JP5138331B2 - 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.

  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

  As a result of intensive studies to solve the above-mentioned problems, the present inventor used a phosphorus-based flame retardant that is hardly soluble in water and an organic polymer compound that is hardly soluble in water after drying by heating. It has been found that good flame retardancy can be imparted to the phenolic resin foam laminate without impairing practical properties including the above, and has led to the present invention.

  That is, the present invention is as follows.

The first of the present invention is a flame retardant phenolic resin foam laminate comprising a phenolic resin foam sandwiched between two face materials,
Phosphorus flame retardant having a water-solubility and a decomposition temperature of 200 ° C. or higher is 0.5 to 30 g / m ² per unit area of the face material, and a water-insoluble organic polymer compound is 100 weight of the phosphorus flame retardant. 2 to 300 parts by weight with respect to the part, and is present in the surface of the face material and in the face material.

In the flame retardant phenolic resin foam laminate of the present invention,
The density of the flame retardant phenolic resin foam laminate is 10 to 150 kg / m ³ or less, the foam has a self-efficacy of 60% or more, and a thermal conductivity of 0.036 W / (m · K) or less, The foam contains a flammable foaming agent;
The phosphorus flame retardant is ammonium polyphosphate,
Is included as a preferred embodiment.

2nd of this invention is a manufacturing method of the flame-retardant phenolic resin foam laminated board of the said invention, Comprising:
Two coating solutions obtained by dispersing a phosphorus-based flame retardant having a decomposition temperature of 200 ° C. or more in water in an aqueous solution in which a water-insoluble organic polymer compound is finely dispersed or dissolved after heat drying. It is applied to at least one face material and dried by heating. On one face material, a foamable resin composition comprising a phenol resin, a foaming agent, and a curing catalyst is discharged, and the top surface of the foamable resin composition is placed on the other surface. After the coating with the face material, the foamable resin composition is foamed and cured.

3rd of this invention is a manufacturing method of the flame-retardant phenolic resin foam laminated board of the said invention, Comprising:
A foamable resin composition comprising 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, and the foamable resin composition is foamed. After curing
A coating solution obtained by dispersing a phosphorus-based flame retardant having a solubility in water and a decomposition temperature of 200 ° C. or higher in an aqueous solution in which an organic polymer compound hardly soluble in water is finely dispersed or dissolved after heat drying. It is characterized by being applied to at least one of the face materials and heat-dried.

In the method for producing a flame retardant phenolic resin foam laminate of the present invention,
The aqueous solution in which the organic polymer compound hardly soluble in water after the heat drying is finely dispersed or dissolved is an aqueous solution of acrylic latex or polyvinyl alcohol, or a mixture thereof,
Is 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.

  Hereinafter, the present invention will be specifically described.

  The flame retardant phenolic resin foam laminate of the present invention comprises a phenol resin foam sandwiched between two face materials, and a flame retardant and an organic polymer compound adhere to the surface of the face material and the face material. Yes. In the present invention, the flame retardant adheres well to the face material by using an organic polymer compound in combination.

  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 the manufacturing method, a coating liquid in which a flame retardant is dispersed in a face material is applied in advance (pre-coating method), or a coating liquid in which a flame retardant is dispersed after forming a laminate. Is applied to the face material (post-coating method) to impart flame retardancy to the face material. In the present invention, the face material to which the coating 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 0.01 to 3 denier and a basis weight (weight per unit area) of 15 to 80 g / m ² are preferably used. From the viewpoints of bleed resistance and adhesiveness, the synthetic fiber nonwoven fabric preferably has a fiber diameter of 3 denier or less, and if the fiber diameter is smaller than 0.01 denier, the process of manufacturing the nonwoven fabric becomes extremely complicated. It is not preferable. More preferably, it is 0.01-2.5 denier. Further, if the basis weight (weight per unit area) of the synthetic fiber nonwoven fabric is less than 15 g / m ² , the bleed resistance is inferior, which is not preferable. If it exceeds 80 g / m ² , the nonwoven fabric is expensive. After all, it is not preferable from the aspect of economy.

  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 self-efficacy 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 be poor. At the same time, the thermal insulation performance tends to decrease with time. For this reason, the aeration rate 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 liquid in which the flame retardant applied to the face material is dispersed is an aqueous solution in which an organic polymer compound that is sparingly soluble in water after heating and drying is finely dispersed or dissolved in water. A phosphorus flame retardant having a temperature of 200 ° C. or higher is dispersed.

