JP2016101750A - Phenolic resin foam laminate board and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenolic resin foam laminate board in which a plasticizer and a resilient face member are used, and in which the base member has a good surface smoothness.SOLUTION: Provided is a phenolic resin foam laminate board in which a face member is disposed at least to the upper and lower surfaces of a phenolic resin foam having a density of 15 kg/mor more and 50 kg/mor less, and a closed cell percentage in a range of 70% or more, and containing a plasticizer other than a phthalic acid-based compound, and in which, characterized, the face members are a resilient face member, and the smoothness evaluation level of the parent member with the face members peeled off is 1.5 mm or less.SELECTED DRAWING: None

Description

  The present invention relates to a phenolic resin foam laminate and a method for producing the same, and more specifically, the surface of the base material after the face material disposed on the upper and lower surfaces of the phenol resin foam is easily peeled off. The present invention relates to a phenol resin foam laminate having excellent smoothness and a method for producing the same.

  The acid-curing phenolic resin foam made from resol-type phenolic resin is less flammable, generates less smoke, and has good heat insulation properties. Used for building materials such as ceiling materials, fire doors, shutters, etc. in addition to inner wall materials. In addition, the acid curable phenolic resin foam is widely used as a cold insulating material for building materials and industrial plants.

  Here, as a foaming agent used at the time of manufacturing a phenol resin foam, a hydrocarbon-based foaming agent has been recently adopted from the viewpoint of environmental problems. In recent years, a phenolic resin foam laminate has been produced in which a foamable phenolic resin composition is filled between upper and lower face materials, and foamed and cured to provide face materials on the upper and lower surfaces of the phenol resin foam. In this regard, it has been proposed to improve the properties of phenol resin foam by adding a plasticizer to a foamable phenol resin composition containing a phenol resin, a surfactant, a hydrocarbon foaming agent, and an acidic curing agent. Yes.

Specifically, for example, in Patent Document 1, by adding a plasticizer such as polyester polyol or polyethylene glycol to the foamable phenol resin composition, the foam wall of the phenol resin foam is given flexibility and the cells Techniques for suppressing wall deterioration with time have been proposed.
Further, for example, in Patent Document 2, a technique for suppressing the formation of a large dent having a diameter of about 8 to 10 cm in a phenol resin foam by adding a specific polyether polyol to the foamable phenol resin composition. Has been proposed.

Japanese Patent No. 5485600 Japanese Patent No. 2873167

However, when the present inventors repeated research on the production of a phenolic resin foam laminate using a foamable phenolic resin composition containing a plasticizer, the foamable phenolic resin composition was filled between the face materials. However, when producing a phenolic resin foam laminate that is foamed and cured and provided with face materials on the upper and lower surfaces of the phenolic resin foam, if a flexible face material with poor rigidity is used, sufficient foamability is obtained. It became clear that it was difficult to obtain a phenolic resin foam laminate having a practically sufficient smoothness on the surface of the base material after peeling off the face material.
Therefore, the phenol resin foam laminate using a plasticizer and using a flexible face material as the face material, particularly when the face material is peeled off and only the base material is used, There was a need for improved smoothness.

  Therefore, the present inventor has conducted intensive studies to solve the above problems, and has optimized the foaming and molding conditions even in a system in which a plasticizer is added and a flexible face material is used. Thus, it has been found that a phenol resin foam laminate having good base material surface smoothness can be obtained. In the phenolic resin foam laminate obtained by this method, it is possible to use any face material with almost no restrictions on the physical properties (rigidity, etc.) of the face material while adding a plasticizer.

  That is, the present invention provides the following [1] to [15].

[1] Surface material on at least upper and lower surfaces of a phenol resin foam having a density of 15 kg / m ³ or more and 50 kg / m ³ or less and a closed cell ratio of 70% or more and containing a plasticizer other than a phthalic compound. Wherein the face material is a flexible face material, and the smoothness evaluation level of the base material from which the face material is peeled is 1.5 mm or less. Phenol resin foam laminate.
[2] The phenol resin foam laminate according to [1], which contains chlorinated hydrofluoroolefin and / or non-chlorinated hydrofluoroolefin as a foaming agent.
[3] The phenol resin foam laminate according to [1] or [2], which contains a hydrocarbon as a foaming agent.
[4] The phenol resin foam laminate according to any one of [1] to [3], which contains chlorinated hydrocarbon as a foaming agent.
[5] The phenol resin foam laminate according to any one of [1] to [4], wherein the face material contains paper.
[6] The phenol resin foam laminate according to any one of [1] to [5], wherein the face material contains glass fiber.
[7] The phenol resin foam laminate according to any one of [1] to [6], wherein the plasticizer has a plurality of hydroxyl groups.
[8] The phenol resin foam laminate according to [7], wherein the plasticizer contains a polyether polyol.
[9] The polyether polyol is a polyether polyol obtained by addition polymerization of an alkylene oxide containing ethylene oxide as an essential component to an organic compound having two or more hydroxyl groups and / or amino groups in one molecule. The phenolic resin foam laminate according to [8], wherein
[10] The phenol resin foam laminate according to [7], wherein the plasticizer contains a polyester polyol.
[11] The phenol resin foam laminate according to [10], wherein the polyester polyol is a reaction product of a polyvalent carboxylic acid and a polyhydric alcohol.
[12] The plasticizer contains a reaction product of alcohol and at least one selected from the group consisting of phosphoric acid, trimellitic acid, adipic acid, and citric acid, [1] The phenol resin foam laminate according to any one of to [7].
[13] A step of mixing a foamable phenol resin composition containing a phenol resin, a surfactant, a foaming agent, a plasticizer other than a phthalic acid compound, and an acidic curing agent using a mixer, and a mixed foaming property A step of discharging a phenol resin composition onto a face material; and a phenol resin in which the foam material is foamed and cured on the face material, and the face material is disposed on at least the upper and lower surfaces of the phenol resin foam. Obtaining the foam laminate, and the foamable phenolic resin composition comprises a foam nucleating agent in a proportion of 0.1% by mass or more and 1.0% by mass or less with respect to the foaming agent, A flexible face material is used as a material, and the temperature of the foamable phenol resin composition when the foamable phenol resin composition is discharged onto the face material is 25 ° C. or more and 50 ° C. or less. , Phenol Method for producing a fat-foam laminate.
[14] The method for producing a phenol resin foam laminate according to [13], wherein the foaming agent contains a chlorinated hydrofluoroolefin and / or a non-chlorinated hydrofluoroolefin.
[15] The method for producing a phenolic resin foam laminate according to [13] or [14], wherein the foaming agent contains a chlorinated hydrocarbon.

