled to 30 ° C., and the pH was neutralized to 6.4 with a 50 wt% aqueous solution of paratoluenesulfonic acid monohydrate. When this reaction solution was dehydrated at 60 ° C. and the viscosity and water content were measured, the viscosity at 40 ° C. was 5,800 mPa · s, and the water content was 5% by weight. This was designated as phenol resin A.
<Preparation of foamable phenolic resin composition>
Phenolic resin A: 3.5 parts by mass of 96.5 parts by mass of ethylene oxide / propylene oxide block copolymer (manufactured by BASF, product name “Pluronic (registered trademark) F-127”) as a surfactant The ratio was mixed.
100 parts by mass of the obtained phenol resin containing surfactant, 7 parts by mass of a mixture of 50% by mass of isopentane and 50% by mass of isobutane as a blowing agent, and a mixture 11 of 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as a curing catalyst The composition consisting of parts by mass was supplied to a mixing head whose temperature was adjusted to 25 ° C. to obtain a foamable phenol resin composition. Here, the mixer (mixer) used was the one disclosed in JP-A-10-225993. That is, a surfactant-containing phenol resin and a foaming agent introduction port are provided on the upper side surface, and a curing catalyst introduction port is provided on the side surface near the center of the stirring unit where the rotor stirs. The part after the stirring part is connected to a nozzle for discharging the foam. That is, the mixer is composed of the mixing part (A) up to the catalyst inlet, the mixing part (B) from the catalyst inlet to the stirring end part, and the distributing part (C) from the stirring end part to the nozzle. . The distribution part (C) has a plurality of nozzles at the tip, and is designed so that the mixed foamable phenolic resin composition is uniformly distributed. Further, a temperature sensor (D) is set on the central side surface of the mixing part (A) and the lowermost part of the mixing part (B) so that the temperature in the system can be measured. Furthermore, each mixing part and the distribution part are each provided with the jacket for temperature control for enabling temperature adjustment. The temperature measured by this temperature sensor (D) was 36.4 ° C.
<Manufacture of phenolic resin foam laminate>
As the upper and lower surface materials, polyester nonwoven fabrics ("ELTAS (registered trademark) E5012" manufactured by Asahi Kasei Fibers Co., Ltd., basis weight 12 g / m ² ) were used.
The foamable phenolic resin composition described above was supplied onto the moving lower surface material through the multiport distribution pipe. The foamable phenolic resin composition supplied on the lower surface material is coated with the upper surface material, and at the same time, sandwiched between the upper and lower surface materials, sent to a 85 ° C. slat type double conveyor, and cured in a residence time of 15 minutes. Then, it was cured in an oven at 110 ° C. for 2 hours to obtain a phenol resin foam. The slat type double conveyor used at this time is designed to release moisture generated during curing to the outside. Furthermore, PTFE-impregnated glass cloth 1 (product name “HGS-P210”, thickness 0.21 μm, manufactured by Honda Sangyo Co., Ltd.) is arranged as a cloth material having releasability on the molding surface of the slat type double conveyor. Yes (equivalent to FIG. 7). The foamable phenolic resin composition coated with the upper and lower surface materials should be moderately pressed through the surface material from above and below with a cloth material having releasability placed on the molding surface of the slat type double conveyor. Was formed into a plate shape.

(Examples 2 to 5)
PTFE-impregnated glass cloth 2 (manufactured by Yodogawa Hutec Co., Ltd., product name “128D”) and PTFE-impregnated glass cloth 3 (manufactured by Chuko Kasei Kogyo Co., Ltd., product names) “FGB-207-6-1”, antistatic processed product), PTFE-impregnated aramid cloth (product name “HAS-M575” manufactured by Honda Sangyo Co., Ltd.), PTFE woven fabric (product name “Toyoflon” manufactured by Toray Industries, Inc.) (Registered trademark) # 406 ") was used, and a phenol resin foam laminate was produced in the same manner as in Example 1.

(Comparative Example 1)
A phenol resin foam laminate was produced in the same manner as in Example 1 except that the PTFE-impregnated glass cloth 1 as the cloth material was not used.

