JP2012006225A - Laminated plate of phenol resin foamed body, method for manufacturing the same, composite plate, and heat insulating structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated plate of a phenol resin foamed body having improved dimensional stability under the high temperature environment.SOLUTION: The laminated plate of the phenol resin foamed body includes: the phenol resin foamed body having a density of ≥10 kg/mto ≤100 kg/m, an average air bubble diameter of ≥5 μm to ≤200 μm and a closed air bubble ratio of ≥85% to ≤99%; and a face material covering the surface of the phenol resin foamed body. The phenol resin foamed body contains a hydrocarbon, a chlorinated aliphatic hydrocarbon or a combination of these, and shows that the absolute value of the dimensional change ratio after 48 hours at 70°C is ≤0.49%.

Description

  The present invention relates to a phenolic resin foam laminate, a manufacturing method thereof, a composite plate, and a heat insulating structure.

  Phenol resin foam laminates are widely used as building materials and general industrial materials because they have high heat insulating performance, flame retardancy, and heat resistance among foamed plastic heat insulating materials. If you want to ensure the airtight performance of the insulation layer in high-temperature environments that are particularly severe conditions for insulation materials such as roofs of buildings, install a sealing material separately between the insulation materials or between the insulation material and the frame. There was, and it took time and effort of construction.

  Patent Document 1 proposes a method for manufacturing a phenolic resin foam laminate in which a plurality of primary foams are stacked in a hot air curing furnace via a spacer and post-cured at a predetermined temperature and wind speed.

JP 2006-28288 A

  However, in patent document 1, the phenol resin foam laminated board which has the dimensional stability required after construction is not obtained.

  When the inventors want to ensure the airtight performance of the heat insulation layer provided with the phenol resin foam, if the dimensional change rate of the phenol resin foam laminate is extremely small, the heat insulation material is slightly compressed in the in-plane direction. It was found that by tightly fitting while applying airtightness, it is possible to secure the airtight performance after construction without separately installing a sealing material or the like.

  In addition, as a result of intensive studies, the present inventors made the phenol resin foam by making the viscosity of the phenol resin, the moisture content, and the concentration of residual phenol in the phenol resin within a specific range, The inventors have found that a phenol resin foam laminate with improved dimensional stability can be obtained, and have completed the present invention.

The present invention provides the following [1] to [12].
[1] A phenol resin foam having a density of 10 kg / m ³ or more and 100 kg / m ³ or less, an average cell diameter of 5 μm or more and 200 μm or less, and a closed cell ratio of 85% or more and 99% or less, and the phenol resin foam A phenolic resin foam laminate comprising a face material covering the surface, the phenolic resin foam containing hydrocarbon, chlorinated aliphatic hydrocarbon, or a combination thereof, 70 ° C., 48 hours A phenol resin foam laminate, characterized in that the absolute value of the subsequent dimensional change rate is 0.49% or less.
[2] The phenol resin foam laminate according to [1], wherein the volatile content in the phenol resin foam is in the range of 1.0% by weight to 7.0% by weight.
[3] The phenol resin foam laminate according to [1] or [2], wherein the phenol resin foam contains a hydrocarbon and a chlorinated aliphatic hydrocarbon.
[4] The oxygen permeability of the surface ^material, and wherein the at 4.5cm 3 / 24h · ^{m 2} or more [1] to [3] The phenolic foam laminate according to any one of.
[5] The phenol resin foam laminate according to any one of [1] to [4], wherein the thermal conductivity of the phenol resin foam is 0.015 to 0.025 W / m · K. .
[6] A foamable phenolic resin composition comprising a phenolic resin, a curing catalyst, a foaming agent containing a hydrocarbon, a chlorinated aliphatic hydrocarbon, or a combination thereof on a face material, and a surfactant. A method for producing a foamed and cured phenolic resin foam laminate, wherein the residual phenol contained in the phenolic resin is 1.0 wt% or more and 4.3 wt% or less, and the moisture content contained in the phenolic resin is 1 A production method, wherein the phenol resin has a viscosity at 40 ° C. of from 5000 mPa · s to 100,000 mPa · s.
[7] The phenol resin foam laminate according to any one of [1] to [5] or the phenol resin foam laminate produced by the production method according to [6] and a plate member are joined. A composite board characterized in that it is constructed.
[8] The phenol resin foam laminate according to any one of [1] to [5], the phenol resin foam laminate produced by the production method according to [6], and a phenol resin foam laminate. A heat insulating structure comprising: a base material disposed on one main surface side of the material; and a finishing material disposed on the other main surface side of the phenol resin foam laminate.
[9] A first intervening layer disposed between the phenolic resin foam laminate and the base material, and a second intervening layer disposed between the phenolic resin foam laminate and the finishing material are further provided. The heat insulation structure according to [8], which is characterized in that
[10] The heat insulating structure according to [9], wherein the second intervening layer is made of mortar.
[11] The heat insulating structure according to [9], wherein the second intervening layer is made of mortar and a mesh material.
[12] The heat insulating structure according to [9], wherein the second intervening layer includes a plate member.

  ADVANTAGE OF THE INVENTION According to this invention, the phenol resin foam laminated board by which the dimensional stability in the high temperature environment was improved can be provided.