  ADVANTAGE OF THE INVENTION According to this invention, it is a phenol resin foam laminated board using a plasticizer and a flexible surface material, Comprising: The smoothness of the preform | base_material surface can obtain the phenol resin foam laminated board.

  Hereinafter, the present invention will be described in detail according 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 a face material provided on at least the upper and lower surfaces of the phenol resin foam.
And the foam laminated board of this embodiment is excellent in the surface smoothness of the base material obtained by peeling an upper and lower surface material, and is not specifically limited, For example, the base material formed by peeling a face material In a state, it can be used as a building material having excellent flame retardancy and heat insulation. In addition, you may use a foam laminated board as it is, without peeling a face material.

<Phenolic resin foam>
The density of the phenol resin foam of the phenol resin foam laminate of the present embodiment is 15 kg / m ³ or more and 50 kg / m ³ or less, preferably 20 kg / m ³ or more and 40 kg / m ³ or less. When the density is 15 kg / m ³ or more, mechanical strength such as compressive strength can be ensured, and breakage during handling of the foam can be avoided. On the other hand, if the density is 50 kg / m ³ or less, the heat transfer of the resin portion is difficult to increase, so that the heat insulation performance can be maintained. 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 closed cell ratio of the phenol resin foam of the phenol resin foam laminate is 70% or more, preferably 80% or more. If the closed cell ratio is less than 70%, there is a concern that the foaming agent in the phenolic resin foam tends to be replaced with air and the heat insulation performance tends to decrease. The closed cell ratio of the phenol resin foam is determined by, for example, changing the molecular weight and blending amount of the plasticizer, the addition amount of the foam nucleating agent, the temperature of the foamable phenol resin composition discharged from the mixer, and the curing conditions. It can be adjusted to a desired value.

  The average cell diameter of the phenol resin foam of the phenol resin foam laminate is preferably 20 μm or more and 200 μm or less, and more preferably 40 μm or more and 150 μm or less. It can suppress that the density of a foam becomes high as an average bubble diameter is 20 micrometers or more. As a result, since the heat transfer rate of the resin part in the foam can be reduced, the heat insulation performance of the phenol resin foam can be ensured. On the other hand, if the average cell diameter exceeds 200 μm, the thermal conductivity due to radiation increases, and the heat insulating performance of the foam may be reduced. The average cell diameter of the phenol resin foam is determined by, for example, changing the molecular weight and blending amount of the plasticizer, the addition amount of the foam nucleating agent, the temperature of the foamable phenol resin composition discharged from the mixer, and the curing conditions. It can be adjusted to a desired value.

  And the phenol resin foam of a phenol resin foam laminated board contains a plasticizer, for example, a foamable phenol resin containing a phenol resin, a surfactant, a foaming agent, a foaming nucleating agent, a plasticizer, and an acidic curing agent Manufactured from the composition. 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 is 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 preferably 5,000 mPa · s or more and 100,000 mPa · s or less, more preferably 7,000 mPa · s or more and 50,000 mPa · s or less, and further preferably 9,000 mPa · s. · S to 40,000 mPa · s.
The water content of the phenol resin is preferably 1.5% by mass or more and 30% by mass or less.

  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, adducts of alkylene oxide and castor oil, addition 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, and 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.

  As a foaming agent, what is generally used for manufacture of a phenol resin foam can be used. The amount of the foaming agent relative to the phenol resin varies depending on the type of the foaming agent, compatibility with the phenol resin, and loss in the foaming / curing process, but 3.0 parts by mass or more with respect to 100 parts by mass of the phenol resin. The amount is preferably 11.5 parts by mass or less, and more preferably 4.0 parts by mass or more and 9.5 parts by mass or less. If the amount of the foaming agent relative to 100 parts by mass of the phenol resin is less than 3.0 parts by mass, the density becomes too high, which is not preferable. Moreover, since the density will become low too much that the quantity of the foaming agent with respect to a phenol resin is more than 11.5 mass parts, it is unpreferable.

Here, from the viewpoint of obtaining sufficient foamability when the phenol resin foam is molded, the foaming agent preferably contains a hydrocarbon as a constituent component. 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 these, pentanes such as normal pentane, isopentane, cyclopentane and neopentane and butanes such as normal butane, isobutane and cyclobutane are preferably used. These hydrocarbons may be used alone or in combination of two or more.
In addition, when a hydrocarbon is included as a blowing agent, the hydrocarbon content in the blowing agent is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 30% by mass or more. Further preferred.

Moreover, from a viewpoint of improving the heat insulation and flame retardancy of the phenol resin foam, the foaming agent contains chlorinated hydrofluoroolefin and / or non-chlorinated hydrofluoroolefin having low thermal conductivity as a constituent component. Is also preferable.
Specific examples of the chlorinated hydrofluoroolefin include 1-chloro-3,3,3-trifluoropropene (for example, product name: Solstice (registered trademark) LBA). Specific examples of the fluoroolefin include 1,3,3,3-tetrafluoro-1-propene (for example, product name: Solstice (registered trademark) 1234ze), 2,3,3,3-tetrafluoro-1 -Propene, 1,1,1,4,4,4-hexafluoro-2-butene and the like.

  In addition, as blowing agent components other than the above, 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.

