JP5225750B2 - Flame retardant phenolic resin foam laminate and its manufacturing method - Google Patents

Description

  The present invention relates to a flame retardant phenolic resin foam laminated board in which a face material is bonded to the surface of a phenolic resin foam used as a heat insulating material for buildings, a heat insulating material for vehicles, a heat insulating material for equipment, and the like, and a method for producing the same. About.

  The phenolic resin foam laminate used as a heat insulating material is bonded to one or both sides of the phenolic resin foam to protect the phenolic resin foam, which is a relatively brittle material, from being damaged or damaged by external force. It becomes. Such a laminate is a continuous laminate by continuously discharging an uncured foamable resin composition containing a phenolic resin onto a traveling face material, and covering it with another face material, Next, the continuous laminate can be produced by being passed through a double conveyor set at a predetermined temperature and foaming and curing the foamable resin composition.

  The role of the face material in the above manufacturing process is to support the uncured foamable resin composition (lower surface material) and the covering (upper surface material), which are continuously transferred to a double conveyor, thereby producing continuous production. Is possible.

  In Patent Document 1, by using a synthetic fiber nonwoven fabric as a face material, the phenol resin foam prevents the exudation of the phenol resin to the outer surface, reduces discoloration spots of the laminated board, and has excellent adhesive strength of the face material. A body laminate is disclosed.

  Patent Document 2 discloses a method for enhancing flame retardancy by attaching a low-temperature endothermic substance to the surface of a phenol resin foam.

Japanese Patent No. 3523196 JP 2006-160858 A

  In the phenolic resin foam laminate described in Patent Document 1, the phenolic resin foam itself, which is a core material, is easy to carbonize and is not melted by heat, and is excellent in flame retardancy. However, the synthetic fiber nonwoven fabric, which is a face material, is a material made of a synthetic resin, so it is more flammable than a phenol resin. Therefore, in the phenolic resin foam laminate in which the synthetic fiber nonwoven fabric is bonded as a face material, the surface of the laminate has a problem that the flame retardancy is lower than the phenol resin foam itself due to the face material used in combination. It was.

  In the method described in Patent Document 2, a low-temperature endothermic substance is directly attached to the foam, and this does not lead to an improvement in flame retardancy of the face material. Moreover, the effect which raises a flame retardance is still inadequate, and the effect which raises a flame retardance is very small especially with adhesion of a small amount. In addition, since the adhesion of the deposits is insufficient, there are problems such as powder falling off, for example, the adhesiveness of the airtight tape is lowered or the roughness is seen in the heat insulating material for buildings. . Furthermore, when the adhesion amount is increased to increase the flame retardancy, the appearance is inferior and the adhesiveness is further reduced.

  In addition, formaldehyde diffused from a phenol resin foam is considered to have a problem of influence on the human body, and a technique for reducing the diffusion of formaldehyde is required.

  The present invention aims at imparting good flame retardancy with good productivity without using organic solvents, without impairing practical characteristics including appearance, in a phenolic resin foam laminate using a face material. And Furthermore, in this invention, it is providing the phenol resin foam laminated board by which the means to reduce the formaldehyde diffused from a phenol resin foam was taken.

  As a result of intensive studies to solve the above problems, the present inventor has achieved good productivity and good flame retardant without impairing practical properties including appearance by using a water-soluble phosphorus-based flame retardant. It was found that the property can be imparted to the phenol resin foam laminate, and the present invention has been made.

  That is, the present invention is as follows.

A first aspect of the present invention is a phenol resin foam laminate in which a phenol resin foam is sandwiched between two face materials, and includes water-soluble phosphorus on the surface of the at least one face material and in the face material. per unit area 1 to 40 g / m ² of the system flame retardant said surface material, formaldehyde scavenger is present 0.05 to 20 g / m ² per unit area of said surface material, phosphorus-based flame retardant 100 the formaldehyde scavenger is It is 0.5 to 300 parts by weight with respect to parts by weight.

In the flame retardant phenolic resin foam laminate of the present invention,
The phosphorus flame retardant is a mixture of one or more of a phosphate carbamate derivative and a phosphate guanidine derivative;
In the surface of the face material where the phosphorus-based flame retardant is present and in the face material, the water-soluble organic polymer compound is further present in an amount of 2 to 250 parts by weight with respect to 100 parts by weight of the phosphorus-based flame retardant, The total amount of the formaldehyde scavenger and the organic polymer compound is 2.5 to 350 parts by weight with respect to 100 parts by weight of the phosphorus-based flame retardant;
The density of the flame retardant phenolic resin foam laminate is 10 to 150 kg / m ³ or less, the closed cell ratio of the foam is 60% or more, and the thermal conductivity is 0.036 W / (m · K) or less, The foam contains a flammable foaming agent;
Is included as a preferred embodiment.

  In the second aspect of the present invention, a coating liquid obtained by dissolving a water-soluble phosphorus-based flame retardant in water is applied to at least one of the two face materials and dried by heating. On one face material, After discharging a foamable resin composition comprising at least a phenol resin, a foaming agent, and a curing catalyst, and covering the upper surface of the foamable resin composition with the other face material, the foamable resin composition is foam-cured and laminated. Next, a scavenger liquid in which a formaldehyde scavenger is dispersed or dissolved is applied to at least one of the surfaces of the laminate having the face material, and dried.

  In the third aspect of the present invention, a foamable resin composition comprising at least a phenol resin, a foaming agent, and a curing catalyst is discharged onto the face material, and the upper surface of the foamable resin composition is covered with a new face material, Forming a laminate by foaming and curing the foamable resin composition, then dispersing or dissolving a formaldehyde scavenger in water, and further dissolving a water-soluble phosphorus-based flame retardant into the laminate It is characterized in that it is applied to at least one of the surfaces having a body face material and dried by heating.

In the method for producing a flame retardant phenolic resin foam laminate of the present invention,
The coating solution is a mixture of an aqueous solution in which a water-soluble phosphorus-based flame retardant is dissolved and an aqueous solution in which an organic polymer compound that is hardly soluble in water after heat drying is dissolved or finely dispersed,
The aqueous solution in which the organic polymer compound that is sparingly soluble in water after heating and drying is finely dispersed or dissolved is an aqueous solution of acrylic latex or polyvinyl alcohol, or a mixture thereof,
Is further included as a preferred embodiment.

