KR100846048B1 - Process for producing foam - Google Patents

Abstract

The present invention provides a method for producing a foamed styrol product which can prevent the generation of black smoke, improve fire resistance and heat resistance, and can produce a foamed styrol product that can suppress shrinkage deformation caused by fire and heat with good productivity. The phenol resin containing boric acid and aluminum hydroxide is mixed with the prefoamed beads. The coating bead coated with the surface in the coating layer 3 containing boric acid, aluminum hydroxide, and phenol resin is used. The coated beads are dried and pulverized to form a plurality of single particle beads coated on the surface of the coating layer 3. Single particle beads are filled in a mold and then foamed. Steam heat can be efficiently sent between the coating layers 3 of the single particle beads. The heating time and cooling time required for the main foaming of the single particle beads can be extremely short, so that a large amount can be produced at low cost.

Description

Production Method of Foam {PROCESS FOR PRODUCING FOAM}

The present invention relates to a method for producing a foam resistant to fire and heat.

In general, heat insulating boards used in building materials and the like are foamed with resins such as polystyrene in order to provide heat insulating properties, and are molded into predetermined shapes such as board shapes as so-called foamed moldings, and are made to have heat insulating properties by such independent bubbles. These insulating boards have characteristics of light weight, low cost, and excellent heat insulating properties. However, when exposed to high temperatures due to fire or the like, the resin material in these insulating boards has a low melting point, so that the bubbles melt quickly and collapse. For this reason, the whole structure of these insulation boards shrinks rapidly, and since the resin material in these insulation boards starts to vaporize and burn by heat, it gives off black smoke and it accompanies combustion. There is a fear that harmful gas may be generated.

On the other hand, attempts have been made to heat-resistant and flame-retardant such heat-insulating boards, etc., but the materials added in order to give these heat-resistance and flame-retardant properties to the heat-insulating boards deteriorate the properties such as the heat-insulating boards' original heat-insulating properties or increase the cost. Throw it away.

Specifically, as this type of heat resistant board, a wall of bubbles is made of inorganic material containing silicon or oxygen, and synthetic resin containing aluminum hydroxide is integrated on the wall, and non-combustible inorganic particles are disposed therebetween. The structure of one synthetic resin foam is known (for example, refer patent document 1).

Moreover, as this kind of heat-resistant board, a synthetic resin in which a gap between a plurality of inorganic bubble-shaped particles and a plurality of inorganic bubble-shaped particles is mixed and mixed with a foamed resinous inorganic granule which combines these plurality of inorganic bubble-shaped particles with each other. Foam. This synthetic resin foam is a refractory heat insulating agent mixed in the synthetic resin foam in such an amount that the volume of the inorganic granules in the synthetic resin foam is greater than or equal to the gap of many inorganic bubble-shaped particles. And the structure which consists of foaming bodies comprised by inorganic foam, inorganic powder, and synthetic resin foam by foaming of these inorganic powder is known (for example, refer patent document 2).

By the way, compared with the original heat resistant board, all of the above-mentioned synthetic resin foams and foam moldings have the characteristics which should be inherent, such as heat insulation, and the like. In addition, these synthetic resin foams and foamed molded articles also have many restrictions, so that desired heat insulation and flame retardancy cannot be obtained necessarily.

Therefore, the foamed styrol product as the foamed molded product constituting this kind of heat resistant board is coated with a coating film containing the surface of the foamed styrene beads, including boric acid, which is a boric acid-based inorganic substance, and phenolic resin, which is a thermosetting resin.

The coated foamed styrene product is pre-foamed with styrene beads by various treatment methods and then left to mature, and then, for example, in addition to boric acid-based minerals such as boric acid powder or aqueous solution of boric acid, or in addition to the boric acid-based inorganic matters, Thermosetting resins such as phenolic resins and, if necessary, amino foams, polyamide resins, fiber materials and the like are added and then foamed to form a foamed styrole product (for example, refer to Patent Document 3). .

Patent Document 1: Japanese Patent Application Laid-Open No. 53-2463 (Pages 2 to 7, FIGS. 1 to 2)

Patent Document 2: Japanese Patent Laid-Open No. 51-67625 (No. 2 to 3, Fig. 1 to Fig. 2)

Patent Document 3: Japanese Patent Publication No. 3163282 (3rd to 4th pages, Figs. 1 to 2)

However, in the above-described method for producing a foamed styrole product, an additive bead is produced by adding a boric acid-based inorganic material or a thermosetting resin to the pre-foamed beads in which the boric acid-based inorganic material is mixed and pre-foamed. This additive bead is then foamed. Accordingly, when the additive beads are exposed to water vapor and finally foamed, boric acid-based inorganic materials or thermosetting resins flow from the surface of the additive beads, and the surface of the additive beads is coated with boric acid-based inorganic materials and thermosetting resins. There is a fear that it will not be coated. For this reason, since the original beads have to be dried twice and coated with a boric acid-based inorganic substance or the like to the main foam, the main foaming operation takes time, and thus the productivity is not easily improved.

SUMMARY OF THE INVENTION The present invention has been made in view of the above, and a method for producing a molded article that can produce a foam product in which black smoke is prevented during combustion, improves fire resistance and heat resistance, and suppresses shrinkage deformation due to heat can be produced with good productivity. It aims to provide.

The method for producing a foam according to claim 1 comprises pre-foaming a plurality of particles capable of forming a fine hollow body by foaming to form a plurality of pre-foamed particles, and a flame retardant inorganic material and After mixing the thermosetting resin, it is dried and pulverized to form a mixed layer including the flame retardant inorganic material and the thermosetting resin on the surface of each of the plurality of pre-foamed particles, and the mixed layer has a plurality of pre-foams formed on the surface. The formed particles are filled into a mold, and the mold is filled to form a foam having a predetermined shape by subjecting the plurality of pre-foamed particles formed on the surface to water vapor.

Then, a large number of particles which can form a micro hollow body by foaming are prefoamed to form a plurality of prefoamed particles. Thereafter, the flame retardant inorganic material and the thermosetting resin are mixed with the plurality of pre-foamed particles, and then dried and crushed to form a mixed layer including the flame retardant inorganic material and the thermosetting resin on the surface of each of the plurality of pre-foamed particles. do. At this time, a large number of pre-foamed particles having a mixed layer including a flame retardant inorganic material and a thermosetting resin formed on the surface thereof become single particles simultaneously with drying. Thus, the pre-foamed particles having these mixed particles formed on the surface by filling the mold with a plurality of pre-foamed particles formed on the surface of the mold and then steaming the pre-foamed particles with a plurality of pre-foamed particles. Steam can be sent through the gaps in each mixed bed. For this reason, compared with the method of forming a mixed layer over the two layers on the surface of the pre-expanded particles, sufficient flame retardancy can be ensured in the mixed layer of one layer, and a large number of pre-foamed particles can be sent for a shorter time by sending water vapor. Can foam on Therefore, the foam of the predetermined shape which has flame retardance can be manufactured efficiently in a short time. Therefore, black smoke at the time of combustion, such as a fire, is prevented, fire resistance and heat resistance are improved, and the foam which suppressed shrinkage deformation by fire and heat can be manufactured efficiently.

In the method for producing a foam according to claim 2, in the method for producing a foam according to claim 1, a large number of particles capable of forming a micro hollow body by foaming are polystyrene resin particles, and the flame retardant inorganic material includes aluminum hydroxide and It is boric acid and a thermosetting resin is at least one of a phenol resin and a phenol resin.

And many particles which can form a micro hollow body by foaming were made into polystyrene resin particle, and flame-retardant inorganic material was made into aluminum hydroxide and boric acid, and thermosetting resin was made into at least one of a phenol resin and a phenol resin. As a result, it is possible to efficiently produce a foam composed of a plurality of polystyrene resin particles having a mixed layer containing at least one of phenol resin and phenol resin, aluminum hydroxide and boric acid on the surface thereof.

The manufacturing method of the foam of Claim 3 is the manufacturing method of the foam of Claim 1 or 2 WHEREIN: A number of prefoamed particle | grains are mixed with a flame retardant inorganic material and a thermosetting resin, and then dried and pulverized, On the surface of each of these plural pre-foamed particles, a mixed layer comprising each of the flame retardant inorganic material, thermosetting resin and flame retardant is formed.

Then, the flame retardant is mixed with the flame-retardant inorganic material and the thermosetting resin to a plurality of pre-foamed particles, followed by drying and pulverization, and the surface of each of the plurality of pre-foamed particles of the flame retardant inorganic material, the thermosetting resin and the flame retardant. A mixed layer containing each is formed. As a result, the flame retardancy of the foam formed by mainly foaming each of the plurality of pre-foamed particles formed on the surface of the mixed layer is further improved by mixing the flame retardant.

