JP2018171885A - Phenolic resin foam laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenol resin foam laminated plate which prevents a surface material and a phenol resin foam from being peeled and has improved compressive strength in a thickness direction.SOLUTION: A phenol resin foam laminated plate has flexible surface materials arranged on at least upper and lower surfaces of a phenol resin foam, where a surface material peeling strength of the phenol resin foam laminated plate is 0.5 N/25 mm or more, and the phenol resin foam has a density of 10 kg/mor more and 100 kg/mor less, a thickness of 40 mm or more and 300 mm or less, thermal conductivity of 0.023 W/m K or less, a void ratio of 5% or less, and a void aspect ratio of 1.55 or more.SELECTED DRAWING: None

Description

  The present invention relates to a phenolic resin foam laminate.

  In order to improve the workability of phenolic resin foam laminates, it is extremely effective to reduce the product density, but it is widely known that the compressive strength in the thickness direction also decreases as the product density decreases. Therefore, establishment of technology for producing higher strength products has been strongly desired.

  A method for producing a phenolic resin laminate includes a foamable phenol resin composition (hereinafter sometimes simply referred to as “foamable resin composition”) comprising a phenol resin, a foaming agent, a curing catalyst, etc. A method is generally used in which the mixture is kneaded with a dynamic mixer and discharged onto a face material running at a constant speed and then formed into a plate shape between conveyors in a 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, in the foaming / curing process, the foamable resin composition swells in the width direction so as to fill and integrate the spaces between the discharge intervals, so that the orientation of the resin escapes in the width direction. Therefore, 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 a die to each end of a plurality of distribution channels, and discharging each of the dies in a straight line without a gap (Patent Document 2) and a method (Patent Document 3) in which a foamable resin composition is spread in the width direction from the beginning in one flow path using an integrated die (Patent Document 3) are known. By using these methods, the transverse flow of the foamable resin composition in the foaming / curing process in the width direction is suppressed, the orientation of the resin is concentrated in the thickness direction, and the compressive strength in the thickness direction can be increased. is there.

However, in these methods, it takes a long time for the foamable resin composition to have a small thickness when discharged, and for the foamable resin composition to swell and come into contact with the upper surface material. As a result, the resin curing reaction progressed before the foamable resin composition contacted the top surface material, and the adhesion between the top surface material and the resin was likely to occur.
Also, even when the foamable resin composition is continuously thinly ejected, it is difficult to generate a portion on the face material where no resin is ejected when unevenness occurs in the ejection amount, and a phenol resin foam laminate without defects Therefore, a technique that is superior in terms of the yield has been desired.

JP-A-5-154932 JP 2009-263468 A International Publication No. 2009/066621

  An object of this invention is to provide the phenol resin foam laminated board which improved the compressive strength of the thickness direction.

  In the present invention, in order to solve the above-mentioned problems, intensive studies were conducted, and the adhesive properties between the face material and the phenolic resin foam were excellent, without affecting the physical properties of the phenolic resin foam laminate, and the compressive strength in the thickness direction was improved. I found that it can be improved.

That is, the present invention provides the following [1] to [4].
[1]
A phenolic resin foam laminate in which flexible face materials are arranged on at least upper and lower surfaces of the phenol resin foam, and the phenolic resin foam laminate has a face material peel strength of 0.5 N / 25 mm or more, and the phenol The resin foam has a density of 10 kg / m ³ or more and 100 kg / m ³ or less, a thickness of 40 mm or more and 300 mm or less, a thermal conductivity of 0.023 W / m · K or less, a void ratio of 5% or less, and a void aspect ratio of 1. 55 or more phenolic resin foam laminate.
[2]
The phenol resin foam laminate according to [1], wherein the phenol resin foam contains at least one of a hydrocarbon and a chlorinated hydrocarbon.
[3]
The phenol resin foam laminate according to [1] or [2], wherein the phenol resin foam contains at least one of a chlorinated hydrofluoroolefin and a non-chlorinated hydrofluoroolefin.
[4]
The phenol resin foam laminate according to any one of [1] to [3], wherein the phenol resin foam has a closed cell ratio of 80% or more and an average cell diameter of 5 μm to 200 μm.

