JP6993192B2 - Phenol resin foam laminated board and its manufacturing method - Google Patents

Description

The present invention relates to a phenolic resin foam laminated board and a method for producing the same.

Phenol resin foams are used in various fields as heat insulating materials because they are flame-retardant and have high gas barrier properties against foaming agents contained in bubbles among foamed plastic-based heat insulating materials.

The phenol resin foam is produced by foaming and curing a foamable phenol resin composition containing a phenol resin, a foaming agent, a curing catalyst, a surfactant, and an additive between at least two upper and lower face materials. Hydrocarbons such as butane and pentane and halogenated hydrocarbons such as isopropyl chloride are known as foaming agents for conventional phenolic resin foams.

In recent years, with the growing awareness of energy conservation and the environment and the revision of energy conservation standards for buildings, there has been a demand for high heat insulation of buildings such as houses, and recycling of building materials including heat insulating materials used in buildings. Is increasing.

Against this background, halogenated unsaturated hydrocarbons with low thermal conductivity and low global warming potential (GWP) are preferably used as foaming agents. However, since halogenated unsaturated hydrocarbons have high compatibility with phenol resins, it is known that the viscosity of phenol resins decreases when mixed with phenol resins. As a result, there is a problem that the heat insulating performance cannot be maintained for a long period of time because the bubbles become coarse and the bubbles tend to break during foaming. Furthermore, due to the decrease in the viscosity of the phenol resin due to the halogenated unsaturated hydrocarbon, the foamable phenol resin composition exudes from the face material in the foaming and curing steps, which not only deteriorates the appearance but also foams the phenol resin during recycling. There was a problem that it became difficult to separate the body and the face material.

Therefore, in Patent Document 1, a woven fabric or a non-woven fabric made of fibers having a specific range of basis weight or a flat shape is used as a face material, or a face material having a specific range of phenol formaldehyde is used to stain the face material. A phenolic resin foam laminated board with a small amount of output has been proposed.

Further, in Patent Document 2, a face material having a specific range of Frazier air permeability is used, and the closed cell ratio and density of the phenol resin foam are set within the specific range to improve the water absorption of the phenol resin foam. It is disclosed that excellent heat insulating performance can be maintained for a long period of time while being reduced.

Japanese Unexamined Patent Publication No. 2009-255332 Japanese Patent No. 5877913

However, Patent Document 1 has poor heat insulating performance because it is limited to woven fabrics and non-woven fabrics having a specific range of Frazier air permeability and fibers having a specific shape and uses hydrocarbons as a foaming agent. There was a problem that it was enough. Further, in Patent Document 2, the water absorption rate of the phenol resin foam laminated board could be reduced by using a face material having a low Frazier air permeability, but the foamable phenol resin composition is contained in the fibers of the face material. Since it becomes difficult to penetrate, the anchor effect becomes difficult to work, and there is room for improvement in the adhesion strength of the face material. Further, when a face material having a low fragile air permeability is used, it becomes difficult to discharge water and gas generated in the curing process of the phenol resin from the phenol resin foam. Therefore, there is a problem that the internal pressure inside the bubble rises and induces bubble rupture. Therefore, in order to obtain a phenol resin foam having excellent physical properties using the same face material, there is a problem that the production conditions are limited to a specific very narrow range such that the pressure inside the phenol resin foam does not increase. There was also.

Therefore, an object of the present invention is to provide a phenol resin foam laminated board capable of providing a phenol resin foam capable of maintaining excellent heat insulating performance for a long period of time, and a method for producing the same.

The present inventor pays attention to the Frazier air permeability of the face material, and by adjusting the resin exudation area ratio to the face material and the adhesion strength of the face material within a specific range, the face material and the phenol resin foam can be recycled at the time of recycling. It has been found that separation can be easily performed and excellent heat insulating performance can be maintained for a long period of time, and the present invention has been completed.

That is, the present invention provides the following [1] to [14].
[1] A phenol formaldehyde foam laminated board in which face materials are arranged on at least the upper and lower surfaces of a phenol resin foam having a density of 20 kg / m ³ or more and 70 kg / m ³ or less and a closed cell ratio of 80% or more. The phenolic resin foam contains at least one selected from hydrofluoroolefin as a foaming agent, the average boiling point X of the foaming agent is 0 ° C. or higher, and the Frazier air permeability of the face material is 51 cm ³ /. It is characterized in that it is cm ² · sec or more and 500 cm ³ / cm ² · sec or less, the resin exudation area ratio to the face material is 50% or less, and the adhesion strength of the face material is 200 g or more and 2000 g or less. Phenol resin foam laminated board.

[2] The hydrofluoroolefin is at least one selected from the group consisting of 1-chloro-3,3,3-trifluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene. The phenolic resin foam laminated board according to the above [1].

[3] The phenolic resin foam laminated board according to the above [1] or [2], wherein the foaming agent further contains a hydrocarbon.

[4] The hydrocarbon is at least one selected from the group consisting of propane, normal butane, isobutane, normal pentane, isopentane, cyclopentane, normal hexane, isohexane, and cyclohexane [3]. The phenol resin foam laminated board according to.

[5] The phenolic resin foam laminated board according to any one of the above [1] to [4], wherein the foaming agent further contains a chlorinated hydrocarbon.

[6] The phenolic resin foam laminated board according to the above [5], wherein the chlorinated hydrocarbon is isopropyl chloride.

[7] The face material is at least one selected from the group consisting of synthetic fiber non-woven fabric, glass fiber non-woven fabric, glass fiber mixed paper, kraft paper, and metal film. ], The phenolic resin foam laminated board according to any one of the items.

[8] The phenolic resin foam laminated board according to any one of the above [1] to [7], wherein the face material contains at least one of a formaldehyde scavenger and an inorganic filler.

[9] The phenolic resin foam according to any one of the above [1] to [8], wherein the formaldehyde emission rate of the phenol resin foam laminated board is 20 μg / m ² · h or less. Body laminate.

[10] Any one of the above [1] to [9], wherein the amount of change in thermal conductivity at 23 ° C. before and after being left in an atmosphere of 110 ° C. for 14 days is 4.0 mW / mK or less. The phenolic resin foam laminate according to the section.

[11] It is characterized in that at least one selected from a board-shaped material, a sheet-shaped material, and a film-shaped material is bonded to the phenolic resin foam laminated board according to claims [1] to [10]. Insulated composite panel.

[12] The method for producing a phenolic resin foam laminated board according to the above [1].
A foaming phenol resin composition containing a phenol resin, a foaming agent containing at least one selected from the group consisting of hydrofluoroolefins, a surfactant, and a curing catalyst is discharged onto a traveling face material. A method for producing a phenol formaldehyde foam laminated plate that is foamed and cured between at least two face materials, the manufacturing method including at least a premolding step and a heating step performed after the premolding step, and the premolding. The length of the step is 5% or more and 50% or less with respect to the length of the heating step, the atmospheric temperature in the premolding process is 30 ° C. or higher and 70 ° C. or lower, and the viscosity of the phenol resin at 40 ° C. is 4000 mPa. -Manufacture of a phenol formaldehyde foam laminated board characterized by having s or more and 100,000 mPa · s or less and having a Frazier air permeability of the face material of 51 cm ³ / cm ² · sec or more and 500 cm ³ / cm ² · sec or less. Method.

[13] The atmospheric temperature in the heating step is 60 ° C. or higher and 99 ° C. or lower, and the pressure applied to the slat plate of the slat type double conveyor in the heating step is 100 kgf / m ² or more and 2000 kgf / m ² or less. [12] The method for producing a phenol resin foam laminated board according to [12].

