MXPA00007098A - Laminated phenolic resin foamed board and its manufacturing method - Google Patents

Abstract

To provide a foamed phenol resin body laminate, which has excellent surface flatness, improved bending elasticity modulus in the longitudinal direction and bending strength, and improved flexibility, and its appropriate manufacturing method.

Description

FOAMED LAMINATE BOARD OF PHENOLIC RESIN AND ITS MANUFACTURING METHOD Technical Field The present invention relates to a foamed phenol resin laminate, which has a surface uniformity, modulus of elasticity of the bend in the longitudinal direction, resistance to bending and considerably improved flexibility, and has an excellent performance in construction. and adiabatic performance, and its continuous molding method.

Prior Art A method is known, in which a surfactant, foaming agent and catalyst are added and mixed to a phenol resin, this mixed composition is continuously discharged onto a mobile surface material, coated with a top surface material and a foamed phenolic resin body laminate is manufactured by passing it through a double ribbon-type conveyor or an endless belt conveyor. In Japanese Patent Application Kokai, No. Sho 59 [1984] -24639, there is shown a method for manufacturing a foamed body of phenol resin, by the sandwich between rolls, and in Japanese Patent Application Kokai No. Sho 58 [1983] -16838, there is shown a method for manufacturing a foamed body of phenol resin, by a conveyor in the manner in which a ribbon-type conveyor is integrated with an endless belt conveyor. Since the double strip-type conveyor has a structure with a strong mechanical grip pressure, compared to the belt conveyor, the pressure adjustment of the foamed body in the foam-forming process is easy. From this fact, one thinks that one has the advantage, in which the favorable properties of the foamed body, such as the independent foam regime, are easily obtained. In the Japanese Patent Application Kokai No. Sho57 [1982] -91244, a method for the manufacture of phenol foam by the double slat conveyor is presented. It is known that the foamed body of the phenol resin, with high independent rate of foam, is an excellent insulator with a very low thermal conductivity. In Japanese Patent Application Kokai No. Hei [1989] -138244, there is presented a method for manufacturing a foamed body of phenol resin, of closed cells, which includes a process, which forms a mixture of a substance, selected from the high viscosity resol group, urea and dicyandiamide, and a surfactant, and where this mixture is combined with a foaming agent and a catalyst. In its Example 7, the adiabatic performance of the body of the foamed phenol resin, modified with urea, exhibits an excellent property against aging. In other words, it is shown that its excellent adiabatic performance is retained over a prolonged period. However, when using a flexible surface material (non-woven fabric, composed of glass fibers, etc.) as a surface material, in the method employing a ribbon-type conveyor, traces of these slats remain in the product , which is not appropriate and is indicated as an inadmissible problem in Japan (Recent Trends in Chemistry and Technology of Foams of Fenol, Vol. 38, No. 2, pages 50-59, 1987). The problem of the relics of slats is a phenomenon of fin formation or level difference, almost periodically seen in the direction of operation, and, as shown in Figure 4 (in both examples shown in the upper and lower diagrams, the width of the strip is 15.24 cm, the difference in level and formation of fins caused correspond to this width of the slat), its pattern varies. It is thought that the cause of the problem is that each strip of the slat-type conveyor can not eliminate this level difference by finishing sizing, or because the relics of the strip are formed in the gaps between the slats, when the pressure of Foam formation varies excessively in the formation process. The problem of the superficial uniformity of the foamed body is not limited to that of the quality of the product and if the problem is severe, a layer of space (air layer) is generated between the insulator (foamed body) and the sheet material of the other part (for example, the board of the building material, the panels, etc.) in contact with the surface. It becomes a circulating layer of air and hides the adiabatic effect, and there is also the possibility that the material with an excellent adiabatic property like this foamed body, can not provide sufficient performance. Also, when the flexible surface material is used, the laminate of the foamed phenol resin body is apt to be bent and there is difficulty in handling it in the construction, when it is used as a construction material. When the foamed body laminate is used as a sheet-shaped insulator, a size of 90 cm in width and 180 cm in length, which are the standard dimensions of the building materials, is adopted, so the laminate is handled in mostly in a long configuration in the longitudinal direction. For this reason, in particular, bending in the longitudinal direction causes a problem.

The present invention solves the problems, and its objective purpose is to provide a laminate of the foamed phenol resin body, in which the surface uniformity is greatly improved, using the lath-type double conveyor, the remains of laths are not distinct, and the modulus of bending elasticity in the longitudinal direction, bending strength and the same bending are improved, as well as its manufacturing method.