The manufacturing method of the foam of Claim 4 is a manufacturing method of the foam of Claim 3 WHEREIN: A flame retardant is at least any one of red phosphorus and ammonium polyphosphate.

In addition, by using at least one of red phosphorus and ammonium polyphosphate as the flame retardant mixed with the flame retardant inorganic material and the thermosetting resin, the flame retardant can be used separately according to the operating temperature, thereby ensuring the flame retardancy of the foam. It becomes easy.

In the manufacturing method of the foam of Claim 5, in the manufacturing method of the foam of any one of Claims 1-4, a flame-retardant inorganic material is used as a flame-retardant inorganic viscosity modifier, and mica is used as this flame-retardant inorganic viscosity modifier.

And since a flame retardant inorganic material is a flame retardant inorganic viscosity modifier and mica can be adjusted by using mica as this flame retardant inorganic viscosity modifier, fine powder, such as a flame retardant inorganic material, becomes difficult to scatter and fall out at the time of drying. Therefore, the flame retardance can be further improved, and the thermosetting resin can be endured, so that the strength can be further improved, and cracks during combustion can be prevented.

According to the method for producing a foam according to claim 1, compared to the conventional method of forming a mixed layer over two layers on the surface of the pre-expanded particles, it is possible to ensure sufficient flame retardancy in the mixed layer of one layer and to send steam. Thereby, many prefoamed particles can be foamed in a shorter time. Therefore, since a foam having a predetermined shape having flame retardancy can be efficiently produced in a short time, generation of black smoke at the time of combustion such as fire is prevented, fire resistance and heat resistance are improved, and shrinkage deformation caused by fire and heat is suppressed. The prepared foam can be produced with good productivity.

According to the method for producing a foam according to claim 2, a thermosetting resin is used as a polystyrene resin particle and a flame retardant inorganic material as aluminum hydroxide and boric acid, with a number of particles capable of forming a fine hollow body by foaming. By using at least one of the phenol resins, a foam composed of a plurality of polystyrene resin particles having a phenol resin, at least one of the phenol resins, and a mixed layer containing aluminum hydroxide and boric acid formed on the surface thereof can be produced with good productivity. have.

According to the method for producing a foam according to claim 3, by forming a mixed layer comprising each of a flame retardant inorganic material, a thermosetting resin and a flame retardant on each surface of the plurality of pre-foamed particles, a plurality of these pre-foamed particles The flame retardancy of the foam formed from the main foam can be further improved.

According to the method for producing a foam according to claim 4, by using at least one of red phosphorus and ammonium polyphosphate as the flame retardant, the flame retardant can be used depending on the use temperature, thereby making it easier to secure the flame retardancy of the foam. Can be.

According to the method for producing a foam according to claim 5, since the viscosity can be adjusted by using a flame retardant inorganic material as a flame retardant inorganic viscosity modifier and using mica as the flame retardant inorganic viscosity modifier, fine powder such as mixed flame retardant inorganic materials Since it can make it difficult to scatter and fall off during drying, the flame retardant effect can be further improved, and the thermosetting resin can be endured, so that the strength can be further improved, and the crack during combustion You can prevent it.

BRIEF DESCRIPTION OF THE DRAWINGS The perspective view which shows one Embodiment of the foamed styrol product of this invention.

2 is an enlarged cross-sectional view showing a part of the foamed styrol product.

Figure 3 is a photograph showing the combustion state of the foamed styrol product.

(a) Photograph showing 20 seconds after ignition of the foamed styrol product of the present invention

(b) a photograph showing one minute after the ignition of the foamed styrene product

(c) A photograph showing immediately after dyeing of the foamed styrol product

(d) Photograph showing 10 seconds after ignition of conventional foamed styroline product

Figure 4 is a photograph showing Example 5 of the foamed styrol product of the present invention.

(a) Photograph showing a foamed styrol product of Example 5

(b) photographs showing the above-mentioned foamed styrene products

Figure 5 is a photograph showing the combustion test of the in-phase foamed styrene products.

(a) Photo which shows state 30 seconds after commencement of combustion test

(b) Photo which shows state five minutes after commencement of combustion test

(c) Photograph which shows state seven minutes after commencement of combustion test

Figure 6 is a photograph showing the state immediately after the end dyeing 9 minutes of the combustion test of the foamed plastic product.

(a) Photograph showing the entirety of the foamed plastic product after the combustion test

(b) a picture showing the combustion part of the foamed styroline product;

(c) a photograph showing the central portion of the combustion portion of the foamed styrol product

(d) A photograph showing a cross section of the central portion of the combustion portion of the foamed styrol product

7 is a graph showing the results of the cone calorimeter test of Example 6 of the foamed styrol product of the present invention.

Figure 8 is a photograph showing the foamed styrol product.

9 is a photograph showing the foamed styrolean product described above.

[Description of the code]

1: foamed styroline product as foam

2: porous foamed resin particles as particles

3: coating layer as mixed layer

The configuration of one embodiment of the foamed styrol product of the present invention will be described with reference to FIGS. 1 and 2.

1 and 2, 1 is a foamed styrol product as a foam. This foamed styrole product 1 is a polystyrene ({CH ₂ -CH (C ₆ H ₅ )} _n ) resin as a molded body made of a porous foamed resin to which a foaming material is added. It has many porous foamed resin particles 2 foamed in a bubble shape to a predetermined size by foaming of styrene beads, which are beads. Specifically, these porous foamed resin particles 2 contain butane gas or the like in styrene beads. It is a particle impregnated and foamed. In addition, the skin 2a of the styrene beads is formed on the surface that is the outer circumferential surface of these porous foamed resin particles 2.

Each of these porous foamed resin particles 2 is shaped into a substantially spherical shape. In addition, each of these porous foamed resin particles 2 is solidified with each other to form a predetermined shape, for example, a rectangular plate shape as a whole. In other words, the foamed styrol product 1 has a foamed molded structure in which each of the porous foamed resin particles 2 is in close contact with each other and integrally molded. On the other hand, this foamed styrole product 1 is used as a board for building materials used for building materials or materials requiring flame retardancy, for example, panels as structural members, molded articles and lightweight molding members.

And as shown in FIG. 2, the coating layer 3 which is a mixed layer as a coating film is formed in thin thickness on the surface which is the outer periphery surface of the epidermis 2a of each porous foamed resin particle 2, and is coat | covered. The coating layer 3 contains, for example, a flame retardant inorganic compound, a flame retardant, a thermosetting resin, an amino resin, a polyamide resin, a fiber material, and the like, which is a flame retardant inorganic base. Here, as the flame retardant inorganic compound, for example, flame retardant inorganic powders such as aluminum hydroxide (Al ₂ (OH) ₃ ) and magnesium hydroxide (Mg (OH) ₂ ), and boron-based inorganic compounds, for example boric acid (H ₃₎ BO ₃ ) and the like. Moreover, as a flame retardant, the coating layer 3 is made super flame retardant, for example with red phosphorus (P) which is red phosphorus system, ammonium polyphosphate as polyphosphoric acid which is polyphosphoric acid system, etc. The thermosetting resin is, for example, a resol resin or a phenol resin as a phenol resin. Here, the phenolic resin has properties substantially the same as those of the phenolic resin and is not relatively expensive. Therefore, the phenolic resin can be used as a thermosetting resin instead of or in combination with the phenolic resin.

At this time, when red phosphorus is included in the coating layer 3 as a flame retardant, the red phosphorus immediately carbonizes at the time of heating to block oxygen, making it difficult to burn the coating layer 3. In addition, red phosphorus is added to the coating layer 3 when the temperature at the time of main foaming does not rise. In addition, ammonium polyphosphate is added to the coating layer 3 when the temperature at the time of this foaming is raised. At this time, when the porous foamed resin particles 2 under the coating layer 3 are styrene, since the heat resistance temperature is low, the remaining temperature cannot be raised. In this case, red phosphorus is added.

Here, the coating layer 3 has a molecular weight of around 2500, preferably about 3000. In addition, the coating layer 3 is composed of at least one of a boron-based inorganic compound and a flame retardant inorganic compound, and a thermosetting resin in which a flame retardant is mixed and contained as necessary. At this time, the coating layer 3 is integrated by bringing a plurality of porous foamed resin particles 2 into close contact with each other via the coating layer 3. In addition, the resin constituting the bubble-shaped structure of each of these porous foamed resin particles 2 may be any one capable of forming a fine hollow body by a method such as foaming. That is, the resin constituting the porous foamed resin particles 2 is not particularly limited, and for example, general-purpose plastics such as polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyamide, polycarbonate, modified polyphenylene Engineering such as ether, polyether sulfone, polyester ABS, plastic, etc. can be applied.