[14] The method for producing a phenolic resin foam laminated plate according to the above [12] or [13], wherein the boiling point average value X of the foaming agent is 0 ° C. or higher and 50 ° C. or lower.

According to the phenol resin foam laminated board of the present invention, it is possible to provide a phenol resin foam capable of maintaining excellent heat insulating performance for a long period of time.

Further, according to the phenol resin foam laminated board of the present invention, the adhesion strength of the face material is adjusted to a specific range, and at the same time, the foamable phenol resin composition is less exuded from the face material, so that the face material can be used as the face material at the time of recycling. It is possible to provide a phenol resin foam laminate in which the phenol resin foam can be easily separated.

It is a figure which shows the phenol resin foam of this embodiment. It is a figure explaining the method of measuring the face material adhesion strength of the phenol resin foam laminated board of this embodiment.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

(Phenol resin foam laminated board)
Hereinafter, preferred embodiments of the invention will be described in detail.
The phenol resin foam laminate in the present embodiment is a phenol resin foam that exists in a state in which a large number of bubbles (cells) are dispersed in the phenol resin formed by the curing reaction, and at least above the phenol resin foam. It is a laminated body including a face material provided on the lower surface.

The dimensional ratio of the phenol resin foam laminated board is not limited to the ratio shown in FIG. As shown in FIG. 1, in the phenol resin foam laminated board 1 according to the present embodiment, the main surface of the phenol resin foam 3 and the main surface of the face material 2 are in contact with each other, and the phenol resin foam 3 is formed into two sheets. It has a shape sandwiched from above and below by the face material 2.

<Phenol resin foam>
First, the phenol resin foam 3 will be described. The phenol resin foam 3 is obtained, for example, by foaming and curing a foamable phenol resin composition containing a phenol resin, a foaming agent, a curing catalyst, and a surfactant. The effervescent phenol resin composition may optionally contain components other than the above.

The phenolic resin foam 3 of the present embodiment has a density of 20 kg / m ³ or more and 70 kg / m ³ or less, a closed cell ratio of 80% or more, and foams at least one selected from hydrofluoroolefins. It is contained as an agent and is characterized in that the boiling point average value X of the foaming agent is 0 ° C. or higher.

<Phenol resin>
The phenol resin in the present embodiment is obtained, for example, by using phenols and formaldehyde as raw materials and heating them with an alkaline catalyst in a temperature range of 40 to 100 ° C. for polymerization. Further, if necessary, an additive such as urea may be added at the time of polymerizing the phenol resin. Since the synthesized phenol resin usually contains excess water, it is dehydrated to a water content that can be foamed. The starting molar ratio of phenols to aldehydes in the synthesis of phenolic resins is preferably in the range of 1: 1 to 1: 4.5, preferably in the range of 1: 1.5 to 1: 2.5. It is more preferable to have.

Phenols preferably used in the synthesis of phenolic resins include phenols or compounds having a phenol skeleton. Examples of compounds having a phenol skeleton include resorcinol, catechol, o-, m- and p-cresol, xylenols, ethylphenols, p-tert butylphenol and the like. The phenols also include dinuclear phenols.

Examples of aldehydes preferably used in the synthesis of phenolic resins include formaldehyde and aldehyde compounds other than formaldehyde. Examples of the aldehyde compound 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. When these additives are added, the "phenolic resin" refers to a phenolic resin containing the additives.

The phenolic resin of the present embodiment preferably has a viscosity at 40 ° C. of 4000 mPa · s or more and 100,000 mPa · s or less, more preferably 4000 mPa · s or more and 80,000 mPa · s or less, and 5000 mPa · s or more and 60,000 mPa · s. It is more preferably 5000 mPa · s or more and 40,000 mPa · s or less, and most preferably 5000 mPa · s or more and 20000 mPa · s or less.

When the viscosity of the phenol resin at 40 ° C. is 4000 mPa · s or more, it is possible to suppress the exudation of the effervescent phenol resin composition from the face material when foaming and curing, and it is possible to prevent the equipment from becoming dirty. Furthermore, since the foaming speed does not become too fast, the bubble diameter does not become excessively large, and a high closed cell structure can be maintained, the excellent heat insulating performance of the obtained phenol resin foam over a long period of time can be ensured. Can be done. Further, since the effervescent phenol resin composition soaked into the face material 2 does not seep out to the outside of the face material 2, the adhesion strength of the face material 2 is improved without polluting the equipment.

On the other hand, when the viscosity of the phenol resin at 40 ° C. is 100,000 mPa · s or less, the foaming rate of the effervescent phenol resin composition is secured. Therefore, a large amount of foaming agent is not required to obtain the required foaming ratio, liquefaction of the foaming agent due to an increase in pressure of the foaming agent in the bubbles is suppressed, and the heat insulating performance is deteriorated especially in a low temperature region. Can be prevented. In addition, when the viscosity of the phenol resin at 40 ° C. is 100,000 mPa · s or less, molding of the effervescent phenol resin composition becomes easy.

The viscosity of the phenol resin at 40 ° C. can be measured by using the method described in the examples of the present specification.

<Effervescent agent>
The foaming agent contained in the effervescent phenol resin composition contains at least one selected from hydrofluoroolefins, and the effervescent agent used is also contained in the obtained phenol resin foam. The foaming agent can further contain a hydrocarbon and / or a chlorinated hydrocarbon, and the foaming agent used is also contained in the obtained phenol resin foam.

Hydrocarbons are compounds composed only of hydrogen atoms and carbon atoms, and examples thereof include aliphatic hydrocarbons having 3 or more and 6 or less carbon atoms. Examples of aliphatic hydrocarbons having 3 or more and 6 or less carbon atoms include propane, propylene, normal butane, isobutane, butene, butadiene, normal pentane, isopentane, neopentane, penten, hexane, normal hexane, isohexane, hexene and other alkanes and alkenes. , Linear or branched hydrocarbons corresponding to diene; cyclic hydrocarbons such as cyclobutane, cyclopentane, cyclohexene, and the like. Among these, propane, normal butane, isobutane, normal pentane, isopentane, cyclopentane, normal hexane, isohexane, and cyclohexane are preferable. One type of these hydrocarbons may be used alone, or two or more types may be used in combination. The amount of the hydrocarbon used is not particularly limited, but is preferably used in the effervescent phenol resin composition in the range of 0.1 to 15 parts by mass with respect to 100 parts by mass of the phenol resin.

As the chlorinated hydrocarbon, a linear or branched hydrocarbon having 2 or more and 5 or less carbon atoms is preferably used. The number of chlorine atoms bonded to the carbon atom is not limited, but is preferably 1 or more and 4 or less. As the chlorinated hydrocarbon, for example, chloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like are preferable. Of these, propyl chloride and isopropyl chloride are more preferable, and isopropyl chloride is even more preferable. One type of these chlorinated hydrocarbons may be used alone, or two or more types may be used in combination. The amount of the chlorinated hydrocarbon used is not particularly limited, but is preferably used in the foamable phenol resin composition in the range of 0.1 to 15 parts by mass with respect to 100 parts by mass of the phenol resin.

Examples of the hydrofluoroolefin include chlorinated hydrofluoroolefins such as 1-chloro-3,3,3-trifluoropropene (HFO-1233zd); 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze). ), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz), 2,3,3,3-tetrafluoro-1-propen (HFO-1234yf), etc. Hydrofluoroolefins are preferably used. One type of these hydrofluoroolefins may be used alone, or two or more types may be used in combination. Further, any isomer having a cis isomer or a trans isomer can be used. The amount of the hydrofluoroolefin used is not particularly limited, but is preferably used in the effervescent phenol resin composition in the range of 0.1 to 25 parts by mass with respect to 100 parts by mass of the phenol resin.