Description of the Drawings Figure 1 is a manufacturing apparatus used in the method of manufacturing a modified foamed phenol resin body according to the present invention; Figure 2 shows the surface uniformity of the foamed bodies of the present invention and a conventional method. Key: 1. Mixer and spout 2. Lower surface material 3. Upper surface material 4, Double lath conveyor 5, Foam body tensioning device (second double conveyor) Body case to maintain temperature Body case to maintain temperature of a stretched part Cutter 9. Foamed body.

Figure 3 shows the rate of stretching and the ratio of the modulus of elasticity of bending in the longitudinal direction / modulus of elasticity of bending in the width direction; and Figure 4 shows the appearance of the foamed body of the conventional method (oblique view).

Disclosure of the Invention The present invention provides a foamed phenol resin body laminate, formed by bonding a flexible surface material, which has indistinct traces of battens and improved bending in the longitudinal direction, using a double slat-type conveyor, and its manufacturing method. The inventor reviewed the aforementioned objective in his endeavor to achieve it and, as a result, the present invention was completed. In other words, the present invention is as follows. 1) A foamed phenol resin body laminate, characterized in that in a foamed phenol resin body laminate, constituted using a foamed phenol resin body, as a core material, and joining a surface material flexible to both surfaces, without a layer of adhesive, the EMD / DTE ratio of the bending modulus of elasticity, in the longitudinal direction EMD and the bending modulus of elasticity in the width direction, DTE is 1.6 to 2.8. 2) The laminate of the foamed phenol resin body, described in paragraph 1), mentioned above, is characterized in that the phenol resin is a modified phenol resin, containing at least one of the urea, the dicyandiamide and melamine. 3) A method of manufacturing the laminate of the body of the foamed phenol resin, characterized in that in a method for manufacturing this body of foamed phenol resin, adding and mixing a surfactant, a foaming agent and a catalyst to the phenol resin, continuously discharging and the mixing composition onto a flexible surface material, coating the upper surface with the flexible surface material, and passing it through a double slat-type conveyor, the foamed body, which forms a continuous girdle, is passed through the conveyor and stretched in the operating direction in a state before completing the cure. 4) The method of manufacturing the laminate of the foamed phenol resin body, described in paragraph 3), mentioned above, is characterized by the fact that the aforementioned stretching regime in the operation direction is from 4 to 12 %. 5) The method of manufacturing the laminate of the foamed phenol resin body, of paragraphs 3) or 4), mentioned above, is characterized in that the stretching in the operation direction, mentioned above, is carried out by a double conveyor, ribbon type. 6) The method of manufacturing the laminate of the foamed phenol resin body, described in any of paragraphs 3) to 5), mentioned above, is characterized in that the phenol resin is a modified phenol resin, which contains at least one of the urea, the dicyandiamide and the melamine. The biggest difference between the present invention and the prior art is that the EMD / DTE ratio of the bending elastic modulus, in the longitudinal direction EMD and the bending modulus of elasticity in the direction of width ETD is approximately 1.5 as sumo in the foamed phenol resin body laminate of the prior art, while the EMD / ETD ratio is 1.6 as 2.8 in the foamed phenol resin body laminate, of the present invention. The biggest difference in the manufacturing method, between the present invention and the prior art, is that foaming and molding are carried out only by a first double conveyor in the prior art, while, after a foaming and primary molding by the first conveyor, a secondary molding is carried out, stretching in the operating direction in a state before completing the cure (by a second double conveyor, etc.) in the present invention. The role of the constitutional requirement of the present invention, which is different from the aforementioned prior art, is a considerable improvement of the surface uniformity, an improvement of the modulus of elasticity of bending in the longitudinal direction and the strength of the laminate of the resin body. of foamed phenol, an improvement of the bending and a great improvement of the handling property during construction, etc. The laminate of the foamed phenol resin body of this invention should have an EMD / ETD ratio in the range of 1.6 to 2.8. The effects exerted by the ratio of the modulus of elasticity of bending in the longitudinal direction and the width direction in the difficulty of bending the laminate of the foamed body and the ease of handling of the laminate of the foamed body in this invention, will be explained as follows, according to the present inventors. For example, when a foamed body laminate 90 cm wide and 180 cm long is handled, it is held at two ends in the width direction for handling. However, in this case, the laminate of the foamed body tends to bend somewhat in the width direction. When the laminate is maintained at both ends in the width direction, the laminate of the foamed body bends a little in the width direction and becomes a laminate in arch configuration. Likewise, the lamination of the foamed body can be easily maintained by both hands and is very difficult to bend in the longitudinal direction. In other words, if the EMD / DTE ratio of the bending modulus of elasticity, in the longitudinal direction, EMD to that in the width direction, DTE is high, the foamed body laminate can be easily handled and is difficult to bend in the longitudinal direction. For a conventional foamed phenol resin body laminate, formed by bending flexible surface materials, the EMD / DTE ratio of the flexural modulus of bending in the longitudinal direction, EMD to that in the width direction ETD is not greater than 1.5, and the laminate is liable to bend in the longitudinal direction. This is a disadvantage. On the other hand, according to the results of the investigation, obtained by the present inventors, when the EMD / DTE value is 1.6 or higher, the laminate becomes much more difficult to bend in the longitudinal direction during handling.