On the other hand, in the case of the porous expanded resin particles (2) using polystyrene, since the softening point of polystyrene is relatively low at 80 ° C or more and 100 ° C or less, and the long-term continuous use temperature is 50 ° C, it is used in an environment above this temperature. It is necessary to use a high performance plastic such as a polycarbonate resin or a polyamide resin having a higher softening point and stronger strength. Here, since red phosphorus is suitable when long-term continuous use temperature is 50 degreeC, red phosphorus may be added to the coating layer 3. And when the softening point is higher than this, since ammonium polyphosphate is suitable, it is good to add ammonium polyphosphate to a coating layer.

In addition, as the thermosetting resin containing at least one of the boron-based inorganic compound constituting the coating layer 3, the flame retardant inorganic compound and the flame retardant, other than phenol resin or phenol resin, urea resin, melanin resin, guanamine resin, silicone A thermosetting resin such as resin, polyimide or polyamideimide resin can be used.

As the boron-based inorganic compound contained in the coating layer 3, boric acid (Na ₂ B ₄ O ₇ · 10H ₂ O) and the like are suitable as well as boric acid (H ₃ BO ₃ ). In addition, as the flame-retardant inorganic compound in air is included during the coating layer 3, for example, fine hollow glass job Cirrus balloon, aluminum hydroxide (Al ₂ (OH) _3), silicon (Si), or diatomaceous earth addition, more than 200 1㎛ The inorganic powder which is an inorganic fiber as an inorganic material which shows neutral or acidic magnitude | size about about micrometer or less is suitable. As the inorganic powder, various ceramics, carbon black, or the like may be used in order to ensure more flame retardancy. In addition, the flame retardant added in a small amount to the coating layer 3 may dissolve carbonization momentarily at the time of combustion, block oxygen from the outside, and exert an absolute effect on the prevention of combustion.

In addition, as the flame-retardant inorganic material contained in the coating layer (3), the mica (mica) silicate having a bakhyeongsang structure, or alumina (Al ₂ O _3), clay (kaolin or china gray and the like), calcium carbonate (CaCO ₃ ), chromium oxide (Cr ₂ O ₃ or CrO _2, etc.), zeolite, pearlite, silica (SiO ₂ ), tin (Sn), talc (talc), titanium (Ti), carbon fibers and the like may be used.

At this time, as a combination of substances contained in the coating layer 3, in order to form a molded body in which a plurality of porous foamed resin particles 2 are in close contact and integrated, a polystyrene and a boron-based inorganic compound, which is a resin forming a bubble-like structure, are formed. Or although a certain adhesiveness is required between the thermosetting resin containing a flame retardant inorganic compound and a flame retardant, even if mutual mutual adhesiveness is not enough, resin which has adhesiveness with respect to both resin as a porous layer as an intermediate layer which is not shown in figure is shown. It is also possible to improve the adhesiveness by inserting between the particles 2 and the coating layer 3.

In addition, by adding and mixing the thermosetting resin contained in the coating layer 3 with other thermosetting resins and thermoplastic resins other than this thermosetting resin, proper hardness, flexibility, toughness, strength, etc. can be provided. Can be. At this time, as other thermosetting resins and thermoplastic resins different from the thermosetting resins, for example, polyimide resin, polyvinyl forma resin, polyether sulfone resin, acrylonitrile polybutadiene copolymer of carboxylic acid, etc. It is available.

The coating layer 3, which is a layer of a thermosetting resin containing a boron-based inorganic compound or a flame retardant inorganic compound, and a flame retardant, constitutes an outer layer of the porous foamed resin particles 2, and is fire resistant to the porous foamed resin particles 2 , Heat resistance and flame retardant. In addition, this coating layer 3 is in the state which solidified or semi-hardened at the temperature in these foaming processes, in order to obtain the foaming process of a grain of beads, and to make a bubble-shaped structure normally.

Resin reinforcing materials such as short carbon fibers, glass fibers, synthetic resin fibers, and natural fibers, which are carbon fibers, are added to the coating layer 3, and the strength, fire resistance, heat resistance, and flame resistance of the coating layer 3 are added. And other characteristics can be improved. Moreover, the hardening accelerator which mixes the thermosetting resin contained in this coating layer 3 with this coating layer 3 is mixed. And this hardening accelerator adjusts the mixing amount of this hardening accelerator, adjusts hardening acceleration of a thermosetting resin, and blocks hardening acceleration of the coating layer 3. Specifically, these curing accelerators are phenol sulfonic acid and toluene sulfonic acid.

Next, the manufacturing method of the foamed styrol product 1 of the said embodiment is demonstrated.

(1) adjustment of raw materials

The raw material is already pretreated by impregnation with a blowing agent and the like, and polystyrene beads containing a blowing agent are used as the grain beads. As this raw bead, there are commercially available polystyrene beads having an original diameter of about 0.2 mm or more and about 1.0 mm or less.

(2) Preliminary foaming process

According to the desired product, the above-mentioned raw beads are pre-foamed at a predetermined ratio, for example, 5 to 90 times or 20 to 100 times (preferably 90 times) to be prefoamed beads. That is, before the coating process described later, the particulate beads are prefoamed. The pre-foamed beads are used after being aged for 24 hours (preferably about 20 hours) from 12 days in order to maintain product stability. In addition, this pre-foamed bead may be consumed in a molding step to be described later within one week as much as possible, and may be used up while a large influence is caused by the diffusion of residual gas in the pre-foamed bead.

At this time, there are various treatment methods such as steam, radiant heat, infrared hot air, and hot water as the pre-foaming method used when producing the pre-foamed beads.

(3) coating process

Among the plurality of pre-foamed beads described above, each of the thermosetting resin, the boron-based inorganic compound, and the flame-retardant inorganic compound is mixed 1: 1 or each alone. At this time, in order to further exert the flame retardant effect of the foamed styrol product (1) made of these many pre-foamed beads, a flame-retardant inorganic compound mixed in these pre-foamed beads among these many pre-foamed beads The flame retardant is used together and mixed so that it may become a ratio of about 5 mass% to about 20 mass% with respect to, to form a coating layer 3 having a predetermined thickness. In other words, the prefoamed beads are mixed so that the total of the thermosetting resin, the boron-based inorganic compound, and the flame retardant inorganic compound is in a ratio of 5 to 1 to 1 to 5.

That is, the boron-based inorganic compound and the flame-retardant inorganic compound may be mixed by the density and the degree of flame retardancy of the boron-based inorganic compound or the flame-retardant inorganic compound in the coating layer 3 constituting the foamed styroline product 1 finally formed. Or a flame retardant such as red phosphorus or ammonium polyphosphate is added to either one of these boron-based inorganic compounds and flame-retardant inorganic compounds.

At this time, when the viscosity of a thermosetting resin rises by the flame-retardant inorganic compound added to the thermosetting resin used as this coating layer 3, and the coating layer 3 is a high viscosity sloppy state, what is called a chocolate form, About 3 mass% or more and 10 mass% or less water, 10 mass% methanol, etc. are added to this thermosetting resin, and the viscosity of this thermosetting resin is adjusted.

Furthermore, ₃₀ PHR was mixed individually or one-to-one with phenol resin (resol) as the thermosetting resin, boric acid (H ₃ BO ₃ ) as the oxygen-based inorganic compound, and aluminum hydroxide as the flame-retardant inorganic compound, alone or in a one-to-one manner. (Perts per Hundred Rub ber) is added at a rate of about 100 PHR. At this time, in order to further increase the flame retardancy of the thermosetting resin, 5 mass% to 20 mass% (preferably about 10 mass% is an appropriate amount) based on the mass of the above-described flame retardant inorganic compound and boron-based inorganic compound. Red phosphorus or ammonium polyphosphate is added as flame retardant. At this time, in order to further improve the flame retardant effect by the coating layer 3, this flame retardant contains red phosphorus or ammonium polyphosphate about 1/20 to 1/30 of a flame retardant inorganic compound.

The thermosetting resin is added with a curing accelerator such as phenol sulfonic acid or toluene sulfonic acid having a solid content of about 75%, and then stirred and dispersed well. At this time, it mixes for 2 to 4 minutes (preferably 2 to 3 minutes) with predetermined machines, such as an automatic stirrer and ribbon mixer which are not shown in figure. And after this mixing, it is stirred for about 4 to 5 minutes.

(4) drying process

A portion of these multiple coated prefoamed beads, with air drying, i.e. air drying, these multiple coated prefoamed beads so that the surface area of the multiple coated prefoamed beads coated by the above-described coating process is as large as possible. Disintegrate.