Here, as the foaming agent, hydrofluorofin may be used alone, or hydrofluorofin may be used in combination with another foaming agent. As a mode in which the hydrofluorofin is used in combination with another foaming agent, a mode in which at least one of a hydrocarbon and a chlorinated hydrocarbon is used in combination is more preferable.

In the present embodiment, the boiling point average value X of the above-mentioned foaming agent is 0 ° C. or higher, preferably 0 ° C. or higher and 50 ° C. or lower, more preferably 0 ° C. or higher and 45 ° C. or lower, and 10 ° C. or higher. It is more preferably 45 ° C. or lower, particularly preferably 10 ° C. or higher and 35 ° C. or lower, particularly preferably 15 ° C. or higher and 35 ° C. or lower, and most preferably 19 ° C. or higher and 32 ° C. or lower.

When the average boiling point of the foaming agent is lower than 0 ° C., the foaming rate becomes excessively high when the phenolic resin foam is produced, bubble rupture is induced, and the closed cell ratio decreases. Then, as the closed cell ratio decreases, the foaming agent in the bubbles becomes easier to replace with air, so that there is a possibility that excellent heat insulating performance cannot be maintained for a long period of time. Further, since the foaming rate becomes excessively high, the foaming rate becomes relatively faster than the curing of the phenol resin, and the foaming pressure becomes high in the oven in a state where the viscosity is relatively low, so that the face material 2 The more effervescent phenolic resin composition exudes. The effervescent phenolic resin composition exuded from the face material 2 not only contaminates the equipment, but also the point that the face material 2 can be separated at the time of recycling and impairs the appearance of the product, and is contained in the phenol from the exuded part. It is not preferable from the viewpoint of health because a small amount of formaldehyde is emitted after construction.

On the other hand, when the average boiling point of the foaming agent is higher than 50 ° C., the foaming pressure when the foamable phenol resin composition is discharged onto the face material described later tends to be low when the phenol resin foam is produced. be. Further, when producing a phenol resin foam, the foaming rate is relatively slower than the curing rate of the phenol resin in the heating step described later, and for example, the foaming phenol resin composition discharged in the form of a plurality of beads. It may be difficult to mold an object into a plate. Therefore, it becomes impossible to form a phenol resin foam having a smooth surface, and there is a concern that streaky marks parallel to the flow direction of the line remain on the surface. Further, since the foaming pressure increases in the heating step described later and the hardness of the phenol resin when the foamable phenol resin composition is pressed against the face material becomes too high, the foamable phenol resin composition becomes the face material 2. Since it does not soak in properly, the adhesion strength of the face material may be weakened.

In this embodiment, the boiling point average value X of the foaming agent can be obtained by the formula (1).
Mean boiling point X = a × Ta + b × Tb + c × Tc + ... (1)
Here, in the above formula (1), the content (molar fraction) of each of the target substances (A, B, C, ...) Is a, b, c, ..., And the boiling point (° C.) is Ta. , Tb, Tc, ... )

<Curing catalyst>
The curing catalyst may be any acidic curing catalyst capable of curing the phenol resin, but an anhydrous acid curing catalyst is preferable. As the anhydrous acid curing catalyst, anhydrous phosphoric acid or anhydrous aryl sulfonic acid is preferable. Examples of the aryl sulfonic acid anhydride include toluene sulfonic acid, xylene sulfonic acid, ethylbenzene sulfonic acid, phenol sulfonic acid, substituted phenol sulfonic acid, xylenol sulfonic acid, substituted xylenol sulfonic acid, dodecylbenzene sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid and the like. Can be mentioned. Then, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol and the like may be added as a curing aid. Further, these curing catalysts may be diluted with a solvent such as ethylene glycol or diethylene glycol. One type of each of the curing catalyst, the curing aid, and the solvent may be used alone, or two or more types may be used in combination. The amount of the curing catalyst used is not particularly limited, but is preferably used in the foamable phenol resin composition in the range of 3 to 30 parts by mass with respect to 100 parts by mass of the phenol resin. The amount of the curing aid and the solvent used can be appropriately set according to the type and amount of the curing catalyst.

<Surfactant>
As the surfactant, those generally used for producing a phenol resin foam can be used, and among them, a nonionic surfactant is effective. For example, the alkylene oxide which is a copolymer of ethylene oxide and propylene oxide, the condensate of alkylene oxide and castor oil, the condensate of alkylene oxide and nonylphenol, the condensate of alkylphenol such as dodecylphenol, and the carbon number of the alkyl ether moiety 14 to 22 polyoxyethylene alkyl ethers, further fatty acid esters such as polyoxyethylene fatty acid esters, silicone compounds such as polydimethylsiloxane, polyalcohols and the like are preferable. One type of these surfactants may be used alone, or two or more types may be used in combination. The HLB of these surfactants is preferably in the range of 8-18. The amount of the surfactant used is not particularly limited, but is preferably used in the foamable phenol resin composition in the range of 0.3 to 10 parts by mass with respect to 100 parts by mass of the phenol resin.

<Phenol resin composition foaming and curing>
For example, the effervescent phenol resin composition is obtained by mixing the above-mentioned phenol resin, the above-mentioned foaming agent, the above-mentioned curing catalyst, and the above-mentioned surfactant in the above-mentioned ratios. The phenol resin foam 3 can be obtained by foaming and curing the obtained foamable phenol resin composition, for example, as described later in the section of "Phenol resin foam laminate".

<Characteristics of phenolic resin foam>
The density of the phenolic resin foam of the present embodiment needs to be 20 kg / m ³ or more and 70 kg / m ³ or less, preferably 20 kg / m ³ or more and 50 kg / m ³ or less, and 20 kg / m ³ or less. It is more preferably 40 kg / m ³ or more, more preferably 25 kg / m ³ or more and 40 kg / m ³ or less, and particularly preferably 25 kg / m ³ or more and 35 kg / m ³ or less.

If the density of the phenolic resin foam 3 is lower than 20 kg / m ³ , the strength is lowered and it becomes difficult to handle during handling. Further, a large amount of foaming agent is required to increase the foaming ratio, and a large amount of foaming agent is contained in the bubbles, resulting in an increase in internal pressure. Due to the increase in the internal pressure in the bubbles, the foaming agent tends to be liquefied and aggregated, so that the heat insulating performance is deteriorated especially in a low temperature region. Further, when the density of the phenol resin foam is higher than 70 kg / m ³ , the ratio of the resin portion in the phenol resin foam contributing to the thermal conductivity increases, and the heat insulating performance of the entire phenol resin foam deteriorates. It ends up.

The density of the phenolic resin foam 3 can be measured by using the method described in the examples of the present specification.

When the closed cell ratio of the phenolic resin foam 3 of the present embodiment becomes low, the gas having a low thermal conductivity contained in the bubbles of the phenolic resin foam 3 is easily replaced with air having a relatively high thermal conductivity, and heat is insulated. Long-term stability of performance deteriorates. Furthermore, there is a risk that the rate at which formaldehyde, which is generated during the curing of the phenol resin and can cause sick house syndrome, diffuses from the foam to the surrounding environment (formaldehyde emission rate) from the inside of the phenol resin foam 3 may increase. be. For these reasons, the closed cell ratio of the phenolic resin foam 3 needs to be 80% or more, preferably 90% or more, further preferably 95% or more, and 97% or more and 100%. The following is particularly preferable.

The closed cell ratio of the phenolic resin foam 3 can be measured by using the method described in the examples of the present specification.

The phenol resin foam 3 of the present embodiment preferably has a thickness of 20 mm or more, more preferably 25 mm or more, further preferably 30 mm or more, and most preferably 40 mm or more.