  In this embodiment, it is important to use a foam nucleating agent for the production of a phenol resin foam. As the foam nucleating agent, a low boiling point substance having a boiling point lower by 50 ° C. or more than that of the foaming agent, such as nitrogen, helium, argon, or air, can be added. 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, and Portland cement, and organic powders such as phenol resin foam powder can also be added. These may be used alone or in combination of two or more.

  The addition amount of the foam nucleating agent to the foaming agent is preferably 0.1% by mass or more and 1.0% by mass or less, with the amount of the foaming agent being 100% by mass, and 0.2% by mass or more and 0.6% by mass or less. The following is more preferable. When the addition amount of the foam nucleating agent is less than 0.1% by mass, uneven foaming is likely to occur, and the smoothness of the surface of the base material when the foam laminate is obtained becomes poor. Moreover, when the addition amount of a foam nucleating agent exceeds 1.0 mass%, foaming of a foamable phenol resin composition will be accelerated | stimulated and the filling property of the foamable phenol resin composition to the space between face materials will become high too much. Therefore, in the case of using a flexible face material having poor rigidity, it becomes difficult to obtain a foam laminate having a smooth base material surface without being able to control foamability.

  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 arylsulfonic acid and its anhydride, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, substituted phenolsulfonic acid, xylenolsulfonic acid, substituted xylenolsulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic 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 parts by mass or more and 30 parts by mass or less, more preferably 8 parts by mass or more with respect to 100 parts by mass of the phenol resin. Used at 25 parts by weight or less. When a mixture of 60% by mass of paratoluenesulfonic acid monohydrate and 40% 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 with respect to 100 parts by mass of the phenol resin. Used in an amount of not less than 20 parts by mass.

  A plasticizer exhibits the effect (henceforth a "plasticizing effect") which reduces the viscosity of a foamable phenol resin composition by adding to a foamable phenol resin composition. And the plasticizer used by this embodiment becomes like this. Preferably it is 0.3 mass part or more and 10 mass parts or less with respect to 100 mass parts of the said phenol resin, More preferably, it is a ratio of 0.3 mass part or more and 5 mass parts or less. It is blended with. When the amount of the plasticizer to be added is too small, the plasticizing effect is not exhibited and the average cell diameter is increased. On the other hand, if the amount of the plasticizer added is too large, the cost increases, which is not preferable. In addition, the plasticizer in a phenol resin foam can be identified and measured in any one of the gas chromatography / mass spectrometry measurement, liquid chromatography / mass spectrometry measurement, and 1H-NMR measurement which are mentioned later.

  The plasticizer is not particularly limited as long as it is a plasticizer other than the phthalic acid compound, and any conventionally known plasticizer can be appropriately selected and used. Specifically, a polyol compound having a plurality of hydroxyl groups, a compound having at least one ester group and a hydroxyl group, a compound having a plurality of ester groups, and the like can be used. Alternatively, two or more types may be used in combination.

  Among these, the plasticizer for the phenol resin foam of the present invention preferably contains a polyol compound having a plurality of hydroxyl groups. Since the above-described polyol compound has hydrophilic properties like the phenol resin, it is compatible with the phenol resin and can form a uniform resin solution. Furthermore, the polyol compound imparts flexibility to the cell wall of the phenol resin foam, and even after a long time has passed, the deterioration of the cell wall such as cracks is suppressed, and the thermal conductivity of the phenol resin foam is reduced. Can provide long-term stability.

Here, as the polyol compound, polyether polyol can be preferably used, and in particular, an alkylene oxide containing ethylene oxide as an essential component in an organic compound having two or more hydroxyl groups and / or amino groups in one molecule. A polyether polyol obtained by addition polymerization can be preferably used. The weight average molecular weight of the polyether polyol is preferably in the range of 200 or more and 20000 or less, more preferably 200 or more and 10,000 or less, and most preferably 300 or more and 5000 or less. In addition, the polyether polyol has an ethylene oxide addition amount of preferably 15% by mass or more, more preferably 30% by mass or more. If the weight average molecular weight exceeds 20,000, there is a possibility that homogeneous mixing with a liquid phenol resin may be difficult. On the other hand, if the weight average molecular weight is less than 200, the foaming agent gas tends to be detached during foam molding or after molding, and there is a risk that dimensional shrinkage will increase. Further, when the ethylene oxide addition amount is less than 15% by mass, there is a possibility that the bubble film is destroyed during foam molding.
As a typical commercial product of such a polyether polyol, the product name, Pionein P-4330-T (weight average molecular weight obtained by using trimethylolpropane as an organic compound is 4300, manufactured by Takemoto Yushi Co., Ltd.) Ethylene oxide addition amount of 30% by mass), pionine P-5050-T (weight average molecular weight obtained using trimethylolpropane as an organic compound is 5000 and ethylene oxide addition amount is 50% by mass), pionine P-5070-T (weight average molecular weight obtained by using trimethylolpropane as the organic compound is 5000 and ethylene oxide addition amount is 70% by mass) and the like can be exemplified.

  In addition, the weight average molecular weight and ethylene oxide addition amount of a polyether polyol here can be calculated | required with the following method.

  The weight average molecular weight is, for example, ethylene oxide (EO) using, as an initiator, a polyfunctional organic compound having two or more hydroxyl groups (calculated as the number of functional groups 1) and / or amino groups (calculated as the number of functional groups 2) in one molecule. ) And propylene oxide (PO) are subjected to addition polymerization, and a hydroxyl value (JIS K1557) of a polyether polyol obtained by addition polymerization is measured and calculated by the following formula.

  Further, the ethylene oxide addition amount (mass percentage) is the integral value (a) of the peak around 3.7 ppm of the NMR chart obtained by 1H-NMR (solvent: deuterated chloroform, concentration: 5 mass%) and around 1.1 ppm. Is calculated by the following formula using the integrated value (b) of the peak.