However, the value of EMD / DTE can not exceed 2.8, because bending in the width direction will become a problem when the EMD / DTE value can not exceed 2.8. It is preferred that the value be in the range of 1.8 to 2.4. The modulus EMD of bending elasticity in the longitudinal direction should be 220 kg / cm2 or greater, preferably 240 kg / cm2 or more, not only in the case when the laminate is maintained at both ends in the width direction but also from the point of view of general management. The modulus DTE of bending elasticity in the width direction should be 80 kg / cm2 or greater, or preferably 100 kg / cm2 or greater, from the same general management point of view. Likewise, the bending strength in the longitudinal direction should be 4.9 kg / cm2 or greater, preferably 5.2 kg / cm2 or greater, in order to prevent the breaking of the bend in the general handling operation. The phenol resin, used in this invention, is a resole phenol resin, prepared by reacting the raw materials, ie, phenol and formaldehyde, with each other, in the presence of a basic catalyst. In order to achieve a relatively low reaction rate in the foaming and curing process and to reduce deterioration over time in the adiabatic function of the product, it is preferred to use a modified phenol resin containing urea and / or the dicyandiamide and melamine, in this invention. With the aforementioned phenol resin used as the core material, the foamed body laminate of this invention is formed by bending a flexible surface material on both sides of the core material, without using a layer of adhesive. Examples of flexible surface materials, which may be used in this invention, include non-woven fabrics, made of polyester, nylon, polypropylene, etc., woven fabrics, non-woven fabrics of glass fibers, calcium hydroxide paper, aluminum oxide, magnesium silicate paper, and other types of paper made of inorganic fibers, as well as strong paper and other types of paper. In general, the flexible surface material is provided in the form of a roll. Among the aforementioned flexible surface materials, non-woven fabrics, woven fabrics and inorganic fiber paper with a fiber sizing, without preferred from the point of view of the adhesive strength between the surface material and the foamed body. In particular, non-woven fabrics of synthetic fibers and paper are more preferred because they are cheap and lamination of the foamed body can be obtained, easy to handle. Likewise, non-woven fabrics with a fiber size of 18 μm or less are preferred in order to prevent the exudation of the foam phenol resin. Likewise, in order to obtain an easy-to-handle surface material, in the manufacturing process and in consideration of the flexural stiffness of the product, it is preferred that the basis weight be in the range of 20 to 400 g / m2. It is preferred that the thickness of the surface material be in the approximate range of 0.1 to 1 mm. Although there is no special limitation on the thickness of the core material, made of the aforementioned phenol resin, the core material is preferred to have a thickness in the range of 3 to 150 mm, because it is used primarily as a material adiabatic. Also, the density is preferred is in the range of 20 to 100 kg / m3. Figure 1 shows an example of the difference in the surface configuration of the foamed bodies, formed according to the method of this invention and the conventional method, the abscissa indicates the position of the foamed body in the longitudinal direction, and the ordinate indicates the measured height (thickness) of the foamed body in the position. In the measurement of the thickness of the foamed body, this foamed body, cut into pieces of 1.1 m in width and 1.2 in length, was placed on a table with a flat surface, and the height of the central portion in the width direction was measured in the longitudinal direction. According to the method of height measurement, first, 12.7 cm portions were measured with intervals of 2.54 cm, and 2.54 cm of the part with a remarkable configuration of fins, corresponding to the joints of the slats, were measured at intervals of 4.23 mm (measured over 76.2 cm as the full length.The thickness was measured under a press force of 5 g, using a mark gauge having a tip with a flat bottom configuration of column with a diameter of 1.5 mm) it can be seen from Figure 1, compared with the foamed body, manufactured by the conventional method, the laminate of the phenol resin body, sheet-shaped, foamed, modified, manufactured by the method of this invention, shows a significant improvement in the superficial uniformity. The variation in thickness of the conventional foamed body is from 26.0 to 28.5 mm, while the variation in thickness in this direction was improved to 27.1 to 27.8 mm. In consideration of the appearance of the laminate of the foamed body and in order to reduce the gap formed between the laminate of the foamed body and the wall or panel surface, when the laminate of the foamed body is used as an adiabatic material, the surface uniformity, measured by a method, which is explained below, it is preferred to be 0.4 mm or smaller. In the following, the method of manufacturing the laminate of the foamed body of this invention will be explained.