The thinner the thickness of the phenol resin foam 3, the more the foamable phenol resin composition discharged onto the face material needs to be strongly compressed and spread in order to obtain the smoothness of the surface. Will increase. For this reason, the adhesive strength between the face material and the phenol resin foam 3 becomes too strong, which makes it difficult to separate the face material and the phenol resin foam 3 at the time of recycling, and also increases the emission rate of formaldehyde. Therefore, it adversely affects the living environment. Furthermore, since the production equipment is polluted by the exudation of the effervescent phenol resin composition from the face material, it is necessary to perform frequent cleaning, and there is a concern that the production efficiency will be significantly deteriorated. For these reasons, the phenol resin foam 3 preferably has a thickness of 20 mm or more.

The formaldehyde emission rate can be measured using the method described in the examples herein. In addition to the closed cell ratio of the phenol resin foam 3 described above, the formaldehyde emission rate is also affected by the Frazier air permeability of the face material of the phenol resin foam laminate and the exudation area ratio of the foamable phenol resin composition. Therefore, it is preferably 20 μg / m ² · h or less, more preferably 10 μg / m ² · h or less, particularly preferably 7 μg / m ² · h or less, and most preferably 5 μg / m ² · h or less.

In the phenolic resin foam 3 of the present embodiment, the amount of change in thermal conductivity at 23 ° C. before and after 14 days in an atmosphere of 110 ° C. corresponding to deterioration of heat insulating performance during long-term use is 4.0 mW / m. It is preferably k or less, more preferably less than 3.0 mW / m · k, further preferably less than 2.0 mW / m · k, and less than 1.5 mW / m · k. Especially preferable. The lower this value is, the more the phenol resin foam 3 can maintain the heat insulating performance for a long period of time.

The thermal conductivity after the accelerated test corresponding to the above-mentioned long-term use can be measured by using the method described in the examples of the present specification.

Next, the face material 2 arranged on at least the upper and lower surfaces of the above-mentioned phenol resin foam 3 will be described. The face material (upper surface material) 2 arranged on the upper surface of the phenol resin foam 3 and the face material (lower surface material) 2 arranged on the lower surface may be the same or different ones. , In order to prevent warping of the phenolic resin foam laminated board 1 at the time of manufacturing, the same one is usually used.

The face material 2 of the present embodiment is preferably a face material having flexibility in order to prevent the face material from breaking during production. Examples of the flexible face material include synthetic fiber non-woven fabrics, synthetic fiber woven fabrics, glass fiber papers, glass fiber woven fabrics, glass fiber non-woven fabrics, glass fiber mixed papers, papers such as kraft paper, and metal films. Among these, synthetic fiber non-woven fabric, glass fiber non-woven fabric, glass fiber mixed paper, kraft paper, and metal film are preferable. These face materials may be perforated, if necessary. In addition, one type of these face materials may be used alone, or two or more types may be used in combination. The metal film or the face material in which the metal film is combined with the above-mentioned other face materials may be provided with holes in advance or online in order to discharge water or gas from the phenol resin foam.

The face material 2 may contain a flame retardant, a formaldehyde scavenger, an inorganic filler, or the like, and preferably contains a formaldehyde scavenger and / or an inorganic filler. The flame retardant, formaldehyde supplement, and inorganic filler may be mixed in the fibers of the face material in advance or coated on the face material, or in the state of the phenol resin foam laminated plate 1, either the upper or lower side or both sides. May be applied to the face material 2 of.

Examples of the flame retardant include bromine compounds such as tetrabromobisphenol A and decabromodiphenyl ether; phosphorus or phosphorus compounds such as aromatic phosphoric acid ester, aromatic condensed phosphoric acid ester, halogenated phosphoric acid ester, ammonium polyphosphate and red phosphorus. Antimon compounds such as antimon trioxide and antimon pentoxide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide can be used. The flame retardant may be used alone or in combination of two or more.

These flame retardants may be kneaded into the fibers of the face material 2, and may be applied to the face material 2 in a state of being added to a binder such as acrylic, polyvinyl alcohol, vinyl acetate, epoxy, and unsaturated polyester. May be. The flame retardant is added to water repellents such as fluororesin-based, silicone resin-based, wax emulsion-based, paraffin-based, and acrylic resin paraffin-wax-based waterproofing agents and asphalt-based waterproofing agents to provide surface water-repellent and waterproofing agents. It may be used. One type of each of these water repellents and waterproofing agents may be used alone, or two or more types may be used in combination. Further, it may be applied to the face material 2 to which the flame retardant is added.

Examples of the formaldehyde trapping agent include a compound having an amino group in the molecule, a compound having an amide group in the molecule, a compound having an imide group in the molecule, a compound having an imino group in the molecule, and a hydrazide group in the molecule. Examples thereof include a compound, a compound having an azine group in the molecule, and a compound having an azole group in the molecule. Among these, compounds having an amino group in the molecule, compounds having an amide group in the molecule, compounds having an imide group in the molecule, compounds having an imino group in the molecule, and compounds having an imino group in the molecule, due to availability and price, etc. Compounds having a hydrazide group are preferred.

Compounds having an amino group in the molecule include amine polymers and derivatives having a double bond, amine copolymers and derivatives having a double bond, polyamines and derivatives, amino acids such as arginine, guanidine and guanidine derivatives, and melamine. Examples include derivatives.

Compounds having an amide group in the molecule include amide polymers and derivatives having a double bond, amide copolymers and derivatives having a double bond, urea and urea derivatives, dicyanodiamides and dicyanodiamide derivatives, semicarbazides and semicarbazide derivatives. , Barbituric acid, and the like.

Examples of the compound having an imide group in the molecule include polymers and derivatives of imide compounds having a double bond, copolymers and derivatives of imide compounds having a double bond, succinimide, glutarimide, phthalimide and the like.

Compounds having an imino group in the molecule include polymers and derivatives of imine compounds having a double bond, copolymers and derivatives of imine compounds having a double bond, imidazole and imidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and Examples thereof include tetrazole derivatives.

Examples of the compound having a hydrazine group in the molecule include a hydrazine salt compound, an alkylhydrazine, a phenylhydrazine, a phenylhydrazine derivative and the like. Examples of the compound having a hydrazide group include carboxylic acid hydrazides such as salicylic acid hydrazide and adipic acid dihydrazide.

The formaldehyde scavenger may be used alone or in combination of two or more.

The face material 2 may contain an inorganic filler in order to adjust the pH of water absorbed by the foam or discharged from the foam via the face material 2. Examples of the inorganic filler include metal hydroxides such as aluminum hydroxide and magnesium hydroxide; metal carbonates such as calcium carbonate, magnesium carbonate, barium carbonate and zinc carbonate; metals such as calcium oxide, magnesium oxide, aluminum oxide and zinc oxide. Oxide: Metal powder such as zinc powder can be mentioned.

These inorganic fillers may be kneaded into the fibers of the face material 2, and are applied to the face material 2 in a state of being added to a binder such as acrylic, polyvinyl alcohol, vinyl acetate, epoxy, and unsaturated polyester. You may.

In addition, one kind of inorganic filler may be used alone, or two or more kinds may be used in combination.

The Frazier air permeability of the face material of the present embodiment needs to be 51 cm ³ / cm ² · sec or more and 500 cm ³ / cm ² · sec or less, and 70 cm ³ / cm ² · sec or more 400 cm ³ / cm ² ·. It is preferably 70 cm ³ / cm ² · sec or more, more preferably 300 cm ³ / cm ² · sec or less, and 150 cm ³ / cm ² · sec or more and 250 cm ³ / cm ² · sec or less. Is particularly preferable, and 150 cm ³ / cm ² · sec or more and 210 cm ³ / cm ² · sec or less is particularly preferable.

