JP7010643B2 - Phenol resin foam laminated board - Google Patents

Description

The present invention relates to a phenolic resin foam laminated board.

It is extremely effective to reduce the product density in improving the workability of the phenolic resin foam laminated board, but it is widely known that the compression strength in the thickness direction also decreases as the product density decreases, and the same density. The establishment of technology for producing higher-strength products has been strongly desired.

The method for producing a phenol resin foam laminated board is to use a foamable phenol resin composition (hereinafter, may be simply referred to as "foamable resin composition") composed of a phenol resin, a foaming agent, a curing catalyst, etc., and a rotary wing or the like. A general method is to knead with a dynamic mixer having a resin, discharge the mixture onto a face material traveling at a constant speed, and then form a plate between the conveyors in the curing furnace. For example, as a method using a plurality of discharge nozzles, a method using a tournament type distribution nozzle is used (Patent Document 1).

However, in the method of discharging from a plurality of discharge nozzles, the foamable resin composition swells in the width direction so as to fill the space between the discharge intervals and integrate with each other in the foaming / curing step, and as a result, the orientation of the resin escapes in the width direction. It was difficult to increase the compressive strength in the thickness direction.

As a method of suppressing the expansion of the foamable resin composition in the width direction, a method of attaching dies to the tips of a plurality of distribution channels and arranging the dies in a straight line without leaving a gap and discharging the dies. (Patent Document 2) and a method of spreading the foamable resin composition in the width direction from the beginning and discharging it in one flow path by using an integrated die (Patent Document 3) are known. By using these methods, it is possible to suppress the lateral flow of the foamable resin composition in the width direction in the foaming / curing step, concentrate the orientation of the resin in the thickness direction, and increase the compressive strength in the thickness direction. be.

However, in these methods, the thickness of the foamable resin composition at the time of ejection becomes thin, and it takes a long time for the foamable resin composition to swell and come into contact with the upper surface material. As a result, the curing reaction of the resin proceeded by the time the foamable resin composition came into contact with the upper surface material, and insufficient adhesion between the upper surface material and the resin was likely to occur.
Further, even when the foamable resin composition is continuously and thinly discharged, it is difficult for the resin to be discharged at all on the face material when the discharge amount is uneven, and the phenol resin foam laminated plate without defects is not likely to occur. A technique superior in yield to the above has been desired.

Japanese Unexamined Patent Publication No. 5-15493 Japanese Unexamined Patent Publication No. 2009-263468 International Publication No. 2009/066621

An object of the present invention is to provide a phenol resin foam laminated board having improved compressive strength in the thickness direction.

In the present invention, diligent studies have been carried out in order to solve the above problems, and the adhesiveness between the face material and the phenol resin foam is excellent without impairing various physical properties of the phenol resin foam laminated board, and the compression strength in the thickness direction is obtained. I found that it could be improved.

That is, the present invention provides the following [1] to [4].
[1]
It is a phenol resin foam laminated board in which flexible face materials are arranged on at least the upper and lower surfaces of the phenol resin foam, and the face material peeling strength of the phenol resin foam laminated board is 0.5 N / 25 mm or more, and the phenol. The density of the resin foam is 10 kg / m3 or more and 100 kg / m3 or less, the thickness is 40 mm or more and 300 mm or less, the thermal conductivity is 0.023 W / m · K or less, the void ratio is 5% or less, and the void aspect ratio is 1.55 or more. , Phenol resin foam laminated board.
[2]
The phenolic resin foam laminated board according to [1], wherein the face material is at least one selected from the group consisting of synthetic fiber non-woven fabric, glass fiber paper, glass fiber non-woven fabric, and papers .
[3]
The phenolic resin foam laminate according to [1] or [2] , wherein the phenol resin foam contains at least one of a hydrocarbon and a chlorinated hydrocarbon.
[4]
The phenol resin foam laminate according to any one of [1] to [3], wherein the phenol resin foam contains at least one of a chlorinated hydrofluoroolefin and a non-chlorinated hydrofluoroolefin.
[5]
The phenol resin foam laminate according to any one of [1] to [4] , wherein the phenol resin foam has a closed cell ratio of 80% or more and an average cell diameter of 5 μm or more and 200 μm or less.

According to the present invention, it is possible to provide a phenol resin foam laminated board having excellent adhesiveness between a face material and a phenol resin foam and having improved compressive strength in the thickness direction.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof. 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>
The phenol resin foam laminated board (hereinafter, may be referred to as “foam laminated board”) in the present embodiment is a phenol resin existing in a state where a large number of bubbles are dispersed in the phenol resin formed by the curing reaction. It is a laminate including a foam and flexible surface materials provided on at least the upper and lower surfaces of the phenol resin foam.
The phenolic resin foam laminated board of the present embodiment can have a higher compressive strength in the thickness direction at the same density. Further, the phenolic resin foam laminated board of the present embodiment has excellent heat insulating performance, is also excellent in mechanical strength, and can be suitably used for heat insulating applications.

The face material peeling strength of the phenolic resin foam laminated board of the present embodiment is 0.5 N / 25 mm or more, preferably 1 N / 25 mm or more, more preferably 2 N / 25 mm or more, and more preferably 3 N / 25 mm or more. Is. If the face material peeling strength is 0.5 N / 25 mm or more, the face material will not be peeled off by a slight external force.
The peel strength of the face material of the phenol resin foam laminated plate can be controlled, for example, by changing the thickness of the foamable resin composition after ejection with respect to the thickness of the phenol resin foam.