  ADVANTAGE OF THE INVENTION According to this invention, the phenol resin foam laminated board which was excellent in the adhesiveness of a face material and a phenol resin foam, and improved the compressive strength of the thickness direction can be provided.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

<Phenolic resin foam laminate>
The phenolic resin foam laminate in this embodiment (hereinafter sometimes referred to as “foam laminate”) is a phenolic resin in which a large number of bubbles are dispersed in a phenolic resin formed by a curing reaction. It is a laminate comprising a foam and flexible face materials provided on at least the upper and lower surfaces of the phenol resin foam.
The phenol resin foam laminate of the present embodiment can have a higher compressive strength in the thickness direction at the same density. Moreover, the phenol resin foam laminated board of this embodiment has the outstanding heat insulation performance, is excellent also in mechanical strength, and can be used suitably for the use for heat insulation.

The face material peel strength of the phenolic resin foam laminate 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. It is. When the face material peel strength is 0.5 N / 25 mm or more, the face material is not peeled off by a slight external force.
In addition, the face material peeling strength of a phenol resin foam laminated board is controllable by changing the thickness of the foamable resin composition after discharge with respect to the thickness of a phenol resin foam, for example.

Generally, when the density of the phenol resin foam on the top material side and the phenol resin foam on the bottom material side of the phenol resin foam laminate is different, the foam laminate may be warped. The warpage of the phenolic resin foam laminate of this embodiment is preferably 6 mm or less, more preferably 5 mm or less, and still more preferably 4 mm or less.
In addition, the curvature of a foam laminated board can be reduced by reducing the area ratio of the part which is not contacting the foamable resin composition immediately after discharge among the lower surface material area, for example.

<Phenolic 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, more preferably 20 kg / m. m ³ or more and 50 kg / m ³ or less. When the density is 10 kg / m ³ or more, a decrease in mechanical strength such as compressive strength in the thickness direction is suppressed, the foam is less likely to be damaged during handling, and 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 insulation performance is deteriorated. The density of the phenol 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 laminate of the present embodiment is 40 mm or more and 300 mm or less. When the thickness is 40 mm or more, a sufficient alignment margin for the resin in the thickness direction is secured, and a product having a 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 process 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 still more preferably 90 mm or more and 200 mm or less.

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

The closed cell ratio of the phenol resin foam of the phenol resin foam laminate of this embodiment is preferably 80% or more, and more preferably 90% or more. When the closed cell ratio is 80% or more, replacement of the foaming agent in the phenol resin foam with air is suppressed, and a decrease in heat insulation performance can be suppressed.
The closed cell ratio of the phenol 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 face material surface, and the curing conditions. It can be adjusted to a desired value by changing the above.

It is preferable that the average cell diameter of the phenol resin foam of the phenol resin foam laminated board of this embodiment is 5 micrometers or more and 200 micrometers or less, More preferably, they are 10 micrometers or more and 150 micrometers or less. When the average cell diameter is 5 μm or more, the density does not increase due to the limit of the thickness of the cell wall, and as a result, it is possible to prevent the heat transfer from the resin part from increasing and the heat insulation performance from decreasing. Further, when the average bubble diameter is 200 μm or less, heat conduction due to radiation is not increased, and deterioration of heat insulation performance can be prevented.
The average cell diameter of the phenol resin foam is, for example, the amount of foam nucleating agent added, the temperature of the foamable phenol resin composition when the foamable phenol resin composition contacts the face material, and the average temperature of the face material surface. It can be adjusted to a desired value by changing the curing conditions.