If the Frazier air permeability of the face material is lower than 51 cm ³ / cm ² · sec, it becomes difficult for the foamable phenol resin composition to enter the voids of the face material 2 in the process of foaming and curing the foamable phenol resin composition. The effect does not improve the adhesive strength of the face material. As a result, the face material 2 is easily peeled off from the phenol resin foam laminated board 1 during handling during construction and after construction, which is not preferable. Further, if the Frazier air permeability of the face material 2 is extremely low, it becomes difficult to release the water generated or contained in the foaming phenol resin composition in the process of foaming and curing to the outside of the phenol resin foam. As a result, the internal foaming pressure becomes excessively high, the bubbles are induced to break, and a poor phenol resin foam having a low closed cell ratio can be obtained.

On the other hand, if the Frazier air permeability of the face material exceeds 500 cm ³ / cm ² · sec, the effervescent phenolic resin composition discharged onto the face material exudes from the face material 2 in the process of foaming and curing, and the manufacturing equipment. Will pollute. Further, since a large amount of the foamable phenol resin composition soaks into the face material 2, the adhesion strength of the face material 2 becomes too strong, and when the phenol resin foam laminate 1 is recycled, the phenol resin foam 3 and the face material 2 are used. There is a risk that the separation of 2 will be difficult. Further, since rapid foaming is likely to occur, the closed cell ratio of the phenol resin foam 3 may decrease, and the heat insulating performance over a long period of time may deteriorate.

The Frazier air permeability of the face material 2 can be measured by using the method described in the examples of the present specification.

<Manufacturing method of phenol resin foam laminated board>
As a method for producing the phenol resin foam laminated plate 1 of the present embodiment described above, for example, a foaming phenol resin composition containing a phenol resin, a curing catalyst, a foaming agent, and a surfactant is at least. It is a manufacturing method of foaming and curing between two face materials, and the manufacturing method includes at least a premolding step and a heating step. The premolding process is performed at an atmospheric temperature of 30 ° C. or higher and 70 ° C. or lower, the heating step is performed at an atmospheric temperature of 60 ° C. or higher and 99 ° C. or lower, and the viscosity of the phenol resin at 40 ° C. is 4000 mPa · s or higher and 100,000 mPa. -It is preferably s or less.

Here, the reason why it is preferable to use a phenol resin having a viscosity at 40 ° C. of 4000 mPa · s or more and 100,000 mPa · s or less is as described above in the above section <Phenolic resin foam>.

The method for foaming and curing the effervescent phenol resin composition for obtaining the phenol resin foam 3 of the present embodiment is not limited to the above method.

The method of arranging the effervescent phenol resin composition between the two face materials 2 is not particularly limited, but the effervescent phenol resin composition is continuously discharged onto the running lower surface material 2 and further effervescent phenol. A method of covering the surface (upper surface) of the resin composition opposite to the surface in contact with the lower surface material 2 with the other surface material (upper surface material) 2 can be mentioned.

The heating method in the preforming process and the heating step described above is not particularly limited as long as the effervescent phenol resin composition can be foamed and cured, but heating in an oven is preferable.

<Pre-molding process>
In the pre-molding process, the effervescent phenolic resin composition continuously discharged between the upper and lower face materials is pressed from above the face material 2 by a single or a plurality of doctor blades or rollers to partially form a board before proceeding to the heating process. Can be molded into. If the pressing is insufficient, the smoothness of the effervescent phenol resin composition becomes insufficient, and the foaming and reaction proceed non-uniformly in the next heating step, resulting in a poor foam having non-uniform physical properties. Not preferred. Further, since the low-viscosity effervescent phenol resin composition in which the reaction has not progressed so much and the face material 2 do not sufficiently adhere to each other, there is a concern that the face material adhesion strength may be insufficient.

On the other hand, if the pressing force is too strong, the effervescent phenolic resin composition having a low viscosity exudes from the face material 2 and contaminates the equipment. Further, since the adhesive strength of the face material becomes too strong, it becomes difficult to separate the foam 3 and the face material 2 when the phenol resin foam 3 is recycled, which is not preferable.

The length of the premolding process is 5% or more and 50% or less, preferably 7% or more and 45% or less, more preferably 10% or more and 40% or less, and 10% or more with respect to the length of the heating step. 35% or less is more preferable, 10% or more and 30% or less is particularly preferable, and 10% or more and 25% or less is most preferable.

When the length of the premolding process is less than 5% of the length of the heating process, the foaming phenol resin composition does not sufficiently cure in the premolding process, and the foaming phenol having a low viscosity in the heating process does not proceed sufficiently. The resin composition rapidly foams. Therefore, not only the bubble rupture is induced, but also a large amount of the effervescent phenol resin composition having a viscosity lower than that of the face material is exuded, the formaldehyde emission rate is high, and the face material adhesion strength is too strong. Problems such as the face material not being able to be peeled off during recycling occur.

On the other hand, if the length of the premolding process is 50% or more of the length of the heating step, the viscosity of the effervescent phenol resin composition becomes too high, so that the foaming ratio required in the heating step can be obtained. Not only is it not present, but it is not preferable because the viscosity at the time of premolding is too high and the adhesive strength of the face material is weak, resulting in a poor foam with poor smoothness.

The atmospheric temperature in the premolding process is 30 ° C. or higher and 70 ° C. or lower, preferably 30 ° C. or higher and 60 ° C. or lower, more preferably 30 ° C. or higher and 50 ° C. or lower, and most preferably 30 ° C. or higher and 40 ° C. or lower.

<Heating process>
In the heating step, the effervescent phenol resin composition is foamed and molded into a predetermined thickness and shape by the effervescent pressure, and the curing of the phenol resin is further promoted from the premolding process.

The atmospheric temperature (in-oven temperature) in the heating step is 60 ° C. or higher and 99 ° C. or lower, more preferably 60 ° C. or higher and 95 ° C. or lower, further preferably 65 ° C. or higher and 90 ° C. or lower, and 70 ° C. or higher and 90 ° C. The temperature is particularly preferably 70 ° C. or higher, and most preferably 70 ° C. or higher and 85 ° C. or lower.

If the atmospheric temperature in the heating step is lower than 60 ° C., the curing reaction of the phenol resin does not proceed sufficiently, so that the phenol resin foam 3 may be uncured and problems such as shrinkage may occur. In addition, since the foaming pressure does not become sufficiently high, there is a concern that the adhesive strength of the face material will be insufficient. If the atmospheric temperature in the heating step is higher than 99 ° C., the temperature near the surface of the effervescent phenol resin composition in contact with the face material 2 becomes too high. As a result, there is a possibility that bubbles in the vicinity of the surface may be ruptured to obtain a poor phenol resin foam 3 having a low closed cell ratio. Further, since the foaming pressure becomes too high, the foamable phenol resin composition exudes from the face material 2, which is not preferable.

Further, in the heating step, it is necessary that the boiling point average value X of the foaming agent is lower than the atmospheric temperature in the first heating step. This is because if the boiling point average value X of the foaming agent is equal to or higher than the atmospheric temperature of the first heating step, foaming by the foaming agent is not sufficiently performed.

When an oven (hereinafter referred to as "oven") is used in the heating step, the oven may have an endless steel belt type double conveyor or a slat type double conveyor, but a slat type double conveyor is preferably used. Using these, it is possible to obtain a foam that has been further cured by curing it in an oven while forming it into a plate shape while controlling the foaming pressure of the foam partially cured in the premolding process. The endless steel belt type double conveyor or the slat type double conveyor may be arranged in the whole or partially of the oven. Further, the temperature inside the oven does not have to be uniform over the entire area, and may have a plurality of temperature zones.