Generally, in the phenol resin foam laminated board, if the density of the phenol resin foam on the upper surface material side and the phenol resin foam on the lower surface material side are different, the foam laminated board may warp. The warp of the phenolic resin foam laminated board of the present embodiment is preferably 6 mm or less, more preferably 5 mm or less, still more preferably 4 mm or less.
The warp of the foam laminated board can be reduced, for example, by reducing the area ratio of the portion of the lower surface material area that is not in contact with the foamable resin composition immediately after ejection.

<Phenol resin foam>
The density of the phenol resin foam of the phenol resin foam laminate of the present embodiment is 10 kg / m ³ or more and 100 kg / m ³ or less, preferably 15 kg / m ³ or more and 70 kg / m ³ or less, and more preferably 20 kg / m 3 or less. It is m ³ or more and 50 kg / m ³ or less. When the density is 10 kg / m ³ or more, the decrease in mechanical strength such as the compressive strength in the thickness direction is suppressed, the foam is less likely to be damaged during handling, and the surface brittleness is also reduced. Further, when the density is 100 kg / m ³ or less, there is no possibility that the heat transfer of the resin portion increases and the heat insulating performance deteriorates. The density of the phenolic resin foam can be adjusted to a desired value mainly by changing the ratio of the foaming agent and the curing conditions.

The thickness of the phenol resin foam of the phenol resin foam laminated plate of the present embodiment is 40 mm or more and 300 mm or less. When the thickness is 40 mm or more, the alignment allowance of the resin in the thickness direction is sufficiently secured, and a product having high compressive strength in the thickness direction can be produced. On the other hand, when the thickness is 300 mm or less, the internal heat generation in the foaming / curing step can be sufficiently released to the outside of the resin, and a product having a high closed cell ratio can be produced. The thickness is preferably 60 mm or more and 200 mm or less, more preferably 75 mm or more and 200 mm or less, and further preferably 90 mm or more and 200 mm or less.

The thermal conductivity of the phenol resin foam of the phenol resin foam laminated plate of the present embodiment is 0.023 W / m · K or less, preferably 0.021 W / m · K or less, preferably 0.019 W / m · K. The following is more preferable.

The closed cell ratio of the phenol resin foam of the phenol resin foam laminated plate of the present embodiment is preferably 80% or more, more preferably 90% or more. When the closed cell ratio is 80% or more, the replacement of the foaming agent in the phenol resin foam with air is suppressed, and the deterioration of the heat insulating performance can be suppressed.
The closed cell ratio of the phenolic resin foam is, for example, the amount of the foam nucleating agent added, the temperature of the foamable resin composition when the face material and the foamable resin composition are in contact, the average temperature of the surface material surface, and the curing conditions. It can be adjusted to the desired value by making changes such as.

The average bubble diameter of the phenol resin foam of the phenol resin foam laminated plate of the present embodiment is preferably 5 μm or more and 200 μm or less, and more preferably 10 μm or more and 150 μm or less. When the average bubble diameter is 5 μm or more, the density does not increase due to the limit of the thickness of the bubble wall, and as a result, it is possible to prevent the heat transfer of the resin portion from increasing and the heat insulating performance from deteriorating. Further, when the average bubble diameter is 200 μm or less, heat conduction due to radiation is not increased, and deterioration of heat insulating performance can be prevented.
The average cell diameter of the phenol resin foam is, for example, the amount of the foam nucleating agent added, the temperature of the foamable phenol resin composition when the foamable phenol resin composition comes into contact with the face material, and the average temperature of the surface material surface. , Can be adjusted to the desired value by changing the curing conditions and the like.

Generally, the phenolic resin foam has relatively large (usually about 1 mm or more in diameter) spherical or amorphous voids inside. Usually, it is considered that these voids are formed by coalescence of bubbles, non-uniform vaporization of the foaming agent, entrainment of air or the like in the foaming process, or the like.
In the present invention, the void ratio is defined as follows. That is, a cross section perpendicular to the front and back surfaces of the phenolic resin foam laminated plate is cut out, the voids existing in the cross section are measured by the method described later, and the voids having an area of 2 mm ² or more for each void are defined as voids. The value obtained by dividing the total area of all voids on the cross section by the cross-sectional area is defined as the void ratio. Further, the ratio of the length in the thickness direction to the length in the width direction of the void measured by the method described later is defined as the void aspect ratio. The void aspect ratio is an index of the orientation direction of the resin foam.
The void ratio of the phenol resin foam of the phenol resin foam laminated plate of the present embodiment is 5% or less, preferably 3% or less, more preferably 1% or less, still more preferably 0.5% or less. If the void ratio exceeds 5%, the compressive strength in the thickness direction is lowered, and the appearance is not preferable. When a phenolic resin foam laminated board is manufactured using a plurality of discharge nozzles, the void ratio can be reduced by increasing the number of discharge nozzles per unit discharge width, but the difference in performance is substantially eliminated and the difference in performance is eliminated. The void ratio may be 0.02% or more because it causes manufacturing problems such as discharge spots easily occurring, a decrease in the yield of a uniform product, and an increase in handling complexity.
The void aspect ratio of the phenol resin foam of the phenol resin foam laminated board is 1.55 or more, preferably 1.95 or more, more preferably 2.35 or more, still more preferably 2.75 or more, and particularly preferably 2.75 or more. It is 3.15 or more.