Subsequently, the coated prefoamed beads, which are partially crushed, are dried at a temperature of about 55 ° C. ± 3 ° C., while being crushed until complete monoparticulation. The drying time at this time is, if the coated prefoamed beads are granulated, hot air drying as short as possible, preferably within 5 minutes, more preferably about 3 to 5 minutes. The drying temperature at this time is not preferable because the gas escapes from the coated pre-foamed bead if the temperature is too high. Therefore, the drying temperature is dried at a temperature of about 55 ° C ± 3 ° C. At this time, in the case of using a high magnification of about 60 times or more and about 90 times or less, particular attention is required.

In addition, after the disintegration and drying of these many coated pre-foamed beads are completed, these many coated pre-foamed beads are vibrated with a vibrator to make single particles to obtain single particle beads which are coated single particles.

(5) Main foaming process (heating process)

The single particle beads produced by the drying step described above are automatically filled with air in an automatic molding machine or a mold of a block molding. In this state, by heating with a vapor pressure of about 0.6kg / cm ³ to about 1kg / cm ³ , after forming by heating and vacuum-cooled vacuum cooling as in the molding method of ordinary expandable polystyrene resin (EPS) Demould. At this time, in general, the larger the foaming rate, the shorter the heating amount and cooling time.

Specifically, when the foaming rate of the foamed styrole product 1 is about 80 times, the heating time is about 30 seconds to 60 seconds. Therefore, it is suitable for the foamed styrene product 1 foamed at high magnification. However, depending on the size of the molded article, a heating time of about 60 seconds is usually sufficient.

In addition, as another molding method, a good foamed styrene product 1 can be produced even by a high frequency heating method, a hot plate heating method, or a hot press method, but generally takes one cycle as compared with the steam molding method. However, in the case of the high frequency heating method and the like, by forming while adhering the single particle beads to the metal plate, the panel can be paneled very efficiently. In addition, it may be molded using a flattening filling by a normal steam molding method or a high frequency heating method or the like, or a flattening by a flattening method of horizontally filling the rice as if it is weighed.

With this main foam, these single particle beads are formed on the outer surface of these single particle beads and expand and contact with each other with a coating layer 3 composed of a boron-based inorganic compound, a flame retardant inorganic compound, and a flame retardant. . At this time, the inner layer and the outer layer of these single-particle beads are cured and cured together with the coating layer 3 on the outer surface of the adjacent single-particle beads by heating. As a result, the porous resin foamed particles are bonded to each other in a cell (cell) shape to form a cell (cell) group, thereby forming a foamed styrene product 1 which is a molded article having a predetermined shape according to the inner surface of the mold.

As described above, according to the above embodiment, the pre-foaming of the bead is made into pre-foamed beads. Subsequently, the pre-foamed beads are mixed with a thermosetting resin containing a flame retardant inorganic compound to prepare prefoamed beads coated with a surface in the coating layer 3 containing these flame retardant inorganic compounds and thermosetting resins, and then these preliminary beads. The foamed beads were dried and pulverized to single particles.

As a result, in the coating layer 3 including the flame retardant inorganic compound and the thermosetting resin, a large number of pre-foamed particles coated on the surface become single particles to form a large number of single particle beads. Therefore, by filling these molds with a plurality of single particle beads and then foaming them, heat can be efficiently and reliably sent to the gaps of the coating layer 3 covering the surfaces of each of the plurality of single particle beads. Therefore, in order to make the main foaming time of these many single particle beads short in time by the effect of the heating using the water vapor | steam at the time of this foaming, and the vacuum cooling after that, many of these stages are not used. Since particle beads can be foamed more reliably in a short time, the time required for the main foaming of many of these single particle beads can be significantly shortened.

At this time, the molecular weight of the phenol resin in the coating layer 3 of the surface of these many single particle beads is made about 3000, and the usage-amount of the hardening accelerator to this coating layer is adjusted, and at the time of this foaming of these many single particle beads, By adjusting the timing of the heating, using a steam to heat the main foam of a large number of single particle beads, the coating layer 3 becomes difficult to flow from the surface of these many single particle beads. Therefore, as compared to the case of the double coat, which is a method of coating the surface of a plurality of single particle beads in two stages, sufficient flame retardancy is secured in a single coat sufficient to form a single coating layer on the surface of the plurality of single particle beads. Since the process of coating the surface of these many single particle beads can be abbreviate | omitted one step. For this reason, the drying of many pre-foamed beads is not as difficult as before, and single-particle beads can be manufactured quickly in large quantities.

Specifically, the thickness of the foamed styroline product 1 finally produced is about 100 mm or more and about 600 mm or less, and is 3 minutes or more due to the heating time of about 30 seconds to about 60 seconds and the effect of subsequent vacuum cooling. Since the main foam of the foamed styrole product 1 can be cycled in about one minute or less, the mass production of this foamed styrole product 1 is enabled.

Therefore, the foamed styrol product 1 formed of the main foam of these many single particle beads can be manufactured efficiently. For this reason, as shown to FIG.3 (a)-FIG.3 (c), the predetermined | prescribed which was able to prevent generation | occurrence | production of the black smoke at the time of combustion, can improve fire resistance, and can suppress the shrinkage deformation by heat. The shaped foamed styrol product 1 can be produced with high productivity. At this time, as shown in FIG.3 (c), the surface of the ignited and carbonized part of foamed styrol product remains smooth even immediately after dyeing. On the other hand, as shown in Fig. 3 (d), in the conventional polystyrene, since a large amount of black smoke is generated even in a state after 10 seconds of ignition, it is not easy to take a combustion state in a photograph.

Therefore, it exhibits excellent fire resistance and heat resistance against fire and heat, such as fire, and melts at the time of fire, without impairing the shoe resistance, heat resistance and lightness of conventional resin foam boards, and easy handling and low cost. It is possible to suppress the generation of black smoke and toxic gases without burning without contracting.

At this time, when the coating layer 3 is extremely low molecular weight or when the curing of the resin is late, the coating layer 3 may flow from a plurality of single particle beads, but in this case, the coating layer 3 It is not preferable because it adheres to the inner surface of the mold.

In addition, as compared with the conventional foamed styrene products in which the foamed styrene beads are mixed with the boric acid-based inorganic material and then pre-foamed, the boric acid-based inorganic material is added again, and then foamed. In view of low raw material filling and the like, cost reduction at a high magnification (a conventional half) can be achieved, and production efficiency can be improved.

In addition, the porous foamed resin particles 2 were made of polystyrene resin, and the flame retardant inorganic compounds contained in the coating layer 3 on the surface of the porous foamed resin particles 2 were boric acid of aluminum hydroxide and oxygen-based inorganic compounds. In addition, the thermosetting resin contained in this coating layer 3 was made into phenol resin. As a result, by containing the boron-based inorganic compound in the coating layer 3, when the coating layer 3 is complexed, cracks are less likely to occur in the coating layer 3 and the generation of smoke is reduced. In addition, since the foamed styrol product 1 can be produced easily and inexpensively in a manufacturing method such as conventional foamed polystyrene, the foamed styrole product 1 can be produced more productively.

In addition to the oxygen-based inorganic compound, the flame retardant inorganic compound, and the flame retardant, the thermosetting resin contained in the coating layer 3 includes fiber reinforcing materials such as carbon fibers, hollow particle materials such as silica, pearlite, and syras balloon, neutral or acidic. Inorganic powder is added. As a result, the foamed styrole product 1 to be produced becomes stronger against fire, and the shrinkage deformation caused by heat can be reliably suppressed, and the fiber of the fiber material in the coating layer 3 of the foamed styrole product 1 is incorporated. By this, the strength can be further improved. Therefore, the fire resistance and the flame retardance of the foamed styrol product 1 to be manufactured can be further improved, and shrinkage deformation can be further suppressed.

At this time, when it is desired to further improve the flame retardancy, a flame retardant such as ammonium polyphosphate or red phosphorus is further added at a ratio of 5% or more and 10% or less in the inorganic powder. As a result, the flame retardancy by the carbonization effect, ie, the oxygen blocking effect, of the foamed styroline product 1 produced can be further improved. In addition, by using red phosphorus or ammonium polyphosphate as the flame retardant to be mixed in the coating layer 3, the flame retardant can be classified according to the use temperature at the time of foaming, so that the flame retardancy of the foamed styrole product 1 can be secured. This can be done more easily.

In addition, the curing accelerator is mixed with a plurality of prefoamed beads together with an oxygen-based inorganic compound, a flame retardant inorganic compound, and a thermosetting resin, followed by drying and pulverization to form a plurality of single-particle magnetized single particle beads. As a result, hardening of the coating layer 3 at the time of carrying out these foaming of many single particle beads can be adjusted by adjustment of the quantity of the hardening accelerator contained in this coating layer 3. Therefore, a large number of single-particle beads whose surface is coated and single-particle-coated in this coating layer 3 can be foamed more efficiently in a short time.