At this time, the pressing force applied to the foam from the slat plate is 100 kgf / m ² to 2000 kgf / m ² , preferably 200 kgf / m ² to 1500 kgf / m ² , more preferably 200 kgf / m ² to 1000 kgf / m ² , and further. It is preferably 200 kgf / m ² to 800 kgf / m ² , and most preferably 300 kgf / m ² to 800 kgf / m ² .

If the pressing force applied to the foam from the slat plate is less than 100 kgf / m ² , the effervescent phenol resin composition does not sufficiently permeate the face material, and excellent adhesive strength of the face material 2 cannot be obtained. Further, since sufficient pressing pressure cannot be obtained, the effervescent phenol resin composition partially molded into a board shape in the premolding process cannot be sufficiently molded, and the smoothness becomes insufficient, which is preferable. do not have. On the other hand, if it exceeds 2000 kgf / m ² , the exudation of the effervescent phenol resin composition through the face material increases, which is not preferable.

The exudation amount is preferably 50% or less, more preferably 40% or less, still more preferably 30% or less, particularly preferably 20% or less, most preferably 50% or less, as measured by the exudation area ratio to the face material 2 described later. It is preferably 10% or less.

If the exudation area ratio exceeds 50%, the adhesion strength of the face material 2 becomes too high, and the peelability of the face material described later becomes poor, so that the face material 2 and the phenol resin foam 3 cannot be separated at the time of recycling. Therefore, it is not preferable. On the other hand, since the phenol resin foam 3 is present in a large amount on the surface of the face material 2, a larger amount of formaldehyde is emitted than the phenol resin foam, which adversely affects the living environment. Is also unfavorable.

<Post-curing process>
The phenolic resin foam laminated board 1 produced from the heating step is cut to a predetermined size and then further heated in the post-curing step to proceed with curing and drying. The atmospheric temperature in the post-curing step is preferably 60 ° C. or higher and 110 or lower. If the temperature is lower than 60 ° C., the curing reaction does not proceed sufficiently, and if the temperature is higher than 110 ° C., the pressure inside the phenolic resin foam becomes too high, which is not preferable because it induces deformation and bubble rupture.

<Insulation composite panel>
The phenolic resin foam laminated board 1 is used alone or in various applications by being bonded to an external member. Examples of the external member include a board-shaped material, a sheet-shaped / film-shaped material, and a combination thereof. Board-like materials include ordinary plywood, structural plywood, particle board, OSB, and other wood-based boards, as well as wood wool cement board, wood piece cement board, gypsum board, flexible board, medium density fiber board, and calcium silicate board. , Magnesium silicate plate, volcanic vitreous multi-layer plate and the like are suitable. The sheet-like and film-like materials include polyester non-woven fabric, polypropylene non-woven fabric, inorganic-filled glass fiber non-woven fabric, glass fiber non-woven fabric, paper, calcium carbonate paper, polyethylene-processed paper, polyethylene film, plastic moisture-proof film, asphalt waterproof paper, and aluminum. Foil (with or without holes) is suitable.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. The following items were measured and evaluated for the phenol resin, phenol resin foam, and face material.

<Density of phenolic resin foam>
A 20 cm square board cut out from the obtained phenol resin foam laminated board was used as a sample, and after removing the face material from this sample, the mass and the apparent volume were measured and determined according to JIS K 7222.

<Phenol resin foam closed cell ratio>
The measurement was carried out by the following method with reference to ASTM D 2856-94 (1998) A.
A cube specimen of about 25 mm square was cut out from the central portion in the thickness direction of the phenol resin foam 3 in the phenol resin foam laminated plates obtained in Examples and Comparative Examples. When a thin piece having a uniform thickness of 25 mm could not be obtained, the surface of a cube piece having a size of about 25 mm square was sliced by about 1 mm, and the piece having a uniform thickness was used.

<Average cell diameter of phenolic resin foam>
With reference to the method described in JIS-K-6402, the average cell diameter of the phenol resin foam was measured by the following method.
The center of the phenolic resin foam in the thickness direction was cut parallel to the front and back surfaces, and a photograph was taken in which the cut cross section was magnified 50 times. Four straight lines with a length of 9 cm (corresponding to 1,800 μm in the actual foam cross section) were drawn at arbitrary positions in the obtained photographs, and the average value of the number of bubbles crossed by each straight line was calculated. The average bubble diameter is a value calculated by dividing 1,800 μm by the average value of the number of bubbles crossed.

The length of each side was measured with a caliper, the apparent volume (V1: cm ³ ) was calculated, and the mass of the specimen (W: 4 significant digits, g) was measured. Subsequently, using an air pycnometer (Tokyo Science Co., Ltd., trade name "MODEL1000"), the closed space volume (V2: cm ³ ) of the specimen was measured according to the method described in Method A of ASTM D 2856.
Further, the average bubble diameter (t: cm) was measured according to the above-mentioned average bubble diameter measuring method, and the surface area (A: cm ² ) of the sample was calculated from the length of each side of the sample.
From the obtained t and A, the opening volume (Va: cm ³ ) of the cut bubbles on the surface of the specimen was calculated from the following equation (4). The density of the solid phenol resin was 1.3 g / cm ³ , and the volume (Vs: cm ³ ) of the solid portion constituting the bubble wall contained in the sample was calculated from the following equation (5).
Va = (A × t) /1.14 ・ ・ ・ (4)
Vs = W / 1.3 ... (5)
From the above results, the closed cell ratio was calculated by the following formula (6).
Closed cell ratio (%) = [(V2-Vs) / (V1-Va-Vs)] × 100 ... (6)

Foam samples under the same production conditions were measured 6 times, and the average value was used as a representative value.

<Frazier air permeability of face material>
The Frazier air permeability of the face material was measured as follows according to JIS L 1096: 2010 8.26.1 A method (Frazil type method).
The face material was cut into 200 mm × 200 mm to form a test piece, which was attached to one end of a cylinder of a Frazier type testing machine (“Frazil Permiameter FP-2 type” manufactured by Toyo Seiki Seisakusho Co., Ltd.). After attaching the test piece, the suction fan and the air hole were adjusted so that the inclined barometer showed a pressure of 125 Pa by an adjusting resistor, and the pressure indicated by the vertical barometer at that time was measured. The amount of air passing through the test piece (cm ³ / cm ² · sec) was calculated from the measured pressure and the type of air holes used, and used as the Frazier air permeability of the face material.

<Exuding area ratio>
After marking the part where the effervescent phenol resin composition exudes from the face material by enclosing it with magic, the 300 x 300 mm area of the phenol resin foam laminate is photographed with a digital camera, and after color tone correction, a pixel counter is used. The number of pixels at the location where the resin composition exuded was counted by software and the number of pixels in the entire 30 cm × 30 cm area was counted, and the resin exudation area ratio was calculated by the following formula.
Exuding area ratio (%) = (number of pixels in the area surrounded by magic / number of pixels in the entire 300 mm area) x 100
The exudation area ratio is obtained by averaging the measurement results of a 300 × 300 mm test piece sampled from a total of three locations from the center and left and right ends in the width direction of the phenol resin foam laminated board (for example, width 910 mm, length 1820 mm). I asked for it.