Generally, a phenol resin foam has a relatively large (usually, a diameter of about 1 mm or more) spherical or irregular void inside thereof. Usually, these voids are considered to be formed by coalescence of bubbles, non-uniform vaporization of the foaming agent, or entrainment of air or the like in the foaming process.
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 laminate is cut out, the voids existing in the cross section are measured by the method described later, and each void has an area of 2 mm ² or more as a void, The value obtained by dividing the total area of all voids on the cross section by the cross-sectional area is taken as the void ratio. Moreover, let the ratio of the length to the thickness direction with respect to the length to the width direction of the void measured by the method mentioned later be a 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 laminate of this embodiment is 5% or less, preferably 3% or less, more preferably 1% or less, and even more preferably 0.5% or less. If the void ratio exceeds 5%, it causes a decrease in compressive strength in the thickness direction and is not preferable in appearance. In addition, when manufacturing a phenolic resin foam laminate using a plurality of discharge nozzles, the void ratio can be reduced by increasing the number of discharge nozzles per unit discharge width, but there is substantially no difference in performance. Since voids are likely to occur and manufacturing problems such as a reduction in the yield of uniform products and an increase in handling complexity occur, the void ratio may be 0.02% or more.
The void aspect ratio of the phenol resin foam of the phenol resin foam laminate is 1.55 or more, preferably 1.95 or more, more preferably 2.35 or more, still more preferably 2.75 or more, particularly preferably. 3.15 or more.

  And the phenol resin foam of a phenol resin foam laminated board is manufactured from the foamable phenol resin composition containing a phenol resin, surfactant, a foaming agent, a foaming nucleus agent, and an acidic hardening | curing agent, for example. The foamable phenol resin composition may optionally contain components other than those described above.

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

  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 phenol resin in this embodiment are phenol itself and other phenols. Examples of other phenols include resorcinol, catechol, o-, m- And p-cresol, xylenols, ethylphenols, p-tertbutylphenol and the like. Dinuclear phenols can also be used.
The aldehyde may be a compound that can serve as an aldehyde source, and as the aldehyde, it is preferable to use formaldehyde itself, other aldehydes or derivatives thereof. Examples of other aldehydes include glyoxal, acetaldehyde, chloral, furfural, benzaldehyde and the like.
Note that urea, dicyandiamide, melamine, or the like may be added to the phenol resin as an additive. In the present specification, when these additives are added, the “phenol resin” refers to the one after the additives are added.

  The viscosity at 40 ° C. of the phenol resin 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, the lateral flow of the resin can be suppressed during the discharge of the foamable resin composition in the foam laminate manufacturing process, and the discharge form can be optimized.

  The surfactant, foaming agent and foaming nucleating agent contained in the foamable phenol resin composition may be added in advance to the phenol resin, or may be added simultaneously with the acidic curing agent.

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

Although it does not specifically limit as a structural component of a foaming agent, It is preferable to use the hydrocarbon (HCs) and hydrofluorocarbon (HFCs) which do not destroy an ozone layer. In particular, since the global warming potential is small, it is more preferable to use hydrocarbons.
Moreover, as a foaming agent, it is preferable to use at least one of a hydrocarbon and a chlorinated hydrocarbon from a viewpoint of improving the heat insulation performance of a phenol resin foam laminated board, suppressing manufacturing cost. Moreover, it is preferable to contain at least one of a chlorinated hydrofluoroolefin and a non-chlorinated hydrofluoroolefin from a viewpoint of improving the heat insulation performance of a phenol resin foam laminated board more.

  The hydrocarbon is preferably a cyclic or chain alkane, alkene or alkyne having 3 to 7 carbon atoms, specifically, normal butane, isobutane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, normal hexane, Examples include isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, and cyclohexane. 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 hydrofluorocarbons include hydrofluoropropene, hydrochlorofluoropropene, hydrobromofluoropropene, hydrofluorobutene, hydrochlorofluorobutene, hydrobromofluorobutene, hydrofluoroethane, hydrochlorofluoroethane, hydrobromofluoroethane, etc. Can do. These hydrofluorocarbons may be used alone or in combination of two or more.

  Here, the hydrocarbon content 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 relative to the phenolic resin varies depending on the type of foaming agent, compatibility with the phenolic resin, and loss in the foaming / curing process, but is 3.0 parts by mass or more to 100 parts by mass of the phenolic 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. It is preferable that the amount of the foaming agent with respect to the phenol resin is 3.0 parts by mass or more because the density does not become too high. Moreover, it is preferable that the amount of the foaming agent with respect to the phenol resin is 11.5 parts by mass or less because the density does not become too low.