In addition, prior to the coating step of forming the coating layer 3 on the surface of the porous foamed resin particles 2, the pre-foamed beads having the pre-foamed particles are pre-foamed at a predetermined ratio. do. As a result, since the thickness of the coating layer 3 which covers the surface of this porous foamed resin particle 2 can be adjusted, the main foaming process of the prefoamed bead after this coating layer 3 is formed can be made smooth.

In addition, the foamed styrene product (1) which coated the surface of the porous foamed resin particles (2) with a coating layer (3) made of a boron-based inorganic compound, a flame-retardant inorganic compound, and a thermosetting resin, is called a foamed product such as a polystyrene foamed molded product. By the bubble-shaped structure of the porous foamed resin particles 2 constituting the styrol product 1, it is possible to effectively exhibit shoe resistance and heat resistance. At this time, the heat-insulating effect is enhanced by the bubble-like structure of the porous foamed resin particles 2, and the coating layer 3 is flame retardant due to heat resistance or oxygen blocking effect due to rapid carbonization for heating such as fire. It contributes to the effect of more.

Moreover, the exact reaction of what kind of reaction the coating layer 3 consisting of a mixture of boron-based inorganic compounds, flame-retardant inorganic compounds and thermosetting resins will cause upon heating is not clear, but the thermosetting resin is thermoset with heating. It is thought that the bubble-shaped structure which the porous foamed resin particle 2 has is maintained. As the vitrification of the oxygen-based inorganic compound proceeds to a higher temperature, the thermosetting resin retaining these cured bubble-like shapes is blocked from the vitrified boron-based inorganic compound from the outside air. In addition, aluminum hydroxide, a flame-retardant inorganic compound used in combination, is also useful, releasing moisture (H ₂ O) to the outside air, preventing combustibility, and carbonization such as a small amount of red phosphorus, and also rapidly blocking oxygen from outside air. It is thought that combustion and disappearance are thereby prevented.

At this time, the reaction in which the boron-based inorganic compound is vitrified is widely known. For example, boric acid changes into pyroboric acid (H ₂ B ₄ O ₇ ) via metaboric acid (HBO ₂ ) to form a glass, and changes to boric anhydride (B ₂ O ₃ ) at a higher temperature. At this time, the vitrification of boric acid advances easily by presence of a sodium salt or the like. Therefore, the thermosetting resin which maintains a bubble-shaped structure by hardening in fire and heat, such as a fire, and the porous foamed resin particles 2 melted and cured in the process of hardening this thermosetting resin to cover oxygen from outside air, etc. As long as it can block and prevent reaction at a higher temperature, the combination of the inorganic compound which should be mixed with this thermosetting resin is not limited to the said one Embodiment.

In addition, when heating of the foamed styrole product 1 proceeds, the reaction zone of the foamed styrole product 1 also advances to some extent with the progress of the heating, but the porosity by the porous foamed resin particles 2 described above. Since the range of heating is limited by the foamed structure being maintained, the heating of the foamed styrol product 1 does not proceed more than a certain amount.

Therefore, the porous foamed resin which supports the shape of the porous foamed resin particle 2 which comprises this foamed styrole product 1 is a porous foamed resin by the heating process at the time of manufacturing this foamed styrole product 1, It fuses with the thermosetting resin in the coating layer 3 which coat | covers the particle | grains 2, and is integrated. In addition, the porous foamed resin particles 2 and the coating layer 3 are formed by vitrification of boron-based inorganic compounds and the blocking of external air by rapid carbonization such as red phosphorus, or by synergistic effects with the waterproofing of moisture by flame-retardant inorganic compounds. The shape of is maintained. As a result, the heat conduction into the foamed styrol product 1 is interrupted, and the progress of this heat transfer is prevented. For this reason, with this heating, even if these porous foamed resin particles 2 are burned, since the burned range is limited to the area of the surface of the porous foamed resin particles 2, the generation of black smoke and toxic gas is caused. Can be largely prevented.

In addition, properties such as light weight, strength, water resistance, stability as a material, and the like of the foamed styrole product 1 also include boron-based inorganic compounds, flame-retardant inorganic compounds, and inorganic additives that cover the surface of the porous foamed resin particles 2. The coating layer 3 itself which is composed of red phosphorus or ammonium polyphosphate and thermosetting resin at about 20% by mass or more is relatively light, thin, chemically stable, and has a constant strength. At this time, since the strength which can be calculated | required with respect to this foamed styrol product 1 is about the surface load which is comparatively uniform, characteristics, such as the strength which it has originally, can be maintained.

Moreover, it can manufacture efficiently or effectively by using foaming molding processes, such as foamed polystyrene conventionally, as a manufacturing method of this foamed styrol product (1). Therefore, in order to form the porous foamed resin particles 2, a pre-foamed bead containing a foaming agent or impregnated with a foaming gas and pre-treated to complete foaming at a desired magnification, a boron-based inorganic compound, a flame-retardant inorganic compound and a small amount The coating layer 3 is formed by coating with a thermosetting resin mixed with a flame retardant such as red phosphorus or ammonium polyphosphate, to form a single particle. Thereafter, the coating layer 3 is formed and the single particle beads formed into single particles are heated to be foamed to obtain a foamed styrole product 1 having a predetermined shape.

As a result, a boron-based inorganic compound, a flame-retardant inorganic compound, and a flame-retardant inorganic compound and flame retardant are formed on the outer surface of the porous foamed resin particles 2 forming the original bubble-shaped structure by the coating layer 3 constituting the foamed styrole product 1. It has the same effect as the configuration of overlapping a plurality of thermosetting resin layers having a flame retardant carbide blocking action composed of a flame retardant. Therefore, a very fast coating layer 3 can be formed on the surface of the porous foamed resin particles 2.

In addition, the structure in which the coating layer 3 is formed on the surface of the porous foamed resin particles 2 maintains fire resistance, flame retardancy, and shape retention which could not be achieved by the porous foamed resin particles 2 constituting the bubble-shaped structure. Properties such as properties can be imparted to the foamed styrol product 1. At this time, the thermosetting resin in which the boron-based inorganic compound constituting the coating layer 3, flame retardant aluminum hydroxide, and some red phosphorus or ammonium polyphosphate is mixed with the porous foamed resin particles 2 forming a bubble-like structure. In order to coat | cover a surface, it is good also as a method of apply | coating a liquid precursor of a thermosetting resin or an uncured thermosetting resin by various methods, or dissolving in a solvent, such as alcohol, and then increasing the solvent.

In this case, the method may be appropriately selected depending on the type and properties of the thermosetting resin, and the porous foamed resin particles (2) having appropriate characteristics and fluidity under the conditions such as heating of the foaming process described above and formed into the main foam (2). What is necessary is just to be able to produce the coating layer 3 of uniform film thickness in the surface of ().

On the other hand, the coating layer 3 of uniform film thickness is formed on the surface, and the semi-cured pre-foamed bead of the state which has been hardened to some extent is filled in a mold as it is, and it is 5 to 6 minutes at the temperature of about 110 degreeC by indirect heat. Although the foamed styrol product 1 can be formed by heating and cooling to a degree, generally, in this method, the molding time is too long. Accordingly, the pre-foamed beads whose surfaces are uniformly coated in the coating layer 3 are dried in a warm air at a temperature of about 55 ° C. ± 3 ° C., and the blocks blocked by a small amount of pressure are crushed, granulated, and shaken. By vibrating, the single particles are more completely made into a plurality of single particle beads. The drying at this time may be somewhat longer in air drying, but in the case of forced drying, it is finished in about 3 to 5 minutes at a temperature of about 55 ° C ± 3 ° C. That is, it is because the single particle of prefoamed beads is aimed at.

Therefore, the air drying is made to be a small block by advancing the disintegration of the beads pre-foamed to some extent with a little length, and if possible, drying is completed within 3 minutes at a temperature of about 55 ° C. ± 3 ° C. to single particles. That is, the thermosetting resin in these prefoamed beads obtains stage B, which is the flow based on this standard, from stage A before the flow made as a reference, and is completely cured at stage C beyond the flow made based on this standard. For this reason, heating and drying at a temperature of about 55 ° C. ± 3 ° C. centering on air drying is desired to stop the curing of the thermosetting resin at about the middle of the B stage. When particle | grains generate | occur | produce, it is made as short as 2 minutes and 3 minutes as much as possible.

In other words, when the thermosetting resin in these prefoamed beads is completely cured after advancing to the C stage, the fusion hardening between the beads prefoamed in the foamed styrol product 1 molded into these prefoamed beads can be performed. This is because the fusion bonding between these prefoamed beads cannot be performed, and thus the strength of the manufactured foamed styrole product 1 cannot be ensured.