The phenol resin foam of the phenol resin foam laminate is produced from, for example, a foaming phenol resin composition containing a phenol resin, a surfactant, a foaming agent, a foam nucleating agent, and an acidic curing agent. The effervescent phenol resin composition may optionally contain components other than the above.

As the phenol resin, a resole-type phenol resin synthesized from an alkali metal hydroxide or an alkaline earth metal hydroxide can be used. The resol type phenol resin is synthesized by heating phenols and aldehydes as raw materials with an alkaline catalyst in a temperature range of 40 to 100 ° C. Further, if necessary, an additive such as urea may be added during or after the synthesis of the resol type phenol resin. When adding urea, it is more preferable to mix urea that has been methylolated with an alkaline catalyst in advance with the resol type phenol resin. Since the resol-type phenol resin after synthesis usually contains an excess amount of water, the amount of water is adjusted to be suitable for foaming at the time of foaming. In addition, the phenolic resin includes aliphatic hydrocarbons or alicyclic hydrocarbons having a high boiling point, or mixtures thereof, diluents for adjusting viscosity such as ethylene glycol and diethylene glycol, and other material recycled powders as necessary. And additives can also be added.

The starting molar ratio of phenols to aldehydes during the synthesis of the phenolic resin is preferably in the range of 1: 1 to 1: 4.5, more preferably in the range of 1: 1.5 to 1: 2.5. ..

Here, the phenols preferably used in the synthesis of the phenolic resin in the present embodiment are phenol itself and other phenols, and examples of other phenols include resorcinol, catechol, o-, and m-. And p-cresol, xylenols, ethylphenols, p-tert butylphenol and the like. Also, dinuclear phenols can be used.
Further, the aldehydes may be any compound that can be an aldehyde source, and it is preferable to use formaldehyde itself, other aldehydes or derivatives thereof as the aldehydes. Examples of other aldehydes include glyoxal, acetaldehyde, chloral, furfural, benzaldehyde and the like.
Urea, dicyandiamide, melamine and the like may be added to the phenol resin as additives. In the present specification, when these additives are added, the "phenolic resin" refers to those after the additives have been added.

The viscosity of the phenol resin at 40 ° C. is 4,000 mPa · s or more, preferably 6,000 mPa · s or more. When the viscosity of the phenol resin at 40 ° C. is 4,000 mPa · s or more, it is possible to suppress the lateral flow of the resin at the time of discharging the foamable resin composition in the foam laminated board manufacturing process, and it is possible to optimize the discharge form.

The surfactant, foaming agent and foaming nucleating agent contained in the effervescent phenol resin composition may be added in advance to the phenol resin or may be added at the same time as the acid curing agent.

As the surfactant, those generally used for producing phenolic resin foams can be used, but among them, nonionic surfactants are effective, for example, alkylene which is a copolymer of ethylene oxide and propylene oxide. Oxides, condensates of alkylene oxides and castor oil, condensation products of alkylene oxides with alkylphenols such as nonylphenol and dodecylphenol, polyoxyethylene alkyl ethers with 14 to 22 carbon atoms in the alkyl ether moiety, and more. Fatty ester such as polyoxyethylene fatty acid ester, silicone compound such as polydimethylsiloxane, polyalcohol and the like are preferable. These surfactants may be used alone or in combination of two or more. The amount used is not particularly limited, but is preferably used in the range of 0.3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the phenol resin.

The constituent components of the foaming agent are not particularly limited, but it is preferable to use hydrocarbons (HCs) and hydrofluorocarbons (HFCs) that do not destroy the ozone layer. In particular, it is more preferable to use a hydrocarbon because of its small global warming potential.
Further, as the foaming agent, it is preferable to use at least one of a hydrocarbon and a chlorinated hydrocarbon from the viewpoint of improving the heat insulating performance of the phenol resin foam laminated board while suppressing the manufacturing cost. Further, from the viewpoint of further improving the heat insulating performance of the phenol resin foam laminated board, it is preferable to contain at least one of a chlorinated hydrofluoroolefin and a non-chlorinated hydrofluoroolefin.

As the hydrocarbon, cyclic or chain-shaped alkanes, alkanes, and alkynes having 3 to 7 carbon atoms are preferable, and specifically, normalbutane, isobutane, cyclobutane, normalpentane, isopentane, cyclopentane, neopentane, normal hexane, and the like. Examples thereof include 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 hydrocarbons may be used alone or in combination of two or more.

Examples of the hydrofluorocarbon include hydrofluoropropene, hydrochlorofluoropropene, hydrobromofluoropropene, hydrofluorobutene, hydrochlorofluorobutene, hydrobromofluorobutene, hydrofluoroethane, hydrochlorofluoroethane, and hydrobromofluoroethane. Can be done. These hydrofluorocarbons may be used alone or in combination of two or more.