<Face material adhesion strength>
The adhesive strength of the face material of the phenolic resin foam laminated board was measured and determined as follows (see FIG. 1).
First, the phenolic resin foam laminated board is cut into a width of 50 mm and a length of 120 mm (the length direction coincides with the product MD direction), and one of the face materials (a) and (b) located on the upper and lower surfaces. The face material (b) of the above was peeled off. Then, the laminated board after peeling the face material (b) was cut in a direction parallel to the upper and lower surfaces to prepare the evaluation sample 1 having the face material (a) and having a width of 50 mm, a length of 120 mm, and a thickness of 25 mm.

Next, using a cutter, a notch with a depth of 20 mm was made in the thickness direction from the surface on the side having no face material (a) at a position 20 mm from one end in the length direction of the evaluation sample. At the cut position, the base material of the evaluation sample was carefully divided in the thickness direction. At this time, a force in the length direction was not applied so that the face material (a) (corresponding to the face material in FIG. 1) would not be peeled off from the base material.

Then, the portion of the evaluation sample from which the base metal is divided is held on the side where the length of the base metal is long by the clamp 7 so as to be at an angle of 45 ° with the horizontal plane as shown in FIG. The container 6 connected by the metal wire 5 to the tip of the portion where the length of the material is short was set via the clamp 4.

Then, water was continuously charged into the empty container 6 using a pump at a charging rate of 100 g / min. The mass of water in the container 6 when the face material 2 was peeled off by 50 mm from the cut position in the length direction of the evaluation sample was measured. The same operation was performed twice, and the average value of the total masses of the clamp 4, the metal wire 5, the container 6, and the obtained water was taken as the face material adhesion strength (a).

Further, separately, an evaluation sample having a face material (b), a width of 50 mm, a length of 120 mm, and a thickness of 25 mm was prepared, and the face material adhesion strength (b) was obtained in the same manner as the face material adhesion strength (a). .. Then, the lower value of the face material adhesion strength (a) and the face material adhesion strength (a) was taken as the face material adhesion strength (unit: g) of the phenol resin foam laminated board.

<Hand peelability of face material of phenol resin foam laminate>
Based on the following criteria, a four-point evaluation of ◎, 〇, △, and × was performed.
⊚: The face material can be easily peeled off by hand.
〇: A part of the face material is torn when the face material is peeled off by hand.
Δ: The phenol resin foam is broken when the face material is peeled off by hand.
X: The face material cannot be peeled off by hand, or the face material is significantly torn when peeled off.

<Identification of the type of foaming agent component in the phenol resin foam and calculation of the molar ratio of each foaming agent component>
First, using standard gases of halogenated unsaturated hydrocarbons, hydrocarbons, and halogenated saturated hydrocarbons used as foaming agents, the retention time under the following GC / MS measurement conditions was determined.

Next, the face material was peeled off from the phenol resin foam laminated plates obtained in Examples and Comparative Examples, and about 10 g of the phenol resin foam sample and the metal shavings were placed in a 10 L container (product name "Tedlar bag") and sealed. Then, 5 L of nitrogen was injected. The sample was scraped from the top of the tedler bag using a file and finely crushed. Subsequently, the sample was placed in a temperature controller whose temperature was adjusted to 81 ° C. for 10 minutes while still in the tedler bag. 100 μL of the gas generated in the tedler bag was sampled and GC / MS analysis was performed under the measurement conditions shown below to identify the type of foaming agent component in the phenol resin foam.

The types of halogenated unsaturated hydrocarbons, hydrocarbons, and halogenated saturated hydrocarbons were identified from pre-determined retention times and mass spectra. Further, separately, the detection sensitivity of the generated gas component was measured by each standard gas, and the composition ratio was calculated from the detection area area and the detection sensitivity of each gas component obtained by GC / MS. The molar ratio of each gas component was calculated from the composition ratio and the molar mass of each identified gas component.

(GC / MS measurement conditions)
Gas Chromatography: Agilent Technologies "Agient 7890"
Column: "InertCap 5" manufactured by GL Sciences (inner diameter 0.25 mm, film thickness 5 μm, length 30 m)
Carrier gas: Helium flow rate: 1.1 ml / min Injection port temperature: 150 ° C
Injection method: Split method (1:50)
Sample injection volume: 100 μL
Column temperature: Hold at -60 ° C for 5 minutes, raise to 150 ° C at 50 ° C / min, then hold for 2.8 minutes Mass spectrometry: "Q1000GC type" manufactured by JEOL Ltd.
Ionization method: Electron ionization method (70eV)
Scan range: m / Z = 10 to 500
Voltage: -1300V
Ion source temperature: 230 ° C
Interface temperature: 150 ° C

<Formaldehyde emission rate of phenol resin foam>
The emission rate of formaldehyde in the phenolic resin foam was measured according to JIS A 1901.

<Amount of change in thermal conductivity at 23 ° C before and after leaving in an atmosphere of 110 ° C for 14 days>
First, the initial thermal conductivity of the phenolic resin foam was measured in an environment of 23 ° C. by the following method in accordance with JIS A 1412-: 1999.

The phenolic resin foam was cut into 600 mm squares. The specimen obtained by cutting was placed in an atmosphere of 23 ± 1 ° C. and a humidity of 50 ± 2%, and the change in mass with time was measured every 24 hours. The state of the specimen was adjusted until the mass change rate after 24 hours became 0.2% by mass or less. The condition-adjusted specimen was peeled off from the face material so as not to damage the foam, and then introduced into a thermal conductivity measuring device placed in the same environment.

The thermal conductivity was measured using a single test piece and a symmetrical configuration measuring device (Hideko Seiki Co., Ltd., trade name "HC-074 / 600"). The thermal conductivity in an environment of 23 ° C. was measured under the conditions of 13 ° C. for the low temperature plate and 33 ° C. for the high temperature plate.

Subsequently, the thermal conductivity at 23 ° C. was measured after being left in an atmosphere of 110 ° C. for 14 days by the following operation. The sample for which the measurement of the initial thermal conductivity was completed was placed in a circulating oven whose temperature was controlled to 110 ° C. for 14 days to perform an accelerated test. Then, the specimen was placed in an atmosphere of 23 ± 1 ° C. and a humidity of 50 ± 2%, and the change over time of the mass was measured every 24 hours. The state of the specimen was adjusted until the mass change rate after 24 hours became 0.2% by mass or less. Subsequently, according to the above-mentioned method for measuring thermal conductivity, the thermal conductivity was measured in an atmosphere of 110 ° C. and in an environment of 23 ° C. after being left for 14 days.

The amount of change in thermal conductivity at 23 ° C before and after leaving in an atmosphere of 110 ° C for 14 days is obtained by subtracting the initial thermal conductivity at 23 ° C from the thermal conductivity at 23 ° C after leaving in an atmosphere of 110 ° C for 14 days. Calculated by.

<Viscosity of phenolic resin at 40 ° C>
The viscosity of the phenol resin at 40 ° C is measured using a rotary viscometer (manufactured by Toki Sangyo Co., Ltd., R-100 type, rotor part is 3 ° x R-14) and stabilized at 40 ° C for 3 minutes. It was set as a value.

<Synthesis of phenolic resin>
First, 3500 kg of 52% by mass formaldehyde aqueous solution (52% by mass formalin) and 2510 kg of 99% by mass phenol (including water as impurities) are charged in the reactor, stirred by a propeller rotary stirrer, and the internal liquid of the reactor by a temperature controller. The temperature was adjusted to 40 ° C. Then, the temperature was raised while adding a 50% by mass sodium hydroxide aqueous solution to carry out the reaction. When the Ostwald viscosity reaches 60 cm Stokes (= 60 × 10 ^-6 m ² / s, measured value at 25 ° C), the reaction solution is cooled and urea is added to 570 kg (equivalent to 15 mol% of the amount of formaldehyde charged). Added. Then, the reaction solution was cooled to 30 ° C., and the pH was neutralized to 6.4 with a 50% by mass aqueous solution of p-toluenesulfonic acid monohydrate.