(Comparative Example 2)
A phenolic resin foam laminate was produced in the same manner as in Example 1 except that silicone release paper (manufactured by Lintec Corporation, product name “K8P”) was used as the cloth material.

(Comparative Example 3)
A phenol resin foam laminate was produced in the same manner as in Example 1 except that a polyethylene sheet having a thickness of 0.15 μm was used as the cloth material.

  Table 1 below shows the conditions of Examples and Comparative Examples and the evaluation results of the obtained phenolic resin foam laminate.

In Examples 1-5, the continuous operation over 4 hours was possible, without the contamination of manufacturing equipment becoming a problem. Further, in the obtained phenolic resin foam laminate, the area ratio of the exuded portion of the face material is within a range of 50 to 80%, and the surface obstructed area ratio of the exuded portion is within a range of 20 to 75%. there were. Furthermore, the surface layer part combustibility evaluation level of a foam laminated board became 21% or more, and it has confirmed that the flame retardance improved.
On the other hand, in Comparative Example 1, the area ratio of the exuded part of the face material was less than 50%, and the area ratio of the surface obstructed part of the exuded part was less than 20%. Furthermore, the surface layer portion combustibility evaluation level of the foam laminate was less than 21%. Furthermore, the adhesion of phenolic resin to the production facility became prominent after 1 hour from the start of production, and the subsequent continuous operation could not be performed. In Comparative Example 2, the area ratio of the exuded part of the face material exceeded 80%, and the area ratio of the surface blocking part of the exuded part exceeded 75%. By the way, tearing occurred at the edge of the release paper as a fabric material immediately after the start of production, and the tearing gradually proceeded thereafter, so that the operation exceeding 1 hour could not be performed. In Comparative Example 3, although the cloth material was not torn, the area ratio of the exuded portion of the face material exceeded 80%, and the area ratio of the surface obstructed portion of the exuded part exceeded 75%.

  The phenol resin foam laminated board of this invention can be utilized suitably as a heat insulating material for buildings.

DESCRIPTION OF SYMBOLS 1 Discharge part 2 Face material 3 Foamable phenol resin composition 4 Cloth material 5 Phenol resin foam laminated board 6 Oven 7 Slat conveyor conveyance part

Claims (7)

A phenol resin foam, and a face material having a basis weight of 30 g / m ² or less on at least one surface of the phenol resin foam,
The area ratio of the exuded portion of the face material is 50% or more and 80% or less, and
The phenol resin foam laminate, wherein a surface blocking portion area ratio of the oozing portion is 20% or more and 75% or less. The closed cell ratio of the phenol resin foam is 80% or more,
The phenolic resin foam laminate according to claim 1. The manufacturing method of a phenol resin foam laminated board provided with the process of following (a)-(c):
(A) The process of arrange | positioning the face material whose fabric weight is 30 g / m < ² > or less between the cloth material which has mold release property which consists of a woven fabric or a nonwoven fabric, and a foamable phenol resin composition;
(B) a step of foam-curing the foamable phenol resin composition to obtain a phenol resin foam; and (c) a step of peeling the cloth material from the face material to obtain a phenol resin foam laminate. The cloth material is a woven or non-woven cloth made of fluororesin fibers, or a cloth coated with fluororesin,
The cloth is selected from the group consisting of glass cloth, aramid cloth, carbon cloth, metal fiber cloth, polyarylate cloth, polybenzoxazole cloth, polyethylene cloth, polypropylene cloth, nylon cloth, polyester cloth, alumina cloth, and silica cloth. The manufacturing method of the phenol resin foam laminated board of Claim 3 which is at least 1 type.   The method for producing a phenolic resin foam laminate according to claim 3 or 4, wherein the cloth material is used as an endless belt conveyor.   The manufacturing method of the phenol resin foam laminated board of Claim 3 or 4 with which the said fabric material is arrange | positioned and used on the molding surface of a double slat conveyor.   The method for producing a phenolic resin foam laminate according to claim 3 or 4, wherein the cloth material is endless, and the endless cloth material is used by covering an outer periphery on a molding surface of a double slat conveyor.