Figure 2 explains the method of manufacturing a modified foamed phenol resin body of the present invention and a manufacturing apparatus used in the method. 1 is an apparatus that mixes the phenol resin, foaming agent and acid catalyst, by a mixer and supplies the phenol resin foam to the surface material. 2 and 3 are the lower surface material, which operates continuously, and the upper surface material, 4 is a double slat-type conveyor, consisting of the metal plate, etc., which rotates at a fixed speed in the direction of the arrow head. This double ribbon conveyor 4 has the role of foaming and curing while being configured to the prescribed thickness, heating a foam phenol resin, continuously guided (the heater is not shown in the figure). 5 is an apparatus that grasps a foamed body F, of continuous strip shape, passed through the double slat conveyor 4, mentioned above, and stretches it to a prescribed amplification (hereinafter named a second double conveyor 5). In order to properly stretch the foamed body F in a continuous girdle shape, a box body 7, to maintain the temperature of the stretched part and, if necessary, a heater, are installed in the outlet part of the double conveyor 4. , ribbon-like, mentioned above, to maintain this foamed body G at the appropriate temperature (the heater is not shown in the figure). At the outlet of the double conveyor 4, of the ribbon type, the curing of the foamed body F, in the form of a continuous strip, is almost completed; however, it has a flexibility to the extent that slight deformation is possible. It is not convenient to cure the foamed body G, in the form of a continuous strip, to a state which is capable of deformation at the outlet of the double conveyor 4, of the ribbon type, because the stretching effect becomes poor. The curing state should be adjusted to a convenient range at the outlet of the conveyor 4 by appropriately adjusting the operating conditions, i.e., the amount of the catalyst and the temperature of the conveyor. The modified phenol resin, which contains at least one of the urea, dicyandiamide and melamine, is preferred since its curing state at the outlet of the conveyor (4) can be easily maintained in an appropriate state, due to its moderate reactivity of healing. In order to reduce the change over time in the thermal conductivity of the laminate of the foamed body, it is necessary to further cure the laminate after keeping it at a temperature in the range of 60 to 10 ° C for several hours (post-cure).

The continuous foamed body F is stretched by adjusting the transport of the second double conveyor 5 greater than the transport of the double conveyor, of the ribbon type; however, it is convenient for the second double conveyor 5 which is capable of controlling the grip pressure by a pressure regulator, which uses the air pressure, oil pressure, etc., to grip a foamed body F of strip form continue, at an appropriate pressure. Next, the relationship between the stretching regime and the ratio of the bending elasticity EMD in the longitudinal direction of the laminate of this invention to the bending elasticity ED in the width direction will be explained. Figure 3 shows an improvement of the ratio of the bending modulus of elasticity in the longitudinal direction EMD and the bending modulus of elasticity in the direction of width ETD. The abscissa indicates the rate of stretching and the ordinate indicates the modulus of elasticity of bending in the longitudinal direction Em, and the modulus of elasticity of bending in the direction of width ETD. From Figure 3, the ratio of the modulus of elasticity of bending in the longitudinal direction / modulus of elasticity of bending in the width direction of the modified foamed phenol resin body of the present invention is 1.5., in an unstretched state, at 1.9 by a stretch of 4% and up to 2.8 by a stretch of 12%, and an improved foamed body is obtained, which is difficult to bend in the longitudinal direction and has excellent construction properties. If the value of EMD / DTE is 1.6 or more, the effect of the difficulty of bending in the longitudinal direction at the time of handling is different and preferable, and if the value of the ratio of EMD / ETD is greater than 2.8, bending in the width direction causes a problem, which is not appropriate. The stretching regime in the present invention is a ratio of the transport of the second double conveyor and the ribbon-type conveyor (first conveyor) and is expressed by the following equation: Stretching regime = (transport of the second double conveyor / conveyor transport of ribbon type - 1) x 100 (%).