FIG. 1 is a schematic view showing a phenolic resin foam laminate according to this embodiment. FIG. 2 is a cross-sectional view showing a heat insulating structure using the phenol resin foam laminate according to the present embodiment. FIG. 3 is a front view showing a heat insulation structure using a phenol resin foam laminate, and is a diagram showing how the phenol resin foam laminates are arranged. FIG. 4 is a cross-sectional view showing a specific example of a heat insulating structure using the phenol resin foam laminate according to this embodiment.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In addition, the dimensional ratio of drawing is not restricted to the ratio of illustration.

  The phenol resin foam laminate 1 according to the present embodiment has two surfaces of the phenol resin foam 3 so that the main surface of the phenol resin foam 3 and the main surface of the face material 2 are in contact with the face material 2. A shape sandwiched between the materials 2 is formed.

(Phenolic resin foam)
First, the phenol resin foam 3 will be described. The phenol resin foam includes a phenol resin, a curing catalyst for the resin, a foaming agent containing a hydrocarbon, a chlorinated aliphatic hydrocarbon, or a combination thereof, and a surfactant. Is obtained by foaming and curing.

  The phenol resin can be obtained, for example, by heating and polymerizing phenol and formalin as raw materials with an alkali catalyst in a temperature range of 40 to 100 ° C. Moreover, you may add additives, such as urea, at the time of resole resin polymerization as needed. When urea is added, it is more preferable to mix urea that has been methylolated with an alkali catalyst in advance into the resole resin. Since the phenol resin after synthesis normally contains excess water, it is dehydrated to a foamable water content. The moisture content in the phenolic resin is 1% by weight to 10% by weight, preferably 1% by weight to 7% by weight, more preferably 2% by weight to 5% by weight, and particularly preferably 2% by weight to 4.5% by weight. % Or less.

  The starting molar ratio of phenols to aldehydes in the phenolic resin is preferably from 1: 1 to 1: 4.5, more preferably from 1: 1.5 to 1: 2.5. Examples of the phenols preferably used in the synthesis of the phenol resin include phenol or a compound having a phenol skeleton. Examples of the compound having a phenol skeleton include resorcinol, catechol, o-, m- and p-cresol, xylenols, ethylphenols, p-tertbutylphenol and the like. Dinuclear phenols can also be used.

  Examples of aldehydes used in the production of phenol resin include formaldehyde or aldehyde compounds other than formaldehyde. Examples of aldehyde compounds other than formaldehyde include glyoxal, acetaldehyde, chloral, furfural, benzaldehyde and the like. Urea, dicyandiamide, melamine, and the like may be added to the aldehydes as additives. In addition, when adding these additives, a phenol resin refers to the thing after adding an additive.

  The viscosity of the phenol resin is 5000 mPa · s or more and 100000 mPa · s or less at 40 ° C. From the viewpoint of securing the closed cell ratio and production cost, it is preferably 7000 mPa · s or more and 50000 mPa · s or less, and more preferably 10,000 mPa · s or more and 40000 mPa · s or less.

  Residual phenol contained in the phenolic resin is 1.0% by weight or more and 4.3% by weight or less, more preferably 2.3% by weight or more and 4% by weight from the viewpoint of easy adjustment of the phenolic resin and securing foamability. 0.25% by weight or less, most preferably 2.7% by weight or more and 4.2% by weight or less. If the manufactured phenol resin foam contains too much residual phenol, the resin portion of the phenol foam is softened due to the plasticizing effect, and it is considered that the dimensional change is increased.

  The phenol resin may contain an additive. For example, phthalic acid esters and glycols that are generally used as plasticizers, such as ethylene glycol and diethylene glycol, can be used. In addition, aliphatic hydrocarbons, high-boiling alicyclic hydrocarbons, or mixtures thereof may be used. The content of the additive is desirably 0.5 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the phenol resin. If these additives are added too much, the viscosity of the phenolic resin is remarkably lowered, and foam breakage is induced at the time of curing and foaming, and if it is too little, the meaning of containing the additives is lost. For this reason, More preferably, it is 1.0 to 10 weight part.

  From the viewpoint of the global warming potential, the blowing agent has a hydrocarbon, a chlorinated aliphatic hydrocarbon, or a combination thereof as an essential component, and the weight ratio in the blowing agent is a hydrocarbon, a chlorinated aliphatic hydrocarbon, Alternatively, these combinations may be contained in an amount of 50% by weight or more, more preferably 60% by weight or more, further preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. The blowing agent is preferably a hydrocarbon, a chlorinated aliphatic hydrocarbon, or a combination of a hydrocarbon and a chlorinated aliphatic hydrocarbon among these combinations. When hydrocarbons and chlorinated aliphatic hydrocarbons are used in combination, the thermal conductivity tends to be lower than when hydrocarbons are used alone, making the most of the characteristics of hydrocarbons and chlorinated hydrocarbons. A seed or a blend of three is preferred.

  The hydrocarbon blowing agent is preferably a cyclic or chain alkane, alkene, alkyne having 3 to 7 carbon atoms, specifically, normal butane, isobutane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, Examples thereof include normal hexane, isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, and the like. Among them, normal pentane, isopentane, cyclopentane, neopentane pentane and normal butane, isobutane, cyclobutane butane are preferably used. These hydrocarbon foaming agents may be used alone or in combination of two or more.

  As the chlorinated aliphatic hydrocarbon foaming agent, a linear or branched one having 2 to 5 carbon atoms is used. Although the number of bonded chlorine atoms is not limited, 1 to 4 is preferably used, and examples thereof include chloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. It is done. Of these, propyl chloride and isopropyl chloride are more preferably used. These chlorinated aliphatic hydrocarbons may be used alone or in combination of two or more.