Here, the content ratio of the hydrocarbon in the foaming agent is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. The amount of the foaming agent with respect to the phenol resin varies depending on the type of foaming agent, compatibility with the phenol resin, and loss in the foaming / curing process, but is 3.0 parts by mass or more with respect to 100 parts by mass of the phenol resin. It is preferably 5 parts by mass or less, and more preferably 4.0 parts by mass or more and 9.5 parts by mass or less. When the amount of the foaming agent with respect to the phenol resin is 3.0 parts by mass or more, the density does not become too high, which is preferable. Further, when the amount of the foaming agent with respect to the phenol resin is 11.5 parts by mass or less, the density does not become too low, which is preferable.

As the foaming agent component other than hydrofluorocarbon and hydrocarbon, chlorinated hydrocarbons such as chlorinated aliphatic hydrocarbons can also be used. As the chlorinated aliphatic hydrocarbon, a linear or branched hydrocarbon having 2 to 5 carbon atoms is used. The number of bonded chlorine atoms is not limited, but is preferably 1 to 4, and examples thereof include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Of these, propyl chloride and isopropyl chloride, which are chloropropanes, are more preferably used. These chlorinated aliphatic hydrocarbons may be used alone or in combination of two or more.

Further, as the foaming agent, chlorinated hydrofluoroolefin and / or non-chlorinated hydrofluoroolefin can also be used. Specific examples of the chlorinated hydrofluoroolefin include 1-chloro-3,3,3-trifluoropropene.
Further, as the non-chlorinated hydrofluoroolefin, specifically, 1,3,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene, 1,1, Examples thereof include 1,4,4,4-hexafluoro-2-butene.
Here, the content ratio of the chlorinated or non-chlorinated hydrofluoroolefin in the foaming agent is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more from the viewpoint of flame retardancy. It is particularly preferably 70% by mass or more, and particularly preferably 80% by mass or more and 100% by mass or less.

These foaming agents may be used alone or in combination of two or more, and may be arbitrarily selected.

Further, as the foaming nucleating agent, a low boiling point substance having a boiling point lower than that of the foaming agent by 50 ° C. or more, such as nitrogen, helium, argon, and air, may be added to the foaming agent and used. In addition, as a solid foam nucleating agent, aluminum hydroxide powder, aluminum oxide powder, calcium carbonate powder, talc, clay (kaolin), silica stone powder, silica sand, mica, calcium silicate powder, wallastnite, glass powder, glass Inorganic powder such as beads, fly ash, silica fume, gypsum powder, hosand, slag powder, alumina cement, and Portoland cement, and organic powder such as phenol resin foam powder may be added to the foaming agent. .. These may be used alone or in combination of two or more.

The acidic curing agent may be any acidic curing agent capable of curing the phenol resin, and phosphoric acid, aryl sulfonic acid, or an anhydride thereof is preferable. Examples of the aryl sulfonic acid and its anhydride include toluene sulfonic acid, xylene 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. And their anhydrides are mentioned, and these may be used alone or in combination of two or more. In this embodiment, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol and the like may be added as a curing aid. Further, these curing agents may be diluted with a solvent such as ethylene glycol and diethylene glycol.

The amount of the acidic curing agent used varies depending on the type, and when anhydrous phosphoric acid is used, it is preferably 5 parts by mass or more and 30 parts by mass or less, and more preferably 8 parts by mass or more and 25 parts by mass with respect to 100 parts by mass of the phenol resin. Used in less than part. When a mixture of 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol is used, it is preferably 3 parts by mass or more and 30 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the phenol resin. Used below.

<Lumber>
As the face material arranged on at least the upper and lower surfaces of the phenol resin foam, a face material that is flexible and has high gas permeability is preferable. Examples of such face materials include synthetic fiber non-woven fabrics, glass fiber papers, glass fiber non-woven fabrics, and papers. Among such face materials, a face material having an oxygen permeability measured in accordance with ASTM ^D3985-95 of 4.5 cm 3/24 hm ² or more is particularly preferable as a gas permeability. When a synthetic fiber non-woven fabric is used for the face material, the amount of grain is 15 to 80 g / from the viewpoint of the exudation of the thermosetting resin to the face material during foaming and the adhesiveness between the thermosetting resin and the face material. m ² is preferable, and when a glass fiber non-woven fabric is used as the face material, the grain size is preferably 30 to 200 g / m ² .

Further, the phenolic resin foam laminated board is used for various purposes by using it alone or by joining it with an external member. Examples of the external member include one and a combination of a board-shaped material and a sheet-shaped / film-shaped material. 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.

<Manufacturing method of phenol resin foam laminated board>
Next, a method for manufacturing the above-mentioned phenol resin foam laminated board will be described.

The method for producing a phenolic resin foam laminate according to the present embodiment is a mixing step of mixing the above-mentioned foamable phenol resin composition with a mixer, and the mixed foaming phenol resin composition is distributed by a plurality of ejection nozzles. A foam laminate that manufactures a phenol resin foam laminate by expanding the foamable phenol resin composition discharged onto the bottom material and inflating it until it adheres to the top material. It is a continuous manufacturing method including a manufacturing process. The widening referred to here means widening the discharge port in a direction orthogonal to the traveling direction of the face material (width direction of the face material).

Particularly important points in the method for producing the phenolic resin foam laminated plate according to the present embodiment are the contact area ratio of the foamable resin composition with the lower surface material and the foamable resin composition after discharge in the discharge step. The thickness is appropriately controlled by adjusting the shape of the tip of the discharge nozzle and the number of discharge nozzles.
The phenolic resin foam laminate of the present embodiment is formed by optimizing the thickness of the foamable resin composition after ejection and the gap ratio of the face material so that the resin is oriented in the thickness direction and the phenolic resin foam and the upper surface material are formed. It is possible to achieve both adhesiveness and improve the compressive strength in the thickness direction without impairing various physical properties of the phenolic resin foam laminated plate.