The draw rate used also depends on the operating conditions, such as the temperature of the first furnace; however, it is preferred to establish it at 4-12%. If the stretching regime is less than 4%, the improvement of the surface uniformity, which is the stretching effect, and the improvement of the modulus of elasticity of bending in the longitudinal direction EMD and the modulus of elasticity of bending in the direction of Wide ETD are sometimes insufficient. Also, if the stretching regime is well beyond 12%, the cross section of the surface material is sometimes interrupted, which is not preferred. Thus, it is more preferred that the stretching regime be in the range of 4-8%. Although there is no special limitation on the transport speed of the first slat-type conveyor, mentioned above, it is preferred to be in the range of 1 to 80 m / min, from the point of view of productivity. Although there is no special limitation on the transport speed of the second ribbon-type conveyor, it is preferred to be in the range of 1 to 90 m / min, from the point of view of productivity. The phenol resin used in the present invention is a resole phenol resin, obtained by reacting phenol- and formaldehyde as starting raw materials, in the presence of a basic catalyst. As a more preferred embodiment of the present invention, a modified phenol resin, containing urea and / or dicyandiamide and melamine, may be mentioned. The basic process for the manufacture of the modified phenol resin is as follows: (i) Preparation of a resole phenol resin, which uses phenol and formaldehyde as starting raw materials, in the presence of a basic catalyst. (ii) Neutralization of the resin with an acid. (iii) Process for forming a modified phenol resin by adding urea and / or dicyanamide to the aforementioned resole resin. (iv) Removal of moisture by a vacuum separator, etc.

Phenol and formaldehyde, which are the starting raw materials, are more appropriately used in their molar ratio of 1: 1.7 to 1: 3, and they are synthesized by adding a basic catalyst, such as sodium hydroxide and hydroxide. potassium and heating at 40-100 ° C. Formaldehyde can be used appropriately at a concentration of usually 30-60%. The amount of urea and / or dicyandiamide and melamine added, which are the modifiers, is more preferably in the range of 5 to 30% of formaldehyde, which is a starting raw material. If the amount of urea and / or dicyandiamide and melamine added is less than 5 mol%, the advantage of the excellent anti-aging characteristic of adiabatic performance is sometimes lost. Also, if the amount of urea and / or dicyandiamide and melamine added is greater than 30 mol%, the mechanical strength of the foamed body deteriorates, which is not preferable. Modifiers can also be added before and after neutralization; however, it is more preferred to use a sufficient temperature to allow sufficient time in the formaldehyde-free reaction. Usually, the reaction time of about 6 hours is sufficient at 30 ° C. Next, in a modified phenol resin, the free moisture in the resin is reduced using a vacuum separator, etc., to obtain an appropriate range of moisture regime and viscosity for foaming. Usually, the resin is prepared so that the humidity regime is 4-10% and the viscosity at 40 ° C is around 4,000 to 40,000 cps. A surfactant is dissolved in the modified phenol resin, with the aforementioned moisture regime and viscosity, prepared and a foaming agent and a curing catalyst are added and mixed with it in a mixing head and discharged continuously on the lower surface material, which goes through a conduit. As the method of unloading onto the surface material, a method can be used which moves the conduit back and forth perpendicular to the direction of advance of the surface material, a multi-door distribution tube method, etc. As the surfactant, used in the present invention, a nonionic surfactant is generally used. For example, silicone surfactants, such as polydimethylsiloxane, block copolymers of ethylene oxide and propylene oxide, condensed with alkylphenol, such as alkylene oxide and nonylphenol and dodecylphenol, condensates of alkylene oxide and Castor oil, and esters of fatty acids, such as the polyoxyethylene fatty acid ester, are mentioned. These surfactants can be used alone or in combinations of several of them. As the foaming agent, used in the present invention, HFCs, such as difluoromethane (HFC 32), 1,1,1,2-tetrafluoroethane (HFC 134a) and 1,1-difluoroethane (HFC 152a), CFCs, such as 1-chloro-l, 1-difluoroethane (HCF C142b), and hydrocarbons, such as butane, n-pentane, cyclopentane and isopentane, can be used. As the curing catalyst, used in the present invention, acidic compounds, such as inorganic acids and organic acids are used; however, aromatic sulfonic acids, such as toluenesulfonic acid, xylene sulfonic acid and phenolsulfonic acid, are used appropriately. As an auxiliary to the cure, resorcinol, cresol, o-methylol phenol, p-methylol phenol, etc. can also be added. The curing catalyst and the curing aid can also be diluted in a solvent, such as diethylene glycol, and used. The foamed phenol resin mixture, sandwiched between the upper and lower surface materials, is passed through a double slat-type conveyor, followed by foaming and curing to obtain a foamed body, in the form of a continuous strip. However, when the temperature of the double conveyor is less than 60 ° C, the material can not be foamed or cured completely. As a result, the thermal conductivity and resistance of the foamed body laminate becomes low. On the other hand, when the temperature of the double conveyor is greater than 110 ° C, the cell film of the foamed body is destroyed. As a result, the thermal conductivity deteriorates. Consequently, the temperature of the double slat conveyor must be in the range of 60 to 110 ° C. After passing through the double slat conveyor, and stretching by the second double conveyor, the foamed body of continuous strip shape is cut to a prescribed length in the longitudinal direction and then further cured in a post-cure operation. When the post-cure temperature is less than 60 ° C, the thermal conductivity of the laminate of the foamed body changes with time, and the dimensions of this laminate of the foamed body change significantly at a high temperature (such as at 90 ° C) . On the other hand, when the post-cure temperature is higher than 140 ° C, the foamed body becomes brittle, and the mechanical strength of the foamed body laminate becomes low. Consequently, the post-cure temperature should be in the range of 60 to 140 ° C. The foamed body laminate of this invention is particularly suitable for various types of adiabatic building materials, because it has low heat conductivity, high flame resistance, high heat resistance, low smoke formation property, and good capacity of process.