  In addition, as blowing agent components other than hydrofluorocarbons and hydrocarbons, chlorinated hydrocarbons such as chlorinated aliphatic hydrocarbons can also be used. As the chlorinated aliphatic hydrocarbon, a linear or branched one 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, isopentyl chloride and the like. 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.

Moreover, a chlorinated hydrofluoroolefin and / or a non-chlorinated hydrofluoroolefin can also be used as a foaming agent. 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, 1,4,4,4-hexafluoro-2-butene and the like.
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, and further preferably 60% by mass or more, from the viewpoint of flame retardancy. Particularly preferably, it is 70% by mass or more, and particularly preferably 80% by mass or more and 100% by mass or less.

  In addition, these foaming agents may be used independently, may be used in combination of 2 or more types, and can be selected arbitrarily.

  Further, as the foam nucleating agent, a low-boiling substance having a boiling point lower by 50 ° C. or more than the foaming agent, such as nitrogen, helium, argon, or air, may be added to the foaming agent. Also, as solid foam nucleating agent, aluminum hydroxide powder, aluminum oxide powder, calcium carbonate powder, talc, sand clay (kaolin), quartzite powder, quartz sand, mica, calcium silicate powder, wollastonite, glass powder, glass Inorganic powders such as beads, fly ash, silica fume, gypsum powder, borax, slag powder, alumina cement, Portland cement, and organic powders 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 an acidic curing agent that can cure the phenol resin, and phosphoric acid, arylsulfonic acid, or an anhydride thereof is preferable. As aryl sulfonic acid and its anhydride, 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, etc. And anhydrides thereof. These may be used alone or in combination of two or more. In this embodiment, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol or the like may be added as a curing aid. In addition, these curing agents may be diluted with a solvent such as ethylene glycol or 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 to 30 parts by mass, more preferably 8 to 25 parts by mass with respect to 100 parts by mass of the phenol resin. Used in parts or less. 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, 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 in:

<Face material>
The face material disposed on at least the upper and lower surfaces of the phenol resin foam is preferably a face material that is flexible and has high gas permeability. Examples of such face materials include synthetic fiber nonwoven fabric, glass fiber paper, glass fiber nonwoven fabric, and papers. Such out of face material, as a gas-permeable surface material oxygen permeability measured according to ASTM D3985-95 is 4.5cm ³ / 24h · m ² or more is particularly preferable. In the case of using a synthetic fiber nonwoven fabric for the face material from the viewpoint of the seepage of the thermosetting resin during foaming to the face material and the adhesiveness between the thermosetting resin and the face material, the basis weight is 15 to 80 g / m ² is preferable, and when a glass fiber nonwoven fabric is used for the face material, the basis weight is preferably 30 to 200 g / m ² .

  Moreover, the phenol resin foam laminate is used for various purposes by using it alone and joining it with an external member. Examples of the external member include a board-like material and a sheet-like / film-like material 1 and combinations thereof. Board-like materials include ordinary plywood, structural plywood, particle board, OSB, and other wood-based boards, and wood wool cement board, wood chip cement board, gypsum board, flexible board, medium density fiber board, calcium silicate board A magnesium silicate plate, a volcanic glassy multilayer plate and the like are preferable. Sheet and film materials include polyester nonwoven fabric, polypropylene nonwoven fabric, inorganic filled glass fiber nonwoven fabric, glass fiber nonwoven fabric, paper, calcium carbonate paper, polyethylene processed paper, polyethylene film, plastic moisture-proof film, asphalt waterproof paper, aluminum A foil (with or without holes) is preferable.

<Method for producing phenolic resin foam laminate>
Next, the manufacturing method of the phenol resin foam laminated board mentioned above is demonstrated.

  The manufacturing method of the phenol resin foam laminate according to the present embodiment includes a mixing step of mixing the above-described foamable phenol resin composition with a mixer, and distributing the mixed foamable phenol resin composition by a plurality of discharge nozzles. And a foam laminate for producing a phenolic resin foam laminate by inflating the foamable phenolic resin composition discharged on the bottom surface material until it adheres to the top surface material. It is a continuous manufacturing system provided with a manufacturing process. In addition, the widening said here refers to expanding an ejection port with respect to the direction (width direction of a face material) orthogonal to the running direction of a face material.