  The phosphorus-based flame retardant used in the present invention is hardly soluble in water and has a decomposition temperature of 200 ° C. or higher. If a flame retardant that is readily soluble in water is used in the phenolic resin foam laminate, the flame retardant tends to adsorb moisture under high humidity, so it tends to get wet, and if the decomposition temperature is too low, the flame retardant effect is low and a large amount It becomes necessary to apply, and properties such as appearance are deteriorated. In addition, a flame retardant that is liquid at room temperature is not preferable because it causes stickiness and easily becomes dirty. Therefore, the phosphorus-based flame retardant used in the present invention has a melting point of 50 ° C. or higher, and the amount of flame retardant dissolved in water when mixed with 100 g of flame retardant per 100 g of water at 20 ° C. is 30 g or less, preferably 10 g or less. A phosphorus compound having a decomposition temperature of 200 to 600 ° C. is preferably used.

  Examples of the phosphorus-based flame retardant used in the present invention include aromatic condensed esters, melamine phosphate, melamine polyphosphate, ammonium polyphosphate, and the like, and these compounds can be used alone or in admixture of two or more. In particular, ammonium polyphosphate is particularly preferable because the surface of the phenolic resin foam laminate hardly adsorbs water even under high humidity and has a high flame retardant effect. Among ammonium polyphosphates, those having a high molecular weight having a degree of polymerization of 500 or more are particularly preferred. The ammonium polyphosphate may be surface-coated with silicone, melamine or the like.

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, 0.5 to 30 g / m ² is preferable per unit area of the face material, more preferably 1 to 15 g / m ² , and still more preferably ² to 8 g / m ² .

  If the particle size of the phosphorus-based flame retardant is too large, it is difficult to apply uniformly, and if it is too small, the face material becomes white and it becomes difficult to see symbols and patterns printed on the face material, or it is scattered during preparation of the coating liquid. Therefore, it is preferably 0.5 to 500 μm, more preferably 2 to 100 μm, and particularly preferably 5 to 50 μm.

  In addition, as other flame retardants, for example, halogen flame retardants, metal hydroxides, metal compounds such as metal oxides, etc. may be used in combination. And metal hydroxides having crystal water such as magnesium hydroxide and aluminum hydroxide which are hardly soluble in water and hardly show deliquescence on the surface of the phenol resin foam laminate.

  The aqueous solution in which an organic polymer compound slightly soluble in water after heating and drying used in the present invention is finely dispersed or dissolved is an aqueous solution in which an organic polymer compound slightly soluble in water before and after heating and drying is finely dispersed, or An aqueous solution in which an organic polymer compound which is easily soluble in water before heat drying and hardly soluble in water after heat drying is dissolved. In the present invention, a coating liquid obtained by dispersing a flame retardant in the aqueous solution is applied to the face material, and then heated and dried to adhere the flame retardant and the organic polymer compound to the face material. The organic polymer compound adhering to the face material is hardly soluble in water.

  Specific examples include various latexes and aqueous solutions of polyvinyl alcohol, and 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, the organic polymer compound that is hardly soluble in water after heat drying tends to be insufficiently fixed if the amount is too small relative to the flame retardant, and if it is too large, the organic polymer compound itself is a combustible material. Since flame retardancy tends to decrease, the amount is preferably 2 to 300 parts by weight, more preferably 5 to 100 parts by weight, and particularly preferably 10 to 50 parts by weight with respect to 100 parts by weight of the flame retardant.

  In the present invention, the above-mentioned phosphorus-based flame retardant is dispersed in an aqueous solution in which an organic polymer compound that is sparingly soluble in water after heat drying is finely dispersed or dissolved, to prepare a coating solution. Apply to face material and heat dry.

  In addition to the above-mentioned components, various additives such as preservatives, thickeners, dispersants, penetrants may be added to the coating liquid containing the phosphorus-based flame retardant and organic polymer compound of the present invention. , Colorants, anti-sagging agents, plasticizers, UV absorbers, antioxidants, antifoaming agents, extenders, polyhydric alcohols such as mono-, di-, tripentaerythritol, surfactants, etc. You may add in the range which does not impair.

  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. Phosphorus flame retardant, organic polymer compound, etc. Is attached 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 production, the coating liquid is applied to the face material with an automatic coating machine, and continuously dried in a drying facility, and the target amount of phosphorus-based flame retardant and organic polymer compound are added to the surface of the face material and in the face material. The method of adhering to is preferable.