  According to the present invention, the flame retardancy of the face material of the phenolic resin foam laminate is improved without impairing the practical characteristics including the appearance, so that the flame retardance of the entire laminate is improved. Therefore, the flame retardant phenolic resin foam laminate according to the present invention is preferably used as a heat insulating material for buildings, a heat insulating material for vehicles, a heat insulating material for equipment, and the like. In addition, since the flame retardant phenolic resin foam laminate according to the present invention is provided with a formaldehyde scavenger at the same time as the flame retardant, the formaldehyde diffused from the laminate can be reduced and used safely.

  Hereinafter, the present invention will be specifically described.

  The flame retardant phenolic resin foam laminate of the present invention comprises a phenolic resin foam sandwiched between two face materials, and the flame retardant and formaldehyde scavenger adhere to at least one surface of the face material and the face material. doing.

  The method for producing the flame retardant phenolic resin foam laminate of the present invention is basically the same as the conventional method for producing a phenol resin foam laminate, and a foaming agent and a curing catalyst are added to the phenol resin and mixed. As the foamable resin composition, a laminating method is used in which a phenol resin foam is produced by continuously discharging onto a traveling face material and further covering the upper surface with the face material, and then completing the foam curing. In this case, the face material and the foam are bonded by the adhesive force of the phenol resin itself, and it is not necessary to use an adhesive.

  In the present invention, in such a manufacturing method, a coating solution in which a flame retardant is dissolved in a face material is applied in advance (pre-coating method), or a coating solution in which a flame retardant is dissolved after forming a laminate. Is applied to the face material (post-coating method) to impart flame retardancy to the face material. Further, in the present invention, when the pre-coating method is used, a scavenger liquid in which the formaldehyde scavenger is finely dispersed or dissolved is applied to the face material of the laminate after the phenol resin is foamed, and the post-coating method is applied. When used, the laminate is given formaldehyde scavenging action by adding a formaldehyde scavenger to the coating solution.

  In the present invention, the face material to which the coating liquid or the scavenger liquid is applied may be both of the two face materials that sandwich the foam or only one of them.

The face material used in the present invention is a breathable face material such as a nonwoven fabric, a woven fabric, or paper, preferably a paper or a nonwoven fabric, more preferably a nonwoven fabric, and particularly preferably a synthetic fiber nonwoven fabric. Among synthetic fiber nonwoven fabrics, those having a fiber diameter of 1 μm to 20 μm and a basis weight (weight per unit area) of 5 to 80 g / m ² are preferably used. The fiber diameter of the synthetic fiber nonwoven fabric is preferably 20 μm or less from the viewpoint of bleed resistance (resistance to oozing of the foamable resin composition) and adhesiveness, and when the fiber diameter is smaller than 1 μm, the nonwoven fabric is produced. This process becomes extremely complicated and is not preferable.

Further, if the basis weight of the synthetic fiber nonwoven fabric is smaller than 5 g / m ² , the bleed resistance is inferior, and this is not preferable. If it exceeds 80 g / m ² , the nonwoven fabric is expensive, which is also economical. It is not preferable, More preferably, it is 15-80 g / m < ² >.

  Incidentally, the fiber diameter of the synthetic fiber nonwoven fabric is obtained by taking a 500 times magnified photograph of the face material using a scanning electron microscope, and from the shallower depth of focus, that is, from the surface side of the photograph, the average diameter per 10 fibers. To evaluate. The measurement conditions of the scanning electron microscope are Hitachi Electron Microscope S-800, the acceleration voltage is 20 kilovolts, and the sample pretreatment is gold sputtering for 3 minutes under a current condition of 15 mA.

  Although it does not specifically limit as a synthetic fiber nonwoven fabric used for this invention, Raw materials, such as polyester, a polypropylene, polyamide, are preferable, and the nonwoven fabric made from a polyester or a polypropylene is used suitably from the physical property side.

  The phenol resin which is a resin raw material in the present invention is heated in a temperature range of 40 to 100 ° C. using phenol and formaldehyde as raw materials and an alkali metal hydroxide or alkaline earth metal hydroxide as a catalyst, respectively, by a known method. And polymerized. The starting molar ratio of phenols to aldehydes of the resol type phenolic resin used in the present invention is preferably 1: 1 to 1: 4, more preferably 1: 1.5 to 1: 2.0. . Various kinds of modifiers such as urea, amines, amides, epoxy compounds, monosaccharides, starches, poval resins, polyvinyl alcohol resins, and lactones may be added to the resol type phenol resin. The resol type phenol resin is used with an appropriate viscosity by adjusting the water content.

  Examples of the blowing agent include blowing agents having a boiling point in the range of −30 to 100 ° C. such as water, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, petroleum ether, and cyclopentane, diene. Cycloaliphatic hydrocarbons such as chlorohexane, methyl chloride, methylene chloride, ethyl chloride, 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, 1-chloro-1,1-difluoroethane, 1,1 , 1-trifluoroethane, dichlorodifluoromethane, 1,2-dichlorotetrafluoroethane, halogenated hydrocarbons such as monochlorotrifluoroethane, and mixtures thereof. Further, examples of the gaseous foaming agent include gases such as carbon dioxide, air, and nitrogen.

  In particular, flammable foaming agents such as non-halogen aliphatic hydrocarbons, cycloaliphatic hydrocarbons, ethers and the like are essential components, and non-halogen carbon dioxide, nitrogen, When air, helium, argon, or the like is mixed, it is preferable because the influence on the environment is small and the heat insulation performance can be improved. These foaming agents may be used alone, or two or more foaming agents may be mixed and used.

  As the curing catalyst, acidic compounds such as inorganic acids and organic acids are used. Aromatic sulfonic acids such as toluenesulfonic acid, xylenesulfonic acid and phenolsulfonic acid are preferably used. As a curing aid, resorcinol, cresol, o-methylolphenol, p-methylolphenol or the like can be added. Furthermore, a curing catalyst and a curing aid can be diluted with a solvent such as diethylene glycol.