EXAMPLES Next, the present invention will be explained in more detail with the application examples and the comparative examples. Each value measured in the application examples is based on the following methods. (1) Surface Uniformity A foamed laminate was cut to approximately 1.1 m in width and approximately 1.2 m in length and placed on a table with a flat surface, and the height in the direction of the central width was measured at intervals of usually 2.54 cm and therefore as of 12.7 cm longitudinally. Next, 2.54 cm of the part with a severe configuration of fin formation, corresponding to the joints of the slats, was measured in 0.423 cm intervals, and 56 points were measured repeatedly over 76.2 cm as the total length. At that time, the standard deviation (mm) of these height values is assumed to be surface uniformity. In other words: Equality of surface (mm) = where: n: number of measured points (n = 56) Xi: height in each position (mm). (2) Thickness Measurement Thickness was measured at a push point of 5 g, using a marker gauge having a tip with a flat bottom configuration of column with a diameter of 1.5 mm. (3) Flexibility module for bending and bending resistance Measured in accordance with ASTM C 203. (4) Density Measure according to JIS K 7222. Also, the density of the laminate of the foamed body is the density measured for this foamed body, after removing the surface material by its detachment.

Application Example 1 and Comparative Example 1 (1) Modified composition of phenol resin 3500 kg of 52% formaldehyde and 2510 kg of 99% phenol were charged to a reactor, stirred with a rotary propellant stirrer, and the temperature of the liquid in the reactor was adjusted to 40 ° C by a temperature regulator. Then, a 50% aqueous solution of NaOH was added and the temperature rose while stirring. Then, the reaction was carried out. When the Ostwald viscosity reached 60 cps (measured value at 25 ° C), the reaction solution was cooled and 570 kg of urea (corresponding to 15 mol% of the amount of formaldehyde charged) were added. Next, 50% of an aqueous aromatic sulfonic acid solution was added and neutralized to obtain a modified phenol resin. Next, the aforementioned resin was dehydrated by a thin film evaporator until the amount of moisture reached 6% by weight, and a resin with a viscosity of 600 cps was obtained at 40 ° C. A mixture of 4% by weight of Pluronic F-127 (ethylene oxide-propylene oxide block copolymer, obtained by BASF) and Herfoam Pl (ethoxylated alkylphenol) obtained by Huntsman Chemical Co.) at a weight ratio of 1 : 1, the resin was added as a surface-active agent and dissolved, in this way the modified phenol resin composition was obtained. (2) Foam Body Manufacturing The aforementioned modified phenol resin composition, the foam forming agent, CFC 142b, and the catalyst, were supplied in the following composition to a mixing head and supplied to the lower surface material in motion through a multi-door distribution tube. Also, perfluoroalkane (3M Pafamansflide 5050) was added in 2 parts by weight, as a foam auxiliary to the foaming agent, CFC 142b. Phenol resin modified in 100 parts by weight Foaming agent in 13.5 parts by weight Catalyst, in 13.3 parts by weight. As the catalyst, an organosulfonic acid mixture composition, presented in Japanese Patent Application Kokai No. Sho 63 [1988] -10642 was used, and as the surface material, a non-woven fabric, made of polyester, Spun Bond ET5030 (obtained from Asahi Chemical Industry CO., Ltd. a density of 30 g / m2, a thickness of 0.15 mm and a fiber size of 1 μm) was used. Next, the foamed body was coated with the same kind of material from the upper surface and supplied to the double conveyor, ribbon type. The speed of operation of the double conveyor, ribbon type was 2.05 m / min and the temperature was maintained at 80-90 ° C over the entire length. Then, the continuous foamed body, which passed through the double ribbon-like conveyor, was held vertically by a second double conveyor, as shown in Figure 2, and the transport was changed to 2.13 m / min (Example 