Here, as the organic compound having two or more hydroxyl groups and / or amino groups in one molecule, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, bisphenol A, bisphenol F, glycerin, trimethylolpropane, hexane Examples include triol, triethanolamine, pentaerythritol, ethylenediamine, methyl glucoside, diethylenetriamine, sorbitol, sucrose and the like. Among them, glycerin, trimethylolpropane and a mixture thereof are preferably used.
Examples of alkylene oxides other than ethylene oxide include propylene oxide, butylene oxide, and styrene oxide. Among these, propylene oxide is generally used.
Further, as the addition polymerization catalyst, for example, potassium hydroxide, sodium hydroxide and the like are preferably used.

  You may use the said polyether polyol in combination of 2 or more type as needed. In addition, when the blending amount is in the range of 0.3 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the phenol resin, the effect of suppressing the detachment of the foaming agent gas during the foam molding and the foam after foam molding. This is preferable because the shrinkage suppressing effect is good.

  Moreover, as a polyol type compound, polyester polyol can also be used preferably. The weight average molecular weight of the polyester polyol is preferably 200 or more and 10,000 or less, more preferably 200 or more and 5000 or less, from the viewpoint of imparting flexibility to the cell walls of the phenol resin foam.

（式中、Ａは二価カルボン酸残基であり、Ｒは二価アルコール残基であり、ｎは１以上の整数である。）
で表されるものが好ましい。これらは１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 As the polyester polyol, a reaction product of a polyvalent carboxylic acid and a polyhydric alcohol, for example, a polybasic carboxylic acid selected from divalent to tetravalent carboxylic acids, a polyhydric alcohol selected from divalent to pentavalent alcohols, and Reaction products of the general formula:

(In the formula, A is a divalent carboxylic acid residue, R is a dihydric alcohol residue, and n is an integer of 1 or more.)
The thing represented by these is preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the above general formula, preferred divalent carboxylic acids forming the residue A include, for example, aromatic divalent carboxylic acids, aliphatic divalent carboxylic acids, alicyclic divalent carboxylic acids, and the like, preferably naphthalene. -2,3-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclohexane-1,2-dicarboxylic acid, And cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, and the like.

  Further, the dihydric alcohol forming the skeleton R is an aromatic glycol, an aliphatic glycol or an alicyclic glycol, among which, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, cyclopentane-1,2-diol , Cyclopentane-1,2-dimethanol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclopentane-1,4-dimethanol, 2,5-norbornane Aliases such as diols Recall or alicyclic glycol are particularly preferred.

  A preferred polyester polyol has a molecular structure containing both one ester skeleton and one hydroxyl group, and has hydrophilic properties similar to the phenol resin, and therefore has good compatibility with the phenol resin. Yes, a uniform resin solution can be formed.

  Moreover, you may use these polyester polyols in combination of 2 or more type as needed. The blending amount is preferably 0.3 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more and 5 parts by mass or less, with respect to 100 parts by mass of the phenol resin. While maintaining, the effect which brings about the long-term stability of the thermal conductivity of the phenol resin foam by the softness | flexibility provision to the cell wall of a phenol resin foam becomes high, and it is preferable.

  The plasticizer preferably contains a reaction product of alcohol and at least one selected from the group consisting of phosphoric acid, trimellitic acid, adipic acid, and citric acid. Specific examples of these plasticizers include phosphoric esters such as triamyl phosphate, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, and 2-ethylhexyl diphenyl phosphate; (2-ethylhexyl); adipate such as bis (2-ethylhexyl) adipate, dioctyl adipate, diisononyl adipate, diisodecyl adipate; tributyl acetyl citrate, tributyl citrate, triethyl citrate, trimethyl citrate, And citric acid esters such as tripropyl acid; These ester compounds may be used in combination of two or more as required, and can be variously selected according to the purpose.

<Face material>
As the face material disposed on at least the upper and lower surfaces of the phenol resin foam, a flexible face material (flexible face material) is used. Examples of the flexible face material used include nonwoven fabrics and woven fabrics mainly composed of polyester, polypropylene, nylon, craft paper, glass fiber mixed paper, calcium hydroxide paper, aluminum hydroxide paper, magnesium silicate paper, etc. Paper, inorganic fiber nonwoven fabrics such as glass fiber nonwoven fabrics, and the like are preferable, and these may be mixed (or laminated). In particular, when the face material is peeled from the obtained phenolic resin foam laminate and only the base material is used, inexpensive papers that can be discarded after peeling are preferable. These face materials are usually provided in a roll form. Further, as the flexible face material, a material obtained by kneading an additive such as a flame retardant may be used. Note that the method for bonding the face material and the phenol resin foam is not particularly limited, and the adhesive due to the adhesive force when the phenol resin foam is thermally cured on the surface of the face material or an adhesive such as an epoxy resin is used. It does not matter if you do it.

<Properties of phenolic resin foam laminate>
In the phenol resin foam laminate of this embodiment, the smoothness evaluation level of the base material (phenol resin foam) formed by peeling the upper and lower surface materials is 1.5 mm or less, more preferably 1.0 mm. Or less, and more preferably 0.5 mm or less. The smoothness evaluation level of the base material is usually 0.1 mm or more. The smoothness evaluation level of the base material is a desired value mainly due to changes in the molecular weight and blending amount of the plasticizer, the addition amount of the foam nucleating agent, the temperature of the foamable phenol resin composition discharged from the mixer, and the like. Can be adjusted.

Here, the smoothness evaluation level of the base material is obtained by measuring the dimension in the thickness direction of the base material of the obtained phenolic resin foam laminate as follows.
The “dimension in the thickness direction” in the present embodiment refers to the dimension of the shortest side among the three sides of the foam laminate, and usually the foamable phenolic resin composition on the face material during the production of the foam laminate. It is the dimension in the direction in which the product expands and grows.

When measuring the smoothness evaluation level of the base material, a phenol resin foam laminate having an area of two sides excluding the side having the smallest dimension (thickness direction) among the three sides is 10,000 mm ² or more. Measured.
With respect to the base material obtained by peeling the face material from the phenol resin foam laminate to be measured, the number of measurement points and the number of measurement points are 20 with an interval of at least 10 mm. And the dimension (thickness) of the thickness direction of a base material is measured in each position, and it evaluates as a smoothness evaluation level by the following formula | equation (a).
Smoothness evaluation level (mm) = (maximum thickness−minimum thickness) (a)
The phenolic resin foam laminate is based on the premise that the face material can be peeled by hand, and when the face material is peeled off, part of the resin may ooze into the face material side. This resin content is not particularly considered, and the thickness of the base material surface after peeling is evaluated.