In the manufacturing method of the phenolic resin foam laminate according to the present embodiment, particularly important points are the area ratio of contact with the lower surface material of the foamable resin composition and the foamable resin composition after discharge in the discharge process. The thickness is appropriately controlled by adjusting the shape of the discharge nozzle tip and the number of discharge nozzles.
The phenol resin foam laminate of the present embodiment is made by optimizing the thickness and the gap ratio of the face material after discharging the foamable resin composition, and the orientation in the thickness direction of the resin and the phenol resin foam and the top surface material. The adhesive strength can be compatible, and the compressive strength in the thickness direction can be improved without impairing the physical properties of the phenol resin foam laminate.

Of the lower surface material area, the area ratio (referred to as the gap ratio in the present specification) of the portion where the foamable resin composition immediately after discharge is not in contact is 20% or more and less than 60%, preferably 30% or more and 50 %. The smaller the clearance ratio, the more preferably, the lateral flow of the foamable resin composition is suppressed, but when it is less than 20%, the foamed resin composition thickness at the time of discharge becomes too thin, and the foam discharged on the lower surface material. It takes a long time for the conductive 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, and the adhesiveness between the upper surface material and the resin is deteriorated and the surface material peeling strength on the upper surface material side is reduced. Problems arise. In addition, when the foamable resin composition is continuously discharged thinly, a spot where no resin is discharged on the face material occurs when the discharge amount is uneven, and the phenolic resin foam laminate without defects is collected. The problem is that the rate drops. On the other hand, when the clearance 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. Moreover, the thickness of the joint portion between the foamed resin compositions discharged adjacently becomes thin, the smoothness of the top surface side of the phenol resin foam laminate is deteriorated, and the top surface side of the phenol resin foam A difference in density occurs on the lower surface material side, and warpage occurs.
The “clearance 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 ruler position. The foamable resin composition was adjusted so as to reach after a minute, and the total length was calculated by reading the length of the part where the foamable resin composition was not in contact with the ruler, and that value was 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 foamable resin composition after discharge relative to the thickness of the phenol resin foam (hereinafter referred to as the thickness ratio) 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 becomes worse, and the surface material peeling strength on the upper surface material side decreases. The orientation direction of the phenol 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%, there is not enough elongation margin in the thickness direction of the foamable resin composition. Further, the orientation in the thickness direction becomes insufficient, and the compressive strength in the thickness direction decreases.
The “thickness ratio” is calculated as follows. A ruler is placed on the lower surface material so that it is oriented perpendicular to the face material, and the foamable resin composition discharged from one nozzle reaches the position where the ruler stands about 1 minute after discharge. The value obtained by multiplying the value by dividing the value by the thickness of the phenolic resin foam, and measuring the distance from the bottom surface material to the position farthest in the thickness direction. Is the thickness ratio.

  The above-mentioned “clearance ratio” and “thickness ratio” can be controlled by the following method.

When the tip shape 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 increases, and the thickness ratio also increases. 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 at the tip of the discharge nozzle was defined as follows. 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 direction horizontal to the thickness direction when drawing a rectangle in contact with the outer periphery of the tip opening surface of the discharge nozzle. The value A was defined as the aspect ratio of the discharge nozzle tip. The tip opening surface of the discharge nozzle may be rectangular.
The aspect ratio of the discharge nozzle tip 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 discharge nozzles, the aspect ratio of the discharge nozzle tip of the core nozzle 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 is almost unchanged. For this reason, when the number of discharge nozzles per unit discharge width is increased, the thickness ratio decreases and the clearance ratio increases. Also, since the time until the coalescence of the expandable resin compositions discharged adjacent to each other is reduced, the amount of entrainment of air is suppressed and the void ratio is reduced, which is preferable. This is likely to occur, resulting in a reduction in the yield of a uniform product, and production problems such as increased handling complexity.
The number of discharge nozzles per unit discharge width refers to a value obtained by dividing the total number of discharge nozzles by the length between both ends in the width direction of the face material of the foamable resin composition discharged from the nozzles.
The number of discharge nozzles per unit discharge width is from 14 / m to 55 / m, and preferably from 20 / m to 45 / m.