1 of Application), 2.17 m / min (Application Example 2), 2.23 m / min (Application Example 3, and 2.30 m / min (Application Example 4) (the stretching rate corresponded to 4%, 6%, 9% and 12%, respectively) Under each condition, the modified foamed phenol laminates were manufactured.The stretching in the operating direction was carried out by passing the exit of the double conveyor, ribbon type; however, the foamed body of continuous girdle form at the exit of the ribbon-like double conveyor had flexibility to the extent that it was recovered after thinking slightly with one finger. The healing was not complete. Also, the obtained foamed body had a good condition without exudation of the resin. On the other hand, in Comparative Example 1, the second double conveyor was kept in an open state, and a continuous foamed laminate was manufactured without extraction. Likewise, in Comparative Example 2, a continuous foamed laminate was removed by the second double conveyor; however, the speed of the second double conveyor was set at 2.09 m / min. In Comparative Example 3, the conveyor speed was 2.56 m / min and a foamed laminate was similarly manufactured (the stretch rate corresponded to 0%, 2% and 25%, respectively). In all the examples of application and comparative examples mentioned, in the second double conveyor, the load was adjusted by an air cylinder, and thus an excessive load was not applied to the foamed body. The continuous foamed laminate was cut to 1.9 m in length, by a cutter installed on the back of the second double conveyor, and the cure was completed by a post-cure oven. This post-cure was carried out by gradually raising the oven temperature from room temperature to 92 ° C, as shown below, and the cure was finished after about 4 hours. Retention at 75 ° C for 15 minutes, then Retention at 80 ° C for 30 minutes, then Retention at 85 ° C for 30 minutes, then Retention at 92 ° C for 140 minutes, then cooling to room temperature. The density of the laminate of the foamed body obtained was 27 kg / m3 and the thickness was around 27 mm. The flexibility, which means the recovery of the shape when the foamed body, after the post-cure was pressed by a finger, was not recognized. Figure 1 shows the surface configuration of a foamed body at a stretch rate of 6% (Application Example 2) and a surface configuration of a foamed body of the conventional method; it is seen that the uniformity of the surface configuration is markedly improved in the manufacturing method of the present invention. Table 1 summarizes the surface uniformity, ratio of the modulus of elasticity of bending in the longitudinal direction / modulus of elasticity of bending in the direction of width, modulus of elasticity of bending and resistance of bending of the foamed bodies obtained in Examples 1- 5 of Application and Comparative Examples 1-4. The case where the foamed body was removed by the second conveyor in Comparative Example 1 corresponds to the conventional manufacturing method. In an interval of the stretching regime from 4 to 12%, the surface uniformity was markedly improved, and the ratio of the modulus of elasticity of bending in the longitudinal direction / modulus of elasticity of bending in the width direction is also increased to 1.89- 2.78, compared to 1.5, when the stretch rate is 0%. The modulus of elasticity of bending in the longitudinal direction is also improved from 200 kg / cm2 for the rolling with a drawing rate of 0%, to 300 kg / cm2 for rolling with a drawing rate of 12%. The bending strength in the longitudinal direction is similarly improved from 4.8 kg / cm2 for rolling at a stretch rate from 0% to 5.6% for rolling with a stretch of 12%. In Comparative Example 2, the phenomenon was generated in which the foamed body of strip form was left between the double lath conveyor, and the second double conveyor, and continuous molding was impossible. When the stretching regime of Comparative Example 3 was adjusted to 25%, stretching of the foamed body could not be followed and this foamed body fractured, so molding was impossible.