(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 includes a mixing step of mixing the above-described foamable phenol resin composition with a mixer, a discharge step of discharging the mixed foamable phenol resin composition onto the face material, and a surface. A continuous production method comprising a foam laminate production process for producing a phenol resin foam laminate from a phenol resin composition discharged on a material is common, but face materials were used up and down in a mold It is also possible to employ a batch foaming method.

  In the continuous manufacturing method, the phenolic resin composition discharged on the lower surface material is coated with the upper surface material, and then pre-molded so as to be leveled from the vertical direction while foaming and curing, and then plate-shaped while proceeding with foaming and curing. It will be molded into.

  In the continuous manufacturing method, as a method of preforming or forming, a method using a slat type double conveyor, a method using a metal roll or a steel plate, and a method using a combination of these for manufacturing purposes, etc. Various methods can be cited. Among these, for example, in the case of molding using a slat type double conveyor, the foamable phenol resin composition coated with the upper and lower face materials is continuously guided into the slat type double conveyor, and then heated. While adjusting the pressure to a predetermined thickness by applying pressure from above and below, it can be foamed and cured to be formed into a plate shape.

Here, in the production of the phenol resin foam laminate of this embodiment, in order to obtain a desired smoothness evaluation level even in a system in which a plasticizer is added and a flexible face material is used, foaming is performed. It is important to control the initial foaming of the conductive phenol resin composition. For that purpose, it is important to control the temperature of the foamable phenol resin composition discharged (applied) onto the face material as well as optimizing the amount of the foam nucleating agent in the foamable phenol resin composition. Specifically, the temperature of the foamable phenol resin composition is preferably 25 ° C. or more and 50 ° C. or less, and more preferably 30 ° C. or more and 45 ° C. or less. When the temperature exceeds 50 ° C., foaming is promoted too much, so that the smoothness of the base material is deteriorated. On the other hand, when the temperature is lower than 25 ° C., the curing of the foamable phenolic resin composition becomes slow, and both foaming and curing are not preferable.
In the case where the foamable phenol resin composition contains chlorinated hydrofluoroolefin and / or non-chlorinated hydrofluoroolefin as a foaming agent, optimization of the amount of the above-mentioned foaming nucleating agent and foamable phenol resin at the time of discharge The temperature control of the composition can be applied as a particularly preferable technique for improving the level of smoothness of the phenol resin foam laminate.

  In order to achieve a desired level of smoothness evaluation, it is important to achieve curing while controlling the foamed state. The details will be described below.

  When a foaming agent mixture (foamable phenolic resin composition) containing a plasticizer is discharged onto a face material and a flexible face material that is inferior in rigidity is used for foaming and curing, the foamability cannot be fully controlled and smooth. There is a problem that it is difficult to obtain a foam laminate having a rough base material surface.

  As a result of intensive studies to solve this problem, it is important that the surface of the phenolic resin foam is cured without delay at almost the same time as the foaming phenolic resin composition is filled in the foaming space between the upper and lower surface materials. I found out.

  Specifically, it is important to control the foamed state while keeping the foamed state uniform. For this purpose, it is preferable to adjust the addition amount of the foam nucleating agent to the foaming agent to 0.1% by mass or more and 1.0% by mass or less while adding the foam nucleating agent, and 0.2% by mass or more and 0% by mass. It was found that it was more preferable to set the amount to 6% by mass or less. It was also found that the temperature of the foamable phenol resin composition discharged (applied) onto the face material is preferably 25 ° C. or more and 50 ° C. or less, more preferably 30 ° C. or more and 45 ° C. or less. And in this embodiment, based on the said knowledge, even if it is the type | system | group which added the plasticizer and used the flexible face material, the smoothness evaluation level of a base material is the outstanding smoothness of 1.5 mm or less. It has become possible to provide a phenol resin foam laminate having a property and a method for producing a phenol resin foam laminate.

  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>
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 amount of formaldehyde) Added. 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. As a result, the viscosity at 40 ° C. was 6,100 mPa · s and the water content was 5.1% by mass. 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. Further, as a plasticizer, adipic acid-based polyester polyol (manufactured by Dainippon Ink & Chemicals, Inc., trade name “Polysizer W-230-S”) is 0.3 with respect to 100 parts by mass of phenol resin AU. Part by mass was added. 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 50% by mass of isopentane and 50% by mass of isobutane as a blowing agent, and 0.3% by mass of nitrogen as a foam nucleating agent with respect to the blowing agent Furthermore, a foamable phenol 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, and the multiport distribution pipe And fed onto the moving bottom material. 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 a plurality of nozzles at the tip, and is designed so that the mixed foamable phenolic resin composition is uniformly distributed.

  The temperature of the foamable phenolic resin composition supplied on the lower surface material is an internal position near the center of the discharged foamable phenolic resin composition at the position where the foamable phenolic resin composition is discharged onto the face material. A thermometer was inserted and measured. The measured temperature of the foamable phenolic resin composition was 38 ° C., and the foamable phenolic resin composition was coated with the upper surface material, and at the same time, sandwiched between the upper and lower surface materials. 1 temperature control section; dwell time 4 minutes), pre-formed to equalize using multiple rolls, then sent to oven (second temperature control section) with 83 ° C slat type double conveyor It was. The preformed foamable phenolic resin composition was cured for 15 minutes in a slat type double conveyor and then cured in an oven at 110 ° C. for 2 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. As the face material, a craft paper face material, which is a flexible face material, was used.

  And the characteristics of the obtained phenolic resin foam laminate (density of phenol resin foam, closed cell ratio and average cell diameter, presence of plasticizer, presence of hydrocarbon, hydrofluoroolefin and chlorinated hydrocarbon, and The smoothness evaluation level of the base material was evaluated by the following method.