  About the usage-amount of a foaming agent, it is used preferably in the range of 1-25 weight part with respect to 100 weight part of phenol resins. More preferably, it is 1 to 15 parts by weight with respect to 100 parts by weight of the phenol resin.

  As the surfactant, those generally used for the production of phenol resin foams can be used. Among them, nonionic surfactants are effective, for example, alkylene oxide which is a copolymer of ethylene oxide and propylene oxide. Or a condensation product of alkylene oxide and castor oil, a condensation product of alkylene oxide and nonylphenol, alkylphenol such as dodecylphenol, polyoxyethylene alkyl ether having 14 to 22 carbon atoms in the alkyl ether portion, and polyoxyethylene fatty acid Fatty acid esters such as esters, silicone compounds such as polydimethylsiloxane, and polyalcohols are preferred. These surfactants may be used alone or in combination of two or more. Moreover, there is no restriction | limiting in particular about the usage-amount, However, It is preferably used in 0.3-10 weight part with respect to 100 weight part of phenol resins.

  The curing catalyst may be an acidic curing catalyst that can cure the phenol resin, but an acid anhydride curing catalyst is preferable. As the acid anhydride curing catalyst, phosphoric anhydride and aryl sulfonic anhydride are preferable. Examples of the aryl sulfonic anhydride include toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, substituted phenol sulfonic acid, xylenol sulfonic acid, substituted xylenol sulfonic acid, dodecyl benzene sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid, and the like. These may be used alone or in combination of two or more. Further, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol and the like may be added as a curing aid. In addition, these curing catalysts 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 hardening | curing agent, It uses preferably in the range of 3-30 weight part with respect to 100 weight part of phenol resins.

  A foamable phenol resin composition can be obtained by mixing the phenol resin, the curing catalyst, the foaming agent, and the surfactant in the proportions described above. A foamed phenolic resin composition can be obtained by foaming and curing the resulting foamable phenolic resin composition as described below. The volatile content in the phenol resin foam is preferably 1.0% by weight or more and 7.0% by weight or less, more preferably 1.1% by weight or more and 7.0% by weight or less. More preferably, it is 2% by weight or more and 6.8% by weight or less, and most preferably 1.3% by weight or more and 6.8% by weight or less. If the volatile content is too high, a large amount of volatile matter is diffused from the phenol resin foam into the atmosphere after construction or in a high-temperature environment. This is not preferable because the pressure of the pressure is reduced, causing a large dimensional change. On the other hand, enormous energy and time are required to produce a phenol resin foam having a volatile content of less than 1.0% by weight. Here, the volatile content of the phenol resin foam of the present invention can be measured based on EN1604, and according to the test method, it is considered that the mixture of moisture and foaming agent is dominant.

The density of the obtained phenolic resin foam is 10 kg / m ³ or more and 100 kg / m ³ or less, preferably 15 kg / m ³ or more and 80 kg / m ³ or less, more preferably 15 kg / m ³ or more and 40 kg / m ³ or less. More preferably, it is 15 kg / m ³ or more and 30 kg / m ³ or less, and most preferably 15 kg / m ³ or more and 28 kg / m ³ or less.

(Phenolic resin foam laminate)
Next, the phenol resin foam laminate 1 will be described. The phenol resin foam laminate 1 is a surface opposite to the surface of the foamable phenol resin composition that contacts the face material by continuously discharging the foamable phenol resin composition described above onto the face material that travels. Is coated with another face material, foamed and cured.

  It is preferable that the face material 2 sandwiching the phenol resin foam 3 has flexibility from the viewpoint of production efficiency. Examples of the face material having flexibility include synthetic fiber nonwoven fabric, synthetic fiber woven fabric, glass fiber paper, glass fiber woven fabric, glass fiber nonwoven fabric, glass fiber mixed paper, paper, metal film, or a combination thereof. . These face materials may contain a flame retardant in order to impart flame retardancy, for example, bromine compounds such as tetrabromobisphenol A and decabromodiphenyl ether which are generally used as flame retardants, aromatic phosphorus Acid esters, aromatic condensed phosphate esters, halogenated phosphate esters, phosphorus or phosphorus compounds such as red phosphorus, antimony compounds such as antimony trioxide and antimony pentoxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide Can be used. These flame retardants may be kneaded into the fibers of the face material, and may be added to a binder such as acrylic, polyvinyl alcohol, vinyl acetate, epoxy, or unsaturated polyester. Further, the surface treatment can be performed with a water repellent or an asphalt waterproofing agent such as a fluororesin system, a silicone resin system, a wax emulsion system, a paraffin system, and an acrylic resin paraffin wax combined system. These water repellents and waterproofing agents may be used alone, or may be applied to the face material by adding the above flame retardant.

The face material preferably has high gas permeability. As such a face material, synthetic fiber nonwoven fabric, glass fiber paper, glass fiber nonwoven fabric, and papers are preferably used. Among such face material, as a gas-permeable, compliant with ASTM D3985-95, oxygen permeability is particularly preferably 4.5cm ³ / 24h · ^{m 2} or more at a surface material. From the viewpoint of the seepage of the thermosetting resin during foaming to the face material and the adhesion between the thermosetting resin and the face material, when using a synthetic fiber nonwoven fabric for the face material, the basis weight is 15 to 80 g / m ² is preferable, and when a glass fiber nonwoven fabric is used, the basis weight is preferably 30 to 200 g / m ² .