As a result, in the state which the single-particle beads which the surface was coat | covered by the coating layer 3, and became single-particle bead filled in the metal mold | die, water vapor is applied between these single-particle beads, and these single-particle beads are foamed, and these single-particle beads are carried out. Water vapor can be reliably sent between the coating layers 3 of beads. Therefore, the main foam of these single particle beads can be molded more efficiently in a short time. Therefore, the foamed styrol product 1 molded into the main foam by the vapor of these single particle beads can be manufactured more efficiently.

Example 1

It was confirmed that the foamed styrol product 1 of the above embodiment was experimentally produced using the following starting materials and the like to exhibit the same effect.

a Pre-foamed expanded polystyrene resin (pre-expanded beads): 50x 100PHR

b Resol resin (thermosetting resin) 75 PHR (for prefoamed beads)

c Phenolic sulfonic acid (hardening accelerator) 7.5 PHR (for thermosetting resin)

d Boric acid (boron-based inorganic compound) 30 PHR (for prefoamed beads)

e Aluminum hydroxide (flame retardant inorganic compound) 30 PHR (for prefoamed beads)

f Red phosphorus (flame retardant) 10PHR (for boron-based inorganic compound and flame retardant inorganic compound)

Then, the foam coating beads formed by mixing the a to f was air dried and then roughly crushed. Thereafter, the mixture is dried for 5 to 10 minutes at a temperature of 55 ° C ± 3 ° C, pulverized, vibrated with a vibrator, and granulated to form a plurality of single particle beads whose surface is covered by the coating layer 3.

In addition, after filling a large number of these single particle beads in a mold, in the case of the hot plate press method using a hot plate using a mold having a length of 230 mm x width 230 mm x thickness 30 mm, after heating at a temperature of 110 ° C. for about 5 minutes, 20 Cool for about a minute to form a foamed styrol product (1).

At this time, the main properties of the foamed plastic product (1) has a density of 76kg / m ^3, a compressive strength 42N / cm ^2, and the absorption rate is 0.31g / 100cm ^2, the oxygen index was 38.7.

Example 2

Moreover, it confirmed that the foamed styrol product 1 of the said embodiment was experimentally produced using the following raw materials etc., and showed the same effect.

a Pre-foamed polystyrene resin (pre-expanded beads): 60 times 100PHR

b Resol resin (thermosetting resin) 90 PHR (for prefoamed beads)

c Phenolic sulfonic acid (hardening accelerator) 10PHR (about thermosetting resin)

d Boric acid (boron-based inorganic compound) 1 PHR (for prefoamed beads)

e Aluminum hydroxide (flame retardant inorganic compound) 59 PHR (for prefoamed beads)

f Red phosphorus (flame retardant) 15 PHR (for boron-based inorganic compound and flame retardant inorganic compound)

g Methanol 5PHR (for thermosetting resin)

h Acrylic resin emulsion (2.5 PHR to 3 PHR) solution 2 PHR (for prefoamed beads)

Then, c is added to b and mixed for about 1 minute. Then, g is added to about 5 PHR of b to lower the viscosity to lower the viscosity. Subsequently, the mixture is mixed in order of d, e, and f in order to form chocolate in the order of e, d, and f.

Furthermore, after mixing this chocolate-like thing into a put in the stirrer, stirring, it stirred for 2 to 3 minutes, and finally, h put about 20 mass% of a, stirred for 1 to 2 minutes, and coated it. Make a bead.

Thereafter, the coated beads are roughly disintegrated while being discharged and air-dried immediately from the stirrer, and further disintegrated to form single particles, and finally vibrated with a vibrator and completely granulated to form a plurality of single particle beads.

And many of these single particle beads are shape | molded by the steam method which is an automatic molding method. Specifically, these single particle beads were filled into a heating mold having a height of 300 mm in height x 300 in width x 30 mm in thickness, then heated with 0.6 kg / cm ³ of steam for about 40 seconds and then cooled for about 2 minutes to expand the foamed styrol. The product 1 is formed.

At this time, the main physical properties of the foamed styrole product 1 are 0.047 g / cm ³ (JIS A 9511), the compressive strength is 25 N / cm ² (JIS K 7220), and the water absorption is 0.27 g / 100 cm ^2. (JIS K 9511), the thermal conductivity (abnormal hot wire method) was 0.033 W / mK, and the oxygen index was 32 (JIS K 7201 A1).

Example 3

Furthermore, it confirmed that the foamed styrol product 1 of the said embodiment was experimentally produced using the following raw materials etc., and showed the same effect.

a Pre-foamed expanded polystyrene resin (pre-expanded beads): 80x 100PHR

b Resol resin (thermosetting resin) 110 PHR (for pre-foamed beads)

c Phenolic sulfonic acid (hardening accelerator) 10PHR (about thermosetting resin)

d Boric acid (boron-based inorganic compound) 35 PHR (35 mass% of pre-foamed beads)

e Aluminum hydroxide (flame retardant inorganic compound) 35 PHR (35 mass% of prefoamed beads)

f Red phosphorus (flame retardant) 10PHR (7% by mass of boron-based inorganic compounds and flame-retardant inorganic compounds)

g Methanol 5PHR (for thermosetting resin)

h Nitrile butadiene emulsion 3% by mass aqueous solution 20PHR (relative to prefoamed beads)

Then, c is added to b and mixed well for about 1 minute. Then, 5 g PHR of b is mixed and mixed well to obtain a low viscosity. Subsequently, this mixture is mixed while mixing in order of e, d, and f in order to obtain a chocolate shape.

In addition, this chocolate-shaped thing was put into a stirrer and mixed into prepared a, then stirred for 2 to 3 minutes, and then h was added and stirred for 1 to 2 minutes to form a coating bead from the stirrer. Discharge.

Thereafter, simultaneously with the discharge from the stirrer, the coated beads are made as thin as possible to increase the surface area and air-dried to roughly disintegrate while taking a certain haze. In addition, the roughly pulverized coating beads were subjected to a warm air of about 55 ° C. ± 3 ° C., dried for 5 to 8 minutes, further pulverized and singled, and finally singled with a vibrator to prepare a plurality of single particle beads. Store and use it.

And, many of these stored single particle beads are steam-molded by the automatic molding method. Specifically, many of these single particle beads were filled into a mold having a height of 300 mm in height x 300 mm in width x 30 mm in thickness, and then heated at a vapor pressure of 0.6 kg / cm ³ for about 35 seconds and then cooled for about 2 minutes. Foamed plastic article 1 is formed.

At this time, the main properties of the foamed plastic product (1) has a density of 0.04g / cm ^3, and a compressive strength of 20N / cm ^2, and the absorption rate is 0.3g / 100cm ^2, a thermal conductivity of 0.032W / m · K And an oxygen index of 30.5.

As a result, the flame retardant contained in the coating layer 3 of the foamed styrole product 1 generally has a low fire resistance temperature and a high heat resistance temperature when the porous foamed resin particles 2 such as polystyrene are used. Is better. On the other hand, when the porous foamed resin particles 2 having fire resistance and heat resistance of 100 ° C. or more are used, the decomposition temperature of the porous foamed resin particles 2 is suitable since the effect is greater than that of red ammonium polyphosphate. . Therefore, when using expanded polystyrene resin foamed at high magnification, red phosphorus is generally suitable because of its greater effect at lower temperatures than ammonium polyphosphate.

In addition, the foamed styrole product 1 molded in each of the above-described embodiments can exhibit fire resistance, heat resistance, and flame resistance in the use of conventional foamed molded products such as polystyrene and polyurethane, and has not been applicable in the past. It can also be used suitably. In addition, the molding die may be a three-dimensional box-shaped article of various shapes, a foamed molded article containing a pattern, or the like. In addition, the resin reinforcing material added to the thermosetting resin constituting the coating layer 3, an inorganic material in the form of powder particles, and a combination of resins can impart new characteristics and can be applied to various applications. .

For example, as a building material, the roofing material, such as a heat insulation machine, the heat insulating material, such as an external insulation material, a ceiling, or a floor, can be considered. Moreover, as a lightweight flame retardant board for various uses, a panel, a building tool, a partition, a wall material, etc. can be considered. Moreover, as a heat insulating structural material for various uses, a heating and cooling duct, the heat insulating material of a cold storage, thermal insulation installation, a mannequin, etc. can be considered.

Therefore, the above-mentioned foamed styrole product (1) is a foamed molded product for these various uses, and has the same light weight and heat insulating properties as conventional foamed molded products such as foamed polystyrene and polyurethane foam. It is excellent in flame retardancy and shape retention and can cope with safety aspects of disaster countermeasures such as fire. In addition, the coating layer 3 which covers the surface of the porous foamed resin particle 2 is suitably selected from the kind of resin which comprises this coating layer 3, or mixed with other types of resin, an inorganic substance, or an organic substance. By doing so, properties, such as flexibility, a strength, and hardness, can be provided more suitably, for example.