<Phenolic resin foam density>
A 20 cm square phenolic resin foam laminate was used as a sample, and after removing the face material from this sample, the mass and the apparent volume were measured according to JIS K7222.

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

<Average cell diameter of phenol resin foam>
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 1,800 μm was defined as an average cell diameter.

<Analysis of plasticizer in phenol resin foam>
Whether or not a plasticizer is contained in the phenol resin foam of the phenol resin foam laminate can be confirmed by the following method.
1 g of a sample collected from the phenol resin foam portion of the phenol resin foam laminate is pulverized and subjected to Soxhlet extraction with methanol (150 mL) (7 hours). After concentrating and drying at 40 ° C. with an evaporator, vacuum drying (normal temperature, 30 minutes) is performed. After measuring dry mass, it melt | dissolves in 5 mL of methanol, and performs analytical measurement by the method in any one of the following (1)-(3) using the obtained methanol solution.
(1) Gas chromatography / mass (GC / MS) analysis measurement The following apparatus and conditions can be selected as GC / MS analysis conditions.
GC device: Agilent Technologies 7890A
Inlet temperature: 320 ° C
Column: DB-1MS (30 m × 0.25 mmφ), liquid phase thickness 0.25 μm
Column temperature: 40 ° C. (5 min hold), 20 ° C./min temperature rise, 320 ° C. (11 min hold)
MS equipment: Agilent Technologies 5975C MSD
Ion source temperature: 230 ° C
Interface temperature: 300 ° C
Ionization method: Electron ionization method (2) Liquid chromatography / mass (LC / MS) analysis measurement The following apparatus and conditions can be selected as LC / MS analysis conditions.
LC equipment: Waters, UPLC
Column: Shiseido, CAPCELL PAK C18 IF2 2um (2.1mm ID × 50mm)
Column temperature: 40 ° C
Detection PDA: 210-400 nm
Flow rate: 0.3 mL / min Mobile phase: A = 10 mM Ammonium acetate
B = 10 nM Ammonium acetate / AcCN / IPA (1/4/5)
MS equipment: Waters, Synapt G2
Ionization method: ESI +
Scan range: m / z 150-3000
(3) 1H-NMR measurement 1.0 mL of a methanol solution is sampled, and the collected solution is air-dried and then vacuum-dried (methanol extracted dry product) to which deuterated chloroform is added, and 1H-NMR measurement is performed. . For example, the following devices and measurement conditions can be selected.
Device: JEOL RESONANCE JNM-ECS400
Resonance frequency: 400 MHz
Pulse width: 45 °
Solvent: Deuterated chloroform Chemical shift standard: Tetramethylsilane (TMS) 0 ppm

<Analysis of hydrocarbons, hydrofluoroolefins and chlorinated hydrocarbons in phenol resin foam>
Whether or not hydrocarbons, hydrofluoroolefins, and chlorinated hydrocarbons are contained in the phenol resin foam of the phenol resin foam laminate can be confirmed by the following method.
A sample collected from the phenolic resin foam part of the phenolic resin foam laminate is pulverized in a suitable solvent selected from pyridine, toluene, tetrahydrofuran, dimethylformamide, etc. in a sealed container, and then hydrocarbons, hydrofluoroolefins And chlorinated hydrocarbons can be extracted and subjected to gas chromatography for identification. An example is shown below.
From the vicinity of the thickness direction center of the foam laminate from which the face material has been removed in advance, a lump of about 0.1 g of phenol resin foam cut out with a cutter knife is subdivided into dice shapes with sides of about 1 to 2 mm, and the volume is divided. Is put in a 20 mL bottle, and 10 mL of tetrahydrofuran is added and sealed. The mixture is pulverized and extracted while being immersed in a shaker at room temperature for 5 hours, and the solution is subjected to gas chromatography / mass (GC / MS) analysis measurement under the following conditions. The GC / MS analysis conditions were as follows.
GC device: Agilent 7890A
Inlet temperature: 300 ° C
Column: Supelco Equity-1 (30 m × 0.25 mmφ), liquid phase thickness 1 μm
Column temperature: 40 ° C. (5 min hold), 10 ° C./min temperature rise, 320 ° C. (7 min hold)
MS equipment: JEOL Q1000GC
Ion source temperature: 250 ° C
Interface temperature: 300 ° C
Ionization method: Electron ionization method

<Smoothness evaluation level of base material>
A phenol resin foam laminate having an upper and lower surface area of 10,000 mm ² was used as a sample, and the face material was carefully peeled from the sample by hand. In addition, the face material could be easily peeled by hand, and the bleeding of the resin on the face material side could not be confirmed visually.
And regarding the base material obtained by peeling off the face material from the sample, the thickness was measured at 20 points with an interval of 10 mm, and the smoothness evaluation level was determined by the following equation (a).
Smoothness evaluation level (mm) = (maximum thickness−minimum thickness) (a)

(Example 2)
Nitrogen as a foam nucleating agent was added in an amount of 0.6% by mass with respect to the foaming agent, and the temperature of the foamable phenol resin composition supplied onto the lower surface material was 47 ° C., in the same manner as in Example 1, A phenol resin foam laminate was obtained.

(Example 3)
Addition of adipic acid-based polyester polyol (trade name “Polysizer W-230-S”, manufactured by Dainippon Ink and Chemicals, Inc.) with respect to 100 parts by mass of phenol resin AU: the face material is glass fiber mixed paper A phenol resin foam laminate was obtained in the same manner as in Example 2 except that the amount was 4.8 parts by mass and the temperature of the foamable phenol resin composition supplied onto the lower surface material was 40 ° C.

Example 4
Phenolic resin AU: The addition amount of adipic acid-based polyester polyol (Dainippon Ink Chemical Co., Ltd., trade name “Polysizer W-230-S”) is set to 0.4 parts by mass with respect to 100 parts by mass. 5.4 parts by mass of 1,3,3,3-tetrafluoro-1-propene is used as a foaming agent, and 0.6% by mass of nitrogen is added to the foaming agent as a foam nucleating agent, and supplied onto the lower surface material. A phenolic resin foam laminate was obtained in the same manner as in Example 3 except that the temperature of the foamable phenolic resin composition was 45 ° C.