  As a blending example of the foamable resin composition used in the present invention, it is desirable to add 3 to 40 parts by weight, preferably 5 to 30 parts by weight of the above-mentioned curing catalyst with respect to 100 parts by weight of the raw material phenol resin. When the amount of catalyst is less than 3 parts by weight, the foam is not sufficiently cured, and the closed cell ratio and mechanical strength are inferior, which is not preferable, and the amount of catalyst exceeds 40 parts by weight. Then, the physical properties of the foam are also inferior, which is not preferable.

  In the foamable resin composition, a surfactant generally used for producing a phenol resin foam is used for foam control, and among them, a nonionic surfactant is effective. For example, a copolymer of ethylene oxide and propylene oxide, a condensate of an alkylene oxide and an alkylphenol such as nonylphenol or dodecylphenol, and the like can be given. These surfactants may be used alone or in combination. Although there is no restriction | limiting in particular also about the usage-amount, It adds and uses it in 0.5-10 weight part with respect to 100 weight part (resin part except a moisture content) of phenol resin. If the addition amount of the surfactant is less than 0.5 parts by weight, the effect of the surfactant is not sufficient, there is a problem that the closed cell ratio is low and the mechanical strength is inferior, and the amount exceeds 10 parts by weight. Even if added, the effect of the surfactant is not improved so much, which is not preferable because it is economically disadvantageous, or the foam is softened and the mechanical strength becomes insufficient. Preferably it is 1-5 weight part.

If the density of the flame retardant phenolic resin foam laminate of the present invention is too small, the mechanical strength such as compressive strength tends to be small, and it tends to be damaged during handling, and if it is too large, the heat insulation performance tends to decrease. For this reason, 10-150 kg / m < ³ > is preferable and the density of a foam is more preferable 15-100 kg / m < ³ >.

  In addition, if the closed cell ratio of the foam of the flame retardant phenolic resin foam laminate of the present invention is too small, the flammable foaming agent contained in the foam is likely to be dissipated from the surface during combustion, and the flame retardancy tends to deteriorate. At the same time, the thermal insulation performance tends to decrease with time. For this reason, the closed cell ratio of the foam is preferably 60% or more, more preferably 80% or more, and particularly preferably 90% or more and 100% or less.

  In addition, if the thermal conductivity of the foam is too high, the speed at which heat is transmitted to the inside of the foam laminate is high at the time of combustion, and the combustible foaming agent contained therein is easily dissipated from the surface at the time of combustion, and the flame retardancy is poor. Therefore, it is preferably 0.036 W / (m · K) or less, more preferably 0.028 W / (m · K) or less, and desirably 0.022 W / (m · K) or less.

  In the present invention, the coating solution in which the flame retardant applied to the face material is dissolved is obtained by dissolving a water-soluble phosphorus-based flame retardant.

  The water-soluble phosphorus-based flame retardant used in the present invention is a phosphorus-based flame retardant that is 30% by weight or more soluble in water at 20 ° C. in view of the stability of the coating liquid and uniform coating properties. Examples thereof include guanidine phosphate derivatives, carbamate phosphate derivatives, and ammonium phosphate, and these compounds can be used alone or in admixture of two or more. In particular, a guanidine phosphate derivative and a carbamate phosphate phosphate are particularly preferable because they have little moisture adsorption on the surface of the phenol resin foam laminate and high flame retardancy even under high humidity. Therefore, in the present invention, it is preferable to use one kind of a guanidine phosphate derivative or a carbamate phosphate derivative, or a mixture of two or more kinds.

In the present invention, the amount of the phosphorus-based flame retardant present in the surface of the face material of the phenolic resin foam laminate and the face material is insufficient if the amount is too small, and if it is too large, the amount of the flame retardant is practical including the appearance. In order to impair the characteristics, 1 to 40 g / m ² is preferable per unit area of the face material, more preferably ² to 30 g / m ² , and still more preferably 3 to 20 g / m ² .

  Moreover, as other flame retardants, for example, sulfamic acid flame retardants, boric acid flame retardants, halogen flame retardants, metal hydroxides, metal compounds such as metal oxides, and the like may be used in combination.

  In the present invention, when the coating liquid is applied by a post-coating method, a formaldehyde scavenger is added to the coating liquid.

  The formaldehyde scavenger used in the present invention can capture formaldehyde efficiently in a small amount, does not deteriorate the appearance even when applied, and the stability of the aqueous solution is not limited to an aqueous solution containing a phosphorus flame retardant. It is a compound that reacts with formaldehyde because it is high, for example, a compound having an amino group in the molecule, a compound having an amide group, a compound having an imide group, a compound having an imino group, a compound having a hydrazide group, an azine group And compounds having an azole group. These formaldehyde scavengers may be used alone or in combination of two or more. A compound having an amino group in the molecule, a compound having an amide group, a compound having an imide group, a compound having an imino group, or a compound having a hydrazide group is preferable because of availability and price.

  Examples of the compound containing an amino group include amine polymers having a double bond and derivatives thereof, amine copolymers having a double bond and derivatives thereof, polyamines and derivatives thereof, amino acids such as arginine, guanidine and guanidine derivatives, Examples include melamine derivatives. Examples of the compound containing an amide group include amide polymers having a double bond and derivatives thereof, amide copolymers having a double bond and derivatives thereof, urea and urea derivatives, dicyanodiamide and dicyanodiamide derivatives, semicarbazide and Semicarbazide derivatives, barbituric acid, and the like. Examples of the compound having an imide group include a polymer of an imide compound having a double bond and a derivative thereof, a copolymer of an imide compound having a double bond and a derivative thereof, succinimide, glutarimide, and phthalimide. Further, the compound having an imino group includes a polymer of an imine compound having a double bond and a derivative thereof, a copolymer of an imine compound having a double bond and a derivative thereof, an imidazole and an imidazole derivative, a pyrazole and a pyrazole derivative, and a tetrazole. And tetrazole derivatives. Examples of the compound having a hydrazine group include hydrazine salt compounds, alkyl hydrazines, phenyl hydrazines, and phenyl hydrazine derivatives. Examples of the compound having a hydrazide group include carboxylic acid hydrazides such as salicylic acid hydrazide and adipic acid dihydrazide.