The area ratio (referred to as the gap ratio in the present specification) of the area of the lower surface material where the foamable resin composition is not in contact immediately after ejection is 20% or more and less than 60%, preferably 30% or more and 50. Less than%. The smaller the clearance ratio, the more the cross-flow of the foamable resin composition is suppressed, which is preferable. It takes a long time for the sex resin composition to swell and come into contact with the upper surface material. As a result, when the foamable resin composition comes into contact with the upper surface material, the curing reaction of the resin proceeds, the adhesiveness between the upper surface material and the resin deteriorates, and the face material peeling strength on the upper surface material side decreases. Problems arise. Further, when the foamable resin composition is continuously and thinly discharged, when the discharge amount becomes uneven, there are some places where the resin is not discharged on the face material, and the yield of the phenol resin foam laminated board without defects is generated. The problem is that the rate drops. On the other hand, when the gap ratio is 60% or more, the foamable resin composition flows laterally in the width direction, the orientation in the thickness direction is lowered, and the compressive strength in the thickness direction is lowered. Further, the thickness of the joint portion between the foamable resin compositions discharged adjacent to each other becomes thin, and the smoothness of the upper surface material side of the phenol resin foam laminate becomes worse, and the smoothness of the upper surface material side of the phenol resin foam laminate becomes poor. A density difference occurs on the lower surface material side, and warpage occurs.
The "gap ratio" is about 1 after the ruler is placed on the lower surface material so as to be horizontal in the width direction of the face material and the foamable resin composition discharged from each nozzle is discharged to the position of the ruler. Adjust so that it reaches after a minute, read the length of the part where the foamable resin composition is not in contact on the ruler, calculate the total length, and use that value as the foamable resin composition discharged from the nozzle. After dividing by the length between both ends in the width direction of the face material, it was obtained by multiplying by 100.

The thickness of the effervescent resin composition after ejection (hereinafter referred to as a thickness ratio) with respect to the thickness of the phenol resin foam is 18% or more and 45% or less, preferably 25% or more and 40% or less. When the thickness ratio is less than 18%, it takes a long time for the foamable resin composition to come into contact with the upper surface material, the adhesiveness between the upper surface material and the resin is deteriorated, and the peeling strength of the face material on the upper surface material side is lowered. The orientation direction of the phenolic resin foam is mainly determined by the stretching direction of the foamable resin composition in the curing reaction step, and when the thickness ratio exceeds 45%, the stretching allowance is insufficient in the thickness direction of the foamable resin composition. , The orientation in the thickness direction becomes insufficient, and the compression strength in the thickness direction decreases.
The "thickness ratio" is calculated as follows. A ruler is erected on the lower surface material so as to be oriented perpendicular to the face material, and the foamable resin composition ejected from one nozzle reaches the position where the ruler is erected about 1 minute after ejection. The value obtained by measuring the distance from the bottom surface material to the position where the foamable resin composition is farthest in the thickness direction, dividing the value by the thickness of the phenol resin foam, and then multiplying by 100. Is the thickness ratio.

The above-mentioned "gap ratio" and "thickness ratio" can be controlled by the following methods.

When the shape of the tip of the discharge nozzle is made longer in the thickness direction, the shape of the foamable resin composition to be discharged also becomes longer in the thickness direction, the gap ratio is increased, and the thickness ratio is also increased. On the contrary, when the tip shape of the discharge nozzle is made shorter in the thickness direction, the shape of the discharged resin is also shortened in the thickness direction, the gap ratio is lowered, and the thickness ratio is also lowered.
The aspect ratio of the tip of the discharge nozzle was defined as follows. When a rectangle in contact with the outer circumference of the tip opening surface of the discharge nozzle is drawn, the maximum length in the direction perpendicular to the thickness direction of the product to be produced is A, and the maximum length in the horizontal direction in the thickness direction is B, B / The value of A was taken as the aspect ratio of the tip of the discharge nozzle. The shape of the tip opening surface of the discharge nozzle may be rectangular.
The aspect ratio of the tip of the discharge nozzle is 0.225 or more and 0.600 or less, preferably 0.280 or more and 0.450 or less, and more preferably 0.300 or more and 0.400 or less. When there are a plurality of ejection nozzles, the aspect ratios of the ejection nozzle tips of the nuclear nozzles may be the same or different.

When the discharge amount is constant, even if the number of discharge nozzles per unit discharge width is changed, the length in the thickness direction with respect to the length in the width direction of the face material of the foamable resin composition discharged from each nozzle. The ratio of is almost the same. Therefore, if the number of ejection nozzles per unit ejection width is increased, the thickness ratio and the clearance ratio decrease . Further, since the time required for coalescence of the foamable resin compositions discharged adjacent to each other due to expansion is shortened, the amount of air entrainment is suppressed and the void ratio is reduced, which is preferable. In addition to being prone to occur and reducing the yield of uniform products, manufacturing problems such as increased handling complexity occur.
The number of ejection nozzles per unit ejection width is a value obtained by dividing the total number of ejection nozzles by the length between both ends of the foamable resin composition ejected from the nozzles in the width direction.
The number of discharge nozzles per unit discharge width is 14 / m or more and 55 / m or less, preferably 20 / m or more and 45 / m or less.