  The foam phenolic resin composition sandwiched between two face materials foams on the face material. In order to cure the foamed phenol resin composition (foam), for example, the following first oven and second oven can be used.

  The first oven generates hot air of 60 to 110 ° C. and has an endless steel belt type double conveyor or a slat type double conveyor. In this oven, an uncured foam can be cured while being formed into a plate shape to obtain a partially cured foam. The first oven may have a uniform temperature over the entire region, and may have a plurality of temperature zones.

  The second oven generates hot air of 40 to 120 ° C. to post-cure the foam partially cured in the first oven. Partially cured boards may be stacked at regular intervals using spacers or trays. If the temperature in the second oven is too high, the pressure of the foaming agent inside the foam bubbles will be too high, leading to bubble breakage, and if it is too low, it may take too much time for the phenol resin reaction to proceed. Therefore, 80 to 110 ° C. is more preferable.

  In addition, the said foaming and hardening method is not limited to the above-mentioned method.

  As described above, according to the method for producing a phenolic resin foam laminate according to the present embodiment, using a foaming agent having a low global warming potential, high dimensional stability after construction in a high-temperature environment particularly severe for the heat insulating material. A phenol resin foam laminate having the present invention can be provided.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

<Synthesis of phenolic resin>
The reactor was charged with 3500 kg of 52 wt% formaldehyde and 2510 kg of 99 wt% phenol, stirred with a propeller rotary stirrer, and the temperature inside the reactor was adjusted to 40 ° C. with a temperature controller. Next, the reaction was carried out by increasing the temperature while adding a 50 wt% aqueous sodium hydroxide solution. When the Ostwald viscosity reaches 60 centistokes (= 60 × 10 ⁻⁶ m ² / s, measured value at 25 ° C.), the reaction solution is cooled and 570 kg of urea (corresponding to 15 mol% of the charged amount of formaldehyde) Added. Thereafter, the reaction solution was cooled to 30 ° C. to obtain a 50 wt% aqueous solution of paratoluenesulfonic acid monohydrate, and the pH was neutralized to 6.4.

  After the reaction solution was concentrated at 60 ° C., the residual phenol was measured and found to be 3.1% by weight. This is designated as phenol resin A. Phenol resins B to G shown in Table 2 were obtained by changing the concentration time or adding water after concentration. The reaction time at the time of phenol resin synthesis | combination was adjusted, and the phenol resin HJ was obtained by concentrating the obtained reaction liquid similarly at 60 degreeC. The resin characteristics of the obtained phenol resins A to J are determined by the following method. Table 2 shows the physical properties of the obtained phenol resins A to J.

<Residual phenol>
Residual phenol in the phenolic resin is determined by the following method.
1 mg of phenol resin was dissolved in 1 ml of methanol, and measurement was performed under the following conditions. Apparatus: LC-VP type high performance liquid chromatography column manufactured by Shimadzu Corporation Column: Xbridge C18 3.5 μm (inner diameter 3 mm × 100 mm) manufactured by Waters, column temperature: 40 ° C.
Eluent: Water / acetonitrile Gradient condition: Water / acetonitrile = 90/10 (0 min)
Water / acetonitrile = 0/100 (20 minutes)
Water / acetonitrile = 90/10 (20.1 minutes)
Water / acetonitrile = 90/10 (35 minutes)
Flow rate: 0.47 ml / min Detection: 270 nm
Injection volume: 5 μL
The concentration of residual phenol was calculated from a calibration curve prepared using 10 μg / ml and 100 μg / ml solutions of a phenol preparation (manufactured by Wako Pure Chemicals, reagent grade).

<Moisture content>
The moisture content in the phenol resin was measured using a Karl Fischer moisture meter MKA-510 (manufactured by Kyoto Electronics Industry Co., Ltd.).

<Viscosity of phenolic resin>
A rotational viscometer (manufactured by Toki Sangyo Co., Ltd., R-100 type, rotor part 3 ° × R-14) was used, and the measured value was obtained after stabilization at 40 ° C. for 3 minutes.

(Example 1)
An ethylene oxide-propylene oxide block copolymer (manufactured by BASF, Pluronic F-127) as a surfactant was mixed at a ratio of 2.0 parts by weight with respect to 100 parts by weight of the phenol resin A. A composition comprising 7 parts by weight of foaming agent A shown in Table 1 as a foaming agent and 14 parts by weight of a mixture of 80% by weight of xylene sulfonic acid and 20% by weight of diethylene glycol as an acid curing catalyst with respect to 100 parts by weight of the mixed phenol resin. The product was supplied to a mixing head whose temperature was adjusted to 25 ° C., and supplied to a moving face material through a multiport distribution pipe. The mixer (mixer) used was the one disclosed in JP-A-10-225993. That is, on the upper side surface of the mixer, there is a resin composition obtained by adding a surfactant to a phenol resin, and a foaming agent introduction port, and a curing catalyst introduction port is provided on the side surface near the center of the stirring unit where the rotor stirs. It has. The part after the stirring part is connected to a nozzle for discharging the foam. That is, the mixing section (front stage) up to the catalyst introduction port, the mixing section (rear stage) from the catalyst introduction port to the stirring end section, and the distribution section from the stirring end section to the nozzle are configured. The distribution unit has a plurality of nozzles at the tip, and is designed so that the mixed foamable phenolic resin composition is uniformly distributed.