  Among these compounds that react with formaldehyde, those having low solubility in water are difficult to absorb moisture on the surface of the flame retardant phenolic resin foam laminate even under high humidity, and the adhesion of the airtight tape is reduced. For this reason, a compound having a solubility in water at 20 ° C. of 100 g or less per 100 g of water is more preferred, and a compound having a solubility of 30 g or less per 100 g of water is particularly preferred. The formaldehyde scavenger is dissolved or finely dispersed in an aqueous solution together with the phosphorus-based flame retardant and the organic polymer compound described below, but even a water-insoluble compound is finely dispersed in water to form a foamed phenolic resin. It is possible to apply uniformly to the face material surface of the body laminate.

  In the case where a phosphorus-based flame retardant is attached to the face material in advance by the pre-coating method, and the formaldehyde scavenger is separately attached to the face material of the laminate after foaming, the formaldehyde scavenger listed above In the case of being water-soluble, a scavenger solution may be prepared by applying an aqueous solution, and if insoluble in water, it may be dispersed in water.

If the amount of formaldehyde scavenger flame retardant phenolic resin foam laminate on the surface of the face material and the face material is too small, formaldehyde scavenger will be described later. Although not as high as the organic polymer compound, the flame retardancy tends to be lowered and the appearance is slightly deteriorated. Therefore, 0.05 to 20 g / m ² per unit area of the face material is preferable, and 0.1 10 to 10 g / m ² is more preferable, and 0.2 to 5 g / m ² is particularly preferable.

  Furthermore, the amount of the formaldehyde scavenger used in the present invention sufficiently exhibits the formaldehyde scavenging effect, and the formaldehyde scavenger tends to lower the flame retardancy. Since it is easy to do, it is 0.5-300 weight part with respect to 100 weight part of phosphorus flame retardants, Preferably it is 1-200 weight part, More preferably, it is 1.5-100 weight part.

  The organic polymer compound that is hardly soluble in water after drying by heating, used in the present invention, can be dissolved or finely dispersed in water at 60 ° C. or higher, and becomes highly insoluble in water at 50 ° C. or lower after heating and drying. It is a molecular compound or an organic polymer compound that is sparingly soluble in water both before and after heating and drying.

  In the present invention, a coating liquid in which the organic polymer compound is dissolved or finely dispersed is applied to the face material, and then heated and dried to adhere the organic polymer compound to the face material. The organic polymer compound adhering to the face material is hardly soluble in water.

  Specifically, examples of the aqueous solution in which the organic polymer compound is dissolved or finely dispersed in water include various latexes and aqueous solutions of polyvinyl alcohol. These can be used alone or in admixture of two or more. Examples of the latex include natural rubber latex, synthetic rubber latex, acrylic latex, vinyl acetate latex, and vinylidene chloride latex. Further, latex and an aqueous solution of polyvinyl alcohol having a saponification degree of 85 mol% or more are preferable because the surface of the phenolic resin foam laminate is difficult to be wet even under high humidity, and in particular, polyvinyl alcohol having a saponification degree of 95 mol% or more. This aqueous solution is particularly preferable because the surface of the phenolic resin foam laminate can easily be kept dry even under high humidity, and can be easily washed with hot water when the coating equipment is soiled with the coating solution.

  In the present invention, an organic polymer compound that is sparingly soluble in water after heat-drying is used in combination with the phosphorus-based flame retardant according to the present invention, so that a film made of an organic polymer is formed on the surface of the face material. Since the flame retardant is partially encapsulated in the coating or is unevenly distributed on the surface layer portion of the coating, moisture adsorption on the surface of the phenolic resin foam laminate can be reduced even under high humidity. However, if the amount of the organic polymer compound is too small, a sufficient film cannot be formed, and the effect of suppressing moisture adsorption cannot be seen. If the amount is too large, the organic polymer compound itself is a flammable material, resulting in a decrease in flame retardancy. When using organic polymer compounds that are difficult to dissolve in water after drying because the organic polymer compounds may gel due to the effects of flame retardants, etc. Is preferably 2 to 250 parts by weight, more preferably 5 to 175 parts by weight, and particularly preferably 10 to 100 parts by weight with respect to 100 parts by weight of the flame retardant.

  Furthermore, the total amount of the formaldehyde scavenger and the organic polymer compound used in the present invention exhibits the effect of suppressing moisture adsorption by the organic polymer compound and the effect of capturing formaldehyde sufficiently, and the organic polymer compound and formaldehyde are also used. When the amount of the organic polymer compound is too large, the flame retardant effect is likely to be lowered, so that 2.5 to 350 parts by weight is preferable with respect to 100 parts by weight of the phosphorus-based flame retardant, and 7 to 250 parts by weight is more preferable. -150 parts by weight are particularly preferred.

  In the present invention, a coating solution in which the phosphorus flame retardant is dissolved is prepared, the coating solution is applied to a face material, and is heated and dried. More preferably, a coating liquid obtained by mixing the above-described aqueous solution in which the phosphorus-based flame retardant is dissolved with the aqueous solution in which the organic polymer compound that is hardly soluble in water after heating and drying is mixed or dissolved is used as a face material. Apply and heat dry.

  In the present invention, the coating liquid containing a phosphorus-based flame retardant, in addition to the above components, various additives as necessary, such as preservatives, thickeners, dispersants, penetrants, colorants, Anti-sagging agents, plasticizers, UV absorbers, antioxidants, antifoaming agents, extenders, polyhydric alcohols such as mono-, di- and tripentaerythritol, surfactants, etc. May be added.

  The method of applying the coating liquid to the face material can be applied by a generally used method. For example, brush coating, roller brush coating, spray coating, roll coating, impregnation coating, curtain flow coating, etc. are generally used methods. Select the appropriate coating method according to the viscosity of the coating liquid, the concentration and coating amount of each component, and the coating speed, and then evaporate the moisture in the heating and drying process to obtain a phosphorus flame retardant, formaldehyde scavenger, etc. Adhere to the face material.