The discharge spots between the discharge nozzles were defined as follows.
Two hours after the start of ejection of the effervescent phenolic resin composition, the ejection speed of the upper and lower surface materials is temporarily increased, and n strip-shaped effervescent resin compositions ejected onto the traveling lower surface material (hereinafter referred to as “)”. The bead weights Wn were measured so that the "beads") did not come into contact with each other. Here, the average value of Wn was set to Wave, the ratio Qn of the discharge amount in each bead was calculated from the following formula (1), and the difference Q between the maximum value Qmax and the minimum value Qmin of Qn was defined as the discharge spot. (Equation (2)).
Qn = (Wn-Wave) / Wave ... (1)
Q = Qmax-Qmin ... (2)
The discharge spot is preferably 1.00 or less, more preferably 0.60 or less, still more preferably 0.20 or less from the viewpoint of uniform product yield.

The phenolic resin foam laminated board of the present embodiment can be suitably used, for example, as a heat insulating material for buildings.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Synthesis of phenolic resin>
Charge the reactor with 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), stir with a propeller rotary stirrer, and adjust the temperature of the internal liquid of the reactor with 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 centistokes (60 × 10 ^-6 m ² / s, measured value at 25 ° C), the reaction solution is cooled and 570 kg of urea (equivalent to 15 mol% of the amount of formaldehyde charged) is added. did. Then, the reaction solution was cooled to 30 ° C., and the pH was neutralized to 6.3 with a 50% by mass aqueous solution of p-toluenesulfonic acid monohydrate.

When this reaction solution was dehydrated at 60 ° C. and the viscosity and water content were measured by the following methods, the viscosity at 40 ° C. was 6,100 mPa · s. This is referred to as phenol resin AU.

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

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

(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 AU. This is referred to as phenol resin A-U1.

5.6 parts by mass of a mixture of 20% by mass of isopentane and 80% by mass of isopropyl chloride as a foaming agent and 0.3% by mass of nitrogen as a foaming nucleating agent with respect to 1: 100 parts by mass of this phenol resin A-U. %, And 13 parts by mass of a mixture of 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol was added as an acidic curing agent to supply an effervescent phenolic resin composition to the mixing head of the mixer for multiport. It was discharged at a flow rate of 40 kg / hr so that the total width of the foamable resin discharge portion was 1000 mm on the moving lower surface material through the pipe. As the mixer (mixer), the one disclosed in Japanese Patent Application Laid-Open No. 10-225993 was used. That is, there is an introduction port for the phenol resin A-U1 and a foaming agent containing a foaming nucleating agent on the upper side surface of the mixer, and an introduction port for the acidic curing agent is provided on the side surface near the center of the stirring portion where the rotor stirs. I used the equipped mixer. After the stirring part, it is connected to a nozzle for discharging the foam. That is, the mixer is composed of a mixing section (front stage) up to the acid curing agent introduction port, a mixing section (second stage) from the acid curing agent introduction port to the stirring end section, and a distribution section from the stirring end section to the nozzle. There is. The distribution unit has 32 nozzles at the tip and is designed so that the mixed effervescent phenolic resin composition is uniformly distributed. The aspect ratio of the tip of each discharge nozzle was 0.333.

As the face material, a polyester non-woven fabric (“Spanbond E05030” manufactured by Asahi Kasei Fibers Co., Ltd., basis weight 30 g / m ² , thickness 0.15 mm) was used. While foaming the foamable resin composition that came out of the mixer, it was sent to a slat type double conveyor in an atmosphere of 78 ° C so as to be sandwiched between face materials, and cured so that the thickness of the foam became 100 mm with a residence time of 20 minutes. After that, it was cured in an oven at 110 ° C. for 3 hours to obtain a phenol resin foam laminated board. In the slat type double conveyor, the slat type double conveyor was formed into a plate shape by applying appropriate pressure from above and below through the face material.

Then, the thickness, density, closed cell ratio, average cell diameter, compression strength in the thickness direction, thermal conductivity, void ratio, void aspect ratio, and phenol resin of the obtained phenol resin foam laminate. The warpage of the foam laminate and the peeling strength of the face material were measured by the following methods.

<Thickness>
Prepare 10 pieces of 50 mm square phenol resin foam laminated board from which the face material has been removed, mark the center of the front and back of each, measure the thickness with a caliper, and use the average value of the 10 pieces as phenol. The thickness of the resin foam was used.

<Density>
A 20 cm square phenol resin foam laminated board was used as a sample, and after removing the face material from this sample, the mass and apparent volume of the phenol resin foam were measured and determined according to JIS K7222.

<Close cell ratio>
Measured according to ASTM-D-2856. Specifically, after removing the face material from the phenolic resin foam laminate, a cylindrical sample with a diameter of 35 mm to 36 mm is hollowed out with a cork borer, cut to a height of 30 mm to 40 mm, and then an air comparison hydrometer. The sample volume was measured by the standard usage method (manufactured by Tokyo Science Co., Ltd., type 1,000). The value obtained by subtracting the volume of the wall (part other than bubbles and voids) calculated from the sample mass and the density of the phenol resin from the sample volume divided by the apparent volume calculated from the outer dimensions of the sample is divided by the phenol resin. The closed cell ratio of the foam was used. Here, the density of the phenol resin was set to 1.3 kg / L.