In addition, although various characteristics are required in the future, in other words, since the greatest strength of the expanded polystyrene resin is a high magnification of the foaming ratio, the above-described manufacturing method covers the surface in the coating layer 3 in comparison with the polystyrene beads, so that this coating layer In (3), the density of the grains of the porous foamed resin particles 2 coated with the surface becomes about twice the mass. Therefore, beads of expanded polystyrene foamed at a high magnification of about 80 to 90 times are used, except for requiring a special strength.

In addition, as the flame retardant inorganic compound, an inorganic material having as small a density as possible is used, and the weight is reduced so as to be close to the density of ordinary styrene, urethane, phenol foam and the like. At this time, when the expanded polystyrene resin is foamed at a high magnification, the heating time and cooling time are shortened, resulting in a lighter product density. Thus, the material ratio can be reduced, and the thermal conductivity can be improved.

In addition, although the so-called flame retardant grade 3 can be ensured in the foamed styroline product 1 produced in each of the above examples, in order to further improve the flame retardancy of the foamed styroline product 1, and to secure so-called flame retardant grade 2 It is also conceivable to mix various ceramics, diatomaceous earth, carbon black and the like as the mixing agent of the coating layer 3 of the foamed styrol product 1.

Example 4

Moreover, it confirmed that the foamed styrol product 1 of the said embodiment was experimentally produced using the following raw materials etc., and showed the same effect.

a Pre-foamed expanded polystyrene resin (pre-expanded beads): 70 times 100PHR

b Resol resin (thermosetting resin) 120 PHR (for prefoamed beads)

C toluene sulfonic acid (curing accelerator) 9PHR (about thermosetting resin)

d Aluminum hydroxide (flame retardant inorganic compound) 80 PHR (for prefoamed beads)

e Acetic acid (boron-based inorganic compound) 10 PHR (for pre-expanded beads)

f Mica (flame retardant inorganic material) 10 PHR (for prefoamed beads)

g red phosphorus (flame retardant) 5PHR (for prefoamed beads)

On the other hand, the expansion ratio of the expanded polystyrene resin varies depending on the required strength, but in general, it is preferable to use a 60-100 or more magnification as the thickness of the expanded polystyrene resin. In general, when the expansion ratio is large, the mass of the expanded polystyrene resin serving as the base material decreases. Therefore, in general, the resol resin may be 120 PHR or more and 150 PHR or less with respect to the expanded polystyrene resin.

Furthermore, toluene sulfonic acid may be used in the range of 6 PHR or more and 10 PHR or less with respect to the resol resin. In addition, although aluminum hydroxide needs to consider cost and burning loss, in addition to releasing moisture at the temperature rise, odors and smoke are not included. Since there are advantages such as adsorption, it may be used as much as possible. In addition, boric acid is desired to be used in large quantities because of its low density. However, some of the boric acid may be eluted by steam at the time of molding. Therefore, the boric acid may be used in the range of 1% by mass to 15% by mass. In the case of the site condition of the factory equipment which directly drains the cooling water to a river on the manufacture of the product 1, it is better to reduce the use rate of boric acid to about 1% as much as possible.

In addition, mica is used as a flame-retardant inorganic viscosity modifier, and generally, it is good to use it in the range of 5 PHR or more and 50 PHR or less with respect to foamed polystyrene resin. In particular, the resol resin is inorganic flame retardant based on foamed polystyrene resin as in Example 4 When used in large quantities as a powder and dried through a step of drying by vibration, subsequent steps may cause scattering or dropping of fine powder, which is not preferable in terms of environmental hygiene. On the other hand, by adding mica to the expanded polystyrene resin, the viscosity of the expanded polystyrene resin can be adjusted, so that fine powder does not scatter during drying and other inorganic additives do not fall off. It can be made preferable from a viewpoint. Moreover, since the other flame retardant added to the expanded polystyrene resin does not fall off, the flame retardancy of the foamed styrole product 1 can be further improved. At the same time, by adding mica to the foamed polystyrene resin, some stickiness is produced in the resol resin added as a binder to the foamed polystyrene resin, so that the strength of the foamed styrene product 1 can be further improved, and the foaming The problem that a crack generate | occur | produces at the time of burning of the styrol product 1 can be prevented to some extent.

Furthermore, since red phosphorus is generally a very expensive material, it is good to suppress and use about 5 PHR or more and 10 PHR or less with respect to foamed polystyrene resin as much as possible, preferably about 7.5 PHR or less.

As a result, the foamed styrene product 1 having a density of 0.075 and a fusion rate of 100% can be produced. Then, as a combustion test, a portable cylinder not shown is developed and the flame length is set to about 25 cm or more and 30 cm or less, and the portable cylinder is approached 10 mm away from the foamed plastic product 1, and the flame is exposed for 9 minutes. It burned, but in the part which fired this foamed styrole product 1, after 4 seconds, the flame | dye disappeared and the depth of the carbonized part was about 49 mm.

Example 5

Furthermore, it was confirmed that the foamed styrol product 1 of the above embodiment was experimentally produced using the following raw materials and the like to exhibit the same effect.

a Pre-foamed expanded polystyrene resin (pre-expanded beads): 90x 100PHR

b Resol resin (thermosetting resin) 150 PHR (for prefoamed beads)

c toluene sulfonic acid (curing accelerator) 8.5 PHR (about curable resin)

d Aluminum hydroxide (flame retardant inorganic compound) 150 PHR (for prefoamed beads)

e Boric acid (boron inorganic compound) 5PHR (for prefoamed beads)

f Mica (flame retardant inorganic material) 20 PHR (for prefoamed beads)

g red phosphorus (flame retardant) 5PHR (for prefoamed beads)

As a result, as shown in Fig. 4 (a) and Fig. 4 (b), the foamed styrol product 1 having a density of 0.0812 and a fusion rate of 100% can be produced. As shown in Figs. 5 (a) to 5 (c), the portable cylinder is developed as a combustion test and the length of the flame is set to about 25 cm or more and 30 cm or less. The flame was burned for 10 minutes by approaching a distant position, and as shown in Figs. 6 (a) to 6 (c), the foamed styrole product 1 was lit for 0 seconds, that is, for 9 minutes. At the time passed, when the portable bomb was removed, the afterglow disappeared. In addition, as shown in FIG.6 (d), the carbonized part of the foamed styrol product 1 after this combustion was about 42 mm in depth.

TABLE 1

             Exam conditions   Sample direction     level   Sample area 0.008840m ²   Sample thickness    48.6mm   Sample mass    35.60 g    Copy 50.0kW / m ²   Exhaust flow 0.024m ³ / sec  Distance from sample    25 mm   Exam time    600.00 sec

TABLE 2

                      Test result   Total calorific value (THR) 10.24MJ / m ²   Maximum heat generation rate (HRR) 52.47kW / m ² at24.80sec   Average heat generation rate (HRR) 17.32 kW / m ²   Average fever rate T60 32.76 kW / m ²   Average fever rate T180 21.60kW / m ²   Average fever rate T300 20.92 kW / m ²     Final mass     23.80 g     Mass loss     11.40 g     Ignition time     10.1sec     Burning time    589.9sec   200k over duration      0.0sec   200k total time      0.0sec  Average combustion effective calorific value (HOC)      7.94MJ / kg  Average mass loss rate (MLR) 2.106 g / sm ²  Average specific photosensitization 729.15m ² / kg

Therefore, as shown in Table 2 under the test conditions shown in Table 1, the total calorific value of the cone calorimeter test by heating for 10 minutes of the foamed plastic product 1 was 10.24 MJ / m ² . Therefore, with the semi-combustible material specified in the cone calorimeter test, that is, the heating time for 10 minutes, the total calorific value is almost equal to ⁸ MJ / m ² , and at 100 g / m ² or less, the maximum exothermic rate is continued for 10 seconds or more. It could be set as the foamed styrol product (1) which does not exceed 200 kW / m <^2> .

In addition, the addition amount of aluminum hydroxide in the foamed styrol product (1) is 170 PHR for the prefoamed beads, the addition amount of boric acid is 15 PHR for the prefoamed beads, and the amount of red phosphorus is 7.5 PHR for the prefoamed beads. As shown in Table 3, the cone calorimeter test by heating for 10 minutes was carried out about the foamed styrol product (1) prepared by changing to. As shown in Table 4, the total calorific value was 8.84 MJ / m ² . It became.