Figure 2 shows the rate of stretching and the ratio of the modulus of elasticity of bending in the longitudinal direction / modulus of elasticity in the width direction of the foamed bodies, obtained in Application Examples 1.4 and Comparative Example 1. It can be seen that together with the stretching regime, the ratio of the modulus of elasticity of bending in the longitudinal direction / modulus of elasticity of bending in the width direction is improved and a difficulty in bending in the longitudinal direction is obtained.

Example 4 Comparative Similar to Application Example 1, except for the use of an aluminum hydroxide paper (made by Water Papermaking KK a density of 140 g / m and a thickness of 0.4 mm) as a surface material, adjusting the amount ( g / min) of the modified phenol resin of Application Example 1, the foaming agent, CFC 142b, and the catalyst supplied to the mixing head as follows, adjusting the range of the double conveyor, ribbon-like, by 20 mm, and by adjusting the stretching rate to 0%, a laminate of the modified foamed phenol resin body was obtained. Composition of modified phenol resin at 10 parts by weight Perforating agent at 8 parts by weight Catalyst at 9.5 parts by weight The thickness of the foamed body laminate obtained was around 20 mm and the density was 40 kg / m3. The ratio of the bend modulus of elasticity in the longitudinal direction / modulus of elasticity of bending in the direction of width of the laminate of the foamed body was around 1.2, which is insufficient. Also, the surface uniformity was as poor as 0.51 mm. In the appearance, the relics of slats were remarkable and the quality of the product was inferior.

Application Example 5 Similar to Application Example 1, except for the use of grafting paper (trade name: N Liner, manufactured by Honshu Paper Co., Ltd., a density of 120 g / m2 and a thickness of 0.2 mm) as the surface material, by adjusting the amount of the modified phenol resin of Application Example 1, the foaming agent, HFC 134a and the catalyst supplied to the mixing head as follows, and adjusted to a 5% draw rate, were obtained a laminate of the body of foamed phenol resin, modified.

As an assistant, the perfluoroether (Ausimont, manufactured by USA Co.) "Galden HT-55" at 2 parts by weight, was added to the HFC 134a foaming agent. Composition of phenol resin modified to 100 parts by weight Foaming agent to 15 parts by weight Catalyst to 13 parts by weight. The thickness of the laminate of the foamed body obtained was around 27 mm and the density of 27 kg / m3. However, the ratio of the bending modulus of elasticity in the longitudinal direction / modulus of elasticity of bending in the direction of the laminate width of the foamed body of Application Example 5 was 1.86. The bending was difficult in the longitudinal direction and the handling property was excellent. The surface uniformity of the laminate of the foamed body was as good as 0.16 mm. In the appearance, the vestiges of the slats remained, and the quality of the product was excellent. Thus, for the laminates of the foamed body, obtained by the manufacturing method of the present invention, the ratio of the modulus of elasticity of bending in longitudinal direction / direction of width was high. Likewise, the uniformity of the surface form was excellent and the quality of the product was good.

Table 1

Claims (6)

1. A laminate of a foamed phenol resin body, characterized in that this laminate of the foamed phenol resin body is constituted using a foamed phenol resin body as a core material and attaching a flexible surface material to both surfaces, without a layer of adhesive, the ratio of EMD / DTE of the modulus of elasticity of bending in the longitudinal direction, EMD and the modulus of elasticity of bending in the direction of the width, E is from 1.6 to 2.8.

2. The laminate of the foamed phenol resin body according to claim 1, characterized in that the phenol resin is a modified phenol resin, containing at least one of the urea, the dicyandiamide and the melamine.

3. A method of manufacturing the laminate of the foamed phenol resin body, characterized in that, in a method of manufacturing this body of the foamed phenol resin, by adding and mixing a surfactant, a foaming agent and a catalyst to a phenol resin, continuously discharging the mixed composition on a flexible surface material, coating the upper surface with the flexible surface material, and passing it through a double, ribbon-like conveyor, the foamed body in the form of a continuous strip, passed through of the conveyor, it is stretched in the direction of operation, in a state before finishing the cure.

4. The method of manufacturing the laminate of the foamed phenol resin body, according to claim 3, characterized in that the stretching regime, in the above-mentioned operation direction, is from 4 to 12%.

5. The method of manufacturing the laminate of the foamed phenol resin body, according to claim 3 6 4, characterized in that the stretching in the above-mentioned operation direction is carried out by a double slat-type conveyor.

6. The method of manufacturing the laminate of the foamed phenol resin body according to any of claims 3 to 5, characterized in that the phenol resin is a modified phenol resin, containing at least one of the urea, the dicyandiamide and melamine.