  By changing the type and concentration of each component contained in the coating liquid applied to the face material and changing the coating amount, the components, component ratio, and application amount applied to the face material are changed, and the intended flame retardant, etc. A face material having a component, a component ratio, and an adhesion amount can be produced. In industrial manufacturing, a coating solution is applied to a face material with an automatic coating machine, dried continuously in a drying facility, and a target amount of a phosphorus-based flame retardant is adhered to the surface of the face material and the face material. Is preferred.

  In the pre-coating method, the type and concentration of formaldehyde scavenger adhering to the face material can be changed by changing the type, concentration and amount of formaldehyde scavenger contained in the scavenger liquid in which formaldehyde scavenger is dispersed or dissolved. Can be changed. Further, the scavenger liquid can be applied using the same application method as the above coating liquid, and can be applied by hand coating, etc. After applying, it may be dried with a dryer.

  In the present invention, it is preferable to use a face material in which the phosphorus-based flame retardant is present on the surface and the face material on both sides of the laminated plate. However, a steel sheet is bonded to one side by post-processing, or a cement layer is provided on one side. In the case where high flame retardancy is required only on one side, such as attaching, a face material that does not contain the phosphorus-based flame retardant according to the present invention may be used on that side. As described above, when a laminated board in which the phosphorus-based flame retardant is attached only to one face material is manufactured by the pre-coating method, the face material for discharging the foamable resin composition, and the face material for covering the composition. It does not matter which of the coating liquid is applied.

  Next, the present invention will be specifically described with reference to Examples and Comparative Examples.

  The properties of the phenolic resin foam laminates in the examples and comparative examples were measured and evaluated as follows.

(1) Density of flame retardant phenolic resin foam laminate (JIS K 7222 compliant method)
From the phenol resin foam laminate, the mass and volume of a 20 cm square size cut in the full thickness direction with the face material attached were measured, and the density of the phenol resin foam was calculated from the mass and volume.

(2) Closed cell ratio (according to ASTM-D-2856)
The flame-retardant phenolic resin foam laminate is divided into 3 parts in both the vertical and horizontal directions, and a sample is cut out from the center of each divided area to a size of 20 mm x 20 mm x thickness 25 mm. Peel off and use an air pycnometer (Tokyo Science Co., Ltd., trade name "MODEL1000") to measure the volume of the closed cell part excluding the open cell part, and obtain the closed cell rate by the following formula. Was defined as the closed cell ratio of the foam. When the thickness was less than 25 mm, the original thickness was maintained, and the face material was peeled off for measurement.

Closed cell ratio (%) = {closed cell volume (cm ³ ) / apparent volume of phenol resin foam (cm ³ )} × 100

(3) Thermal conductivity of phenolic resin foam (JIS A 1412-2 compliant method)
A flame retardant phenolic resin foam laminate is cut to a uniform thickness of 300 mm x 300 mm and a thickness of 20 to 25 mm, and the face material is peeled off so as not to damage the foamed part. Using a measuring device (Hideki Seiki Co., Ltd., trade name “HC-074 / 304”), it was sandwiched between a heating plate adjusted to 33 ° C. and a cooling heating plate adjusted to 13 ° C. Measurement was performed at an average specimen temperature of 23 ° C. In addition, when the thickness was less than 20 mm, a plurality of sheets were stacked and measured so as to have a uniform thickness of 20 to 25 mm.

(4) Flame retardancy (JIS K 6911-1955 compliant law)
In accordance with the JIS K 6911 flame resistance method of 5.24.1A, the test piece is cut into a thickness of 10 ± 0.5 mm including the face material from the surface layer of the sample, and 15 mm, 20 mm and 25 mm from the end (free end). The test was carried out with a marked line attached to the surface having the face material as the lower surface. The test piece is five pieces, and when the results do not match, the best result and the worst result are excluded, and the evaluation is made with three pieces. When the results of the three pieces did not match, the result of burning the most among the three pieces was taken as the evaluation result.

Evaluation was performed according to the following criteria.
A: The flame is removed, the fire is extinguished within 1 second, and the combustion distance is 15 mm or less. A: The flame is removed, the fire is extinguished within 1 second, and the combustion distance exceeds 15 mm and is 20 mm or less. Δ: The flame is removed, 1 Fire extinguishing within 2 seconds, and combustion distance exceeds 20 mm and 25 mm or less ×: Combustion distance exceeds 25 mm or continues to burn for more than 1 second after removing the flame

(5) Formalin emission rate: (JIS A 1901-2003 compliant method)
The formaldehyde emission rate of the flame retardant phenolic resin foam laminate was determined according to the JIS A 1901 small chamber 20L method.

The test piece is cut into a dimension of 165 × 165 mm square with face materials on both sides, leaving 147 × 147 mm on both front and back surfaces, and the cut surface and the outer periphery of the test piece are sealed with aluminum tape, with an exposed area of approximately 0.044 m ^2. Prepared to be. The ventilation frequency is set to 0.5 times / hr, and 10 L of air discharged from the container is collected on the 7th day by a collection tube (GL Science, trade name “GL-Pak mini AERO DNPH”). Collected, extracted formalin with acetonitrile, analyzed by high performance liquid chromatograph at a detection wavelength of 360 nm, measured formalin emission rate, and evaluated according to the following criteria.

A: 3 μg / (m ² · h) or less ○: 3 μg / (m ² · h) to 5 μg / (m ² · h) or less Δ: 5 μg / (m ² · h) to 10 μg / (m Less than ² · h) ×: 10 μg / (m ² · h) or more

(6) Appearance An evaluation was made as to whether or not a phenomenon of reducing the commercial value such as a feeling of roughness or powder falling occurred on the surface by using a face material coated with a coating liquid in which a flame retardant was dispersed.

  The phenol resin foam laminate using the face material not coated with the coating liquid was compared with the flame retardant phenolic resin foam laminate using the coated face material, and evaluated according to the following criteria. About the example, it evaluated about what applied the coating liquid of the comparative example to the face material of the phenol resin foam laminated board using the face material which has not apply | coated the coating liquid.

A: There is no difference in appearance and touch between the flame retardant coated product and the flame retardant non-coated product.
○: When comparing the flame retardant coated product and the flame retardant non-coated product side by side, there is a slight difference in surface roughness, but when viewed separately, the difference is not apparent.
(Triangle | delta): A flame retardant coated product has a slightly rough feeling in a touch compared with a flame retardant uncoated product, or some powder fall is seen.
X: A clear difference is observed between the flame retardant coated product and the flame retardant non-coated product in both appearance and touch, and the flame retardant coated product has a clear roughness or powder fall off.