  The foamable phenolic resin composition supplied on the face material should be sandwiched between two face materials at the same time the surface opposite to the face material is in contact with the other face material. , And sent to a 85 ° C. slat type double conveyor. After curing with a residence time of 15 minutes, it was cured in an oven at 110 ° C. for 2 hours to obtain a phenol resin foam. A plate-like phenolic resin foam laminate was obtained by applying moderate pressure to the foamable phenolic resin foam from above and below with a slat type double conveyor via a face material.

As the face material, a polyester non-woven fabric (“Spunbond E05030” manufactured by Asahi Kasei Fibers Co., Ltd., basis weight 30 g / m ² , thickness 0.15 mm) was used.

(Example 2)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the phenol resin was changed to the phenol resin B.

(Example 3)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the phenol resin was changed to phenol resin C.

Example 4
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that phenol resin D was used as phenol resin D, and 8.0 wt% of a mixture of 50 wt% isopentane and 50 wt% isobutane with respect to the phenol resin.

(Example 5)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the phenol resin was changed to phenol resin E.

(Example 6)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the phenol resin was changed to the phenol resin H.

(Example 7)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the phenol resin was changed to phenol resin I.

(Example 8)
The phenol resin was changed to the phenol resin B, the foaming agent B was changed to the foaming agent B shown in Table 1, and the temperature of the slat type double conveyor oven was changed to 80 ° C. and the residence time was changed to 20 minutes. A foam laminate was obtained.

Example 9
The phenol resin was changed to phenol resin B, the foaming agent C was changed to the foaming agent C shown in Table 1, and the temperature of the slat type double conveyor oven was changed to 80 ° C. and the residence time was changed to 20 minutes. A foam laminate was obtained.

(Example 10)
The phenol resin was changed to the phenol resin B, the foaming agent D was changed to the foaming agent D shown in Table 1, the temperature of the slat type double conveyor oven was changed to 80 ° C., and the residence time was changed to 20 minutes. A foam laminate was obtained.

(Example 11)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the phenol resin was changed to phenol resin B and the foaming agent was changed to foaming agent E shown in Table 1.

(Comparative Example 1)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the phenol resin was changed to phenol resin F.

(Comparative Example 2)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the phenol resin was changed to phenol resin J.

(Comparative Example 3)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the phenol resin was changed to the phenol resin G.

  The characteristic of the phenol resin foam obtained by the Example and the comparative example and the phenol resin foam volume board is calculated | required with the following method.

<Volatile content>
Volatiles content, 105 ° C. of phenolic foam, the weight after drying 48 hours W _D, when the weight W _O before drying, was calculated by the equation shown below.
Volatiles content _{[wt%] = 100 × (} W O -W D) / W D

<Dimensional change rate at 70 ° C.>
Dimensional change rate at 70 ° C. is cut vertically and horizontally 200mm angle phenolic foam, refers to one direction of the dimensional change rate [Delta] [epsilon] _b of the vertical or horizontal determined by the test method shown in EN1604. The length and width are directions perpendicular to the thickness direction of the phenol resin foam. Specifically, it is a value after leaving a phenol resin foam of 200 mm square in length and breadth at a temperature of 70 ° C. for 48 hours. [Delta] [epsilon] _b is calculated by the following equation.
Δε _b = 100 × (b _t −b ₀ ) / b ₀
In the formula, b ₀ is an initial dimension, and b _t is a dimension after being left for 48 hours.

<Closed cell ratio>
A cylindrical sample with a diameter of 35 mm to 36 mm is punched out of a phenol resin foam with a cork borer and cut to a height of 30 mm to 40 mm, and then a standard method of using an air-comparing hydrometer (Tokyo Science, Model 1000) The sample volume was measured by The closed cell ratio is a value obtained by subtracting the volume of the bubble wall calculated from the sample weight and the resin density from the sample volume and dividing the value by the apparent volume calculated from the outer dimension of the sample. The measurement was performed according to ASTM-D-2856. Here, the density of the phenol resin was 1.3 kg / L.

<Phenolic resin foam density>
This is a value obtained by measuring a weight and an apparent volume of a 20 cm square phenolic resin foam laminated plate as a sample and measuring the sample by removing the face material. The measurement was performed according to JIS-K-7222.

<Thermal conductivity of foam products>
The phenol resin foam was cut into 200 mm squares in length and width, and measured according to a JIS-A-1412 flat plate heat flow meter method at a low temperature plate of 5 ° C and a high temperature plate of 35 ° C.

<Foaming properties>
The foamability was evaluated in three stages of A, B, and C by observing the obtained foam laminate. Evaluate the difference between the distance between the upper slat and the lower slat of the slat type double conveyor and the thickness of the foam laminate, and the difference is 0 to 2 mm for A, 2 to 5 mm for B, 5 mm or more Was designated C.

  Table 2 shows the results.

<Comprehensive evaluation>
(Criteria for comprehensive evaluation: dimensional change rate x foamability)
As shown in Table 2, each of the foam laminates according to Examples 1 to 11 has a smaller dimensional change rate than the foam laminates according to Comparative Examples 1 to 3, and has a high closed cell ratio. In addition, the foamability is good and the overall evaluation is A. Comparative Example 1 had poor foaming properties, Comparative Example 2 had a large dimensional change rate, and Comparative Example 3 had an overall evaluation of C because the closed cell ratio of the foam was extremely poor.