(Example 5)
Example 4 except that 5.4 parts by mass of 1-chloro-3,3,3-trifluoropropene was used as a foaming agent, and the temperature of the foamable phenol resin composition supplied onto the bottom material was 43 ° C. Similarly, a phenol resin foam laminate was obtained.

(Example 6)
As a plasticizer, a polyether polyol [trade name: Pionein P-4330, having a weight average molecular weight of 4300 and an ethylene oxide addition amount of 30% by mass obtained by addition polymerization of ethylene oxide and propylene oxide to trimethylolpropane (organic compound). -T, Takemoto Yushi Co., Ltd.] is added to 0.5 parts by mass with respect to 100 parts by mass of phenol resin AU, and 0.4% by mass of nitrogen as a foaming nucleating agent is added to the foaming agent. A phenolic resin foam laminate was obtained in the same manner as in Example 1 except that the temperature of the foamable phenolic resin composition supplied onto the lower surface material was 46 ° C.

(Example 7)
Polyether polyol [trade name: Pionein P-4330-T, manufactured by Takemoto Yushi Co., Ltd.] is added to 4.5 parts by mass with respect to 100 parts by mass of phenol resin AU, and the foamable phenol supplied onto the bottom surface material. A phenol resin foam laminate was obtained in the same manner as in Example 6 except that the temperature of the resin composition was 40 ° C.

(Example 8)
Polyether polyol [trade name: Pionine P-4330-T, manufactured by Takemoto Yushi Co., Ltd.] is added in an amount of 0.3 parts by mass with respect to 100 parts by mass of phenol resin AU, and 50% by mass of isopentane and 1% as a blowing agent , 3,3,3-tetrafluoro-1-propene is used in an amount of 5.4 parts by mass, and the foam nucleating agent is added in an amount of 0.3% by mass with respect to the foaming agent. A phenolic resin foam laminate was obtained in the same manner as in Example 6 except that the temperature of the foamable phenol resin composition supplied above was 44 ° C.

Example 9
The temperature of the foamable phenol resin composition supplied on the lower surface material using 5.4 parts by mass of a mixture of 50% by mass of isopentane and 50% by mass of 1-chloro-3,3,3-trifluoropropene as a foaming agent. A phenol resin foam laminate was obtained in the same manner as in Example 8 except that the temperature was 42 ° C.

(Example 10)
Example 1 except that 5.6 parts by mass of a mixture of 50% by mass of isopentane and 50% by mass of isopropyl chloride was used as a foaming agent, and the temperature of the foamable phenolic resin composition supplied onto the bottom material was 43 ° C. Similarly, a phenol resin foam laminate was obtained.

(Example 11)
Phenolic resin AU: The addition amount of adipic acid-based polyester polyol (Dainippon Ink Chemical Co., Ltd., trade name “Polysizer W-230-S”) is set to 0.4 parts by mass with respect to 100 parts by mass. A phenol resin foam laminate was prepared in the same manner as in Example 2 except that 5.6 parts by mass of isopropyl chloride was used as the foaming agent, and the temperature of the foamable phenol resin composition supplied on the bottom material was 45 ° C. Obtained.

(Example 12)
A foamable phenolic resin composition used on a lower surface material, using 5.4 parts by mass of a mixture of 50% by mass of 1,3,3,3-tetrafluoro-1-propene and 50% by mass of isopropyl chloride as a foaming agent. A phenol resin foam laminate was obtained in the same manner as in Example 4 except that the temperature was set to 44 ° C.

(Example 13)
Of a foamable phenol resin composition supplied on the bottom material using 5.4 parts by mass of a mixture of 50% by mass of 1-chloro-3,3,3-trifluoropropene and 50% by mass of isopropyl chloride as a foaming agent. A phenol resin foam laminate was obtained in the same manner as in Example 12 except that the temperature was 42 ° C.

(Comparative Example 1)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that nitrogen as the foam nucleating agent was not added and the temperature of the foamable phenol resin composition supplied onto the lower surface material was 46 ° C. .

(Comparative Example 2)
Nitrogen as a foam nucleating agent was added in an amount of 1.1% by mass with respect to the foaming agent, and the temperature of the foamable phenolic resin composition supplied onto the lower surface material was 35 ° C., as in Example 1, A phenol resin foam laminate was obtained.

(Comparative Example 3)
A foaming phenol which is a mixture of 15% by mass of isopentane and 85% by mass of 2-chloropropane as a foaming agent, is added with 1.1% by mass of nitrogen as a foam nucleating agent to the foaming agent, and is supplied onto the lower surface material. A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the temperature of the resin composition was 51 ° C.

(Comparative Example 4)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the temperature of the foamable phenol resin composition supplied onto the lower surface material was 53 ° C. by raising the temperature during mixing with the mixer.

(Comparative Example 5)
Nitrogen as a foam nucleating agent was added in an amount of 1.1% by mass with respect to the foaming agent, and the temperature of the foamable phenol resin composition supplied on the lower surface material was 35 ° C. A phenol resin foam laminate was obtained.

(Comparative Example 6)
A phenol resin foam laminate was obtained in the same manner as in Example 6 except that the temperature of the foamable phenol resin composition supplied onto the bottom material was set to 54 ° C. by raising the temperature during mixing with the mixer.

  The evaluation results of the characteristics of the phenol resin foam laminates obtained in Examples 1 to 13 and Comparative Examples 1 to 6 are summarized in Table 1.