  The phenol resin and polyvinyl alcohol aqueous solution used in the following examples and comparative examples were prepared as follows.

<Synthesis of phenolic resin>
The reactor was charged with 5,000 g of 37% by weight formaldehyde (Wako Pure Chemical Industries, reagent special grade) and 3,000 g of 99% phenol (Wako Pure Chemical Industries, reagent special grade) and stirred with a propeller rotary stirrer, and a temperature controller. The temperature inside the reactor was adjusted to 40 ° C. Next, 60 g of a 50 wt% aqueous sodium hydroxide solution was added and the reaction mixture was raised from 40 ° C. to 85 ° C. and held for 110 minutes. Thereafter, the reaction solution was cooled to 5 ° C. This was designated as phenol resin A.

  On the other hand, 1,080 g of 37 wt% formaldehyde, 1,000 g of water and 78 g of 50 wt% aqueous sodium hydroxide were added to another reactor, and 1,600 g of urea (Wako Pure Chemical Industries, reagent special grade) was charged, propeller rotating type The temperature inside the reactor was adjusted to 40 ° C. using a temperature controller. Subsequently, the reaction liquid was raised from 40 ° C. to 70 ° C. and held for 60 minutes. This was methylolurea U. Next, 1,350 g of methylol urea U was mixed with 8,060 g of phenol resin A, and the liquid temperature was raised to 60 ° C. and held for 1 hour. Next, the reaction solution was cooled to 30 ° C., and the pH was neutralized to 6 with a 50 wt% aqueous solution of paratoluenesulfonic acid monohydrate. When this reaction solution was dehydrated at 60 ° C. and the viscosity and water content were measured, the viscosity at 40 ° C. was 5,700 mPa · s, and the water content was 5% by weight. This was designated as phenol resin AU-1.

  Next, except having changed the dehydration time at 60 degreeC, it carried out similarly to phenol resin AU-1, and obtained phenol resin AU-2. The viscosity at 40 ° C. of the phenol resin AU-2 was 1,000 mPa · s, and the water content was 9% by weight.

<Preparation of aqueous polyvinyl alcohol solution>
Polyvinyl alcohol aqueous solution-1: 1900 parts by weight of purified water was added to 100 parts by weight of fully saponified polyvinyl alcohol (Nippon Vinegar Poval, trade name “JF-17”, saponification degree 98-99 mol%). The mixture was stirred with a propeller rotary stirrer and held at 23 ° C. for 30 minutes, then heated to 95 ° C. at a rate of 1 ° C./min and held at 95 ° C. for 60 minutes to dissolve polyvinyl alcohol. Then, it cooled to room temperature and prepared polyvinyl alcohol aqueous solution-1 (henceforth "PVA-1").

  Polyvinyl alcohol aqueous solution-2: 900 parts by weight of purified water was added to 100 parts by weight of completely saponified polyvinyl alcohol (Nippon Vinegar Poval, trade name “JF-05”, saponification degree 98 to 99 mol%). Except for the above, a polyvinyl alcohol aqueous solution-2 (hereinafter abbreviated as “PVA-2”) was prepared in the same manner as in the polyvinyl alcohol aqueous solution-1.

<Production of phenolic resin foam laminate>
[Phenolic resin foam laminate-1]
Phenolic resin AU-1: 100 parts by weight of ethylene oxide-propylene oxide block copolymer (BASF, trade name “Pluronic F127”) as a surfactant was mixed at a ratio of 4 parts by weight. Next, with respect to 100 parts by weight of phenol resin, 8 parts by weight of normal pentane as a blowing agent, 80% by weight of xylene sulfonic acid (Taika Corporation, trade name “Taikatox 110”) and 20% by weight of diethylene glycol as a curing catalyst. 10 parts by weight of the mixture was continuously fed to a pin mixer whose temperature was adjusted to 15 ° C. and stirred uniformly. It is designed so that moisture generated during the curing reaction can be released to the outside, and a polyester nonwoven fabric (Asahi Kasei Fibers Co., Ltd., trade name “Spunbond E01040”) is pasted on the inside as a face material in a thickness of 25 mm × 400 mm × 400 mm Pour 110 g of the mixture coming out of the mixer into a mold and hold it in an oven at 80 ° C. for 2 hours to hold a phenolic resin foam laminate -1 (hereinafter referred to as “laminate” —25 mm thick, 400 mm long and 400 mm wide). 1 ”).

[Phenolic resin foam laminate-2]
A phenol resin foam laminate 2 (hereinafter abbreviated as “laminate 2”) was produced in the same manner as laminate 1 except that the foaming conditions were 95 ° C. for 2 hours.

[Phenolic resin foam laminate-3]
A phenol resin foam laminate-3 (hereinafter abbreviated as “laminate-3”) is used in the same manner as the laminate-1 except that the phenolic resin A-U-2 is used and the foaming condition is 95 ° C. for 2 hours. ) Was produced.

( Reference Example 1)
40% aqueous solution of carbamate phosphate (Daikyo Chemical Co., Ltd., trade name “Bicol TP”) (hereinafter abbreviated as “Bicol TP”): 100 parts by weight, purified water: 300 parts by weight, aqueous solution containing 6% by weight of formaldehyde scavenger (Miki RIKEN Co., Ltd., trade name “RIKEN RESIN FC-8G”) (hereinafter abbreviated as “FC-8G”): 35.6 parts by weight were sufficiently mixed to prepare a coating solution.

The coating liquid is applied to one side having the face material of Laminate-3 with a 16.34 g / m ² brush per unit area, and then dried for 2 minutes with a 120 ° C. dryer to obtain a solid content of 1.58 g / unit area. m ² was adhered to the face material. The coating liquid was similarly applied to the surface having the other face material of the laminate and dried to obtain a flame retardant phenolic resin foam laminate (hereinafter abbreviated as “flame retardant laminate”).