  Next, a usage example of the phenol resin foam laminate 1 according to this embodiment will be described with reference to FIGS. 2, 3, and 4.

  FIG. 2 is a cross-sectional view showing a heat insulating structure 100 using the phenolic resin foam laminate 1 according to this embodiment. As shown in FIG. 2, the heat insulating structure 100 includes a phenol resin foam laminate 1, a base material 10 disposed on one main surface 1 a side of the phenol resin foam laminate 1, and a phenol resin foam laminate. 1, the finishing material 20 disposed on the other main surface 1 b side, the first intervening layer 30 disposed between the phenol resin foam laminate 1 and the base material 10, the phenol resin foam laminate 1, And a second intervening layer 40 disposed between the finishing material 20. Such a heat insulating structure 100 can be applied to, for example, an outer heat insulating structure, an inner heat insulating structure, a heat insulating roof structure, and the like.

  The base material 10 is a portion that becomes a base for the phenol resin foam laminate 1 and the finishing material 20. For example, the base material 10 is a wall, a roof, a ceiling, and a floor in a building of a structure. More specifically, the base material 10 is composed of tile, glass, stone, block, brick, RC, lightweight cellular concrete, wood, iron plate, inorganic plate, steel frame, and the like.

  The finishing material 20 covers the base material 10 and the phenol resin foam laminate 1. For example, the finishing material 20 is an exterior material, an interior material, or a waterproof material. More specifically, the exterior material is a top coating material, a finishing tile, a finishing board made of wood, resin, metal, inorganic, or a composite thereof. The interior material is a board, tile, or the like made of cloth, wood, resin, metal, inorganic, or a composite thereof. The waterproof material is a waterproof sheet, asphalt, or the like.

  The intervening layers 30 and 40 are configured by any one of a plate member, a sheet member, and a bonding layer in which the fluid is cured. Or the intervening layer 30 is comprised by combining any two types among a plate member, a sheet | seat member, and a joining layer, or all the types. Examples of the plate member include a gypsum board, a cement board, a calcium silicate board, a metal board, a solid wood board, a plywood board, and a resin board. Moreover, you may use the board which joined these as a board | plate member. The sheet member is, for example, a mesh material or a sheet made of metal, glass, gypsum, calcium silicate, wood, resin, or the like. A joining layer has fluidity at the time of construction, can be applied to members, and can join members by curing. The bonding layer is, for example, mortar, an adhesive or the like. As the adhesive, for example, an adhesive based on a urethane-based resin, an epoxy-based resin, an acrylic resin, a silicon-based resin, a modified silicon-based resin, a mixed composition thereof, or the like can be used.

  The first intervening layer 30 and the second intervening layer 40 may have the same material configuration, or may have different material configurations. The heat insulating structure 100 may include only one of the first intervening layer 30 and the second intervening layer 40. The heat insulating structure 100 does not include both the first intervening layer 30 and the second intervening layer 40, and may be configured by the phenol resin foam laminate 1, the base material 10, and the finishing material 20. It is also possible to use a trunk edge for the intervening layers 30 and 40.

  The members in the heat insulating structure 100 are joined by mechanical joining, joining by curing of a fluid such as an adhesive or mortar, or a combination of both. The mechanical joining is joining using, for example, a screw, a bolt, a nail, a dowel, or the like.

  Specifically, when the first intervening layer 30 is not provided and the phenolic resin foam laminate 1 is directly joined to the base material 10, the phenol resin foam laminate 1 is mechanically joined to the base material 10. Fixed to. When the finishing material 20 is directly joined to the phenolic resin foam laminate 1 without the second intervening layer 40, the finishing material 20 is fixed to the phenolic resin foam laminate 1 by mechanical joining. Is done. Further, when the first intervening layer 30 and the second intervening layer 40 are not provided and the phenolic resin foam laminate 1 and the finishing material 20 are directly joined to the base material 10, the phenol resin foam laminate 1 and the finish are finished. The material 20 is fixed to the base material 10 by mechanical joining.

  When the first intervening layer 30 does not include a plate member or a sheet member and includes only a bonding layer in which a fluid such as an adhesive or mortar is cured, the phenol resin foam laminate 1 is a bonding layer in the first intervening layer 30. It is fixed to the base material 10 by the bonding force. At this time, the joint force between the phenolic resin foam laminate 1 and the base material 10 may be increased by using mechanical joint as well. Further, when the second intervening layer 40 does not include a plate member or a sheet member and includes only a bonding layer in which a fluid such as an adhesive or mortar is cured, the finishing material 20 is bonded to the bonding layer in the second intervening layer 40. It is fixed to the phenolic resin foam laminate 1 by force. At this time, the joint force between the phenolic resin foam laminate 1 and the finishing material 20 may be increased by using mechanical joint as well.

  When the 1st intervening layer 30 contains the solid member by a plate member, a sheet | seat member, or these combination, the said solid member and the base material 10 are joined by mechanical joining, joining by hardening of a fluid, or combined use of both. Be joined. Moreover, the said solid member and the phenol resin foam laminated board 1 are joined by mechanical joining, joining by hardening of a fluid, or combined use of both. When the 2nd intervening layer 40 contains the solid member by a plate member, a sheet member, or these combination, the said solid member and the phenol resin foam laminated board 1 are joined by mechanical joining, the hardening of a fluid, or Joined by the combined use of both. Moreover, the said solid member and the finishing material 20 are joined by mechanical joining, joining by hardening of a fluid, or combined use of both. In addition, when using joining by hardening of a fluid, the intervening layers 30 and 40 become a structure containing a joining layer.