  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 flame retardant phenolic resin foam laminate (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.
◎: Remove the flame, extinguish the fire within 1 second, and the combustion distance is 15 mm or less ○: Remove the flame, extinguish the fire within 1 second, and the combustion distance is 20 mm or less Δ: Remove the flame, within 1 second Fire extinguishing and combustion distance is 25 mm or less ×: Combustion distance exceeds 25 mm or continues to burn for more than 1 second after removing the flame

(5) Adhesive strength Evaluation was performed with the adhesiveness of the airtight tape. Air-tight waterproofing with 25mm-thick flame-retardant phenolic resin foam laminate cut to 100mm square, cut to 25mm width and 70mm length, folded 10mm in the longitudinal direction to the adhesive surface side, and adhesive part 50mm in length A single-sided tape (Koyo Chemical Co., Ltd., Ace Cross 011 Black) is attached to the center of the face material on one side of the flame-retardant phenolic resin laminate.

The surface to which the airtight tape is bonded is the lower surface, floated in water, and kept at 23 ° C. for 72 hours. Then, the change of the adhesive force of the airtight tape was evaluated according to the following evaluation criteria.
A: It has a sufficiently strong adhesive force before the test, and no decrease in the adhesive force is observed after the immersion test.
◯: Adhesive strength sufficiently strong before test and slightly lower adhesive strength than before immersion, but strong adhesive strength after immersion test.
(Triangle | delta): Although it has the strong adhesive force before a test, after the immersion test, the fall of the adhesive force is clearly seen compared with before immersion. However, peeling does not occur even if the foam is lifted by holding the end (folded portion) of the airtight tape.
X: Although it has a strong adhesive force before the test, after the immersion test, partial peeling is observed, or peeling occurs when the foam is lifted by holding the end of the airtight tape (folded part). Alternatively, the adhesive force of the airtight tape is already very weak at the time of bonding before the immersion test.

(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 to which the coating liquid was not applied and the flame retardant phenol resin foam laminate using the applied face material were compared and evaluated according to the following criteria. In addition, about the comparative example, 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 was evaluated.
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 the feeling of roughness on the surface, but the difference cannot be seen when viewed separately.
(Triangle | delta): A flame retardant coated product has a slightly rough feeling compared with a flame retardant non-coated product, or a slight 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.

(7) Detergency The maintenance performance of the coating / dryer soiled by the scattered coating liquid during continuous coating of the coating liquid in which the flame retardant was dispersed was evaluated.

  The coating liquid was repeatedly applied and dried on the screw part of a stainless steel bolt (M16 × 1.5, length 70 mm, effective screw length 38 mm, material SUS304), and 2 ± 0.2 g was applied almost uniformly. The drying temperature was the same temperature time as in the examples and comparative examples. Moreover, about the example apply | coated with powder, the application | coating method in an example was repeated, 2 ± 0.2g was apply | coated, and what was not able to apply | coat to a screw part was not evaluated but evaluation was impossible.

Evaluation was made according to the following criteria.
A: The film applied to the screw part swells and peels off after being immersed in warm water of 95 ° C. for 20 minutes, or is immediately immersed in warm water of 40 ° C. after being immersed in warm water of 95 ° C. for 20 minutes, The film coated on the screw part can be easily peeled off by rubbing with a toothbrush (Sunstar Co., Ltd., trade name “Auratsu”).
○: After being immersed in warm water of 95 ° C for 20 minutes, the film applied to the screw part cannot be completely removed by transferring it quickly to warm water of 40 ° C and rubbing with a toothbrush. It can be easily removed by rubbing with EA109DD-3 (hair length: 15 mm).
Δ: Immersed in warm water of 95 ° C. for 20 minutes, quickly transferred to 40 ° C. warm water, and rubbed with a toothbrush, so that the film applied to the screw part is not peeled off, but can be peeled off by rubbing strongly with a brass brush.
X: After immersing in warm water of 95 ° C. for 20 minutes, the film is quickly transferred to 40 ° C. warm water and rubbed strongly with a brass brush to leave a part of the film in the thread.
-: Cannot be applied to the screw part and cannot be evaluated

  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: 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-17”, saponification degree 98 to 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 (it abbreviates as PVA-1 in a following example).

  Polyvinyl alcohol aqueous solution-2: Polyvinyl alcohol aqueous solution-1 except that partially saponified polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd., trade name “KH-17”, saponification degree 78.5-81.5 mol%) was used. In the same manner, an aqueous polyvinyl alcohol solution-2 (abbreviated as PVA-2 in the following examples) was prepared.