<Average bubble diameter>
The average bubble diameter was measured by the following method with reference to the method described in JIS K6402.
A 50-fold magnified photograph of the cut surface of the test piece obtained by cutting the center of the phenolic resin foam laminated plate in the thickness direction parallel to the front and back surfaces was taken, and a 9 cm avoiding voids was taken on the obtained photograph. Draw four straight lines of the length (corresponding to 1,800 μm in the actual foam cross section), calculate the number of cells measured according to the number of bubbles crossed by each straight line, and use the average value of them. The value obtained by dividing 1800 μm was taken as the average bubble diameter.

<Compressive strength in the thickness direction>
After removing the face material from the obtained phenol resin foam laminate, the compressive strength of the phenol resin foam in the thickness direction is determined by JIS K7220 (the compressive strength of the rigid foam plastic and the deformation rate corresponding to the compressive strength; It was measured according to the compressive stress at the time of 5% deformation).

<Thermal conductivity>
Of the 200 mm square foam laminated board, slices are cut in the thickness direction along one of the main surfaces thereof, and the thickness of 50 mm at the center of the thickness is extracted as a sample at a low temperature plate of 13 ° C. and a high temperature plate of 33 ° C. The measurement was performed according to the flat plate heat flow meter method of JIS A1412. For the phenol resin foam having a thickness of less than 50 mm, the face material was peeled off and used for the measurement as it was without slicing in the thickness direction.

<Warp>
After carefully peeling off the upper and lower surface materials of the phenol resin foam laminate cut out to a size of 1000 mm × 1000 mm to form a phenol resin foam, a thread is stretched between one diagonal apex, and the phenol resin foam is separated from the thread. Read and record the maximum distance when a vertical line is drawn on the main surface. Furthermore, a thread is stretched between the other diagonal vertices and measured and recorded in the same manner. The same measurement was performed by turning it upside down, and the largest value among these four measured values was defined as warpage. If the thread does not become a straight line when the thread is stretched between the diagonal vertices, the warp is not calculated. The thread is not straight).

<Void ratio and void aspect ratio>
Five 150 mm square foam laminates are prepared, and the "void ratio" and "void aspect ratio" are evaluated for four surfaces (thickness x 150 mm side surfaces) other than the main surface of each foam laminate by the following method. did.
Make a color copy of each evaluation surface, fill the voids of 2 mm ² or more with a black ballpoint pen, etc., and then use analysis software (WinRooF2015, manufactured by Mitani Corporation) to fill the scanned image with the total of all voids on each surface. The value obtained by dividing the area by the total area of each surface was calculated and used as the "void ratio". In addition, the aspect ratios of all the voids on each surface were calculated, and the average value was defined as the "void aspect ratio". The aspect ratio of the void is B / A when a rectangle consisting of a side having a length A perpendicular to the thickness direction and a side having a length B horizontal to the thickness direction is drawn so as to be in contact with the outer circumference of each void. Defined as the value of.
The same operation was performed on a total of 20 evaluation surfaces, and their average values were defined as the void ratio and the void aspect ratio.
If it was difficult to confirm a void of 2 mm ² or more, an enlarged copy was made as appropriate, and evaluation was performed by converting the magnification.
If the total number of voids evaluated is less than 10 even after performing the above operation, a cross section perpendicular to the front and back surfaces of the 150 mm square foam laminate is further cut out and the cross section other than the main surface is evaluated. This was carried out until the total number of evaluated voids was 10 or more.

<Face material peel strength>
The obtained foam laminated board was cut out in parallel in the thickness direction so as to have a width of 25 mm and a length of 150 mm, and a 90-degree peeling test of the face material was carried out at a speed of 200 mm / min with a peeling length of 85 mm, and the maximum value thereof. Was measured. This operation was performed on both the front and back surface materials, and the smaller value was taken as the face material peel strength.

(Example 2)
A phenolic resin foam laminate having a foam thickness of 40 mm was obtained in the same manner as in Example 1 except that the flow rate of the foamable resin composition was 16 kg / hr and the mixture was cured in an oven at 110 ° C. for 1 hour. ..

(Example 3)
A phenolic resin foam laminate having a foam thickness of 75 mm was obtained in the same manner as in Example 1 except that the flow rate of the foamable resin composition was 30 kg / hr and the mixture was cured in an oven at 110 ° C. for 2 hours. ..

(Example 4)
A phenolic resin foam laminate having a foam thickness of 160 mm was obtained in the same manner as in Example 1 except that the flow rate of the foamable resin composition was 64 kg / hr and the mixture was cured in an oven at 110 ° C. for 5 hours. ..

(Example 5)
A phenolic resin foam laminate having a foam thickness of 200 mm was obtained in the same manner as in Example 1 except that the flow rate of the foamable resin composition was 80 kg / hr and the mixture was cured in an oven at 110 ° C. for 6 hours. ..

(Example 6)
A phenolic resin foam laminated plate having a foam thickness of 100 mm was obtained in the same manner as in Example 1 except that the number of tip nozzles of the distribution portion of the foamable resin composition was 16.