The discharge spots between the discharge nozzles were defined as follows.
At the time when the discharge of the foamable phenol resin composition has started for 2 hours, the discharge speed of the upper and lower surface materials is temporarily increased, and the n strip-shaped foamable resin compositions (hereinafter referred to as “n”) discharged onto the traveling lower surface material Each bead weight Wn was measured so that the beads were not in contact with each other. Here, the average value of Wn is set to Wave, the ratio Qn of the discharge amount in each bead is calculated from the following formula (1), and the difference Q between the maximum value Qmax and the minimum value Qmin in Qn is set as discharge spots. (Formula (2)).
Qn = (Wn−Wave) / Wave (1)
Q = Qmax−Qmin (2)
From the viewpoint of uniform product yield, the discharge spots are preferably 1.00 or less, more preferably 0.60 or less, and still more preferably 0.20 or less.

  The phenol resin foam laminate of this embodiment can be suitably used for, for example, a heat insulating material of a building.

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

<Synthesis of phenolic resin>
A reactor is charged with 3500 kg of a 52 wt% formaldehyde aqueous solution (52 wt% formalin) and 2510 kg of 99 wt% phenol (including water as an impurity), stirred with a propeller rotating stirrer, and the temperature inside the reactor is adjusted with a temperature controller. Adjusted to 40 ° C. Next, the reaction was carried out by raising the temperature while adding a 50 mass% aqueous sodium hydroxide solution. When the Ostwald viscosity reaches 60 centistokes (60 × 10 ⁻⁶ m ² / s, measured value at 25 ° C.), the reaction solution is cooled and 570 kg of urea (corresponding to 15 mol% of the charged formaldehyde) is added. did. Thereafter, the reaction solution was cooled to 30 ° C., and the pH was neutralized to 6.3 with a 50 mass% aqueous solution of paratoluenesulfonic acid monohydrate.

  The reaction solution was dehydrated at 60 ° C. and the viscosity and water content were measured by the following method. The viscosity at 40 ° C. was 6,100 mPa · s. This is designated as phenol resin A-U.

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

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

Example 1
Phenol resin AU: 100 parts by mass of ethylene oxide / propylene oxide block copolymer (manufactured by BASF, Pluronic F-127) as a surfactant was mixed at a ratio of 2.0 parts by mass. This is designated as phenol resin A-U1.

  The phenol resin A-U1: 100 parts by mass, 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 mass of nitrogen as a foam nucleating agent with respect to the foaming agent. %, And a foamable phenolic resin composition obtained by adding 13 parts by mass of a mixture of 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as an acidic curing agent is supplied to the mixing head of the mixer. Through the piping, it was discharged at a flow rate of 40 kg / hr on the moving lower surface material so that the entire width of the foamable resin discharge portion was 1000 mm. In addition, the mixer (mixer) used what was disclosed by Unexamined-Japanese-Patent No. 10-225993. That is, there is an inlet for the foaming agent containing the phenol resin A-U1 and the foaming nucleating agent on the upper side surface of the mixer, and an inlet for the acidic curing agent is provided on the side surface near the center of the agitating portion where the rotor stirs. The equipped mixer was used. The part after the stirring part is connected to a nozzle for discharging the foam. That is, the mixer is composed of the mixing part (front stage) up to the acidic curing agent introduction port, the mixing part (rear stage) from the acidic curing agent introduction port to the stirring end part, and the dispensing end as the stirring end part to the nozzle. Yes. The distribution unit has 32 nozzles at the tip, and is designed to uniformly distribute the mixed foamable phenolic resin composition. The aspect ratio of each discharge nozzle tip was set to 0.333.

As the face material, a polyester nonwoven fabric (“Spunbond E05030” manufactured by Asahi Kasei Fibers Co., Ltd., basis weight 30 g / m ² , thickness 0.15 mm) was used. The foamable resin composition coming out of the mixer is foamed and 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 becomes 100 mm in a residence time of 20 minutes. And then cured in an oven at 110 ° C. for 3 hours to obtain a phenolic resin foam laminate. In addition, in the slat type double conveyor, it was formed into a plate shape by applying moderate pressure from above and below through the face material.