<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, a mixture of 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 with respect to 100 parts by weight of a phenol resin. 10 parts by weight were continuously supplied 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, and a phenolic resin foam laminate-1 (hereinafter referred to as laminate-1) having a thickness of 25 mm, a length of 400 mm, and a width of 400 mm Abbreviated).

[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 2 hours at 95 ° C.

[Phenolic resin foam laminate-3]
Phenol resin foam laminate-3 (hereinafter abbreviated as laminate-3) was used in the same manner as laminate-1 except that phenol resin A-U-2 was used and the foaming conditions were 95 ° C. for 2 hours. Produced.

( Reference Example 1)
Ammonium polyphosphate (CBC, trade name “FR CROS484”, degree of polymerization 1000 or more, average particle size (d50) 18 μm) (abbreviated as CROS484 in the following examples): 8 parts by weight, PVA-1: 10 parts by weight, Purified water: 162 parts by weight were sufficiently mixed to prepare a coating solution. In addition, it put into the airtight container so that ammonium polyphosphate fine powder might not settle, and stirring was continued with the rotary stirrer just before application | coating.

After applying the coating liquid to a polyester non-woven fabric (Asahi Kasei Fibers Co., Ltd., trade name “Spunbond E01040”, hereinafter abbreviated as face material 1040) with 18.0 g / m ² brush per unit area, 2 The mixture was dried and a solid content of 0.9 g / m ² per unit area was adhered to the face material. The foam material was prepared by attaching the above face material with a flame retardant attached to the inside of a 25 mm × 400 mm × 400 mm thick mold designed to release moisture generated during the curing reaction to the outside.

  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, 8 parts by weight of normal pentane as a foaming agent and 80% by weight of xylene sulfonic acid (Taika Corporation, trade name “Taikatox 110”) as a curing catalyst and 20% by weight of diethylene glycol with respect to 100 parts by weight of phenol resin 10 parts by weight are continuously supplied to a pin mixer whose temperature is adjusted to 15 ° C. and uniformly stirred, and 110 g of the foamable resin composition that has come out of the mixer is poured into the prepared foaming mold, and the oven at 80 ° C. For 2 hours to obtain a flame-retardant phenolic resin foam laminate (hereinafter abbreviated as flame-retardant laminate) having a thickness of 25 mm, a length of 400 mm, and a width of 400 mm.

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

(Example 2)
CROS 484: 15 parts by weight, PVA-1: 30 parts by weight, purified water: 180 parts by weight, a coating solution is prepared, 22.5 g / m ² per unit area is applied to the face material 1040 and dried, and the unit area A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that a solid content of 1.8 g / m ² was applied to the face material. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 3)
CROS 484: 15 parts by weight, PVA-1: 100 parts by weight, purified water: 115 parts by weight, a coating solution is prepared, 23.0 g / m ² per unit area is applied to the face material 1040 and dried, and the unit area A solid content of 2.5 g / m ² was applied to the face material. A flame-retardant laminate as in Reference Example 1 except that the face material was used, phenol resin AU-2 was used as the phenol resin of the foamable resin composition, and the foaming conditions were 95 ° C. for 2 hours. And evaluated. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

( Reference Example 4)
CROS 484: 15 parts by weight, acrylic latex (Asahi Kasei Chemicals, trade name “Polytron E-390M”, solid content concentration 50%) (abbreviated as latex 390M in the following examples): 72 parts by weight, purified water: 87 parts by weight The coating liquid is prepared using 17.4 g / m ² per unit area and dried on the face material 1040, and a solid content of 5.1 g / m ² per unit area is adhered to each face material, and the foaming conditions are set. A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that the temperature was 95 ° C. for 2 hours. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 5)
CROS 484: 25 parts by weight, PVA-1: 50 parts by weight, purified water: 75 parts by weight, a coating solution is prepared, 15.0 g / m ² per unit area is applied to the face material 1040 and dried, and the unit area A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that a solid content of 3.0 g / m ² was applied to the face material. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 6)
Ammonium polyphosphate surface-treated with silane (CBC, trade name “FR CROS486”, polymerization degree 1000 or more, average particle size (d50) 18 μm): 40 parts by weight, PVA-1: 40 parts by weight, latex 390M: 8 parts by weight Part, purified water: 88 parts by weight of a coating solution is prepared, 17.6 g / m ² per unit area is applied to the face material 1040 and dried, and the solid content is 4.8 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 it was adhered to the substrate. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 7)
CROS 484: 40 parts by weight, PVA-1: 30 parts by weight, latex 390M: 24 parts by weight, purified water: 94 parts by weight, a coating solution is prepared, and 18.8 g / m ² per unit area is applied to the face material 1040. A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that it was applied and dried, and a solid content of 5.5 g / m ² per unit area was adhered to the face material. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 8)
Ammonium polyphosphate coated with melamine resin (CBC, trade name “TERRAJU C-80”, polymerization degree 1000 or more, average particle size (d50) 19 μm): 40 parts by weight, aluminum hydroxide (Sakai Industrial Co., Ltd., trade name “ B-315 "): 20 parts by weight, PVA-1: 150 parts by weight, latex 390M: 10 parts by weight, purified water: 110 parts by weight, and a coating solution is prepared, and the face material 1040 is 33 g / m per unit area. ² was applied and dried, and a flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that a solid content of 8.0 g / m ² per unit area was adhered to the face material. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