(Example 7)
A phenolic resin foam laminated plate having a foam thickness of 100 mm was obtained in the same manner as in Example 1 except that the number of tip nozzles of the distribution portion of the foamable resin composition was 48.

(Example 8)
A phenolic resin foam laminated plate having a foam thickness of 100 mm was obtained in the same manner as in Example 1 except that the tip aspect ratio of each discharge port of the distribution portion of the foamable resin composition was set to 0.250. ..

(Example 9)
A phenolic resin foam laminated plate having a foam thickness of 100 mm was obtained in the same manner as in Example 1 except that the tip aspect ratio of each discharge port of the distribution portion of the foamable resin composition was 0.500. ..

(Example 10)
Foaming in the same manner as in Example 1 except that a glass fiber non-woven fabric (trade name "Dura Glass Type DH70 (grain size 70 g / m ² , thickness 0.67 mm)", manufactured by Jones Manville Co., Ltd.) was used as the face material. A phenolic resin foam laminated board having a body thickness of 100 mm was obtained.

(Example 11)
Except for adding 6.6 parts by mass of a mixture of 25% by mass of cyclopentane and 75% by mass of 1-chloro-3,3,3-trifluoropropene as a foaming agent to 1: 100 parts by mass of phenol resin A-U. In the same manner as in Example 1, a phenol resin foam laminated board having a foam thickness of 100 mm was obtained.

(Example 12)
Except for adding 6.8 parts by mass of a mixture of 40% by mass of isopropyl chloride and 60% by mass of 1-chloro-3,3,3-trifluoropropene as a foaming agent to 1: 100 parts by mass of the phenol resin A-U. In the same manner as in Example 1, a phenol resin foam laminated board having a foam thickness of 100 mm was obtained.

(Example 13)
In the same manner as in Example 1, the foam was prepared in the same manner as in Example 1 except that 5.4 parts by mass of a mixture of 70% by mass of cyclopentane and 30% by mass of isobutane was added as a foaming agent to 1: 100 parts by mass of the phenol resin A-U. A phenolic resin foam laminated plate having a thickness of 100 mm was obtained.

(Comparative Example 1)
The effervescent phenolic resin composition is the same as that of Example 1 except that the effervescent phenolic resin composition is poured into a die of the same structural type as that disclosed in Example 1 of International Publication No. 2009-066621 through a multi-port branch pipe and discharged. Then, a phenol resin foam laminated board having a foam thickness of 100 mm was obtained.

(Comparative Example 2)
The number of flow paths in the distribution section of the foamable resin composition is 32, and the shape of the one disclosed in Example 1 of JP-A-2009-263468 is partially changed at each tip (opening interval of die tip is 3.5 mm, A phenolic resin foam laminated plate having a foam thickness of 100 mm was obtained in the same manner as in Example 1 except that a die produced with a die width of 28 mm) was attached and discharged.
In this case, the foamable resin composition discharged from the 32 flow paths was integrated with the adjacent resins immediately after the discharge.

(Comparative Example 3)
A phenolic resin foam laminated plate having a foam thickness of 100 mm was obtained in the same manner as in Example 1 except that the number of tip nozzles of the distribution portion of the foamable resin composition was 12.

(Comparative Example 4)
A phenolic resin foam laminated plate having a foam thickness of 100 mm was obtained in the same manner as in Example 1 except that the number of tip nozzles of the distribution portion of the foamable resin composition was 60.

(Comparative Example 5)
A phenolic resin foam laminated plate having a foam thickness of 100 mm was obtained in the same manner as in Example 1 except that the tip aspect ratio of each discharge port of the distribution portion of the foamable resin composition was set to 0.200. ..

(Comparative Example 6)
A phenolic resin foam laminated plate having a foam thickness of 100 mm was obtained in the same manner as in Example 1 except that the tip aspect ratio of each discharge port of the distribution portion of the foamable resin composition was 0.667. ..

Tables 1 and 2 show the production conditions in the above Examples and Comparative Examples, and the physical properties of the obtained foam laminated board.

The phenolic resin foam laminated board of the present invention can be suitably used as a heat insulating material for construction.

Claims (5)

It is a phenol resin foam laminated board in which flexible face materials are arranged on at least the upper and lower surfaces of the phenol resin foam, and the face material peeling strength of the phenol resin foam laminated board is 0.5 N / 25 mm or more, and the phenol. The density of the resin foam is 10 kg / m ³ or more and 100 kg / m ³ or less, the thickness is 40 mm or more and 300 mm or less, the thermal conductivity is 0.023 W / m · K or less, the void ratio is 5% or less, and the void aspect ratio is 1. Phenol resin foam laminated board which is 55 or more. The phenolic resin foam laminated board according to claim 1, wherein the face material is at least one selected from the group consisting of synthetic fiber non-woven fabric, glass fiber paper, glass fiber non-woven fabric, and papers. The phenol resin foam laminate according to claim 1 or 2 , wherein the phenol resin foam contains at least one of a hydrocarbon and a chlorinated hydrocarbon. The phenol resin foam laminate according to any one of claims 1 to 3, wherein the phenol resin foam contains at least one of a chlorinated hydrofluoroolefin and a non-chlorinated hydrofluoroolefin. The phenolic resin foam laminate according to any one of claims 1 to 4 , wherein the phenolic resin foam has a closed cell ratio of 80% or more and an average cell diameter of 5 μm or more and 200 μm or less.