  The obtained flame-retardant laminate was evaluated for density, closed cell ratio, thermal conductivity, flame retardancy, formalin diffusion rate, and appearance. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 2)
Bicol TP: 100 parts by weight, FC-8G: 160 parts by weight, PVA-1: 96 parts by weight are sufficiently mixed to prepare a coating solution, and coating is performed on each surface having the face material of laminate-1 solution was 22.3 g / m ² coating and drying per unit area, except for a unit area per solid content 3.4 g / m ² was attached to each surface material, a flame燃積layer plate in the same manner as in reference example 1 Obtained and evaluated. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 3)
Bicol TP: 100 parts by weight, aqueous solution containing 28% by weight of formaldehyde scavenger (Miki Riken Co., Ltd., trade name “Riken Resin FC-478”) (hereinafter abbreviated as “FC-478”): 400 parts by weight, PVA-1: 320 parts by weight are sufficiently mixed to prepare a coating liquid, and 51.3 g / m ^{2 of the} coating liquid is applied to each surface having the face material of the laminate 2 and dried per unit area. A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that 10.5 g / m ^{2 of} solid content was adhered to each face material. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

Example 4
47% aqueous solution of guanidine phosphate derivative (Daikyo Chemical Co., Ltd., trade name “Bicol No. 415”) (hereinafter abbreviated as “Bicol 415”): 100 parts by weight, purified water: 100 parts by weight, FC-8G: 118 parts by weight Part, acrylic latex (Asahi Kasei Chemicals Co., Ltd., trade name “Polytron E-390M”, solid content concentration 50%) (hereinafter abbreviated as “latex 390M”)): 23.5 parts by weight are thoroughly mixed, and the coating solution is prepared. prepared, the surface of each with a surface material laminate -1, coating liquid 29.1 g / m ² coating and drying per unit area, solid per unit area fraction 5.6 g / m ² of each surface member A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that it was adhered to the substrate. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 5)
Bicol 415: 100 parts by weight, FC-8G: 391.7 parts by weight, PVA-2: 235 parts by weight, latex 390M: 35.3 parts by weight are sufficiently mixed to prepare a coating solution. On each surface having the face material, 64.9 g of the coating solution was applied for 4 minutes with a drying time of 2 times, and was applied and dried twice to apply 129.8 g / m ² per unit area. A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that 0 g / m ² was adhered to each face material. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 6)
Bicol TP: 100 parts by weight, FC-8G: 44.4 parts by weight, PVA-1: 53.3 parts by weight, latex 390M: 16 parts by weight are sufficiently mixed to prepare a coating solution. in each face having a face material, repeatedly coated and dried twice coating Solution 40.5 g, and 81.0 g / m ² coated per unit area, the solid per unit area fraction 20.0 g / m ² each A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that it was attached to a face material. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 7)
Bicol TP: 100 parts by weight, FC-8G: 38.0 parts by weight, latex 390M: 6.8 parts by weight are sufficiently mixed to prepare a coating liquid, and each surface having the face material of laminate-1 is prepared. , to minutes 4 the coating Composition 63.4g dry time, repeated twice coated and dried, and 126.8g / m ² coated per unit area, each side member of the unit area per solid content 40.0 g / m ² A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that it was adhered to the substrate. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 8)
Bicol TP: 100 parts by weight, purified water: 300 parts by weight, latex 390M: 5.3 parts by weight were sufficiently mixed to prepare a coating solution.

A coating liquid is applied to a polyester non-woven fabric (Asahi Kasei Fibers Co., Ltd., trade name “Spunbond E01040”, hereinafter abbreviated as “surface material 1040”) with 15.2 g / m ² brush per unit area, followed by drying at 120 ° C. And dried for 2 minutes to adhere 1.6 g / m ^{2 of} solid content per unit area to the face material. The face material was affixed to the inside of a 25 mm × 400 mm × 400 mm thick mold designed to release moisture generated during the curing reaction to prepare a foaming mold.

  Phenolic resin AU-1: 100 parts by weight of ethylene oxide-propylene oxide block copolymer (BASF, trade name “Pluronic F127”) as a surfactant was mixed at a ratio of 4 parts by weight. Next, with respect to 100 parts by weight of phenol resin, 8 parts by weight of normal pentane as a blowing agent, 80% by weight of xylene sulfonic acid (Taika Corporation, trade name “Taikatox 110”) and 20% by weight of diethylene glycol as a curing catalyst. 10 parts by weight of the mixture is continuously supplied to a pin mixer adjusted to 15 ° C. and stirred uniformly, 110 g of the mixture coming out of the mixer is poured into the prepared foaming mold, and 2 parts are put into an 80 ° C. oven. Holding for a time, a phenol resin foam laminate (flame retardant laminate) having a thickness of 25 mm, a length of 400 mm, and a width of 400 mm was obtained.

Further, 100-8 parts by weight of FC-8G and 100 parts by weight of purified water are sufficiently mixed to prepare a scavenger liquid, and the scavenger liquid per unit area is formed on one surface having the face material of the obtained flame-retardant laminate. After applying with 26.7 g / m ² brush, it was dried for 2 minutes with a 120 ° C. drier to adhere 0.8 g / m ² of the scavenger solid content per unit area to the face material. In the same manner, a scavenger was adhered to the surface having the other face material of the flame retardant laminate.

The obtained flame retardant laminate was evaluated in the same manner as in Reference Example 1. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

Example 9
A coating liquid is prepared using 100 parts by weight of Bicol TP and 160 parts by weight of PVA-1, and 32.5 g / m ^{2 is} applied to the face material 1040 and dried to obtain a solid content of 6 g / m ² per unit area. A flame retardant laminate was obtained in the same manner as in Example 8 except that it was adhered to the substrate. Furthermore, using FC-8G as a scavenger liquid, 25.0 g / m ^{2 was} applied and dried on each surface having the face material of the obtained flame-retardant laminate, and the scavenger solid content per unit area was 1.5 g / A laminated board was obtained and evaluated in the same manner as in Example 8 except that m ² was adhered to the face material. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 10)
Bicoal TP: 100 parts by weight, PVA-1: 32 parts by weight, latex 390M: 8 parts by weight, a coating solution is prepared, 35.0 g / m ^{2 is} applied to the face material 1040 and dried, and the solid content per unit area A flame retardant laminate was obtained in the same manner as in Example 8 except that 11.4 g / m ² was adhered to the face material. Further, using FC-8G as a scavenger solution, 20 g / m ^{2 is} applied and dried on each surface having the face material of the obtained flame-retardant laminate, and the solid content per unit area is 1.2 g / m ² . A laminated board was obtained and evaluated in the same manner as in Example 8 except that it was adhered to the material. These results are shown in Table 2.