Example 9
Ammonium polyphosphate coated with melamine resin (CBC, trade name “FR CROS487”, polymerization degree 1000 or more, average particle size (d50) 18 μm): 70 parts by weight, PVA-1: 600 parts by weight prepared, the 67.0 g / m ² per unit area of the surface material 1040 is applied, except that dried 4 minutes at 120 ° C. dryer unit area per solid content 13 g / m ² is adhered to the surface material, reference In the same manner as in 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.

( Reference Example 10)
CROS 484: 200 parts by weight, PVA-2: 90 parts by weight, purified water: 290 parts by weight, a coating solution was prepared, 58.0 g / m ² per unit area was applied to the face material 1040, and a 120 ° C. dryer. The flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 1 except that the material was dried for 4 minutes and a solid content of 20.9 g / m ² per unit area was adhered to the face material. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

( Reference Example 11)
After applying the coating liquid prepared in Reference Example 1 with 18.0 g / m ² brush per unit area on one side having the face material of Laminate-1, it was dried for 2 minutes with a 120 ° C. drier, per unit area A solid content of 0.9 g / 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. 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 12)
The coating liquid 22.5 g / m ² prepared in Example ² was applied to each surface having the face material of Laminate-1 and dried to obtain a solid content of 1.8 g / m ² per unit area. A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 11 except that the film was attached to. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 13)
In each face having a face plate laminate -3, a coating solution 23.0 g / m ² prepared in Example 3 was coated and dried, each face member unit area per solid content 2.5 g / m ² A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 11 except that the film was attached to. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

( Reference Example 14)
The coating liquid 17.4 g / m ² prepared in Reference Example 4 was applied to each surface having the face material of the laminate 2 and dried to obtain 5.1 g / m ^{2 of} solid content per unit area. A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 11 except that the film was attached to. The configuration is shown in Table 1, and the evaluation results are shown in Table 2. These results are shown in Table 2.

(Example 15)
The coating liquid 15.0 g / m ² prepared in Example 5 was applied to each surface having the face material of Laminate-1 and dried to obtain a solid content of 3.0 g / m ² per unit area. A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 11 except that the film was attached to. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 16)
The coating liquid 17.6 g / m ² prepared in Example 6 was applied to each surface having the face material of Laminate-1 and dried to obtain a solid content of 4.8 g / m ² per unit area. A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 11 except that the film was attached to. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 17)
The coating liquid 18.8 g / m ² prepared in Example 7 was applied to each surface having the face material of Laminate-1 and dried to obtain a solid content of 5.5 g / m ² per unit area. A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 11 except that the film was attached to. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 18)
The coating liquid 33 g / m ² prepared in Example 8 was applied to each surface having the face material of Laminate-1 and dried to adhere 8.0 g / m ^{2 of} solid content per unit area to each face material. A flame retardant laminate was obtained in the same manner as in Reference Example 11 except that the evaluation was performed. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Example 19)
The coating liquid 67.0 g / m ² prepared in Example 9 was applied to each surface having the face material of Laminate-1 and dried for 4 minutes with a 120 ° C. drier. A laminate was obtained and evaluated in the same manner as in Reference Example 11 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.

( Reference Example 20)
The coating liquid 58.0 g / m ² prepared in Reference Example 10 was applied to each surface having the face material of Laminate-1 and dried with a 120 ° C. dryer for 4 minutes to obtain a solid content of 20. A laminate was obtained and evaluated in the same manner as in Reference Example 11 except that 9 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.