  From Table 1, the base material of the phenol resin foam laminate obtained in Examples 1 to 13 has smoothness superior to that of the phenol resin foam laminate obtained in Comparative Examples 1 to 6. You can see that

[1] Surface material on at least upper and lower surfaces of a phenol resin foam having a density of 15 kg / m ³ or more and 50 kg / m ³ or less and a closed cell ratio of 70% or more and containing a plasticizer other than a phthalic compound. Wherein the face material is a flexible face material, and the smoothness evaluation level of the base material from which the face material has been peeled is 1.0 mm or less. Phenol resin foam laminate.
[2] The phenol resin foam laminate according to [1], which contains chlorinated hydrofluoroolefin and / or non-chlorinated hydrofluoroolefin as a foaming agent.
[3] The phenol resin foam laminate according to [1] or [2], which contains a hydrocarbon as a foaming agent.
[4] The phenol resin foam laminate according to any one of [1] to [3], which contains chlorinated hydrocarbon as a foaming agent.
[5] The phenol resin foam laminate according to any one of [1] to [4], wherein the face material contains paper.
[6] The phenol resin foam laminate according to any one of [1] to [5], wherein the face material contains glass fiber.
[7] The phenol resin foam laminate according to any one of [1] to [6], wherein the plasticizer has a plurality of hydroxyl groups.
[8] The phenol resin foam laminate according to [7], wherein the plasticizer contains a polyether polyol.
[9] The polyether polyol is a polyether polyol obtained by addition polymerization of an alkylene oxide containing ethylene oxide as an essential component to an organic compound having two or more hydroxyl groups and / or amino groups in one molecule. The phenolic resin foam laminate according to [8], wherein
[10] The phenol resin foam laminate according to [7], wherein the plasticizer contains a polyester polyol.
[11] The phenol resin foam laminate according to [10], wherein the polyester polyol is a reaction product of a polyvalent carboxylic acid and a polyhydric alcohol.
[12] The plasticizer contains a reaction product of alcohol and at least one selected from the group consisting of phosphoric acid, trimellitic acid, adipic acid, and citric acid, [1] The phenol resin foam laminate according to any one of to [7].
[13] A step of mixing a foamable phenol resin composition containing a phenol resin, a surfactant, a foaming agent, a plasticizer other than a phthalic acid compound, and an acidic curing agent using a mixer, and a mixed foaming property A step of discharging a phenol resin composition onto a face material; and a phenol resin in which the foam material is foamed and cured on the face material, and the face material is disposed on at least the upper and lower surfaces of the phenol resin foam. Obtaining the foam laminate, and the foamable phenolic resin composition comprises a foam nucleating agent in a proportion of 0.1% by mass or more and 1.0% by mass or less with respect to the foaming agent, A flexible face material is used as a material, and the temperature of the foamable phenol resin composition when discharging the foamable phenol resin composition onto the face material is 25 ° C. or more and 47 ° C. or less. , Phenol Method for producing a fat-foam laminate.
[14] The method for producing a phenol resin foam laminate according to [13], wherein the foaming agent contains a chlorinated hydrofluoroolefin and / or a non-chlorinated hydrofluoroolefin.
[15] The method for producing a phenolic resin foam laminate according to [13] or [14], wherein the foaming agent contains a chlorinated hydrocarbon.

Claims (15)

The density is 15 kg / m ³ or more and 50 kg / m ³ or less, the closed cell ratio is 70% or more, and face materials are arranged on at least the upper and lower surfaces of the phenol resin foam containing a plasticizer other than the phthalic acid compound. A phenolic resin foam laminate,
The face material is a flexible face material;
The phenol resin foam laminate, wherein the base material from which the face material is peeled has a smoothness evaluation level of 1.5 mm or less.   The phenol resin foam laminate according to claim 1, wherein the foaming agent comprises chlorinated hydrofluoroolefin and / or non-chlorinated hydrofluoroolefin.   The phenol resin foam laminate according to claim 1, wherein the foam includes a hydrocarbon.   The phenol resin foam laminate according to any one of claims 1 to 3, wherein the foaming agent contains chlorinated hydrocarbon.   The phenol resin foam laminate according to any one of claims 1 to 4, wherein the face material contains paper.   The phenol resin foam laminate according to any one of claims 1 to 5, wherein the face material contains glass fiber.   The phenolic resin foam laminate according to any one of claims 1 to 6, wherein the plasticizer has a plurality of hydroxyl groups.   The phenol resin foam laminate according to claim 7, wherein the plasticizer contains a polyether polyol.   The polyether polyol is a polyether polyol obtained by addition polymerization of an alkylene oxide containing ethylene oxide as an essential component to an organic compound having two or more hydroxyl groups and / or amino groups in one molecule. The phenolic resin foam laminate according to claim 8.   The phenol resin foam laminate according to claim 7, wherein the plasticizer contains a polyester polyol.   The phenol resin foam laminate according to claim 10, wherein the polyester polyol is a reaction product of a polyvalent carboxylic acid and a polyhydric alcohol.   The plasticizer contains a reaction product of at least one selected from the group consisting of phosphoric acid, trimellitic acid, adipic acid and citric acid and an alcohol. The phenolic resin foam laminate according to any one of the above. A step of mixing a foamable phenolic resin composition containing a phenolic resin, a surfactant, a foaming agent, a plasticizer other than a phthalic acid compound, and an acidic curing agent using a mixer;
Discharging the mixed foamable phenolic resin composition onto the face material;
Foaming and curing the foamable phenolic resin composition discharged on the face material to obtain a phenol resin foam laminate having face materials disposed on at least upper and lower surfaces of the phenol resin foam; and
Including
The foamable phenolic resin composition includes a foam nucleating agent at a ratio of 0.1% by mass or more and 1.0% by mass or less with respect to the foaming agent,
Using a flexible face material as the face material,
The method for producing a phenolic resin foam laminate, characterized in that the temperature of the foamable phenol resin composition when discharging the foamable phenol resin composition onto the face material is 25 ° C or more and 50 ° C or less.   The said foaming agent contains a chlorinated hydrofluoroolefin and / or a non-chlorinated hydrofluoroolefin, The manufacturing method of the phenol resin foam laminated board of Claim 13 characterized by the above-mentioned.   The method for producing a phenolic resin foam laminate according to claim 13 or 14, wherein the foaming agent contains a chlorinated hydrocarbon.