(Comparative Example 1)
Brushes (ESCO Co., Ltd.) in powder form so that sodium bicarbonate (Wako Pure Chemical Industries, reagent special grade) is 30.0 g / m ² per unit area on each face having the face material of Laminate-1 It was imprinted and applied with product number EA928AG-17). The obtained flame retardant laminate was evaluated in the same manner as in Reference Example 1. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Comparative Example 2)
Bicoal TP: 100 parts by weight, purified water: 500 parts by weight, FC-8G: 571 parts by weight are used to prepare a coating solution, and 20.5 g of the coating solution is applied to each surface having the face material of Laminate-1. A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that / m ² was applied and dried, and a solid content of 1.3 g / m ² per unit area was adhered to each face material. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Comparative Example 3)
Bicoal TP: 100 parts by weight, FC-8G: 8 parts by weight, a coating solution was prepared, and 67.5 g of the coating solution was applied to each surface having the face material of Laminate-1 for a drying time of 4 minutes. repeated twice coated and dried, and 135.0 g / m ² coated per unit area, except for a unit area per solid content 50.6 g / m ² was attached to each side member is, in the same manner as in reference example 1 A flame retardant laminate was obtained and evaluated. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Comparative Example 4)
Bicoal TP: 100 parts by weight, FC-8G: 2.67 parts by weight, PVA-1: 120 parts by weight were used to prepare a coating solution. A laminate was obtained and evaluated in the same manner as in Reference Example 1 except that 55.67 g / m ² was applied and dried, and a solid content of 11.54 g / m ² per unit area was adhered to each face material. . The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Comparative Example 5)
Bicoal TP: 100 parts by weight, FC-478: 1428.6 parts by weight, latex 390M: 96 parts by weight, a coating solution was prepared, and the coating solution 50 was applied to each surface having the face material of Laminate-1. the to minutes 4 drying time .8G, except that repeatedly applying and drying twice, 101.6 g / m ² coated per unit area was deposited solid per unit area fraction 30.5 g / m ² on each side member Were obtained in the same manner as in Reference Example 1 and evaluated. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

  The flame-retardant phenolic resin foam laminate of the present invention is used as a heat insulating material for buildings, a heat insulating material for vehicles, a heat insulating material for equipment, and the like.

Claims (7)

A phenolic resin foam laminate comprising a phenolic resin foam sandwiched between two face materials, wherein a water-soluble phosphorus-based flame retardant is present on the surface of the at least one face material and in the face material. per unit area 1 to 40 g / m ² of formaldehyde scavenger is present 0.05 to 20 g / ^{m 2} per unit area of said surface material, 0 the formaldehyde scavenger is relative to 100 parts by weight of phosphorus-based flame retardant. 5 to 300 parts by weight der is, in the surface and face material surface member to which the phosphorus-based flame retardants and formaldehyde scavenger is present, further, the organic polymer compound the phosphorus-based flame retardant 100 weight poorly water-soluble The total amount of the formaldehyde scavenger and the organic polymer compound is 2.5 to 350 parts by weight with respect to 100 parts by weight of the phosphorus-based flame retardant. Flame retardant phenolic resin Foam laminate. The flame-retardant phenolic resin foam laminate according to claim 1, wherein the phosphorus-based flame retardant is a mixture of one or more of a phosphate carbamate derivative and a phosphate guanidine derivative.   The flame retardant phenolic resin foam laminate according to claim 1 or 2, wherein the water-insoluble organic polymer compound is one or more of latex and polyvinyl alcohol. The density of the flame retardant phenolic resin foam laminate is 10 to 150 kg / m ³ , the closed cell ratio of the foam is 60% or more, and the thermal conductivity is 0.036 W / (m · K) or less, The flame-retardant phenolic resin foam laminate according to any one of claims 1 to 3, wherein the foam contains a combustible foaming agent. It is a manufacturing method of the flame-retardant phenolic resin foam laminated board in any one of Claims 1-4,
A coating solution obtained by mixing an aqueous solution in which a water-soluble phosphorus-based flame retardant is dissolved in water and an aqueous solution in which an organic polymer compound that is hardly soluble in water after heating and drying is dissolved or finely dispersed is used. It is applied to at least one face material and dried by heating. On one face material, a foamable resin composition comprising at least a phenol resin, a foaming agent and a curing catalyst is discharged, and the foamable resin composition is After the upper surface is coated with the other face material, the foamable resin composition is foamed and cured to form a laminate, and then the formaldehyde scavenger is dispersed or dispersed on at least one of the faces of the laminate having the face material. A method for producing a flame retardant phenolic resin foam laminate, wherein the dissolved scavenger liquid is applied and dried. It is a manufacturing method of the flame-retardant phenolic resin foam laminated board in any one of Claims 1-4,
A foamable resin composition comprising at least a phenol resin, a foaming agent, and a curing catalyst is discharged on the face material, and the upper surface of the foamable resin composition is covered with a new face material, and the foamable resin composition is A foam is cured to form a laminate, and then an aqueous solution in which a formaldehyde scavenger is dispersed or dissolved in water and a water-soluble phosphorus-based flame retardant is dissolved in water, and becomes insoluble in water after drying by heating. A flame retardant phenol, characterized in that a coating liquid obtained by mixing an aqueous solution in which an organic polymer compound is dissolved or finely dispersed is applied to at least one of the surfaces of the laminate having a face material and dried by heating. A method for producing a resin foam laminate. The flame retardant according to claim 5 or 6 , wherein the aqueous solution in which the organic polymer compound that is hardly soluble in water after heat drying is finely dispersed or dissolved is an aqueous solution of acrylic latex or polyvinyl alcohol, or a mixture thereof. A method for producing a phenolic resin foam laminate.