This reaction solution was concentrated at 60 ° C. to obtain phenol resin A. The viscosity of the phenol resin A at 40 ° C. was 20000 mPa · s. Then, the concentration time was appropriately changed to obtain phenol resins B to F having the viscosities (40 ° C.) shown in Table 1.

(Example 1)
A block copolymer of ethylene oxide-propylene oxide (manufactured by BASF, "Pluronic F-127") was mixed at a ratio of 2.0 parts by mass with respect to 100 parts by mass of the phenol resin A. 102 parts by mass of the obtained composition containing the phenol resin A and the surfactant, 11 parts by mass of the foaming agent A shown in Table 2 as a foaming agent, 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as a curing catalyst. The effervescent phenol resin composition obtained by supplying the mixture consisting of 14 parts by mass of the mixture to the mixing head of the mixer whose temperature has been adjusted to 25 ° C. is a bottom material (face material in Table 3) which is moved through a multi-port branch pipe. A) Supplied above. As the mixer used, the one disclosed in Japanese Patent Application Laid-Open No. 10-225993 was used. That is, on the upper side surface of the mixer, there is an introduction port for the composition obtained by adding a surfactant to the phenol resin and the foaming agent, and the curing catalyst is on the side surface near the center of the stirring part where the rotor stirs. A mixer equipped with an inlet was used. After the stirring part, it is connected to a nozzle for discharging the foam. That is, the mixer is composed of a mixing unit (front stage) up to the curing catalyst introduction port, a mixing unit (rear stage) from the curing catalyst introduction port to the stirring end part, and a distribution part from the stirring end part to the nozzle. The distribution unit has a plurality of nozzles at the tip and is designed so that the mixed effervescent phenol resin composition is uniformly distributed.

At the same time, the surface of the foamable phenol resin composition supplied onto the lower surface material (face material A in Table 3) on the side opposite to the side in contact with the lower surface material is covered with the upper surface material (face material A in Table 3). The effervescent phenolic resin composition was sandwiched between two upper and lower facing materials and transported to a premolding process having a length ratio with respect to the heating step as shown in Table 4. Then, it was transferred to a heating process having a slatted double conveyor. In the heating step, the mixture was allowed to stay at 80 ° C. (atmospheric temperature) for 15 minutes and cured, and then cured in an oven at 110 ° C. (atmospheric temperature) for 2 hours (second heating step). A plate-shaped phenol resin foam laminated plate was obtained by applying a pressure of 720 kgf / m ² to the phenol resin foam from above and below via the face material by the slat type double conveyor. A 15% by mass aqueous solution of urea was applied to the upper surface material side of the obtained phenol resin foam laminated plate at 30 g / m ² and dried in a drying oven at 120 ° C. for 2 minutes.

In Examples 2 to 14 and Comparative Examples 1 to 7, the conditions were changed as shown in Tables 1 to 4, and phenol resin foam laminated plates were obtained in the same manner as in Example 1. The obtained results are shown in Table 4.

From Table 4, the phenol resin foams in the phenol resin foam laminates obtained in Examples 1 to 14 are compared with the phenol resin foams in the phenol resin foam laminates obtained in Comparative Examples 1 to 7. Therefore, the adhesive strength of the face material is within an appropriate range, the face material does not peel off during use, and the face material and the phenol resin foam can be separated at the time of recycling. In addition, it is possible to provide a comfortable living environment because it has excellent heat insulation performance for a long period of time and the amount of formaldehyde emitted after construction is small.

According to the present invention, it is possible to provide a phenol resin foam capable of retaining excellent heat insulating performance for a long period of time.

1 Phenol resin foam laminate 2 Face material 3 Phenol resin foam 4 Clamp 5 Metal wire 6 Container 7 Clamp

Claims (13)

A phenol resin foam laminated board having face materials arranged on at least the upper and lower surfaces of a phenol resin foam having a density of 20 kg / m ³ or more and 70 kg / m ³ or less and a closed cell ratio of 80% or more. The foam contains at least one selected from hydrofluoroolefin as a foaming agent, the average boiling point X of the foaming agent is 0 ° C. or higher, and the phenol formaldehyde air permeability of the face material is 51 cm ³ / cm ² . It is sec or more and 500 cm ³ / cm ² · sec or less, the resin exudation area ratio to the face material is 30 % or less, and the adhesion strength of the face material is 200 g or more and 2000 g or less, and the phenol resin foaming. A phenol formaldehyde foam laminated board characterized in that the emission rate of formaldehyde of the body laminated board is 10 μg / m ² · h or less . The hydrofluoroolefin is at least one selected from the group consisting of 1-chloro-3,3,3-trifluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene. The phenolic resin foam laminated board according to claim 1. The phenolic resin foam laminate according to claim 1 or 2, wherein the foaming agent further contains a hydrocarbon. The phenol according to claim 3, wherein the hydrocarbon is at least one selected from the group consisting of propane, normal butane, isobutane, normal pentane, isopentane, cyclopentane, normal hexane, isohexane, and cyclohexane. Resin foam laminated board. The phenolic resin foam laminated board according to any one of claims 1 to 4, wherein the foaming agent further contains a chlorinated hydrocarbon. The phenolic resin foam laminated board according to claim 5, wherein the chlorinated hydrocarbon is isopropyl chloride. One of claims 1 to 6, wherein the face material is at least one selected from the group consisting of synthetic fiber non-woven fabric, glass fiber non-woven fabric, glass fiber mixed paper, kraft paper, and metal film. The phenolic resin foam laminated board according to item 1. The phenolic resin foam laminate according to any one of claims 1 to 7, wherein the face material contains at least one of a formaldehyde scavenger and an inorganic filler. The phenol according to any one of claims 1 to 8 , wherein the amount of change in thermal conductivity at 23 ° C. before and after being left in an atmosphere of 110 ° C. for 14 days is 4.0 mW / mK or less. Resin foam laminated board. Heat insulation characterized by joining at least one selected from a board-like material, a sheet-like material, and a film-like material with the phenolic resin foam laminated plate according to any one of claims 1 to 9 . Composite panel. The method for producing the phenolic resin foam laminated board according to claim 1.
A foaming phenol resin composition containing a phenol resin, a foaming agent containing at least one selected from the group consisting of hydrofluoroolefins, a surfactant, and a curing catalyst is discharged onto a traveling face material. A method for producing a phenol formaldehyde foam laminated plate that is foamed and cured between at least two face materials, the manufacturing method including at least a premolding step and a heating step performed after the premolding step, and the premolding. The length of the step is 5% or more and 50% or less with respect to the length of the heating step, the atmospheric temperature in the premolding step is 30 ° C. or higher and 70 ° C. or lower, and the viscosity of the phenol resin at 40 ° C. is 4000 mPa. -Manufacture of a phenol formaldehyde foam laminated board characterized by having s or more and 100,000 mPa · s or less and having a Frazier air permeability of the face material of 51 cm ³ / cm ² · sec or more and 500 cm ³ / cm ² · sec or less. Method. 11. The method according to claim 11 , wherein the atmospheric temperature in the heating step is 60 ° C. or higher and 99 ° C. or lower, and the pressure applied to the slat plate of the slat type double conveyor in the heating step is 100 kgf / m ² or more and 2000 kgf / m ² or less. Method for manufacturing a phenol resin foam laminated board. The method for producing a phenolic resin foam laminated plate according to claim 11 or 12 , wherein the boiling point average value X of the foaming agent is 0 ° C. or higher and 50 ° C. or lower.

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