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

<Thickness>
Prepare 10 pieces with the face material removed from the 50 mm square phenolic resin laminate, mark the center of each front and back, measure the thickness with calipers, and calculate the average of the 10 thicknesses as phenol. It was set as the thickness of the resin foam.

<Density>
A 20 cm square phenol resin foam laminate was used as a sample, and after removing the face material from this sample, the mass and the apparent volume of the phenol resin foam were measured in accordance with JIS K7222.

<Closed cell ratio>
Measured according to ASTM-D-2856. Specifically, after removing the face material from the phenolic resin foam laminate, a cylindrical sample having a diameter of 35 mm to 36 mm is pierced with a cork borer and trimmed to a height of 30 mm to 40 mm, and then an air comparison specific gravity meter The sample volume was measured by the standard usage method (manufactured by Tokyo Science Co., Ltd., type 1,000). The value obtained by subtracting the volume of the wall (parts other than bubbles and voids) calculated from the sample mass and the density of the phenol resin from the sample volume, and dividing the value by the apparent volume calculated from the external dimensions of the sample is the phenol resin. The closed cell ratio of the foam was used. Here, the density of the phenol resin was 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.
Take a photograph of the cut surface of the test piece obtained by cutting almost the center in the thickness direction of the phenolic resin laminate in parallel to the front and back surfaces, and enlarge the cut surface by 50 times. 4 lines (corresponding to 1,800 μm in the actual foam cross section) are drawn, and the number of cells measured according to the number of bubbles crossed by each straight line is obtained by each straight line, and the average value thereof is obtained. A value obtained by dividing 1800 μm was defined as an average cell diameter.

<Compressive strength in the thickness direction>
After removing the face material from the obtained phenolic resin foam laminate, the compressive strength in the thickness direction of the phenolic resin foam was changed to JIS K7220 (deformation rate corresponding to the compressive strength and compressive strength of the hard foam plastic; (Compressive stress at 5% deformation)).

<Thermal conductivity>
Of the 200 mm square foam laminate, sliced in the thickness direction along one of its main surfaces, and extracted a 50 mm thickness portion at the center of the thickness as a sample, at a low temperature plate of 13 ° C. and a high temperature plate of 33 ° C. It measured according to the plate heat flow meter method of JIS A1412. In addition, about the thing whose thickness of a phenol resin foam is less than 50 mm, without slicing in the thickness direction, the face material was peeled and it used for the measurement as it was.

<Warpage>
The top and bottom materials of the phenolic resin foam laminate cut out to a size of 1000 mm × 1000 mm are carefully peeled to form a phenolic resin foam, and then a yarn is stretched between the diagonal vertices. Read and record the maximum distance when a perpendicular is made to the main surface. Further, a yarn is stretched between the other diagonal vertices and measured and recorded in the same manner. The same measurement was performed by turning upside down, and the largest value among these four measurement values was defined as warpage. In addition, when the yarn does not become a straight line when the yarn is stretched between the diagonal vertices, the warp is not calculated (if the phenolic resin foam laminate is measured in a convex state, the distance between the diagonal lines is not calculated. Thread is not straight).

<Void ratio and void aspect ratio>
Prepare five 150mm square foam laminates and evaluate the "void ratio" and "void aspect ratio" for the four sides (thickness x 150mm side surfaces) other than the main surface of each foam laminate by the following methods. did.
After taking a color copy of each evaluation surface and painting a space of 2 mm ² or more with a black ballpoint pen, etc., the scanned image is analyzed using the analysis software (WinRooF2015, manufactured by Mitani Corp.) and the total of all voids on each surface A value obtained by dividing the area by the total area of each surface was calculated and used as the “void ratio”. Further, the aspect ratio of all voids on each surface was calculated, and the average value was defined as “void aspect ratio”. It should be noted that the aspect ratio of the void is B / A when a rectangle composed 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 in contact with the outer periphery of each void. Defined as the value of.
The same operation was performed on a total of 20 evaluation surfaces, and the average values thereof were defined as the void ratio and void aspect ratio.
In addition, when it was difficult to confirm the space | gap of 2 mm < ² > or more, the enlarged copy was made suitably and it evaluated by converting into magnification.
In addition, when the total number of voids evaluated even when the above operation is performed is less than 10, the cross section perpendicular to the front and back surfaces of the 150 mm square foam laminate is further cut out to evaluate the cross section other than the main surface, It implemented until the total number of the evaluated void became ten or more.