(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)
CROS 484: 15 parts by weight, purified water: 115 parts by weight, a coating solution is prepared, and 13.0 g / m ² of the coating solution is applied to each surface having the face material of laminate-2 and dried. A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 11 except that a solid content of 1.5 g / m ² per unit area was adhered to each face material. In addition, the flame retardancy is large compared to the other examples, the burning distance is 1 point for 15 mm or less, the burning distance is over 15 mm, 1 point for 20 mm or less, the burning distance is over 20 mm, 3 points for 25 mm or less Met. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Comparative Example 3)
CROS484: 4 parts by weight, PVA-1: 10 parts by weight, purified water: 196 parts by weight. A coating liquid was prepared, and the coating liquid 21.0 g / A flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 11 except that m ² was applied and dried, and a solid content of 0.5 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 4)
CROS 484: 350 parts by weight, PVA-1: 70 parts by weight, purified water: 210 parts by weight, a coating solution was prepared, and the coating solution 63 g / m ² was applied to each surface having the face material of the laminate 1. A flame retardant laminate was obtained in the same manner as in Reference Example 11, except that the solid content was 35.7 g / m ² per unit area and adhered to each face material. Evaluation was performed. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Comparative Example 5)
CROS 484: 15 parts by weight, PVA-1: 2.5 parts by weight, purified water: 157.5 parts by weight were used to prepare a coating liquid, and the coating liquid was applied to each side having the face material of laminate-1 17.5 g / m ² was coated and dried, except that the unit area per solid 1.525g / m ² was attached to each side member may give to flame燃積layer plate in the same manner as in reference example 11, the evaluation went. The configuration is shown in Table 1, and the evaluation results are shown in Table 2.

(Comparative Example 6)
CROS484: 15 parts by weight, Latex 390M: 110 parts by weight, and purified water 125 parts by weight, a coating solution was prepared, and the coating solution 25.0 g / m ² was applied to each surface having the face material of Laminate-1. Was applied and dried, and a flame retardant laminate was obtained and evaluated in the same manner as in Reference Example 11 except that a solid content of 7.0 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.

  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 flame retardant phenolic resin foam laminate comprising a phenolic resin foam sandwiched between two face materials,
Phosphorus flame retardant having a solubility in water of 200 ° C. or higher and a particle size of 2 to 100 μm is 1 to 15 g / m ² per unit area of the face material, and an organic polymer compound hardly soluble in water is the above The flame-retardant phenolic resin foam laminate, which is present in 5 to 100 parts by weight with respect to 100 parts by weight of the phosphorus-based flame retardant, in the surface of the face material and in the face material. The density of the flame retardant phenolic resin foam laminate is 10 to 150 kg / m ³ or less, the foam has a self-efficacy of 60% or more, and a thermal conductivity of 0.036 W / (m · K) or less, The flame retardant phenolic resin foam laminate according to claim 1, wherein the foam contains a combustible foaming agent. The flame-retardant phenolic resin foam laminate according to claim 1 or 2, wherein the phosphorus-based flame retardant is ammonium polyphosphate having a degree of polymerization of 500 or more . The flame retardant phenolic resin foam laminate according to any one of claims 1 to 3, wherein the face material is a synthetic fiber nonwoven fabric containing at least one selected from the group consisting of polyester, polypropylene and polyamide. It is a manufacturing method of the flame-retardant phenolic resin foam laminated board as described in any one of Claims 1-4 ,
Two coating solutions obtained by dispersing a phosphorus-based flame retardant having a decomposition temperature of 200 ° C. or more in water in an aqueous solution in which a water-insoluble organic polymer compound is finely dispersed or dissolved after heat drying. It is applied to at least one face material and dried by heating. On one face material, a foamable resin composition comprising a phenol resin, a foaming agent, and a curing catalyst is discharged, and the top surface of the foamable resin composition is placed on the other surface. A method for producing a flame retardant phenolic resin foam laminate, wherein the foamable resin composition is foam-cured after being coated with the face material. It is a manufacturing method of the flame-retardant phenolic resin foam laminated board as described in any one of Claims 1-4 ,
A foamable resin composition comprising 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, and the foamable resin composition is foamed. A coating liquid obtained by dispersing a phosphorus-based flame retardant having a poor solubility in water and a decomposition temperature of 200 ° C. or higher in an aqueous solution in which an organic polymer compound that is sparingly soluble in water is finely dispersed or dissolved after being heated and dried. Is applied to at least one of the two face materials and dried by heating. A method for producing a flame retardant phenolic resin foam laminate. The flame retardant phenol according to claim 5 or 6 , wherein the aqueous solution in which an organic polymer compound 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 resin foam laminate.