TABLE 3

             Exam conditions   Sample direction      level   Sample area 0.008840m ²   Sample thickness    49.7 mm   Sample mass    36.40 g    Copy 50.0kW / m ²   Exhaust flow 0.024m ³ / sec  Distance from sample    25 mm   Exam time   600.00 sec

TABLE 4

                      Test result   Total calorific value (THR) 8.84 MJ / m ²   Maximum heat generation rate (HRR) 32.12kW / m ² at26.80sec   Average heat generation rate (HRR) 15.16 kW / m ²   Average fever rate T60 20.68kW / m ²   Average fever rate T180 16.10 kW / m ²   Average fever rate T300 15.53 kW / m ²     Final mass     23.08g     Mass loss     13.32 g     Ignition time     25.3 sec     Burning time    574.7sec   200k over duration      0.0sec   200k total time      0.0sec  Average combustion effective calorific value (HOC)      5.87MJ / kg  Average mass loss rate (MLR) 2.382 g / sm ²  Average specific photosensitization 2.16m ² / kg

As a result, the foamed styrol product 1 has a total heat generation amount equal to ⁸ MJ / m ² even more at a heating time of 10 minutes, and at 100 g / m ² or less, the maximum exothermic rate is continued for more than 10 seconds for 200 kW / m ^2. It was possible to use the foamed plastic product (1) not exceeding the

Furthermore, as shown in Table 5 and Table 6, by laminating an aluminum foil (not shown) on the surface of the foamed styrene product 1 which is a non-flammable expanded styrene index board, it is heated for 20 minutes at 200 g / m ² or less. Since the total calorific value of the cone calorimeter test can be sufficiently reduced to 8 MJ / m ² or less, it is used as a semi-combustible material and is also made of aluminum foil or a calcium silicate plate having a thickness of about 5 and 6 mm, about 4 and 5 mm. It can be used as a nonflammable material by complexing with other materials, such as mortar laminated | stacked at the thickness of.

TABLE 5

             Exam conditions   Sample direction      level   Sample area 0.008840m ²   Sample thickness    48.4mm   Sample mass    37.70 g    Copy 50.0kW / m ²   Exhaust flow 0.024m ³ / sec  Distance from sample    25 mm   Exam time  1200.00sec

TABLE 6

                      Test result   Total calorific value (THR) 1.71 MJ / m ²   Maximum heat generation rate (HRR) 2.81kW / m ² at24.80sec   Average heat generation rate (HRR) 1.44 kW / m ²   Average fever rate T60 0.42 kW / m ²   Average fever rate T180 0.97 kW / m ²   Average fever rate T300 1.33 kW / m ²     Final mass     33.02g     Mass loss      4.68 g     Ignition time        ―     Burning time      0.0sec   200k over duration      0.0sec   200k total time      0.0sec  Average combustion effective calorific value (HOC)      3.22MJ / kg  Average mass loss rate (MLR) 0.464 g / sm ²  Average specific photosensitization 217.28m ² / kg

That is, as shown in Table 6, when aluminum foil was laminated | stacked on the surface of the foamed styrol product 1, the total calorific value in the cone calorimeter test by heating for 20 minutes became 1.71 MJ / m <^2> . Therefore, since the total calorific value in the cone calorimeter test by heating for 20 minutes becomes 8 MJ / m <^2> or less, it becomes a non-combustible material, and the cone calorimeter by heating for 20 minutes by use of an aluminum foil as mentioned above is mentioned. Cleared the incombustibles in the test leisurely.

Example 6

Further, by improving the blending ratio of the raw materials of the foamed styrole product 1 of Example 5 as follows, the 6.63MJ which was afforded to the test value of the semi-non-combustible material by the cone calorimeter test finally with a long-awaited material group. / m ² could be cleared.

a Pre-foamed expanded polystyrene resin (pre-expanded beads): 90x 100PHR

b Resol resin (thermosetting resin) 225 PHR (for prefoamed beads)

c toluene sulfonic acid (curing accelerator) 8.5 PHR (about curable resin)

d Aluminum hydroxide (flame retardant inorganic compound) 225 PHR (for prefoamed beads)

e Boric acid (boron-based inorganic compound) 10 PHR (for prefoamed beads)

f Mica (flame retardant inorganic material) 30 PHR (for prefoamed beads)

g red phosphorus (flame retardant) 10 PHR (for prefoamed beads)

Then, as shown in Table 7, the cone calorimeter test by heating for 10 minutes was performed on the foamed styrene product (1) prepared at the blending ratio of the raw materials, and as shown in Table 8, the total calorific value was 6.63 MJ. / m ²

TABLE 7

             Exam conditions   Sample direction      level   Sample area 0.008840m ²   Sample thickness    49.8mm   Sample mass    51.60 g    Copy 50.0kW / m ²   Exhaust flow 0.024m ³ / sec  Distance from sample    25 mm   Exam time   600.00 sec

TABLE 8

                      Test result   Total calorific value (THR) 6.63MJ / m ²   Maximum heat generation rate (HRR) 15.88kW / m ² at460.70sec   Average heat generation rate (HRR) 11.05kW / m ²   Average fever rate T60 2.42kW / m ²   Average fever rate T180 5.73 kW / m ²   Average fever rate T300 7.78 kW / m ²     Final mass     38.04 g     Mass loss     13.56 g     Ignition time        ―     Burning time      0.0sec   200k over duration      0.0sec   200k total time      0.0sec  Average combustion effective calorific value (HOC)      4.33MJ / kg  Average mass loss rate (MLR) 2.467 g / sm ²  Average specific photosensitization 347.53m ² / kg

As a result, the foamed styrol product 1 has a total calorific value of 8 MJ / m ² or less at a heating time of 10 minutes, and as shown in FIG. 7, the maximum exothermic rate is 10 seconds or more at 100 g / m ² or less. It continued not to exceed 200 kW / m <^2> . Therefore, this foamed styrole product 1 is a semi-non-combustible 10-minute cone calorimeter test capable of maintaining a shape that is resistant to flame and does not generate moisture and generates little smoke or gas as an organic foam insulation. It can be used as a semi-combustible material satisfying the condition of ⁸ MJ / m ² .

That is, as a heat insulating material composed of styrol foam and other organic foams, the non-flammable material is only a non-flammable material in a 10-minute semi-non-flammable test by the cone calorimeter test in the material alone. 1) is convinced that the present invention is wonderful and innovative and can contribute a lot to the world because mass production is possible, it is inexpensive and can be used as a semi-combustible material.

As shown in Fig. 8, a foamed plastic product having a size of 910 mm (3 characters) x 1820 mm (6 characters) x 600 mm (thickness) or 910 mm (3 characters) x 3640 mm (12 characters) x 600 mm (thickness) A) phosphorus molded board can be shape | molded by the cycle every 4 minutes. In addition, as shown in Fig. 9, by cutting the molded plate at once at regular intervals along the thickness direction and dividing the thickness, a plurality of sheets of foamed styrole product 1 of a constant thickness can be produced at the same time. In addition to being able to enlarge the production of the foamed styrol product 1, productivity can be significantly improved.

[Industry availability]

As mentioned above, the manufacturing method of the foam of this invention is used widely as a manufacturing method, such as foam used for a building material, etc., for example.

Claims (5)

Polystyrene resin particles, polyethylene resin particles, polypropylene resin particles, polyvinyl chloride resin particles, polyamide resin particles, polycarbonate resin particles, modified polyphenylene ether resin particles, polyethersulfone resin particles, and polyester ABS resin particles Pre-foam any one of the resin particles selected from the group consisting of a plurality of pre-foamed particles, These multiple pre-foamed particles are mixed with at least one flame retardant inorganic material and thermosetting resin selected from the group consisting of aluminum hydroxide, magnesium hydroxide and boric acid, and then dried and pulverized to remove these multiple pre-foamed particles. Forming a mixed layer containing the flame-retardant inorganic material and thermosetting resin on the surface of each particle, Filling the mold with a plurality of pre-foamed particles formed on the surface of this mixed layer, A method for producing a foam, characterized in that the mold is filled to form a foam having a predetermined shape by subjecting a plurality of pre-foamed particles formed on the surface thereof to water by steam. The method of claim 1, wherein the pre-foamed particles are polystyrene resin particles, The flame retardant inorganic material is aluminum hydroxide and boric acid, The thermosetting resin is at least one selected from the group consisting of phenol resin, phenol resin, urea resin, melanin resin, guanamine resin, silicone resin, polyimide resin and polyamideimide resin. The flame retardant inorganic material and thermosetting according to claim 1, wherein the plurality of pre-foamed particles are mixed with a flame-retardant inorganic material and a thermosetting resin together with a flame retardant, followed by drying and pulverization. A method for producing a foam, characterized by forming a mixed layer comprising each of a resin and a flame retardant. The method for producing a foam according to claim 3, wherein the flame retardant is at least one of red phosphorus and ammonium polyphosphate. The flame retardant inorganic material according to any one of claims 1 to 4 is a flame retardant inorganic viscosity modifier, Mica is used as this flame retardant inorganic regulator, The manufacturing method of foam.

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