  FIG. 3 is a front view showing the heat insulating structure 100, and is a view showing how to arrange the phenol resin foam laminates 1. FIG. 3 shows a state before the second intervening layer 40 and the finishing material 20 are bonded to the main surface 1b of the phenolic resin foam laminate 1 of the heat insulating structure 100. FIG. 3A is a prior art, and the heat insulating structure 100 has a plurality of phenolic resin foam laminates 1 arranged in the same plane, and between adjacent phenol resin foam laminates 1. A filling material 50 is filled in the gap. As the filler 50, mortar, an adhesive, a sealing material, or the like is used.

  FIG.3 (b) is a front view which shows the heat insulation structure 100 of this invention, and the several phenol resin foam laminated board 1 is located in a line without gap. When conventional heat insulating materials are arranged without gaps, cracks may occur in the mortar as the intervening layer. On the other hand, since the phenol resin foam laminate 1 according to the present embodiment has a small dimensional change rate, it is possible to prevent cracking of the mortar, the adhesive, and the finishing material even when they are arranged without gaps. Thus, since it becomes possible to arrange the phenol resin foam laminated board 1 without gap, the heat insulation in the heat insulation structure 100 improves.

  When constructing the heat insulating structure 100 as described above, the plate member included in the first intervening layer 30 or the second intervening layer 40 and the phenol resin foam laminate 1 are treated as a pre-bonded composite plate. Also good. For example, a gypsum board or hard board and a phenolic resin foam laminate 1 bonded together can be handled as a single composite board. This facilitates handling during construction.

  The phenol resin foam laminate 1 used in the heat insulating structure 100 as described above has a small shrinkage with time. Therefore, when the phenolic resin foam laminate 1 according to this embodiment is in close contact with other members to form a laminated structure, the influence of shrinkage with time can be reduced. Specifically, even when the mating member to be laminated is a member having a low extensibility and a low tensile strength, such as mortar, the phenolic resin foam laminate 1 is cracked by the mating member. Can be suppressed. Moreover, even if the mating member to be laminated is a member having low tensile property and high tensile strength, such as gypsum board or hard board, for example, a bonded product of the mating member and the phenolic resin foam laminate 1 Is hard to warp.

  FIG. 4A is a cross-sectional view showing an inner heat insulating structure 100 </ b> A using the phenol resin foam laminate 1. In the case of the inner heat insulating structure 100A, for example, the base material 10A is a wall, ceiling, and floor made of blocks, bricks, RC, lightweight cellular concrete, wood, iron plate, steel frames, etc., and the first intervening layer 30A is made of adhesive or mortar. The second intervening layer 40A is a plaster board, a cement board, a calcium silicate board, a solid wood board, a plywood, a resin board, etc., and the finishing material 20A is a board made of cloth, wood, resin, metal, inorganic, or a composite thereof. And interior materials such as tiles. For example, when a plate member such as gypsum board is used as the second intervening layer 40A, when an adhesive is used to join the plate member to the phenolic resin foam laminate 1 or the finishing material 20A, the second intervening layer 40A is an adhesive. It becomes the structure also including the joining layer by. At the time of construction, a plate member such as a plaster board related to the second intervening layer 40A, in which the phenol resin foam laminate 1 is bonded in advance, may be handled as the composite plate 200A.

  When the phenol resin foam laminate 1 according to the present embodiment is used for the inner heat insulating structure 100A, the shrinkage with time of the heat insulator is small, so the phenol resin foam laminate 1 as a heat insulator and a hard interior material such as gypsum board In the pasted product, it is difficult to generate a large warp. For example, when the composite plate 200A in which the phenol resin foam laminate 1 and the plate member are joined in advance is used for construction, if the warpage of the composite plate 200A becomes large, a large force is required to correct the warp during construction. Is required. Further, when the large warp is forcibly corrected, there is a possibility that a crack is generated in the composite plate 200A. In addition, even after the construction, a force that causes warping acts on the phenolic resin foam laminate 1 and the plate member. On the other hand, occurrence of such a problem can be suppressed by using the phenol resin foam laminate 1 according to this embodiment.

  FIG. 4B is a cross-sectional view showing an outer heat insulating structure 100 </ b> B using the phenol resin foam laminate 1. In the case of the outer heat insulating structure 100B, for example, the base material 10B is a wall made of block, brick, RC, lightweight cellular concrete, wood, iron plate, steel frame, etc., the first intervening layer 30B is an adhesive or mortar, The intervening layer 40B is a mortar or an adhesive, and may be used in combination with a sheet member such as a mesh material or sheet made of metal, glass, resin, or the like for the purpose of strengthening the intervening layer. For example, the intervening layer may be composed of mortar and mesh material. The finishing material 20B is an exterior material such as a top coating material, a finishing tile, or a finishing board material.