<Surface peel strength>
The obtained foam laminate was cut out in parallel to the thickness direction so that the width was 25 mm and the length was 150 mm, and a 90-degree peel test of the face material was carried out at a speed of 200 mm / min with a 85 mm peel length. Was measured. This operation was performed on both the front and back material sides, and the smaller value was defined 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 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 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 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 cured in an oven at 110 ° C. for 6 hours. .

(Example 6)
A phenol resin foam laminate having a foam thickness of 100 mm was obtained in the same manner as in Example 1 except that the number of nozzles at the tip of the distribution part of the foamable resin composition was 16.

(Example 7)
A phenol resin foam laminate having a foam thickness of 100 mm was obtained in the same manner as in Example 1, except that the number of nozzles at the tip of the distribution part of the foamable resin composition was 48.

(Example 8)
A phenolic resin foam laminate 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 part of the foamable resin composition was 0.250. .

Example 9
A phenolic resin foam laminate 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 dispensing part of the foamable resin composition was 0.500. .

(Example 10)
Foaming was carried out in the same manner as in Example 1 except that a glass fiber nonwoven fabric (trade name “Dura Glass Type DH70 (weight per unit area 70 g / m ² , thickness 0.67 mm)”, manufactured by Jones Manville) was used as the face material. A phenol resin foam laminate 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 blowing agent to 100 parts by mass of phenol resin A-U. In the same manner as in Example 1, a phenol resin foam laminate 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 blowing agent to 100 parts by mass of phenol resin A-U. In the same manner as in Example 1, a phenol resin foam laminate having a foam thickness of 100 mm was obtained.

(Example 13)
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 blowing agent to 100 parts by mass of phenol resin A-U. A phenol resin foam laminate having a thickness of 100 mm was obtained.

(Comparative Example 1)
The foamable phenolic resin composition was the same as in Example 1, except that the foamed phenolic resin composition was flowed into and discharged through a multiport distribution pipe into a die structurally the same type as that disclosed in Example 1 of International Publication No. 2009-066621. Thus, a phenol resin foam laminate having a foam thickness of 100 mm was obtained.

(Comparative Example 2)
The number of flow paths in the distribution part of the foamable resin composition is 32, and the shape of what is disclosed in Example 1 of JP2009-263468 is partially changed at each tip (the opening distance of the die tip is 3.5 mm, A phenol resin foam laminate 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 discharge.

(Comparative Example 3)
A phenol resin foam laminate having a foam thickness of 100 mm was obtained in the same manner as in Example 1 except that the number of nozzles at the tip of the distribution part of the foamable resin composition was set to 12.

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

(Comparative Example 5)
A phenolic resin foam laminate 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 part of the foamable resin composition was 0.200. .

(Comparative Example 6)
A phenolic resin foam laminate 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 laminates.

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

Claims (4)

A phenolic resin foam laminate in which flexible face materials are arranged on at least upper and lower surfaces of the phenol resin foam, and the phenolic resin foam laminate has a face material peel strength of 0.5 N / 25 mm or more, and the phenol The resin foam has a density of 10 kg / m ³ or more and 100 kg / m ³ or less, a thickness of 40 mm or more and 300 mm or less, a thermal conductivity of 0.023 W / m · K or less, a void ratio of 5% or less, and a void aspect ratio of 1. 55 or more phenolic resin foam laminate.   The phenol resin foam laminate according to claim 1, wherein the phenol resin foam contains at least one of a hydrocarbon and a chlorinated hydrocarbon.   The phenol resin foam laminate according to claim 1 or 2, wherein the phenol resin foam contains at least one of a chlorinated hydrofluoroolefin and a non-chlorinated hydrofluoroolefin.   4. The phenol resin foam laminate according to claim 1, 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. 5. Board.