  When the phenol resin foam laminate 1 according to the present embodiment is used for the outer heat insulating structure 100B, since the shrinkage with time of the phenol resin foam laminate 1 as a heat insulator is small, the gap between the joints between the heat insulators after construction Therefore, surface cracks are less likely to occur, and the deterioration of the heat insulation performance due to the gaps can be suppressed, and the ingress of rainwater and the deterioration of the heat insulation performance due to the cracks can be prevented. In particular, when using a mortar or top coating material generally used in the outer heat insulating structure, by using the phenol resin foam laminate 1 according to the present embodiment, problems such as cracks can be reduced, Further, it is not necessary to increase the thickness of the second intervening layer or the finishing material in order to prevent cracking.

  FIG. 4C is a cross-sectional view showing a heat insulating roof structure 100 </ b> C using the phenol resin foam laminate 1. In the case of the heat insulating roof structure 100C, for example, the base material 10C is a roof base made of block, brick, RC, lightweight cellular concrete, wood, iron plate, steel frame, etc., and the first intervening layer 30C is an adhesive, asphalt or mortar. The second intervening layer 40C is also an adhesive, asphalt or mortar, and the finishing material 20C is a waterproof sheet or asphalt. For example, when a plate member such as a hard board is used as the second intervening layer 40C, if an adhesive is used to join the plate member to the phenolic resin foam laminate 1 or the finishing material 20C, the second intervening layer 40C is an adhesive. It becomes the structure also including the joining layer by. At the time of construction, a plate member related to the second intervening layer 40C and the phenol resin foam laminate 1 bonded in advance may be handled as the composite plate 200C. Furthermore, in the case of a heat insulating roof structure, the first intervening layer 30 and the second intervening layer 40 are not used, but only the mechanical joining such as screws, bolts, nails, and gibbles, the mechanical joining and the first interposing layer 30 or the second intervening Bonding using the layer 40 together may be used.

  When a plate member having low extensibility and high tensile strength, such as a hard board, is applied as the second intervening layer 40C, by using the phenol resin foam laminate 1 as a heat insulating material, the same action as the inner heat insulating structure 100A is obtained. An effect can be obtained. Further, when a material having low extensibility and low tensile strength, such as mortar, is applied as the second intervening layer 40C, by using the phenol resin foam laminate 1 as a heat insulating material, the same action as the outer heat insulating structure 100B can be obtained. An effect can be obtained.

  DESCRIPTION OF SYMBOLS 1 ... Phenol resin foam laminated board, 2 ... Face material, 3 ... Phenol resin foam, 10, 10A, 10B, 10C ... Base material, 20, 20A, 20B, 20C ... Finishing material, 30, 30A, 30B, 30C ... 1st intervening layer, 40, 40A, 40B, 40C ... 2nd intervening layer, 100 ... heat insulation structure, 100A ... inner heat insulation structure, 100B ... outer heat insulation structure, 100C ... heat insulation roof structure, 200A, 200C ... composite board.

Claims (12)

A phenol resin foam having a density of 10 kg / m ³ or more and 100 kg / m ³ or less, an average cell diameter of 5 μm or more and 200 μm or less, and a closed cell ratio of 85% or more and 99% or less, and covering the surface of the phenol resin foam A phenolic resin foam laminate comprising:
The phenolic resin foam contains hydrocarbons, chlorinated aliphatic hydrocarbons, or combinations thereof,
A phenol resin foam laminate, characterized in that the absolute value of dimensional change after 70 hours at 70 ° C. is 0.49% or less.   2. The phenol resin foam laminate according to claim 1, wherein a content of volatile components in the phenol resin foam is in a range of 1.0 wt% or more and 7.0 wt% or less.   The phenol resin foam laminate according to claim 1 or 2, wherein the phenol resin foam contains a hydrocarbon and a chlorinated aliphatic hydrocarbon. The oxygen permeability of the surface material is phenolic foam laminate according to any one of claims 1 to 3, characterized in that 4.5cm 3 / 24h ^· m ² or more.   The phenol resin foam laminate according to any one of claims 1 to 4, wherein the thermal conductivity of the phenol resin foam is 0.015 to 0.025 W / m · K. A foamable phenolic resin composition comprising a phenolic resin, a curing catalyst, a foaming agent containing a hydrocarbon, a chlorinated aliphatic hydrocarbon, or a combination thereof, and a surfactant is formed on the face material. A method for producing a phenolic resin foam laminate to be cured,
Residual phenol contained in the phenol resin is 1.0 wt% or more and 4.3 wt% or less, and a moisture content contained in the phenol resin is 1.0 wt% or more and 10.0 wt% or less. A viscosity of the resin at 40 ° C. is from 5000 mPa · s to 100,000 mPa · s.   The phenol resin foam laminate according to any one of claims 1 to 5, or the phenol resin foam laminate produced by the production method according to claim 6, and a plate member. A composite board characterized by that. The phenol resin foam laminate according to any one of claims 1 to 5, or the phenol resin foam laminate produced by the production method according to claim 6,
A base material disposed on one main surface side of the phenol resin foam laminate; and
And a finishing material disposed on the other main surface side of the phenolic resin foam laminate. A first intervening layer disposed between the phenolic resin foam laminate and the base material;
The heat insulating structure according to claim 8, further comprising a second intervening layer disposed between the phenol resin foam laminate and the finishing material.   The heat insulation structure according to claim 9, wherein the second intervening layer is made of mortar.   The heat insulation structure according to claim 9, wherein the second intervening layer is made of mortar and a mesh material.   The heat insulating structure according to claim 9, wherein the second intervening layer includes a plate member.

Images